U.S. patent application number 17/018459 was filed with the patent office on 2020-12-31 for photosensitive resin composition, method for manufacturing cured relief pattern, and semiconductor apparatus.
This patent application is currently assigned to ASAHI KASEI KABUSHIKI KAISHA. The applicant listed for this patent is ASAHI KASEI KABUSHIKI KAISHA. Invention is credited to Yoshito IDO, Taihei INOUE, Mitsutaka NAKAMURA, Takahiro SASAKI, Daisuke SASANO, Tomohiro YORISUE, Tomoshige YUNOKUCHI.
Application Number | 20200409263 17/018459 |
Document ID | / |
Family ID | 1000005080121 |
Filed Date | 2020-12-31 |
United States Patent
Application |
20200409263 |
Kind Code |
A1 |
YORISUE; Tomohiro ; et
al. |
December 31, 2020 |
PHOTOSENSITIVE RESIN COMPOSITION, METHOD FOR MANUFACTURING CURED
RELIEF PATTERN, AND SEMICONDUCTOR APPARATUS
Abstract
A photosensitive resin composition containing a resin and a
compound each having a structure specified by the present
specification provides a cured film having excellent adhesiveness
to copper wiring.
Inventors: |
YORISUE; Tomohiro; (Tokyo,
JP) ; INOUE; Taihei; (Tokyo, JP) ; IDO;
Yoshito; (Tokyo, JP) ; NAKAMURA; Mitsutaka;
(Tokyo, JP) ; YUNOKUCHI; Tomoshige; (Tokyo,
JP) ; SASANO; Daisuke; (Tokyo, JP) ; SASAKI;
Takahiro; (Tokyo, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ASAHI KASEI KABUSHIKI KAISHA |
Tokyo |
|
JP |
|
|
Assignee: |
ASAHI KASEI KABUSHIKI
KAISHA
Tokyo
JP
|
Family ID: |
1000005080121 |
Appl. No.: |
17/018459 |
Filed: |
September 11, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
15742975 |
Jan 9, 2018 |
10831101 |
|
|
PCT/JP2017/012743 |
Mar 28, 2017 |
|
|
|
17018459 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H05K 2201/0154 20130101;
C08K 5/33 20130101; C08K 5/375 20130101; G03F 7/0048 20130101; G03F
7/0226 20130101; G03F 7/0387 20130101; G03F 7/162 20130101; G03F
7/0388 20130101; G03F 7/0233 20130101; C08L 2203/20 20130101; G03F
7/037 20130101; H05K 3/287 20130101; G03F 7/031 20130101; H05K
3/022 20130101; C08L 77/00 20130101 |
International
Class: |
G03F 7/022 20060101
G03F007/022; G03F 7/031 20060101 G03F007/031; G03F 7/023 20060101
G03F007/023; G03F 7/038 20060101 G03F007/038; C08L 77/00 20060101
C08L077/00; G03F 7/004 20060101 G03F007/004; G03F 7/037 20060101
G03F007/037; G03F 7/16 20060101 G03F007/16 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 31, 2016 |
JP |
2016-073576 |
Apr 20, 2016 |
JP |
2016-084497 |
Apr 21, 2016 |
JP |
2016-085535 |
Apr 22, 2016 |
JP |
2016-086482 |
May 9, 2016 |
JP |
2016-094177 |
Claims
1. A negative-type photosensitive resin composition, comprising:
(A) a polyimide precursor in the form of a polyamic acid, polyamic
acid ester or polyamic acid salt represented by the following
general formula (18): ##STR00225## {wherein, X.sub.1 and X.sub.2
respectively and independently represent a tetravalent organic
group, Y.sub.1 and Y.sub.2 respectively and independently represent
a divalent organic group, n1 and n2 respectively and independently
represent an integer of 2 to 150, and R.sub.1 and R.sub.2
respectively and independently represent a hydrogen atom, saturated
aliphatic group having 1 to 30 carbon atoms, aromatic group,
monovalent organic group represented by the following general
formula (2): ##STR00226## (wherein, R.sub.3, R.sub.4 and R.sub.5
respectively and independently represent a hydrogen atom or organic
group having 1 to 3 carbon atoms, and m.sub.1 represents an integer
of 2 to 10), or monovalent ammonium ion represented by the
following general formula (3): ##STR00227## (wherein, R.sub.6,
R.sub.7 and R.sub.8 respectively and independently represent a
hydrogen atom or organic group having 1 to 3 carbon atoms, and
m.sub.2 represents an integer of 2 to 10), provided that X.sub.1
and X.sub.2 are not the same and Y.sub.1 and Y.sub.2 are not the
same}; (B) a photosensitizer; and, (C) a solvent.
2. The negative-type photosensitive resin composition according to
claim 1, wherein X.sub.1 and X.sub.2 in general formula (18) are at
least one selected from the group consisting of a group represented
by the following general formula (4): ##STR00228## {wherein, a1
represents an integer of 0 to 2, R.sub.9 represents a hydrogen
atom, fluorine atom or monovalent organic group having 1 to 10
carbon atoms, and in the case a plurality of R.sub.9 are present,
may be mutually the same or different}, a group represented by the
following general formula (5): ##STR00229## {wherein, a2 and a3
respectively and independently represent an integer of 0 to 4, a4
and a5 respectively and independently represent an integer of 0 to
3, R.sub.10 to R.sub.13 respectively and independently represent a
hydrogen atom, fluorine atom or monovalent organic group having 1
to 10 carbon atoms, and in the case a plurality of R.sub.10 to
R.sub.13 are present, may mutually be the same or different}, a
group represented by the following general formula (6):
##STR00230## {wherein, n2 represents an integer of 0 to 5, X.sub.n1
represents a single bond or divalent organic group, in the case a
plurality of X.sub.n1 are present, may mutually be the same or
different, X.sub.m1 represents a single bond or divalent organic
group, at least one of X.sub.m1 and X.sub.n1 represents a single
bond or an organic group selected from the group consisting of an
oxycarbonyl group, oxycarbonylmethylene group, carbonylamino group,
carbonyl group and sulfonyl group, a6 and a8 respectively and
independently represent an integer of 0 to 3, a7 represents an
integer of 0 to 4, R.sub.14, R.sub.15 and R.sub.16 respectively and
independently represent a hydrogen atom, fluorine atom or
monovalent organic group having 1 to 10 carbon atoms, and in the
case a plurality of R.sub.14, R.sub.15 and R.sub.16 are present,
may mutually be the same or different}, and a group represented by
the following general formula (8): ##STR00231## {wherein, n4
represents an integer of 0 to 5, X.sub.m2 and X.sub.n3 respectively
and independently represent an organic group having 1 to 10 carbon
atoms that may contain a fluorine atom but does not contain a
heteroatom other than fluorine, an oxygen atom or a sulfur atom, in
the case of a plurality of X.sub.n3 are present, may be mutually
the same or different, all and a13 respectively and independently
represent an integer of 0 to 3, a12 represents an integer of 0 to
4, R.sub.19, R.sub.20 and R.sub.21 respectively and independently
represent a hydrogen atom, fluorine atom or monovalent organic
group having 1 to 10 carbon atoms, and in the case of a plurality
of R.sub.19, R.sub.20 and R.sub.21 are present, may mutually be the
same or different}.
3. The negative-type photosensitive resin composition according to
claim 1, wherein Y.sub.1 and Y.sub.2 in general formula (18)
represent at least one selected from the group consisting of a
group represented by the following general formula (7):
##STR00232## {wherein, n3 represents an integer of 1 to 5, Y.sub.n2
represents an organic group having 1 to 10 carbon atoms that may
contain a fluorine atom but does not contain a heteroatom other
than fluorine, an oxygen atom or a sulfur atom, in the case a
plurality of Y.sub.n2 are present, may mutually be the same or
different, a9 and a10 respectively and independently represent an
integer of 0 to 4, R.sub.17 and R.sub.18 respectively and
independently represent a hydrogen atom, fluorine atom or
monovalent organic group having 1 to 10 carbon atoms, and in the
case a plurality of R.sub.17 and R.sub.18 are present, may mutually
be the same or different}, a group represented by the following
general formula (9): ##STR00233## {wherein, n5 represents an
integer of 0 to 5, Y.sub.n4 represents a single bond or a divalent
organic group, in the case of a plurality of Y.sub.n4 are present,
may be mutually the same or different, in the case n4 is 2 or more,
at least one of Y.sub.n4 represents a single bond or an organic
group selected from the group consisting of an oxycarbonyl group,
oxycarbonylmethylene group, carbonylamino group, carbonyl group and
sulfonyl group, a14 and a15 respectively and independently
represent an integer of 0 to 4, R.sub.22 and R.sub.23 respectively
and independently represent a hydrogen atom, fluorine atom or
monovalent organic group having 1 to 10 carbon atoms, and in the
case a plurality of R.sub.22 and R.sub.23 are present, may be
mutually the same or different}, and a group represented by the
following general formula (10): ##STR00234## {wherein, a16 to a19
respectively and independently represent an integer of 0 to 4,
R.sub.24 to R.sub.27 respectively and independently represent a
hydrogen atom, fluorine atom or monovalent organic group having 1
to 10 carbon atoms, and in the case a plurality of R.sub.24 to
R.sub.27 are present, may mutually be the same or different}.
4. The negative-type photosensitive resin composition according to
claim 2, wherein at least one of X.sub.1 and X.sub.2 in general
formula (18) is selected from the group consisting of those
represented by general formulas (4), (5), (6) and (8), and at least
one of Y.sub.1 and Y.sub.2 in general formula (18) is selected from
the group consisting of those represented by the following general
formulas (7), (9) and (10): ##STR00235## {wherein, n3 represents an
integer of 1 to 5, Y.sub.n2 represents an organic group having 1 to
10 carbon atoms that may contain a fluorine atom but does not
contain a heteroatom other than fluorine, an oxygen atom or a
sulfur atom, in the case a plurality of Y.sub.n2 are present, may
mutually be the same or different, a9 and a10 respectively and
independently represent an integer of 0 to 4, R.sub.17 and R.sub.18
respectively and independently represent a hydrogen atom, fluorine
atom or monovalent organic group having 1 to 10 carbon atoms, and
in the case a plurality of R.sub.17 and R.sub.18 are present, may
mutually be the same or different}, ##STR00236## {wherein, n5
represents an integer of 0 to 5, Y.sub.n4 represents a single bond
or a divalent organic group, in the case of a plurality of Y.sub.n4
are present, may be mutually the same or different, in the case n4
is 2 or more, at least one of Y.sub.n4 represents a single bond or
an organic group selected from the group consisting of an
oxycarbonyl group, oxycarbonylmethylene group, carbonylamino group,
carbonyl group and sulfonyl group, a14 and a15 respectively and
independently represent an integer of 0 to 4, R.sub.22 and R.sub.23
respectively and independently represent a hydrogen atom, fluorine
atom or monovalent organic group having 1 to 10 carbon atoms, and
in the case a plurality of R.sub.22 and R.sub.23 are present, may
be mutually the same or different}, and ##STR00237## {wherein, a16
to a19 respectively and independently represent an integer of 0 to
4, R.sub.24 to R.sub.27 respectively and independently represent a
hydrogen atom, fluorine atom or monovalent organic group having 1
to 10 carbon atoms, and in the case a plurality of R.sub.24 to
R.sub.27 are present, may mutually be the same or different}.
5. The negative-type photosensitive resin composition according to
claim 2, wherein, in general formula (18), at least one of X.sub.1
and X.sub.2 is represented by general formula (8) and at least one
of Y.sub.1 and Y2 is represented by the following general formula
(7): ##STR00238## {wherein, n3 represents an integer of 1 to 5,
Y.sub.n2 represents an organic group having 1 to 10 carbon atoms
that may contain a fluorine atom but does not contain a heteroatom
other than fluorine, an oxygen atom or a sulfur atom, in the case a
plurality of Y.sub.n2 are present, may mutually be the same or
different, a9 and a10 respectively and independently represent an
integer of 0 to 4, R.sub.17 and R.sub.18 respectively and
independently represent a hydrogen atom, fluorine atom or
monovalent organic group having 1 to 10 carbon atoms, and in the
case a plurality of R.sub.17 and R.sub.18 are present, may mutually
be the same or different}.
6. The negative-type photosensitive resin composition according to
claim 2, wherein, in general formula (18), X.sub.1 is represented
by general formula (8) and Y.sub.1 is represented by the following
general formula (7): ##STR00239## {wherein, n3 represents an
integer of 1 to 5, Y.sub.n2 represents an organic group having 1 to
10 carbon atoms that may contain a fluorine atom but does not
contain a heteroatom other than fluorine, an oxygen atom or a
sulfur atom, in the case a plurality of Y.sub.n2 are present, may
mutually be the same or different, a9 and a10 respectively and
independently represent an integer of 0 to 4, R.sub.17 and R.sub.18
respectively and independently represent a hydrogen atom, fluorine
atom or monovalent organic group having 1 to 10 carbon atoms, and
in the case a plurality of R.sub.17 and R.sub.18 are present, may
mutually be the same or different}.
7. The negative-type photosensitive resin composition according to
claim 1, wherein the solvent (C) includes at least one selected
from the group consisting of N-methyl-2-pyrrolidone,
.gamma.-butyrolactone, dimethylsulfoxide, tetrahydrofurfuryl
alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate,
N,N-dimethylacetoacetamide, .epsilon.-caprolactone, and
1,3-dimethyl-2-imidazolidinone.
8. The negative-type photosensitive resin composition according to
claim 7, wherein the solvent (C) includes at least two selected
from the group consisting of N-methyl-2-pyrrolidone,
.gamma.-butyrolactone, dimethylsulfoxide, tetrahydrofurfuryl
alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate,
N,N-dimethylacetoacetamide, .epsilon.-caprolactone, and
1,3-dimethyl-2-imidazolidinone.
9. The negative-type photosensitive resin composition according to
claim 8, wherein the solvent (C) includes .gamma.-butyrolactone and
dimethylsulfoxide.
10. A photosensitive resin composition containing a photosensitive
polyimide precursor, wherein a focus margin of a rounded-out
concave relief pattern is 8 .mu.m or more, the rounded-out concave
relief pattern being obtained by carrying out the following in
order: spin-coating the resin composition onto a sputtered Cu wafer
substrate; obtaining a spin-coated film having a film thickness of
13 .mu.m by heating the spin-coated wafer substrate on a hot plate
for 270 seconds at 110.degree. C.; exposing a rounded-out concave
pattern with a mask size of 8 .mu.m by changing the focus from the
surface of the film to the bottom of the film 2 .mu.m at a time
using the surface of the spin-coated film as a reference; forming a
relief pattern by developing the exposed wafer; and heat-treating
the developed wafer in a nitrogen atmosphere for 2 hours at
230.degree. C.
11. The photosensitive resin composition according to claim 10,
wherein the focus margin is 12 .mu.m or more.
12. The photosensitive resin composition according to claim 10,
wherein the cross-sectional angle of a cured product of the
photosensitive polyimide precursor in the form of a cured relief
pattern is 60.degree. to 90.degree..
13. The photosensitive resin composition according to claim 10,
wherein the photosensitive polyimide precursor is a polyamic acid
derivative having a radical-polymerizable substituent in a side
chain thereof.
14. The photosensitive resin composition according to claim 10,
wherein the photosensitive polyimide precursor contains a structure
represented by the following general formula (21): ##STR00240##
{wherein, X.sub.1a represents a tetravalent organic group, Y.sub.1a
represents a divalent organic group, n.sub.1a represents an integer
of 2 to 150, and R.sub.1a and R.sub.2a respectively and
independently represent a hydrogen atom, monovalent organic group
represented by the following general formula (22): ##STR00241##
(wherein, R.sub.3a, R.sub.4a and R.sub.5a respectively and
independently represent a hydrogen atom or organic group having 1
to 3 carbon atoms, and m.sub.1a represents an integer of 2 to 10),
or a saturated aliphatic group having 1 to 4 carbon atoms, provided
that R.sub.1a and R.sub.2a are not both simultaneously hydrogen
atoms}.
15. The photosensitive resin composition according to claim 14,
wherein, in general formula (21), X.sub.1a represents at least one
tetravalent organic group selected from group consisting of the
following formulas (23) to (25): ##STR00242## and Y.sub.1a
represents at least one divalent organic group selected from the
group consisting of a group represented by the following general
formula (26): ##STR00243## {wherein, R.sub.6a to R.sub.9a represent
hydrogen atoms or monovalent aliphatic groups having 1 to 4 carbon
atoms and may mutually be the same or different}, a group
represented by the following formula (27): ##STR00244## and a group
represented by the following formula (28): ##STR00245## {wherein,
R.sub.10a and R.sub.11a respectively and independently represent a
fluorine atom, trifluoromethyl group or methyl group}.
16. The photosensitive resin composition according to claim 10,
further containing a photopolymerization initiator.
17. The photosensitive resin composition according to claim 16,
wherein the photopolymerization initiator contains a component
represented by the following general formula (29): ##STR00246##
{wherein, Z represents a sulfur atom or oxygen atom, R.sub.12a
represents a methyl group, phenyl group or divalent organic group,
and R.sub.13a to R.sub.15a respectively and independently represent
a hydrogen atom or monovalent organic group}.
18. The photosensitive resin composition according to claim 10,
further containing an inhibitor.
19. The photosensitive resin composition according to claim 18,
wherein the inhibitor is at least one selected from the group
consisting of a hindered phenol-type inhibitor and nitroso-type
inhibitor.
20. A method for producing a cured relief pattern comprising:
forming a photosensitive resin layer on a substrate by coating the
photosensitive resin composition according to claim 10 on the
substrate; exposing the photosensitive resin layer to light;
forming a relief pattern by developing the photosensitive resin
layer after exposing to light; and forming a cured relief pattern
by heat-treating the relief pattern.
21. The method according to claim 20, wherein the substrate
comprises copper or copper alloy.
Description
[0001] This application is a Divisional of U.S. application Ser.
No. 15/742,975, which is the U.S. National Stage of
PCT/JP2017/012743, filed Mar. 28, 2017, which claims priority to
Application Nos. JP 2016-094177, filed May 9, 2016, JP 2016-086482,
filed Apr. 22, 2016, JP 2016-085535, filed Apr. 21, 2016, JP
2016-084497, filed Apr. 20, 2016, and JP 2016-073576, filed Mar.
31, 2016. The disclosure of each of these applications is herein
incorporated by reference in its entirety.
TECHNICAL FIELD
[0002] The present invention relates to a photosensitive resin
composition used to form a relief pattern of, for example, an
insulating material of an electronic component or a passivation
film, buffer coat film or interlayer insulating film of a
semiconductor device, a method for producing a cured relief pattern
using the same, and a semiconductor device.
BACKGROUND ART
[0003] Polyimide films having superior heat resistance, electrical
properties and mechanical properties have conventionally been used
for the insulating materials of electronic components and the
passivation films, buffer coat films and interlayer insulating
films of semiconductor devices. Among these polyimide resins, those
supplied in the form of photosensitive polyimide precursors are
capable of easily forming a heat-resistant relief pattern by
subjecting the polyimide precursor to thermal imidization treatment
by coating, exposing to light, developing and curing. These
photosensitive polyimide precursors have the characteristic of
enabling a considerable reduction in processing time in comparison
with conventional non-photosensitive polyimides.
[0004] On the other hand, the methods used to mount semiconductor
devices on printed wiring boards have changed in recent years from
the viewpoints of improving the degree of integration and function
and reducing chip size. Structures are being employed in which a
polyimide coating makes direct contact with the solder bump in the
manner of the transition from conventional mounting methods using
metal pins or lead-tin eutectic solder to higher density mounting
methods such as ball grid arrays (BGA) or chip size packaging
(CSP). The coating is required to have high heat resistance and
chemical resistance during formation of such bump structures. A
method has been disclosed for improving the heat resistance of
polyimide coatings or polybenzoxazole coatings by adding a thermal
crosslinking agent to a composition containing a polyimide
precursor or polybenzoxazole precursor (see Patent Document 1).
[0005] Moreover, the wiring resistance of semiconductor devices can
no longer be ignored due to the increasing miniaturization of
semiconductor devices. Thus, the change is being made from
previously used gold or aluminum wiring to copper or copper alloy
wiring having lower resistance, and there are many cases in which
surface protective films or interlay insulating films are formed on
the copper and copper alloy. Consequently, adhesion with copper or
copper alloy wiring has come to have a considerable effect on the
reliability of semiconductor elements, thus resulting in a need for
enhanced adhesion with copper and copper alloy wiring (see Patent
Document 2).
PRIOR ART DOCUMENTS
Patent Documents
[0006] [Patent Document 1] Japanese Unexamined Patent Publication
No. 2003-287889
[0007] [Patent Document 2] Japanese Unexamined Patent Publication
No. 2005-336125
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
[0008] Although there is a method consisting of adding an additive
component to a resin composition for the purpose of improving the
adhesion with copper and copper alloy in order to respond to the
needs as explained above (see, for example, Patent Document 2),
this method was unable to obtain sufficient adhesion.
[0009] With the foregoing in view, an object of the present
invention is to provide a negative-type photosensitive resin
composition that yields a cured film demonstrating superior
adhesion to copper wire, a pattern formation and production method
for forming a polyimide pattern using the photosensitive resin
composition, and a semiconductor device.
Means for Solving the Problem
[0010] The inventors of the present invention found that a
photosensitive resin composition can be obtained that yields a
cured film demonstrating superior adhesion to copper wire by using
a resin having a specific structure and a compound, thereby leading
to completion of the present invention. Namely, the present
invention is as indicated below.
[0011] [1] A negative-type photosensitive resin composition
including:
[0012] (A) a polyimide precursor in the form of a polyamic acid,
polyamic acid ester or polyamic acid salt represented by the
following general formula (1):
##STR00001##
{wherein, X represents a tetravalent organic group, Y represents a
divalent organic group, n.sub.1 represents an integer of 2 to 150,
and R.sub.1 and R.sub.2 respectively and independently represent a
hydrogen atom, saturated aliphatic group having 1 to 30 carbon
atoms, aromatic group, monovalent organic group represented by the
following general formula (2):
##STR00002##
(wherein, R.sub.2, R.sub.4 and R.sub.5 respectively and
independently represent a hydrogen atom or organic group having 1
to 3 carbon atoms, and m.sub.1 represents an integer of 2 to 10),
or monovalent ammonium ion represented by the following general
formula (3):
##STR00003##
(wherein, R.sub.6, R.sub.7 and R.sub.8 respectively and
independently represent a hydrogen atom or organic group having 1
to 3 carbon atoms, and m.sub.2 represents an integer of 2 to 10)},
and,
[0013] (B) a photosensitizer; wherein,
[0014] the component (A) is a blend of at least one of the
following resins (A1) to (A3) with the following resin (A4):
[0015] (A1) a resin in which X in general formula (1) is a group
represented by the following general formula (4):
##STR00004##
{wherein, a1 represents an integer of 0 to 2, R.sub.9 represents a
hydrogen atom, fluorine atom or monovalent organic group having 1
to 10 carbon atoms, and in the case a plurality of R.sub.9 are
present, may be mutually the same or different}, a group
represented by the following general formula (5):
##STR00005##
{wherein, a2 and a3 respectively and independently represent an
integer of 0 to 4, a4 and a5 respectively and independently
represent an integer of 0 to 3, R.sub.10 to R.sub.13 respectively
and independently represent a hydrogen atom, fluorine atom or
monovalent organic group having 1 to 10 carbon atoms, and in the
case a plurality of R.sub.10 to R.sub.13 are present, may mutually
be the same or different}, a group represented by the following
general formula (6):
##STR00006##
{wherein, n2 represents an integer of 0 to 5, X.sub.n1 represents a
single bond or divalent organic group, in the case a plurality of
X.sub.n1 are present, may mutually be the same or different,
X.sub.m1 represents a single bond or divalent organic group, at
least one of X.sub.m1 and X.sub.n1 represents a single bond or an
organic group selected from the group consisting of an oxycarbonyl
group, oxycarbonylmethylene group, carbonylamino group, carbonyl
group and sulfonyl group, a6 and a8 respectively and independently
represent an integer of 0 to 3, a7 represents an integer of 0 to 4,
R.sub.14, R.sub.15 and R.sub.16 respectively and independently
represent a hydrogen atom, fluorine atom or monovalent organic
group having 1 to 10 carbon atoms, and in the case a plurality of
R.sub.14, R.sub.15 and R.sub.16 are present, may mutually be the
same or different}; and, Y in general formula (1) represents a
group represented by the following general formula (7):
##STR00007##
{wherein, n3 represents an integer of 1 to 5, Y.sub.n2 represents
an organic group having 1 to 10 carbon atoms that may contain a
fluorine atom but does not contain a heteroatom other than
fluorine, an oxygen atom or a sulfur atom, in the case a plurality
of Y.sub.n2 are present, may mutually be the same or different, a9
and a10 respectively and independently represent an integer of 0 to
4, R.sub.17 and R.sub.18 respectively and independently represent a
hydrogen atom, fluorine atom or monovalent organic group having 1
to 10 carbon atoms, and in the case a plurality of R.sub.17 and
R.sub.18 are present, may mutually be the same or different};
[0016] (A2) a resin in which X in general formula (1) is a group
represented by the following general formula (8):
##STR00008##
{wherein, n4 represents an integer of 0 to 5, X.sub.m2 and X.sub.n3
respectively and independently represent an organic group having 1
to 10 carbon atoms that may contain a fluorine atom but does not
contain a heteroatom other than fluorine, an oxygen atom or a
sulfur atom, in the case of a plurality of X.sub.n2 are present,
may be mutually the same or different, a11 and a13 respectively and
independently represent an integer of 0 to 3, a12 represents an
integer of 0 to 4, R.sub.19, R.sub.20 and R.sub.21 respectively and
independently represent a hydrogen atom, fluorine atom or
monovalent organic group having 1 to 10 carbon atoms, and in the
case of a plurality of R.sub.19, R.sub.20 and R.sub.21 are present,
may mutually be the same or different}, and Y in general formula
(1) is a group represented by the following general formula
(9):
##STR00009##
{wherein, n5 represents an integer of 0 to 5, Y.sub.n4 represents a
single bond or a divalent organic group, in the case of a plurality
of Y.sub.n4 are present, may be mutually the same or different, in
the case n4 is 2 or more, at least one of Y.sub.n4 represents a
single bond or an organic group selected from the group consisting
of an oxycarbonyl group, oxycarbonylmethylene group, carbonylamino
group, carbonyl group and sulfonyl group, a14 and a15 respectively
and independently represent an integer of 0 to 4, R.sub.22 and
R.sub.23 respectively and independently represent a hydrogen atom,
fluorine atom or monovalent organic group having 1 to 10 carbon
atoms, and in the case a plurality of R.sub.22 and R.sub.23 are
present, may be mutually the same or different}, or a group
represented by the following general formula (10):
##STR00010##
{wherein, a16 to a19 respectively and independently represent an
integer of 0 to 4, R.sub.24 to R.sub.27 respectively and
independently represent a hydrogen atom, fluorine atom or
monovalent organic group having 1 to 10 carbon atoms, and in the
case a plurality of R.sub.24 to R.sub.27 are present, may mutually
be the same or different};
[0017] (A3) a resin in which X in general formula (1) is a group
represented by general formula (4), (5) or (6), and Y in general
formula (1) is a group represented by general formula (9) or (10);
and,
[0018] (A4) a resin in which X in general formula (1) is a group
represented by general formula (8), and Y in general formula (1) is
a group represented by general formula (7).
[0019] [2] The negative-type photosensitive resin composition
described in [1], wherein the group represented by general formula
(6) is at least one group selected from the group consisting of
groups represented by the following general formula (X1):
##STR00011##
{wherein, a20 and a21 respectively and independently represent an
integer of 0 to 3, a22 represents an integer of 0 to 4, R.sub.28 to
R.sub.30 respectively and independently represent a hydrogen atom,
fluorine atom or organic group having 1 to 10 carbon atoms, and in
the case a plurality of R.sub.28 to R.sub.30 are present, may be
mutually the same or different}, the group represented by general
formula (7) is at least one group selected from the group
consisting of groups represented by the following general formula
(Y1):
##STR00012##
{wherein, a23 to a26 respectively and independently represent an
integer of 0 to 4, R.sub.31 to R.sub.34 respectively and
independently represent a hydrogen atom, fluorine atom or
monovalent organic group having 1 to 10 carbon atoms, and in the
case a plurality of R.sub.31 to R.sub.34 are present, may mutually
be the same or different}, the group represented by general formula
(8) is at least group selected from the group consisting of groups
represented by the following general formula (X2):
##STR00013##
{wherein, a27 and a28 respectively and independently represent an
integer of 0 to 3, R.sub.35 and R.sub.36 respectively and
independently represent a hydrogen atom, fluorine atom or
monovalent organic group having 1 to 10 carbon atoms, and in the
case a plurality of R.sub.35 and R.sub.36 are present, may mutually
be the same or different}, and the group represented by general
formula (9) is at least one group selected from the group
consisting of groups represented by the following general formula
(Y2):
##STR00014##
{wherein, a29 to a32 respectively and independently represent an
integer of 0 to 4, R.sub.37 to R.sub.40 respectively and
independently represent a hydrogen atom, fluorine atom or
monovalent organic group having 1 to 10 carbon atoms, and in the
case a plurality of R.sub.37 to R.sub.40 are present, may mutually
be the same or different}.
[0020] [3] The negative-type photosensitive resin composition
described in [1] or [2], wherein, in general formula (1) of (A1),
50 mol % or more of X is a group represented by general formula
(4), (5) or (6), and 50 mol % or more of Y is a group represented
by general formula (7).
[0021] [4] The negative-type photosensitive resin composition
described in any of [1] to [3], wherein, in general formula (1) of
(A2), 50 mol % or more of X is a group represented by general
formula (8), and 50 mol % or more of Y is a group represented by
general formula (9) or (10).
[0022] [5] The negative-type photosensitive resin composition
described in any of [1] to [4], wherein, in general formula (1) of
(A3), 50 mol % or more of X is a group represented by general
formula (4), (5) or (6), and 50 mol % or more of Y is a group
represented by general formula (9) or (10).
[0023] [6] The negative-type photosensitive resin composition
described in any of [1] to [5], wherein, in general formula (1) of
(A4), 50 mol % or more of X is a group represented by general
formula (8), and 50 mol % or more of Y in general formula (1) is a
group represented by formula (7).
[0024] [7] The negative-type photosensitive resin composition
described in any of [1] to [6], wherein the content of (A4) is 10%
by weight to 90% by weight of the sum of the weights of (A1) to
(A4).
[0025] [8] The negative-type photosensitive resin composition
described in any of [1] to [7], wherein the sum of the weights of
(A1) to (A4) is 50% or more of the total weight of component
(A).
[0026] [9] The negative-type photosensitive resin composition
described in any of [1] to [8], wherein 50 mol % or more of X in
general formula (1) of (A1) is a group represented by general
formula (4), (5) or (6), and 50 mol % or more of Y in general
formula (1) of (A1) is a group represented by the following formula
(11).
##STR00015##
[0027] [10] The negative-type photosensitive resin composition
described in any of [1] to [9], wherein 50 mol % or more of X in
general formula (1) of (A2) is a group represented by the following
formula (12):
##STR00016##
and 50 mol % or more of Y in general formula (1) of (A2) is a group
represented by formula (9) or (10).
[0028] [11] The negative-type photosensitive resin composition
described in any of [1] to [10], wherein 50 mol % or more of X in
general formula (1) of (A4) is a group represented by formula (12),
and 50 mol % or more of Y in general formula (1) of (A4) is a group
represented by formula (11).
[0029] [12] The negative-type photosensitive resin composition
described in [11], wherein 80 mol % or more of X in general formula
(1) of (A4) is a group represented by formula (12), and 80 mol % or
more of Y in general formula (1) is a group represented by formula
(11).
[0030] [13] The negative-type photosensitive resin composition
described in [11] or [12], containing a solvent (C1) having a
boiling point of 200.degree. C. to 250.degree. C. and a solvent
(C2) having a boiling point of 160.degree. C. to 190.degree. C.
[0031] [14] The negative-type photosensitive resin composition
described in [11] or [12], wherein the solvent (C) includes at
least two types selected from the group consisting of
.gamma.-butyrolactone, dimethylsulfoxide, tetrahydrofurfuryl
alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate,
N,N-dimethylacetoacetamide, .epsilon.-caprolactone and
1,3-dimethyl-2-imidazolidinone.
[0032] [15] The negative-type photosensitive resin composition
described in [14], wherein the solvent (C1) is
.gamma.-butyrolactone and the solvent (C2) is
dimethylsulfoxide.
[0033] [16] The negative-type photosensitive resin composition
described in any of [13] to [15], wherein the weight of the solvent
(C2) is 5% to 50% of the sum of the weights of the solvent (C1) and
the solvent (C2).
[0034] [17] The negative-type photosensitive resin composition
described in any of [1] to [16], containing a solvent (C1) having a
boiling point of 200.degree. C. to 250.degree. C. and a solvent
(C2) having a boiling point of 160.degree. C. to 190.degree. C.
[0035] [18] The negative-type photosensitive resin composition
described in [17], wherein the solvent (C) includes at least two
types selected from the group consisting of .gamma.-butyrolactone,
dimethylsulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate,
dimethyl succinate, dimethyl malonate, N,N-dimethylacetoacetamide,
.epsilon.-caprolactone and 1,3-dimethyl-2-imidazolidinone.
[0036] [19] The negative-type photosensitive resin composition
described in [18], wherein the solvent (C1) is
.gamma.-butyrolactone and the solvent (C2) is
dimethylsulfoxide.
[0037] [20] The negative-type photosensitive resin composition
described in any of [17] to [19], wherein the weight of the solvent
(C2) is 5% to 50% of the sum of the weights of the solvent (C1) and
the solvent (C2).
[0038] [21] A negative-type photosensitive resin composition
including:
[0039] (A) a polyimide precursor in the form of a polyamic acid,
polyamic acid ester or polyamic acid salt represented by the
following general formula (18):
##STR00017##
{wherein, X.sub.1 and X.sub.2 respectively and independently
represent a tetravalent organic group, Y.sub.1 and Y.sub.2
respectively and independently represent a divalent organic group,
n1 and n2 respectively and independently represent an integer of 2
to 150, and R.sub.1 and R.sub.2 respectively and independently
represent a hydrogen atom, saturated aliphatic group having 1 to 30
carbon atoms, aromatic group, monovalent organic group represented
by the general formula (2) or monovalent ammonium ion represented
by general formula (3), provided that X.sub.1 and X.sub.2 are not
the same and Y.sub.1 and Y.sub.2 are not the same};
[0040] (B) a photosensitizer; and,
[0041] (C) a solvent.
[0042] [22] The negative-type photosensitive resin composition
described in [21], wherein X.sub.1 and X.sub.2 in general formula
(18) are at least one type selected from the group consisting of a
group represented by the following general formula (4):
##STR00018##
{wherein, a1 represents an integer of 0 to 2, R.sub.9 represents a
hydrogen atom, fluorine atom or monovalent organic group having 1
to 10 carbon atoms, and in the case a plurality of R.sub.9 are
present, may be mutually the same or different}, a group
represented by the following general formula (5):
##STR00019##
{wherein, a2 and a3 respectively and independently represent an
integer of 0 to 4, a4 and a5 respectively and independently
represent an integer of 0 to 3, R.sub.10 to R.sub.13 respectively
and independently represent a hydrogen atom, fluorine atom or
monovalent organic group having 1 to 10 carbon atoms, and in the
case a plurality of R.sub.10 to R.sub.13 are present, may mutually
be the same or different}, a group represented by the following
general formula (6):
##STR00020##
{wherein, n2 represents an integer of 0 to 5, X.sub.n1 represents a
single bond or divalent organic group, in the case a plurality of
X.sub.n1 are present, may mutually be the same or different,
X.sub.m1 represents a single bond or divalent organic group, at
least one of X.sub.m1 and X.sub.n1 represents a single bond or an
organic group selected from the group consisting of an oxycarbonyl
group, oxycarbonylmethylene group, carbonylamino group, carbonyl
group and sulfonyl group, a6 and a8 respectively and independently
represent an integer of 0 to 3, a7 represents an integer of 0 to 4,
R.sub.14, R.sub.15 and R.sub.16 respectively and independently
represent a hydrogen atom, fluorine atom or monovalent organic
group having 1 to 10 carbon atoms, and in the case a plurality of
R.sub.14, R.sub.15 and R.sub.16 are present, may mutually be the
same or different}, and a group represented by the following
general formula (8):
##STR00021##
{wherein, n4 represents an integer of 0 to 5, X.sub.m2 and X.sub.n3
respectively and independently represent an organic group having 1
to 10 carbon atoms that may contain a fluorine atom but does not
contain a heteroatom other than fluorine, an oxygen atom or a
sulfur atom, in the case of a plurality of X.sub.n3 are present,
may be mutually the same or different, a11 and a13 respectively and
independently represent an integer of 0 to 3, a12 represents an
integer of 0 to 4, R.sub.19, R.sub.20 and R.sub.21 respectively and
independently represent a hydrogen atom, fluorine atom or
monovalent organic group having 1 to 10 carbon atoms, and in the
case of a plurality of R.sub.19, R.sub.20 and R.sub.21 are present,
may mutually be the same or different}.
[0043] [23] The negative-type photosensitive resin composition
described in [21] or [22], wherein Y.sub.1 and Y.sub.2 in general
formula (18) represent at least one type selected from the group
consisting of a group represented by the following general formula
(7):
##STR00022##
{wherein, n3 represents an integer of 1 to 5, Y.sub.n2 represents
an organic group having 1 to 10 carbon atoms that may contain a
fluorine atom but does not contain a heteroatom other than
fluorine, an oxygen atom or a sulfur atom, in the case a plurality
of Y.sub.n2 are present, may mutually be the same or different, a9
and a10 respectively and independently represent an integer of 0 to
4, R.sub.17 and R.sub.18 respectively and independently represent a
hydrogen atom, fluorine atom or monovalent organic group having 1
to 10 carbon atoms, and in the case a plurality of R.sub.17 and
R.sub.18 are present, may mutually be the same or different}, a
group represented by the following general formula (9):
##STR00023##
{wherein, n5 represents an integer of 0 to 5, Y.sub.n4 represents a
single bond or a divalent organic group, in the case of a plurality
of Y.sub.n4 are present, may be mutually the same or different, in
the case n4 is 2 or more, at least one of Y.sub.n4 represents a
single bond or an organic group selected from the group consisting
of an oxycarbonyl group, oxycarbonylmethylene group, carbonylamino
group, carbonyl group and sulfonyl group, a14 and a15 respectively
and independently represent an integer of 0 to 4, R.sub.22 and
R.sub.23 respectively and independently represent a hydrogen atom,
fluorine atom or monovalent organic group having 1 to 10 carbon
atoms, and in the case a plurality of R.sub.22 and R.sub.23 are
present, may be mutually the same or different}, and a group
represented by the following general formula (10):
##STR00024##
{wherein, a16 to a19 respectively and independently represent an
integer of 0 to 4, R.sub.24 to R.sub.27 respectively and
independently represent a hydrogen atom, fluorine atom or
monovalent organic group having 1 to 10 carbon atoms, and in the
case a plurality of R.sub.24 to R.sub.27 are present, may mutually
be the same or different}.
[0044] [24] The negative-type photosensitive resin composition
described in [22] or [23], wherein at least one of X.sub.1 and
X.sub.2 in general formula (18) is selected from the group
consisting of those represented by general formulas (4), (5), (6)
and (8), and at least one of Y.sub.1 and Y.sub.2 in general formula
(18) is selected from the group consisting of those represented by
general formulas (7), (9) and (10).
[0045] [25] The negative-type photosensitive resin composition
described in any of [22] to [24], wherein, in general formula (18),
at least one of X.sub.1 and X.sub.2 is represented by general
formula (8) and at least one of Y.sub.1 and Y2 is represented by
general formula (7).
[0046] [26] The negative-type photosensitive resin composition
described in any of [22] to [25], wherein, in general formula (18),
X.sub.1 is represented by general formula (8) and Y.sub.1 is
represented by general formula (7).
[0047] [27] The negative-type photosensitive resin composition
described in any of [21] to [26], wherein the solvent (C) includes
at least one type selected from the group consisting of
N-methyl-2-pyrrolidone, .gamma.-butyrolactone, dimethylsulfoxide,
tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate,
dimethyl malonate, N,N-dimethylacetoacetamide,
.epsilon.-caprolactone and 1,3-dimethyl-2-imidazolidinone.
[0048] [28] The negative-type photosensitive resin composition
described in [27], wherein the solvent (C) includes at least two
types selected from the group consisting of N-methyl-2-pyrrolidone,
.gamma.-butyrolactone, dimethylsulfoxide, tetrahydrofurfuryl
alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate,
N,N-dimethylacetoacetamide, .epsilon.-caprolactone and
1,3-dimethyl-2-imidazolidinone.
[0049] [29] The negative-type photosensitive resin composition
described in [28], wherein the solvent (C) includes
.gamma.-butyrolactone and dimethylsulfoxide.
[0050] [30] The negative-type photosensitive resin composition
described in any of [1] to [29], wherein the photosensitizer (B) is
a photo-radical initiator.
[0051] [31] The negative-type photosensitive resin composition
described in any of [1] to [30], wherein the photosensitizer (B)
contains a component represented by the following general formula
(13):
##STR00025##
{wherein, Z represents a sulfur atom or oxygen atom, R.sub.41
represents a methyl group, phenyl group or divalent organic group,
and R.sub.42 to R.sub.44 respectively and independently represent a
hydrogen atom or monovalent organic group}.
[0052] [32] The negative-type photosensitive resin composition
described in [31], wherein the component represented by general
formula (13) is at least one member selected from the group
consisting of compounds represented by the following general
formulas (14) to (17).
##STR00026##
[0053] [33] A method for producing a cured relief pattern,
including the steps of:
[0054] (1) forming a negative-type photosensitive resin layer on a
substrate by coating the negative-type photosensitive resin
composition described in any of [1] to [32] on the substrate;
[0055] (2) exposing the negative-type photosensitive resin layer to
light;
[0056] (3) forming a relief pattern by developing the
photosensitive resin layer after exposing to light; and,
[0057] (4) forming a cured relief pattern by heat-treating the
relief pattern.
[0058] [34] A photosensitive resin composition containing a
photosensitive polyimide precursor, wherein the focus margin of a
rounded-out concave relief pattern is 8 .mu.m or more, the
rounded-out concave relief pattern being obtained by going through
the following steps (1) to (5) in that order:
[0059] (1) spin-coating the resin composition onto a sputtered Cu
wafer substrate;
[0060] (2) obtaining a spin-coated film having a film thickness of
13 .mu.m by heating a spin-coated wafer substrate on a hot plate
for 270 seconds at 110.degree. C.;
[0061] (3) exposing a rounded-out concave pattern with a mask size
of 8 .mu.m by changing the focus from the surface of the film to
the bottom of the film 2 .mu.m at a time using the surface of the
spin-coated film as a reference;
[0062] (4) forming a relief pattern by developing the exposed
wafer; and,
[0063] (5) heat-treating the developed wafer in a nitrogen
atmosphere for 2 hours at 230.degree. C.
[0064] [35] The photosensitive resin composition described in [34],
wherein the focus margin is 12 .mu.m or more.
[0065] [36] The photosensitive resin composition described in [34]
or [35], wherein the cross-sectional angle of a cured product of
the photosensitive polyimide precursor in the form of a cured
relief pattern is 60.degree. to 90.degree..
[0066] [37] The photosensitive resin composition described in any
of [34] to [36], wherein the photosensitive polyimide precursor is
a polyamic acid derivative having a radical-polymerizable
substituent in a side chain thereof.
[0067] [38] The photosensitive resin composition described in any
of [34] to [37], wherein the photosensitive polyimide precursor
contains a structure represented by the following general formula
(21):
##STR00027##
{wherein, X.sub.1a represents a tetravalent organic group, Y.sub.1a
represents a divalent organic group, n.sub.1a represents an integer
of 2 to 150, and R.sub.1a and R.sub.2a respectively and
independently represent a hydrogen atom, monovalent organic group
represented by the following general formula (22):
##STR00028##
(wherein, R.sub.3a, R.sub.4a and R.sub.5a respectively and
independently represent a hydrogen atom or organic group having 1
to 3 carbon atoms, and m.sub.1a represents an integer of 2 to 10),
or a saturated aliphatic group having 1 to 4 carbon atoms, provided
that R.sub.1a and R.sub.2a are not both simultaneously hydrogen
atoms}.
[0068] [39] The photosensitive resin composition described in [38],
wherein, in general formula (21), X.sub.1a represents at least one
tetravalent organic group selected from the group consisting of the
following formulas (23) to (25):
##STR00029##
and Y.sub.1a represents at least one divalent organic group
selected from the group consisting of a group represented by the
following general formula (26):
##STR00030##
{wherein, R.sub.6a to R.sub.9a represent hydrogen atoms or
monovalent aliphatic groups having 1 to 4 carbon atoms and may
mutually be the same or different}, a group represented by the
following formula (27):
##STR00031##
and a group represented by the following formula (28):
##STR00032##
{wherein, R.sub.10a and R.sub.11a respectively and independently
represent a fluorine atom, trifluoromethyl group or methyl
group}.
[0069] [40] The photosensitive resin composition described in any
of [34] to [39], further containing a photopolymerization
initiator.
[0070] [41] The photosensitive resin composition described in [40],
wherein the photopolymerization initiator contains a component
represented by the following general formula (29):
##STR00033##
{wherein, Z represents a sulfur atom or oxygen atom, R.sub.12a
represents a methyl group, phenyl group or divalent organic group,
and R.sub.13a to R.sub.15a respectively and independently represent
a hydrogen atom or monovalent organic group}.
[0071] [42] The photosensitive resin composition described in any
of [34] to [41], further containing an inhibitor.
[0072] [43] The photosensitive resin composition described in [42],
wherein the inhibitor is at least one type selected from the group
consisting of a hindered phenol-type inhibitor and nitroso-type
inhibitor.
[0073] [44] A method for producing a cured relief pattern including
the following steps (6) to (9):
[0074] (6) forming a photosensitive resin layer on a substrate by
coating the photosensitive resin composition described in any of
[34] to [43] on the substrate;
[0075] (7) exposing the photosensitive resin layer to light;
[0076] (8) forming a relief pattern by developing the
photosensitive resin layer after exposing to light; and,
[0077] (9) forming a cured relief pattern by heat-treating the
relief pattern.
[0078] [45] The method described in [44], wherein the substrate
comprises copper or copper alloy.
Effects of the Invention
[0079] According to the present invention, a photosensitive resin
composition can be obtained that yields a cured film demonstrating
superior adhesion to copper wiring by incorporating a polyimide
precursor having a specific structure in a photosensitive resin
composition, and a method for producing a cured relief pattern that
forms a pattern using the photosensitive resin composition, along
with a semiconductor device, can be provided.
BRIEF DESCRIPTION OF THE DRAWINGS
[0080] FIG. 1A is a drawing for explaining a cross-sectional angle
of a relief pattern of the present invention along with a method
for evaluating the same.
[0081] FIG. 1B is a drawing for explaining a cross-sectional angle
of a relief pattern of the present invention along with a method
for evaluating the same.
[0082] FIG. 1C is a drawing for explaining a cross-sectional angle
of a relief pattern of the present invention along with a method
for evaluating the same.
[0083] FIG. 1D is a drawing for explaining a cross-sectional angle
of a relief pattern of the present invention along with a method
for evaluating the same.
[0084] FIG. 1E is a drawing for explaining a cross-sectional angle
of a relief pattern of the present invention along with a method
for evaluating the same.
MODE FOR CARRYING OUT THE INVENTION
[0085] The following provides a detailed explanation of the present
invention. Furthermore, throughout the present description,
structures represented by the same reference symbols in general
formulas may be mutually the same or different in the case a
plurality thereof is present in a molecule.
First Aspect
[0086] A first aspect of the present invention is a photosensitive
resin composition as indicated below.
[0087] <Photosensitive Resin Composition>
[0088] In an embodiment of the present invention, a photosensitive
resin composition has for essential components thereof a polyimide
precursor (A) having a specific structure and a photosensitive
component (B). Thus, the following provides an explanation of the
polyimide precursor (A) having a specific structure, the
photosensitive component (B) and other components.
[0089] (A) Polyimide Precursor Resin
[0090] The following provides an explanation of the resin (A) used
in the present invention. The resin (A) of the present invention is
a polyimide precursor in the form of a polyamic acid, polyamic acid
ester or polyamic acid salt represented by the following general
formula (1):
##STR00034##
{wherein, X represents a tetravalent organic group, Y represents a
divalent organic group, n.sub.1 represents an integer of 2 to 150,
and R.sub.1 and R.sub.2 respectively and independently represent a
hydrogen atom, saturated aliphatic group having 1 to 30 carbon
atoms, aromatic group, monovalent organic group represented by the
following general formula (2):
##STR00035##
(wherein, R.sub.3, R.sub.4 and R.sub.5 respectively and
independently represent a hydrogen atom or organic group having 1
to 3 carbon atoms, and m.sub.1 represents an integer of 2 to 10),
or monovalent ammonium ion represented by the following general
formula (3):
##STR00036##
(wherein, R.sub.6, R.sub.7 and R.sub.8 respectively and
independently represent a hydrogen atom or organic group having 1
to 3 carbon atoms, and m.sub.2 represents an integer of 2 to
10)}.
[0091] The present invention is characterized by the combined use
of at least one of the following resins (A1) to (A3) and the
following resin (A4) as resins preferably used in the present
invention in this polyimide precursor.
[0092] As a specific example thereof, (A1) is a resin in which X in
general formula (1) contains a structure represented by the
following general formula (4), (5) or (6), and Y in general formula
(1) contains a structure represented by the following general
formula (7).
[0093] Here, X in general formula (1) contains a structure
represented by general formula (4):
##STR00037##
{wherein, a1 represents an integer of 0 to 2, R.sub.9 represents a
hydrogen atom, fluorine atom or monovalent organic group having 1
to 10 carbon atoms, and in the case a plurality of R.sub.9 are
present, may be mutually the same or different}, a structure
represented by the following general formula (5):
##STR00038##
{wherein, a2 and a3 respectively and independently represent an
integer of 0 to 4, a4 and a5 respectively and independently
represent an integer of 0 to 3, R.sub.10 to R.sub.13 respectively
and independently represent a hydrogen atom, fluorine atom or
monovalent organic group having 1 to 10 carbon atoms, and in the
case a plurality of R.sub.10 to R.sub.13 are present, may mutually
be the same or different}, or a structure represented by the
following general formula (6):
##STR00039##
{wherein, n2 represents an integer of 0 to 5, X.sub.n1 represents a
single bond or divalent organic group, in the case a plurality of
X.sub.n1 are present, may mutually be the same or different,
X.sub.m1 represents a single bond or divalent organic group, at
least one of X.sub.m1 or X.sub.n1 represents a single bond or an
organic group selected from the group consisting of an oxycarbonyl
group, oxycarbonylmethylene group, carbonylamino group, carbonyl
group and sulfonyl group, a6 and a8 respectively and independently
represent an integer of 0 to 3, a7 represents an integer of 0 to 4,
R.sub.14, R.sub.15 and R.sub.16 respectively and independently
represent a hydrogen atom, fluorine atom or monovalent organic
group having 1 to 10 carbon atoms, and in the case a plurality of
R.sub.14, R.sub.15 and R.sub.16 are present, may mutually be the
same or different}; and, Y in general formula (1) contains a
structure represented by the following general formula (7):
##STR00040##
{wherein, n3 represents an integer of 1 to 5, Y.sub.n2 represents
an organic group having 1 to 10 carbon atoms that may contain a
fluorine atom but does not contain a heteroatom other than
fluorine, an oxygen atom or a sulfur atom, in the case a plurality
of Y.sub.n2 are present, may mutually be the same or different, a9
and a10 respectively and independently represent an integer of 0 to
4, R.sub.17 and R.sub.18 respectively and independently represent a
hydrogen atom, fluorine atom or monovalent organic group having 1
to 10 carbon atoms, and in the case a plurality of R.sub.17 and
R.sub.18 are present, may mutually be the same or different}.
[0094] In addition, resin (A2) is a resin in which X in general
formula (1) contains a structure represented by the following
general formula (8) and Y in general formula (1) contains a
structure represented by the following general formula (9) or (10).
Here, X contains a structure represented by general formula
(8):
##STR00041##
{wherein, n4 represents an integer of 0 to 5, X.sub.m2 and X.sub.n2
respectively and independently represent an organic group having 1
to 10 carbon atoms that may contain a fluorine atom but does not
contain a heteroatom other than fluorine, an oxygen atom or a
sulfur atom, in the case of a plurality of X.sub.n2 are present,
may be mutually the same or different, a11 and a13 respectively and
independently represent an integer of 0 to 3, a12 represents an
integer of 0 to 4, R.sub.19, R.sub.20 and R.sub.21 respectively and
independently represent a hydrogen atom, fluorine atom or
monovalent organic group having 1 to 10 carbon atoms, and in the
case of a plurality of R.sub.19, R.sub.20 and R.sub.21 are present,
may mutually be the same or different}, and Y in general formula
(1) contains a structure represented by the following general
formula (9):
##STR00042##
{wherein, n5 represents an integer of 0 to 5, Y.sub.n4 represents a
single bond or a divalent organic group, in the case of a plurality
of Y.sub.n4 are present, may be mutually the same or different, in
the case n4 is 1 or more, at least one of Y.sub.n4 represents a
single bond or an organic group selected from the group consisting
of an oxycarbonyl group, oxycarbonylmethylene group, carbonylamino
group, carbonyl group and sulfonyl group, a14 and a15 respectively
and independently represent an integer of 0 to 4, R.sub.22 and
R.sub.23 respectively and independently represent a hydrogen atom,
fluorine atom or monovalent organic group having 1 to 10 carbon
atoms, and in the case a plurality of R.sub.22 and R.sub.23 are
present, may be mutually the same or different}, or a structure
represented by the following general formula (10):
##STR00043##
{wherein, a16 to a19 respectively and independently represent an
integer of 0 to 4, R.sub.24 to R.sub.27 respectively and
independently represent a hydrogen atom, fluorine atom or
monovalent organic group having 1 to 10 carbon atoms, and in the
case a plurality of R.sub.24 to R.sub.27 are present, may mutually
be the same or different}.
[0095] In addition, resin (A3) is a resin in which X in general
formula (1) contains a structure represented by formula (4), (5) or
(6) and Y in general formula (1) contains a structure represented
by formula (9) or (10).
[0096] Moreover, resin (A4) is a resin in which X in general
formula (1) contains a structure represented by general formula (8)
and Y in general formula (1) contains a structure represented by
general formula (7).
[0097] As has been described above, in the present invention, the
combination of resins is a combination comprising at least one of
resin (A1), (A2) or (A3) and resin (A4).
[0098] The structure represented by general formula (6) is
preferably a structure selected from the following group (X1) from
the viewpoint of adhesion:
##STR00044##
{wherein, a20 and a21 respectively and independently represent an
integer of 0 to 3, a22 represents an integer of 0 to 4, R.sub.28 to
R.sub.30 respectively and independently represent a hydrogen atom,
fluorine atom or monovalent organic group having 1 to 10 carbon
atoms, and in the case a plurality of R.sub.28 to R.sub.30 are
present, may be mutually the same or different}.
[0099] The structure represented by general formula (7) is
preferably a structure selected form the following group (Y1) from
the viewpoint of adhesion:
##STR00045##
{wherein, a23 to a26 respectively and independently represent an
integer of 0 to 4, R.sub.31 to R.sub.34 respectively and
independently represent a hydrogen atom, fluorine atom or
monovalent organic group having 1 to 10 carbon atoms, and in the
case a plurality of R.sub.31 to R.sub.34 are present, may be
mutually the same or different}.
[0100] In addition, the structure represented by general formula
(8) is preferably a structure selected from the following group
(X2) from the viewpoint of adhesion:
##STR00046##
{wherein, a27 and a28 respectively and independently represent an
integer of 0 to 3, R.sub.35 and R.sub.36 respectively and
independently represent a hydrogen atom, fluorine atom or
monovalent organic group having 1 to 10 carbon atoms, and in the
case a plurality of R.sub.35 and R.sub.36 are present, may be
mutually the same or different}.
[0101] Moreover, the structure represented by general formula (9)
is preferably a structure represented by the following group (Y2)
from the viewpoint of adhesion:
##STR00047##
{wherein, a29 to a32 respectively and independently represent an
integer of 0 to 4, R.sub.3-7 to R.sub.40 respectively and
independently represent a hydrogen atom, fluorine atom or
monovalent organic group having 1 to 10 carbon atoms, and in the
case a plurality of R.sub.37 to R.sub.40 are present, may be
mutually the same or different}.
[0102] Although there are no particular limitations on X in general
formula (1) of resin (A1) provided it contains a structure
represented by general formula (4), (5) or (6), from the viewpoint
of adhesion, a structure represented by general formula (4), (5) or
(6) preferably accounts for 50 mol % or more of X and more
preferably accounts for 80 mol % or more.
[0103] Although there are no particular limitations on Y in general
formula (1) of resin (A1) provided it contains a structure
represented by general formula (7), from the viewpoint of adhesion,
a structure represented by general formula (7) preferably accounts
for 50 mol % or more of Y and more preferably accounts for 80 mol %
or more.
[0104] Although there are no particular limitations on X in general
formula (1) of resin (A2) provided it contains a structure
represented by general formula (8), from the viewpoint of adhesion,
a structure represented by general formula (8) preferably accounts
for 50 mol % or more of X and more preferably accounts for 80 mol %
or more.
[0105] Although there are no particular limitations on Y in general
formula (1) of resin (A2) provided it contains a structure
represented by general formula (9) or (10), from the viewpoint of
adhesion, a structure represented by general formula (9) or (10)
preferably accounts for 50 mol % or more of Y and more preferably
accounts for 80 mol % or more.
[0106] Although there are no particular limitations on X in general
formula (1) of resin (A3) provided it contains a structure
represented by general formula (4), (5) or (6), from the viewpoint
of adhesion, a structure represented by general formula (4), (5) or
(6) preferably accounts for 50 mol % or more of X and more
preferably accounts for 80 mol % or more.
[0107] Although there are no particular limitations on Y in general
formula (1) of resin (A3) provided it contains a structure
represented by general formula (9) or (10), from the viewpoint of
adhesion, a structure represented by general formula (9) or (10)
preferably accounts for 50 mol % or more of Y and more preferably
accounts for 80 mol % or more.
[0108] Although there are no particular limitations on X in general
formula (1) of resin (A4) provided it contains a structure
represented by general formula (7), from the viewpoint of adhesion,
a structure represented by general formula (7) preferably accounts
for 50 mol % or more of X and more preferably accounts for 80 mol %
or more.
[0109] Although there are no particular limitations on Y in general
formula (1) of resin (A4) provided it contains a structure
represented by general formula (8), from the viewpoint of adhesion,
a structure represented by general formula (8) preferably accounts
for 50 mol % or more of Y and more preferably accounts for 80 mol %
or more.
[0110] Although there are no particular limitations on the
proportions of resins (A1) to (A4) in component (A), from the
viewpoint of adhesion, the total weight thereof preferably accounts
for 50 mol % or more, and more preferably accounts for 80 mol % or
more, of the total weight of component (A).
[0111] The parts by weight of resin (A4) are preferably 10% to 90%
of the sum of the weights of resins (A1) to (A4) from the viewpoint
of adhesion.
[0112] Although the reason for the improvement of adhesion
resulting from mixing resin (A4) with at least one the resins (A1)
to (A3) is not certain, the inventors of the present invention have
surmised this to be attributable to that indicated below.
[0113] Although resins (A1) to (A3) have numerous structures such
as biphenyl groups or polar groups within their polymers that
promote interaction between molecules, resin (A4) has few groups
capable of interacting between molecules. Thus, resins (A1) to (A3)
mutually aggregate due to interaction within their resin films,
enabling them to form portions having a somewhat high glass
transition temperature and portions having a low glass transition
temperature within their resin films. These portions are in a
relationship in the manner of a tackifier and elastomer of a hot
melt adhesive as used in the field of adhesives during heat curing,
and this is thought to result in improved adhesion.
[0114] Examples of methods used to impart photosensitivity to a
resin composition using a polyimide precursor include ester bonding
and ionic bonding. The former is a method consisting of introducing
a photopolymerizable group, or in other words, a compound having an
olefinic double bond, into a side chain of a polyimide precursor by
ester bonding, while the latter is a method consisting of imparting
a photopolymerizable group by bonding an amino group of
(meth)acrylic compound having an amino group with a carboxyl group
of a polyimide precursor through an ionic bond.
[0115] The aforementioned ester-bonded polyimide precursor is
obtained by first preparing a partially esterified tetracarboxylic
acid (to also be referred to as an acid/ester form) by reacting a
tetracarboxylic dianhydride containing the tetravalent organic
group X in general formula (1) with an alcohol having
photopolymerizable unsaturated double bond, and optionally, a
saturated aliphatic alcohol having 1 to 4 carbon atoms, followed by
subjecting this to amide polycondensation with a diamine containing
the divalent organic group Y in general formula (1).
[0116] (Preparation of Acid/Ester Form) In the present invention,
examples of the tetracarboxylic dianhydride containing the
tetravalent organic group X preferably used to prepare the
ester-bonded polyimide precursor that forms a structure represented
by general formula (4) include pyromellitic anhydride. Examples of
those that form a structure represented by general formula (5)
include 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride. Examples
of those that form a structure represented by general formula (6)
include benzophenone-3,3',4,4'-tetracarboxylic dianhydride,
biphenyl-3,3'4,4'-tetracarboxylic dianhydride,
diphenylphosphone-3,3',4,4'-tetracarboxylic dianhydride and
p-phenylenebis(trimellitate anhydride). Examples of those that form
a structure represented by general formula (8) include, but are not
limited to diphenylether-3,3',4,4'-tetracarboxylic dianhydride,
diphenylether-2,2',3,3'-tetracarboxlic dianhydride,
diphenylmethane-3,3'4,4'-tetracarboxylic dianhydride,
2,2-bis(3,4-phthalic anhydride)propane and 2,2-bis(3,4-phthalic
anhydride)-1,1,1,3,3,3-hexafluoropropane. In addition, these can
naturally be used alone or two or more types may be used as a
mixture. From the viewpoint of adhesion,
phenylethyl-3,3',4,4'-tetracarboxylic dianhydride is particularly
preferable as an acid anhydride that forms a structure represented
by general formula (8).
[0117] It is more preferable that 50 mol % or more of the acid
anhydride represented as structure X in general formula (1) of the
aforementioned resin (A4) is 4,4'-oxydiphthalic dianhydride, and 80
mol % or more of the diamine represented as structure Y in general
formula (1) of resin (A4) is 4,4'-diaminodiphenyl ether.
[0118] In addition, It is more preferable that 80 mol % or more of
the acid anhydride represented as structure X in general formula
(1) of the aforementioned resin (A4) is 4,4'-oxydiphthalic
dianhydride, and 80 mol % or more of the diamine represented as
structure Y in general formula (1) of resin (A4) is
4,4'-diaminodiphenyl ether.
[0119] In the present invention, examples of alcohols having a
photopolymerizable unsaturated double bond preferably used to
prepare the ester-bonded polyimide precursor include
2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol,
2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl
vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate,
2-hydroxy-3-butyoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl
acrylate, 2-hydroxy-3-butoxypropyl acrylate,
2-hydroxy-3-t-butoxypropyl acrylate,
2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl
alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl
alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone,
2-hydroxy-3-methoxyopropyl methacrylate, 2-hydroxy-3-butoxypropyl
methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate,
2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl
methacrylate and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.
[0120] Alcohols such as methanol, ethanol, n-propanol, isopropanol,
n-butanol or tert-butanol can also be used by mixing a portion
thereof with the aforementioned alcohols.
[0121] In the present embodiment, a copolymer represented by the
following general formula (18) can also be used for the polyimide
precursor (A):
##STR00048##
{wherein, X.sub.1 and X.sub.2 respectively and independently
represent a tetravalent organic group, Y.sub.1 and Y.sub.2
respectively and independently represent a divalent organic group,
n1 and n2 respectively and independently represent an integer of 2
to 150, and R.sub.1 and R.sub.2 respectively and independently
represent a hydrogen atom, saturated aliphatic group having 1 to 30
carbon atoms, aromatic group, monovalent organic group represented
by the general formula (2) or monovalent ammonium ion represented
by general formula (3), provided that X.sub.1 and X.sub.2 are not
the same and Y.sub.1 and Y.sub.2 are not the same}.
[0122] Although there are no particular limitations on X.sub.1 and
X.sub.2 according to the present embodiment provided they are
tetravalent organic groups, they are respectively and independently
preferably one type selected from the group consisting of groups
represented by the aforementioned general formulas (4), (5), (6)
and (8) from the viewpoints of copper adhesion and chemical
resistance.
[0123] Although there are no particular limitations on Y.sub.1 and
Y.sub.2 according to the present embodiment provided they are
tetravalent organic groups, they are respectively and independently
preferably one type selected from the group consisting of groups
represented by the aforementioned general formulas (7), (9) and
(10) from the viewpoints of copper adhesion and chemical
resistance.
[0124] Among these, preferably group X.sub.1 is represented by
general formula (8) and group Y.sub.1 is represented by general
formula (7) form the viewpoints of copper adhesion and chemical
resistance, and more preferably group X.sub.1 is represented by
general formula (8), group X.sub.2 is represented by one type
selected from the group consisting of groups represented by general
formulas (4), (5) and (6), group, group Y.sub.1 is represented by
general formula (7), and group Y.sub.2 is represented by one type
selected from the group consisting of groups represented by general
formulas (9) and (10) from the viewpoints of copper adhesion and
chemical resistance.
[0125] A desired acid/ester form can be obtained by carrying out an
acid anhydride esterification reaction by dissolving and mixing the
aforementioned preferable tetracarboxylic dianhydride of the
present invention with an aforementioned alcohol in the presence of
a basic catalyst such as pyridine and in a suitable reaction
solvent followed by stirring for 4 to 10 hours at a temperature of
20.degree. C. to 50.degree. C.
[0126] A reaction solvent that completely dissolves the acid/ester
form and the polyimide precursor, which is the amide
polycondensation product of the acid/ester form and a diamine
component, is preferable for the aforementioned reaction solvent,
and examples thereof include N-methyl-2-pyrrolidone,
N,N-dimethylacetoamide, N,N-dimethylformamide, dimethylsulfoxide,
tetramethyl urea and .gamma.-butyrolactone.
[0127] Examples of other reaction solvents include ketones, esters,
lactones, ethers and halogenated hydrocarbons, and examples of
hydrocarbons include acetone, methyl ethyl ketone, methyl isobutyl
ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl
acetate, diethyl oxalate, ethylene glycol dimethyl ether,
diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane,
1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene,
o-dichlorobenzene, hexane, heptane, benzene, toluene and xylene.
These may be used alone or two or more types may be used as a
mixture as necessary.
[0128] (Preparation of Polyimide Precursor)
[0129] After converting the acid/ester form to a polyacid anhydride
by adding a suitable dehydration condensation agent such as
dicyclocarbodiimide,
1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline,
1,1-carbonyldioxy-di-1,2,3-benzotriazole or N,N'-disuccinimidyl
carbonate to the aforementioned acid/ester form (typically in the
form of a solution of the aforementioned reaction solvent) while
cooling with ice and mixing therewith, a solution or dispersion of
a diamine containing the divalent organic group Y preferably used
in the present invention dissolved or dispersed in a different
solvent is dropped therein followed by amide polycondensation to
obtain the target polyimide precursor.
[0130] Examples of diamines containing the divalent organic group Y
preferably used in the present invention that form a structure
represented by general formula (7) include 4,4-diaminodiphenyl
ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether,
4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide,
3,3'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene,
1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene,
bis[4-(4-aminophenoxy)phenyl] ether, bis[4-(3-aminophenoxy)phenyl]
ether, 2,2-bis(aminophenyl)propane,
2,2-bis(4-aminophenyl)hexafluoropropane,
2,2-bis[4-(4-aminophenoxy)phenyl]propane,
2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane and those in
which a portion of the hydrogen atoms on the benzene ring thereof
is substituted with a substituent such as a methyl group, ethyl
group, trifluoromethyl group, hydroxymethyl group, hydroxyethyl
group or halogen atom, such as
3,3'-dimethyl-4,4'-diaminodiphenylmethane or
2,2'-dimethyl-4,4'-diaminodiphenylmethane. Examples those that form
a structure represented by general formula (9) include
p-phenylenediamine, m-phenylenediamine,
4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone,
3,3'-diaminodiphenylsulfone, 4,4'-diaminobiphenyl,
3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl,
4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone,
3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane,
3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane,
bis[4-(4-aminophenoxy)phenyl]sulfone,
bis[4-(3-aminophenoxy)phenyl]sulfone,
4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl,
1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl) benzene,
o-toluidine sulfone, 4-aminophenyl-4'-aminobenzoate,
4,4'-diaminobenzanilide and those in which a portion of the
hydrogen atoms on the benzene ring thereof is substituted with a
substituent such as a methyl group, ethyl group, trifluoromethyl
group, hydroxymethyl group, hydroxyethyl group or halogen atom,
such as 2,2'-dimethyl-4,4'-diaminobiphenyl,
2,2'-bis(trifluoromethyl)benzidine,
3,3'-dimethoxy-4,4'-diaminobiphenyl or
3,3'-dichloro-4,4'-diaminobiphenyl. Examples of those that form a
structure represented by general formula (10) include, but are not
limited to, 9,9-bis(4-aminophenyl)fluorene.
[0131] As was previously described, in the present invention, in
those compounds represented by structure X in general formula (1)
of resin (A1), 50 mol % or more is more preferably a structure
represented by general formula (4), (5) or (6), and in diamines
represented by structure Y in general formula (1), 50 mol % or more
is more preferably 4,4'-diaminodiphenyl ether.
[0132] In addition, in acid dianhydrides represented by structure X
in general formula (1) of resin (A2), 50 mol % or more is more
preferably 4,4'-oxydiphthalic dianhydride, and in diamines
represented by structure Y in general formula (1), 50 mol % or more
is more preferably a structure represented by general formula (9)
or (10).
[0133] In addition, a diaminosiloxane such as
1,3-bis(3-aminopropyl)tetramethyldisiloxane or
1,3-bis(3-aminopropyl)tetraphenyldisiloxane can be copolymerized
when preparing the polyimide precursor for the purpose of improving
adhesion between various types of substrates and the resin layer
formed on a substrate by coating the photosensitive resin
composition of the present invention on a substrate.
[0134] Following completion of the amide polycondensation reaction,
the polymer can be purified by filtering out absorption byproducts
of the dehydration condensation agent also present in the reaction
solution as necessary, followed by adding a poor solvent such as
water, an aliphatic lower alcohol or a mixture thereof to the
resulting polymer component, precipitating the polymer component,
and further repeating re-dissolution and re-precipitation
procedures and vacuum drying to isolate the target polyimide
precursor. In order to improve the degree of purification, a
solution of this polymer may be passed through a column packed with
an anion and/or cation exchange resin swollen with a suitable
organic solvent to remove any ionic impurities.
[0135] On the other hand, the aforementioned ionic-bonded polyimide
precursor is typically obtained by reacting a diamine with a
tetracarboxylic dianhydride. In this case, at least one of R.sub.1
and R.sub.2 in the aforementioned general formula (1) is a hydrogen
atom.
[0136] A tetracarboxylic dianhydride containing a structure of the
aforementioned group (X1) is preferable for the tetracarboxylic
dianhydride for resins (A1) and (A3), while an anhydride of a
tetracarboxylic acid containing a structure of the aforementioned
group (X2) is preferable for resins (A2) and (A4). A
tetracarboxylic anhydride containing a structure of the
aforementioned group (Y1) is preferable as diamine for resins (A1)
and (A4), while a diamine containing a structure of the
aforementioned group (Y2) is preferable for resins (A2) and (A3).
The addition of a (meth)acrylic compound having an amino group to
be subsequently described to the resulting polyamic acid results in
the formation of a salt due to ionic bonding between a carboxyl
group of the polyamic acid and an amino group of the (meth)acrylic
compound having an amino group, resulting in a polyamic acid salt
imparted with a photopolymerizable group.
[0137] A dialkylaminoacrylate or dialkylaminomethacrylate such as
dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate,
diethylaminoethyl acrylate, diethylaminoethyl methacrylate,
dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate,
diethylaminopropyl acrylate, diethylaminopropyl methacrylate,
dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate,
diethylaminobutyl acrylate or diethylaminobutyl methacrylate is
preferable for the (meth)acrylic compound having an amino group,
and among these, a dialkylaminoacrylate or
dialkylaminomethacrylate, in which the alkyl group on the amino
group has 1 to 10 carbon atoms and the alkyl chain has 1 to 10
carbon atoms, is preferable from the viewpoint of
photosensitivity.
[0138] The incorporated amount of these (meth)acrylic compounds
having an amino group based on 100 parts by weight of the resin (A)
is 1 part by weight to 20 parts by weight and preferably 2 parts by
weight to 15 parts by weight form the viewpoint of
photosensitivity. The incorporation of 1 part by weight or more of
the photosensitizer (B) in the form of the (meth)acrylic compound
having an amino group based on 100 parts by weight of the resin (A)
results in superior photosensitivity, while the incorporation of 20
parts by weight or less resulting in superior thick film
curability.
[0139] The molecular weight of the aforementioned ester-bonded and
ionic-bonded polyimide precursors in the case of measuring by gel
permeation chromatography based on standard polystyrene conversion
is preferably 8,000 to 150,000 and more preferably 9,000 to 50,000.
Mechanical properties are favorable in the case of a weight average
molecular weight of 8,000 or more, while dispersibility in
developer and resolution of the relief pattern are favorable in the
case of a weight average molecular weight of 150,000 or less. The
use of tetrahydrofuran or N-methyl-2-pyrrolidone is recommended for
the developing solvent during gel permeation chromatography. In
addition, weight average molecular weight is determined from a
calibration curve prepared using standard monodisperse polystyrene.
The standard monodisperse polystyrene is recommended to be selected
from the organic solvent-based standard sample STANDARD SM-105
manufactured by Showa Denko K.K.
[0140] [Photosensitive Component (B)]
[0141] Next, an explanation is provided of the photosensitive
component (B) used in the present invention.
[0142] A photopolymerization initiator and/or photoacid generator
that generates radicals by absorbing and decomposing at a specific
wavelength is preferably used for the photosensitive component (B).
The incorporated amount of the photosensitive component (B) in the
photosensitive resin composition is 1 part by weight to 50 parts by
weight based on 100 parts by weight of the resin (A).
Photosensitivity and patterning properties are demonstrated when
incorporated at 1 part by weight or more, while the properties of
the photosensitive resin layer improve after curing when
incorporated at 50 parts by weight or less.
[0143] In the case of a photopolymerization initiator, the resin
(A) is cured by radicals generated by a chain transfer reaction
with the main chain backbone of the resin (A) or by a radical
polymerization reaction with a (meth)acrylate group introduced into
the resin (A).
[0144] The photopolymerization initiator used for the
photosensitizer (B) is preferably a photo-radical polymerization
initiator, and preferable examples thereof include, but are not
limited to, photoacid generators in the manner of benzophenone
derivatives such as benzophenone and benzophenone derivatives such
as methyl o-benzoyl benzoate, 4-benzoyl-4'-methyl diphenyl ketone,
dibenzyl ketone or fluorenone, acetophenone derivatives such as
2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone or
1-hydroxycyclohexyl phenyl ketone, thioxanthone and thioxanthone
derivatives such as 2-methylthioxanthone, 2-isopropylthioxanthone
or diethylthioxanthone, benzyl and benzyl derivatives such as
benzyldimethylketal or benzyl-.beta.-methoxyethylacetal, benzoin
and benzoin derivatives such as benzoin methyl ether, oximes such
as 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime,
1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime,
1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime,
1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime,
1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime or
1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, N-arylglycines
such as N-phenylglycine, peroxides such as benzoyl peroxide,
aromatic biimidazoles, titanocenes or
.alpha.-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide. Among
the aforementioned photopolymerization initiators, oximes are more
preferable particularly from the viewpoint of photosensitivity.
[0145] Among the aforementioned oxime photopolymerization
initiators, those having a structure represented by the following
general formula (13) are more preferable, and those having a
structure represented by any of the following formulas (14) to (17)
are most preferable from the viewpoint of adhesion:
##STR00049##
{wherein, Z represents a sulfur atom or oxygen atom, R.sub.41
represents a methyl group, phenyl group or divalent organic group,
and R.sub.42 to R.sub.44 respectively and independently represent a
hydrogen atom or monovalent organic group.}
##STR00050##
[0146] In the case of using a photoacid generator for the
photosensitive component (B) in a negative-type photosensitive
resin composition, in addition to the photoacid generator
demonstrating acidity by irradiating with an active light beam in
the manner of ultraviolet light, due to that action, it has the
effect of causing a component (D) to be subsequently described in
the form of a crosslinking agent to crosslink with a resin in the
form of component (A) or causing polymerization of crosslinking
agents. Examples of photoacid generators used include diaryl
sulfonium salts, triazole sulfonium salts, dialkyl phenacyl
sulfonium salts, diaryl iodonium salts, aryl diazonium salts,
aromatic tetracarboxylic acid esters, aromatic sulfonic acid
esters, nitrobenzyl esters, oxime sulfonic acid esters, aromatic
N-oxyimidosulfonates, aromatic sulfamides, haloalkyl
group-containing hydrocarbon-based compounds, haloalkyl
group-containing heterocyclic compounds and naphthoquinone
diazido-4-sulfonic acid esters. Two or more types of these
compounds can be used in combination or in combination with other
sensitizers as necessary. Among the aforementioned photoacid
generators, aromatic oxime sulfonic acid esters and aromatic
N-oxyimidosulfonates are more preferable from the viewpoint of
photosensitivity in particular.
[0147] (C) Solvent
[0148] The photosensitive resin composition of the present
invention may also contain a solvent (C) in order to use as a
solution of the photosensitive resin composition by dissolving each
component of the photosensitive resin composition to form a
varnish. From the viewpoint of solubility in the resin (A), a polar
organic solvent is preferably used as solvent. More specifically,
the solvent is a solvent that contains the previously described
solvents (reaction solvents), examples thereof include
N,N-dimethylformamide, N-methyl-2-pyrrolidone,
N-ethyl-2-pyrrolidone, N,N-dimethylacetoamide, dimethylsulfoxide,
diethylene glycol dimethyl ether, cyclopentanone,
.gamma.-butyrolactone, .alpha.-acetyl-.gamma.-butyrolactone,
tetramethyl urea, 1,3-dimethyl-2-imidazolinone,
N-cyclohexyl-2-pyrrolidone, tetrahydrofurfuryl alcohol, ethyl
acetoacetate, dimethyl succinate, dimethyl malonate,
N,N-dimethylacetoacetamide, .epsilon.-caprolactone and
1,3-dimethyl-2-imidazolidinone, and these can be used alone or two
or more types can be used in combination.
[0149] In particular, the use of at least two types selected from
the group consisting of .gamma.-butyrolactone, dimethylsulfoxide,
tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate,
dimethyl malonate, N,N-dimethylacetoacetamide,
.epsilon.-caprolactone, and 1,3-dimethyl-2-imidazolidinone is
preferable from the viewpoint of copper adhesion.
[0150] The aforementioned solvent can be used within the range of,
for example, 30 parts by weight to 1500 parts by weight, and
preferably within the range of 100 parts by weight to 1000 parts by
weight, based on 100 parts by weight of the resin (A) corresponding
to the desired coated film thickness and viscosity of the
photosensitive resin composition.
[0151] Moreover, the solvent may contain a solvent containing an
alcohol from the viewpoint of improving storage stability of the
photosensitive resin composition. Alcohols able to be used are
typically alcohols that have an alcoholic hydroxyl group but do not
have an olefinic double bond within a molecule thereof, and
specific examples thereof include alkyl alcohols such as methyl
alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol,
n-butyl alcohol, isobutyl alcohol or tert-butyl alcohol, lactic
acid esters such as ethyl lactate, propylene glycol monoalkyl
ethers such as propylene glycol 1-methyl ether, propylene glycol
2-methyl ether, propylene glycol 1-ethyl ether, propylene glycol
2-ethyl ether, propylene glycol 1-(n-propyl) ether or propylene
glycol 2-(n-propyl) ether, monoalcohols such as ethylene glycol
methyl ether, ethylene glycol ethyl ether or ethylene glycol
n-propyl ether, 2-hydroxyisobutyric acid esters, and dialcohols
such as ethylene glycol and propylene glycol. Among these, lactic
acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyric
acid esters and ethyl alcohol are preferable, and in particular,
ethyl lactate, propylene glycol 1-methyl ether, propylene glycol
1-ethyl ether and propylene glycol 1-(n-propyl) ether are more
preferable.
[0152] In the case the solvent contains an alcohol that does not
have an olefinic double bond, the content of alcohol not having an
olefinic double bond present in the entire solvent is preferably 5%
by weight to 50% by weight and more preferably 10% by weight to 30%
by weight. In the case the aforementioned content of the alcohol
not having an olefinic double bond is 5% by weight or more, storage
stability of the photosensitive resin composition is favorable,
while in the case the content thereof is 50% by weight or less,
solubility of the resin (A) is favorable.
[0153] In the case of using two or more types of the aforementioned
solvent (C) in combination, from the viewpoint of adhesion, a
solvent (C1) having a boiling point of 200.degree. C. to
250.degree. C. and a solvent (C2) having a boiling point of
160.degree. C. to 190.degree. C. are more preferably used after
mixing.
[0154] Specific examples of the solvent (C1) having a boiling point
of 200.degree. C. to 250.degree. C. include N-methyl-2-pyrrolidone,
N-ethyl-2-pyrrolidone, .gamma.-butyrolactone and
1,3-dimethyl-2-imidazolinone. Among these, N-methylpyrrolidone and
.gamma.-butyrolactone are more preferable and .gamma.-butyrolactone
is most preferable, from the viewpoint of adhesion.
[0155] Specific examples of the solvent (C2) having a boiling point
of 160.degree. C. to 190.degree. C. include N,N-dimethylacetoamide,
dimethylsulfoxide, diethylene glycol dimethyl ether, tetramethyl
urea and propylene glycol. Among these, dimethylsulfoxide is most
preferable from the viewpoint of adhesion.
[0156] Moreover, the combination of .gamma.-butyrolactone and
dimethylsulfoxide is most preferable for the combination of
solvents (C1) and (C2) from the viewpoint of adhesion. In the case
of using a mixture of (C1) and (C2), although there are no
particular limitations on the ratios thereof, the weight of (C2)
based on the total weight of (C1) and (C2) is preferably 50% or
less from the viewpoint of solubility of component (A), and is more
preferably 5% to 30%, and most preferably 5% to 20%, from the
viewpoint of adhesion.
[0157] Although the reason for the improvement in adhesion
resulting from the combined use of (C1) and (C2) as solvent is
unclear, the inventors of the present invention have surmised this
to be attributable to that indicated below.
[0158] When the photosensitive resin composition is coated onto a
substrate and the solvent is dried, the solvent (C2) having a
comparatively low boiling point first volatilizes gradually as a
result of using solvents having different boiling points. As a
result, although orientation of resins (A1) to (A3) having groups
capable of demonstrating interaction between molecules as
previously described and their subsequent aggregation are promoted
as a result thereof, since there is little volatilization of the
solvent (C1) having a high boiling point, resin (A4) having few
groups capable of interacting is maintained in a dissolved state.
As a result, partial separation between resins (A1) to (A3) and
resin (A4) occurs efficiently, and adhesion is thought to improve
for the previously described reason.
[0159] A crosslinking agent (D) may also be contained in the
photosensitive resin composition of the present invention. The
crosslinking agent can be a crosslinking agent capable of
crosslinking the resin (A) or forming a crosslinked network by
itself when heat-curing a relief pattern formed using the
photosensitive resin composition of the present invention. The
crosslinking is further able to enhance heat resistance and
chemical resistance of a cured film formed from the photosensitive
resin composition.
[0160] Examples of crosslinking agents having a single thermal
crosslinking group include ML-26X, ML-4X, ML-236TMP, 4-Methylol
3M6C, ML-MC, ML-TBC (trade names, all manufactured by Honshu
Chemical Industry Co., Ltd.) and Type P-a Benzoxazine (trade name,
Shikoku Chemicals Corp.), examples of those having two thermal
crosslinking groups include DM-BI25X-F, 46DMOC, 46DMOIPP, 46DMOEP
(trade names, all manufactured by Asahi Yukizai Corp.), DML-MBPC,
DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP,
DML-POP, DML-OC, Dimethylol Bis-C, Dimethylol BisOC-P, DML-BisOC-Z,
DML-BisOCHP-Z, DML-PFP, DML-PSBP, DML-MB25, DML-MtrisPC,
DML-Bis25X-34XL and DML-Bis25X-PCHP (trade names, all manufactured
by Honshu Chemical Industry Co., Ltd.), Nikalac MX-290 (trade name,
manufactured by Sanwa Chemical Co., Ltd.), Type B-a Benzoxazine,
Type B-m Benzoxazine (trade names, manufactured by Shikoku
Chemicals Corp.), 2,6-dimethoxymethyl-4-t-butylphenol and
2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol,
examples of those having three thermal crosslinking groups include
TriML-P, TriML-35XL, TriML-TrisCR-HAP (trade names, all
manufactured by Honshu Chemical Industry Co., Ltd.), examples of
those having four thermal crosslinking groups include TM-BIP-A
(trade name, Asahi Yukizai Corp.), TML-BP, TML-HQ, TML-pp-BPF,
TML-BPA, TMOM-BP (trade names, all manufactured by Honshu Chemical
Industry Co., Ltd.), Nikalac MX-280 and Nikalac MX-270 (trade
names, manufactured by Sanwa Chemical Co., Ltd.), examples of those
having six thermal crosslinking groups include HML-TPPHBA,
HML-TPHAP (trade names, manufactured by Honshu Chemical Industry
Co., Ltd.), Nikalac MW-390 and Nikalac MW-100LM (trade names,
manufactured by Sanwa Chemical Co., Ltd.).
[0161] Among these, crosslinking agents containing two thermal
crosslinking groups are used preferably in the present invention,
and particularly preferable examples thereof include 46DMOC,
46DMOEP (trade names, manufactured by Asahi Yukizai Corp.),
DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCDML, DML-PTBP, DML-34X,
DML-EP, DML-POP, Dimethylol BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC
(trade names, all manufactured by Honshu Chemical Industry Co.,
Ltd.), Nikalac MX-290 (trade name, manufactured by Sanwa Chemical
Co., Ltd.), Type B-a Benzoxazine, Type B-m Benzoxazine (trade
names, manufactured by Shikoku Chemicals Corp.),
2,6-dimethoxymethyl-4-t-butylphenol and
2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol,
TriML-P, Tri-ML-35XL (trade names, manufactured by Honshu Chemical
Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi
Yukizai Corp.), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (trade
names, all manufactured by Honshu Chemical Industry Co., Ltd.),
Nikalac MX-280, Nikalac MX-270 (trade names, manufactured by Sanwa
Chemical Co., Ltd.), HML-TPPHBA and HML-TPHAP (trade names,
manufactured by Honshu Chemical Industry Co., Ltd.). In addition,
more preferable examples thereof include Nikalac MX-290, Nikalac
MX-280, Nikalac MX-270 (trade names, all manufactured by Sanwa
Chemical Co., Ltd.), Type B-a Benzoxazine, Type B-m Benzoxazine
(trade names, manufactured by Shikoku Chemicals Corp.), Nikalac
MW-390 and Nikalac MW-100LM (trade names, manufactured by Sanwa
Chemical Co., Ltd.).
[0162] The incorporated amount of crosslinking agent contained by
the photosensitive resin composition with respect to the balance
with various properties other than heat resistance and chemical
resistance is preferably 0.5 parts by weight to 20 parts by weight
and more preferably 2 parts by weight to 10 parts by weight based
on 100 parts by weight of the resin (A). In the case the
incorporated amount is 0.5 parts by weight or more, favorable heat
resistance and chemical resistance are demonstrated, while in the
case the incorporated amount is 20 parts by weight or less, storage
stability is superior.
[0163] (E) Organic Titanium Compound
[0164] The photosensitive resin composition of the present
invention may also contain an organic titanium compound (E). The
containing of the organic titanium compound (E) allows the
formation of a photosensitive resin layer having superior chemical
resistance even in the case of having cured at a low temperature of
about 250.degree. C.
[0165] Examples of organic titanium compounds able to be used for
the organic titanium compound (E) include those in which an organic
chemical substance is bound to a titanium atom through a covalent
bond or ionic bond.
[0166] Specific examples of the organic titanium compound (E)
include following I) to VII):
[0167] I) titanium chelate compounds: titanium chelate compounds
having two or more alkoxy groups are more preferable since they
allow the obtaining of storage stability of the negative-type
photosensitive resin composition as well as a favorable pattern,
and specific examples thereof include titanium
bis(triethanolamine)diisopropoxide, titanium
di(n-butoxide)bis(2,4-pentanedionate), titanium diisopropoxide
bis(2,4-pentanedionate), titanium diisopropoxide
bis(tetramethylheptanedionate) and titanium diisopropoxide
bis(ethylacetoacetate).
[0168] II) Tetraalkoxytitanium compounds: examples thereof include
titanium tetra(n-butoxide), titanium tetraethoxide, titanium
tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium
tetraisopropoxide, titanium tetramethoxide, titanium
tetramethoxypropoxide, titanium tetramethylphenoxide, titanium
tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium
tetrastearyloxide and titanium
tetrakis[bis{2,2-(allyloxymethyl)butoxide}].
[0169] III) Titanocene compounds: examples thereof include titanium
pentamethylcyclopentadienyl trimethoxide,
bis(.eta..sup.5-2,4-cyclopentadien-1-yl) bis(2,6-difluorophenyl)
titanium and bis(.eta..sup.5-2,4-cyclopentadien-1-yl)
bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) titanium.
[0170] IV) Monoalkoxy titanium compounds: examples thereof include
titanium tris(dioctylphosphate)isopropoxide and titanium
tris(dodecylbenzenesulfonate)isopropoxide.
[0171] V) Titanium oxide compounds: examples thereof include
titanium oxide bis(pentanedionate), titanium oxide
bis(tetramethylheptanedionate) and phthalocyanine titanium
oxide.
[0172] VI) Titanium tetraacetylacetonate compounds: examples
thereof include titanium tetraacetylacetonate.
[0173] VII) Titanate coupling agents: examples thereof include
isopropyltridecylbenzenesulfonyl titanate.
[0174] Among these, the organic titanium compound (E) is preferably
at least one type of compound selected from the group consisting of
the aforementioned titanium chelate compounds (I),
tetraalkoxytitanium compounds (II) and titanocene compounds (III)
from the viewpoint of demonstrating more favorable chemical
resistance. Titanium diisopropoxide bis(ethylacetoacetate),
titanium tetra(n-butoxide) and
bis(.eta..sup.5-2,4-cyclopentadien-1-yl)
bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) titanium are
particularly preferable.
[0175] The incorporated amount in the case of incorporating the
organic titanium compound (E) is preferably 0.05 parts by weight to
10 parts by weight and more preferably 0.1 parts by weight to 2
parts by weight based on 100 parts by weight of the resin (A). In
the case the incorporated amount is 0.05 parts by weight or more,
favorable heat resistance and chemical resistance are demonstrated,
while in the case the incorporated amount is 10 parts by weight or
less, storage stability is superior.
[0176] (F) Other Components
[0177] The photosensitive resin composition of the present
invention may further contain other components in addition to the
aforementioned components (A) to (E). For example, in the case of
forming a cured film on a substrate composed of copper or copper
alloy using the photosensitive resin composition of the present
invention, an azole compound can be optionally incorporated to
inhibit discoloration on the copper.
[0178] Examples of azole compounds include 1H-triazole,
5-methyl-1H-triazole, 5-ethyl-1H-triazole,
4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole,
4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole,
phenyltriazole, p-ethoxyphenyltriazole,
5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole,
hydroxyphenyltriazole, 1,5-dimethyltriazole,
4,5-diethyl-1H-triazole, 1H-benzotriazole,
2-(5-methyl-2-hydroxyphenyl)benzotriazole,
2-[2-hydroxy-3,5-bis(.alpha.,.alpha.-dimethylbenzyl)phenyl]benzotriazole,
2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole,
2-(3-t-butyl-5-methyl-2-hydroxyphenyl)benzotriazole,
2-(3,5-ti-t-amyl-2-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole,
hydroxyphenylbenzotriazole, tolyltriazole,
5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole,
4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole,
1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole,
5-amino-1H-tetrazole and 1-methyl-1H-tetrazole.
[0179] Particularly preferable examples include tolyltriazole,
5-methyl-1H-benzotriazole and 4-methyl-1H-benzotriazole. In
addition, one type of these azole compounds of a mixture of two or
more types may be used.
[0180] The incorporated amount in the case the photosensitive resin
composition contains the aforementioned azole compound is
preferably 0.1 parts by weight to 20 parts by weight and more
preferably 0.5 parts by weight to 5 parts by weight based on 100
parts by weight of the resin (A). In the case the incorporated
amount of the azole compound based on 100 parts by weight of the
resin (A) is 0.1 parts by weight or more, discoloration of the
copper or copper alloy surface is inhibited in the case of having
formed the photosensitive resin composition of the present
invention on copper or copper alloy, while in the case the
incorporated amount is 20 parts by weight or less, photosensitivity
is superior.
[0181] In addition, a hindered phenol compound can be optionally
incorporated in order to inhibit discoloration on the copper
surface. Examples of hindered phenol compounds include, but are not
limited to, 2,6-di-t-butyl-4-methylphenol,
2,5-di-t-butyl-hydroquinone,
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
4,4'-methylene-bis(2,6-di-t-butylphenol),
4,4'-thiobis(3-methyl-6-t-butylphenol),
4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylene
glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate],
1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxphenyl)propionate],
N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamide),
2,2'-methylene-bis(4-methyl-6-t-butylphenol),
2,2'-methylene-bis(4-ethyl-6-t-butylphenol),
[0182]
pentaerythryl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate-
], tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate,
1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene,
1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-
-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(-
1H,3H,5H)-trione,
1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(-
1H,3H,5H)-trione,
1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-
-2,4,6-(1H,3H,5H)-trione,
[0183]
1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tri-
azine-2,4,6-(1H,3H,5H)-trione,
1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1-
H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,-
6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-
-2,4,6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4-
,6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-
-2,4,6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-
-2,4,6-(1H,3H,5H)-trione,
[0184]
1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-
-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(-
1H,3H,5H)-trione, and
1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4-
,6-(1H,3H,5H)-trione. Among these,
1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(-
1H,3H,5H)-trione is particularly preferable.
[0185] The incorporated amount of the hindered phenol compound is
preferably 0.1 parts by weight to 20 parts by weight, and more
preferably 0.5 parts by weight to 10 parts by weight from the
viewpoint of photosensitivity, based on 100 parts by weight of the
resin (A). In the case the incorporated amount of the hindered
phenol compound based on 100 parts by weight of the resin (A) is
0.1 parts by weight or more, discoloration and corrosion of the
copper or copper alloy is prevented in the case of having formed
the photosensitive resin composition of the present invention on
copper or copper alloy, while in the case the incorporated amount
is 20 parts by weight or less, photosensitivity is superior.
[0186] A sensitizer can be optionally incorporated to improve
photosensitivity. Examples of this sensitizer include Michler's
ketone, 4,4'-bis(diethylamino)benzophenone,
2,5-bis(4'-diethylaminobenzal)cyclopentane,
2,6-bis(4'-diethylaminobenzal)cyclohexanone,
2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone,
4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone,
p-diethylaminocinnamylidene indanone, p-dimethylaminobenzylidene
indanone, 2-(p-dimethylaminophenylbiphenylene)benzothiazole,
2-(p-dimethylaminophenylvinylene)benzothiazole,
2-(p-dimethylaminophenylvinylene)isonaphthothiazole,
1,3-bis(4'-dimethylaminobenzal)acetone,
1,3-bis(4'-diethylaminobenzal)acetone,
3,3'-carbonyl-bis(7-diethylaminocoumarin),
3-acetyl-7-dimethylaminocoumarin,
3-ethoxycarbonyl-7-dimethylaminocoumarin,
3-benzyloxycarbonyl-7-dimethylaminocoumarin,
3-methoxycarbonyl-7-diethylaminocoumarin,
3-ethoxycarbonyl-7-diethylaminocoumarin,
N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine,
N-p-tolyldiethanolamine, N-phenylethanolamine,
4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl
diethylaminobenzoate, 2-mercaptobenzimidazole,
1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole,
2-(p-dimethylaminostyryl)benzoxazole,
2-(p-dimethylaminostyryl)benzothiazole,
2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole and
2-(p-dimethylaminobenzoyl)styrene. These can be used alone or, for
example, 2 to 5 types can be used in combination.
[0187] The incorporated amount of the sensitizer in the case the
photosensitive resin composition contains a sensitizer for
improving photosensitivity is preferably 0.1 parts by weight to 25
parts by weight based on 100 parts by weight of the resin (A).
[0188] In addition, a monomer having a photopolymerizable
unsaturated bond can be optionally incorporated to improve
resolution of a relief pattern. The monomer is preferably a
(meth)acrylic compound that undergoes a radical polymerization
reaction by a photopolymerization initiator, and although not
limited to that indicated below, examples thereof include compounds
such as mono- or diacrylates and methacrylates of ethylene glycol
or polyethylene glycol such as diethylene glycol dimethacrylate or
tetraethylene glycol dimethacrylate, mono- or diacrylates and
methacrylates of propylene glycol or polypropylene glycol, mono-,
di- or triacrylates, methacrylates, cyclohexane diacrylates, and
dimethacrylates of glycerol, diacrylates and dimethacrylates of
1,4-butanediol, diacrylates and dimethacrylates of 1,6-hexanediol,
diacrylates and dimethacrylates of neopentyl glycol, mono- or
diacrylates, methacrylates, benzene trimethacrylates, isobornyl
acrylates and methacrylates, acrylamides and derivatives thereof,
methacrylamides and derivatives thereof and trimethylolpropane
triacrylates and methacrylates of bisphenol A, triacrylates and
methacrylates of glycerol, di- tri- or tetraacrylates and
methacrylates of pentaerythritol, and ethylene oxide or propylene
oxide adducts of these compounds.
[0189] In the case the photosensitive resin composition contains
the aforementioned monomer having a photopolymerizable unsaturated
bond in order to improve the resolution of a relief pattern, the
incorporated amount of the photopolymerizable monomer having an
unsaturated bond is preferably 1 part by weight to 50 parts by
weight based on 100 parts by weight of the resin (A).
[0190] In addition, an adhesive assistant can be optionally
incorporated to improve adhesion between a substrate and a film
formed using the photosensitive resin composition of the present
invention. Examples of adhesive assistants include silane coupling
agents such as .gamma.-aminopropyldimethoxysilane,
N-(.beta.-aminoethyl)-.gamma.-aminopropylmethyldimethoxysilane,
.gamma.-glycidoxypropylmethyldimethoxysilane,
.gamma.-mercaptopropylmethyldimethoxysilane,
3-methacryloxypropyldimethoxymethylsilane,
3-methacryloxypropyltrimethoxysilane,
dimethoxymethyl-3-piperidinopropylsilane,
diethoxy-3-glycidoxypropylmethylsilane,
N-(3-diethoxymethylsilylpropyl)succinimide,
N-[3-(triethoxysilyl)propyl]phthalamic acid,
benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic
acid,
benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic
acid, 3-(triethoxysilyl)propylsuccinic anhydride,
N-phenylaminopropyltrimethoxysilane,
3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane,
3-(trialkoxysilyl)propyl succinic anhydride or
3-(triethoxysilylpropyl)-tert-butylcarbamate, and aluminum-based
adhesive assistants such as aluminum tris(ethylacetoacetate),
aluminum tris(acetylacetonate) or aluminum ethylacetylacetate
diisopropylate.
[0191] Among these adhesive assistants, silane coupling agents are
more preferable from the viewpoint of adhesive strength. In the
case the photosensitive resin composition contains an adhesive
assistant, the incorporated amount of the adhesive assistant is
preferably 0.5 parts by weight to 25 parts by weight based on 100
parts by weight of the resin (A).
[0192] In addition, a thermal polymerization inhibitor can be
optionally incorporated to improve viscosity and photosensitivity
stability of the photosensitive resin composition when storing in a
state of a solution containing a solvent in particular. Examples of
thermal polymerization inhibitors include hydroquinone,
N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine,
N-phenylnaphthylamine, ethyldiamine tetraacetic acid,
1,2-cyclohexanediamine tetraacetic acid, glycol ether diamine
tetraacetic acid, 2,6-di-tert-butyl-p-methylphenol,
5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol,
2-nitroso-1-naphthol,
2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol,
N-nitroso-N-phenylhydroxylamine ammonium salt and
N-nitroso-N-(1-naphthyl) hydroxylamine ammonium salt.
[0193] The incorporated amount of the thermal polymerization
inhibitor in the case of incorporating in the photosensitive resin
composition is preferably within the range of 0.005 parts by weight
to 12 parts by weight based on 100 parts by weight of the resin
(A).
[0194] <Method for Producing Cured Relief Pattern and
Semiconductor Device>
[0195] In addition, the present invention provides a method for
producing a cured relief pattern, comprising (1) a step for forming
a resin layer on a substrate by coating the aforementioned
photosensitive resin composition of the present invention on the
substrate, (2) a step for exposing the resin layer to light, (3) a
step for forming a relief pattern by developing the resin layer
after exposing to light, and (4) a step for forming a cured relief
pattern by heat-treating the relief pattern. The following provides
an explanation of a typical aspect of each step.
[0196] (1) Step for Forming a Resin Layer on s Substrate by Coating
Photosensitive Resin
[0197] composition on the substrate
[0198] In the present step, the photosensitive resin composition of
the present invention is coated onto a substrate followed by drying
as necessary to form a resin layer. A method conventionally used to
coat photosensitive resin compositions can be used, examples of
which include coating methods using a spin coater, bar coater,
blade coater, curtain coater or screen printer, and spraying
methods using a spray coater.
[0199] A coating film composed of the photosensitive resin
composition can be dried as necessary. A method such as air drying,
or heat drying or vacuum drying using an oven or hot plate, is used
for the drying method. More specifically, in the case of carrying
out air drying or heat drying, drying can be carried out under
conditions consisting of 1 minute to 1 hour at 20.degree. C. to
140.degree. C. The resin layer can be formed on the substrate in
this manner.
[0200] (2) Step for Exposing Resin Layer to Light
[0201] In the present step, the resin layer formed in the manner
described above is exposed to an ultraviolet light source and the
like either directly or through a photomask having a pattern or
reticle using an exposure device such as a contact aligner, mirror
projector or stepper.
[0202] Subsequently, post-exposure baking (PEB) and/or
pre-development baking may be carried out using an arbitrary
combination of temperature and time as necessary for the purpose of
improving photosensitivity and the like. Although the range of
baking conditions preferably consists of a temperature of
40.degree. C. to 120.degree. C. and time of 10 seconds to 240
seconds, the range is not limited thereto provided various
properties of the photosensitive resin composition of the present
invention are not impaired.
[0203] (3) Step for Forming Relief Pattern by Developing Resin
Layer after Exposure
[0204] In the present step, unexposed portions of the
photosensitive resin layer are developed and removed following
exposure. An arbitrary method can be selected and used for the
development method from among conventionally known photoresist
development methods, examples of which include the rotary spraying
method, paddle method and immersion method accompanying ultrasonic
treatment. In addition, post-development baking using an arbitrary
combination of temperature and time may be carried out as necessary
after development for the purpose of adjusting the form of the
relief pattern.
[0205] A good solvent with respect to the photosensitive resin
composition or a combination of this good solvent and a poor
solvent is preferable for the developer used for development. For
example, in the case of a photosensitive resin composition that
does not dissolve in an aqueous alkaline solution, preferable
examples of good solvents include N-methylpyrrolidone,
N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetoamide, cyclopentanone,
cyclohexanone, .gamma.-butyrolactone and
.alpha.-acetyl-.gamma.-butyrolactone, while preferable examples of
poor solvents include toluene, xylene, methanol, ethanol, isopropyl
alcohol, ethyl lactate, propylene glycol methyl ether acetate and
water. In the case of using a mixture of good solvent and poor
solvent, the proportion of poor solvent to good solvent is
preferably adjusted according to the solubility of polymer in the
photosensitive resin composition. In addition, two or more types of
each solvent, such as a combination of several types of each
solvent, can also be used.
[0206] (4) Step for Forming Cured Relief Pattern by Heat-Treating
Relief Pattern
[0207] In the present step, the relief pattern obtained by
developing in the manner previously described is converted to a
cured relief pattern by heating. Various methods can be selected
for the heat curing method, examples of which include heating with
a hot plate, heating using an oven, and heating using a
programmable oven that allows the setting of a temperature program.
Heating can be carried out under conditions consisting of, for
example, 30 minutes to 5 hours at 180.degree. C. to 400.degree. C.
Air may be used for the atmospheric gas during heat curing, or an
inert gas such as nitrogen or argon can be used.
[0208] <Semiconductor Device>
[0209] The present invention also provides a semiconductor device
that contains a cured relief pattern obtained according to the
method for producing a cured relief pattern of the present
invention described above. The present invention also provides a
semiconductor device containing a semiconductor element in the form
of a base material and a cured relief pattern of a resin formed
according to the aforementioned method for producing a cured relief
pattern on the aforementioned base material. In addition, the
present invention can be applied to a method for producing a
semiconductor device that uses a semiconductor element for the base
material and contains the aforementioned method for producing a
cured relief pattern as a portion of the process thereof. The
semiconductor device of the present invention can be produced by
combining with known methods for producing semiconductor devices by
forming the cured relief pattern formed according to the
aforementioned method for producing a cured relief pattern as a
surface protective film, interlayer insulating film, rewiring
insulating film, flip-chip device protective film or protective
film of a semiconductor device having a bump structure.
[0210] The photosensitive resin composition according to the first
aspect of the present invention is also useful in applications such
as the interlayer insulation of a multilayer circuit, cover coating
of a flexible copper-clad board, solder-resistive film or liquid
crystal alignment film.
Second Aspect
[0211] Semiconductors (to also be referred to as "elements") are
mounted on printed boards using various methods corresponding to
the objective. Conventional elements were typically fabricated by a
wire bonding method in which a connection is made from an external
terminal of the element (pad) to a lead frame with a fine wire.
However, with today's current higher element speeds in which the
operating frequency has reached the GHz range, differences in the
wiring lengths of each terminal during mounting are having an
effect on element operation. Consequently, in the case of mounting
elements for high-end applications, it has become necessary to
accurately control the lengths of mounting wires, and it has become
difficult to satisfy this requirement with wire bonding.
[0212] Thus, flip-chip mounting has been proposed in which, after
having formed a rewiring layer on the surface of a semiconductor
chip and formed a bump (electrode) thereon, the chip is turned over
(flipped) followed by directly mounting on the printed board. As a
result of being able to accurately control wiring distance, this
flip-chip mounting is being employed in elements for high-end
applications handling high-speed signals, and because of its small
mounting size, is also being employed in cell phone applications,
thereby resulting in a rapid increase in demand. More recently, a
semiconductor chip mounting technology known as fan-out wafer level
(FOWL) packaging has been proposed that consists of dicing
preprocessed wafers to produce individual chips followed by
reconstructing the individual chips on a support and sealing with a
molding resin, and finally separating from the support followed by
forming a rewiring layer (see, for example, Japanese Unexamined
Patent Publication No. 2005-167191). Fan-out wafer level packaging
offers the advantage of being able to reduce package height in
addition to realizing high-speed transmission and reduced
costs.
[0213] However, in addition to increasing diversity in the types of
supports due to the growing diversification of package mounting
technologies in recent years, since the types of rewiring layers
have also become increasingly diverse, there is the problem of a
considerable decrease in resolution due to the occurrence of shifts
in focus depth during exposure of a photosensitive resin
composition. For this reason, problems have occurred such as the
occurrence of signal delays or decreases in yield caused by
disconnections in the rewiring layer.
[0214] With the foregoing in view, an object of the second aspect
of the present invention is to provide a photosensitive resin
composition that allows the production of a semiconductor device
that exhibits little signal delay and demonstrates favorable
electrical properties, and is capable of preventing decreases in
yield caused by the occurrence of disconnections during formation
of the semiconductor device.
[0215] The inventors of the present invention found that, by
selecting and using a specific photosensitive resin composition
having a focus margin of a specific value or higher, a
semiconductor device can be produced that has little signal delay
and demonstrates favorable electrical properties, and is capable of
preventing decreases in yield caused by the occurrence of
disconnections during the formation of the semiconductor device,
thereby leading to completion of the second aspect of the present
invention. Namely, the second aspect of the present invention is as
indicated below.
[0216] [1] A photosensitive resin composition containing a
photosensitive polyimide precursor in which the focus margin of a
rounded out concave relief pattern is 8 .mu.m or more, the rounded
out concave relief pattern being obtained by going through the
following steps (1) to (5) in that order:
[0217] (1) spin-coating the resin composition onto a sputtered Cu
wafer substrate;
[0218] (2) obtaining a spin-coated film having a film thickness of
13 .mu.m by heating a spin-coated wafer substrate on a hot plate
for 270 seconds at 110.degree. C.;
[0219] (3) exposing a rounded out convex pattern having a mask size
of 8 .mu.m by changing the focus from the surface of the film to
the bottom of the film 2 .mu.m at a time using the surface of the
spin-coated film as a reference;
[0220] (4) forming a relief pattern by developing the exposed
wafer; and,
[0221] (5) heat-treating the developed wafer in a nitrogen
atmosphere for 2 hours at 230.degree. C.
[0222] [2] The photosensitive resin composition described in [1],
wherein the focus margin is 12 .mu.m or more.
[0223] [3] The photosensitive resin composition described in [1] or
[2], wherein the cross-sectional angle of a cured product of the
photosensitive polyimide precursor in the form of a cured relief
pattern is 60.degree. to 90.degree..
[0224] [4] The photosensitive resin composition described in any of
[1] to [3], wherein the photosensitive polyimide precursor is a
polyamic acid derivative having a radical-polymerizable substituent
in a side chain thereof.
[0225] [5] The photosensitive resin composition described in any of
[1] to [4], wherein the photosensitive polyimide precursor contains
a structure represented by the following general formula (21):
##STR00051##
{wherein, X.sub.1a represents a tetravalent organic group, Y.sub.1a
represents a divalent organic group, n.sub.1a represents an integer
of 2 to 150, and R.sub.1a and R.sub.2a respectively and
independently represent a hydrogen atom, monovalent organic group
represented by the following general formula (22):
##STR00052##
(wherein, R.sub.3a, R.sub.4a and R.sub.5a respectively and
independently represent a hydrogen atom or organic group having 1
to 3 carbon atoms, and m.sub.1a represents an integer selected from
2 to 10), or a saturated aliphatic group having 1 to 4 carbon
atoms, provided that R.sub.1a and R.sub.2a are not both
simultaneously hydrogen atoms}.
[0226] [6] The photosensitive resin composition described in [5],
wherein X.sub.1a in general formula (21) represents one or more
types of tetravalent organic groups selected from the following
formulas (23) to (25):
##STR00053##
and Y.sub.1a represents one or more types of divalent organic
groups selected from a group represented by the following general
formula (26):
##STR00054##
{wherein, R.sub.6a to R.sub.9a represent hydrogen atoms or
monovalent aliphatic groups having 1 to 4 carbon atoms and may
mutually be the same or different}, the following formula (27):
##STR00055##
or the following formula (28):
##STR00056##
{wherein, R.sub.10a and R.sub.11a respectively and independently
represent a fluorine atom, trifluoromethyl group or methyl
group}.
[0227] [7] The photosensitive resin composition described in any of
[1] to [6], further containing a photopolymerization initiator.
[0228] [8] The photosensitive resin composition described in [7],
wherein the photopolymerization initiator contains a component
represented by the following general formula (29):
##STR00057##
{wherein, Z represents a sulfur atom or oxygen atom, R.sub.12a
represents a methyl group, phenyl group or divalent organic group,
and R.sub.13a to R.sub.15a respectively and independently represent
a hydrogen atom or monovalent organic group}.
[0229] [9] The photosensitive resin composition described in any of
[1] to [8], further containing an inhibitor.
[0230] [10] The photosensitive resin composition described in [9],
wherein the inhibitor is at least one type selected from a hindered
phenol-type inhibitor and nitroso-type inhibitor.
[0231] [11] A method for producing a cured relief pattern including
the following steps (6) to (9):
[0232] (6) forming a photosensitive resin layer on a substrate by
coating the photosensitive resin composition described in any of
[1] to [10] on the substrate;
[0233] (7) exposing the photosensitive resin layer to light;
[0234] (8) forming a relief pattern by developing the
photosensitive resin layer after exposing to light; and,
[0235] (9) forming a cured relief pattern by heat-treating the
relief pattern.
[0236] [12] The method described in [11], wherein the substrate is
formed from copper or copper alloy.
[0237] According to a second aspect of the present invention, a
photosensitive resin composition, which is able to prevent the
occurrence of disconnections and decreases in yield when forming a
semiconductor device, and allows the production of a semiconductor
device having little signal delay and favorable electrical
properties, by using a photosensitive polyimide precursor having a
focus margin of a fixed value or more, a method for producing a
cured relief pattern using the photosensitive resin composition,
and a semiconductor device having the cured relief pattern, can be
provided.
[0238] The second aspect of the present invention is the
photosensitive resin composition indicated below.
[0239] [Photosensitive Resin Composition]
[0240] The photosensitive resin composition of the present
embodiment is characterized by the focus margin of a rounded out
concave relief pattern being 8 .mu.m or more, the rounded out
concave relief pattern being obtained by going through the
following steps (1) to (5) in that order:
[0241] (1) a step for spin-coating the resin composition onto a
sputtered Cu wafer substrate;
[0242] (2) a step for obtaining a spin-coated film having a film
thickness of 13 .mu.m by heating a spin-coated wafer substrate on a
hot plate for 270 seconds at 110.degree. C.;
[0243] (3) a step for exposing a rounded out convex pattern having
a mask size of 8 .mu.m by changing the focus from the surface of
the film to the bottom of the film 2 .mu.m at a time using the
surface of the spin-coated film as a reference;
[0244] (4) a step for forming a relief pattern by developing the
exposed wafer; and,
[0245] (5) a step for heat-treating the developed wafer in a
nitrogen atmosphere for 2 hours at 230.degree. C. The use of this
photosensitive resin composition makes it possible to prevent the
occurrence of disconnections and decreases in yield when forming a
semiconductor device even in the case of the occurrence of warping
and deformation of the substrate or in the case of poor surface
flatness of the lower layer of the multilayer rewiring layer
causing the focus depth during exposure to shift from a desired
location. Moreover, a semiconductor device can be produced that has
little signal delay and favorable electrical properties.
[0246] [Photosensitive Polyimide Precursor]
[0247] The following provides an explanation of the polyimide
precursor used in the present invention. The resin component of the
photosensitive resin composition of the present invention is a
polyamide having a structural unit represented by the following
general formula (21). The polyimide precursor is converted to a
polyimide by subjecting to cyclization treatment while heating (at,
for example, 200.degree. C. or higher):
##STR00058##
{wherein, X.sub.1a represents a tetravalent organic group, Y.sub.1a
represents a divalent organic group, n.sub.1a represents an integer
of 2 to 150, and R.sub.1a and R.sub.2a respectively and
independently represent a hydrogen atom, monovalent organic group
represented by the following general formula (22):
##STR00059##
(wherein, R.sub.3a, R.sub.4a and R.sub.5a respectively and
independently represent a hydrogen atom or organic group having 1
to 3 carbon atoms, and m1a represents an integer selected from 2 to
10), or a saturated aliphatic group having 1 to 4 carbon atoms,
provided that R.sub.1a and R.sub.2a are not both simultaneously
hydrogen atoms}.
[0248] In the aforementioned general formula (21), examples of the
tetravalent organic group represented by X.sub.1a preferably
include, but are not limited to, organic groups having 6 to 40
carbon atoms, more preferably an aromatic group or alicyclic group
having a --COOR.sub.1 group and a --COOR.sub.2 group at mutually
ortho positions with a --CONN-- group, and even more preferably
structures represented by the following formula (60).
##STR00060##
[0249] In addition, these may be used alone or two or more types
may be combined. Among these, X.sub.1a preferably has a structure
represented by the following structural formulas (23) to (25).
##STR00061##
[0250] In the aforementioned general formula (21), the divalent
organic group represented by Y.sub.1a is preferably an aromatic
group having 6 to 40 carbon atoms, such as a group represented by
the following formula (61):
##STR00062##
or a structure represented by the following formula (62).
##STR00063##
[0251] Among these, Y.sub.1a is particularly preferably at least
one type of divalent organic group selected from the group
consisting of groups represented by the following general formula
(26):
##STR00064##
{wherein, R.sub.6a to R.sub.9a represent hydrogen atoms or
monovalent aliphatic groups having 1 to 4 carbon atoms and may be
the same or different}, groups represented by the following formula
(27),
##STR00065##
and groups represented by the following formula (28):
##STR00066##
{wherein, R.sub.10a and R.sub.11a respectively and independently
represent a fluorine atom, trifluoromethyl group or methyl group}.
These may be used alone or two or more types may be combined.
[0252] The polyimide precursor of the present invention represented
by the aforementioned formula (21) is obtained by first preparing a
partially esterified tetracarboxylic acid (to also be referred to
as an acid/ester form) by reacting a tetracarboxylic dianhydride
containing the tetravalent organic group X.sub.1a with an alcohol
having photopolymerizable unsaturated double bond and a saturated
aliphatic alcohol having 1 to 4 carbon atoms, followed by
subjecting this to amide polycondensation with a diamine containing
the divalent organic group Y.sub.1a.
[0253] (Preparation of Acid/Ester Form)
[0254] Examples of the tetracarboxylic dianhydride containing the
tetravalent organic group X.sub.1a preferably used in the present
invention include, but are not limited to, pyromellitic anhydride,
diphenylether-3,3',4,4'-tetracarboxylic dianhydride,
benzophenone-3,3',4,4'-tetracarboxylic dianhydride,
biphenyl-3,3'4,4'-tetracarboxylic dianhydride,
diphenylphosphone-3,3',4,4'-tetracarboxylic dianhydride,
diphenylmethane-3,3'4,4'-tetracarboxylic dianhyride,
2,2-bis(3,4-phthalic anhydride)propane and 2,2-bis(3,4-phthalic
anhydride)-1,1,1,3,3,3-hexafluoropropane. In addition, these can
naturally be used alone or two or more types may be used as a
mixture.
[0255] Examples of alcohols having a photopolymerizable unsaturated
double bond preferably used in the present invention include
2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol,
2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl
vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate,
2-hydroxy-3-butyoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl
acrylate, 2-hydroxy-3-butoxypropyl acrylate,
2-hydroxy-3-t-butoxypropyl acrylate,
2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl
alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl
alcohol, 2-hydroxy-3-methoxyopropyl methacrylate,
2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl
methacrylate, 2-hydroxy-3-butoxypropyl methacrylate,
2-hydroxy-3-t-butoxypropyl methacrylate and
2-hydroxy-3-cyclohexyloxypropyl methacrylate.
[0256] Saturated aliphatic alcohols having 1 to 4 carbon atoms,
such as methanol, ethanol, n-propanol, isopropanol, n-butanol or
tert-butanol, can also be used by mixing a portion thereof with the
aforementioned alcohols.
[0257] A desired acid/ester form can be obtained by carrying out an
acid anhydride esterification reaction by dissolving and mixing the
aforementioned preferable tetracarboxylic dianhydride and alcohol
of the present invention in the presence of a basic catalyst such
as pyridine and in a suitable reaction solvent followed by stirring
for 4 to 10 hours at a temperature of 20.degree. C. to 50.degree.
C.
[0258] A reaction solvent that completely dissolves the acid/ester
form and the polyimide precursor, which is the amide
polycondensation product of the acid/ester form and a diamine
component, is preferable for the reaction solvent, and examples
thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetoamide,
N,N-dimethylformamide, dimethylsulfoxide, tetramethyl urea and
.gamma.-butyrolactone.
[0259] Examples of other reaction solvents include ketones, esters,
lactones, ethers and halogenated hydrocarbons, and examples of
hydrocarbons include acetone, methyl ethyl ketone, methyl isobutyl
ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl
acetate, diethyl oxalate, ethylene glycol dimethyl ether,
diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane,
1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene,
o-dichlorobenzene, hexane, heptane, benzene, toluene and xylene.
These may be used alone or two or more types may be used as a
mixture as necessary.
[0260] (Preparation of Polyimide Precursor)
[0261] A suitable dehydration condensation agent, such as
dicyclocarbodiimide,
1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline,
1,1-carbonyldioxy-di-1,2,3-benzotriazole or N,N'-disuccinimidyl
carbonate is added to and mixed with the aforementioned acid/ester
form while cooling with ice to convert the acid/ester form to a
polyacid anhydride. Subsequently, a solution or dispersion of a
diamine containing the divalent organic group Y preferably used in
the present invention in a different solvent is dropped therein
followed by amide polycondensation to obtain the target polyimide
precursor.
[0262] Examples of diamines containing the divalent organic group
Y.sub.1a preferably used in the present invention include, but are
not limited to, p-phenylene diamine, m-phenylene diamine,
4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether,
3,3'-diaminodiphenyl ether, 2,2'-dimethylbiphenyl-4,4'-diamine,
2,2-bis(trifluoromethyl)bendizine, 4,4'-diaminodiphenyl sulfide,
3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide,
4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone,
3,3'-diaminodiphenylsulfone, 4,4'-diaminobiphenyl,
3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl,
4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone,
3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane,
3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane,
1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene,
1,3-bis(3-aminophenoxy)benzene,
bis[4-(4-aminophenoxy)phenyl]sulfone,
bis[4-(3-aminophenoxy)phenyl]sulfone,
4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl,
bis[4-(4-aminophenoxy)phenyl] ether, bis[4-(3-aminophenoxy)phenyl]
ether, 1,4-bis(4-aminophenyl)benzene,
1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene,
2,2-bis(4-aminophenyl)propane,
2,2-bis(4-aminophenyl)hexafluoropropane,
2,2-bis[4-(4-aminophenoxy)phenyl]propane,
2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane,
1,4-bis(3-aminopropyldimethylsilyl)benzene, o-toluidine sulfone,
9,9-bis(4-aminophenyl)fluorene, and those in which a portion of the
hydrogen atoms on the benzene ring thereof is substituted with a
substituent such as a methyl group, ethyl group, hydroxymethyl
group, hydroxyethyl group or halogen atom, e.g.,
3,3'-dimethyl-4,4'-diaminodiphenylmethane,
2,2'-dimethyl-4,4'-diaminodiphenylmethane,
3,3'-dimethoxy-4,4'-diaminobiphenyl or
3,3'-dichloro-4,4'-diaminobiphenyl, as well as mixtures
thereof.
[0263] In addition, a diaminosiloxane such as
1,3-bis(3-aminopropyl)tetramethyldisiloxane or
1,3-bis(3-aminopropyl)tetraphenyldisiloxane can be copolymerized
for the purpose of improving adhesion between various types of
substrates.
[0264] Following completion of the reaction, after filtering out
absorption byproducts of the dehydration condensation agent also
present in the reaction solution as necessary, a poor solvent such
as water, an aliphatic lower alcohol or a mixture thereof is added
to the resulting polymer component to precipitate the polymer
component. Moreover, the polymer can be purified by repeating
re-dissolution and re-precipitation procedures followed by vacuum
drying to isolate the target polyimide precursor. In order to
improve the degree of purification, a solution of this polymer may
be passed through a column packed with an anion exchange resin
swollen with a suitable organic solvent to remove any ionic
impurities.
[0265] The molecular weight of the polyimide precursors in the case
of measuring by gel permeation chromatography based on standard
polystyrene conversion is preferably 8,000 to 150,000 and more
preferably 9,000 to 50,000. Mechanical properties are improved in
the case of a weight average molecular weight of 8,000 or more,
while dispersibility in developer and resolution of the relief
pattern are improved in the case of a weight average molecular
weight of 150,000 or less. The use of tetrahydrofuran or
N-methyl-2-pyrrolidone is recommended for the developing solvent
during gel permeation chromatography. In addition, molecular weight
is determined from a calibration curve prepared using standard
monodisperse polystyrene. The standard monodisperse polystyrene is
recommended to be selected from the organic solvent-based standard
sample STANDARD SM-105 manufactured by Showa Denko K.K.
[0266] [Photopolymerization Initiator]
[0267] The photosensitive resin composition according to the
present invention may further contain a photopolymerization
initiator.
[0268] Examples of photopolymerization initiators preferably
include, but are not limited to, benzophenone and benzophenone
derivatives such as methyl o-benzoyl benzoate, 4-benzoyl-4'-methyl
diphenyl ketone, dibenzyl ketone or fluorenone, acetophenone
derivatives such as 2,2'-diethoxyacetophenone,
2-hydroxy-2-methylpropiophenone or 1-hydroxycyclohexyl phenyl
ketone, thioxanthone and thioxanthone derivatives such as
2-methylthioxanthone, 2-isopropylthioxanthone or
diethylthioxanthone, benzyl and benzyl derivatives such as
benzyldimethylketal or benzyl-.beta.-methoxyethylacetal, benzoin
and benzoin derivatives such as benzoin methyl ether, oximes such
as 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime,
1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime,
1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime,
1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime,
1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime or
1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, N-arylglycines
such as N-phenylglycine, peroxides such as benzoyl perchloride and
aromatic biimidazoles. In addition, when using these
photopolymerization initiators, they may be used alone or two or
more types may be used as a mixture. Among the aforementioned
photopolymerization initiators, oxime-based compounds represented
by the following general formula (29):
##STR00067##
{wherein, Z represents a sulfur atom or oxygen atom, R.sub.12a
represents a methyl group, phenyl group or divalent organic group,
and R.sub.13a to R.sub.15a respectively and independently represent
a hydrogen atom or monovalent organic group.} are used preferably.
Among these, compounds represented by the following formula
(63)
##STR00068##
formula (64);
##STR00069##
formula (65):
##STR00070##
or formula (66):
##STR00071##
or mixtures thereof are particularly preferable. A compound
represented by formula (63) is commercially available as TR-PBG-305
manufactured by Changzhou Tronly New Electronic Materials Co.,
Ltd., a compound represented by formula (64) is commercially
available as TR-PBG-3057 manufactured by Changzhou Tronly New
Electronic Materials Co., Ltd., and a compound represented by
formula (65) is commercially available as Irgacure OXE-01
manufactured by BASF Corp.
[0269] The added amount of the photopolymerization initiator is 0.1
parts by weight to 20 parts by weight, and preferably 1 part by
weight to 15 parts by weight from the viewpoint of
photosensitivity, based on 100 parts by weight of the polyimide
precursor. The addition of 0.1 parts by weight or more of the
photopolymerization initiator based on 100 parts by weight of the
polyimide precursor results in superior photosensitivity, and
electrical properties are superior due improvement of focus margin.
In addition, addition of 20 parts by weight or less of the
photopolymerization initiator based on 100 parts by weight of the
polyimide precursor results in superior thick film curability, and
electrical properties are superior due to improvement of focus
margin.
[0270] [Thermal Polymerization Inhibitor]
[0271] A thermal polymerization inhibitor can be optionally added
to the photosensitive resin composition according to the present
invention. Examples of thermal polymerization inhibitors used
include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol,
phenothiazine, N-phenylnaphthylamine, ethyldiamine tetraacetic
acid, 1,2-cyclohexanediamine tetraacetic acid, glycol ether diamine
tetraacetic acid, 2,6-di-tert-butyl-p-methylphenol,
5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol,
2-nitroso-1-naphthol,
2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol,
N-nitroso-N-phenylhydroxylamine ammonium salt and
N-nitroso-N-(1-naphthyl) hydroxylamine ammonium salt.
[0272] The amount of thermal polymerization inhibitor added to the
photosensitive resin composition is preferably within the range of
0.005 parts by weight to 1.5 parts by weight based on 100 parts by
weight of the polyimide precursor. If the amount of thermal
polymerization inhibitor is within this range, a photocrosslinking
reaction proceeds easily during exposure, swelling is suppressed
during exposure causing the focus margin to expand and resulting in
favorable electrical properties, and storage stability of the
composition is favorable resulting in an increase in
photosensitivity stability, thereby making this preferable.
[0273] Although there are no particular limitations on the
aforementioned initiator and inhibitor according to the present
embodiment provided the focus margin is 8 .mu.m or more, a
combination of an oxime-based initiator and a hindered phenol-based
inhibitor or an oxime-based initiator and a nitroso-based inhibitor
tend to yield a focus margin of 8 .mu.m or more, thereby making
this preferable.
[0274] In addition, a combination of an oxime-based initiator and
hindered phenol-based inhibitor or an oxime-based initiator and a
nitroso-based inhibitor is preferable from the viewpoints of copper
adhesion, cross-sectional angle after curing, and film
properties.
[0275] [Sensitizer]
[0276] A sensitizer can be optionally added to the photosensitive
resin composition according to the present invention in order to
improve focus margin. Examples of this sensitizer include Michler's
ketone, 4,4'-bis(diethylamino)benzophenone,
2,5-bis(4'-diethylaminobenzal)cyclopentane,
2,6-bis(4'-diethylaminobenzal)cyclohexanone,
2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone,
4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone,
p-diethylaminocinnamylidene indanone, p-dimethylaminobenzylidene
indanone, 2-(p-dimethylaminophenylbiphenylene)benzotriazole,
2-(p-dimethylaminophenylvinylene)benzotriazole,
2-(p-dimethylaminophenylvinylene)isonaphthothiazole,
1,3-bis(4'-dimethylaminobenzal)acetone,
1,3-bis(4'-diethylaminobenzal)acetone,
3,3'-carbonyl-bis(7-diethylaminocoumarin),
3-acetyl-7-dimethylaminocoumarin,
3-ethoxycarbonyl-7-dimethylaminocoumarin,
3-benzyloxycarbonyl-7-dimethylaminocoumarin,
3-methoxycarbonyl-7-diethylaminocoumarin,
3-ethoxycarbonyl-7-diethylaminocoumarin,
N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine,
N-p-tolyldiethanolamine, N-phenylethanolamine,
4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl
diethylaminobenzoate, 2-mercaptobenzimidazole,
1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole,
2-(p-dimethylaminostyryl)benzoxazole,
2-(p-dimethylaminostyryl)benzothiazole,
2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole and
2-(p-dimethylaminobenzoyl)styrene. These can be used alone or, for
example, 2 to 5 types can be used in combination.
[0277] The sensitizer for improving photosensitivity is preferably
used at 0.1 parts by weight to 15 parts by weight and more
preferably used at 1 part by weight to 12 parts by weight, based on
100 parts by weight of the polyimide precursor. If the amount
sensitizer is within the range of 0.1 parts by weight to 15 parts
by weight, the sensitizer no longer swells during exposure, focus
margin expands and electrical properties are favorable, thereby
making this preferable, or the resulting photosensitization effect
is favorable enabling the photocrosslinking reaction to proceed
adequately, thereby making this preferable.
[0278] [Monomer]
[0279] A monomer having a photopolymerizable unsaturated bond can
be optionally added to the photopolymerizable resin composition
according to the present invention to improve resolution of a
relief pattern. The monomer is preferably a (meth)acrylic compound
that undergoes a radical polymerization reaction by a
photopolymerization initiator, and although there are no particular
limitations thereon, examples thereof include compounds such as
mono- or diacrylates and methacrylates of ethylene glycol or
polyethylene glycol such as diethylene glycol dimethacrylate or
tetraethylene glycol dimethacrylate, mono- or diacrylates and
methacrylates of propylene glycol or polypropylene glycol, mono-,
di- or triacrylates, methacrylates, cyclohexane diacrylates, and
dimethacrylates of glycerol, diacrylates and dimethacrylates of
1,4-butanediol, diacrylates and dimethacrylates of 1,6-hexanediol,
diacrylates and dimethacrylates of neopentyl glycol, mono- or
diacrylates, methacrylates, benzene trimethacrylates, isobornyl
acrylates and methacrylates, acrylamides and derivatives thereof,
methacrylamides and derivatives thereof and trimethylolpropane
triacrylates and methacrylates of bisphenol A, di- or triacrylates
and methacrylates of glycerol, di- tri- or tetraacrylates and
methacrylates of pentaerythritol, and ethylene oxide or propylene
oxide adducts of these compounds.
[0280] The aforementioned monomer having a photopolymerizable
unsaturated bond for improving resolution of a relief pattern is
preferably used at 1 part by weight to 50 parts by weight based on
100 parts by weight of the polyimide precursor.
[0281] [Solvent]
[0282] A solvent can be used in the photosensitive resin
composition according to the present invention in order to use as a
solution of the photosensitive resin composition by dissolving each
component of the photosensitive resin composition to form a
varnish. From the viewpoint of solubility in the polyimide
precursor, a polar organic solvent is preferably used as solvent.
More specifically, examples thereof include N,N-dimethylformamide,
N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone,
N,N-dimethylacetoamide, dimethylsulfoxide, diethylene glycol
dimethyl ether, cyclopentanone, .gamma.-butyrolactone,
.alpha.-acetyl-.gamma.-butyrolactone, tetramethyl urea,
1,3-dimethyl-2-imidazolinone and N-cyclohexyl-2-pyrrolidone, and
these can be used alone or two or more types can be used in
combination. Among these, a combination of N-methyl-2-pyrrolidone
or dimethylsulfoxide and .gamma.-butyrolactone is preferable from
the viewpoint of polyimide solubility, and the mixing ratio of the
dimethylsulfoxide and .gamma.-butyrolactone is such that the weight
ratio of dimethylsulfoxide is preferably 50% by weight or less and
most preferably 5% by weight to 20% by weight.
[0283] The aforementioned solvent can be used within the range of,
for example, 30 parts by weight to 1500 parts by weight based on
100 parts by weight of the polyimide precursor corresponding to the
desired coated film thickness and viscosity of the photosensitive
resin composition.
[0284] Moreover, a solvent containing an alcohol is preferable for
improving storage stability of the photosensitive resin
composition.
[0285] Alcohols able to be used are typically alcohols that have an
alcoholic hydroxyl group but do not have an olefinic double bond
within a molecule thereof, and specific examples thereof include
alkyl alcohols such as methyl alcohol, ethyl alcohol, n-propyl
alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol or
tert-butyl alcohol, lactic acid esters such as ethyl lactate,
propylene glycol monoalkyl ethers such as propylene glycol 1-methyl
ether, propylene glycol 2-methyl ether, propylene glycol 1-ethyl
ether, propylene glycol 2-ethyl ether, propylene glycol
1-(n-propyl) ether or propylene glycol 2-(n-propyl) ether,
monoalcohols such as ethylene glycol methyl ether, ethylene glycol
ethyl ether or ethylene glycol n-propyl ether, 2-hydroxyisobutyric
acid esters, and dialcohols such as ethylene glycol or propylene
glycol. Among these, lactic acid esters, propylene glycol monoalkyl
ethers, 2-hydroxyisobutyric acid esters and ethyl alcohol are
preferable, and in particular, ethyl lactate, propylene glycol
1-methyl ether, propylene glycol 1-ethyl ether and propylene glycol
1-(n-propyl) ether are more preferable.
[0286] The content of alcohol not having an olefinic double bond
present in the entire solvent is preferably 5% by weight to 50% by
weight and more preferably 10% by weight to 30% by weight. In the
case the aforementioned content of the alcohol not having an
olefinic double bond is 5% by weight or more, storage stability of
the photosensitive resin composition is favorable, while in the
case the content thereof is 50% by weight or less, solubility of
the polyimide precursor is favorable.
[0287] [Other Components]
[0288] The photosensitive resin composition of the present
invention may contain the following components (A) to (D) as
components other than the components previously described.
[0289] (A) Azole Compound
[0290] The photosensitive resin composition of the present
invention may contain an azole compound represented by the
following general formula (67), the following general formula (68)
or the following general formula (69). In the case of forming the
photosensitive resin composition of the present invention on copper
or copper alloy, for example, the azole compound has the action of
preventing discoloration of the copper or copper alloy:
##STR00072##
{wherein, R.sub.24a and R.sub.25a respectively and independently
represent a hydrogen atom, linear or branched alkyl group having 1
to 40 carbon atoms, or alkyl group or aromatic group having 1 to 40
carbon atoms substituted with a carboxyl group, hydroxyl group,
amino group or nitro group, and R.sub.26a represents a hydrogen
atom, phenyl group, or alkyl group or aromatic group substituted
with an amino group or silyl group},
##STR00073##
{wherein, R.sub.27a represents a hydrogen atom, carboxyl group,
hydroxyl group, amino group, nitro group, linear or branched alkyl
group having 1 to 40 carbon atoms, or alkyl group or aromatic group
having 1 to 40 carbon atoms substituted with a carboxyl group,
hydroxyl group, amino group or nitro group, and R.sub.28a
represents a hydrogen atom, phenyl group, or alkyl group or
aromatic group having 1 to 40 carbon atoms substituted with an
amino group or silyl group}, and
##STR00074##
{wherein, R.sub.29a represents a hydrogen atom, linear or branched
alkyl group having 1 to 40 carbon atoms, or alkyl group or aromatic
group having 1 to 40 carbon atoms substituted with a carboxyl
group, hydroxyl group, amino group or nitro group, and R30a
represents a hydrogen atom, phenyl group, or alkyl group or
aromatic group having 1 to 40 carbon atoms substituted with an
amino group or silyl group}.
[0291] Examples of azole compounds represented by the
aforementioned general formula (67) include, but are not limited
to, 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole,
4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole,
4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole,
phenyltriazole, p-ethoxyphenyltriazole,
5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole,
hydroxyphenyltriazole and 1,5-dimethyltriazole,
4,5-diethyl-1H-triazole,
[0292] examples represented by the aforementioned general formula
(68) include, but are not limited to, 1H-benzotriazole,
2-(5-methyl-2-hydroxyphenyl)benzotriazole,
2-[2-hydroxy-3,5-bis(.alpha.,.alpha.-dimethylbenzyl)phenyl]benzotriazole,
2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole,
2-(3-t-butyl-5-methyl-2-hydroxyphenyl)benzotriazole,
2-(3,5-ti-t-amyl-2-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole,
hydroxyphenylbenzotriazole, tolyltriazole,
5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole,
4-carboxy-1H-benzotriazole and 5-carboxy-1H-benzotriazole, and
[0293] examples represented by the aforementioned general formula
(69) include, but are not limited to, 1H-tetrazole,
5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole
and 1-methyl-1H-tetrazole. Among these, tolyltriazole,
5-methyl-1H-benzotriazole and 4-methyl-1H-benzotriazole are
particularly preferable from the viewpoint of inhibiting
discoloration of copper or copper alloy. In addition, these azole
compounds may be used alone or two or more types may be used as a
mixture.
[0294] The amount of azole compound added is 0.1 parts by weight to
20 parts by weight, and preferably 0.5 parts by weight to 5 parts
by weight from the viewpoint of photosensitivity, based on 100
parts by weight of the polyimide precursor. If the added amount of
azole compound to 100 parts by weight of the polyimide precursor is
0.1 parts by weight or more, discoloration of the surface of copper
or copper alloy is inhibited in the case of having formed the
photosensitive resin composition of the present invention on copper
or copper alloy, while in the case the amount added is 20 parts by
weight or less, a favorable relief pattern is obtained in the case
of having formed the photosensitive resin composition of the
present invention on copper or copper alloy.
[0295] (B) Hindered Phenol Compound
[0296] The photosensitive resin composition of the present
invention may further contain a hindered phenol compound (B) as a
compound that has the action of preventing discoloration of copper
or copper alloy in the case of forming on copper or copper alloy,
for example. Here, the hindered phenol compound refers to a
compound having a structure represented by the following general
formula (70), general formula (71), general formula (75), general
formula (76) or general formula (77) in a molecule thereof:
##STR00075##
{wherein, R.sub.31a represents a t-butyl group, R.sub.32a and
R.sub.34a respectively and independently represent a hydrogen atom
or alkyl group, R.sub.33a represents a hydrogen atom, alkyl group,
alkoxy group, hydroxyalkyl group, dialkylaminoalkyl group, hydroxyl
group or alkyl group substituted with a carboxyl group, and
R.sub.35a represents a hydrogen atom or alkyl group},
##STR00076##
{wherein, R.sub.36a represents a t-butyl group, R.sub.37a,
R.sub.38a and R.sub.39a respectively and independently represent a
hydrogen atom or alkyl group, and R.sub.40a represents an alkylene
group, divalent sulfur atom, dimethylene thiol ether group, or
group represented by the following general formula (72):
[Chemical Formula 89]
CH.sub.2CH.sub.2COO--R.sub.41a--OOCCH.sub.2CH.sub.2 (72)
(wherein, R.sub.41a represents an alkyl group having 1 to 6 carbon
atoms, diethylene thiol ether group or group represented by the
following formula (72-1):
[Chemical Formula 90]
--CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2 (72-1)
or group represented by the following formula (72-2),
##STR00077##
{wherein, R.sub.42a represents a t-butyl group, cyclohexyl group or
methylcyclohexyl group, R.sub.43a, R.sub.44a and R.sub.45a
respectively and independently represent a hydrogen atom or alkyl
group, and R.sub.46a represents an alkylene group, sulfur atom or
terephthalic acid ester},
##STR00078##
{wherein, R.sub.47a represents a t-butyl group, R.sub.49a and
R.sub.50a respectively and independently represent a hydrogen atom
or alkyl group, and R.sub.51a represents an alkyl group, phenyl
group, isocyanurate group or propionate group}, and
##STR00079##
{wherein, R.sub.52a and R.sub.53a respectively and independently
represent a hydrogen atom or monovalent organic group having 1 to 6
carbon atoms, R.sub.55a represents an alkyl group, phenyl group,
isocyanurate group or propionate group, and R.sub.54a represents a
group represented by the following general formula (78):
##STR00080##
(wherein, R.sub.56a, R.sub.57a and R.sub.58a respectively and
independently represent a hydrogen atom or monovalent organic group
having 1 to 6 carbon atoms, provided at least two of R.sub.56a,
R.sub.57a and R.sub.58a represent monovalent organic groups having
1 to 6 carbon atoms), or a phenyl group}.
[0297] The hindered phenol compound has the action of preventing
discoloration of copper or copper alloy in the case of forming the
photosensitive resin composition of the present invention on copper
or copper alloy, for example. In the present invention, as a result
of using a specific phenol compound, namely a phenol compound
represented by the aforementioned general formula (70), general
formula (71), general formula (75), general formula (76) or general
formula (77), the advantage is obtained of being able to obtain a
polyimide of high resolution without causing discoloration or
corrosion of the copper or copper alloy.
[0298] Examples of hindered phenol compounds represented by the
aforementioned general formula (70) include, but are not limited
to, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone,
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, and
isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, examples of
hindered phenol compounds represented by the aforementioned general
formula (71) include, but are not limited to,
4,4'-methylene-bis(2,6-di-t-butylphenol),
4,4'-thiobis(3-methyl-6-t-butylphenol),
4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylene
glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate],
1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxphenyl)propionate]
and N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamide),
examples represented by the aforementioned general formula (75)
include, but are not limited to,
2,2'-methylene-bis(4-methyl-6-t-butylphenol) and
2,2'-methylene-bis(4-ethyl-6-t-butylphenol), examples represented
by the aforementioned general formula (76) include, but are not
limited to,
pentaerythryl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate and
1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene,
examples represented by the aforementioned general formula (77)
include, but are not limited to,
1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-
-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(-
1H,3H,5H)-trione,
1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(-
1H,3H,5H)-trione,
1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-
-2,4,6-(1H,3H,5H)-trione,
1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine--
2,4,6-(1H,3H,5H)-trione,
1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1-
H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,-
6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-
-2,4,6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4-
,6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-
-2,4,6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-
-2,4,6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3-
H,5H)-trione,
1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(-
1H,3H,5H)-trione, and
1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4-
,6-(1H,3H,5H)-trione. Among these,
1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(-
1H,3H,5H)-trione is particularly preferable.
[0299] The added amount of the hindered phenol (B) is 0.1 parts by
weight to 20 parts by weight, and preferably 0.5 parts by weight to
10 parts by weight from the viewpoint of photosensitivity, based on
100 parts by weight of the polyimide precursor. If the added amount
of hindered phenol compound (B) based on 100 parts by weight of the
polyimide precursor is 0.1 parts by weight or more, discoloration
and corrosion of copper or copper alloy is prevented in the case of
having formed the photosensitive resin composition of the present
invention on copper or copper alloy, for example, while if the
added amount is 20 parts by weight or less, photosensitivity is
superior.
[0300] (C) Organic Titanium Compound
[0301] The photosensitive resin composition of the present
invention may also contain an organic titanium compound (C) as a
compound that improves chemical resistance. There are no particular
limitations on organic titanium compounds able to be used for the
component (C) provided an organic chemical substance is bound to a
titanium atom through a covalent bond or ionic bond.
[0302] Specific examples of the organic titanium compound (C)
include compounds indicated in I) to VII below.
[0303] I) Titanium chelate compounds: titanium chelate compounds
having two or more alkoxy groups are more preferable since they
allow the obtaining of stability of the compound and a favorable
pattern, and specific examples thereof include titanium
bis(triethanolamine)diisopropoxide, titanium
di(n-butoxide)bis(2,4-pentanedionate), titanium diisopropoxide
bis(2,4-pentanedionate), titanium diisopropoxide
bis(tetramethylheptanedionate) and titanium diisopropoxide
bis(ethylacetoacetate).
[0304] II) Tetraalkoxytitanium compounds: examples thereof include
titanium tetra(n-butoxide), titanium tetraethoxide, titanium
tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium
tetraisopropoxide, titanium tetramethoxide, titanium
tetramethoxypropoxide, titanium tetramethylphenoxide, titanium
tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium
tetrastearyloxide and titanium
tetrakis[bis{2,2-(allyloxymethyl)butoxide}].
[0305] III) Titanocene compounds: examples thereof include titanium
pentamethylcyclopentadienyl trimethoxide,
bis(.eta..sup.5-2,4-cyclopentadien-1-yl) bis(2,6-difluorophenyl)
titanium and bis(.eta..sup.5-2,4-cyclopentadien-1-yl)
bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) titanium.
[0306] IV) Monoalkoxy titanium compounds: examples thereof include
titanium tris(dioctylphosphate)isopropoxide and titanium
tris(dodecylbenzenesulfonate)isopropoxide.
[0307] V) Titanium oxide compounds: examples thereof include
titanium oxide bis(pentanedionate), titanium oxide
bis(tetramethylheptanedionate) and phthalocyanine titanium
oxide.
[0308] VI) Titanium tetraacetylacetonate compounds: examples
thereof include titanium tetraacetylacetonate.
[0309] VII) Titanate coupling agents: examples thereof include
isopropyltridecylbenzenesulfonyl titanate.
[0310] Among these, the organic titanium compound (C) is preferably
at least one type of compound selected from the group consisting of
the aforementioned titanium chelate compounds (I),
tetraalkoxytitanium compounds (II) and titanocene compounds (III)
from the viewpoint of demonstrating more favorable chemical
resistance.
[0311] The added amount of these organic titanium compounds is
preferably 0.05 parts by weight to 10 parts by weight and more
preferably 0.1 parts by weight to 2 parts by weight based on 100
parts by weight of the polyimide precursor. If the added amount is
0.05 parts by weight or more, favorable heat resistance or chemical
resistance are demonstrated, while in the case the added amount is
10 parts by weight or less, storage stability is superior.
[0312] (D) Adhesive Assistant
[0313] In addition, an adhesive assistant (D) can be optionally
added to improve adhesion between a substrate and a film formed
using the photosensitive resin composition of the present
invention. Examples of adhesive assistants include silane coupling
agents such as .gamma.-aminopropyldimethoxysilane,
N-(.beta.-aminoethyl)-.gamma.-aminopropylmethyldimethoxysilane,
.gamma.-glycidoxypropylmethyldimethoxysilane,
.gamma.-mercaptopropylmethyldimethoxysilane,
3-methacryloxypropyldimethoxymethylsilane,
3-methacryloxypropyltrimethoxysilane,
dimethoxymethyl-3-piperidinopropylsilane,
diethoxy-3-glycidoxypropylmethylsilane,
N-(3-diethoxymethylsilylpropyl)succinimide,
N-[3-triethoxysilyl]propylamide acid,
benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic
acid,
benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic
acid, 3-(triethoxysilyl)propylsuccinic anhydride or
N-phenylaminopropyltrimethoxysilane, and aluminum-based adhesive
assistants such as aluminum tris(ethylacetoacetate), aluminum
tris(acetylacetonate) or aluminum ethylacetylacetate
diisopropylate.
[0314] Among these adhesive assistants, silane coupling agents are
more preferable from the viewpoint of adhesive strength. The added
amount of the adhesive assistant is preferably within the range of
0.5 parts by weight to 25 parts by weight based on 100 parts by
weight of the polyimide precursor.
[0315] Heat resistance and chemical resistance can be further
enhanced by adding a crosslinking agent that is capable of
crosslinking the polyimide precursor or forming a crosslinked
network by itself. An amino resin or derivative thereof is
preferably used for the crosslinking agent, and among these, a
glycol urea resin, hydroxyethylene urea resin, melamine resin,
benzoguanamine resin or derivatives thereof are used preferably.
The crosslinking agent is particularly preferably an
alkoxymethylated melamine compound, and an example thereof is
hexamethoxymethylmelamine.
[0316] The added amount of crosslinking agent with respect to the
balance with various properties other than heat resistance and
chemical resistance is preferably 2 parts by weight to 40 parts by
weight and more preferably 5 parts by weight to 30 parts by weight
based on 100 parts by weight of the polyimide precursor. In the
case the added amount is 2 parts by weight or more, favorable heat
resistance and chemical resistance are demonstrated, while in the
case the added amount is 40 parts by weight or less, storage
stability is superior.
[0317] The following provides an explanation of the cross-sectional
angle of a relief pattern in the present embodiment. In the present
embodiment, a photosensitive resin composition allowing the
production of a semiconductor device having a wide focus margin and
favorable electrical properties preferably has a cross-sectional
angle between a concave relief pattern and the substrate of 60
degrees to 90 degrees. If the cross-sectional angle is within this
range, a normal relief pattern can be formed without the occurrence
of bridging, the focus margin is large, and there is no occurrence
of disconnections, thereby making this preferable.
[0318] In addition, if the cross-sectional angle is below this
range, it becomes difficult to form the rewiring layer, thereby
making this undesirable. The cross-sectional angle is more
preferably 60 degrees to 85 degrees.
[0319] <Method for Producing Cured Relief Pattern and
Semiconductor Device>
[0320] In addition, the present invention provides a method for
producing a cured relief pattern, comprising the following steps
(6) to (9):
[0321] (6) a step for forming a resin layer on a substrate by
coating the photosensitive resin composition of the present
invention on the substrate;
[0322] (7) a step for exposing the resin layer to light;
[0323] (8) a step for forming a relief pattern by developing the
resin layer after exposing to light; and,
[0324] (9) a step for forming a cured relief pattern by
heat-treating the relief pattern. The following provides of a
typical aspect of each step.
[0325] (6) Step for forming a resin layer on a substrate by coating
the photosensitive resin on the substrate
[0326] In the present step, the photosensitive resin composition of
the present invention is coated onto a substrate followed by drying
as necessary to form a resin layer. A method conventionally used to
coat photosensitive resin compositions can be used, examples of
which include coating methods using a spin coater, bar coater,
blade coater, curtain coater or screen printer, and spraying
methods using a spray coater.
[0327] The method for forming a relief pattern using the
photosensitive resin composition of the resin may consist of
forming the resin layer not only by forming the resin layer on the
substrate by coating the photosensitive resin composition on the
substrate, but also by forming the photosensitive resin composition
into the form of a film followed by laminating a layer of the
photosensitive resin composition on the substrate. In addition, a
film of the photosensitive resin composition according to the
present invention may be formed on a support base material, and the
support base material may be removed before or after laminating
when using the film.
[0328] A coating film composed of the photosensitive resin
composition can be dried as necessary. A method such as air drying,
or heat drying or vacuum drying using an oven or hot plate, is used
for the drying method. More specifically, in the case of carrying
out air drying or heat drying, drying can be carried out under
conditions consisting of 1 minute to 1 hour at 20.degree. C. to
140.degree. C. The resin layer can be formed on the substrate in
this manner.
[0329] (7) Step for exposing resin layer to light
[0330] In the present step, the resin layer formed in the manner
described above is exposed to an ultraviolet light source and the
like either directly or through a photomask having a pattern or
reticle using an exposure device such as a contact aligner, mirror
projector or stepper.
[0331] Subsequently, post-exposure baking (PEB) and/or
pre-development baking may be carried out using an arbitrary
combination of temperature and time as necessary for the purpose of
improving photosensitivity and the like. Although the range of
baking conditions preferably consists of a temperature of
40.degree. C. to 120.degree. C. and time of 10 seconds to 240
seconds, the range is not limited thereto provided various
properties of the photosensitive resin composition of the present
invention are not impaired.
[0332] (8) Step for forming relief pattern by developing resin
layer after exposing to light
[0333] In the present step, unexposed portions of the
photosensitive resin layer are developed and removed following
exposure. An arbitrary method can be selected and used for the
development method from among conventionally known photoresist
development methods, examples of which include the rotary spraying
method, paddle method and immersion method accompanying ultrasonic
treatment. In addition, post-development baking using an arbitrary
combination of temperature and time may be carried out as necessary
after development for the purpose of adjusting the form of the
relief pattern.
[0334] A good solvent with respect to the photosensitive resin
composition or a combination of this good solvent and a poor
solvent is preferable for the developer used for development.
Examples of good solvents include N-methylpyrrolidone,
N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetoamide, cyclopentanone,
cyclohexanone, .gamma.-butyrolactone and
.alpha.-acetyl-.gamma.-butyrolactone, while preferable examples of
poor solvents include toluene, xylene, methanol, ethanol, isopropyl
alcohol, ethyl lactate, propylene glycol methyl ether acetate and
water. In the case of using a mixture of good solvent and poor
solvent, the proportion of poor solvent to good solvent is
preferably adjusted according to the solubility of polymer in the
photosensitive resin composition. In addition, two or more types of
each solvent, such as a combination of several types of each
solvent, can also be used.
[0335] (9) Step for forming cured relief pattern by heat-treating
relief pattern
[0336] In the present step, the relief pattern obtained by
developing in the manner previously described is converted to a
cured relief pattern by heating. Various methods can be selected
for the heat curing method, examples of which include heating with
a hot plate, heating using an oven, and heating using a
programmable oven that allows the setting of a temperature program.
Heating can be carried out under conditions consisting of, for
example, 30 minutes to 5 hours at 180.degree. C. to 400.degree. C.
Air may be used for the atmospheric gas during heat curing, or an
inert gas such as nitrogen or argon can be used.
[0337] <Semiconductor Device>
[0338] The present invention also provides a semiconductor device
that contains a cured relief pattern obtained according to the
method for producing a cured relief pattern of the present
invention described above. The present invention also provides a
semiconductor device containing a semiconductor element in the form
of a base material and a cured relief pattern of a resin formed
according to the aforementioned method for producing a cured relief
pattern on the aforementioned base material. In addition, the
present invention can be applied to a method for producing a
semiconductor device that uses a semiconductor element for the base
material and contains the aforementioned method for producing a
cured relief pattern as a portion of the process thereof. The
semiconductor device of the present invention can be produced by
combining with known methods for producing semiconductor devices by
forming the cured relief pattern formed according to the
aforementioned method for producing a cured relief pattern as a
surface protective film, interlayer insulating film, rewiring
insulating film, flip-chip device protective film, fan out device
protective film or protective film of a semiconductor device having
a bump structure.
[0339] The photosensitive resin composition according to the second
aspect of the present invention is also useful in applications such
as the interlayer insulation of a multilayer circuit, cover coating
of a flexible copper-clad board, solder-resistive film or liquid
crystal alignment film.
Third Aspect
[0340] Elements are mounted on printed boards using various methods
corresponding to the purpose. Conventional elements were typically
fabricated by a wire bonding method in which a connection is made
from an external terminal of the element (pad) to a lead frame with
a fine wire. However, with today's current higher element speeds in
which the operating frequency has reached the GHz range,
differences in the wiring lengths of each terminal during mounting
are having an effect on element operation. Consequently, in the
case of mounting elements for high-end applications, it has become
necessary to accurately control the lengths of mounting wires, and
it has become difficult to satisfy this requirement with wire
bonding.
[0341] Thus, flip-chip mounting has been proposed in which, after
having formed a rewiring layer on the surface of a semiconductor
chip and formed a bump (electrode) thereon, the chip is turned over
(flipped) followed by directly mounting on the printed board (see,
for example, Japanese Unexamined Patent Publication No.
2001-338947). As a result of being able to accurately control
wiring distance, this flip-chip mounting is being employed in
elements for high-end applications handling high-speed signals, and
because of its small mounting size, is also being employed in cell
phone applications, thereby resulting in a rapid increase in
demand. In the case of using a polyimide material for flip-chip
mounting, the process goes through a step for forming a metal
wiring layer after a pattern has been formed in the polyimide
layer. The metal wiring layer is normally formed by roughening the
surface of the polyimide layer by subjecting to plasma etching,
followed by forming a metal layer serving as the plating seed layer
by sputtering at a thickness of 1 .mu.m or less, and then forming
the metal wiring layer by electrolytic plating using this metal
layer as an electrode. Although Ti is typically used for the metal
of the seed layer at this time, Cu is used as the metal of the
rewiring layer formed by electrolytic plating.
[0342] With respect to this metal rewiring layer, the rewired metal
layer and resin layer are required to demonstrate high adhesion.
However, there have conventionally been cases in which adhesion
between the rewiring Cu layer and resin layer decreases due to the
effects of the resin and additives that form the photosensitive
resin composition and the effects of the production method used
when forming the rewiring layer. A decrease in adhesion between the
rewired Cu layer and resin layer results in a decrease in
insulation reliability of the rewiring layer.
[0343] With the foregoing in view, an object of the third aspect of
the present invention is to provide a method for forming a rewiring
layer demonstrating a high level of adhesion with a Cu layer, and a
semiconductor device having this rewiring layer.
[0344] The inventors of the present invention found that the
aforementioned object can be achieved by combining a photosensitive
polyimide precursor and a specific compound, thereby leading to
completion of the third aspect of the present invention. Namely,
the third aspect of the present invention is as indicated
below.
[0345] [1] A photosensitive resin composition comprising: [0346] a
photosensitive polyimide precursor in the form of a component (A);
and [0347] a component (B) represented by the following general
formula (B1):
##STR00081##
[0347] {wherein, R.sub.s1 to R.sub.s5 respectively and
independently represent a hydrogen atom or monovalent organic
group}.
[0348] [2] The photosensitive resin composition described in [1],
wherein component (A) is a polyamic acid derivative having a
radical-polymerizable substituent in a side chain thereof.
[0349] [3] The photosensitive resin composition described in [1] or
[2], wherein component (A) is a photosensitive polyimide precursor
containing a structure represented by the following general formula
(A1):
##STR00082##
{wherein, X represents a tetravalent organic group, Y represents a
divalent organic group, and R.sub.5b and R.sub.6b respectively and
independently represent a hydrogen atom, a monovalent organic group
represented by the following general formula (R1):
##STR00083##
(wherein, R.sub.7b, R.sub.8b and R.sub.9b respectively and
independently represent a hydrogen atom or organic group having 1
to 3 carbon atoms, and p represents an integer of 2 to 10), or a
saturated aliphatic group having 1 to 4 carbon atoms, provided that
R.sub.5b and R.sub.6b are not both simultaneously hydrogen
atoms}.
[0350] [4] The photosensitive resin composition described in any of
[1] to [3], wherein component (B) contains a structure represented
by the following formula (B2).
##STR00084##
[0351] [5] The photosensitive resin composition describe in any of
[1] to [4], wherein X in general formula (A1) contains at least one
type of tetravalent organic group selected from the following (C1)
to (C3):
##STR00085##
and Y contains at least one type of divalent organic group selected
from the following group (D1):
##STR00086##
{wherein, R.sub.10b to R.sub.13b represent hydrogen atoms or
aliphatic groups having 1 to 4 carbon atoms, and may mutually be
the same or different}, and following group (D2).
##STR00087##
[0352] [6] The photosensitive resin composition described in any of
[1] to [5], wherein the content of component (B) based on 100 parts
by weight of component (A) is 0.1 parts by weight to 10 parts by
weight.
[0353] [7] The photosensitive resin composition described in any of
[1] to [6], wherein the content of component (B) based on 100 parts
by weight of component (A) is 0.5 parts by weight to 5 parts by
weight.
[0354] [8] A method for producing a cured relief pattern including
the following steps:
[0355] (1) a coating step for forming a photosensitive resin layer
on a substrate by coating the photosensitive resin composition
described in any of [1] to [7] on the substrate,
[0356] (2) an exposure step for exposing the photosensitive resin
layer to light,
[0357] (3) a development step for forming a relief pattern by
developing the photosensitive resin layer after exposing to light;
and,
[0358] (4) a heating step for forming a cured relief pattern by
heat-treating the relief pattern.
[0359] [9] A semiconductor device having a substrate and a cured
relief pattern obtained according to the method described in [8]
formed on the substrate, wherein
[0360] the cured relief pattern contains a polyimide resin and a
compound represented by the following general formula (B1):
##STR00088##
{wherein, R.sub.s1 to R.sub.s5 respectively and independently
represent a hydrogen atom or monovalent organic group}.
[0361] According to this third aspect of the present invention, a
photosensitive resin composition, in which a photosensitive resin
demonstrating a high level of adhesion between a Cu layer and a
polyimide layer, is obtained by combining a photosensitive
polyimide precursor and a specific compound, a method for forming a
cured relief pattern using the photosensitive resin composition,
and a semiconductor device having the cured relief pattern, can be
provided.
[0362] The following provides a detailed explanation of the present
third aspect. Furthermore, throughout the present description, in
the case a plurality of structures represented by the same
reference symbol in the general formulas are present within a
molecule, those structures may be the same or different.
[0363] <Photosensitive Resin Composition>
[0364] The photosensitive resin composition of the present
invention contains a photosensitive polyimide precursor in the form
of a component (A) and a component (B) represented by the following
general formula (B1):
##STR00089##
{wherein, R.sub.s1 to R.sub.s5 respectively and independently
represent a hydrogen atom or monovalent organic group}.
[0365] [Photosensitive Polyimide Precursor (A)]
[0366] The following provides an explanation of the photosensitive
polyimide precursor of component (A) used in the present
invention.
[0367] A photosensitive polyimide precursor having an i-line
absorbance of 0.8 to 2.0, as measured for a 10 .mu.m thick film
obtained after coating in the form of single solution and
prebaking, is preferably used for the photosensitive polyimide
precursor in the present invention.
[0368] The photosensitive resin composition of the present
invention preferably contains a photosensitive polyimide precursor
(A) that satisfies the aforementioned requirements in order to give
the sides of an opening in the cured relief pattern obtained from
the photosensitive resin composition a forward tapered shape (shape
in which the opening diameter in the top of a film is larger than
the opening diameter in the bottom of the film).
[0369] After having prebaked the photosensitive polyimide precursor
alone, the i-line absorbance of a 10 .mu.m thick film can be
measured for a coating film formed on quartz with an ordinary
spectrophotometer. In the case the thickness of the film formed is
not 10 .mu.m, i-line absorbance can be determined for a thickness
of 10 .mu.m by converting absorbance obtained for the film to a
thickness of 10 .mu.m in accordance with Lambert-Beer's Law.
[0370] If the i-line absorbance is 0.8 to 2.0, mechanical
properties and physical properties of the coating film are
superior, and since i-line absorbance of the coating film is such
that light suitably reaches to the bottom, curing is able to
proceed to the bottom of the coating film in the case of a
negative-type film, thereby making this preferable.
[0371] The photosensitive polyimide precursor (A) of the present
invention preferably has a polyamic acid ester for the main
component thereof. Here, the main component refers to containing
this resin at 60% by weight or more, and preferably at 80% by
weight or more, based on the total amount of resin. In addition,
other resins may be contained as necessary.
[0372] The weight average molecular weight (Mw) of the
photosensitive polyimide precursor (A) as determined by gel
permeation chromatography (GPC) based on standard polystyrene
conversion is preferably 1,000 or more and more preferably 5,000 or
more from the viewpoints of heat resistance and mechanical
properties of the film obtained following heat treatment. The upper
limit of weight average molecular weight (Mw) is preferably 100,000
or less. The upper limit is more preferably 50,000 or less from the
viewpoint of solubility with respect to the developer.
[0373] In the photosensitive resin composition of the present
invention, the most preferable photosensitive polyimide precursor
(A) from the viewpoints of heat resistance and photosensitivity is
an ester-type photosensitive polyimide precursor containing a
structure represented by the following general formula (A1):
##STR00090##
{wherein, X represents a tetravalent organic group, Y represents a
divalent organic group, and R.sub.5b and R.sub.6b respectively and
independently represent a hydrogen atom, a monovalent organic group
represented by the following general formula (R1):
##STR00091##
(wherein, R.sub.7b, R.sub.8b and R.sub.9b respectively and
independently represent a hydrogen atom or organic group having 1
to 3 carbon atoms, and p represents an integer of 2 to 10), or a
saturated aliphatic group having 1 to 4 carbon atoms, provided that
R.sub.5b and R.sub.6b are not both simultaneously hydrogen
atoms}.
[0374] From the viewpoint of realizing both heat resistance and
photosensitivity, examples of the tetravalent organic group
represented by X in the aforementioned general formula (A1)
preferably include, but are not limited to, organic groups having 6
to 40 carbon atoms, more preferably an aromatic group or alicyclic
group having a --COOR.sub.1 group and a --COOR.sub.2 group at
mutually ortho positions with a --CONH-- group, and even more
preferably structures represented by the following formula
(90):
##STR00092## ##STR00093##
{wherein, R.sub.25b represents a hydrogen atom, fluorine atom or
monovalent group selected from hydrocarbon groups having 1 to 10
carbon atoms and fluorine-containing hydrocarbon groups having 1 to
10 carbon atoms, 1 represents an integer of 0 to 2, m represents an
integer of 0 to 3 and n represents an integer of 0 to 4}. In
addition, the structure of X may be one type or a combination of
two or more types. Group X having a structure represented by the
aforementioned formulas is particularly preferable from the
viewpoint of realizing both heat resistance and
photosensitivity.
[0375] From the viewpoint of realizing both heat resistance and
photosensitivity, examples of the divalent organic group
represented by Y in the aforementioned general formula (A1)
preferably include aromatic groups having 6 to 40 carbon atoms such
as the structures represented by the following formula (91):
##STR00094## ##STR00095##
{wherein, R.sub.25b represents a hydrogen atom, fluorine atom or
monovalent group selected from the group consisting of hydrocarbon
groups having 1 to 10 carbon atoms and fluorine-containing
hydrocarbon groups having 1 to 10 carbon atoms, and n represents an
integer of 0 to 4}. In addition, the structure of Y may be one type
or a combination of two or more types. Group Y having a structure
represented by the aforementioned formula (91) is particularly
preferable from the viewpoint of realizing both heat resistance and
photosensitivity.
[0376] Group R.sub.7b in the aforementioned general formula (R1) is
preferably a hydrogen atom or methyl group, and R.sub.8b and
R.sub.9b are preferably hydrogen atoms from the viewpoint of
photosensitivity. In addition, p is an integer of 2 to 10, and
preferably an integer of 2 to 4, from the viewpoint of
photosensitivity.
[0377] In the case of using a polyimide precursor for the resin
(A), examples of methods used to impart photosensitivity to the
photosensitive resin composition include ester bonding and ionic
bonding. The former is a method consisting of introducing a
photopolymerizable group, or in other words, a compound having an
olefinic double bond, into a side chain of a polyimide precursor by
ester bonding, while the latter is a method consisting of imparting
a photopolymerizable group by bonding an amino group of
(meth)acrylic compound having an amino group with a carboxyl group
of a polyimide precursor through an ionic bond.
[0378] The aforementioned ester-bonded polyimide precursor is
obtained by first preparing a partially esterified tetracarboxylic
acid (to also be referred to as an acid/ester form) by reacting a
tetracarboxylic dianhydride containing the tetravalent organic
group X with an alcohol having photopolymerizable unsaturated
double bond, and optionally, a saturated aliphatic alcohol having 1
to 4 carbon atoms, followed by subjecting this to amide
polycondensation with a diamine containing the divalent organic
group Y.
[0379] (Preparation of Acid/Ester Form)
[0380] In the present invention, examples of the tetracarboxylic
dianhydride containing the tetravalent organic group X preferably
used to prepare the ester-bonded polyimide precursor include, but
are not limited to, acid dianhydrides having a structure
represented by the aforementioned general formula (90) such as
pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic
dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride,
biphenyl-3,3'4,4'-tetracarboxylic dianhydride,
diphenylphosphone-3,3',4,4'-tetracarboxylic dianhydride,
diphenylmethane-3,3'4,4'-tetracarboxylic dianhydride,
2,2-bis(3,4-phthalic anhydride)propane or 2,2-bis(3,4-phthalic
anhydride)-1,1,1,3,3,3-hexafluoropropane. Preferable examples
include, but are not limited to, pyromellitic anhydride,
diphenylether-3,3',4,4'-tetracarboxylic dianhydride,
biphenyl-3,3'4,4'-tetracarboxylic dianhydride, preferably
pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic
dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride and
biphenyl-3,3'4,4'-tetracarboxylic dianhydride, and more preferably
pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic
dianhydride and biphenyl-3,3'4,4'-tetracarboxylic dianhydride. In
addition, these may be used alone or two or more types may be used
as a mixture.
[0381] In the present invention, examples of alcohols having a
photopolymerizable group preferably used to prepare the
ester-bonded polyimide precursor include 2-acryloyloxyethyl
alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol,
methylol vinyl ketone, 2-hydroxyethyl vinyl ketone,
2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butyoxypropyl
acrylate, 2-hydroxy-3-phenoxypropyl acrylate,
2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl
acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate,
2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol,
2-methacrylamidoethyl alcohol, 2-hydroxy-3-methoxyopropyl
methacrylate, 2-hydroxy-3-butoxypropyl methacrylate,
2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl
methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate and
2-hydroxy-3-cyclohexyloxypropyl methacrylate.
[0382] Saturated aliphatic alcohols able to be optionally used
together with the aforementioned alcohols having a
photopolymerizable group are preferably saturated aliphatic
alcohols having 1 to 4 carbon atoms. Specific examples thereof
include methanol, ethanol, n-propanol, isopropanol, n-butanol and
tert-butanol.
[0383] A desired acid/ester form can be obtained by carrying out an
acid anhydride esterification reaction by mixing the aforementioned
preferable tetracarboxylic dianhydride of the present invention
with an aforementioned alcohol preferably in the presence of a
basic catalyst such as pyridine and preferably and in a suitable
reaction solvent to be subsequently described followed by stirring
for 4 to 10 hours at a temperature of 20.degree. C. to 50.degree.
C.
[0384] [Preparation of Photosensitive Polyimide Precursor]
[0385] The acid/ester form is converted to a polyacid anhydride by
adding a suitable dehydration condensation agent to the
aforementioned acid/ester form (typically in the form of a solution
dissolved in the aforementioned reaction solvent) while cooling
with ice and mixing therewith. Next, a solution or dispersion of a
diamine containing the divalent organic group Y preferably used in
the present invention dissolved or dispersed in a different solvent
is dropped therein followed by amide polycondensation to obtain the
target photosensitive polyimide precursor. A diaminosiloxane may be
used in combination with the aforementioned diamine having the
divalent organic group Y.
[0386] Examples of the aforementioned dehydration condensation
agent include dicyclocarbodiimide,
1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline,
1,1-carbonyldioxy-di-1,2,3-benzotriazole and N,N'-disuccinimidyl
carbonate.
[0387] An intermediate in the form of a polyacid anhydride is
obtained in the manner described above.
[0388] In the present invention, examples of diamines having the
divalent organic group Y preferably used in the reaction with the
polyacid anhydride obtained in the manner described above include
diamines having a structure represented by the aforementioned
general formula (91), such as p-phenylenediamine,
m-phenylenediamine, 4,4'-diaminodiphenyl ether,
3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether,
4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide,
3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylsulfone,
3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone,
4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl,
4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone,
3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane,
3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane,
1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene,
1,3-bis(3-aminophenoxy)benzene,
bis[4-(4-aminophenoxy)phenyl]sulfone,
bis[4-(3-aminophenoxy)phenyl]sulfone,
4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl,
bis[4-(4-aminophenoxy)phenyl] ether, bis[4-(3-aminophenoxy)phenyl]
ether, 1,4-bis(4-aminophenyl)benzene,
1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene,
2,2-bis(4-aminophenyl)propane,
2,2-bis(4-aminophenyl)hexafluoropropane,
2,2-bis[4-(4-aminophenoxy)phenyl]propane,
2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane,
1,4-bis(3-aminopropyldimethylsilyl)benzene, o-toluidine sulfone or
9,9-bis(4-aminophenyl)fluorene, those in which a portion of the
hydrogen atoms on the benzene ring thereof is substituted with a
substituent such as a methyl group, ethyl group, hydroxymethyl
group, hydroxyethyl group or halogen atom, and mixtures
thereof.
[0389] Specific examples of the aforementioned substituents include
3,3'-dimethyl-4,4'-diaminobiphenyl,
2,2'-dimethyl-4,4'-diaminobiphenyl,
3,3'-dimethyl-4,4'-diaminodiphenylmethane,
2,2'-dimethyl-4,4'-diaminodiphenylmethane,
3,3'-dimethoxy-4,4'-diaminobiphenyl,
3,3'-dichloro-4,4'-diaminobiphenyl,
2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl,
2,2'-bis(fluoro)-4,4'-diaminobiphenyl,
4,4'-diaminooctafluorobiphenyl and mixtures thereof. Among these,
examples of substituents that are used preferably include
p-phenylenediamine, 4,4'-diaminodiphenyl ether,
2,2'-dimethyl-4,4'-diaminobiphenyl,
2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl,
2,2'-bis(fluoro)-4,4'-diaminobiphenyl and
4,4'-diaminooctafluorobiphenyl, while more preferable examples
include p-phenylenediamine, 4,4'-diaminodiphenyl ether and mixtures
thereof. These diamines are not limited to the aforementioned
examples thereof.
[0390] Diaminosiloxanes are used in combination with the
aforementioned diamine containing the divalent organic group Y when
preparing the photosensitive polyimide precursor (A) for the
purpose of improving adhesion between various types of substrates
and a coating film formed from the photosensitive resin composition
of the present invention. Specific examples of such
diaminosiloxanes include
1,3-bis(3-aminopropyl)tetramethyldisiloxane and
1,3-bis(3-aminopropyl)tetraphenyldisiloxane.
[0391] Following completion of the amide polycondensation reaction,
after filtering out absorption byproducts of the dehydration
condensation agent also present in the reaction solution as
necessary, a suitable poor solvent such as water, an aliphatic
lower alcohol or a mixture thereof is added to a solution
containing the polymer component to precipitate the polymer
component. Moreover, after purifying the polymer by repeating
re-dissolution and re-precipitation procedures as necessary, vacuum
drying is carried out to isolate the target photosensitive
polyimide precursor. In order to improve the degree of
purification, a solution of this polymer may be passed through a
column packed with an anion exchange resin and/or cation exchange
resin swollen with a suitable organic solvent to remove any ionic
impurities.
[0392] From the viewpoints of heat resistance and mechanical
properties of the film obtained following heat treatment, the
weight average molecular weight (Mw) of the ester-bonded polyimide
precursor in the case of measuring by gel permeation chromatography
(GPC) based on standard polystyrene conversion is preferably 1,000
or more and more preferably 5,000 or more. The upper limit of
weight average molecular weight (Mw) is preferably 100,000 or less.
The upper limit of weight average molecular weight (Mw) is more
preferably 50,000 or less from the viewpoint of solubility with
respect to the developer. The use of tetrahydrofuran or
N-methyl-2-pyrrolidone is recommended for the developing solvent
during gel permeation chromatography. Molecular weight is
determined from a calibration curve prepared using standard
monodisperse polystyrene. The standard monodisperse polystyrene is
recommended to be selected from the organic solvent-based standard
sample STANDARD SM-105 manufactured by Showa Denko K.K.
[0393] Various values can be adopted for the i-line absorbance of a
prebaked film formed alone for the photosensitive polyimide
precursor (A) synthesized according to a method like that described
above corresponding to the molecular structure thereof. However,
since the i-line absorbance of a mixture is the arithmetic mean of
the i-line absorbance of each component, the i-line absorbance of a
10 .mu.m thick film following prebaking of the photosensitive
polyimide precursor (A) can be made to be 0.8 to 2.0 while
maintaining balance among mechanical properties, heat resistance
and the like by combining two or more types of the photosensitive
polyimide precursor (A) at a suitable ratio.
[0394] [Component (B)]
[0395] Next, an explanation is provided of component (B) used in
the present invention.
[0396] Component (B) used in the present invention is an oxime
ester having an i-line absorbance of a 0.001% by weight solution of
0.1 to 0.2, an h-line absorbance of 0.02 to 0.1, and a g-line
absorbance of 0.02 or less. These oxime esters have
photosensitivity and are essential for patterning a photosensitive
resin by photolithography.
[0397] From the viewpoint of adhesion with Cu, the i-line
absorbance of a 0.001% by weight solution is preferably 0.1 to 0.2,
h-line absorbance is preferably 0.02 to 0.1, and g-line absorbance
is preferably 0.02 or less. Adhesion with Cu decreases in the case
i-line absorbance exceeds 0.2, h-line absorbance exceeds 0.1 and
g-line absorbance exceeds 0.02, while sensitivity decreases in the
case i-line absorbance is less than 0.1 and h-line absorbance is
less than 0.02.
[0398] Component (B) able to be used in the present invention
contains a structure represented by the following general formula
(B1):
##STR00096##
{wherein, R.sub.a1 to R.sub.s5 respectively and independently
represent a hydrogen atom or monovalent organic group}.
[0399] Here, a hydrogen atom or a group selected from a linear,
branched or cyclic alkyl group, alkylaryl group and arylalkyl group
is respectively and independently preferably used for R.sub.s1 to
R.sub.s5. Specific examples thereof include a methyl group, ethyl
group, n-propyl group, isopropyl group, n-butyl group, isobutyl
group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl
group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl
group, n-octyl group, isooctyl group, n-decyl group, isodecyl
group, cyclopropyl group, cyclobutyl group, cyclopentyl group,
cyclohexyl group, methylcyclopentyl group, cyclopentylmethyl group,
methylcyclohexyl group, cyclohexylmethyl group, phenyl group, tolyl
group, xylyl group and benzyl group.
[0400] Compounds represented by the following general formula (B2)
are preferably used for component (B):
##STR00097##
An example thereof is TR-PBG-346 manufactured by Changzhou Tronly
New Electronic Materials Co., Ltd.
[0401] Component (B) is used at an added amount of 0.1 parts by
weight to 10 parts by weight, and preferably 0.5 parts by weight to
5 parts by weight, based on 100 parts by weight of the
photosensitive polyimide precursor (A). In the case the added
amount of component (B) is 0.1 parts by weight or more based on 100
parts by weight of the photosensitive polyimide precursor (A), the
effect of inhibiting the formation of voids at the interface
between the Cu layer and polyimide layer is adequately demonstrated
following a high-temperature storage test. In addition, if the
added amount of component (B) is 10 parts by weight or less based
on 100 parts by weight of the photosensitive polyimide precursor
(A), filterability and coatability of the composition improve.
[0402] The oxime ester used in the present invention, when
examining the g-line absorbance, h-line absorbance and i-line
absorbance of a 0.001% by weight solution thereof, is characterized
in that i-line absorbance is 0.1 to 0.2, h-line absorbance is 0.02
to 0.1, and g-line absorbance is 0.02 or less. Normally, when used
as a polymerization inhibitor, only the i-line absorbance of the
oxime ester is high, while g-line and h-line absorbance are not
observed. On the other hand, since some oxime esters demonstrate
hardly any g-line, h-line or i-line absorbance, it is necessary to
use the oxime ester in combination with a sensitizer.
[0403] On the basis of these characteristic g-line, h-line and
i-line absorbance spectra, the oxime ester of the present invention
is able to improve adhesion with Cu as a result of generating a
specific amount of not only a polymerization-initiating radical
when exposed, but also generating a specific amine, and that amine
specifically interacting with Cu.
[0404] [Other Component (C)]
[0405] The photosensitive resin composition of the present
invention may further contain a component other than the
aforementioned photosensitive polyimide precursor (A) and the
component (B).
[0406] The photosensitive resin composition of the present
invention is used as a liquid photosensitive resin composition by
dissolving each of the aforementioned components and optional
components used as necessary in a solvent to form a varnish.
Consequently, in addition to a solvent, examples of other component
(C) include a resin other than the photosensitive polyimide
precursor of component (A), sensitizer, monomer having a
photopolymerizable unsaturated bond, adhesive assistant, thermal
polymerization inhibitor, azole compound and hindered phenol
compound.
[0407] Examples of the aforementioned solvent include polar organic
solvents and alcohols.
[0408] A polar organic solvent is preferably used for the solvent
from the viewpoints of solubility with respect to the
photosensitive polyimide precursor (A). Specific examples thereof
include N,N-dimethylformamide, N-methyl-2-pyrrolidone,
N-ethyl-2-pyrrolidone, N,N-dimethylacetoamide, dimethylsulfoxide,
diethylene glycol dimethyl ether, cyclopentanone,
.gamma.-butyrolactone, .alpha.-acetyl-.gamma.-butyrolactone,
tetramethyl urea, 1,3-dimethyl-2-imidazolinone and
N-cyclohexyl-2-pyrrolidone, and these can be used alone or two or
more types can be used in combination.
[0409] A solvent containing an alcohol is preferable for the
solvent used in the present invention from the viewpoint of
improving storage stability of the photosensitive resin
composition. Alcohols able to be used preferably are typically
alcohols that have an alcoholic hydroxyl group but do not have an
olefinic double bond within a molecule thereof.
[0410] Specific examples thereof include alkyl alcohols such as
methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol,
n-butyl alcohol, isobutyl alcohol or tert-butyl alcohol, lactic
acid esters such as ethyl lactate, propylene glycol monoalkyl
ethers such as propylene glycol 1-methyl ether, propylene glycol
2-methyl ether, propylene glycol 1-ethyl ether, propylene glycol
2-ethyl ether, propylene glycol 1-(n-propyl) ether or propylene
glycol 2-(n-propyl) ether, monoalcohols such as ethylene glycol
methyl ether, ethylene glycol ethyl ether or ethylene glycol
n-propyl ether, 2-hydroxyisobutyric acid esters, and dialcohols
such as ethylene glycol and propylene glycol.
[0411] Among these, lactic acid esters, propylene glycol monoalkyl
ethers, 2-hydroxyisobutyric acid esters and ethyl alcohol are
preferable, and in particular, ethyl lactate, propylene glycol
1-methyl ether, propylene glycol 1-ethyl ether and propylene glycol
1-(n-propyl) ether are more preferable.
[0412] In addition, ketones, esters, lactones, ethers, halogenated
hydrocarbons and hydrocarbons can also be used preferably.
[0413] Specific examples thereof include ketones such as acetone,
methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,
esters such as methyl acetate, ethyl acetate, butyl acetate or
diethyl oxalate, lactones such as .gamma.-butyrolactone, ethers
such as ethylene glycol dimethyl ether, diethylene glycol dimethyl
ether or tetrahydrofuran, halogenated hydrocarbons such as
dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane,
chlorobenzene or o-dichlorobenzene, and hydrocarbons such as
hexane, heptane, benzene, toluene or xylene. These may be used
alone or two or more types may be used as a mixture as
necessary.
[0414] The aforementioned solvent can be used within the range of,
for example, 30 parts by weight to 1500 parts by weight, and
preferably within the range of 100 parts by weight to 1000 parts by
weight, based on 100 parts by weight of the photosensitive
polyimide precursor (A) corresponding to the desired coated film
thickness and viscosity of the photosensitive resin composition. In
the case the solvent contains an alcohol that does not have an
olefinic double bond, the content of alcohol not having an olefinic
double bond present in the entire solvent is preferably 5% by
weight to 50% by weight and more preferably 10% by weight to 30% by
weight. In the case the aforementioned content of the alcohol not
having an olefinic double bond is 5% by weight or more, storage
stability of the photosensitive resin composition is favorable,
while in the case the content thereof is 50% by weight or less,
solubility of the photosensitive polyimide precursor (A) is
favorable.
[0415] The photosensitive resin composition of the present
invention may further contain a resin component other than the
photosensitive polyimide precursor (A) described above. Examples of
resin components able to be contained include polyimides,
polyoxazoles, polyoxazole derivatives, phenol resins, polyamides,
epoxy resins, siloxane resins and acrylic resins. The incorporated
amount of these resin components is preferably within the range of
0.01 parts by weight to 20 parts by weight based on 100 parts by
weight of the photosensitive polyimide precursor (A).
[0416] The photosensitive resin composition of the present
invention can optionally incorporate a sensitizer for improving
photosensitivity. Examples of the sensitizer include Michler's
ketone, 4,4'-bis(diethylamino)benzophenone,
2,5-bis(4'-diethylaminobenzal)cyclopentane,
2,6-bis(4'-diethylaminobenzal)cyclohexanone,
2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone,
4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone,
p-diethylaminocinnamylidene indanone, p-dimethylaminobenzylidene
indanone, 2-(p-dimethylaminophenylbiphenylene)benzothiazole,
2-(p-dimethylaminophenylvinylene)benzothiazole,
2-(p-dimethylaminophenylvinylene)isonaphthothiazole,
1,3-bis(4'-dimethylaminobenzal)acetone,
1,3-bis(4'-diethylaminobenzal)acetone,
3,3'-carbonyl-bis(7-diethylaminocoumarin),
3-acetyl-7-dimethylaminocoumarin,
3-ethoxycarbonyl-7-dimethylaminocoumarin,
3-benzyloxycarbonyl-7-dimethylaminocoumarin,
3-methoxycarbonyl-7-diethylaminocoumarin,
3-ethoxycarbonyl-7-diethylaminocoumarin,
N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine,
N-p-tolyldiethanolamine, N-phenylethanolamine,
4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl
diethylaminobenzoate, 2-mercaptobenzimidazole,
1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole,
2-(p-dimethylaminostyryl)benzoxazole,
2-(p-dimethylaminostyryl)benzothiazole,
2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole,
2-(p-dimethylaminobenzoyl) styrene, diphenylacetoamide,
benzanilide, N-methylacetoanilide and 3',4'-dimethylacetoanilide.
These can be used alone or, for example, 2 to 5 types can be used
in combination.
[0417] The incorporated amount of the sensitizer in the case the
photosensitive resin composition contains a sensitizer for
improving photosensitivity is preferably 0.1 parts by weight to 25
parts by weight based on 100 parts by weight of the photosensitive
polyimide precursor (A).
[0418] A monomer having a photopolymerizable unsaturated bond can
be optionally incorporated in the photosensitive resin composition
of the present invention to improve resolution of a relief pattern.
The monomer is preferably a (meth)acrylic compound that undergoes a
radical polymerization reaction by a photopolymerization
initiator.
[0419] In particular, examples thereof include, but are not limited
to compounds such as mono- or di(meth)acrylates of ethylene glycol
or polyethylene glycol such as diethylene glycol dimethacrylate or
tetraethylene glycol dimethacrylate, mono- or di(meth)acrylates of
propylene glycol or polypropylene glycol, mono-, di- or
tri(meth)acrylates of 1,4-butanediol and di(meth)acrylates of
1,6-hexanediol, di(meth)acrylates of neopentyl glycol, mono- or
di(meth)acrylates of bisphenol A, benzene trimethacrylates,
isobornyl (meth)acrylates, acrylamides and derivatives thereof,
methacrylamides and derivatives thereof, trimethylolpropane
tri(meth)acrylates, di- or tri(meth)acrylates of glycerol, di, tri-
or tetra(meth)acrylates of pentaerythritol, and ethylene oxide or
propylene oxide adducts of these compounds.
[0420] In the case the photosensitive resin composition contains
the aforementioned monomer having a photopolymerizable unsaturated
bond in order to improve the resolution of a relief pattern, the
incorporated amount of the photopolymerizable monomer having an
unsaturated bond is preferably 1 part by weight to 50 parts by
weight based on 100 parts by weight of the photosensitive polyimide
precursor (A).
[0421] An adhesive assistant can be optionally incorporated in the
photosensitive resin composition of the present invention to
improve adhesion between a substrate and a film formed from the
photosensitive resin composition. Examples of adhesive assistants
include silane coupling agents such as
.gamma.-aminopropyldimethoxysilane,
N-.beta.-aminoethyl)-.gamma.-aminopropylmethyldimethoxysilane,
.gamma.-glycidoxypropylmethyldimethoxysilane,
.gamma.-mercaptopropylmethyldimethoxysilane,
3-methacryloxypropyldimethoxymethylsilane,
3-methacryloxypropyltrimethoxysilane,
dimethoxymethyl-3-piperidinopropylsilane,
diethoxy-3-glycidoxypropylmethylsilane,
N-(3-diethoxymethylsilylpropyl)succinimide,
N-[3-triethoxysilyl]propylamide acid,
benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic
acid,
benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic
acid, 3-(triethoxysilyl)propylsuccinic anhydride or
N-phenylaminopropyltrimethoxysilane, and aluminum-based adhesive
assistants such as aluminum tris(ethylacetoacetate), aluminum
tris(acetylacetonate) or aluminum ethylacetylacetate
diisopropylate.
[0422] Among these adhesive assistants, silane coupling agents are
used more preferably from the viewpoint of adhesive strength. In
the case the photosensitive resin composition contains an adhesive
assistant, the incorporated amount of the adhesive assistant is
preferably 0.5 parts by weight to 25 parts by weight based on 100
parts by weight of the photosensitive polyimide precursor (A).
[0423] A thermal polymerization inhibitor can be optionally
incorporated in the photosensitive resin composition of the present
invention to improve viscosity and photosensitivity stability of
the photosensitive resin composition during storage particularly in
the case of storing in the form of a solution containing a solvent.
Examples of thermal polymerization inhibitors used include
hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol,
phenothiazine, N-phenylnaphthylamine, ethyldiamine tetraacetic
acid, 1,2-cyclohexanediamine tetraacetic acid, glycol ether diamine
tetraacetic acid, 2,6-di-tert-butyl-p-methylphenol,
5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol,
2-nitroso-1-naphthol,
2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol,
N-nitroso-N-phenylhydroxylamine ammonium salt and
N-nitroso-N-(1-naphthyl) hydroxylamine ammonium salt.
[0424] The incorporated amount of the thermal polymerization
inhibitor in the case of incorporating in the photosensitive resin
composition is preferably within the range of 0.005 parts by weight
to 12 parts by weight based on 100 parts by weight of the
photosensitive polyimide precursor (A).
[0425] For example, in the case of forming a cured film on a
substrate composed of copper or copper alloy using the
photosensitive resin composition of the present invention, a
nitrogen-containing heterocyclic compound such as an azole compound
or purine derivative can be optionally incorporated to inhibit
discoloration of the copper. Examples of azole compounds include
1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole,
4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole,
4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole,
phenyltriazole, p-ethoxyphenyltriazole,
5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole,
hydroxyphenyltriazole, 1,5-dimethyltriazole,
4,5-diethyl-1H-triazole, 1H-benzotriazole,
2-(5-methyl-2-hydroxyphenyl)benzotriazole,
2-[2-hydroxy-3,5-bis(.alpha.,.alpha.-dimethylbenzyl)phenyl]benzotriazole,
2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole,
2-(3-t-butyl-5-methyl-2-hydroxyphenyl)benzotriazole,
2-(3,5-ti-t-amyl-2-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole,
hydroxyphenylbenzotriazole, tolyltriazole,
5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole,
4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole,
1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole,
5-amino-1H-tetrazole and 1-methyl-1H-tetrazole. Particularly
preferable examples include one or more types selected from
tolyltriazole, 5-methyl-1H-benzotriazole and
4-methyl-1H-benzotriazole. One type of these azole compounds or a
mixture of two or more types may be used.
[0426] Specific examples of purine derivatives include purine,
adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine,
uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine,
2-hydroxyadenine, 2-methyladenine, 1-methyladenine,
N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine,
9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)
adenine, 8-aminoadenine, 6-amino-8-phenyl-9H-purine,
1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine,
N-methylguanine, 7-(2-hydroxyethyl)guanine,
N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine,
5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine,
8-azaxanthine, 8-azahypoxanthine and derivatives thereof.
[0427] The incorporated amount in the case the photosensitive resin
composition contains the aforementioned azole compound or purine
derivative is preferably 0.1 parts by weight to 20 parts by weight,
and more preferably 0.5 parts by weight to 5 parts by weight from
the viewpoint of photosensitivity, based on 100 parts by weight of
the photosensitive polyimide precursor (A). In the case the
incorporated amount of the azole compound based on 100 parts by
weight of the photosensitive polyimide precursor (A) is 0.1 parts
by weight or more, discoloration of the copper or copper alloy
surface is inhibited in the case of having formed the
photosensitive resin composition of the present invention on copper
or copper alloy, while in the case the incorporated amount is 20
parts by weight or less, photosensitivity is superior.
[0428] A hindered phenol compound can be optionally incorporated
instead of the aforementioned azole compound or together with
aforementioned azole compound in order to inhibit discoloration of
the copper surface. Examples of hindered phenol compounds include,
but are not limited to, 2,6-di-t-butyl-4-methylphenol,
2,5-di-t-butyl-hydroquinone,
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
4,4'-methylene-bis(2,6-di-t-butylphenol),
4,4'-thiobis(3-methyl-6-t-butylphenol),
4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylene
glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate],
1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxphenyl)propionate],
N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamide),
2,2'-methylene-bis(4-methyl-6-t-butylphenol),
2,2'-methylene-bis(4-ethyl-6-t-butylphenol),
pentaerythryl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate,
1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene,
1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-
-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(-
1H,3H,5H)-trione,
1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(-
1H,3H,5H)-trione,
1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-
-2,4,6-(1H,3H,5H)-trione,
1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine--
2,4,6-(1H,3H,5H)-trione,
1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1-
H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,-
6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-
-2,4,6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4-
,6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-
-2,4,6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-
-2,4,6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3-
H,5H)-trione,
1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(-
1H,3H,5H)-trione, and
1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4-
,6-(1H,3H,5H)-trione. Among these,
1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(-
1H,3H,5H)-trione is particularly preferable.
[0429] The incorporated amount of the hindered phenol compound is
preferably 0.1 parts by weight to 20 parts by weight, and more
preferably 0.5 parts by weight to 10 parts by weight from the
viewpoint of photosensitivity, based on 100 parts by weight of the
photosensitive polyimide precursor (A). In the case the
incorporated amount of the hindered phenol compound based on 100
parts by weight of the photosensitive polyimide precursor (A) is
0.1 parts by weight or more, discoloration and corrosion of the
copper or copper alloy is prevented in the case of, for example,
having formed the photosensitive resin composition of the present
invention on copper or copper alloy, while in the case the
incorporated amount is 20 parts by weight or less, superior
photosensitivity of the photosensitive resin composition is
maintained.
[0430] A crosslinking agent may also be contained in the
photosensitive resin composition of the present invention. The
crosslinking agent can be a crosslinking agent capable of
crosslinking the photosensitive polyimide precursor (A) or forming
a crosslinked network by itself when heat-curing a relief pattern
formed using the photosensitive resin composition of the present
invention. The crosslinking agent is further able to enhance heat
resistance and chemical resistance of a cured film formed from the
photosensitive resin composition.
[0431] Examples of crosslinking agents include compounds containing
a methylol group and/or alkoxymethyl group in the form of Cymel
(Registered Trade Mark) 300, 301, 303, 370, 325, 327, 701, 266,
267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170 or 1174, UFR 65 or
300, and Mycoat 102 or 105 (all manufactured by Mitsui-Cytec),
Nikalac (Registered Trade Mark) MX-270, -280 or -290, Nikalac MS-11
and Nikalac MW-30, -100, -300, -390 or -750 (all manufactured by
Sanwa Chemical Co., Ltd.), DML-OCHP, DML-MBPC, DML-BPC, DML-PEP,
DML-34X, DML-PSBP, DML-PTBP, DML-PCHP, DML-POP, DML-PFP, DML-MBOC,
BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT,
TMOM-BP, TMOM-BPA or TML-BPAF-MF (all manufactured by Honshu
Chemical Industry Co., Ltd.), benzenedimethanol,
bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene,
bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone,
hydroxymethylphenyl hydroxymethyl benzoate,
bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl,
bis(methoxymethyl)benzene, bis(methoxymethyl)cresol,
bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl
ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl
methoxymethyl benzoate, bis(methoxymethyl)biphenyl and
dimethylbis(methoxymethyl)biphenyl.
[0432] In addition, other examples include oxirane compounds in the
form of phenol novolac epoxy resin, cresol novolac epoxy resin,
bisphenol epoxy resin, trisphenol epoxy resin, tetraphenol epoxy
resin, phenol-xylylene epoxy resin, naphthol-xylylene epoxy resin,
phenol-naphthol epoxy resin, phenol-dicyclopentadiene epoxy resin,
alicyclic epoxy resin, aliphatic epoxy resin, diethylene glycol
diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol
diglycidyl ether, trimethylolpropane polyglycidyl ether,
1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether, glycerol
triglycidyl ether, ortho-secondary-butylphenyl glycidyl ether,
1,6-bis(2,3-epoxypropoxy)naphthalene, diglycerol polyglycidyl
ether, polyethylene glycol glycidyl ether, YDB-340, YDB-412,
YDF-2001, YDF-2004 (trade names, all manufactured by Nippon Steel
Chemical Co., Ltd.), NC-3000-H, EPPN-501H, EOCN-1020, NC-7000L,
EPPN-201L, XD-1000, EOCN-4600 (trade names, all manufactured by
Nippon Kayaku Co, Ltd.), Epikote (Registered Trade Mark) 1001,
Epikote 1007, Epikote 1009, Epikote 5050, Epikote 5051, Epikote
1031S, Epikote 180S65, Epikote 157H70, YX-315-75 (trade names, all
manufactured by Japan Epoxy Resins Co., Ltd.), EHPE3150, Placcel
G402, PUE101, PUE105 (trade names, all manufactured by Daicel
Chemical Industries, Ltd.), Epiclon (Registered Trade Mark) 830,
850, 1050, N-680, N-690, N-695, N-770, HP-7200, HP-820,
EXA-4850-1000 (trade names, all manufactured by DIC Corp.), Denacol
(Registered Trade Mark) EX-201, EX-251, EX-203, EX-313, EX-314,
EX-321, EX-411, EX-511, EX-512, EX-612, EX-614, EX-614B, EX-711,
EX-731, EX-810, EX-911, EM-150 (trade names, all manufactured by
Nagase Chemtex Corp.), Epolight (Registered Trade Mark) 70P and
Epolight 100MF (trade names, both manufactured by Kyoeisha Chemical
Co., Ltd.).
[0433] In addition, other examples include isocyanate compounds in
the form of 4,4'-diphenylmethane diisocyanate, tolylene
diisocyanate, 1,3-phenylene-bismethylene diisocyanate,
cyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate,
hexamethylene diisocyanate, Takenate (Registered Trade Mark) 500,
600, Cosmonate (Registered Trade Mark) NBDI, ND (trade names, all
manufactured by Mitsui Chemicals, Inc.), Duranate (Registered Trade
Mark) 17B-602X, TPA-B80E, MF-B60X, MF-K60X and E402-B80T (trade
names, all manufactured by Asahi Kasei Chemicals Corp.).
[0434] In addition, although other examples include bismaleimide
compounds in the form of 4,4'-diphenylmethane bismaleimide,
phenylmethane maleimide, m-phenylene bismaleimide, bisphenol A
diphenyl ether bismaleimide,
3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide,
4-methyl-1,3-phenylene bismaleimide,
1,6'-bismaleimido-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether
bismaleimide, 4,4'-diphenylsulfide bismaleimide,
1,3-bis(3-maleimidophenoxy)benzene,
1,3-bis(4-maleimidophenoxy)benzene, BMI-1000, BMI-1100, BMI-2000,
BMI-2300, BMI-3000, BMI-4000, BMI-5100, BMI-7000, BMI-TMH, BMI-6000
and BMI-8000 (trade names, all manufactured by Daiwa Kasei Kogyo
Co., Ltd.), they are not limited thereto provided they are
compounds that demonstrate thermal crosslinking in the manner
described above.
[0435] The incorporated amount in the case of using a crosslinking
agent is preferably 0.5 parts by weight to 20 parts by weight and
more preferably 2 parts by weight to 10 parts by weight based on
100 parts by weight of the photosensitive polyimide precursor (A).
In the case the incorporated amount is 0.5 parts by weight or more,
favorable heat resistance and chemical resistance are demonstrated,
while in the case the incorporated amount is 20 parts by weight or
less, storage stability is superior.
[0436] <Method for Forming Cured Relief Pattern>
[0437] The present invention also provides a method for forming a
cured relief pattern.
[0438] The method for forming a cured relief pattern in the present
invention is characterized by including the following steps in the
order shown below:
[0439] (1) a coating step for forming a photosensitive resin layer
on a substrate by coating the previously described photosensitive
resin composition of the present invention on the substrate;
[0440] (2) an exposure step for exposing the photosensitive resin
layer to light;
[0441] (3) a development step for forming a relief pattern by
developing the photosensitive resin layer after exposing to light;
and,
[0442] (4) a heating step for forming a cured relief pattern by
heat-treating the relief pattern.
[0443] The following provides an explanation of a typical aspect of
each step.
[0444] (1) Coating Step
[0445] In the present step, a photosensitive resin layer is formed
by coating the photosensitive resin composition of the present
invention onto a substrate followed by drying as necessary.
[0446] Examples of substrates that can be used include metal
substrates composed of silicon, aluminum, copper or copper alloy,
resin substrates such as those composed of epoxy, polyimide or
polybenzoxazole, substrates having a metal circuit formed in the
aforementioned resin substrate, and substrates obtained by
laminating a plurality of metal layers or metal and resin
layers.
[0447] In the present invention, the effect of the present
invention of inhibiting the formation of voids at the interface
between a Cu layer and polyimide layer can be particularly
preferably obtained by using a substrate of which at least the
surface thereof is composed of Cu, the present invention can also
be applied to other substrates.
[0448] A method conventionally used to coat photosensitive resin
compositions can be used for the coating method, examples of which
include coating methods using a spin coater, bar coater, blade
coater, curtain coater or screen printer, and spraying methods
using a spray coater.
[0449] A photosensitive resin composition film can be dried as
necessary. A method such as air drying, or heat drying or vacuum
drying using an oven or hot plate, is used for the drying method.
Drying is preferably carried out under conditions such that
imidization of the photosensitive polyimide precursor (polyamic
acid ester) in the photosensitive resin composition does not occur.
More specifically, in the case of carrying out air drying or heat
drying, drying can be carried out under conditions consisting of 1
minute to 1 hour at 20.degree. C. to 140.degree. C. The
photosensitive resin layer can be formed on the substrate in this
manner.
[0450] (2) Exposure Step
[0451] In the present step, the photosensitive resin layer formed
in the manner described above is exposed to light. Examples of
exposure devices used include a contact aligner, mirror projector
and stepper. Exposure can be carried out by exposing either
directly or through a photomask having a pattern or reticle. The
light source used for exposure is, for example, an ultraviolet
light source.
[0452] Following exposure, post-exposure baking (PEB) and/or
pre-development baking may be carried out using an arbitrary
combination of temperature and time as necessary for the purpose of
improving photosensitivity and the like. Although the range of
baking conditions preferably consists of a temperature of
40.degree. C. to 120.degree. C. and time of 10 seconds to 240
seconds, the range is not limited thereto provided various
properties of the photosensitive resin composition of the present
invention are not impaired.
[0453] (3) Development Step
[0454] In the present step, unexposed portions of the
photosensitive resin layer are developed and removed following
exposure. A conventionally known photoresist development method can
be selected and used for the development method used to develop the
photosensitive resin layer after exposure (irradiation). Examples
thereof include the rotary spraying method, paddle method and
immersion method accompanying ultrasonic treatment. In addition,
post-development baking using an arbitrary combination of
temperature and time may be carried out as necessary after
development for the purpose of adjusting the form of the relief
pattern. The temperature of post-development baking can be, for
example, 80.degree. C. to 130.degree. C. and the duration can be,
for example 0.5 to 10 minutes.
[0455] A good solvent with respect to the photosensitive resin or a
combination of a good solvent and a poor solvent is preferable for
the developer used for development. Preferable examples of good
solvents include N-methyl-2-pyrrolidone,
N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetoamide, cyclopentanone,
cyclohexanone, .gamma.-butyrolactone and
.alpha.-acetyl-.gamma.-butyrolactone, while preferable examples of
poor solvents include toluene, xylene, methanol, ethanol, isopropyl
alcohol, ethyl lactate, propylene glycol methyl ether acetate and
water. In the case of using a mixture of good solvent and poor
solvent, the proportion of poor solvent to good solvent is
preferably adjusted according to the solubility of polymer in the
photosensitive resin composition. In addition, two or more types of
each solvent, such as a combination of several types of each
solvent, can also be used.
[0456] (4) Heating Step
[0457] In the present step, the relief pattern obtained by
developing in the manner previously described is converted from the
polyimide to a cured relief pattern by heating to evaporate the
photosensitive component together with imidizing the photosensitive
polyimide precursor (A).
[0458] Various methods can be selected for the heat curing method,
examples of which include heating with a hot plate, heating using
an oven, and heating using a programmable oven that allows the
setting of a temperature program. Heating can be carried out under
conditions consisting of, for example, 30 minutes to 5 hours at
200.degree. C. to 400.degree. C. Air may be used for the
atmospheric gas during heat curing, or an inert gas such as
nitrogen or argon can be used.
[0459] A cured relief pattern can be produced in the manner
described above.
[0460] <Semiconductor Device>
[0461] The present invention also provides a semiconductor device
that has a cured relief pattern obtained according to the method
for producing a cured relief pattern of the present invention
described above.
[0462] The aforementioned semiconductor device can be a
semiconductor device having a semiconductor element in the form of
a base material and a cured relief pattern formed according to the
aforementioned method for producing a cured relief pattern on the
aforementioned base material.
[0463] Namely, the semiconductor device of the present invention is
characterized by having a base material and a cured relief pattern
formed on the base material, and the aforementioned cured relief
pattern is characterized by containing a polyimide resin and a
compound represented by the aforementioned general formula (B1).
The aforementioned semiconductor device can be produced according
to a method that uses a semiconductor element for the base material
and contains the aforementioned method for producing a cured relief
pattern as a portion of the process thereof. The semiconductor
device of the present invention can be produced by combining with
known methods for producing semiconductor devices by forming the
cured relief pattern formed according to the aforementioned method
for producing a cured relief pattern as, for example, a surface
protective film, interlayer insulating film, rewiring insulating
film, flip-chip device protective film or protective film of a
semiconductor device having a bump structure.
[0464] In the case of applying the semiconductor device of the
present invention to a relief pattern composed of metal rewiring
layer composed of a Cu layer and a polyimide resin, the formation
of voids at the interface thereof is inhibited resulting in a high
level of adhesion and superior properties.
[0465] The photosensitive resin composition according to the third
aspect of the present invention is also useful in applications such
as the interlayer insulation of a multilayer circuit, cover coating
of a flexible copper-clad board, solder-resistive film or liquid
crystal alignment film in addition to applying to a semiconductor
device as described above.
Fourth Aspect
[0466] Elements are mounted on printed boards using various methods
corresponding to the objective. Conventional elements were
typically fabricated by a wire bonding method in which a connection
is made from an external terminal of the element (pad) to a lead
frame with a fine wire. However, with today's current higher
element speeds in which the operating frequency has reached the GHz
range, differences in the wiring lengths of each terminal during
mounting are having an effect on element operation. Consequently,
in the case of mounting elements for high-end applications, it has
become necessary to accurately control the lengths of mounting
wires, and it has become difficult to satisfy this requirement with
wire bonding.
[0467] Thus, flip-chip mounting has been proposed in which, after
having formed a rewiring layer on the surface of a semiconductor
chip and formed a bump (electrode) thereon, the chip is turned over
(flipped) followed by directly mounting on the printed board (see,
for example, Japanese Unexamined Patent Publication No.
2001-338947). As a result of being able to accurately control
wiring distance, this flip-chip mounting is being employed in
elements for high-end applications handling high-speed signals, and
because of its small mounting size, is also being employed in cell
phone applications, thereby resulting in a rapid increase in
demand. More recently, fan-out mounting has been proposed as an
advanced form of flip-chip mounting that consists of dicing
preprocessed wafers to produce individual chips in order to
increase the number of pins accessible from the semiconductor chip,
followed by embedding the diced chips in resin to produce a molded
resin substrate and then forming a rewiring layer on the substrate.
In the case using a material such as polyimide, polybenzoxazole or
phenol resin for this flip-chip mounting or fan-out mounting, the
process goes through a metal wiring layer formation step after
having formed a pattern in the resin layer. The metal wiring layer
is normally formed by roughening the surface of the resin layer by
subjecting to plasma etching, followed by forming a metal layer
serving as the plating seed layer by sputtering at a thickness of 1
.mu.m or less, and then forming the metal wiring layer by
electrolytic plating using this metal layer as an electrode.
Although Ti is typically used for the metal of the seed layer at
this time, Cu is used as the metal of the rewiring layer formed by
electrolytic plating.
[0468] Moreover, in the case of printed boards or build-up boards,
although continuity in the vertical direction was conventionally
achieved by laminating a substrate, laminated with metal foil or
metal, with a non-photosensitive insulating resin and forming holes
in the insulating resin layer with a drill or laser, more recently,
due to the increasingly fine pitch of the wiring, it has become
necessary to form smaller diameter holes, and a technique has been
adopted that consists of using a photosensitive resin composition
for the insulating resin on the substrate and forming the holes by
photolithography. In this case, after having formed a seed layer on
the resin by laminating or pressing Cu foil on the insulating
resin, or by electrolytic plating or sputtering, the conductive
layer is formed by electrolytic plating of Cu and the like (see,
for example, Japanese Patent No. 5219008 and Japanese Patent No.
4919501).
[0469] A metal rewiring layer formed from a photosensitive resin
composition and Cu in this manner is required to demonstrate a high
level of adhesion between the rewired metal layer and resin layer
following reliability testing. Examples of the reliability testing
carried out here include a high-temperature storage test consisting
of storing in air at a high temperature of 125.degree. C. or higher
for 100 hours or more, a high-temperature operation test consisting
of confirming operation after having stored in air at a high
temperature of about 125.degree. C. for 100 hours or more while
connecting the wires and applying a voltage, a heat cycle test
consisting of repeatedly subjecting to a low-temperature state of
about -65.degree. C. to -40.degree. C. in air and a
high-temperature state of about 125.degree. C. to 150.degree. C. in
cycles, a high-temperature, high-humidity storage test consisting
of storing at a temperature of 85.degree. C. or higher in a water
vapor atmosphere having humidity of 85% or higher, a
high-temperature, high-humidity bias test consisting of carrying
out the above test while connecting the wires and applying a
voltage, and a solder reflow test consisting of passing multiple
times through a solder reflow oven in air or nitrogen at
260.degree. C.
[0470] However, in the case of carrying out reliability testing in
the form of a high-temperature storage test, there was the problem
of voids forming at the interface contacted by the rewired Cu layer
and resin layer. The formation of voids at the interface between
the Cu layer and resin layer ends up causing a decrease in adhesion
between the two layers.
[0471] With the foregoing in view, an object of the fourth aspect
of the present invention is to provide a rewiring layer produced by
combining a specific Cu surface treatment method and a specific
photosensitive resin composition formed on silicon, glass, a dummy
substrate, or substrate in which diced silicon chips are arranged
and embedded in a molding resin, wherein there is no formation of
voids at the interface between a Cu layer and a resin layer
following a high-temperature storage test.
[0472] The inventors of the present invention found that, by
treating the surface of a Cu layer, formed on silicon, glass, a
dummy substrate, or a substrate in which diced silicon chips are
arranged and embedded in a molding resin, with a specific method
and combining with a specific photosensitive resin composition, a
wiring layer having superior high-temperature storage test
performance can be obtained, thereby leading to completion of the
present invention. Namely, the fourth aspect of the present
invention is as indicated below.
[0473] [1] A rewiring layer having a copper layer, formed on
silicon, glass, compound semiconductor, printed board, build-up
board, dummy substrate or substrate in which diced silicon chips
are arranged and embedded in a molding resin, and in which surface
irregularities having a maximum height of 0.1 .mu.m to 5 .mu.m are
formed on the surface thereof, and a cured relief pattern layer,
wherein the cured relief pattern is obtained by curing a
photosensitive resin composition.
[0474] [2] A method for producing the rewiring layer described in
[1], comprising:
[0475] (1) forming a photosensitive resin composition on a copper
layer by coating a photosensitive resin composition onto a copper
layer, formed on silicon, glass, compound semiconductor, printed
board, build-up board, dummy substrate or substrate in which diced
silicon chips are arranged and embedded in a molding resin, in
which surface irregularities having a maximum height of 0.1 .mu.m
to 5 .mu.m are formed on the surface thereof,
[0476] (2) exposing the photosensitive resin layer to light,
[0477] (3) forming a relief pattern by developing the
photosensitive resin layer after exposing to light, and
[0478] (4) forming a cured relief pattern by heat-treating the
relief pattern.
[0479] [3] The rewiring layer described in [1] or the method
described in [2], wherein the photosensitive resin composition
contains:
[0480] (A) 100 parts by weight of at least one type of resin
selected from the group consisting of polyamic acid, polyamic acid
ester, polyamic acid salt, polyhydroxyamide, polyaminoamide,
polyamide, polyamide-imide, polyimide, polybenzoxazole and novolac
resin, polyhydroxystyrene and phenol resin, and
[0481] (B) 1 part by weight to 50 parts by weight of a
photosensitizer based on 100 parts by weight of the resin.
[0482] [4] The rewiring layer described in [1] or [3] or the method
described in [2] or [3], wherein the resin (A) is at least one type
of resin selected from the group consisting of a polyimide
precursor containing the following general formula (40), a
polyamide containing the following general formula (43), a
polyoxazole precursor containing the following general formula
(44), a polymide containing the following general formula (45) and
novolac, polyhydroxystyrene resin and phenol resin containing the
following general formula (46):
##STR00098##
{wherein, X.sub.1c represents a tetravalent organic group, Y.sub.1c
represents a divalent organic group, n.sub.1c represents an integer
of 2 to 150 and R.sub.1c and R.sub.2c respectively and
independently represent a hydrogen atom, saturated aliphatic group
having 1 to 30 carbon atoms, aromatic group, monovalent organic
group represented by the following general formula (41):
##STR00099##
(wherein, R.sub.3c, R.sub.4c and R.sub.5c respectively and
independently represent a hydrogen atom or organic group having 1
to 3 carbon atoms, and m.sub.1c represents an integer of 2 to 10),
saturated aliphatic group having 1 to 4 carbon atoms, or a
monovalent ammonium ion represented by the following general
formula (42):
##STR00100##
(wherein, R.sub.6c, R.sub.7c and R.sub.8c respectively and
independently represent a hydrogen atom or organic group having 1
to 3 carbon atoms, and m.sub.2c represents an integer of 2 to
10);
##STR00101##
{wherein, X.sub.2c represents a trivalent organic group having 6 to
15 carbon atoms, Y.sub.2c represents a divalent organic group
having 6 to 35 carbon atoms and may have the same structure or a
plurality of structures, R.sub.9c represents an organic group
having 3 to 20 carbon atoms and having at least one
radical-polymerizable unsaturated bond, and n.sub.2c represents an
integer of 1 to 1000};
##STR00102##
{wherein, Y.sub.3c represents a tetravalent organic group having a
carbon atom, Y.sub.4c, X.sub.3c and X.sub.4c respectively and
independently represent a divalent organic group having two or more
carbon atoms, n.sub.3c represents an integer of 1 to 1000, n.sub.4c
represents an integer of 0 to 500, n.sub.3c/(n.sub.3c+n.sub.4c) is
greater than 0.5, and there are no restrictions on the arrangement
order of the n.sub.3c number of dihydroxydiamide units containing
X.sub.3c and Y.sub.3c or the n.sub.4c number of diamide units
containing X.sub.4c and Y.sub.4c};
##STR00103##
{wherein, X.sub.5c represents a tetra to tetradecavalent organic
group, Y.sub.5c represents a divalent to dodecavalent organic
group, R.sub.10c and R.sub.11c respectively and independently
represent an organic group having at least one of a phenolic
hydroxyl group, sulfonate group and thiol group, n.sub.5c
represents an integer of 3 to 200, and m.sub.3c and m.sub.4c
represent integers of 0 to 10};
##STR00104##
{wherein, a represents an integer of 1 to 3, b represents an
integer of 0 to 3, 1.ltoreq.(a+b).ltoreq.4, R.sub.12c represents a
monovalent substituent selected from the group consisting of a
monovalent organic group having 1 to 20 carbon atoms, halogen atom,
nitro group and cyano group, a plurality of R.sub.12c may be the
same or different in the case b is 2 or 3, and X.sub.C represents a
divalent organic group selected from the group consisting of a
divalent aliphatic group having 2 to 10 carbon atoms that may or
may not have an unsaturated bond, divalent alicyclic group having 3
to 20 carbon atoms, divalent alkylene oxide group represented by
the following general formula (47):
[Chemical Formula 120]
--C.sub.pH.sub.2pO-- (47)
(wherein, p represents an integer of 1 to 10), and divalent organic
group having an aromatic ring having 6 to 12 carbon atoms}.
[0483] [5] The rewiring layer or method described in [4] containing
a phenol resin having a repeating unit represented by general
formula (46), wherein X.sub.C in general formula (46) represents a
divalent organic group selected from the group consisting of a
divalent group represented by the following general formula
(48):
##STR00105##
{wherein, R.sub.13c, R.sub.14c, R.sub.15c and R.sub.16c
respectively and independently represent a hydrogen atom,
monovalent aliphatic group having 1 to 10 carbon atoms, or
monovalent aliphatic group having 1 to 10 carbon atoms in which all
or a portion of the hydrogen atoms are substituted with fluorine
atoms, n.sub.6c represents an integer of 0 to 4, R.sub.17c in the
case n.sub.6c is an integer of 1 to 4 represents a halogen atom,
hydroxyl group or monovalent organic group having 1 to 12 carbon
atoms, at least one of R.sub.6c is a hydroxyl group, and a
plurality of R.sub.17c may be mutually the same or different in the
case n.sub.5c is an integer of 2 to 4}, and a divalent organic
group selected from the group consisting of a divalent alkylene
oxide group represented by the following general formula (49):
##STR00106##
{wherein, R.sub.18c, R.sub.19c, R.sub.20c and R.sub.21c
respectively and independently represent a hydrogen atom,
monovalent aliphatic group having 1 to 10 carbon atoms, or
monovalent aliphatic group having 1 to 10 carbon atoms in which all
or a portion of the hydrogen atoms are substituted with fluorine
atoms, and W represents a single bond, or a divalent organic group
selected from the group consisting of an aliphatic group having 1
to 10 carbon atoms optionally substituted with fluorine atoms,
alicyclic group having 3 to 20 carbon atoms optionally substituted
with fluorine atoms, divalent alkylene oxide group represented by
the following general formula (47):
[Chemical Formula 123]
--C.sub.pH.sub.2pO-- (47)
(wherein, p represents an integer of 1 to 10), and divalent group
represented by the following general formula (50)}.
##STR00107##
[0484] [6] A rewiring layer having a copper layer, formed on
silicon, glass, compound semiconductor, printed board, build-up
board, dummy substrate or substrate in which diced silicon chips
are arranged and embedded in a molding resin, and having an alloy
layer containing copper and tin on the surface thereof as well as a
layer of silane coupling agent thereon, and a cured relief pattern
layer, wherein, the cured relief pattern is obtained by curing a
photosensitive resin composition.
[0485] [7] A method for producing the rewiring layer described in
[6], comprising:
[0486] (1) forming a photosensitive resin composition on a copper
layer by coating a photosensitive resin composition onto a copper
layer, formed on silicon, glass, compound semiconductor, printed
board, build-up board, dummy substrate or substrate in which diced
silicon chips are arranged and embedded in a molding resin, and
having an alloy layer containing copper and tin on the surface
thereof as well as a layer of silane coupling agent thereon,
[0487] (2) exposing the photosensitive resin layer to light,
[0488] (3) forming a relief pattern by developing the
photosensitive resin layer after exposing to light, and
[0489] (4) forming a cured relief pattern by heat-treating the
relief pattern.
[0490] [8] The rewiring layer described in [6] or the method
described in [7], wherein the photosensitive resin composition
contains:
[0491] (A) 100 parts by weight of at least one type of resin
selected from the group consisting of polyamic acid, polyamic acid
ester, polyamic acid salt, polyhydroxyamide, polyaminoamide,
polyamide, polyamide-imide, polyimide, polybenzoxazole and novolac
resin, polyhydroxystyrene and phenol resin, and
[0492] (B) 1 part by weight to 50 parts by weight of a
photosensitizer based on 100 parts by weight of the resin.
[0493] [9] The rewiring layer described in [6] or [8] or the method
described in [7] or [8], wherein the resin (A) is at least one type
of resin selected from the group consisting of a polyimide
precursor containing the following general formula (40), a
polyamide containing the following general formula (43), a
polyoxazole precursor containing the following general formula
(44), a polymide containing the following general formula (45) and
novolac, polyhydroxystyrene resin and phenol resin containing the
following general formula (46):
##STR00108##
{wherein, X.sub.1c represents a tetravalent organic group, Y.sub.1c
represents a divalent organic group, n.sub.1c represents an integer
of 2 to 150, and R.sub.1c and R.sub.2c respectively and
independently represent a hydrogen atom, saturated aliphatic group
having 1 to 30 carbon atoms, aromatic group, monovalent organic
group represented by the following general formula (41):
##STR00109##
(wherein, R.sub.3c, R.sub.4c and R.sub.5c respectively and
independently represent a hydrogen atom or organic group having 1
to 3 carbon atoms, and m.sub.1c represents an integer of 2 to 10),
saturated aliphatic group having 1 to 4 carbon atoms, or a
monovalent ammonium ion represented by the following general
formula (42):
##STR00110##
(wherein, R.sub.5c, R.sub.7c and R.sub.8c respectively and
independently represent a hydrogen atom or organic group having 1
to 3 carbon atoms, and m.sub.2c represents an integer of 2 to
10);
##STR00111##
{wherein, X.sub.2c represents a trivalent organic group having 6 to
15 carbon atoms, Y.sub.2c represents a divalent organic group
having 6 to 35 carbon atoms and may have the same structure or a
plurality of structures, R.sub.9c represents an organic group
having 3 to 20 carbon atoms and having at least one
radical-polymerizable unsaturated bond, and n.sub.2c represents an
integer of 1 to 1000};
##STR00112##
{wherein, Y.sub.3c represents a tetravalent organic group having a
carbon atom, Y.sub.4c, X.sub.3c and X.sub.4c respectively and
independently represent a divalent organic group having two or more
carbon atoms, n.sub.3c represents an integer of 1 to 1000, n.sub.4c
represents an integer of 0 to 500, n.sub.3c/(n.sub.3c+n.sub.4c) is
greater than 0.5, and there are no restrictions on the arrangement
order of the n.sub.3c number of dihydroxydiamide units containing
X.sub.3c and Y.sub.3c or the n.sub.4c number of diamide units
containing X.sub.4c and Y.sub.4c};
##STR00113##
{wherein, X.sub.5c represents a tetra to tetradecavalent organic
group, Y.sub.5c represents a divalent to dodecavalent organic
group, R.sub.10c and R.sub.11c respectively and independently
represent an organic group having at least one of a phenolic
hydroxyl group, sulfonate group and thiol group, n.sub.5c
represents an integer of 3 to 200, and m.sub.3c and m.sub.4c
represent integers of 0 to 10};
##STR00114##
{wherein, a represents an integer of 1 to 3, b represents an
integer of 0 to 3, 1.ltoreq.(a+b).ltoreq.4, R.sub.12c represents a
monovalent substituent selected from the group consisting of a
monovalent organic group having 1 to 20 carbon atoms, halogen atom,
nitro group and cyano group, a plurality of R.sub.12c may be the
same or different in the case b is 2 or 3, and X.sub.C represents a
divalent organic group selected from the group consisting of a
divalent aliphatic group having 2 to 10 carbon atoms that may or
may not have an unsaturated bond, divalent alicyclic group having 3
to 20 carbon atoms, divalent alkylene oxide group represented by
the following general formula (47):
[Chemical Formula 132]
--C.sub.pH.sub.2pO-- (47)
(wherein, p represents an integer of 1 to 10), and divalent organic
group having an aromatic ring having 6 to 12 carbon atoms}.
[0494] [10] The rewiring layer or method described in [9] wherein
the photosensitive resin composition contains a phenol resin having
a repeating unit represented by general formula (46), and X.sub.C
in general formula (46) represents a divalent organic group
selected from the group consisting of a divalent group represented
by the following general formula (48):
##STR00115##
{wherein, R.sub.13c, R.sub.14c, R.sub.15c and R.sub.16c
respectively and independently represent a hydrogen atom,
monovalent aliphatic group having 1 to 10 carbon atoms, or
monovalent aliphatic group having 1 to 10 carbon atoms in which all
or a portion of the hydrogen atoms are substituted with fluorine
atoms, n.sub.5c represents an integer of 0 to 4, R.sub.17c in the
case n.sub.5c is an integer of 1 to 4 represents a halogen atom,
hydroxyl group or monovalent organic group having 1 to 12 carbon
atoms, at least one of R.sub.6c is a hydroxyl group, and R.sub.17c
may be mutually the same or different in the case n.sub.6c is an
integer of 2 to 4}, and a divalent organic group represented by the
following general formula (49):
##STR00116##
{wherein, R.sub.18c, R.sub.19c, R.sub.20c and R.sub.21c
respectively and independently represent a hydrogen atom,
monovalent aliphatic group having 1 to 10 carbon atoms, or
monovalent aliphatic group having 1 to 10 carbon atoms in which all
or a portion of the hydrogen atoms are substituted with fluorine
atoms, and W represents a single bond, or a divalent organic group
selected from the group consisting of an aliphatic group having 1
to 10 carbon atoms optionally substituted with fluorine atoms,
alicyclic group having 3 to 20 carbon atoms optionally substituted
with fluorine atoms, divalent alkylene oxide group represented by
the following general formula (47):
[Chemical Formula 135]
--C.sub.pH.sub.2pO-- (47)
(wherein, p represents an integer of 1 to 10), and divalent group
represented by the following general formula (50)
##STR00117##
[0495] According to the fourth aspect of the present invention, a
rewiring layer having superior high-temperature storage test
performance can be provided by treating the surface of a Cu layer,
formed on a silicon substrate, glass substrate, compound
semiconductor substrate, printed board, build-up board, dummy
substrate or substrate in which diced silicon chips are arranged
and embedded in a molding resin, according to a specific method and
combining with a specific photosensitive resin composition.
[0496] The following provides a detailed explanation of the fourth
aspect of the present invention. Furthermore, throughout the
present description, structures represented by the same reference
symbols in general formulas may be mutually the same or different
in the case a plurality thereof is present in a molecule.
[0497] <Substrate>
[0498] Examples of the substrate used to form the rewiring layer of
the present invention include any of silicon substrates, glass
substrates, compound semiconductor substrates, printed boards,
build-up boards, dummy substrates or substrates in which diced
silicon chips are arranged and embedded in a molding resin. The
substrate may be round or rectangular.
[0499] A silicon substrate may be a substrate in which a
semiconductor and fine wires are formed internally or a substrate
in which there are no components formed internally. In addition,
electrodes or surface irregularities formed from Al and the like
may be formed on the surface thereof, or a passivation film
composed of SiO.sub.2 or SiN may be formed on the substrate or
through holes passing through the substrate may be formed
therein.
[0500] There are no limitations on the material of the glass
substrate provided it is a material made of glass such as
non-alkali glass or silica glass. In addition, surface
irregularities may be formed on the top and a rewiring layer may be
formed on the bottom, or through holes may be formed that pass
through the substrate.
[0501] Examples of compound semiconductor substrates include
substrates having a compound semiconductor such as SiC, GaAs or
GaP. In this case as well, the substrate may be a substrate in
which a semiconductor and fine wires are formed internally or a
substrate in which there are no components formed internally. In
addition, electrodes or surface irregularities formed from Al and
the like may be formed on the surface thereof, or a passivation
film composed of SiO.sub.2 or SiN may be formed on the substrate or
through holes passing through the substrate may be formed
therein.
[0502] The printed board may be an ordinary wiring board obtained
by laminating an insulating resin layer with a core material, such
as a single-sided board, double-sided board or laminated board, and
through holes may be formed that pass through the wiring board or
blind via holes may be formed between wiring.
[0503] A build-up board is a type of printed board, and refers to
that obtained not by a single lamination, but rather by
sequentially laminating an insulating layer or Cu-adhered
insulating layer onto a core material.
[0504] A dummy substrate is the generic term for substrates that do
not remain on the finished product as a result of pulling apart the
substrate and wiring layer after having formed a wiring layer
thereon. The material may be any of resin, silicon or glass, and
the method used to finally pull part the substrate and wiring layer
may be any arbitrary method, such as a chemical treatment method in
which adhered portions are dissolved with a solvent, a heat
treatment method in which adhered portions are separated by
heating, and an optical treatment method in which adhered portions
are separated by irradiating with laser light.
[0505] Substrates in which diced silicon chips are arranged and
embedded in a sealing resin refer to substrates obtained by
initially incorporating a semiconductor or rewiring layer in a
silicon wafer followed by dicing to put into the form of ordinary
silicon chips, and then arranging the chips on a different
substrate and molding from above with a sealing resin and the
like.
[0506] <Formation of Copper Layer>
[0507] In the present invention, the copper layer is formed by
forming a seed layer by ordinary sputtering followed by forming the
copper layer by electrolytic plating. Ordinary Ti/Cu is used for
the seed layer, and the thickness thereof is normally 1 .mu.m or
less. In the case of sputtering on resin, the resin surface is
preferably roughened by plasma etching in advance from the
viewpoint of adhesion with the resin. In addition, electroless
plating can also be used to form the seed layer instead of
sputtering.
[0508] In order to form copper wiring, after having formed a seed
layer followed by forming a resist layer on the surface thereof and
patterning the resist to a desired pattern by exposure and
development, copper is deposited on only the patterned portion by
electrolytic plating. Subsequently, the resist is stripped using a
stripper followed by removing the seed layer by flash etching.
[0509] In addition, an example of method frequently used with
printed boards consists of forming a Cu layer on resin by
laminating a resin layer and Cu foil.
[0510] <Copper Surface Treatment>
[0511] Examples of methods used to treat the surface of copper in
the present invention include a method consisting of microetching
the surface of the copper to form surface irregularities having a
maximum height of 0.1 .mu.m to 5 .mu.m, and a method consisting of
forming an alloy layer containing tin on the copper surface by
carrying out electroless tin plating on the copper surface followed
by further reacting with a silane coupling agent.
[0512] An explanation is first provided of microetching. Copper can
be etched by, for example, an aqueous cupric chloride solution
under acidic conditions. At this time, due to the additional
presence of a specific compound such as a compound having an amino
group, instead of uniformly dissolving the copper surface, portions
that are easily dissolved and portions that are difficult to
dissolve are formed on the copper surface, thereby enabling the
formation of surface irregularities having a maximum height of 0.1
.mu.m to 5 .mu.m (see, for example, Patent Document 2). Here,
maximum height refers to the length from the apex to the trough of
the surface irregularities in the case of viewing a profile of the
surface irregularities on the surface by using as a reference the
case in which the copper surface has been etched uniformly. From
the viewpoint of adhesion between the copper and resin, the maximum
height is preferably 0.1 .mu.m or more and more preferably 0.2
.mu.m or more, and from the viewpoint of insulating reliability,
the maximum height is preferably 5 .mu.m or less and more
preferably 2 .mu.m or less. In addition, the surface of the copper
having surface irregularities formed therein may be further treated
with a rust inhibitor after having carried out microetching.
[0513] Next, an explanation is provided of the method consisting of
treating the copper surface with a silane coupling agent. Since
silane coupling agents have difficulty in reacting with hydroxyl
groups of the copper surface, it is effective to deposit tin having
greater reactivity with the silane coupling agent than with copper
on the surface of the copper by carrying out electroless tin
plating on the surface thereof followed by treating with the silane
coupling agent (see, for example, Patent Document 3). At this time,
the alloy layer on the coper surface may contain tin as well as
nickel or other arbitrary metals.
[0514] Suitable examples of silane coupling agents able to be used
in the present invention include those having an epoxy group, amino
group, acryloxy group, methacryloxy group or vinyl group. An
example of a method used to treat with a silane coupling agent
consists of contacting a 1% aqueous solution of the silane coupling
agent with a metal surface for 30 minutes.
[0515] In this manner, migration of copper following a
high-temperature storage test can be inhibited by changing the
state of interaction between the copper and resin from the case of
being untreated by forming minute surface irregularities in the
copper surface or forming a layer of a silane coupling agent
through an alloy layer with tin.
[0516] Next, an explanation is provided of the photosensitive resin
composition contained in the insulating layer present in the
rewiring layer.
[0517] <Photosensitive Resin Composition>
[0518] The present invention has as essential components
thereof:
[0519] (A) 100 parts by weight of at least one type of resin
selected from the group consisting of polyamic acid, polyamic acid
ester, polyamic acid salt, polyhydroxyamide, polyaminoamide,
polyamide, polyamide-imide, polyimide, polybenzoxazole and novolac
resin, polyhydroxystyrene and phenol resin, and
[0520] (B) 1 part by weight to 50 parts by weight of a
photosensitizer based on 100 parts by weight of the resin (A).
[0521] Resin (A)
[0522] The following provides an explanation of the resin (A) used
in the present invention. The resin (A) of the present invention
has for the main component thereof at least one type of resin
selected from the group consisting of polyamic acid, polyamic acid
ester, polyamic acid salt, polyhydroxyamide, polyaminoamide,
polyamide, polyamide-imide, polyimide, polybenzoxazole and novolac
resin, polyhydroxystyrene and phenol resin. Here, the main
component refers to containing these resins at 60% by weight or
more, and preferably at 80% by weight or more, based on the total
amount of resin. In addition, other resins may be contained as
necessary.
[0523] The weight average molecular weight of these resins as
determined by gel permeation chromatography based on standard
polystyrene conversion is preferably 200 or more and more
preferably 5,000 or more from the viewpoints of heat resistance and
mechanical properties following heat treatment. The upper limit is
preferably 500,000 or less, and the case of using in the form of a
photosensitive resin composition, the upper limit is more
preferably 20,000 or less from the viewpoint of solubility with
respect to the developer.
[0524] In the present invention, the resin (A) is a photosensitive
resin in order to form a relief pattern. The photosensitive resin
is a photosensitive resin composition used together with the
photosensitizer (B) to be subsequently described that causes
development by dissolving or not dissolving in the subsequent
development step.
[0525] Examples of photosensitive resins include polyamic acid,
polyamic acid ester, polyamic acid salts, polyhydroxyamide,
polyaminoamide, polyamide, polyamide-imide, polyimide,
polybenzoxazole and novolac resin, polyhydroxystyrene and phenol
resin, and among these, polyamic acid ester, polyamic acid salt,
polyamide, polyhydroxyamide, polyimide and phenol resin are used
preferably due to the superior heat resistance and mechanical
properties of the resin following heat treatment. In addition,
these photosensitive resins can be selected corresponding to the
desired application, such as by preparing a negative-type or
positive-type photosensitive resin composition with the
photosensitizer (B) to be subsequently described.
[0526] [Polyamic Acid, Polyamic Acid Ester and Polyamic Acid Salt
(A)]
[0527] One example of the most preferable resin (A) from the
viewpoints of heat resistance and photosensitivity in the
photosensitive resin composition of the present invention is a
polyamic acid, polyamic acid ester or polyamic acid salt containing
a structure represented by the general formula (40):
##STR00118##
{wherein, X.sub.1c represents a tetravalent organic group, Y.sub.1c
represents a divalent organic group, n.sub.1c represents an integer
of 2 to 150, and R.sub.1c and R.sub.2c respectively and
independently represent a hydrogen atom, saturated aliphatic group
having 1 to 30 carbon atoms, monovalent organic group represented
by the following general formula (41):
##STR00119##
(wherein, R.sub.1c, R.sub.4c and R.sub.5c respectively and
independently represent a hydrogen atom or organic group having 1
to 3 carbon atoms, and m.sub.1c represents an integer of 2 to 10),
saturated aliphatic group having 1 to 4 carbon atoms, or a
monovalent ammonium ion represented by the following general
formula (42):
##STR00120##
(wherein, R.sub.6c, R.sub.7c and R.sub.8c respectively and
independently represent a hydrogen atom or organic group having 1
to 3 carbon atoms, and m.sub.2c represents an integer of 2 to
10)}.
[0528] Since polyamic acids, polyamic acid esters and polyamic acid
salts are converted to polyimide by subjecting to cyclization
treatment by heating (at, for example, 200.degree. C. or higher),
they are treated as polyimide precursors. These polyimide
precursors are suitable for use in negative-type photosensitive
resin compositions.
[0529] In the aforementioned general formula (40), the tetravalent
organic group represented by X.sub.1c is preferably an organic
group having 6 to 40 carbon atoms, and more preferably an aromatic
group or alicyclic group having a --COOR.sub.1 group and a
--COOR.sub.2 group at mutually ortho positions with a --CONH--
group from the viewpoint of realizing both heat resistance and
photosensitivity. Examples of the tetravalent organic group
represented by X.sub.1c preferably include, but are not limited to,
organic groups having 6 to 40 carbon atoms containing an aromatic
ring, and more preferably structures represented by the following
formula (90):
##STR00121## ##STR00122##
{wherein R.sub.25b represents a hydrogen atom, fluorine atom or
monovalent group selected from hydrocarbon groups having 1 to 10
carbon atoms and fluorine-containing hydrocarbon groups having 1 to
10 carbon atoms, 1 represents an integer of 0 to 2, m represents an
integer of 0 to 3 and n represents an integer of 0 to 4}. In
addition, the structure of X.sub.1c may be one type or a
combination of two or more types. Group X.sub.1c having a structure
represented by the aforementioned formulas is particularly
preferable from the viewpoint of realizing both heat resistance and
photosensitivity.
[0530] From the viewpoint of realizing both heat resistance and
photosensitivity, examples of the divalent organic group
represented by Y.sub.1c in the aforementioned general formula (1)
preferably include, but are not limited to, aromatic groups having
6 to 40 carbon atoms such as the structures represented by the
following formula (91):
##STR00123## ##STR00124##
{wherein, R.sub.25b represents a hydrogen atom, fluorine atom or
monovalent group selected from hydrocarbon groups having 1 to 10
carbon atoms and fluorine-containing hydrocarbon groups having 1 to
10 carbon atoms, and n represents an integer of 0 to 4}. In
addition, the structure of Y.sub.1c may be one type or a
combination of two or more types. Group Y.sub.1c having a structure
represented by the aforementioned formula (91) is particularly
preferable from the viewpoint of realizing both heat resistance and
photosensitivity.
[0531] Group R.sub.3c in the aforementioned general formula (41) is
preferably a hydrogen atom or methyl group, and R.sub.4c and
R.sub.5c are preferably hydrogen atoms from the viewpoint of
photosensitivity. In addition, m.sub.1c is an integer of 2 to 10,
and preferably an integer of 2 to 4, from the viewpoint of
photosensitivity.
[0532] In the case of using a polyimide precursor for the resin
(A), examples of methods used to impart photosensitivity to the
photosensitive resin composition include ester bonding and ionic
bonding. The former is a method consisting of introducing a
photopolymerizable group, or in other words, a compound having an
olefinic double bond, into a side chain of a polyimide precursor by
ester bonding, while the latter is a method consisting of imparting
a photopolymerizable group by bonding an amino group of
(meth)acrylic compound having an amino group with a carboxyl group
of a polyimide precursor through an ionic bond.
[0533] The aforementioned ester-bonded polyimide precursor is
obtained by first preparing a partially esterified tetracarboxylic
acid (to also be referred to as an acid/ester form) by reacting a
tetracarboxylic dianhydride containing the aforementioned
tetravalent organic group X.sub.1c with an alcohol having
photopolymerizable unsaturated double bond, and optionally, a
saturated aliphatic alcohol having 1 to 4 carbon atoms, followed by
subjecting this to amide polycondensation with a diamine containing
the aforementioned divalent organic group Y.sub.1.
[0534] (Preparation of Acid/Ester Form)
[0535] In the present invention, examples of the tetracarboxylic
dianhydride containing the tetravalent organic group X.sub.1c
preferably used to prepare the ester-bonded polyimide precursor
include, but are not limited to, tetracarboxylic dianhydrides
represented by the aforementioned general formula (90) such as
pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic
dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride,
biphenyl-3,3'4,4'-tetracarboxylic dianhydride,
diphenylphosphone-3,3',4,4'-tetracarboxylic dianhydride,
diphenylmethane-3,3'4,4'-tetracarboxylic dianhydride,
2,2-bis(3,4-phthalic anhydride)propane or 2,2-bis(3,4-phthalic
anhydride)-1,1,1,3,3,3-hexafluoropropane, while preferable examples
include, but are not limited to, pyromellitic anhydride,
diphenylether-3,3',4,4'-tetracarboxylic dianhydride,
benzophenone-3,3',4,4'-tetracarboxylic dianhydride and
biphenyl-3,3'4,4'-tetracarboxylic dianhydride. In addition, these
may be used alone or two or more types may be used as a
mixture.
[0536] In the present invention, examples of alcohols having a
photopolymerizable unsaturated double bond preferably used to
prepare the ester-bonded polyimide precursor include
2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol,
2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl
vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate,
2-hydroxy-3-butyoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl
acrylate, 2-hydroxy-3-butoxypropyl acrylate,
2-hydroxy-3-t-butoxypropyl acrylate,
2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl
alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl
alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone,
2-hydroxy-3-methoxyopropyl methacrylate, 2-hydroxy-3-butoxypropyl
methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate,
2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl
methacrylate and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.
[0537] Saturated aliphatic alcohols having 1 to 4 carbon atoms,
such as methanol, ethanol, n-propanol, isopropanol, n-butanol or
tert-butanol, can be partially mixed and used for the
aforementioned alcohols.
[0538] A desired acid/ester form can be obtained by carrying out an
acid anhydride esterification reaction by dissolving and mixing the
aforementioned preferable tetracarboxylic dianhydride of the
present invention with an aforementioned alcohol in the presence of
a base catalyst such as pyridine and in a solvent to be
subsequently described followed by stirring for 4 to 10 hours at a
temperature of 20.degree. C. to 50.degree. C.
[0539] [Preparation of Polyimide Precursor]
[0540] The target polyimide precursor can be obtained by adding a
suitable dehydration condensation agent, such as
dicyclocarbodiimide,
1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline,
1,1-carbonyldioxy-di-1,2,3-benzotriazole or N,N'-disuccinimidyl
carbonate, to the aforementioned acid/ester form (typically in the
form of a solution dissolved in the a reaction solvent to be
subsequently described) while cooling with ice and mixing therewith
to convert the acid/ester form to a polyacid anhydride, and
dropping in a solution or dispersion of a diamine containing the
divalent organic group Y.sub.1 preferably used in the present
invention dissolved or dispersed in a different solvent followed by
amide polycondensation. Alternatively, the target polyimide
precursor can be obtained by converting the acid moiety of the
aforementioned acid/ester form to an acid chloride using thionyl
chloride and the like, followed by reacting with a diamine compound
in the presence of a base such as pyridine.
[0541] Examples of diamines containing the divalent organic group
Y.sub.1c preferably used in the present invention include diamines
having a structure represented by the aforementioned general
formula (91), and examples of specific compounds include, but are
not limited to, p-phenylenediamine, m-phenylenediamine,
4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether,
3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide,
3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide,
4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone,
3,3'-diaminodiphenylsulfone, 4,4'-diaminobiphenyl,
3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl,
4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone,
3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane,
3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane,
1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene,
[0542] 1,3-bis(3-aminophenoxy)benzene,
bis[4-(4-aminophenoxy)phenyl]sulfone,
bis[4-(3-aminophenoxy)phenyl]sulfone,
4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl,
bis[4-(4-aminophenoxy)phenyl] ether, bis[4-(3-aminophenoxy)phenyl]
ether, 1,4-bis(4-aminophenyl)benzene,
1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene,
2,2-bis(aminophenyl)propane,
2,2-bis(4-aminophenyl)hexafluoropropane,
2,2-bis[4-(4-aminophenoxy)phenyl]propane,
2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane,
1,4-bis(3-aminopropyldimethylsilyl)benzene, o-toluidine sulfone and
9,9-bis(4-aminophenyl)fluorene, those in which a portion of the
hydrogen atoms on the benzene ring thereof is substituted with a
substituent, such as a methyl group, ethyl group, hydroxymethyl
group, hydroxyethyl group or halogen atom, such as
3,3'-dimethyl-4,4'-diaminobiphenyl,
2,2'-dimethyl-4,4'-diaminobiphenyl,
3,3'-dimethyl-4,4'-diaminodiphenylmethane,
2,2'-dimethyl-4,4'-diaminodiphenylmethane,
3,3'-dimethoxy-4,4'-diaminobiphenyl,
3,3'-dichloro-4,4'-diaminobiphenyl, 2,2'-dimethylbenzidine,
2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl,
2,2'-bis(fluoro)-4,4'-diaminobiphenyl or
4,4'-diaminooctafluorobiphenyl, and preferably p-phenylenediamine,
m-phenylenediamine, 4,4'-diaminodiphenyl ether,
2,2'-dimethylbenzidine,
2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl,
2,2'-bis(fluoro)-4,4'-diaminobiphenyl or
4,4'-diaminooctafluorobiphenyl, and mixtures thereof.
[0543] Diaminosiloxanes such as
1,3-bis(3-aminopropyl)tetramethyldisiloxane or
1,3-bis(3-aminopropyl)tetraphenyldisiloxane can be copolymerized
when preparing the polyimide precursor for the purpose of improving
adhesion between various types of substrates and a resin layer
formed on the substrate by coating the substrate with the
photosensitive resin composition of the present invention.
[0544] Following completion of the amide polycondensation reaction,
after filtering out absorption byproducts of the dehydration
condensation agent also present in the reaction solution as
necessary, a suitable poor solvent such as water, an aliphatic
lower alcohol or a mixture thereof is added to the resulting
polymer component to precipitate the polymer component followed by
purifying the polymer by repeating re-dissolution and
re-precipitation procedures as necessary and vacuum drying to
isolate the target polyimide precursor. In order to improve the
degree of purification, a solution of this polymer may be passed
through a column packed with an anion exchange resin and/or cation
exchange resin swollen with a suitable organic solvent to remove
any ionic impurities.
[0545] On the other hand, the aforementioned ionic-bonded polyimide
precursor is typically obtained by reacting a diamine with a
tetracarboxylic dianhydride. In this case, at least one of R.sub.1c
and R.sub.2c in the aforementioned general formula (40) is a
hydroxyl group.
[0546] An anhydride of a tetracarboxylic acid containing a
structure represented by the aforementioned formula (90) is
preferable for the tetracarboxylic dianhydride, and a diamine
containing a structure represented by the aforementioned formula
(91) is preferable for the diamine. A photopolymerizable group is
imparted by ionic bonding between a carboxyl group and an amino
group by adding a (meth)acrylic compound having an amino group to
be subsequently described to the resulting polyimide precursor.
[0547] A dialkylaminoalkyl acrylate or methacrylate, such as
dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate,
diethylaminoethyl acrylate, diethylaminoethyl methacrylate,
dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate,
diethylaminopropyl acrylate, diethylaminopropyl methacrylate,
dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate,
diethylaminobutyl acrylate or diethylaminobutyl methacrylate, is
preferable for the (meth)acrylic compound having an amino group,
and among these, a dialkylaminoalkyl acrylate or methacrylate in
which the alkyl group on the amino group has 1 to 10 carbon atoms
and the alkyl chain has 1 to 10 carbon atoms is preferable from the
viewpoint of photosensitivity.
[0548] The incorporated amount of these (meth)acrylic compounds
having an amino group based on 100 parts by weight of the resin (A)
is 1 part by weight to 20 parts by weight and preferably 2 parts by
weight to 15 parts by weight form the viewpoint of
photosensitivity. The incorporation of 1 part by weight or more of
the (meth)acrylic compound having an amino group as the
photosensitizer (B) based on 100 parts by weight of the resin (A)
results in superior photosensitivity, while the incorporation of 20
parts by weight or less results in superior thick film
curability.
[0549] The molecular weight of the aforementioned ester-bonded and
ionic-bonded polyimide precursors in the case of measuring by gel
permeation chromatography based on standard polystyrene conversion
is preferably 8,000 to 150,000 and more preferably 9,000 to 50,000.
Mechanical properties are favorable in the case of a weight average
molecular weight of 8,000 or more, while dispersibility in
developer and resolution of the relief pattern are favorable in the
case of a weight average molecular weight of 150,000 or less. The
use of tetrahydrofuran or N-methyl-2-pyrrolidone is recommended for
the developing solvent during gel permeation chromatography. In
addition, weight average molecular weight is determined from a
calibration curve prepared using standard monodisperse polystyrene.
The standard monodisperse polystyrene is recommended to be selected
from the organic solvent-based standard sample STANDARD SM-105
manufactured by Showa Denko K.K.
[0550] [Polyamide (A)]
[0551] Another example of a preferable resin (A) in the
photosensitive resin composition of the present invention is a
polyamide having a structure represented by the following general
formula (43):
##STR00125##
{wherein, X.sub.2c represents a trivalent organic group having 6 to
15 carbon atoms, Y.sub.2c represents a divalent organic group
having 6 to 35 carbon atoms and may have the same structure or a
plurality of structures, R.sub.9c represents an organic group
having 3 to 20 carbon atoms and having at least one
radical-polymerizable unsaturated bond, and n.sub.2c represents an
integer of 1 to 1000}. This polyamide is preferable for use in
negative-type photosensitive resin compositions.
[0552] In the aforementioned general formula (43), the group
represented by R.sub.9c is preferably a group represented by the
following general formula (100):
##STR00126##
{wherein, R.sub.32c represents an organic group having 2 to 19
carbon atoms and at least one radical-polymerizable unsaturated
bond} from the viewpoints of photosensitivity and chemical
resistance.
[0553] In the aforementioned general formula (43), the trivalent
organic group represented by X.sub.2c is preferably a trivalent
organic group having 6 to 15 carbon atoms, preferably an aromatic
group selected from, for example, those groups represented by the
following formula (101),
##STR00127##
and more preferably an aromatic group in which the carboxyl group
and amino group have been removed from the amino group-substituted
isophthalic acid structure.
[0554] In the aforementioned general formula (43), the divalent
organic group represented by Y.sub.2c is preferably an organic
group having 6 to 35 carbon atoms, and more preferably a cyclic
organic group having 1 to 4 optionally substituted aromatic rings
or aliphatic rings or an aliphatic group or siloxane group not
having a cyclic structure. Examples of the divalent organic group
represented by Y.sub.2c include those represented by the following
general formulas (102) and (102-1):
##STR00128##
{wherein, R.sub.33c and R.sub.34c respectively and independently
represent at least one group selected from the group consisting of
a hydroxyl group, methyl group (--CH.sub.3), ethyl group
(--C.sub.2H.sub.5), propyl group (--C.sub.3H.sub.7) and butyl group
(--C.sub.4H.sub.9), and the propyl group and butyl group include
their respective isomers},
##STR00129##
{wherein, m.sub.7c represents an integer of 0 to 8, m.sub.8c and
m.sub.9c respectively and independently represent an integer of 0
to 3, m.sub.10c and m.sub.11c respectively and independently
represent an integer of 0 to 10, and R.sub.35c and R.sub.36c
represent methyl groups (--CH.sub.3), ethyl groups
(--C.sub.2H.sub.5), propyl groups (--C.sub.3H.sub.7), butyl groups
(--C.sub.4H.sub.9) or isomers thereof}.
[0555] Preferable examples of an aliphatic group or siloxane group
not having a cyclic structure include those represented by the
following general formula (103):
##STR00130##
{wherein, m.sub.12c represents an integer of 2 to 12, m.sub.13c
represents an integer of 1 to 3, m.sub.14c represents an integer of
1 to 20, and R.sub.37c, R.sub.38c, R.sub.39c and R.sub.40c
respectively and independently represent an alkyl group having 1 to
3 carbon atoms or an optionally substituted phenyl group}.
[0556] The polyamide resin of the present invention can be
synthesized, for example, in the manner indicated below.
[0557] (Synthesis of Blocked Phthalic Acid Compound)
[0558] First, a compound in which the amino group of a phthalic
acid compound is modified and blocked with a group containing a
radical-polymerizable unsaturated bond to be subsequently described
(to be referred to as a "blocked phthalic acid compound") is
synthesized by reacting 1 mole of a compound having a trivalent
aromatic group X.sub.2c, such as at least one compound selected
from phthalic acid substituted with an amino group, isophthalic
acid substituted with an amino group and terephthalic acid
substituted with an amino group (to be referred to as a "phthalic
acid compound"), with 1 mole of a compound that reacts with an
amino group. These may be used alone or as a mixture.
[0559] The use of a structure in which the phthalic acid compound
is blocked with the aforementioned group containing a
radical-polymerizable unsaturated bond, negative-type
photosensitivity (photocurability) can be imparted to the polyamide
resin.
[0560] The group containing a radical-polymerizable unsaturated
bond is preferably an organic group having 3 to 20 carbon atoms and
a radical-polymerizable unsaturated bond, and particularly
preferably a group containing a methacryloyl group or acryloyl
group.
[0561] The aforementioned blocked phthalic acid compound can be
obtained by reacting the amino group of the phthalic acid compound
with an acid chloride, isocyanate or epoxy compound having 3 to 20
carbon atoms and at least one radical-polymerizable unsaturated
bond.
[0562] Preferable examples of acid chlorides include (meth)acryloyl
chloride, 2-[(meth)acryloyloxy]acetyl chloride,
3-[(meth)acryloyloxy]propionyl chloride, 2-[(meth)acryloyloxy]ethyl
chloroformate and 3-[(meth)acryloyloxypropyl] chloroformate.
Preferable examples of isocyanates include 2-(meth)acryloyloxyethyl
isocyanate, 1,1-bis[(meth)acryloyloxymethyl]ethyl isocyanate and
2-[2-(meth)acryloyloxyethoxy]ethyl isocyanate. Preferable examples
of epoxy compounds include glycidyl (meth)acrylate. Although these
may be used alone or as a mixture, methacryloyl chloride and/or
2-(methacryloyloxy)ethyl isocyanate are used particularly
preferably.
[0563] The use of these blocked phthalic acid compounds in which
the phthalic acid compound is 5-aminoisophthalic acid is preferable
since this allows the obtaining of a polyamide having superior
photosensitivity as well as superior film properties following heat
curing.
[0564] The aforementioned blocking reaction can be allowed to
proceed by stirring, dissolving or mixing the phthalic acid
compound and a blocking agent in the presence of a base catalyst
such as pyridine or a tin-based catalyst such as di-n-butyltin
dilaurate in solvent to be subsequently described as necessary.
[0565] Hydrogen chloride may be produced as a by-product during the
course of the blocking reaction depending on the type of blocking
agent such as in the case of an acid chloride. In this case,
purification is preferably carried out as suitable, such as by
re-precipitating in water or rinsing with water, or by reducing or
removing ionic components by passing through a column packed with
an ion exchange resin, for the purpose of preventing contamination
of subsequent steps.
[0566] (Synthesis of Polyamide)
[0567] The polyamide of the present invention can be obtained by
mixing the aforementioned blocked phthalic acid compound and
diamine compound having the divalent organic group Y.sub.2c in the
presence of a base catalyst such as pyridine or triethylamine in a
solvent to be subsequently described followed by subjecting to
amide polycondensation.
[0568] Examples of methods used to carry out amide polycondensation
include a method consisting of mixing the blocked phthalic acid
compound with the diamine compound after having converted to a
symmetrical polyacid anhydride using a dehydration condensation
agent, a method consisting of mixing the blocked phthalic acid
compound with the diamine compound after having converted to an
acid chloride according to a known method, and a method consisting
of reacting a dicarboxylic acid component with an active
esterifying agent in the presence of a dehydration condensation
agent to convert to an active ester followed by mixing with the
diamine compound.
[0569] Preferable examples of dehydration condensation agents
include dicyclohexylcarbodiimide,
1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline,
1,1-carbonyldioxy-di-1,2,3-benzotriazole and N,N'-disuccinimidyl
carbonate.
[0570] An example of chlorinating agents includes thionyl
chloride.
[0571] Examples of active esterifying agents include
N-hydroxysuccinimide, 1-hydroxybenzotriazole,
N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide, ethyl
2-hydroxyimino-2-cyanoacetate and
2-hydroxyimino-2-cyanoacetoamide.
[0572] The diamine compound having the organic group Y.sub.2c is
preferably at least one diamine compound selected from the group
consisting of aromatic diamine compounds, aromatic bisaminophenol
compounds, alicyclic diamine compounds, linear aliphatic diamine
compounds and siloxane diamine compounds, and a plurality thereof
can be used in combination as desired.
[0573] Examples of aromatic diamine compounds include
p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether,
3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether,
4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide,
3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylsulfone,
3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone,
4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl,
4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone,
3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane,
3,4'-diaminodiphenylmethane,
[0574] 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene,
1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene,
bis[4-(4-aminophenoxy)phenyl]sulfone,
bis[4-(3-aminophenoxy)phenyl]sulfone,
4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl,
bis[4-(4-aminophenoxy)phenyl] ether, bis[4-(3-aminophenoxy)phenyl]
ether, 1,4-bis(4-aminophenyl)benzene,
1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene,
2,2-bis(4-aminophenyl)propane,
2,2-bis(4-aminophenyl)hexafluoropropane,
2,2-bis[4-(4-aminophenoxy)phenyl]propane,
2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane,
1,4-bis(3-aminopropyldimethylsilyl)benzene, o-toluidine sulfone or
9,9-bis(4-aminophenyl)fluorene, and compounds in which a portion of
the hydrogen atoms on the benzene ring thereof is substituted with
one or more groups selected from the group consisting of a methyl
group, ethyl group, hydroxymethyl group, hydroxyethyl group and
halogen atom.
[0575] Examples of diamine compounds in which a hydrogen atom on
the benzene ring is substituted include
3,3'-dimethyl-4,4'-diaminobiphenyl,
2,2'-dimethyl-4,4'-diaminobiphenyl,
3,3'-dimethyl-4,4'-diaminodiphenylmethane,
2,2'-dimethyl-4,4'-diaminodiphenylmethane,
3,3'-dimethoxy-4,4'-diaminobiphenyl and
3,3'-dichloro-4,4'-diaminobiphenyl.
[0576] Examples of aromatic bisaminophenol compounds include
3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl,
3,3'-dihydroxy-4,4'-diaminodiphenylsulfone,
bis(3-amino-4-hydroxyphenyl)methane,
2,2-bis-(3-amino-4-hydroxyphenyl)propane,
2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane,
2,2-bis-(3-hydroxy-4-aminophenyl)hexafluoropropane,
bis-(3-hydroxy-4-aminophenyl)methane,
2,2-bis-(3-hydroxy-4-aminophenyl)propane,
3,3'-dihydroxy-4,4'-diaminobenzophenone,
3,3'-dihydroxy-4,4'-diaminodiphenyl ether,
4,4'-dihydroxy-3,3'-diaminodiphenyl ether,
2,5-dihydroxy-1,4-diaminobenzene, 4,6-diaminoresorcinol,
1,1-bis(3-amino-4-hydroxyphenyl)cyclohexane and
4,4-(a-methylbenzylidene)-bis(2-aminophenol).
[0577] Examples of alicyclic diamine compounds include
1,3-diaminocyclopentane, 1,3-diaminocyclohexane,
d1,3-diamino-1-methylcyclohexane,
3,5-diamino-1,1-dimethylcyclohexane,
1,5-diamino-1,3-dimethylcyclohexane,
1,3-diamino-1-methyl-4-isopropylcyclohexane,
1,2-diamino-4-methylcyclohexane, 1,4-diaminocyclohexane,
1,4-diamino-2,5-diethylcylclohexane,
1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane,
2-(3-aminocyclopentyl)-2-propylamine, menthane diamine, isophorone
diamine, norbornane diamine, 1-cycloheptene-3,7-diamine,
4,4'-methylenebis(cyclohexylamine),
4,4'-methylenebis(2-methylcyclohexylamine),
1,4-bis(3-aminopropyl)piperazine and
3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]-undecane.
[0578] Examples of linear aliphatic diamines include
hydrocarbon-based diamines such as 1,2-diaminoethane,
1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane,
1,10-diaminodecane or 1,12-diaminododecane, and alkylene
oxide-based diamines such as 2-(2-aminoethoxy)ethylamine,
2,2'-(ethylenedioxy)diethylamine or
bis[2-(2-aminoethoxy)ethyl]ether.
[0579] Examples of siloxane diamine compounds
dimethyl(poly)siloxane diamine, such as PAM-E, KF-8010 or X-22-161A
(trade names) manufactured by Shin-etsu Chemical Co., Ltd.
[0580] Following completion of the amide polycondensation reaction,
precipitates derived from the dehydration condensation agent that
have precipitated in the reaction solution are filtered out as
necessary. Next, a poor solvent of polyamide, such as water, an
aliphatic lower alcohol or a mixture thereof, is added to the
reaction solution to precipitate polyamide. Moreover, the
precipitated polyamide is purified by repeatedly re-dissolving and
re-precipitating in a solvent followed by vacuum drying to isolate
the target polyamide. Furthermore, in order to improve the degree
of purification, a solution of this polyamide may be passed through
a column packed with an ion exchange resin to remove any ionic
impurities.
[0581] The weight average molecular weight as of the polyamide as
polystyrene as determined by gel permeation chromatography (GPC) is
preferably 7,000 to 70,000 and more preferably 10,000 to 50,000.
Basic physical properties of the cured relief pattern are ensured
if the weight average molecular weight as polystyrene is 7,000 or
more. In addition, development solubility is ensured when forming a
relief pattern if the weight average molecular weight as
polystyrene is 70,000 or less.
[0582] The use of tetrahydrofuran or N-methyl-2-pyrrolidone is
recommended for the eluent used during GPC. In addition, weight
average molecular weight is determined from a calibration curve
prepared using standard monodisperse polystyrene. The standard
monodisperse polystyrene is recommended to be selected from the
organic solvent-based standard sample STANDARD SM-105 manufactured
by Showa Denko K.K.
[0583] [Polyhydroxyamide (A)]
[0584] Still another example of a preferable resin (A) in the
photosensitive resin composition of the present invention is a
polyhydroxyamide having a structure represented by the following
general formula (44):
##STR00131##
{wherein, Y.sub.3c represents a tetravalent organic group having a
carbon atom, and preferably represents a tetravalent organic group
having two or more carbon atoms, Y.sub.4c, X.sub.3c and X.sub.4c
respectively and independently represent a divalent organic group
having two or more carbon atoms, n.sub.3c represents an integer of
1 to 1000, n.sub.4c represents an integer of 0 to 500,
n.sub.3c/(n.sub.3c+n.sub.4c) is greater than 0.5, and there are no
restrictions on the arrangement order of the n.sub.3c number of
dihydroxydiamide units containing X.sub.3c and Y.sub.3c or the
n.sub.4c number of diamide units containing X.sub.4c and Y.sub.4c}
(and a polyhydroxyamide represented by the aforementioned general
formula (44) may simply be referred to as "polyhydroxyamide").
[0585] The polyoxazole precursor is a polymer having n.sub.3c
number of dihydroxydiamide units (which may be simply referred to
as the dihydroxydiamide unit) in the aforementioned general formula
(44), and may have n.sub.4c number of diamine units (which may be
simply referred to as the diamine unit) in the aforementioned
general formula (44).
[0586] The number of carbon atoms of X.sub.3c is preferably 2 to 40
for the purpose of obtaining photosensitivity, the number of carbon
atoms of X.sub.4c is preferably 2 to 40 for the purpose of
obtaining photosensitivity, and number of carbon atoms of Y.sub.3c
is preferably 2 to 40 for the purpose of obtaining
photosensitivity, and the number of carbons of Y.sub.4c is
preferably 2 to 40 for the purpose of obtaining
photosensitivity.
[0587] The dihydroxydiamide unit can be formed by synthesizing from
a diaminodihydroxy compound (preferably bisaminophenol) having the
structure Y.sub.3c(NH.sub.2).sub.2(OH).sub.2 and a dicarboxylic
acid having the structure X.sub.3c(COOH).sub.2. The following
provides an explanation of a typical aspect thereof using as an
example the case in which the aforementioned diaminodihydroxy
compound is bisaminophenol. The two sets of amino groups and
hydroxyl groups of the bisaminophenol are respectively and mutually
in the ortho position, and the dihydroxydiamide unit changes to a
heat-resistant polyoxazole structure following ring closure caused
by heating at about 250.degree. C. to 400.degree. C. Thus,
polyhydroxyamide can also be said to be a polyoxazole precursor.
n.sub.3c in general formula (44) is preferably 1 to 1000 for the
purpose of obtaining photosensitivity. n.sub.3c is preferably
within the range of 2 to 1000, more preferably within the range of
3 to 50, and most preferably within the range of 3 to 20.
[0588] An n.sub.4c number of the aforementioned diamide units may
be condensed in the polyhydroxyamide as necessary. The diamide unit
can be formed by synthesizing from a diamine having the structure
Y.sub.4c(NH.sub.2).sub.2 and a dicarboxylic acid having the
structure X.sub.4c(COOH).sub.2. n.sub.4c in general formula (44) is
within the range of 0 to 500, and preferable photosensitivity is
obtained as a result of n.sub.4c being 500 or less. n.sub.4c is
more preferably within the range of 0 to 10. Since solubility in
the aqueous alkaline solution used for the developer decreases if
the ratio of the diamide unit to the dihydroxydiamide unit is
excessively high, the value of n.sub.3c/(n.sub.3c+n.sub.4c) of
general formula (44) is greater than 0.5, preferably 0.7 or more,
and most preferably 0.8 or more.
[0589] Examples of bisaminophenols in the form of diaminodihydroxy
compounds having the structure Y.sub.3c(NH.sub.2).sub.2(OH).sub.2
include 3,3'-dihydroxybenzidine,
3,3'-diamino-4,4'-dihydroxybiphenyl,
4,4'-diamino-3,3'-dihydroxybiphenyl,
3,3'-diamino-4,4'-dihydroxybiphenylsulfone,
4,4'-diamino-3,3'-dihydroxydiphenylsulfone,
bis-(3-amino-4-hydroxyphenyl)methane,
2,2-bis-(3-amino-4-hydroxypheny)propane,
2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane,
2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane,
bis-(4-amino-3-hydroxyphenyl)methane,
2,2-bis-(4-amino-3-hydroxyphenyl)propane,
4,4'-diamino-3,3'-dihydroxybenzophenone,
3,3'-diamino-4,4'-dihydroxybenzophenone,
4,4'-diamino-3,3'-dihydroxyphenyl ether,
3,3'-diamino-4,4'-dihydroxyphenyl ether,
1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene
and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols can be
used alone or two or more types can be used in combination. The
Y.sub.3c group in these bisaminophenols is preferably represented
by the following general formula (104):
##STR00132##
{wherein, R.sub.s1 and R.sub.82 respectively and independently
represent a hydrogen atom, methyl group, ethyl group, propyl group,
cyclopentyl group, cyclohexyl group, phenyl group or
trifluoromethyl group} from the viewpoint of photosensitivity.
[0590] Examples of diamines having the structure
Y.sub.4c(NH.sub.2).sub.2 include aromatic diamines and silicone
diamines. Among these, examples of aromatic diamines include
m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine,
3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether,
4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylsulfone,
4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone,
3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide,
3,3'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone,
3,4'-diaminodiphenyl ketone, 2,2-bis(4-aminophenyl)propane,
2,2-bis(4-aminophenyl) hexafluoropropane,
1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene,
1,4-bis(4-aminophenoxy)benzene,
4-methyl-2,4-bis(4-aminophenyl)-1-pentene,
[0591] 4-methyl-2,4-bis(4-aminophenyl)-2-pentene,
1,4-bis(.alpha.,.alpha.-dimethyl-4-aminobenzyl)benzene,
imino-di-p-phenylenediamine, 1,5-diaminonaphthalene,
2,6-diaminonaphthalene, 4-methyl-2,4-bis(4-aminophenyl)pentane, 5
(or 6)-amino-1-(4-aminophenyl)-1,3,3-trimethylindane,
bis(p-aminophenyl)phosphine oxide, 4,4'-diaminoazobenzene,
4,4'-diaminodiphenyl urea, 4,4'-bis(4-aminophenoxy)biphenyl,
2,2-bis[4-(4-aminophenoxy)phenyl]propane,
2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane,
2,2-bis[4-(3-aminophenoxy)phenyl]benzophenone,
4,4'-bis(4-aminophenoxy)diphenylsulfone,
4,4'-bis[4-(.alpha.,.alpha.-dimethyl-4-aminobenzyl)phenoxy]benzophenone,
4,4'-bis[4-(.alpha.,.alpha.-dimethyl-4-aminobenzyl)phenoxy]diphenylsulfon-
e, 4,4'-diaminobiphenyl,
[0592] 4,4'-diaminobenzophenone, phenylindanediamine,
3,3'-dimethoxy-4,4'-diaminobiphenyl,
3,3'-dimethyl-4,4'-diaminobiphenyl, o-toluidine sulfone,
2,2-bis(4-aminophenoxyphenyl)propane,
bis(4-aminophenoxyphenyl)sulfone, bis(4-aminophenoxyphenyl)sulfide,
1,4-(4-aminophenoxyphenyl)benzene,
1,3-(4-aminophenoxyphenyl)benzene, 9,9-bis(4-aminophenyl)fluorene,
4,4'-di-(3-aminophenoxy)diphenylsulfone, 4,4'-diaminobenzanilide,
and compounds in which a portion of the hydrogen atoms of the
aromatic core of these aromatic diamines is substituted with one or
more groups or atoms selected from the group consisting of a
chlorine atom, fluorine atom, bromine atom, methyl group, methoxy
group, cyano group and phenyl group.
[0593] In addition, a silicone diamine can be selected for the
aforementioned diamine in order to enhance adhesion with a base
material. Examples of silicone diamines include
bis(4-aminophenyl)dimethylsilane,
bis(4-aminophenyl)tetramethylsiloxane,
bis(4-aminophenyl)tetramethyldisiloxane,
bis(y-aminopropyl)tetramethyldisiloxane,
1,4-bis(y-aminopropyldimethylsilyl)benzene,
bis(4-aminobutyl)tetramethyldisiloxane and
bis(y-aminopropyl)tetraphenyldisiloxane.
[0594] In addition, preferable examples of dicarboxylic acids
having the structure X.sub.3c(COOH).sub.2 or X.sub.4c(COOH).sub.2
include those in which X.sub.3c and X.sub.4c are respectively an
aliphatic group or aromatic group having a linear, branched or
cyclic structure. Among these, an organic group having 2 to 40
carbon atoms optionally containing an aromatic ring or aliphatic
ring is preferable, and X.sub.3c and X.sub.4c can be selected from
aromatic groups represented by the following formula (105):
##STR00133##
{wherein, R.sub.41c represents a divalent group selected from the
group consisting of --CH.sub.2--, --O--, --S--, --SO.sub.2--,
--CO--, --NHCO-- and --C(CF.sub.3).sub.2--}, and these are
preferable from the viewpoint of photosensitivity.
[0595] The terminal group of the polyoxazole precursor may be
blocked with a specific organic group. In the case of using a
polyoxazole precursor blocked with a blocking group, mechanical
properties (and particularly elongation) and the form of the cured
relief pattern of a coating film following heat curing of the
photosensitive resin composition of the present invention can be
expected to be favorable. Preferable examples of such blocking
groups include those represented by the following formula
(106):
##STR00134##
[0596] The weight average molecular weight as of the polyoxazole
precursor as polystyrene as determined by gel permeation
chromatography is preferably 3,000 to 70,000 and more preferably
6,000 to 50,000. In addition, the weight average molecular weight
is preferably 3,000 or more from the viewpoint of physical
properties of the cured relief pattern. The weight average
molecular weight is preferably 70,000 or less from the viewpoint of
resolution. The use of tetrahydrofuran or N-methyl-2-pyrrolidone is
recommended for the developing solvent of gel permeation
chromatography. In addition, molecular weight is determined from a
calibration curve prepared using standard monodisperse polystyrene.
The standard monodisperse polystyrene is recommended to be selected
from the organic solvent-based standard sample STANDARD SM-105
manufactured by Showa Denko K.K.
[0597] [Polyimide (A)]
[0598] Still another example of a preferable resin (A) in the
photosensitive resin composition of the present invention is a
polyimide having a structure represented by the following general
formula (45):
##STR00135##
{wherein, X.sub.5c represents a tetravalent to tetradecavalent
organic group, Y.sub.5c represents a divalent to dodecalvalent
organic group, R.sub.10c and R.sub.11c represent organic groups
having at least one group selected from the group consisting of a
phenolic hydroxyl group, sulfonate group and thiol group, and may
be the same or different, n.sub.5c represents an integer of 3 to
200 and m.sub.3c and m.sub.4c represent integers of 1 to 10}. Here,
a resin represented by general formula (45) does not require
chemical alteration in a heat treatment step since it already
demonstrates adequate film properties, it is particularly
preferable since treatment can be carried out at a lower
temperature.
[0599] X.sub.5c in the structural unit represented by the
aforementioned general formula (45) is preferably a tetravalent to
tetradecavalent organic group having 4 to 40 carbon atoms, and is
more preferably an organic group having 5 to 40 carbon atoms
containing an aromatic ring or aliphatic ring from the viewpoint of
realizing both heat resistance and photosensitivity.
[0600] The polyimide represented by the aforementioned general
formula (45) can be obtained by reacting a tetracarboxylic acid,
corresponding tetracarboxylic dianhydride or tetracarboxylic acid
diester dichloride with a diamine, corresponding diisocyanate
compound or trimethylsilylated diamine. The polyamide can be
typically obtained by reacting a tetracarboxylic dianhydride and
diamine and dehydrating the polyamic acid, which is one the
resulting polyimide precursors, by heating or by chemically
treating with acid or base to close the ring.
[0601] Preferable examples of tetracarboxylic dianhydrides include
aromatic tetracarboxylic dianhydrides such as pyromellitic
dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride,
2,3,3',4,'-biphenyltetracarboxylic dianhydride,
2,2',3,3'-biphenyltetracarboxylic dianhydride,
3,3',4,4'-benzophenonetetracarboxylic dianhydride,
2,2',3,3'-benzophenonetetracarboxylic dianhydride,
2,2-bis(3,4-dicarboxyphenyl)propane dianhydride,
2,2-bis(2,3-dicarboxyphenyl)propane dianhydride,
1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride,
1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride,
bis(3,4-dicarboxyphenyl)methane dianhydride,
bis(2,3-dicarboxyphenyl)methane dianhydride,
bis(3,4-dicarboxyphenyl)sulfone dianhydride,
bis(3,4-dicarboxyphenyl)ether dianhydride,
1,2,5,6-naphthalenetetracarboxylic dianhydride,
9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride,
[0602] 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride,
2,3,6,7-naphthalenetetracarboxylic dianhydride,
2,3,5,6-pyridinetetracarboxylic dianhydride,
3,4,9,10-perylenetetracarboxylic dianhydride or
2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride,
aliphatic tetracarboxylic dianhydrides such as
butanetetracarboxylic dianhydride or
1,2,3,4-cyclopentanetetracarboxylic dianhydride;
3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, and a
compound represented by the following general formula (107):
##STR00136##
{wherein, R.sub.42 represents an oxygen atom or a group selected
from C(CF.sub.3).sub.2, C(CH.sub.3).sub.2 and SO.sub.2, and
R.sub.43c and R.sub.44c may be the same or different and represent
hydrogen atoms or groups selected from a hydroxyl group and thiol
group}.
[0603] Among these, 3,3',4,4'-biphenyltetracarboxylic dianhydride,
2,3,3',4,'-biphenyltetracarboxylic dianhydride,
2,2',3,3'-biphenyltetracarboxylic dianhydride,
3,3',4,4'-benzophenonetetracarboxylic dianhydride,
2,2',3,3'-benzophenonetetracarboxylic dianhydride,
2,2-bis(3,4-dicarboxyphenyl)propane dianhydride,
2,2-bis(2,3-dicarboxyphenyl)propane dianhydride,
1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride,
1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride,
bis(3,4-dicarboxyphenyl)methane dianhydride,
bis(2,3-dicarboxyphenyl)methane dianhydride,
bis(3,4-dicarboxyphenyl)sulfone dianhydride,
[0604] bis(3,4-dicarboxyphenyl)ether dianhydride,
2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride,
3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride,
9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride,
9,9-bis[4-(3,4-dicarboxyphenyl)phenyl]fluorene dianhydride, and
dianhydrides having a structure represented by the following
general formula (108):
##STR00137##
{wherein, R.sub.45c represents an oxygen atom or a group selected
from C(CF.sub.3).sub.2, C(CH.sub.3).sub.2 and SO.sub.2, and
R.sub.45c and R.sub.47c may be the same or different and represent
hydrogen atoms or groups selected from a hydroxyl group and thiol
group}. These are used alone or two or more types are used in
combination.
[0605] Y.sub.5c in the aforementioned general formula (45)
represents a constituent component of a diamine, and this diamine
preferably represents a divalent to dodecavalent organic group
containing an aromatic ring or aliphatic ring, and is particularly
preferably an organic group having 5 to 40 carbon atoms.
[0606] Specific examples of diamines include 3,4'-diaminodiphenyl
ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane,
4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone,
4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenyl sulfide,
4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene,
benzene, m-phenylenediamine, p-phenylenediamine,
1,5-naphthalenediamine, 2,6-naphthalenediamine,
bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone,
bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether,
1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl,
2,2'-diethyl-4,4'-diaminobiphenyl,
3,3'-dimethyl-4,4'-diaminobiphenyl,
[0607] 3,3'-diethyl-4,4'-diaminobiphenyl,
2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl,
3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl,
2,2'-di(trifluorophenyl)-4,4'-diaminobiphenyl,
9,9-bis(4-aminophenyl)fluorene, compounds in which the aromatic
ring thereof is substituted with an alkyl group or halogen atom,
aliphatic cyclohexyldiamines, methylenebis(cyclohexylamines), and
diamines having a structure represented by the following general
formula (109):
##STR00138##
{wherein, R.sub.48c represents an oxygen atom or group selected
from C(CF.sub.3).sub.2, C(CH.sub.3).sub.2 and SO.sub.2, and
R.sub.49c to R.sub.52c may be the same or different and represent
hydrogen atoms or groups selected from a hydroxyl group and thiol
group}.
[0608] Among these, 3,4'-diaminodiphenyl ether,
4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane,
4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone,
4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenyl sulfide,
4,4'-diaminodiphenyl sulfide, m-phenylenediamine,
p-phenylenediamine, 1,4-bis(4-aminophenoxy)benzene and diamines
having a structure represented by the following general formula
(110):
##STR00139##
{wherein, R.sub.53c represents an oxygen atom or group selected
from C(CF.sub.3).sub.2, C(CH.sub.3).sub.2 and SO.sub.2, and
R.sub.54c to R.sub.57c may be the same or different and represent
hydrogen atoms or groups selected from a hydroxyl group and thiol
group} are preferable.
[0609] Among these, 3,4'-diaminodiphenyl ether,
4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane,
4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone,
4,4'-diaminodiphenylsulfone, 1,4-bis(4-aminophenoxy) benzene and
diamines having a structure represented by the following general
formula (111):
##STR00140##
{wherein, R.sub.58c represents an oxygen atom or group selected
from C(CF.sub.3).sub.2, C(CH.sub.3).sub.2 and SO.sub.2, and
R.sub.59c and R.sub.60c may be the same or different and represent
hydrogen atoms or groups selected from a hydroxyl group and thiol
group} are particularly preferable. These are used alone or two or
more types are used in combination.
[0610] R.sub.10c and R.sub.11c in general formula (45) represent
phenolic hydroxyl groups, sulfonate groups or thiol groups. In the
present invention, R.sub.10c and R.sub.11c can consist of a mixture
of phenolic hydroxyl groups, sulfonate groups and/or thiol
groups.
[0611] Since the dissolution rate in an aqueous alkaline solution
can be changed by controlling the amount of alkaline-soluble groups
of R.sub.10c and R.sub.11c, a photosensitive resin composition
having a suitable dissolution rate can be obtained by adjusting in
this manner.
[0612] Moreover, in order to improve adhesion with a base material,
an aliphatic group having a siloxane structure may be copolymerized
for X.sub.5c and Y.sub.5c within a range that does not lower heat
resistance. Specific examples thereof include compounds obtained by
copolymerizing 1 mol % to 10 mol % of a diamine component in the
form bis(3-aminopropyl) tetramethylsiloxane or
bis(p-aminophenyl)octamethylpentasiloxane.
[0613] The aforementioned polyimide can be synthesized by using a
method consisting of obtaining a polyimide precursor by using, for
example, a method consisting of reacting a tetracarboxylic
dianhydride and a diamine compound (in which a portion thereof is
substituted with a monoamine as a terminal blocking agent) at a low
temperature, a method consisting of reacting a tetracarboxylic
dianhydride (in which a portion thereof is substituted with an acid
anhydride, monoacid chloride compound, mono-active ester compound
as a terminal blocking agent) and a diamine compound at a low
temperature, a method consisting of obtaining a diester from a
tetracarboxylic acid and alcohol followed by reacting with a
diamine (in which a portion thereof is substituted with a monoamine
as a terminal blocking agent) in the presence of a condensation
agent, or a method consisting of obtaining a diester from a
tetracarboxylic dianhydride and alcohol followed by converting the
remaining dicarboxylic acid to an acid chloride and reacting with a
diamine (in which a portion thereof is substituted with a monoamine
as a terminal blocking agent), and then completely imidizing this
using a known imidization reaction method, or by using the method
in which the imidization reaction is interrupted so as to
incorporate a partial imide structure into a product (i.e., poly
amide imide in this case), or by using a method consisting of
blending a completely imidized polymer and other polyimide
precursor and partially introducing an imide structure therein.
[0614] The aforementioned polyimide is preferably incorporated so
that the imidization rate is 15% or more based on the total amount
of resin that composes the photosensitive resin composition. The
imidization rate is more preferably 20% or more. Here, imidization
rate refers to the percentage of imide present in all of the resin
that composes the photosensitive resin composition. If the
imidization rate is less than 15%, the amount of shrinkage during
heat curing increases, thereby making this unsuitable for producing
a thick film.
[0615] Imidization rate can be easily calculated using the method
indicated below. First, the infrared absorption spectrum of the
polymer is measured to confirm the presence of absorption peaks of
imide structures attributable to polyimide (present in the vicinity
of 1780 cm.sup.-1 and 1377 cm.sup.-1). Next, the polymer is
heat-treated for 1 hour at 350.degree. C., the infrared absorption
spectrum following heat treatment is measured, and peak intensity
in the vicinity of 1377 cm.sup.-1 is compared with the intensity
prior to heat treatment to calculate the imidization rate in the
polymer prior to heat treatment.
[0616] The molecular weight of the aforementioned polyimide is
preferably 3,000 to 200,000 and more preferably 5,000 to 50,000 in
the case of having measured weight average molecular weight as
polystyrene by gel permeation chromatography. Mechanical properties
are favorable in the case the weight average molecular weight is
3,000 or more, and dispersibility in the developer and resolution
of the relief pattern are favorable in the case the weight average
molecular weight is 50,000 or less.
[0617] The use of tetrahydrofuran or N-methyl-2-pyrrolidone is
recommended for the developing solvent of gel permeation
chromatography. In addition, molecular weight is determined from a
calibration curve prepared using standard monodisperse polystyrene.
The standard monodisperse polystyrene is recommended to be selected
from the organic solvent-based standard sample STANDARD SM-105
manufactured by Showa Denko K.K.
[0618] Phenol resin can also be preferably used in the present
invention.
[0619] [Phenol Resin (A)]
[0620] The phenol resin in the present embodiment refers to a resin
having a repeating unit having a phenolic hydroxyl group. The
phenol resin (A) has the advantage of being able to be cured at a
low temperature (such as 250.degree. C. or lower) since structural
changes in the manner of cyclization (imidization) of the polyimide
precursor during heat curing do not occur.
[0621] In the present embodiment, the weight average molecular
weight of the phenol resin (A) is preferably 700 to 100,000, more
preferably 1,500 to 80,000, and even more preferably 2,000 to
50,000. The weight average molecular weight is preferably 700 or
more from the viewpoint of the applicability to reflow treatment of
the cured film, while on the other hand, the weight average
molecular weight is preferably 100,000 or less from the viewpoint
of alkaline solubility of the photosensitive resin composition.
[0622] Measurement of weight average molecular weight in the
present disclosure is carried out by gel permeation chromatography
(GPC), and can be calculated from a calibration curve prepared
using standard polystyrene.
[0623] From the viewpoints of solubility in an aqueous alkaline
solution, sensitivity and resolution when forming a resist pattern,
and residual stress of the cured film, the phenol resin (A) is
preferably at least one type of phenol resin selected from a
novolac resin, polyhydroxystyrene, phenol resin having a repeating
unit represented by the following general formula (46):
##STR00141##
{wherein, a represents an integer of 1 to 3, b represents an
integer of 0 to 3, 1.ltoreq.(a+b).ltoreq.4, R.sub.12c represents a
monovalent substituent selected from the group consisting of a
monovalent organic group having 1 to 20 carbon atoms, halogen atom,
nitro group and cyano group, a plurality of R.sub.12c may be
mutually the same or different in the case b is 2 or 3, and X
represents a divalent organic group selected from the group
consisting of a divalent aliphatic group having 2 to 10 carbon
atoms that may or may not have an unsaturated bond, divalent
alicyclic group having 3 to 20 carbon atoms, divalent alkylene
oxide group represented by the following general formula (47):
[Chemical Formula 159]
--C.sub.pH.sub.2pO-- (47)
(wherein, p represents an integer of 1 to 10), and divalent organic
group having an aromatic ring having 6 to 12 carbon atoms}, and a
phenol resin modified with a compound having an unsaturated
hydrocarbon group having 4 to 100 carbon atoms.
[0624] (Novolac Resin)
[0625] In the present disclosure, novolac resin refers to all
polymers obtained by condensing a phenol and formaldehyde in the
presence of a catalyst. In general, novolac resin can be obtained
by condensing less than 1 mole of formaldehyde to 1 mole of phenol.
Examples of the aforementioned phenols include phenol, o-cresol,
m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol,
o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol,
2,4-xylenol, 2.5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol,
2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol,
pyrogallol, .alpha.-naphthol and .beta.-naphthol. Specific examples
of novolac resins include phenol/formaldehyde condensed novolac
resin, cresol/formaldehyde condensed novolac resin and
phenol-naphthol/formaldehyde condensed novolac resin.
[0626] The weight average molecular weight of the novolac resin is
preferably 700 to 100,000, more preferably 1,500 to 80,000 and even
more preferably 2,000 to 50,000. The weight average molecular
weight is preferably 700 or more from the viewpoint of
applicability to reflow treatment of the cured film, while on the
other hand, the weight average molecular weight is preferably
100,000 or less from the viewpoint of alkaline solubility of the
photosensitive resin composition.
[0627] (Polyhydroxystyrene)
[0628] In the present disclosure, polyhydroxystyrene refers to all
polymers containing hydroxystyrene as a polymerized unit. A
preferable example of a polyhydroxystyrene is
poly(para-vinyl)phenol. Poly(para-vinyl)phenol refers to all
polymers containing para-vinyl phenol as a polymerized unit. Thus,
a polymerized unit other than hydroxystyrene (such as para-vinyl
phenol) can be used to compose the hydroxystyrene (such as
poly(para-vinyl)phenol) provided it is not inconsistent with the
object of the present invention. The ratio of the number of moles
of hydroxystyrene units in the polyhydroxystyrene based on the
total number of moles of polymerized units is preferably 10 mol %
to 99 mol %, more preferably 20 mol % to 97 mol %, and even more
preferably 30 mol % to 95 mol %. The case of this ratio being 10
mol % or more is advantageous from the viewpoint of alkaline
solubility of the photosensitive resin composition, while the case
of this ratio being 99 mol % or less is advantageous from the
viewpoint of the applicability of reflow treatment to a cured film
obtained by curing a composition containing a copolymer component
to be subsequently described. A polymerized unit other than a
hydroxystyrene (such as para-vinyl phenol) can be any arbitrary
polymerized unit able to copolymerize with a hydroxystyrene (such
as para-vinyl phenol). Examples of copolymer components that yield
a polymerized unit other than a hydroxystyrene (such as para-vinyl
phenol) include, but are not limited to, esters of acrylic acid
such as methyl acrylate, methyl methacrylate, hydroxyethyl
acrylate, butyl methacrylate, octyl acrylate, 2-ethoxyethyl
methacrylate, t-butyl acrylate, 1,5-pentanediol diacrylate,
N,N-diethylaminoethyl acrylate, ethylene glycol diacrylate,
1,3-propanediol diacrylate, decamethylene glycol diacrylate,
decamethylene glycol dimethacrylate, 1,4-cyclohexanediol
diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate,
tripropylene glycol diacrylate, glycerol triacrylate,
2,2-di-(p-hydroxyphenyl)propane dimethacrylate, triethylene glycol
diacrylate, polyoxyethyl-2,2-di(p-hydroxyphenyl)propane
dimethacrylate, triethylene glycol dimethacrylate,
polyoxypropyltrimethyololpropane triacrylate, ethylene glycol
dimethacrylate, butylene glycol dimethacrylate, 1,3-propanediol
dimethacrylate, 1,2,4-butanetriol trimethacrylate,
2,2,4-trimethyl-1,3-pentanediol dimethacrylate, pentaerythritol
trimethacrylate, 1-phenylethylene-1,2-dimethacrylate,
pentaerythritol tetramethacrylate, trimethylolpropane
trimethacrylate, 1,5-pentanediol dimethacrylate or 1,4-benzenediol
dimethacrylate, styrene, and substituted styrenes in the manner of
2-methylstyrene or vinyltoluene, vinyl ester monomers such as vinyl
acrylate or vinyl methacrylate, and o-vinylphenol and
m-vinylphenol.
[0629] In addition, one type of the novolac resin and
polyhydroxystyrene explained above can be used or two or more types
can be used in combination.
[0630] The weight average molecular weight of the
polyhydroxystyrene is preferably 700 to 100,000, more preferably
1,500 to 80,000 and even more preferably 2,000 to 50,000. The
weight average molecular weight is preferably 700 or more from the
viewpoint of applicability to reflow treatment of the cured film,
while on the other hand, the weight average molecular weight is
preferably 100,000 or less from the viewpoint of alkaline
solubility of the photosensitive resin composition.
[0631] (Phenol Resins Represented by General Formula (46)) In the
present embodiment, the phenol resin (A) preferably also contains a
phenol resin having a repeating unit represented by the following
general formula (46):
##STR00142##
{wherein, a represents an integer of 1 to 3, b represents an
integer of 0 to 3, 1.ltoreq.(a+b).ltoreq.4, R.sub.12c represents a
monovalent substituent selected from the group consisting of a
monovalent organic group having 1 to 20 carbon atoms, halogen atom,
nitro group and cyano group, a plurality of R.sub.12c may be
mutually the same or different in the case b is 2 or 3, and X
represents a divalent organic group selected from the group
consisting of a divalent aliphatic group having 2 to 10 carbon
atoms that may or may not have an unsaturated bond, divalent
alicyclic group having 3 to 20 carbon atoms, divalent alkylene
oxide group represented by the following general formula (47):
[Chemical Formula 161]
--C.sub.pH.sub.2pO-- (47)
(wherein, p represents an integer of 1 to 10), and divalent organic
group having an aromatic ring having 6 to 12 carbon atoms}. A
phenol resin having the aforementioned repeating unit can be cured
at a lower temperature in comparison with conventionally used
polyimide resin or polybenzoxazole resin, for example, and is
particularly advantageous from the viewpoint of allowing the
formation of a cured film having favorable elongation. One type of
the aforementioned repeating unit can be present in a phenol resin
molecule or a combination of two or more types can be present.
[0632] In the aforementioned general formula (46), R.sub.12c
represents a monovalent substituent selected from the group
consisting of a monovalent organic group having 1 to 20 carbon
atoms, halogen atom, nitro group and cyano group from the viewpoint
of reactivity when synthesizing a resin according to general
formula (46). From the viewpoint of alkaline solubility, R.sub.12c
preferably represents a monovalent substituent selected from the
group consisting of a halogen atom, nitro group, cyano group,
aliphatic group having 1 to 10 carbon atoms which may or may not
have an unsaturated bond, aromatic group having 6 to 20 carbon
atoms, and the four groups represented by the following general
formula (112):
##STR00143##
{wherein, R.sub.61c, R.sub.62c and R.sub.63c respectively and
independently represent a hydrogen atom, aliphatic group having 1
to 10 carbon atoms which may or may not have an unsaturated bond,
alicyclic group having 3 to 20 carbon atoms or aromatic group
having 6 to 20 carbon atoms, and R.sub.64c represents a divalent
aliphatic group having 1 to 10 carbon atoms which may or may not
have an unsaturated bond, divalent alicyclic group having 3 to 20
carbon atoms, or divalent aromatic group having 6 to 20 carbon
atoms}.
[0633] In the present embodiment, in the aforementioned general
formula (46), although a represents an integer of 1 to 3, a is
preferably 2 from the viewpoints of alkaline solubility and
elongation. In addition, in the case a is 2, the substituted
locations of hydroxyl groups may be any of the ortho, meta or para
positions. In the case a is 3, substituted locations of hydroxyl
groups may be at the 1,2,3-positions, 1,2,4-positions or
1,3,5-positions.
[0634] In the present embodiment, in the aforementioned general
formula (46), since alkaline solubility improves in the case a is
1, a phenol resin selected from a novolac resin and
polyhydroxystyrene (to also be referred to as resin (a2)) can be
further mixed with the phenol resin having a repeating unit
represented by general formula (46) (to also be referred to as
resin (a1)).
[0635] The mixing ratio between resin (a1) and resin (a2) in terms
of the weight ratio thereof is preferably such that (a1)/(a2) is
within the range of 10/90 to 90/10. This mixing ratio is such that
(a1)/(a2) is preferably within the range of 10/90 to 90/10, more
preferably within the range of 20/80 to 80/20, and even more
preferably within the range of 30/70 to 70/30 from the viewpoints
of solubility in an aqueous alkaline solution and elongation of the
cured film.
[0636] The same resins as those indicated in the aforementioned
sections on Novolac Resin and Polyhydroxystyrene can be used for
the novolac resin and polyhydroxystyrene of the aforementioned
resin (a2).
[0637] In the present embodiment, in the aforementioned general
formula (46), although b represents an integer of 0 to 3, b is
preferably 0 or 1 from the viewpoint of alkaline solubility and
elongation. In addition, a plurality of R.sub.12c may be mutually
the same or different in the case b is 2 or 3.
[0638] Moreover, in the present embodiment, in the aforementioned
general formula (46), a and b satisfy the relationship
1.ltoreq.(a+b).ltoreq.4.
[0639] In the present embodiment, in the aforementioned general
formula (46), X represents a divalent organic group selected from
the group consisting of a divalent aliphatic group having 2 to 10
carbon atoms that may or may not have an unsaturated bond, divalent
alicyclic group having 3 to 20 carbon atoms, alkylene oxide group
represented by the aforementioned general formula (47) and divalent
organic group having an aromatic ring having 6 to 12 carbon atoms
from the viewpoint of the form of a cured relief pattern and
elongation of a cured film. Among these divalent organic groups,
from the viewpoint of film toughness after curing, X preferably
represents a divalent organic group selected from the group
consisting of a divalent group represented by the following general
formula (48):
##STR00144##
{wherein, R.sub.13c, R.sub.14c, R.sub.15c and R.sub.16c
respectively and independently represent a hydrogen atom,
monovalent aliphatic group having 1 to 10 carbon atoms or
monovalent aliphatic group having 1 to 10 carbon atoms in which all
or a portion of the hydrogen atoms are substituted with fluorine
atoms, n.sub.6c represents an integer of 0 to 4, and in the case
n.sub.6c represents an integer of 1 to 4, R.sub.17c represents a
halogen atom, hydroxyl group or monovalent organic group having 1
to 12 carbon atoms, at least one of R.sub.17c is a hydroxyl group,
and a plurality of R.sub.17c may be mutually the same or different
in the case n.sub.6c is an integer of 2 to 4}, and a divalent group
represented by the following general formula (49):
##STR00145##
{wherein, R.sub.18c, R.sub.19c, R.sub.20c and R.sub.21c
respectively and independently represent a hydrogen atom,
monovalent aliphatic group having 1 to 10 carbon atoms or
monovalent aliphatic group having 1 to 10 carbon atoms in which all
or a portion of the hydrogen atoms are substituted with fluorine
atoms, W represents a single bond, aliphatic group having 1 to 10
carbon atoms optionally substituted with fluorine atoms, alicyclic
group having 3 to 20 carbon atoms optionally substituted with
fluorine atoms, divalent alkylene oxide group represented by the
following general formula (47):
[Chemical Formula 165]
--C.sub.pH.sub.2pO-- (47)
(wherein, p represents an integer of 1 to 10), and a divalent
organic group selected from the group consisting of divalent groups
represented by the following formula (50)
##STR00146##
[0640] The number of carbon atoms of the aforementioned divalent
organic group X having an aromatic ring having 6 to 12 carbon atoms
is preferably 8 to 75 and more preferably 8 to 40. Furthermore, the
structure of the aforementioned divalent organic group X having an
aromatic ring having 6 to 12 carbon atoms typically differs from a
structure in the aforementioned general formula (46) in which the
OH group and any R.sub.12c group are bound to the aromatic
ring.
[0641] Moreover, from the viewpoints of pattern formability of a
resin composition and elongation of a cured film after curing, the
divalent organic group represented by the aforementioned general
formula (49) is more preferably a divalent organic group
represented by the following formula (113):
##STR00147##
and particularly preferably a divalent organic group represented by
the following formula (114).
##STR00148##
[0642] Among the structures represented by general formula (46), a
structure in which X is represented by the aforementioned formula
(113) or (114) is particularly preferable, the ratio of sites
represented by a structure in which X is represented by formula
(113) or formula (114) is preferably 20% by weight or more and more
preferably 30% by weight or more from the viewpoint of elongation.
The aforementioned ratio is preferably 80% by weight or less, and
more preferably 70% by weight or less, from the viewpoint of
alkaline solubility of the composition.
[0643] In addition, among the phenol resins having a structure
represented by the aforementioned general formula (46), a structure
having both a structure represented by the following general
formula (115) and a structure represented by the following general
formula (116) within the same resin backbone is particularly
preferable from the viewpoints of alkaline solubility of the
composition and elongation of a cured film.
[0644] The following general formula (115) is represented by:
##STR00149##
{wherein, R.sub.21d represents a monovalent group having 1 to 10
carbon atoms selected from the group consisting of hydrocarbon
groups and alkoxy groups, n.sub.7c represents an integer of 2 or 3,
n.sub.8c represents an integer of 0 to 2, m.sub.5c represents an
integer of 1 to 500, 2.ltoreq.(n.sub.7c+n.sub.8c).ltoreq.4, and in
the case n.sub.8c is 2, a plurality of R.sub.21d may be mutually
the same or different}, and the following general formula (116) is
represented by:
##STR00150##
{wherein, R.sub.22c and R.sub.23c respectively and independently
represent a monovalent group having 1 to 10 carbon atoms selected
from the group consisting of hydrocarbon groups and alkoxy groups,
n.sub.9c represents an integer of 1 to 3, n.sub.10c represents an
integer of 0 to 2, n.sub.11c represents an integer of 0 to 3,
m.sub.6c represents an integer of 1 to 500,
2.ltoreq.(n.sub.9c+n.sub.10c).ltoreq.4, in the case n.sub.10c is 2,
a plurality of R.sub.22c may be mutually the same or different, and
in the case n.sub.11c is 2 or 3, a plurality of R.sub.23c may be
mutually the same or different}.
[0645] m.sub.5c in the aforementioned general formula (115) and
m.sub.6c in the aforementioned general formula (116) respectively
indicate the total number of repeating units in the main chain of a
phenol resin. Namely, the repeating unit indicated in brackets in
the structure represented by the aforementioned general formula
(115) and the repeating unit indicated in brackets in the structure
represented by the aforementioned general formula (116) in the main
chain of the phenol resin (A) can be arranged randomly, in blocks
or in a combination thereof. m.sub.5c and m.sub.6c respectively and
independently represent an integer of 1 to 500, the lower limit
thereof is preferably 2 and more preferably 3, and the upper limit
thereof is preferably 450, more preferably 400 and even more
preferably 350. m.sub.5c and m.sub.6c are respectively and
independently preferably 2 or more from the viewpoint of film
toughness after curing and preferably 450 or less from the
viewpoint of solubility in an aqueous alkaline solution. The sum of
m.sub.5c and m.sub.6c is preferably 2 or more, more preferably 4 or
more and even more preferably 6 or more from the viewpoint of film
toughness after curing, and preferably 200 or less, more preferably
175 or less and even more preferably 150 or less from the viewpoint
of solubility in an aqueous alkaline solution.
[0646] In the aforementioned phenol resin (A) having both a
structure represented by the aforementioned general formula (115)
and a structure represented by the aforementioned general formula
(116) in the same resin backbone, a higher molar ratio of the
structure represented by general formula (115) results in better
film properties after curing and superior heat resistance, while on
the other hand, a higher molar ratio of the structure represented
by general formula (116) results in better alkaline solubility and
superior pattern form after curing. Thus, the ratio
m.sub.5c/m.sub.6c of the structure represented by general formula
(115) to the structure represented by general formula (116) is
preferably 20/80 or more, more preferably 40/60 or more and
particularly preferably 50/50 or more from the viewpoint of film
properties after curing, and is preferably 90/10 or less, more
preferably 80/20 or less and even more preferably 70/30 or less
from the viewpoint of alkaline solubility and form of the cured
relief pattern.
[0647] A phenol resin having a repeating unit represented by the
aforementioned general formula (46) typically contains a phenol
compound and a copolymer component (and more specifically, one or
more types of compounds selected from the group consisting of a
copolymer component (and more specifically, a compound having an
aldehyde group (including a compound that forms an aldehyde
compound following decomposition in the manner of trioxane), a
compound having a ketone group, a compound having two methylol
groups in a molecule thereof, a compound having two alkoxymethyl
groups in a molecule thereof, and a compound having two haloalkyl
groups in a molecule thereof), and more typically, can be
synthesized by subjecting these monomer components to a
polymerization reaction. For example, a copolymer component such as
an aldehyde compound, ketone compound, methylol compound,
alkoxymethyl compound, diene compound or haloalkyl compound can be
polymerized with a phenol and/or phenol derivative like that
indicated below (to also be collectively referred to as a "phenol
compound") to obtain the phenol resin (A). In this case, the moiety
in the aforementioned general formula (46) represented by a
structure, in which an OH group and an arbitrary R.sub.12c group
are bound to an aromatic ring, is derived from the aforementioned
phenol compound, while the moiety represented by X is derived from
the aforementioned copolymer component. The charged molar ratio
between the phenol compound and the aforementioned copolymer
component is such that (phenol compound):(copolymerization
component) is preferably 5:1 to 1.01:1 and more preferably 2.5:1 to
1.1:1 from the viewpoints of controlling the reaction and stability
of the resulting phenol resin (A) and photosensitive resin
composition.
[0648] The weight average molecular weight of the phenol resin
having a repeating unit represented by general formula (46) is
preferably 700 to 100,000, more preferably 1,500 to 80,000, and
even more preferably 2,000 to 50,000. The weight average molecular
weight is preferably 700 or more from the viewpoint of the
applicability to reflow treatment of the cured film, while on the
other hand, the weight average molecular weight is preferably
100,000 or less from the viewpoint of alkaline solubility of the
photosensitive resin composition.
[0649] Examples of phenol compounds that can be used to obtain a
phenol resin having a repeating unit represented by general formula
(46) include cresol, ethylcresol, propylphenol, butylphenol,
amylphenol, cyclohexylphenol, hydroxyphenol, benzylphenol,
nitrobenzylphenol, cyanobenzylphenol, adamantanephenol,
nitrophenol, fluorophenol, chlorophenol, bromophenol,
trifluoromethylphenol,
N-(hydroxyphenyl)-5-norbornene-2,3-dicarboximide,
N-(hydroxyphenyl-5-methyl-5-norbornene-2,3-dicarboximide,
trifluoromethylphenol, hydroxybenzoate, methyl hydroxybenzoate,
ethyl hydroxybenzoate, benzyl hydroxybenzoate, hydroxybenzamide,
hydroxybenzaldehyde, hydroxyacetophenone, hydroxybenzophenone,
hydroxybenzonitrile, resorcinol, xylenol, catechol, methyl
catechol, ethyl catechol, hexyl catechol, benzyl catechol,
nitrobenzyl catechol, methyl resorcinol, ethyl resorcinol, hexyl
resorcinol, benzyl resorcinol, nitrobenzyl resorcinol,
hydroquinone, caffeic acid, dihydroxybenzoate, methyl
dihydroxybenzoate, ethyl dihydroxybenzoate, butyl
dihydroxybenzoate, propyl dihydroxybenzoate, benzyl
dihydroxybenzoate, dihydroxybenzamide, dihydroxybenzaldehyde,
dihydroxyacetophenone, dihydroxybenzophenone,
dihydroxybenzonitrile,
N-(dihydroxyphenyl)-5-norbornene-2,3-dicarboximide,
N-(dihydroxyphenyl)-5-methyl-5-norbornene-2,3-dicarboximide,
nitrocatechol, fluorocatechol, chlorocatechol, bromocatechol,
trifluoromethylcatechol, nitroresorcinol, fluororesorcinol,
chlororesorcinol, bromoresorcinol, trifluoromethylresorcinol,
pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene,
trihydroxybenzoic acid, methyl trihydroxybenzoate, ethyl
trihydroxybenzoate, butyl trihydroxybenzoate, propyl
trihydroxybenzoate, benzyl trihydroxybenzoate, trihydroxybenzamide,
trihydroxybenzaldehyde, trihydroxyacetophenone,
trihydroxybenzophenone and trihydroxybenzonitrile.
[0650] Examples of the aforementioned aldehyde compound include
acetoaldehyde, propionaldehyde, pivalaldehyde, butylaldehyde,
pentanal, hexanal, trioxane, glyoxal, cyclohexylaldehyde,
diphenylacetoaldehyde, ethylbutylaldehyde, benzaldehyde, glyoxylic
acid, 5-norbornene-2-carboxyaldehyde, malondialdehyde,
succindialdehyde, glutaraldehyde, salicylaldehyde, naphthoaldehyde
and terephthalaldehyde.
[0651] Examples of the aforementioned ketone compound include
acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone,
dicyclohexyl ketone, dibenzyl ketone, cyclopentanone,
cyclohexanone, bicyclohexanone, cyclohexanedione, 3-butyn-2-one,
2-norbornanone, adamantanone and
2,2-bis(4-oxocyclohexyl)propane.
[0652] Examples of the aforementioned methylol compound include
2,6-bis(hydroxymethyl)-p-cresol,
2,6-bis(hydroxymethyl)-4-ethylphenol,
2,6-bis(hydroxymethyl)-4-propylphenol,
2,6-bis(hydroxymethyl)-4-n-butylphenol,
2,6-bis(hydroxymethyl)-4-t-butylphenol,
2,6-bis(hydroxymethyl)-4-methoxyphenol,
2,6-bis(hydroxymethyl)-4-ethoxyphenol,
2,6-bis(hydroxymethyl)-4-propoxyphenol,
2,6-bis(hydroxymethyl)-4-n-butoxyphenol,
2,6-bis(hydroxymethyl)-4-t-butoxyphenol,
1,3-bis(hydroxymethyl)urea, ribitol, arabitol, allitol,
2,2-bis(hydroxymethyl)butyric acid, 2-benzyloxy-1,3-propanediol,
2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol,
monoacetin, 2-methyl-2-nitro-1,3-propanediol,
5-norbornene-2,2-dimethanol, 5-norbornene-2,3-dimethanol,
pentaerythritol, 2-phenyl-1,3-propanediol, trimethylolethane,
trimethylolpropane, 3,6-bis(hydroxymethyl)durene,
2-nitro-p-xylylene glycol, 1,10-dihydroxydecane,
1,12-dihydroxydodecane, 1,4-bis(hydroxymethyl)cyclohexane,
1,4-bis(hydroxymethyl)cyclohexene,
1,6-bis(hydroxymethyl)adamantane, 1,4-benzenedimethanol,
1,3-benzenedimethanol, 2,6-bis(hydroxymethyl)-1,4-dimethoxybenzene,
2,3-bis(hydroxymethyl)naphthalene,
2,6-bis(hydroxymethyl)naphthalene,
1,8-bis(hydroxymethyl)anthracene, 2,2'-bis(hydroxymethyl)diphenyl
ether, 4,4'-bis(hydroxymethyl)diphenyl ether,
4,4'-bis(hydroxymethyl)diphenyl thioether,
4,4'-bis(hydroxymethyl)benzophenone,
4-hydroxymethylbenzoate-4'-hydroxymethylphenyl,
4-hydroxymethylbenzoate-4'-hydroxymethylanilide,
4,4'-bis(hydroxymethyl)phenyl urea, 4,4'-bis(hydroxymethyl)phenyl
urethane, 1,8-bis(hydroxymethyl)anthracene,
4,4'-bis(hydroxymethyl)biphenyl,
2,2'-dimethyl-4,4'-bis(hydroxymethyl)biphenyl,
2,2-bis(4-hydroxymethylphenyl)propane, ethylene glycol, diethylene
glycol, triethylene glycol, tetraethylene glycol, propylene glycol,
dipropylene glycol, tripropylene glycol and tetrapropylene
glycol.
[0653] Examples of the aforementioned alkoxymethyl compound include
2,6-bis(methoxymethyl)-p-cresol,
2,6-bis(methoxymethyl)-4-ethylphenol,
2,6-bis(methoxymethyl)-4-propylphenol,
2,6-bis(methoxymethyl)-4-n-butylphenol,
2,6-bis(methoxymethyl)-4-t-butylphenol,
2,6-bis(methoxymethyl)-4-methoxyphenol,
2,6-bis(methoxymethyl)-4-ethoxyphenol,
2,6-bis(methoxymethyl)-4-propoxyphenol,
2,6-bis(methoxymethyl)-4-n-butoxyphenol,
2,6-bis(methoxymethyl)-4-t-butoxyphenol, 1,3-bis(methoxymethyl)
urea, 2,2-bis(methoxymethyl) butyric acid,
2,2-bis(methoxymethyl)-5-norbornene,
2,3-bis(methoxymethyl)-5-norbornene,
1,4-bis(methoxymethyl)cyclohexane,
1,4-bis(methoxymethyl)cyclohexene,
1,6-bis(methoxymethyl)adamantane, 1,4-bis(methoxymethyl)benzene,
1,3-bis(methoxymethyl)benzene,
2,6-bis(methoxymethyl)-1,4-dimethoxybenzene,
2,3-bis(methoxymethyl)naphthalene,
2,6-bis(methoxymethyl)naphthalene,
1,8-bis(methoxymethyl)anthracene, 2,2'-bis(methoxymethyl)diphenyl
ether, 4,4'-bis(methoxymethyl)diphenyl ether,
4,4'-bis(methoxymethyl)diphenyl thioether,
4,4'-bis(methoxymethyl)benzophenone,
4-methoxymethylbenzoate-4'-methoxymethylphenyl,
4-methoxymethylbenzoate-4'-methoxymethylanilide,
4,4'-bis(methoxymethyl)phenyl urea, 4,4'-bis(methoxymethyl)phenyl
urethane, 1,8-bis(methoxymethyl)anthracene,
4,4'-bis(methoxymethyl)biphenyl,
2,2'-dimethyl-4,4'-bis(methoxymethyl)biphenyl,
2,2-bis(4-methoxymethylphenyl)propane, ethylene glycol dimethyl
ether, diethylene glycol dimethyl ether, triethylene glycol
dimethyl ether, tetraethylene glycol dimethyl ether, propylene
glycol dimethyl ether, dipropylene glycol dimethyl ether,
tripropylene glycol dimethyl ether and tetrapropylene glycol
dimethyl ether.
[0654] Examples of the aforementioned diene compound include
butadiene, pentadiene, hexadiene, heptadiene, octadiene,
3-methyl-1,3-butadiene, 1,3-butanediol dimethacrylate,
2,4-hexadien-1-ol, methylcyclohexadiene, cyclopentadiene,
cyclohexadiene, cycloheptadiene, cyclooctadiene, dicyclopentadiene,
1-hydroxydicyclopentadiene, 1-methylcyclopentadiene,
methyldicyclopentadiene, diallyl ether, diallyl sulfide, diallyl
adipate, 2,5-norbornadiene, tetrahydroindene,
5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, triallyl
cyanurate, diallyl isocyanurate, triallyl isocyanurate and
diallylpropyl isocyanurate.
[0655] Examples of the aforementioned haloalkyl compound include
xylene dichloride, bis(chloromethyl)dimethoxybenzene,
bis(chloromethyl)durene, bis(chloromethyl)biphenyl,
bis(chloromethyl)biphenyl carboxylic acid,
bis(chloromethyl)biphenyl dicarboxylic acid,
bis(chloromethyl)methylbiphenyl, bis(chloromethyl)dimethylbiphenyl,
bis(chloromethyl)anthracene, ethylene glycol bis(chloroethyl)
ether, diethylene glycol bis(chloroethyl) ether, triethylene glycol
bis(chloroethyl) ether and tetraethylene glycol bis(chloroethyl)
ether.
[0656] Although the phenol resin (A) can be obtained by condensing
the previously described phenol compound and copolymer component by
dehydrating, dehydrohalogenating or dealcoholizing, or by
copolymerizing while cleaving unsaturated bonds, a catalyst may
also be used during polymerization. Examples of acid catalysts
include hydrochloric acid, sulfuric acid, nitric acid, phosphoric
acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic
acid, dimethyl sulfate, diethyl sulfate, acetic acid, oxalic acid,
1-hydroxyethylidene-1,1'-diphosphonic acid, zinc acetate, boron
trifluoride, boron trifluoride-phenol complex and boron
trifluoride-ether complex. On the other hand, examples of alkaline
catalysts include lithium hydroxide, sodium hydroxide, potassium
hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate,
triethylamine, pyridine, 4-N,N-dimoethylaminopyridine, piperidine,
piperazine, 1,4-diazabicyclo[2.2.2]octane,
1,8-diazabicyclo[5.4.0]-7-undecene,
1,5-diazabicyclo[4.3.0]-5-nonene, ammonia and
hexamethylenetetramine.
[0657] The amount of catalyst used to obtain a phenol resin having
a repeating structure represented by general formula (46) is
preferably within the range of 0.01 mol % to 100 mol % based on 100
mol % for the total number of moles of the copolymer component
(namely, component other than the phenol compound), and preferably
the total number of moles of an aldehyde compound, ketone compound,
methylol compound, alkoxymethyl compound, diene compound and
haloalkyl compound.
[0658] Normally, the reaction temperature during the synthesis
reaction of the phenol resin (A) is preferably within the range of
40.degree. C. to 250.degree. C. and more preferably 100.degree. C.
to 200.degree. C., while generally the reaction time is preferably
1 hour to 10 hours. A solvent capable of adequately dissolving the
resin can be used as necessary.
[0659] Furthermore, the phenol resin having a repeating structure
represented by general formula (46) may also be that obtained by
further polymerizing a phenol compound that is not a raw material
of the structure represented by the aforementioned general formula
(7) within a range that does not impair the effects of the present
invention. A range that does not impair the effects of the present
invention refers to, for example, being 30% or less of the total
number of moles of phenol compound serving as raw material of
phenol resin (A).
[0660] (Phenol Resin Modified with Compound Having Unsaturated
Hydrocarbon Group Having 4 to 100 Carbon Atoms)
[0661] A phenol resin modified with a compound having an
unsaturated hydrocarbon group having 4 to 100 carbon atoms is the
reaction product of the reaction product of phenol or a derivative
thereof and a compound having an unsaturated hydrocarbon group
having 4 to 100 carbon atoms (which also may be simply referred to
as the "unsaturated hydrocarbon group-containing compound"
depending on the case) (and this reaction product may also be
referred to as the "unsaturated hydrocarbon group-modified phenol
derivative") and the polycondensation product with an aldehyde or a
phenol compound and an unsaturated hydrocarbon group-containing
compound.
[0662] A phenol derivative the same as that previously described as
a raw material of the phenol resin having a repeating unit
represented by general formula (46) can be used for the phenol
derivative.
[0663] The unsaturated hydrocarbon group of the unsaturated
hydrocarbon group-containing compound preferably contains two or
more unsaturated groups from the viewpoint of residual stress of
the cured film and applicability to reflow treatment. In addition,
the unsaturated hydrocarbon group preferably has 4 to 100 carbon
atoms, more preferably 8 to 80 carbon atoms, and even more
preferably 10 to 60 carbon atoms from the viewpoints of
compatibility when in the form of a resin composition and residual
stress of the cured film.
[0664] Examples of the unsaturated hydrocarbon group-containing
compound include unsaturated hydrocarbon groups having 4 to 100
carbon atoms, polybutadiene having a carboxyl group, epoxidated
polybutadiene, linoleyl alcohol, oleyl alcohol, unsaturated fatty
acids and unsaturated fatty acid esters. Preferable examples of
unsaturated fatty acids include crotonic acid, myristoleic acid,
palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic
acid, erucic acid, nervonic acid, linoleic acid, .alpha.-linolenic
acid, oleostearic acid, stearidonic acid, arachidonic acid,
eisocapentaenoic acid, clupanodonic acid and docosahexaenoic acid.
Among these, unsaturated fatty acid esters in the form of vegetable
oils are particularly preferable from the viewpoints of elongation
of the cured film and flexibility of the cured film.
[0665] Vegetable oils normally include esters of glycerin and
unsaturated fatty acids and consist of non-drying oils having an
iodine value of 100 or lower, semi-drying oils having an iodine
value of greater than 100 to less than 130, and drying oils having
an iodine value of 130 or higher. Examples of non-drying oils
include olive oil, morning glory seed oil, cashew nut oil, sasanqua
oil, camellia oil, castor oil and peanut oil. Examples of
semi-drying oils include corn oil, cottonseed oil and sesame oil.
Examples of drying oils include tung oil, linseed oil, soybean oil,
walnut oil, safflower oil, sunflower oil, perilla oil and mustard
oil. In addition, processed vegetable oils, obtained by processing
these vegetable oils, may also be used.
[0666] Among the aforementioned vegetable oils, a non-drying oil is
preferably used in the reaction between the phenol, phenol
derivative or phenol resin and the vegetable oil from the
viewpoints of improving yield and preventing gelation resulting
from the reaction proceeding excessively rapidly. On the other
hand, a drying oil is used preferably from the viewpoint of
improving adhesion with a resist pattern, mechanical properties and
thermal shock resistance. Among these drying oils, tung oil,
linseed oil, soybean oil, walnut oil or safflower oil is
preferable, and tung oil and linseed oil are more preferable, since
they allow the effects of the present invention to be demonstrated
more effectively and more reliably. One type of these oils is used
alone or two or more types are used in combination.
[0667] The reaction between the phenol or phenol derivative and the
unsaturated hydrocarbon group-containing compound is preferably
carried out at 50.degree. C. to 130.degree. C. The reaction ratio
between the phenol or phenol derivative and unsaturated hydrocarbon
group-containing compound is such that preferably 1 part by weight
to 100 parts by weight, and more preferably 5 parts by weigh to 50
parts by weight, of the unsaturated hydrocarbon group-containing
compound is used based on 100 parts by weight of the phenol or
phenol derivative from the viewpoint of lowering residual stress of
the cured film. If the amount of the unsaturated hydrocarbon
group-containing compound is less than 1 part by weight,
flexibility of the cured film tends to decrease, while if that
amount exceeds 100 parts by weight, heat resistance of the cured
film tends to decrease. In the aforementioned reaction, a catalyst
such as p-toluenesulfonic acid or trifluoromethanesulfonic acid may
be used as necessary.
[0668] A phenol resin modified by an unsaturated hydrocarbon
group-containing compound is formed by polycondensation of the
unsaturated hydrocarbon group-modified phenol derivative formed
according to the aforementioned reaction and an aldehyde. The
aldehyde is selected from, for example, formaldehyde,
acetoaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde,
methoxybenzaldehyde, hydroxyphenylacetoaldehyde,
methoxyphenylacetoaldehyde, crotonaldehyde, chloroacetoaldehyde,
chlorophenylacetoaldehyde, acetone, glyceraldehyde, glyoxylic acid,
methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate,
formyl acetate, methyl formyl acetate, 2-formylpropionate, methyl
2-formylpropionate, pyruvic acid, levulinic acid, 4-acetyl
butyrate, acetonedicarboxylic acid and 3,3',4,4'-benzophenone
tetracarboxylic acid. In addition, a precursor of formaldehyde,
such as paraformaldehyde or trioxane may also be used. One type of
these aldehydes is used alone or two or more types are used in
combination.
[0669] The reaction between the aforementioned aldehyde and the
aforementioned unsaturated hydrocarbon group-modified phenol
derivative is a polycondensation reaction, and conventionally known
conditions for synthesizing phenol resins can be used. The reaction
is preferably carried out in the presence of a catalyst such as an
acid or base, and an acid catalyst is used preferably from the
viewpoint of the degree of polymerization (molecular weight) of the
resin. Examples of acid catalysts include hydrochloric acid,
sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid and
oxalic acid. One type of these acid catalysts can be used alone or
two or more types can be used in combination.
[0670] The aforementioned reaction is preferably carried out at a
normal reaction temperature of 100.degree. C. to 120.degree. C. In
addition, although varying according to the type and amount of
catalyst used, the reaction time is normally 1 hour to 50 hours.
Following completion of the reaction, the reaction product is
subjected to vacuum dehydration at a temperature of 200.degree. C.
or lower to obtain a phenol resin modified by an unsaturated
hydrocarbon group-containing compound. Furthermore, a solvent such
as toluene, xylene or methanol can be used in the reaction.
[0671] The phenol resin modified by an unsaturated hydrocarbon
group-containing compound can also be obtained by polycondensing
the previously described unsaturated hydrocarbon group-modified
phenol derivative with an aldehyde together with a compound other
than phenol in the manner of m-xylene. In this case, the charged
molar ratio of the compound other than phenol to the compound
obtained by reacting the phenol derivative and unsaturated
hydrocarbon group-containing compound is preferably less than
0.5.
[0672] The phenol modified with an unsaturated hydrocarbon
group-containing compound can also be obtained by reacting a phenol
resin with an unsaturated hydrocarbon group-containing compound.
The phenol resin used in this case is a polycondensation product of
a phenol compound (namely, phenol and/or phenol derivative) and an
aldehyde. In this case, the same phenol derivatives and aldehydes
as those previously described can be used for the phenol derivative
and aldehyde, and phenol resin can be synthesized under
conventionally known conditions as previously described.
[0673] Specific examples of phenol resins obtained from a phenol
compound and aldehyde that are preferably used to form the phenol
resin modified with an unsaturated hydrocarbon group-containing
compound include phenol/formaldehyde novolac resin,
cresol/formaldehyde novolac resin, xylenol/formaldehyde novolac
resin, resorcinol/formaldehyde novolac resin and
phenol-naphthol/formaldehyde novolac resin.
[0674] The same unsaturated hydrocarbon group-containing compound
as that previously described with respect to producing an
unsaturated hydrocarbon group-modified phenol derivative that
reacts with an aldehyde can be used for the unsaturated hydrocarbon
group-containing compound that reacts with aldehyde.
[0675] Normally, the reaction between the phenol resin and
unsaturated hydrocarbon group-containing compound is preferably
carried out at 50.degree. C. to 130.degree. C. In addition, the
reaction ratio between the phenol resin and unsaturated hydrocarbon
group-containing compound is such that preferably 1 part by weight
to 100 parts by weight, more preferably 2 parts by weight to 70
parts by weight, and even more preferably 5 parts by weight to 50
parts by weight of the unsaturated hydrocarbon group-containing
compound, are used with respect to 100 parts by weight of the
phenol resin, from the viewpoint of improving flexibility of the
cured film (resist pattern). If the amount of the unsaturated
hydrocarbon group-containing compound is less than 1 part by
weight, flexibility of the cured film tends to decrease, while if
that amount exceeds 100 parts by weight, the possibility of gelling
during the reaction tends to increase and heat resistance of the
cured film tends to decrease. A catalyst such as p-toluenesulfonic
acid or trifluoromethanesulfonic acid may be used during the
reaction between the phenol resin and unsaturated hydrocarbon
group-containing compound as necessary. Furthermore, although
subsequently described in detail, a solvent such as toluene,
xylene, methanol or tetrahydrofuran can be used in the
reaction.
[0676] An acid-modified phenol resin can also be used by allowing
polybasic acid anhydride to further react with phenolic hydroxyl
groups remaining in the phenol resin modified by an unsaturated
hydrocarbon group-containing compound formed according to the
method described below. Acid modification with a polybasic acid
anhydride results in the introduction of a carboxyl group, thereby
further improving solubility in an aqueous alkaline solution (used
as developer).
[0677] There are no particular limitations on the polybasic acid
anhydride provided it has an acid anhydride group formed by
dehydration condensation of the carboxyl groups of a polybasic acid
having a plurality of carboxyl groups. Examples of polybasic acid
anhydrides include dibasic acid anhydrides such as phthalic
anhydride, succinic anhydride, octenylsuccinic anhydride,
pentadodecenylsuccinic anhydride, maleic anhydride, itaconic
anhydride, tetrahydrophthalic anhydride, hexahydrophthalic
anhydride, methyl tetrahydrophthalic anhydride, methyl
hexahydrophthalic anhydride, nadic anhydride,
3,6-endomethylenetetrahydrophthalic anhydride, methyl
endomethylenetetrahydrophthalic anhydride, tetrabromophthalic
anhydride or trimellitic anhydride, and aromatic tetrabasic acid
dianhydrides such as biphenyltetracarboxylic dianhydride,
naphthalene tetracarboxylic dianhydride, diphenyl ether
tetracarboxylic dianhydride, butane tetracarboxylic dianhydride,
cyclopentane tetracarboxylic dianhydride, pyromellitic anhydride or
benzophenone tetracarboxylic dianhydride. One type of these
compounds may be used alone or two or more types may be used in
combination. Among these, the polybasic acid anhydride is
preferably a dibasic acid anhydride, and more preferably one or
more types selected from the group consisting tetrahydrophthalic
anhydride, succinic anhydride and hexahydrophthalic anhydride. In
this case, there is the advantage of allowing the formation of a
resist pattern having a more favorable form.
[0678] The reaction between a phenolic hydroxyl group and polybasic
acid anhydride can be carried out at 50.degree. C. to 130.degree.
C. In this reaction, preferably 0.10 moles to 0.80 moles, more
preferably 0.15 moles to 0.60 moles, and even more preferably 0.20
moles to 0.40 moles of the polybasic acid anhydride are reacted for
1 mole of phenolic hydroxyl groups. If the amount of the polybasic
acid anhydride is less than 0.10 moles, developability tends to
decrease, while if the amount exceeds 0.80 moles, the alkaline
resistance of unexposed portions tends to decrease.
[0679] Furthermore, in the aforementioned reaction, a catalyst may
be contained as necessary from the viewpoint of carrying out the
reaction rapidly. Examples of catalysts include tertiary amines
such as triethylamine, quaternary ammonium salts such as
triethylbenzyl ammonium chloride, imidazole compounds such as
2-ethyl-4-methylimidazole and phosphorous compounds such as
triphenylphosphine.
[0680] The acid value of the phenol resin further modified with a
polybasic acid anhydride is preferably 30 mgKOH/g to 200 mgKOH/g,
more preferably 40 mgKOH/g to 170 mgKOH/g, and even more preferably
50 mgKOH/g to 150 mgKOH/g. If the acid value is lower than 30
mgKOH/g, a longer amount of time tends to be required for alkaline
development in comparison with the case of the acid value being
within the aforementioned ranges, while if the acid value exceeds
200 mgKOH/g, resistance to developer of unexposed portions tends to
decrease in comparison with the case of the acid value being within
the aforementioned ranges.
[0681] The molecular weight of the phenol resin modified with the
unsaturated hydrocarbon group-containing compound is such that the
weight average molecular weight is preferably 1,000 to 100,000 and
more preferably 2,000 to 100,000 in consideration of solubility in
an aqueous alkaline solution and the balance between
photosensitivity and cured film properties.
[0682] The phenol resin (A) of the present embodiment is preferably
a mixture of at least one type of phenol resin selected from a
phenol resin having a repeating unit represented by the
aforementioned general formula (46) and a phenol resin modified
with the aforementioned compound having 4 to 100 carbon atoms and
an unsaturated hydrocarbon group (to be referred to as resin (a3)),
and a phenol resin selected from novolac resin and
polyhydroxystyrene (to be referred to as resin (a4)). The mixing
ratio between the resin (a3) and the resin (a4) in terms of the
weight ratio thereof is such that the ratio of (a3)/(a4) is within
the range of 5/95 to 95/5. This mixing ratio of (a3)/(a4) is
preferably 5/95 to 95/5, more preferably 10/90 to 90/10 and even
more preferably 15/85 to 85/15 from the viewpoints of solubility in
an aqueous alkaline solution, sensitivity and resolution when
forming a resist pattern, residual stress of the cured film, and
applicability to reflow treatment. Those resins indicated in the
previous sections describing novolac resin and polyhydroxystyrene
can be used for the novolac resin and polyhydroxystyrene of the
aforementioned resin (a4).
[0683] (B) Photosensitizer
[0684] The following provides an explanation of the photosensitizer
(B) used in the present invention. The photosensitizer (B) differs
according to whether the photosensitive resin composition of the
present invention is of the negative type in which, for example, a
polyimide precursor and/or polyamide is mainly used for the resin
(A), or is of the positive type in which, for example, at least one
type of polyoxazole precursor, soluble polyimide and phenol resin
is mainly used for the resin (A).
[0685] The incorporated amount of the photosensitizer (B) in the
photosensitive resin composition is 1 part by weight to 50 parts by
weight based on 100 parts by weight of resin (A). The
aforementioned incorporated amount is 1 part by weight or more from
the viewpoint of photosensitivity or patterning properties, and is
50 parts by weight or less from the viewpoint curability of the
photosensitive resin composition or physical properties of the
photosensitive resin layer after curing.
[0686] [Negative-Type Photosensitizer (B): Photopolymerization
Initiator and/or Photoacid Generator]
[0687] First, an explanation is provided of the case of desiring a
negative type. In this case, a photopolymerization initiator and/or
photoacid generator is used for the photosensitizer (B), the
photopolymerization initiator is preferably a photo-radical
polymerization initiator, and preferable examples thereof include,
but are not limited to, photoacid generators in the manner of
benzophenone derivatives such as benzophenone and benzophenone
derivatives such as methyl o-benzoyl benzoate, 4-benzoyl-4'-methyl
diphenyl ketone, dibenzyl ketone or fluorenone, acetophenone
derivatives such as 2,2'-diethoxyacetophenone,
2-hydroxy-2-methylpropiophenone or 1-hydroxycyclohexyl phenyl
ketone, thioxanthone and thioxanthone derivatives such as
2-methylthioxanthone, 2-isopropylthioxanthone or
diethylthioxanthone, benzyl and benzyl derivatives such as
benzyldimethylketal or benzyl-.beta.-methoxyethylacetal,
[0688] benzoin and benzoin derivatives such as benzoin methyl
ether, oximes such as
1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime,
1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime,
1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime,
1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime,
1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime or
1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, N-arylglycines
such as N-phenylglycine, peroxides such as benzoyl perchloride,
aromatic biimidazoles, titanocenes or
.alpha.-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide. Among
the aforementioned photopolymerization initiators, oximes are more
preferable particularly from the viewpoint of photosensitivity.
[0689] In the case of using a photoacid generator for the
photosensitizer (B) in a negative-type photosensitive resin
composition, in addition to the photoacid generator demonstrating
acidity by irradiating with an active light beam in the manner of
ultraviolet light, due to that action, it has the effect of causing
a crosslinking agent to crosslink with a resin in the form of
component (A) or causing polymerization of crosslinking agents.
Examples of this photoacid generator used include diaryl sulfonium
salts, triaryl sulfonium salts, dialkyl phenacyl sulfonium salts,
diaryl iodonium salts, aryl diazonium salts, aromatic
tetracarboxylic acid esters, aromatic sulfonic acid esters,
nitrobenzyl esters, oxime sulfonic acid esters, aromatic
N-oxyimidosulfonates, aromatic sulfamides, haloalkyl
group-containing hydrocarbon-based compounds, haloalkyl
group-containing heterocyclic compounds and
naphthoquinonediazido-4-sulfonic acid esters. Two or more types of
these compounds can be used in combination or in combination with
other sensitizers as necessary. Among the aforementioned photoacid
generators, aromatic oxime sulfonic acid esters and aromatic
N-oxyimidosulfonates are more preferable from the viewpoint of
photosensitivity in particular.
[0690] The incorporated amount of these photosensitizers is 1 part
by weight to 50 parts by weight, and preferably 2 parts by weight
to 15 parts by weight from the viewpoint of photosensitivity, based
on 100 parts by weight of the resin (A). An incorporated amount of
1 part by weight or more based on 100 parts by weight of the resin
(A) results in superior photosensitivity, while an incorporated
amount of 50 parts by weight or less results in superior thick film
curability.
[0691] Moreover, as was previously described, in the case the resin
(A) represented by general formula (1) is of the ionic bonded type,
a (meth)acrylic compound having an amino group is used to impart
photosensitivity to a side chain of the resin (A) through the ionic
bond. In this case, a (meth)acrylic compound having an amino group
is used for the photosensitizer (B), and as was previously
described, a dialkylaminoalkyl acrylate or methacrylate, such as
dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate,
diethylaminoethyl acrylate, diethylaminoethyl methacrylate,
dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate,
diethylaminopropyl acrylate, diethylaminopropyl methacrylate,
dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate,
diethylaminobutyl acrylate or diethylaminobutyl methacrylate, is
preferable, and among these, a dialkylaminoalkyl acrylate or
methacrylate, in which the alkyl group on the amino group has 1 to
10 carbon atoms and the alkyl chain has 1 to 10 carbon atoms, is
preferable from the viewpoint of photosensitivity.
[0692] The incorporated amount of these (meth)acrylic compounds
having an amino group is 1 part by weight to 20 parts by weight,
and preferably 2 parts by weigh to 15 parts by weight from the
viewpoint of photosensitivity, based on 100 parts by weight of the
resin (A). Incorporating 1 part by weight or more of the
(meth)acrylic compound having an amino group based on 100 parts by
weight of the resin (A) results in superior photosensitivity, while
incorporating 20 parts by weight or less results in superior thick
film curability.
[0693] Next, an explanation is provided of the case of desired a
positive type. In this case, a photoacid generator is used for the
photosensitizer (B), and more specifically, although a diazoquinone
compound, onium salt or halogen-containing compound and the like
can be used, a compound having a diazoquinone structure is
preferable from the viewpoints of solvent solubility and storage
stability.
[0694] [Positive-Type Photosensitizer (B): Compound Having a
Quinone Diazide Group]
[0695] Examples of compounds having a quinone diazide group (to
also be referred to as the "quinone diazide compound (B)") include
compounds having a 1,2-benzoquinone diazide structure and compounds
having a 1,2-naphthquinone diazide structure, and include known
substances described in, for example, U.S. Pat. Nos. 2,772,972,
2,797,213 and 3,669,658. The quinone diazide compound (B) is
preferably at least one type of compound selected from the group
consisting of 1,2-naphtoquinonediazido-4-sulfonic acid esters of
polyhydroxy compounds having a specific structure to be
subsequently described, and 1,2-naphthoquinonediazido-5-sulfonic
acid esters of those polyhydroxy compounds (to also be referred to
as "NQD compounds").
[0696] These NQD compounds are obtained by converting a
naphthoquinonediazidosulfonic acid compound to a sulfonyl chloride
with chlorosulfonic acid or thionyl chloride followed by subjecting
the resulting naphthoquinonediazidosulfonyl chloride to a
condensation reaction with a polyhydroxy compound. For example, an
NQD compound can be obtained by esterifying prescribed amounts of a
polyhydroxy compound and 1,2-naphthoquinonediazido-5-sulfonyl
chloride or 1,2-naphthoquinonediazido-4-sulfonyl chloride in the
presence of a base catalyst such as triethylamine and in a solvent
such as dioxane, acetone or tetrahydrofuran, followed by rinsing
the resulting product with water and drying.
[0697] In the present embodiment, the compound (B) having a quinone
diazide group is preferably a 1,2-naphthoquinonediazido-4-sulfonic
acid ester and/or 1,2-naphthoquinonediazido-5-sulfonic acid ester
of a hydroxy compound represented by the following general formulas
(120) to (124) from the viewpoint of sensitivity and resolution
when forming a resist pattern.
[0698] General formula (120) is as indicated below:
##STR00151##
{wherein, X.sub.11 and X.sub.12 respectively and independently
represent a hydrogen atom or monovalent organic group having 1 to
60 carbon atoms (and preferably 1 to 30 carbon atoms), X.sub.13 and
X.sub.14 respectively and independently represent a hydrogen atom
or monovalent organic group having 1 to 60 carbon atoms (and
preferably 1 to 30 carbon atoms), r1, r2, r3 and r4 respectively
and independently represent an integer of 0 to 5, at least one of
r3 and r4 represents an integer of 1 to 5, (r1+r3).ltoreq.5 and
(r2+r4).ltoreq.5}.
[0699] General formula (121) is as indicated below:
##STR00152##
{wherein, Z represents a tetravalent organic group having 1 to 20
carbon atoms, X.sub.15, X.sub.16, X.sub.17 and X.sub.18
respectively and independently represent a monovalent organic group
having 1 to 30 carbon atoms, r6 represents an integer of 0 or 1,
r5, r7, r8 and r9 respectively and independently represent an
integer of 0 to 3, r10, r11, r12 and r13 respectively and
independently represent an integer of 0 to 2, and r10, r11, r12 and
r13 are not all 0}.
[0700] General Formula (122) is as indicated below:
##STR00153##
{wherein, r14 represents an integer of 1 to 5, r15 represents an
integer of 3 to 8, the (r14.times.r15) number of L respectively and
independently represent a monovalent organic group having 1 to 20
carbon atoms, the r15 number of T.sup.1 and the r15 number of
T.sup.2 respectively and independently represent a hydrogen atom or
monovalent organic group having 1 to 20 carbon atoms}.
[0701] General formula (123) is as indicated below:
##STR00154##
{wherein, A represents a divalent organic group containing an
aliphatic tertiary or quaternary carbon atom, and M represents a
divalent organic group and preferably represents a divalent group
selected from three groups represented by the following chemical
formulas}.
##STR00155##
[0702] Moreover, general formula (124) is as indicated below:
##STR00156##
{wherein, r17, r18, r19 and r20 respectively and independently
represent an integer of 0 to 2, at least one of r17, r18, r19 and
r20 is 1 or 2, X.sub.20 to X.sub.29 respectively and independently
represent a hydrogen atom, halogen atom, or a monovalent group
selected from the group consisting of an alkyl group, alkenyl
group, alkoxy group, allyl group and acyl group, and Y.sub.10,
Y.sub.11 and Y.sub.12 respectively and independently represent a
divalent group selected from the group consisting of a single bond,
--O--, --S--, --SO--, --SO.sub.2--, --CO--, --CO.sub.2--,
cyclopentylidene group, cyclohexylidene group, phenylene group and
divalent organic group having 1 to 20 carbon atoms}.
[0703] In still another embodiment, Y.sub.10 to Y.sub.12 in the
aforementioned general formula (124) are preferably, respectively
and independently selected from three divalent organic groups
represented by the following general formulas:
##STR00157##
{wherein, X.sub.30 and X.sub.31 respectively and independently
represent at least one monovalent group selected from the group
consisting of a hydrogen atom, alkyl group, alkenyl group, aryl
group and substituted aryl group, X.sub.32, X.sub.33, X.sub.34 and
X.sub.35 respectively and independently represent a hydrogen atom
or alkyl group, r21 represents an integer of 1 to 5, and X.sub.35,
X.sub.37, X.sub.38 and X.sub.39 respectively and independently
represent a hydrogen atom or alkyl group}.
[0704] Examples of compounds represented by the aforementioned
general formula (120) include hydroxy compounds represented by the
formulas (125) to (129).
[0705] Formula (125) is as indicated below:
##STR00158##
{wherein, r16 respectively and independently represent an integer
of 0 to 2, X.sub.40 respectively and independently represents a
hydrogen atom or monovalent organic group having 1 to 20 carbon
atoms, in the case a plurality of X.sub.40 are present, X.sub.40
may be mutually the same or different, and X.sub.40 is preferably a
monovalent organic group represented by the following general
formula:
##STR00159##
(wherein, r18 represents an integer of 0 to 2, X.sub.41 represents
a monovalent organic group selected from the group consisting of a
hydrogen atom, alkyl group and cycloalkyl group, and in the case
r18 is 2, the two X.sub.41 may be mutually the same or
different)},
[0706] general formula (126) is as indicated below:
##STR00160##
{wherein, X.sub.42 represents a monovalent organic group selected
from the group consisting of an alkyl group having 1 to 20 carbon
atoms, alkoxy group having 1 to 20 carbon atoms, and cycloalkyl
group having 1 to 20 carbon atoms},
[0707] general formula (127) is as indicated below:
##STR00161##
{wherein, r19 respectively and independently represents an integer
of 0 to 2 and X.sub.43 respectively and independently represents a
hydrogen or a monovalent organic group represented by the following
general formula:
##STR00162##
(wherein, r20 represents an integer of 0 to 2, X.sub.45 is selected
from the group consisting of a hydrogen atom, alkyl group and
cycloalkyl group, and in the case r20 is 2, X.sub.45 may be
mutually the same or different), and X.sub.44 is selected from the
group consisting of a hydrogen atom, alkyl group having 1 to 20
carbon atoms and cycloalkyl group having 1 to 20 carbon atoms},
and
[0708] formula (128) and formula (129) indicate the structures
indicated below.
##STR00163##
[0709] A hydroxy compound represented by the following formulas
(130) to (132) is preferable as a compound represented by the
aforementioned general formula (120) since it has high sensitivity
when in the form of a NQD compound and demonstrates little
precipitation in a photosensitive resin composition.
[0710] The structures of formulas (130) to (132) are as indicated
below.
##STR00164##
[0711] A hydroxy compound represented by the following formula
(133) is preferable as a compound represented by the aforementioned
general formula (126) since it has high sensitivity when in the
form of a NQD compound and demonstrates little precipitation in a
photosensitive resin composition.
##STR00165##
[0712] A hydroxy compound represented by the following formulas
(134) to (136) is preferable as a compound represented by the
aforementioned general formula (77) since it has high sensitivity
when in the form of a NQD compound and demonstrates little
precipitation in a photosensitive resin composition.
[0713] The structures of formulas (134) to (136) are as indicated
below.
##STR00166##
[0714] In the aforementioned general formula (121), although there
are no particular limitations thereon provided it is a tetravalent
organic group having 1 to 20 carbon atoms, Z is preferably a
tetravalent group having a structure represented by the following
general formulas:
##STR00167##
[0715] Among compounds represented by the aforementioned general
formula (121), hydroxy compounds represented by the following
formulas (137) to (140) are preferable since they have high
sensitivity when in the form of a NQD compound and demonstrate
little precipitation in a photosensitive resin composition.
[0716] The structures of formulas (137) to (140) are as indicated
below.
##STR00168##
[0717] A hydroxy compound represented by the following formula
(141):
##STR00169##
{wherein, r40 respectively and independently represents an integer
of 0 to 9} is preferable as a compound represented by the
aforementioned general formula (122) since it has high sensitivity
when in the form of a NQD compound and demonstrates little
precipitation in a photosensitive resin composition.
[0718] Hydroxy compounds represented by the following formulas
(142) and (143) are preferable as compounds represented by the
aforementioned general formula (122) since they have high
sensitivity when in the form of a NQD compound and demonstrate
little precipitation in a photosensitive resin composition.
[0719] The structures of formulas (142) and (143) are as indicated
below.
##STR00170##
[0720] An NQD compound of a hydroxy compound represented by the
following formula (144) is specifically preferable as a compound
represented by the aforementioned general formula (123) since it
has high sensitivity and demonstrates little precipitation in a
photosensitive resin composition.
##STR00171##
[0721] In the case the compound (B) having a quinone diazide group
has a 1,2-naphtoquinonediazidosulfonyl group, this group may be any
of a 1,2-naphthoquinonediazido-5-sulfonyl group or
1,2-naphthoquinonediazido-4-sulfonyl group. Since a
1,2-naphthoquinonediazido-4-sulfonyl group absorbs in the i-line
region of a mercury lamp, it is suitable for exposure by i-line
irradiation. On the other hand, since a
1,2-naphthoquinonediazido-5-sulfonyl group is able to also absorb
in the g-line region of a mercury lamp, it is suitable for exposure
by g-line irradiation.
[0722] In the present embodiment, one or both of a
1,2-naphthoquinonediazido-4-sulfonic acid ester compound and
1,2-naphthoquinonediazido-5-sulfonic acid ester compound are
preferably selected corresponding to the wavelength used during
exposure. In addition, a 1,2-naphthoquinonediazidosulfonic acid
ester compound having a 1,2-naphthoquinonediazido-4-sulfonyl group
and 1,2-naphthoquinonediazido-5-sulfonyl group in the same molecule
can also be used, or a mixture of a
1,2-naphthoquinonediazido-4-sulfonic acid ester compound and a
1,2-naphthoquinonediazido-5-sulfonic acid ester compound can be
used by mixing.
[0723] In the compound (B) having a quinone diazide group, the
average esterification rate of the naphthoquinonediazidosulfonyl
ester of the hydroxy compound is preferably 10% to 100% and more
preferably 20% to 100% from the viewpoint of development
contrast.
[0724] Examples of preferable NQD compounds from the viewpoint of
sensitivity and cured film properties such as elongation include
those represented by the following group of general formulas:
##STR00172##
{wherein, Q represents a hydrogen atom or
naphthoquinonediazidosulfonic acid ester group represented by
either of the following formulas:
##STR00173##
provided that all Q are not simultaneously hydrogen atoms}.
[0725] In this case, a naphthoquinonediazidosulfonyl ester compound
having a 4-naphthoquinonediazidosulfonyl group and
5-naphthoquinonediazidosulfonyl group in the same molecule can be
used as an NQD compound, or 4-naphthoquinonediazidosulfonyl ester
compound and 5-naphthoquinonediazidosulfonyl ester compound can be
used as a mixture.
[0726] Among the naphthoquinonediazidosulfonic acid ester groups
described in the previously described paragraph [0193], a group
represented by the following general formula (145) is particularly
preferable.
##STR00174##
[0727] Examples of the aforementioned onium salt include iodonium
salts, sulfonium salts, phosphonium salts, ammonium salt and
diazonium salts, and is preferably an onium salt selected from the
group consisting of a diaryliodonium salt, triarylsulfonium salt
and trialkylsulfonium salt.
[0728] Examples of the aforementioned halogen-containing compound
include haloalkyl group-containing hydrocarbon compounds, and
trichloromethyltriazine is preferable.
[0729] The incorporated amount of these photoacid generators is 1
part by weight to 50 parts by weight and preferably 5 parts by
weight to 30 parts by weight based on 100 parts by weight of the
resin (A). Patterning properties of the photosensitive resin
composition are preferable if the incorporated amount of the
photoacid generator used for the photosensitizer (B) is 1 part by
weight or more, while the tensile elongation rate of a film after
curing the photosensitive resin composition is favorable and
development residue (scum) of exposed portions is low if the
incorporated amount is 50 parts by weight or less.
[0730] The aforementioned NQD compounds may be used alone or two or
more types may be used as a mixture.
[0731] In the present embodiment, the incorporated amount of the
compound (B) having a quinone diazide group in the photosensitive
resin composition is 0.1 parts by weight to 70 parts by weight,
preferably 1 part by weight to 40 parts by weight, more preferably
3 parts by weight to 30 parts by weight, and even more preferably 5
parts by weight to 30 parts by weight based on 100 parts by weight
of the resin (A). Favorable sensitivity is obtained if the
incorporated amount is 0.1 parts by weight or more, while
mechanical properties of the cured film are favorable if the
incorporated amount is 70 parts by weight or less.
[0732] A solvent can be contained in the negative-type resin
composition of the present embodiment in the form of the previously
described polyimide precursor resin composition and polyamide resin
composition, or in the positive-type photosensitive resin
composition in the form of the polyoxazole resin composition,
soluble polyimide resin composition and phenol resin composition,
for the purpose of dissolving these resins.
[0733] Examples of solvents include amides, sulfoxides, ureas,
ketones, esters, lactones, ethers, halogenated hydrocarbons,
hydrocarbons and alcohols, and examples of which that can be used
include N-methyl-2-pyrrolidone, N,N-dimethylacetoamide,
N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, acetone,
methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone,
cyclohexanone, methyl acetate, ethyl acetate, butyl acetate,
diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate,
.gamma.-butyrolactone, propylene glycol monomethyl ether acetate,
propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol,
tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether,
diethylene glycol dimethyl ether, tetrahydrofuran, morpholine,
dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane,
chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane,
benzene, toluene, xylene and mesitylene. Among these, from the
viewpoint of resin solubility, resin composition stability and
adhesion to a substrate, N-methyl-2-pyrrolidone, dimethylsulfoxide,
tetramethylurea, butyl acetate, ethyl lactate,
.gamma.-butyrolactone, propylene glycol monomethyl ether acetate,
propylene glycol monomethyl ether, diethylene glycol dimethyl
ether, benzyl alcohol, phenyl glycol and tetrahydrofurfuryl alcohol
are preferable.
[0734] Among these solvents, those capable of completely dissolving
the polymer formed are particularly preferable, and examples
thereof include N-methyl-2-pyrroliodone, N,N-dimethylacetoamide,
N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea and
.gamma.-butyrolactone.
[0735] Examples of preferable solvents for the aforementioned
phenol resin include, but are not limited to, bis(2-methoxyethyl)
ether, methyl cellosolve, ethyl cellosolve, propylene glycol
monomethyl ether, propylene glycol monomethyl ether acetate,
diethylene glycol dimethyl ether, dipropylene glycol dimethyl
ether, cyclohexanone, cyclopentanone, toluene, xylene,
.gamma.-butyrolactone and N-methyl-2-pyrrolidone.
[0736] In the photosensitive resin composition of the present
invention, the amount of solvent used is preferably within the
range of 100 parts by weight to 1000 parts by weight, more
preferably 120 parts by weight to 700 parts by weight, and even
more preferably 125 parts by weight to 500 parts by weight based on
100 parts by weight of the resin (A).
[0737] The photosensitive resin composition of the present
invention may further contain other components in addition to the
aforementioned components (A) and (B).
[0738] For example, in the case of forming a cured film on a
substrate composed of copper or copper alloy using the
photosensitive resin composition of the present invention, a
nitrogen-containing heterocyclic compound such as an azole compound
or purine derivative can be optionally incorporated to inhibit
discoloration of the copper.
[0739] Examples of azole compounds include 1H-triazole,
5-methyl-1H-triazole, 5-ethyl-1H-triazole,
4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole,
4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole,
phenyltriazole, p-ethoxyphenyltriazole,
5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole,
hydroxyphenyltriazole, 1,5-dimethyltriazole,
4,5-diethyl-1H-triazole, 1H-benzotriazole,
2-(5-methyl-2-hydroxyphenyl)benzotriazole,
2-[2-hydroxy-3,5-bis(.alpha.,.alpha.-dimethylbenzyl)phenyl]benzotriazole,
2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole,
2-(3-t-butyl-5-methyl-2-hydroxyphenyl)benzotriazole,
2-(3,5-ti-t-amyl-2-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole,
hydroxyphenylbenzotriazole, tolyltriazole,
5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole,
4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole,
1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole,
5-amino-1H-tetrazole and 1-methyl-1H-tetrazole.
[0740] Particularly preferable examples include tolyltriazole,
5-methyl-1H-benzotriazole and 4-methyl-1H-benzotriazole. In
addition, one type of these azole compounds or a mixture of two or
more types may be used.
[0741] Specific examples of purine derivatives include purine,
adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine,
uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine,
2-hydroxyadenine, 2-methyladenine, 1-methyladenine,
N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine,
9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)
adenine, 8-aminoadenine, 6-amino-8-phenyl-9H-purine,
1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine,
N-methylguanine, 7-(2-hydroxyethyl)guanine,
N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine,
5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine,
8-azaxanthine, 8-azahypoxanthine and derivatives thereof.
[0742] The incorporated amount in the case the photosensitive resin
composition contains the aforementioned azole compound or purine
derivative is preferably 0.1 parts by weight to 20 parts by weight,
and more preferably 0.5 parts by weight to 5 parts by weight from
the viewpoint of photosensitivity, based on 100 parts by weight of
the resin (A). In the case the incorporated amount of the azole
compound based on 100 parts by weight of the resin (A) is 0.1 parts
by weight or more, discoloration of the copper or copper alloy
surface is inhibited in the case of having formed the
photosensitive resin composition of the present invention on copper
or copper alloy, while in the case the incorporated amount is 20
parts by weight or less, photosensitivity is superior.
[0743] A hindered phenol compound can be optionally incorporated in
order to inhibit discoloration of the copper surface. Examples of
hindered phenol compounds include, but are not limited to,
2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone,
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
4,4'-methylene-bis(2,6-di-t-butylphenol),
4,4'-thiobis(3-methyl-6-t-butylphenol),
4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylene
glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate],
1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxphenyl)propionate],
N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamide),
2,2'-methylene-bis(4-methyl-6-t-butylphenol),
2,2'-methylene-bis(4-ethyl-6-t-butylphenol),
[0744]
pentaerythryl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate-
], tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate,
1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene,
1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-
-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(-
1H,3H,5H)-trione,
1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(-
1H,3H,5H)-trione,
1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-
-2,4,6-(1H,3H,5H)-trione,
[0745]
1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tri-
azine-2,4,6-(1H,3H,5H)-trione,
1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1-
H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,-
6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-
-2,4,6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4-
,6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-
-2,4,6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-
-2,4,6-(1H,3H,5H)-trione,
[0746]
1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-
-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(-
1H,3H,5H)-trione, and
1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4-
,6-(1H,3H,5H)-trione. Among these,
1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(-
1H,3H,5H)-trione is particularly preferable.
[0747] The incorporated amount of the hindered phenol compound is
preferably 0.1 parts by weight to 20 parts by weight, and more
preferably 0.5 parts by weight to 10 parts by weight from the
viewpoint of photosensitivity, based on 100 parts by weight of the
resin (A). In the case the incorporated amount of the hindered
phenol compound based on 100 parts by weight of the resin (A) is
0.1 parts by weight or more, discoloration and corrosion of the
copper or copper alloy is prevented in the case of, for example,
having formed the photosensitive resin composition of the present
invention on copper or copper alloy, while in the case the
incorporated amount is 20 parts by weight or less, photosensitivity
is superior.
[0748] A crosslinking agent may also be contained in the
photosensitive resin composition of the present invention. The
crosslinking agent can be a crosslinking agent capable of
crosslinking the resin (A) or forming a crosslinked network by
itself when heat-curing a relief pattern formed using the
photosensitive resin composition of the present invention. The
crosslinking is further able to enhance heat resistance and
chemical resistance of a cured film formed from the photosensitive
resin composition.
[0749] Examples of crosslinking agents include compounds containing
a methylol group and/or alkoxymethyl group in the form of Cymel
(Registered Trade Mark) 300, 301, 303, 370, 325, 327, 701, 266,
267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170 or 1174, UFR 65 or
300, and Mycoat 102 or 105 (all manufactured by Mitsui-Cytec),
Nikalac (Registered Trade Mark) MX-270, -280 or -290, Nikalac MS-11
and Nikalac MW-30, -100, -300, -390 or -750 (all manufactured by
Sanwa Chemical Co., Ltd.), DML-OCHP, DML-MBPC, DML-BPC, DML-PEP,
DML-34X, DML-PSBP, DML-PTBP, DML-PCHP, DML-POP, DML-PFP, DML-MBOC,
BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT,
TMOM-BP, TMOM-BPA or TML-BPAF-MF (all manufactured by Honshu
Chemical Industry Co., Ltd.), benzenedimethanol,
bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene,
bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone,
hydroxymethylphenyl hydroxymethyl benzoate,
bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl,
bis(methoxymethyl)benzene, bis(methoxymethyl)cresol,
bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl
ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl
methoxymethyl benzoate, bis(methoxymethyl)biphenyl and
dimethylbis(methoxymethyl)biphenyl.
[0750] In addition, other examples include oxirane compounds in the
form of phenol novolac epoxy resin, cresol novolac epoxy resin,
bisphenol epoxy resin, trisphenol epoxy resin, tetraphenol epoxy
resin, phenol-xylylene epoxy resin, naphthol-xylylene epoxy resin,
phenol-naphthol epoxy resin, phenol-dicyclopentadiene epoxy resin,
alicyclic epoxy resin, aliphatic epoxy resin, diethylene glycol
diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol
diglycidyl ether, trimethylolpropane polyglycidyl ether,
1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether, glycerol
triglycidyl ether, ortho-secondary-butylphenyl glycidyl ether,
1,6-bis(2,3-epoxypropoxy)naphthalene, diglycerol polyglycidyl
ether, polyethylene glycol glycidyl ether, YDB-340, YDB-412,
YDF-2001, YDF-2004 (trade names, all manufactured by Nippon Steel
Chemical Co., Ltd.), NC-3000-H, EPPN-501H, EOCN-1020, NC-7000L,
EPPN-201L, XD-1000, EOCN-4600 (trade names, all manufactured by
Nippon Kayaku Co, Ltd.), Epikote (Registered Trade Mark) 1001,
Epikote 1007, Epikote 1009, Epikote 5050, Epikote 5051, Epikote
1031S, Epikote 180S65, Epikote 157H70, YX-315-75 (trade names, all
manufactured by Japan Epoxy Resins Co., Ltd.), EHPE3150, Placcel
G402, PUE101, PUE105 (trade names, all manufactured by Daicel
Chemical Industries, Ltd.), Epiclon (Registered Trade Mark) 830,
850, 1050, N-680, N-690, N-695, N-770, HP-7200, HP-820,
EXA-4850-1000 (trade names, all manufactured by DIC Corp.), Denacol
(Registered Trade Mark) EX-201, EX-251, EX-203, EX-313, EX-314,
EX-321, EX-411, EX-511, EX-512, EX-612, EX-614, EX-614B, EX-711,
EX-731, EX-810, EX-911, EM-150 (trade names, all manufactured by
Nagase Chemtex Corp.), Epolight (Registered Trade Mark) 70P and
Epolight 100MF (trade names, both manufactured by Kyoeisha Chemical
Co., Ltd.).
[0751] In addition, other examples include isocyanate compounds,
such as 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate,
1,3-phenylene-bismethylene diisocyanate,
cyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate,
hexamethylene diisocyanate, Takenate (Registered Trade Mark) 500,
600, Cosmonate (Registered Trade Mark) NBDI, ND (trade names, all
manufactured by Mitsui Chemicals, Inc.), Duranate (Registered Trade
Mark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X and E402-B80T (trade
names, all manufactured by Asahi Kasei Chemicals Corp.).
[0752] In addition, although other examples include bismaleimide
compounds, such as 4,4'-diphenylmethane bismaleimide, phenylmethane
maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether
bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane
bismaleimide, 4-methyl-1,3-phenylene bismaleimide,
1,6'-bismaleimido-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether
bismaleimide, 4,4'-diphenylsulfide bismaleimide,
1,3-bis(3-maleimidophenoxy)benzene,
1,3-bis(4-maleimidophenoxy)benzene, BMI-1000, BMI-1100, BMI-2000,
BMI-2300, BMI-3000, BMI-4000, BMI-5100, BMI-7000, BMI-TMH, BMI-6000
and BMI-8000 (trade names, all manufactured by Daiwa Kasei Kogyo
Co., Ltd.), they are not limited thereto provided they are
compounds that demonstrate thermal crosslinking in the manner
described above.
[0753] The incorporated amount in the case of using a crosslinking
agent is preferably 0.5 parts by weight to 20 parts by weight and
more preferably 2 parts by weight to 10 parts by weight based on
100 parts by weight of the resin (A). In the case the incorporated
amount is 0.5 parts by weight or more, favorable heat resistance
and chemical resistance are demonstrated, while in the case the
incorporated amount is 20 parts by weight or less, storage
stability is superior.
[0754] The photosensitive resin composition of the present
invention may also contain an organic titanium compound. The
containing of an organic titanium compound allows the formation of
a photosensitive resin layer having superior chemical resistance
even in the case of having cured at a low temperature of about
250.degree. C.
[0755] Examples of organic titanium compounds able to be used for
the organic titanium compound include those in which an organic
chemical substance is bound to a titanium atom through a covalent
bond or ionic bond.
[0756] Specific examples of the organic titanium compound include
following I) to VII):
[0757] I) titanium chelate compounds: titanium chelate compounds
having two or more alkoxy groups are more preferable since they
allow the obtaining of storage stability of a negative-type
photosensitive resin composition as well as a favorable pattern,
and specific examples thereof include titanium
bis(triethanolamine)diisopropoxide, titanium
di(n-butoxide)bis(2,4-pentanedionate), titanium diisopropoxide
bis(2,4-pentanedionate), titanium diisopropoxide
bis(tetramethylheptanedionate) and titanium diisopropoxide
bis(ethylacetoacetate).
[0758] II) Tetraalkoxytitanium compounds: examples thereof include
titanium tetra(n-butoxide), titanium tetraethoxide, titanium
tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium
tetraisopropoxide, titanium tetramethoxide, titanium
tetramethoxypropoxide, titanium tetramethylphenoxide, titanium
tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium
tetrastearyloxide and titanium
tetrakis[bis{2,2-(allyloxymethyl)butoxide}].
[0759] III) Titanocene compounds: examples thereof include titanium
pentamethylcyclopentadienyl trimethoxide,
bis(.eta..sup.5-2,4-cyclopentadien-1-yl) bis(2,6-difluorophenyl)
titanium and bis(.eta..sup.5-2,4-cyclopentadien-1-yl)
bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) titanium.
[0760] IV) Monoalkoxy titanium compounds: examples thereof include
titanium tris(dioctylphosphate)isopropoxide and titanium
tris(dodecylbenzenesulfonate)isopropoxide.
[0761] V) Titanium oxide compounds: examples thereof include
titanium oxide bis(pentanedionate), titanium oxide
bis(tetramethylheptanedionate) and phthalocyanine titanium
oxide.
[0762] VI) Titanium tetraacetylacetonate compounds: examples
thereof include titanium tetraacetylacetonate.
[0763] VII) Titanate coupling agents: examples thereof include
isopropyltridecylbenzenesulfonyl titanate.
[0764] Among these, the organic titanium compound is preferably at
least one type of compound selected from the group consisting of
the aforementioned titanium chelate compounds (I),
tetraalkoxytitanium compounds (II) and titanocene compounds (III)
from the viewpoint of demonstrating more favorable chemical
resistance. Titanium diisopropoxide bis(ethylacetoacetate),
titanium tetra(n-butoxide) and
bis(.eta..sup.5-2,4-cyclopentadien-1-yl)
bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) titanium are
particularly preferable.
[0765] The incorporated amount in the case of incorporating the
organic titanium compound is preferably 0.05 parts by weight to 10
parts by weight and more preferably 0.1 parts by weight to 2 parts
by weight based on 100 parts by weight of the resin (A). In the
case the incorporated amount is 0.05 parts by weight or more,
favorable heat resistance and chemical resistance are demonstrated,
while in the case the incorporated amount is 10 parts by weight or
less, storage stability is superior.
[0766] Moreover, an adhesive assistant can be optionally
incorporated to improve adhesion between a substrate and a film
formed using the photosensitive resin composition of the present
invention. Examples of adhesive assistants include silane coupling
agents such as .gamma.-aminopropyldimethoxysilane,
N-(.beta.-aminoethyl)-.gamma.-aminopropylmethyldimethoxysilane,
.gamma.-glycidoxypropylmethyldimethoxysilane,
.gamma.-mercaptopropylmethyldimethoxysilane,
3-methacryloxypropyldimethoxymethylsilane,
3-methacryloxypropyltrimethoxysilane,
dimethoxymethyl-3-piperidinopropylsilane,
diethoxy-3-glycidoxypropylmethylsilane,
N-(3-diethoxymethylsilylpropyl)succinimide,
N-[3-(triethoxysilyl)propyl]phthalamic acid,
benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic
acid,
benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic
acid, 3-(triethoxysilyl)propylsuccinic anhydride,
N-phenylaminopropyltrimethoxysilane,
3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane or
3-(trialkoxysilyl)propyl succinic anhydride, and aluminum-based
adhesive assistants such as aluminum tris(ethylacetoacetate),
aluminum tris(acetylacetonate) or ethylacetylacetate aluminum
diisopropylate.
[0767] Among these adhesive assistants, silane coupling agents are
more preferable from the viewpoint of adhesive strength. In the
case the photosensitive resin composition contains an adhesive
assistant, the incorporated amount of the adhesive assistant is
preferably within the range of 0.5 parts by weight to 25 parts by
weight based on 100 parts by weight of the resin (A).
[0768] Examples of silane coupling agents include, but are not
limited to, 3-mercaptopropyltrimethoxysilane (KBM803: trade name,
manufactured by Shin-etsu Chemical Co., Ltd., Sila-Ace S810: trade
name, manufactured by Chisso Corp.),
3-mercaptopropyltriethoxysilane (SIM6475.0: trade name,
manufactured by Azmax Corp.), 3-mercaptopropylmethyldimethoxysilane
(LS1375: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.,
SIM6474.0: trade name, manufactured by Azmax Corp.),
mercaptomethyltrimethoxysilane (SIM6473.5C, trade name,
manufactured by Azmax Corp.), mercaptomethylmethyldimethoxysilane
(SIM6473.0, trade name, manufactured by Azmax Corp.),
3-mercaptopropyldiethoxymethoxysilane,
3-mercaptopropylethoxydimethoxysilane,
3-mercaptopropyltripropoxysilane,
3-mercaptopropyldiethoxypropoxysilane,
3-mercaptopropylethoxydipropoxysilane,
3-mercaptopropyldimethoxypropoxysilane,
3-mercaptopropylmethoxydipropoxysilane,
2-mercaptoethyltrimethoxysilane,
2-mercaptoethyldiethoxymethoxysilane,
2-mercaptoethylethoxydimethoxysilane,
2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane,
2-mercaptoethylethoxydipropoxysilane,
2-mercaptoethyldimethoxypropoxysilane,
2-mercaptoethylmethoxydipropoxysilane,
4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane,
4-mercaptobutyltripropoxysilane, N-(3-triethoxysilylpropyl)urea
(LS3610: trade name, Shin-Etsu Chemical Co., Ltd., SIU9055.0, trade
name, manufactured by Azmax Corp.), N-(3-trimethoxysilylpropyl)urea
(SIU9058.0: trade name, manufactured by Azmax Corp.),
N-(3-diethoxymethoxysilylpropyl)urea,
N-(3-ethoxydimethoxysilylpropyl)urea,
N-(3-tripropoxysilylpropyl)urea,
N-(3-diethoxypropoxysilylpropyl)urea,
N-(3-ethoxydipropoxysilylpropyl)urea,
N-(3-dimethoxypropoxysilylpropyl)urea,
N-(3-methoxydipropoxysilylpropyl)urea,
N-(3-trimethoxysilylethyl)urea,
N-(3-ethoxydimethoxysilylethyl)urea,
N-(3-tripropoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea,
N-(3-ethoxydipropoxysilylethyl)urea,
N-(3-dimethoxypropoxysilylethyl)urea,
N-(3-methoxydipropoxysilylethyl)urea,
N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea,
N-(3-tripropoxysilylbutyl)urea,
3-(m-aminophenoxy)propyltrimethoxysilane (SLA0598.0: manufactured
by Azmax Corp.), m-aminophenyltrimethoxysilane (SLA0599.0: trade
name, manufactured by Azmax Corp.), p-aminophenyltrimethoxysilane
(SLA0599.1: trade name, manufactured by Azmax Corp.),
aminophenyltrimethoxysilane (SLA0599.2, trade name, manufactured by
Azmax Corp.), 2-(trimethoxysilylethyl)pyridine (SIT8396.0: trade
name, manufactured by Azmax Corp.),
2-(triethoxysilylethyl)pyridine,
2-(dimethoxysilylmethylethyl)pyridine,
2-(di(ethoxysilylmethylethyl)pyridine,
(3-triethoxysilylpropyl)-t-butylcarbamate,
(3-glycidoxypropyl)triethoxysilane, tetramethoxysilane,
tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane,
tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane,
tetrakis(methoxyethoxysilane), tetrakis(methoxy-n-propoxysilane),
tetrakis(ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane),
bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane,
bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane,
bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane,
bis(triethoxysilyl)octadiene,
bis[3-(triethoxysilyl)propyl]disulfide,
bis[3-(triethoxysilyl)propyl]tetrasulfide,
di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane,
bis(pentadionate)titanium-O,O'-bis(oxyethyl)-aminopropyltriethoxysilane,
phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol,
n-propylphenylsilanediol, isopropylphenylsilanediol,
n-butylphenylsilanediol, isobutylphenylsilanediol,
tert-butylphenylsilanediol, diphenylsilanediol,
dimethoxydiphenylsilane, diethoxydiphenylsilane,
dimethoxy-di-p-tolylsilane, ethylmethylphenylsilanol,
n-propylmethylphenylsilanol, isopropylmethylphenylsilanol,
n-butylmethylphenylsilanol, isobutylmethylphenylsilanol,
tert-butylmethylphenylsilanol, ethyl-n-propylphenylsilanol,
ethylisopropylphenylsilanol, n-butylethylphenylsilanol,
isobutylethylphenylsilanol, tert-butylethylphenylsilanol,
methyldiphenylsilanol, ethyldiphenylsilanol,
n-propyldiphenylsilanol, isopropyldiphenylsilanol,
n-butyldiphenylsilanol, isobutyldiphenylsilanol,
tert-butyldiphenylsilanol and triphenylsilanol. These may be used
alone or in combination.
[0769] Among the aforementioned silane coupling agents,
phenylsilanetriol, trimethoxyphenylsilane,
trimethoxy(p-tolyl)silane, diphenylsilanediol,
dimethoxydiphenylsilane, diethoxydiphenylsilane,
dimethoxy-di-p-tolylsilane, triphenylsilane and silane coupling
agents represented by the following structures:
##STR00175##
are particularly preferable as silane coupling agents.
[0770] 0.01 parts by weight to 20 parts by weight based on 100
parts by weight of the resin (A) is preferable for the incorporated
amount of silane coupling agent in the case of incorporating a
silane coupling agent.
[0771] The photosensitive resin composition of the present
invention may further include other components in addition to those
described above. Preferable examples of these components vary
according to whether a negative-type, using, for example, a
polyimide precursor and polyamide, or positive-type, using a
polyoxazole precursor, polyimide and phenol resin, is used for the
resin (A).
[0772] A sensitizer for improving photosensitivity can be
optionally incorporated in the case of a negative-type using a
polyimide precursor and the like for the resin (A). Examples of
sensitizers include Michler's ketone,
4,4'-bis(diethylamino)benzophenone,
2,5-bis(4'-diethylaminobenzal)cyclopentane,
2,6-bis(4'-diethylaminobenzal)cyclohexanone,
2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone,
4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone,
p-diethylaminocinnamylidene indanone, p-dimethylaminobenzylidene
indanone, 2-(p-dimethylaminophenylbiphenylene)benzothiazole,
2-(p-dimethylaminophenylvinylene)benzothiazole,
2-(p-dimethylaminophenylvinylene)isonaphthothiazole,
1,3-bis(4'-dimethylaminobenzal)acetone,
1,3-bis(4'-diethylaminobenzal)acetone,
3,3'-carbonyl-bis(7-diethylaminocoumarin),
3-acetyl-7-dimethylaminocoumarin,
3-ethoxycarbonyl-7-dimethylaminocoumarin,
3-benzyloxycarbonyl-7-dimethylaminocoumarin,
3-methoxycarbonyl-7-diethylaminocoumarin,
3-ethoxycarbonyl-7-diethylaminocoumarin,
N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine,
N-p-tolyldiethanolamine, N-phenylethanolamine,
4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl
diethylaminobenzoate, 2-mercaptobenzimidazole,
1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole,
2-(p-dimethylaminostyryl)benzoxazole,
2-(p-dimethylaminostyryl)benzothiazole,
2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole and
2-(p-dimethylaminobenzoyl)styrene. These can be used alone or, for
example, 2 to 5 types can be used in combination.
[0773] The incorporated amount of the sensitizer in the case the
photosensitive resin composition contains a sensitizer for
improving photosensitivity is preferably 0.1 parts by weight to 25
parts by weight based on 100 parts by weight of the resin (A).
[0774] In addition, a monomer having a photopolymerizable
unsaturated bond can be optionally incorporated to improve
resolution of a relief pattern. The monomer is preferably a
(meth)acrylic compound that undergoes a radical polymerization
reaction by a photopolymerization initiator, and although not
limited to that indicated below, examples thereof include compounds
such as mono- or diacrylates and methacrylates of ethylene glycol
or polyethylene glycol such as diethylene glycol dimethacrylate or
tetraethylene glycol dimethacrylate, mono- or diacrylates and
methacrylates of propylene glycol or polypropylene glycol, mono-,
di- or triacrylates, methacrylates, cyclohexane diacrylates, and
dimethacrylates of glycerol, diacrylates and dimethacrylates of
1,4-butanediol, diacrylates and dimethacrylates of 1,6-hexanediol,
diacrylates and dimethacrylates of neopentyl glycol, mono- or
diacrylates, methacrylates, benzene trimethacrylates, isobornyl
acrylates and methacrylates, acrylamides and derivatives thereof,
methacrylamides and derivatives thereof and trimethylolpropane
triacrylates and methacrylates of bisphenol A, triacrylates and
methacrylates of glycerol, di- tri- or tetraacrylates and
methacrylates of pentaerythritol, and ethylene oxide or propylene
oxide adducts of these compounds.
[0775] In the case the photosensitive resin composition contains
the aforementioned monomer having a photopolymerizable unsaturated
bond in order to improve the resolution of a relief pattern, the
incorporated amount of the photopolymerizable monomer having an
unsaturated bond is preferably 1 part by weight to 50 parts by
weight based on 100 parts by weight of the resin (A).
[0776] In addition, in the case of a negative type using a
polyimide precursor for the resin (A), a thermal polymerization
inhibitor can be optionally incorporated to improve viscosity and
photosensitivity stability of the photosensitive resin composition
when storing in a state of a solution containing a solvent in
particular. Examples of thermal polymerization inhibitors include
hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol,
phenothiazine, N-phenylnaphthylamine, ethyldiamine tetraacetic
acid, 1,2-cyclohexanediamine tetraacetic acid, glycol ether diamine
tetraacetic acid, 2,6-di-tert-butyl-p-methylphenol,
5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol,
2-nitroso-1-naphthol,
2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol,
N-nitroso-N-phenylhydroxylamine ammonium salt and
N-nitroso-N-(1-naphthyl) hydroxylamine ammonium salt.
[0777] The incorporated amount of the thermal polymerization
inhibitor in the case of incorporating in the photosensitive resin
composition is preferably within the range of 0.005 parts by weight
to 12 parts by weight based on 100 parts by weight of the resin
(A).
[0778] On the other hand, in the case of a positive type using a
polyoxazole derivative for the resin (A) in the photosensitive
resin composition of the present invention, dyes, surfactants,
thermal acid generators, solubility enhancers and adhesive
assistants for enhancing adhesion with a base material
conventionally used as additives of photosensitive resin
compositions can be used as necessary in the photosensitive resin
composition to enhance adhesion with a substrate.
[0779] In providing an even more detailed description of the
aforementioned additives, examples of dyes include methyl violet,
crystal violet and malachite green. In addition, examples of
surfactants include nonionic surfactants composed of polyglycols or
derivatives thereof, such as polypropylene glycol or
polyoxyethylene lauryl ether, examples of which include
fluorine-based surfactants such as Fluorad (trade name, Sumitomo 3M
Ltd.), Megafac (trade name, Dainippon Ink & Chemicals, Inc.) or
Lumiflon (trade name, Asahi Glass Co., Ltd.), and organic siloxane
surfactants such as K2341 (trade name, Shin-Etsu Chemical Co.,
Ltd.), DBE (trade name, Chisso Corp.) or Granol (trade name,
Kyoeisha Chemical Co., Ltd.). Examples of adhesive assistants
include alkylimidazoline, butyric acid, alkyl acid,
polyhydroxystyrene, poly(vinyl methyl ether), t-butyl novolac
resin, epoxysilane and epoxy polymers, as well as various types of
silane coupling agents.
[0780] The incorporated amounts of the aforementioned dyes and
surfactants are preferably 0.01 parts by weight to 30 parts by
weight based on 100 parts by weight of the resin (A).
[0781] In addition, a thermal acid generator can be optionally
incorporated from the viewpoint of demonstrating favorable thermal
properties and mechanical properties of the cured product even in
the case of having lowered the curing temperature.
[0782] A thermal acid generator is preferably incorporated from the
viewpoint of demonstrating favorable thermal properties and
mechanical properties of the cured product even in the case of
having lowered the curing temperature.
[0783] Examples of thermal acid generators include salts formed
from strong acid and base such as onium salts and imidosulfonates
having a function that forms an acid as a result of heating.
[0784] Examples of onium salts include diaryliodonium salts such as
aryldiazonium salt or diphenyliodonium salt, di(alkylaryl)iodonium
salts such as di(t-butylphenyl)iodonium salt, trialkylsulfonium
salts such as trimethylsulfonium salt, dialkylmonoarylsulfonium
salts such as dimethylphenylsulfonium salt,
diarylmonoalkylsulfonium salts such as diphenylmethylsulfonium
salt, and triarylsulfonium salts.
[0785] Among these, di(t-butylphenyl)iodonium salt of
para-toluenesulfonic acid, di(t-butylphenyl)iodonium salt of
trifluoromethanesulfonic acid, trimethylsulfonium salt of
trifluoromethanesulfonic acid, dimethylphenylsulfonium salt of
trifluoromethanesulfonic acid, diphenylmethylsulfonium salt of
trifluoromethanesulfonic acid, di(t-butylphenyl)iodonium salt of
nonafluorobutanesulfonic acid, diphenyliodonium salt of
camphorsulfonic acid, diphenyliodonium salt of ethanesulfonic acid,
dimethylphenylsulfonium salt of benzenesulfonic acid and
dimethylphenylsulfonium salt of toluenesulfonic acid are
preferable.
[0786] In addition, salts such as pyridinium salts formed from
strong acids and bases as indicated below can also be used as salts
formed from strong acid and base in addition to the previously
described onium salts. Examples of strong acids include
arylsulfonic acids in the manner of p-toluenesulfonic acid or
benzenesulfonic acid, perfluoroalkylsulfonic acids in the manner of
camphorsulfonic acid, trifluoromethanesulfonic acid or
nonafluorobutanesulfonic acid, and alkylsulfonic acids in the
manner of methanesulfonic acid, ethanesulfonic acid or
butanesulfonic acid. Examples of bases include pyridines and
alkylpyridines in the manner of 2,4,6-trimethylpyridine, and
N-alkylpyridines and halogenated N-alkylpyridines in the manner of
2-chloro-N-methylpyridine.
[0787] Although imidosulfonates such as naphthoylimidosulfonate or
phthalimidosulfonate can be used as imidosulfonate, there are no
particular limitations thereon provided they are compounds capable
of generating acid in the presence of heat.
[0788] The incorporated amount in the case of using a thermal acid
generator is preferably 0.1 parts by weight to 30 parts by weight,
more preferably 0.5 parts by weight to 10 parts by weight, and even
more preferably 1 part by weight to 5 parts by weight, based on 100
parts by weight of the resin (A).
[0789] In the case of a positive-type photosensitive resin
composition, a solubility enhancer can be used to accelerate
removal of resin that is no longer required following
photosensitization. A compound having a hydroxyl group or carboxyl
group, for example, is preferable. Examples of compounds having a
hydroxyl group include ballast agents used in the previously
described naphthoquinone diazide compounds, along with
para-cumylphenol, bisphenols, resorcinols, linear phenol compounds
such as MtrisPC or MtetraPC, non-linear phenol compounds such
asTrisP-HAP, TrisP-PHBA or TrisP-PA (all manufactured by Honshu
Chemical Industry Co., Ltd.), diphenylmethane having 2 to 5 phenol
substituents, 3,3-diphenylpropane having 1 to 5 phenol
substituents, compounds obtained by reacting
2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane and
5-norbornene-2,3-dicarboxylic anhydride at a molar ratio of 1:2,
compounds obtained by reacting bis(3-amino-4-hydroxyphenyl)sulfone
and 1,2-cyclohexylcarboxylic anhydride at a molar ratio of 1:2,
N-hydroxysuccinimide, N-hydroxyphthalimide and
N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide. Examples of
compounds having a carboxyl group include 3-phenyllactic acid,
4-hydroxyphenyllactic acid, 4-hydroxymandelic acid,
3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid,
2-methoxy-2-(1-naphthyl)propionic acid, mandelic acid, atrolactic
acid, .alpha.-methoxyphenylacetic acid, O-acetylmandelic acid and
itaconic acid.
[0790] The incorporated amount in the case of incorporating a
solubility enhancer is preferably 0.1 parts by weight to 30 parts
by weight based on 100 parts by weight of the resin (A).
[0791] <Method for Producing Rewiring Layer>
[0792] The present invention provides a method for producing a
rewiring layer, comprising: (1) a step for forming a resin layer on
a copper layer by coating the previously described photosensitive
resin composition on copper subjected to surface treatment of the
present invention, (2) a step for exposing the resin layer to
light, (3) a step for forming a relief pattern by developing the
resin layer after exposing to light, and (4) a step for forming a
cured relief pattern by heat-treating the relief pattern. The
following provides an explanation of a typical aspect of each
step.
[0793] (1) Step for forming a resin layer on copper by coating the
photosensitive resin on the copper subjected to surface
treatment
[0794] In the present step, the photosensitive resin composition of
the present invention is coated onto copper that has been subjected
to the surface treatment of the present invention followed by
drying as necessary to form a resin layer. A method conventionally
used to coat photosensitive resin compositions can be used,
examples of which include coating methods using a spin coater, bar
coater, blade coater, curtain coater or screen printer, and
spraying methods using a spray coater.
[0795] A coating film composed of the photosensitive resin
composition can be dried as necessary. A method such as air drying,
or heat drying or vacuum drying using an oven or hot plate, is used
for the drying method. More specifically, in the case of carrying
out air drying or heat drying, drying can be carried out under
conditions consisting of 1 minute to 1 hour at 20.degree. C. to
140.degree. C. The resin layer can be formed on copper in this
manner.
[0796] (2) Step for exposing resin layer to light
[0797] In the present step, the resin layer formed in the manner
described above is exposed to an ultraviolet light source and the
like either directly or through a photomask having a pattern or
reticle using an exposure device such as a contact aligner, mirror
projector or stepper.
[0798] Subsequently, post-exposure baking (PEB) and/or
pre-development baking may be carried out using an arbitrary
combination of temperature and time as necessary for the purpose of
improving photosensitivity and the like. Although the range of
baking conditions preferably consists of a temperature of
40.degree. C. to 120.degree. C. and time of 10 seconds to 240
seconds, the range is not limited thereto provided various
properties of the photosensitive resin composition of the present
invention are not impaired.
[0799] (3) Step for forming relief pattern by developing resin
layer after exposing to light
[0800] In the present step, exposed portions or unexposed portions
of the photosensitive resin layer are developed and removed
following exposure. Unexposed portions are developed and removed in
the case of using a negative-type photosensitive resin composition
(such as in the case of using a polyimide precursor for the resin
(A)), while exposed portions are developed and removed in the case
of using a positive-type photosensitive resin composition (such as
in the case of using a polyoxazole derivative for the resin (A)).
An arbitrary method can be selected and used for the development
method from among conventionally known photoresist development
methods, examples of which include the rotary spraying method,
paddle method and immersion method accompanying ultrasonic
treatment. In addition, post-development baking using an arbitrary
combination of temperature and time may be carried out as necessary
after development for the purpose of adjusting the form of the
relief pattern.
[0801] A good solvent with respect to the photosensitive resin
composition or a combination of this good solvent and a poor
solvent is preferable for the developer used for development. In
the case of a photosensitive resin composition that does not
dissolve in an aqueous alkaline solution, for example, preferable
examples of good solvents include N-methylpyrrolidone,
N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetoamide, cyclopentanone,
cyclohexanone, .gamma.-butyrolactone and
.alpha.-acetyl-.gamma.-butyrolactone, while preferable examples of
poor solvents include toluene, xylene, methanol, ethanol, isopropyl
alcohol, ethyl lactate, propylene glycol methyl ether acetate and
water. In the case of using a mixture of good solvent and poor
solvent, the proportion of poor solvent to good solvent is
preferably adjusted according to the solubility of polymer in the
photosensitive resin composition. In addition, two or more types of
each solvent, such as a combination of several types of each
solvent, can also be used.
[0802] On the other hand, in the case of a photosensitive resin
composition that dissolves in an aqueous alkaline solution, the
developer used for development dissolves and removes an aqueous
alkaline solution-soluble polymer, and typically is an aqueous
alkaline solution having an alkaline compound dissolved therein.
The alkaline compound dissolved in the developer may be either an
inorganic alkaline compound or organic alkaline compound.
[0803] Examples of inorganic alkaline compounds include lithium
hydroxide, sodium hydroxide, potassium hydroxide, diammonium
hydrogen phosphate, dipotassium hydrogen phosphate, disodium
hydrogen phosphate, lithium silicate, sodium silicate, potassium
silicate, lithium carbonate, sodium carbonate, potassium carbonate,
lithium borate, sodium borate, potassium borate and ammonia.
[0804] Examples of organic alkaline compounds include
tetramethylammonium hydroxide, tetraethylammonium hydroxide,
trimethylhydroxyethylammonium hydroxide, methylamine,
dimethylamine, trimethylamine, monoethylamine, diethylamine,
triethylamine, n-propylamine, di-n-propylamine, isopropylamine,
diisopropylamine, methyldiethylamine, dimethylethanolamine,
ethanolamine and triethanolamine.
[0805] A water-soluble organic solvent such as methanol, ethanol,
propanol or ethylene glycol, surfactant, storage stabilizer or
resin dissolution inhibitor and the like can be added in a suitable
amount thereof to the aforementioned aqueous alkaline solution as
necessary. The relief pattern can be formed in the above
manner.
[0806] (4) Step for forming cured relief pattern by heat-treating
relief pattern
[0807] In the present step, the relief pattern obtained by
developing in the manner previously described is converted to a
cured relief pattern by heating. Various methods can be selected
for the heat curing method, examples of which include heating with
a hot plate, heating using an oven, and heating using a
programmable oven that allows the setting of a temperature program.
Heating can be carried out under conditions consisting of, for
example, 30 minutes to 5 hours at 180.degree. C. to 400.degree. C.
Air may be used for the atmospheric gas during heat curing, or an
inert gas such as nitrogen or argon can be used.
[0808] <Semiconductor Device>
[0809] According to the fourth aspect of the present invention, the
present invention also provides a semiconductor device that
contains a rewiring layer obtained according to the method for
producing a rewiring layer of the present invention described
above. The present invention also provides a semiconductor device
containing a semiconductor element in the form of a base material
and a rewiring layer formed according to the aforementioned method
for producing a rewiring layer on the aforementioned base material.
In addition, the present invention can be applied to a method for
producing a semiconductor device that uses a semiconductor element
for the base material and contains the aforementioned method for
producing a wiring pattern as a portion of the process thereof.
Fifth Aspect
[0810] Elements are mounted on printed boards using various methods
corresponding to the purpose. Conventional elements were typically
fabricated by a wire bonding method in which a connection is made
from an external terminal of the element (pad) to a lead frame with
a fine wire. However, with today's current higher element speeds in
which the operating frequency has reached the GHz range,
differences in the wiring lengths of each terminal during mounting
are having an effect on element operation. Consequently, in the
case of mounting elements for high-end applications, it has become
necessary to accurately control the lengths of mounting wires, and
it has become difficult to satisfy this requirement with wire
bonding.
[0811] Thus, flip-chip mounting has been proposed in which, after
having formed a rewiring layer on the surface of a semiconductor
chip and formed a bump (electrode) thereon, the chip is turned over
(flipped) followed by directly mounting on the printed board (see,
for example, Japanese Unexamined Patent Publication No.
2001-338947). As a result of being able to accurately control
wiring distance, this flip-chip mounting is being employed in
elements for high-end applications handling high-speed signals, and
because of its small mounting size, is also being employed in cell
phone applications, thereby resulting in a rapid increase in
demand. In the case of using a material such as polyimide,
polybenzoxazole or phenol resin for flip-chip mounting, the process
goes through a step for forming a metal wiring layer after a
pattern has been formed on the resin layer. The metal wiring layer
is normally formed by roughening the surface of the resin layer by
subjecting to plasma etching, followed by forming a metal layer
serving as the plating seed layer by sputtering at a thickness of 1
.mu.m or less, and then forming the metal wiring layer by
electrolytic plating using this metal layer as an electrode.
Although Ti is typically used for the metal of the seed layer at
this time, Cu is used as the metal of the rewiring layer formed by
electrolytic plating.
[0812] With respect to this metal rewiring layer, the rewired metal
layer and resin layer are required to demonstrate high adhesion.
However, there have conventionally been cases in which adhesion
between the rewiring Cu layer and resin layer decreases due to the
effects of the resin and additives that form the photosensitive
resin composition and the effects of the production method used
when forming the rewiring layer. A decrease in adhesion between the
rewired Cu layer and resin layer results in a decrease in
insulation reliability of the rewiring layer.
[0813] On the other hand, microwaves are electromagnetic waves
having a frequency of 300 MHz to 3 GHz, and when radiated onto a
material, act on permanent dipoles contained in the material,
having the effect of locally generating heat in the material.
Ring-closure imidization of polyamic acid, which conventionally
requiring heating to a high temperature of 300.degree. C. or
higher, is known to proceed at 250.degree. C. or lower by utilizing
this effect (see, for example, Japanese Examined Patent Publication
No. 5121115). However, the effects of microwave radiation on
adhesion between resin and Cu have yet to be determined.
[0814] With the foregoing in view, an object of the fifth aspect of
the present invention is to provide a method for forming a rewiring
layer demonstrating a high level of adhesion with a Cu layer.
[0815] The inventors of the present invention found that, during
the course of curing a specific photosensitive resin composition, a
rewiring layer demonstrating high adhesion between a Cu layer and
resin layer can be obtained by irradiating with microwaves, thereby
leading to completion of the present invention. Namely, the fifth
aspect of the present invention is as indicated below.
[0816] [1] A method for producing a rewiring layer, comprising the
steps of:
[0817] preparing a photosensitive resin composition containing 100
parts by weight of at least one type of resin (A) selected from the
group consisting of polyamic acid ester, novolac resin,
polyhydroxystyrene and phenol resin, and 1 part by weight to 50
parts by weight of a photosensitizer (B) based on 100 parts by
weight of the resin (A),
[0818] forming a photosensitive resin layer on a substrate by
coating the photosensitive resin composition onto the
substrate,
[0819] exposing the photosensitive resin layer to light,
[0820] forming a relief pattern by developing the photosensitive
resin layer after exposing to light, and
[0821] curing the relief pattern by irradiating with
microwaves.
[0822] [2] The method described in [1], wherein the curing by
microwave irradiation is carried out at 250.degree. C. or
lower.
[0823] [3] The method described in [1] or [2], wherein the
substrate is formed from copper or copper alloy.
[0824] [4] The method described in any of [1] to [3], wherein the
photosensitive resin is at least one type of resin selected from
the group consisting of a polyamic acid ester containing a
structure represented by the following general formula (40):
##STR00176##
{wherein, X.sub.1c represents a tetravalent organic group, Y.sub.1c
represents a divalent organic group, n.sub.1c represents an integer
of 2 to 150 and R.sub.1c and R.sub.2c respectively and
independently represent a hydrogen atom, saturated aliphatic group
having 1 to 30 carbon atoms, aromatic group, monovalent organic
group represented by the following general formula (41):
##STR00177##
(wherein, R.sub.3c, R.sub.4c and R.sub.5c respectively and
independently represent a hydrogen atom or organic group having 1
to 3 carbon atoms, and m.sub.1c represents an integer of 2 to 10),
or saturated aliphatic group having 1 to 4 carbon atoms}, novolac
resin, polyhydroxystyrene, and phenol resin represented by the
following general formula (46):
##STR00178##
{wherein, a represents an integer of 1 to 3, b represents an
integer of 0 to 3, 1.ltoreq.(a+b).ltoreq.4, R.sub.12c represents a
monovalent substituent selected from the group consisting of a
monovalent organic group having 1 to 20 carbon atoms, halogen atom,
nitro group and cyano group, a plurality of R.sub.12c may be the
same or different in the case b is 2 or 3, and X.sub.C represents a
divalent organic group selected from the group consisting of a
divalent aliphatic group having 2 to 10 carbon atoms that may or
may not have an unsaturated bond, divalent alicyclic group having 3
to 20 carbon atoms, divalent alkylene oxide group represented by
the following general formula (47):
[Chemical Formula 210]
--C.sub.pH.sub.2pO-- (47)
(wherein, p represents an integer of 1 to 10), and a divalent
organic group with an aromatic ring having 6 to 12 carbon
atoms}.
[0825] [5] The method described in [4], wherein the photosensitive
resin composition contains a phenol resin having a repeating unit
represented by general formula (46), and Xc in general formula (46)
is represented by a divalent group represented by the following
general formula (48):
##STR00179##
{wherein, R.sub.13c, R.sub.14c, R.sub.15c and R.sub.16c
respectively and independently represent a hydrogen atom,
monovalent aliphatic group having 1 to 10 carbon atoms, or
monovalent aliphatic group having 1 to 10 carbon atoms in which all
or a portion of the hydrogen atoms are substituted with fluorine
atoms, n.sub.6c represents an integer of 0 to 4, R.sub.17c in the
case n.sub.5c is an integer of 1 to 4 represents a halogen atom,
hydroxyl group or monovalent organic group having 1 to 12 carbon
atoms, at least one of R.sub.6c is a hydroxyl group, and a
plurality of R.sub.17c may be mutually the same or different in the
case n.sub.6c is an integer of 2 to 4}, and the following general
formula (49):
##STR00180##
{wherein, R.sub.18c, R.sub.19c, R.sub.20c and R.sub.21c
respectively and independently represent a hydrogen atom,
monovalent aliphatic group having 1 to 10 carbon atoms, or
monovalent aliphatic group having 1 to 10 carbon atoms in which all
or a portion of the hydrogen atoms are substituted with fluorine
atoms, and W represents a single bond, or a divalent group selected
from the group consisting of aliphatic group having 1 to 10 carbon
atoms optionally substituted with fluorine atoms, alicyclic group
having 3 to 20 carbon atoms optionally substituted with fluorine
atoms, divalent alkylene oxide group represented by the following
general formula (47):
[Chemical Formula 213]
--C.sub.pH.sub.2pO-- (47)
(wherein, p represents an integer of 1 to 10), and a divalent group
represented by the following formula (50)
##STR00181##
[0826] According to the fifth aspect of the present invention, a
method can be provided for forming a rewiring layer demonstrating
high adhesion between a Cu layer and resin layer by irradiating
with microwaves during the course of curing a specific
photosensitive resin composition.
[0827] <Photosensitive Resin Composition>
[0828] The present invention has as essential components thereof:
(A) 100 parts by weight of at least one type of resin selected from
the group consisting of polyamic acid ester, novolac resin,
polyhydroxystyrene and phenol resin, and (B) 1 part by weight to 50
parts by weight of a photosensitizer based on 100 parts by weight
of the resin (A).
[0829] Resin (A)
[0830] The following provides an explanation of the resin (A) used
in the present invention. The resin (A) of the present invention
has for the main component thereof at least one type of resin
selected from the group consisting of polyamic acid ester, novolac
resin, polyhydroxystyrene and phenol resin. Here, the main
component refers to containing these resins at 60% by weight or
more, and preferably at 80% by weight or more, based on the total
amount of resin. In addition, other resins may be contained as
necessary.
[0831] The weight average molecular weight of these resins as
determined by gel permeation chromatography based on standard
polystyrene conversion is preferably 1,000 or more and more
preferably 5,000 or more from the viewpoints of heat resistance and
mechanical properties following heat treatment. The upper limit is
preferably 100,000 or less, and the case of using in the form of a
photosensitive resin composition, the upper limit is more
preferably 50,000 or less from the viewpoint of solubility with
respect to the developer.
[0832] In the present invention, the resin (A) is a photosensitive
resin in order to form a relief pattern. The photosensitive resin
is a photosensitive resin composition used together with the
photosensitizer (B) to be subsequently described that causes
development by dissolving or not dissolving in the subsequent
development step.
[0833] Polyamic acid ester, novolac resin, polyhydroxystyrene and
phenol resin are used as photosensitive resins, and these
photosensitive resins can be selected corresponding to the desired
application, such as whether a negative-type or positive-type
photosensitive resin composition is prepared together with the
photosensitizer (B) to be subsequently described.
[0834] [Polyamic Acid Ester (A)]
[0835] One example of the most preferable resin (A) from the
viewpoints of heat resistance and photosensitivity in the
photosensitive resin composition of the present invention is a
polyamic acid ester containing a structure represented by the
general formula (40):
##STR00182##
{wherein, X.sub.1c represents a tetravalent organic group, Y.sub.1c
represents a divalent organic group, n.sub.1c represents an integer
of 2 to 150 and R.sub.1c and R.sub.2c respectively and
independently represent a hydrogen atom, monovalent organic group
represented by the following general formula (41):
##STR00183##
(wherein, R.sub.3c, R.sub.4c and R.sub.5c respectively and
independently represent a hydrogen atom or organic group having 1
to 3 carbon atoms, and m.sub.1c represents an integer of 2 to 10),
or saturated aliphatic group having 1 to 4 carbon atoms}. The
polyamic acid ester is converted to a polyimide by subjecting to
cyclization treatment by heating (at, for example, 200.degree. C.
or higher). Thus, polyamic acid esters are also referred to as
polyimide precursors. Polymide precursors are preferable for use in
negative-type photosensitive resin compositions.
[0836] In the aforementioned general formula (40), the tetravalent
organic group represented by X.sub.1c is preferably an organic
group having 6 to 40 carbon atoms, and more preferably an aromatic
group or alicyclic group having a --COOR.sub.1c group and a
--COOR.sub.2c group at mutually ortho positions with a --CONH--
group from the viewpoint of realizing both heat resistance and
photosensitivity. Examples of the tetravalent organic group
represented by X.sub.1c preferably include, but are not limited to,
organic groups having 6 to 40 carbon atoms containing an aromatic
ring, and more preferably structures represented by the following
formula (90):
##STR00184## ##STR00185##
{wherein R.sub.25b represents a hydrogen atom, fluorine atom or
monovalent group selected from hydrocarbon groups having 1 to 10
carbon atoms and fluorine-containing hydrocarbon groups having 1 to
10 carbon atoms, 1 represents an integer of 0 to 2, m represents an
integer of 0 to 3 and n represents an integer of 0 to 4}. In
addition, the structure of X.sub.1c may be one type or a
combination of two or more types. Group X.sub.1c having a structure
represented by the aforementioned formulas is particularly
preferable from the viewpoint of realizing both heat resistance and
photosensitivity.
[0837] From the viewpoint of realizing both heat resistance and
photosensitivity, examples of the divalent organic group
represented by Y.sub.1c in the aforementioned general formula (40)
preferably include, but are not limited to, aromatic groups having
6 to 40 carbon atoms such as the structures represented by the
following formula (91):
##STR00186## ##STR00187##
{wherein, R.sub.25b represents a hydrogen atom, fluorine atom or
monovalent group selected from hydrocarbon groups having 1 to 10
carbon atoms and fluorine-containing hydrocarbon groups having 1 to
10 carbon atoms, m represents an integer of 0 to 3, and n
represents an integer of 0 to 4}. In addition, the structure of
Y.sub.1c may be one type or a combination of two or more types.
Group Y.sub.1c having a structure represented by the aforementioned
formula (91) is particularly preferable from the viewpoint of
realizing both heat resistance and photosensitivity.
[0838] Group R.sub.3c in the aforementioned general formula (41) is
preferably a hydrogen atom or methyl group, and R.sub.4c and
R.sub.5c are preferably hydrogen atoms from the viewpoint of
photosensitivity. In addition, m.sub.1c is an integer of 2 to 10,
and preferably an integer of 2 to 4, from the viewpoint of
photosensitivity.
[0839] The polyamic acid ester (A) is obtained by first preparing a
partially esterified tetracarboxylic acid (to also be referred to
as an acid/ester form) by reacting a tetracarboxylic dianhydride
containing the aforementioned tetravalent organic group X.sub.1c
with an alcohol having photopolymerizable unsaturated double bond,
and optionally, a saturated aliphatic alcohol having 1 to 4 carbon
atoms, followed by subjecting this to amide polycondensation with a
diamine containing the aforementioned divalent organic group
Y.sub.1c.
[0840] (Preparation of Acid/Ester Form)
[0841] In the present invention, examples of the tetracarboxylic
dianhydride containing the tetravalent organic group X.sub.1c
preferably used to prepare the polyamic acid ester include, but are
not limited to, acid dianhydrides represented by the aforementioned
general formula (90) such as pyromellitic anhydride,
diphenylether-3,3',4,4'-tetracarboxylic dianhydride,
benzophenone-3,3',4,4'-tetracarboxylic dianhydride,
biphenyl-3,3'4,4'-tetracarboxylic dianhydride,
diphenylphosphone-3,3',4,4'-tetracarboxylic dianhydride,
diphenylmethane-3,3'4,4'-tetracarboxylic dianhydride,
2,2-bis(3,4-phthalic anhydride)propane or 2,2-bis(3,4-phthalic
anhydride)-1,1,1,3,3,3-hexafluoropropane, while preferable examples
include, but are not limited to, pyromellitic anhydride,
diphenylether-3,3',4,4'-tetracarboxylic dianhydride,
benzophenone-3,3',4,4'-tetracarboxylic dianhydride and
biphenyl-3,3'4,4'-tetracarboxylic dianhydride. In addition, these
may be used alone or two or more types may be used as a
mixture.
[0842] In the present invention, examples of alcohols having a
photopolymerizable unsaturated double bond preferably used to
prepare the polyamic acid ester include 2-acryloyloxyethyl alcohol,
1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol
vinyl ketone, 2-hydroxyethyl vinyl ketone,
2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butyoxypropyl
acrylate, 2-hydroxy-3-phenoxypropyl acrylate,
2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl
acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate,
2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol,
2-methacrylamidoethyl alcohol, methylol vinyl ketone,
2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxyopropyl
methacrylate, 2-hydroxy-3-butoxypropyl methacrylate,
2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl
methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate and
2-hydroxy-3-cyclohexyloxypropyl methacrylate.
[0843] Saturated aliphatic alcohols having 1 to 4 carbon atoms,
such as methanol, ethanol, n-propanol, isopropanol, n-butanol or
tert-butanol, can be partially mixed and used for the
aforementioned alcohols.
[0844] A desired acid/ester form can be obtained by carrying out an
acid anhydride esterification reaction by dissolving and mixing the
aforementioned preferable tetracarboxylic dianhydride of the
present invention with an aforementioned alcohol in the presence of
a base catalyst such as pyridine and in a solvent to be
subsequently described followed by stirring for 4 to 10 hours at a
temperature of 20.degree. C. to 50.degree. C.
[0845] [Preparation of Polyamic Acid Ester]
[0846] The target polyimide precursor can be obtained by adding a
suitable dehydration condensation agent, such as
dicyclocarbodiimide,
1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline,
1,1-carbonyldioxy-di-1,2,3-benzotriazole or N,N'-disuccinimidyl
carbonate, to the aforementioned acid/ester form (typically in the
form of a solution dissolved in the aforementioned reaction
solvent) while cooling with ice and mixing therewith to convert the
acid/ester form to a polyacid anhydride, and dropping in a solution
or dispersion of a diamine containing the divalent organic group
Y.sub.ip preferably used in the present invention dissolved or
dispersed in a different solvent followed by amide
polycondensation. Alternatively, the target polyimide precursor can
be obtained by converting the acid moiety of the aforementioned
acid/ester form to an acid chloride using thionyl chloride and the
like, followed by reacting with a diamine compound in the presence
of a base such as pyridine.
[0847] Examples of diamines containing the divalent organic group
Y.sub.1c preferably used in the present invention include diamines
represented by the aforementioned general formula (II), and
examples of specific compounds include, but are not limited to,
p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether,
3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether,
4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide,
3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylsulfone,
3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone,
4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl,
4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone,
3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane,
3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane,
1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene,
[0848] 1,3-bis(3-aminophenoxy)benzene,
bis[4-(4-aminophenoxy)phenyl]sulfone,
bis[4-(3-aminophenoxy)phenyl]sulfone,
4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl,
bis[4-(4-aminophenoxy)phenyl] ether, bis[4-(3-aminophenoxy)phenyl]
ether, 1,4-bis(4-aminophenyl)benzene,
1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene,
2,2-bis(aminophenyl)propane,
2,2-bis(4-aminophenyl)hexafluoropropane,
2,2-bis[4-(4-aminophenoxy)phenyl]propane,
2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane,
1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-toluidine sulfone
and 9,9-bis(4-aminophenyl)fluorene, those in which a portion of the
hydrogen atoms on the benzene ring thereof is substituted with a
substituent, such as a methyl group, ethyl group, hydroxymethyl
group, hydroxyethyl group or halogen atom, such as
3,3'-dimethyl-4,4'-diaminobiphenyl,
2,2'-dimethyl-4,4'-diaminobiphenyl,
3,3'-dimethyl-4,4'-diaminodiphenylmethane,
2,2'-dimethyl-4,4'-diaminodiphenylmethane,
3,3'-dimethoxy-4,4'-diaminobiphenyl,
3,3'-dichloro-4,4'-diaminobiphenyl, 2,2'-dimethylbenzidine,
2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl,
2,2'-bis(fluoro)-4,4'-diaminobiphenyl or
4,4'-diaminooctafluorobiphenyl, and preferably p-phenylenediamine,
m-phenylenediamine, 4,4'-diaminodiphenyl ether,
2,2'-dimethylbenzidine,
2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl,
2,2'-bis(fluoro)-4,4'-diaminobiphenyl or
4,4'-diaminooctafluorobiphenyl, and mixtures thereof.
[0849] Diaminosiloxanes such as
1,3-bis(3-aminopropyl)tetramethyldisiloxane or
1,3-bis(3-aminopropyl)tetraphenyldisiloxane can be copolymerized
when preparing the polyamic acid ester for the purpose of improving
adhesion between various types of substrates and a resin layer
formed on the substrate by coating the substrate with the
photosensitive resin composition of the present invention.
[0850] Following completion of the amide polycondensation reaction,
after filtering out absorption byproducts of the dehydration
condensation agent also present in the reaction solution as
necessary, a suitable poor solvent such as water, an aliphatic
lower alcohol or a mixture thereof is added to the resulting
polymer component to precipitate the polymer component followed by
purifying the polymer by repeating re-dissolution and
re-precipitation procedures as necessary and vacuum drying to
isolate the target polyamic acid ester. In order to improve the
degree of purification, a solution of this polymer may be passed
through a column packed with an anion exchange resin and/or cation
exchange resin swollen with a suitable organic solvent to remove
any ionic impurities.
[0851] The molecular weight of the aforementioned polyamic acid
ester in the case of measuring by gel permeation chromatography
based on standard polystyrene conversion is preferably 8,000 to
150,000 and more preferably 9,000 to 50,000. Mechanical properties
are favorable in the case of a weight average molecular weight of
8,000 or more, while dispersibility in developer and resolution of
the relief pattern are favorable in the case of a weight average
molecular weight of 150,000 or less. The use of tetrahydrofuran or
N-methyl-2-pyrrolidone is recommended for the developing solvent
during gel permeation chromatography. In addition, weight average
molecular weight is determined from a calibration curve prepared
using standard monodisperse polystyrene. The standard monodisperse
polystyrene is recommended to be selected from the organic
solvent-based standard sample STANDARD SM-105 manufactured by Showa
Denko K.K.
[0852] (Novolac Resin (A))
[0853] In the present disclosure, novolac resin refers to all
polymers obtained by condensing a phenol and formaldehyde in the
presence of a catalyst. In general, novolac resin can be obtained
by condensing less than 1 mole of formaldehyde to 1 mole of phenol.
Examples of the aforementioned phenols include phenol, o-cresol,
m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol,
o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol,
2,4-xylenol, 2.5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol,
2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol,
pyrogallol, .alpha.-naphthol and .beta.-naphthol. Specific examples
of novolac resins include phenol/formaldehyde condensed novolac
resin, cresol/formaldehyde condensed novolac resin and
phenol-naphthol/formaldehyde condensed novolac resin.
[0854] The weight average molecular weight of the novolac resin is
preferably 700 to 100,000, more preferably 1,500 to 80,000 and even
more preferably 2,000 to 50,000. The weight average molecular
weight is preferably 700 or more from the viewpoint of
applicability to reflow treatment of the cured film, while on the
other hand, the weight average molecular weight is preferably
100,000 or less from the viewpoint of alkaline solubility of the
photosensitive resin composition.
[0855] (Polyhydroxystyrene (A))
[0856] In the present disclosure, polyhydroxystyrene refers to all
polymers containing hydroxystyrene as a polymerized unit. A
preferable example of a polyhydroxystyrene is
poly(para-vinyl)phenol. Poly(para-vinyl)phenol refers to all
polymers containing para-vinyl phenol as a polymerized unit. Thus,
a polymerized unit other than hydroxystyrene (such as para-vinyl
phenol) can be used to compose the hydroxystyrene (such as
poly(para-vinyl)phenol) provided it is not inconsistent with the
object of the present invention. The ratio of the number of moles
of hydroxystyrene units in the polyhydroxystyrene based on the
total number of moles of polymerized units is preferably 10 mol %
to 99 mol %, more preferably 20 mol % to 97 mol %, and even more
preferably 30 mol % to 95 mol %. The case of this ratio being 10
mol % or more is advantageous from the viewpoint of alkaline
solubility of the photosensitive resin composition, while the case
of this ratio being 99 mol % or less is advantageous from the
viewpoint of the applicability of reflow treatment to a cured film
obtained by curing a composition containing a copolymer component
to be subsequently described. A polymerized unit other than a
hydroxystyrene (such as para-vinyl phenol) can be any arbitrary
polymerized unit able to copolymerize with a hydroxystyrene (such
as para-vinyl phenol). Examples of copolymer components that yield
a polymerized unit other than a hydroxystyrene (such as para-vinyl
phenol) include, but are not limited to, esters of acrylic acid
such as methyl acrylate, methyl methacrylate, hydroxyethyl
acrylate, butyl methacrylate, octyl acrylate, 2-ethoxyethyl
methacrylate, t-butyl acrylate, 1,5-pentanediol diacrylate,
N,N-diethylaminoethyl acrylate, ethylene glycol diacrylate,
1,3-propanediol diacrylate, decamethylene glycol diacrylate,
decamethylene glycol dimethacrylate, 1,4-cyclohexanediol
diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate,
tripropylene glycol diacrylate, glycerol triacrylate,
2,2-di-(p-hydroxyphenyl)propane dimethacrylate, triethylene glycol
diacrylate, polyoxyethyl-2,2-di(p-hydroxyphenyl)propane
dimethacrylate, triethylene glycol dimethacrylate,
polyoxypropyltrimethyololpropane triacrylate, ethylene glycol
dimethacrylate, butylene glycol dimethacrylate, 1,3-propanediol
dimethacrylate, 1,2,4-butanetriol trimethacrylate,
2,2,4-trimethyl-1,3-pentanediol dimethacrylate, pentaerythritol
trimethacrylate, 1-phenylethylene-1,2-dimethacrylate,
pentaerythritol tetramethacrylate, trimethylolpropane
trimethacrylate, 1,5-pentanediol dimethacrylate or 1,4-benzenediol
dimethacrylate, styrene, and substituted styrenes in the manner of
2-methylstyrene or vinyltoluene, vinyl ester monomers such as vinyl
acrylate or vinyl methacrylate, and o-vinylphenol and
m-vinylphenol.
[0857] In addition, one type of the novolac resin and
polyhydroxystyrene explained above can be used or two or more types
can be used in combination.
[0858] The weight average molecular weight of the
polyhydroxystyrene is preferably 700 to 100,000, more preferably
1,500 to 80,000 and even more preferably 2,000 to 50,000. The
weight average molecular weight is preferably 700 or more from the
viewpoint of applicability to reflow treatment of the cured film,
while on the other hand, the weight average molecular weight is
preferably 100,000 or less from the viewpoint of alkaline
solubility of the photosensitive resin composition.
[0859] (Phenol Resins (A) Represented by General Formula (46))
[0860] In the present embodiment, the phenol resin (A) preferably
also contains a phenol resin having a repeating unit represented by
the following general formula (46):
##STR00188##
{wherein, a represents an integer of 1 to 3, b represents an
integer of 0 to 3, 1.ltoreq.(a+b).ltoreq.4, R.sub.12c represents a
monovalent substituent selected from the group consisting of a
monovalent organic group having 1 to 20 carbon atoms, halogen atom,
nitro group and cyano group, a plurality of R.sub.12c may be
mutually the same or different in the case b is 2 or 3, and X.sub.C
represents a divalent organic group selected from the group
consisting of a divalent aliphatic group having 2 to 10 carbon
atoms that may or may not have an unsaturated bond, divalent
alicyclic group having 3 to 20 carbon atoms, divalent alkylene
oxide group represented by the following general formula (47):
[Chemical Formula 220]
--C.sub.pH.sub.2pO-- (47)
(wherein, p represents an integer of 1 to 10), and divalent organic
group having an aromatic ring having 6 to 12 carbon atoms}. A
phenol resin having the aforementioned repeating unit can be cured
at a lower temperature in comparison with conventionally used
polyimide resin or polybenzoxazole resin, for example, and is
particularly advantageous from the viewpoint of allowing the
formation of a cured film having favorable elongation. One type of
the aforementioned repeating unit can be present in a phenol resin
molecule or a combination of two or more types can be present.
[0861] In the aforementioned general formula (46), R.sub.12c
represents a monovalent substituent selected from the group
consisting of a monovalent organic group having 1 to 20 carbon
atoms, halogen atom, nitro group and cyano group from the viewpoint
of reactivity when synthesizing a resin according to general
formula (46). From the viewpoint of alkaline solubility, R.sub.12c
preferably represents a monovalent substituent selected from the
group consisting of a halogen atom, nitro group, cyano group,
aliphatic group having 1 to 10 carbon atoms which may or may not
have an unsaturated bond, aromatic group having 6 to 20 carbon
atoms, and the four groups represented by the following general
formula (160):
##STR00189##
{wherein, R.sub.61c, R.sub.62c and R.sub.63c respectively and
independently represent a hydrogen atom, aliphatic group having 1
to 10 carbon atoms which may or may not have an unsaturated bond,
alicyclic group having 3 to 20 carbon atoms or aromatic group
having 6 to 20 carbon atoms, and R.sub.54c represents a divalent
aliphatic group having 1 to 10 carbon atoms which may or may not
have an unsaturated bond, divalent alicyclic group having 3 to 20
carbon atoms, or divalent aromatic group having 6 to 20 carbon
atoms}.
[0862] In the present embodiment, in the aforementioned general
formula (46), although a represents an integer of 1 to 3, a is
preferably 2 from the viewpoints of alkaline solubility and
elongation. In addition, in the case a is 2, the substituted
locations of hydroxyl groups may be any of the ortho, meta or para
positions. In the case a is 3, substituted locations of hydroxyl
groups may be at the 1,2,3-positions, 1,2,4-positions or
1,3,5-positions.
[0863] In the present embodiment, in the aforementioned general
formula (46), since alkaline solubility improves in the case a is
1, a phenol resin selected from a novolac resin and
polyhydroxystyrene (to also be referred to as resin (a2)) can be
further mixed with the phenol resin having a repeating unit
represented by general formula (46) (to also be referred to as
resin (a1)).
[0864] The mixing ratio between resin (a1) and resin (a2) in terms
of the weight ratio thereof is preferably such that (a1)/(a2) is
within the range of 10/90 to 90/10. This mixing ratio is such that
(a1)/(a2) is preferably within the range of 10/90 to 90/10, more
preferably within the range of 20/80 to 80/20, and even more
preferably within the range of 30/70 to 70/30 from the viewpoints
of solubility in an aqueous alkaline solution and elongation of the
cured film.
[0865] The same resins as those indicated in the aforementioned
sections on Novolac Resin and Polyhydroxystyrene can be used for
the novolac resin and polyhydroxystyrene of the aforementioned
resin (a2).
[0866] In the present embodiment, in the aforementioned general
formula (46), although b represents an integer of 0 to 3, b is
preferably 0 or 1 from the viewpoint of alkaline solubility and
elongation. In addition, a plurality of R.sub.12c may be mutually
the same or different in the case b is 2 or 3.
[0867] Moreover, in the present embodiment, in the aforementioned
general formula (46), a and b satisfy the relationship
1.ltoreq.(a+b).ltoreq.4.
[0868] In the present embodiment, in the aforementioned general
formula (46), X.sub.C represents a divalent organic group selected
from the group consisting of a divalent aliphatic group having 2 to
10 carbon atoms that may or may not have an unsaturated bond,
divalent alicyclic group having 3 to 20 carbon atoms, alkylene
oxide group represented by the aforementioned general formula (47)
and divalent organic group having an aromatic ring having 6 to 12
carbon atoms from the viewpoint of the form of a cured relief
pattern and elongation of a cured film. Among these divalent
organic groups, from the viewpoint of film toughness after curing,
X.sub.C preferably represents a divalent organic group selected
from the group consisting of a divalent group represented by the
following general formula (48):
##STR00190##
{wherein, R.sub.13c, R.sub.14c, R.sub.15c and R.sub.16c
respectively and independently represent a hydrogen atom,
monovalent aliphatic group having 1 to 10 carbon atoms or
monovalent aliphatic group having 1 to 10 carbon atoms in which all
or a portion of the hydrogen atoms are substituted with fluorine
atoms, n.sub.6c represents an integer of 0 to 4, and in the case
n.sub.6c represents an integer of 1 to 4, R.sub.17c represents a
halogen atom, hydroxyl group or monovalent organic group having 1
to 12 carbon atoms, at least one of R.sub.17c is a hydroxyl group,
and a plurality of R.sub.17c may be mutually the same or different
in the case n.sub.6c is an integer of 2 to 4}, and a divalent group
represented by the following general formula (49):
##STR00191##
{wherein, R.sub.18c, R.sub.19c, R.sub.20c and R.sub.21c
respectively and independently represent a hydrogen atom,
monovalent aliphatic group having 1 to 10 carbon atoms or
monovalent aliphatic group having 1 to 10 carbon atoms in which all
or a portion of the hydrogen atoms are substituted with fluorine
atoms, W represents a single bond, aliphatic group having 1 to 10
carbon atoms optionally substituted with fluorine atoms, alicyclic
group having 3 to 20 carbon atoms optionally substituted with
fluorine atoms, divalent alkylene oxide group represented by the
following general formula (47):
[Chemical Formula 224]
--C.sub.pH.sub.2pO-- (47)
(wherein, p represents an integer of 1 to 10), and a divalent
organic group selected from the group consisting of divalent groups
represented by the following formula (50)
##STR00192##
[0869] The number of carbon atoms of the aforementioned divalent
organic group having an aromatic ring having 6 to 12 carbon atoms
is preferably 8 to 75 and more preferably 8 to 40. Furthermore, the
structure of the aforementioned divalent organic group having an
aromatic ring having 6 to 12 carbon atoms typically differs from a
structure in the aforementioned general formula (46) in which the
OH group and any R.sub.12c group are bound to the aromatic
ring.
[0870] Moreover, from the viewpoints of pattern formability of a
resin composition and elongation of a cured film after curing, the
divalent organic group represented by the aforementioned general
formula (50) is more preferably a divalent organic group
represented by the following formula (161):
##STR00193##
and particularly preferably a divalent organic group represented by
the following formula (162).
##STR00194##
[0871] Among the structures represented by general formula (46), a
structure in which X.sub.C is represented by the aforementioned
formula (161) or (162) is particularly preferable, the ratio of
sites represented by a structure in which X.sub.C is represented by
formula (161) or formula (162) is preferably 20% by weight or more
and more preferably 30% by weight or more from the viewpoint of
elongation. The aforementioned ratio is preferably 80% by weight or
less, and more preferably 70% by weight or less, from the viewpoint
of alkaline solubility of the composition.
[0872] In addition, among the phenol resins having a structure
represented by the aforementioned general formula (46), a structure
having both a structure represented by the following general
formula (163) and a structure represented by the following general
formula (164) within the same resin backbone is particularly
preferable from the viewpoints of alkaline solubility of the
composition and elongation of a cured film.
[0873] The following general formula (163) is represented by:
##STR00195##
{wherein, R.sub.21c represents a monovalent group having 1 to 10
carbon atoms selected from the group consisting of hydrocarbon
groups and alkoxy groups, n.sub.7c represents an integer of 2 or 3,
n.sub.8c represents an integer of 0 to 2, m.sub.5c represents an
integer of 1 to 500, 2.ltoreq.(n.sub.7c+n.sub.8c).ltoreq.4, and in
the case n.sub.8c is 2, a plurality of R.sub.21c may be mutually
the same or different}, and the following general formula (164) is
represented by:
##STR00196##
{wherein, R.sub.22c and R.sub.23c respectively and independently
represent a monovalent group having 1 to 10 carbon atoms selected
from the group consisting of hydrocarbon groups and alkoxy groups,
n.sub.9c represents an integer of 1 to 3, n.sub.10c represents an
integer of 0 to 2, n.sub.11c represents an integer of 0 to 3,
m.sub.6c represents an integer of 1 to 500,
2.ltoreq.(n.sub.9c+n.sub.10c).ltoreq.4, in the case n.sub.10c is 2,
a plurality of R.sub.22c may be mutually the same or different, and
in the case H.sub.11c is 2 or 3, a plurality of R.sub.23c may be
mutually the same or different}.
[0874] m.sub.5c in the aforementioned general formula (163) and
m.sub.5c in the aforementioned general formula (164) respectively
indicate the total number of repeating units in the main chain of a
phenol resin. Namely, the repeating unit indicated in brackets in
the structure represented by the aforementioned general formula
(163) and the repeating unit indicated in brackets in the structure
represented by the aforementioned general formula (164) in the main
chain of the phenol resin (A) can be arranged randomly, in blocks
or in a combination thereof. m.sub.5c and m.sub.6c respectively and
independently represent an integer of 1 to 500, the lower limit
thereof is preferably 2 and more preferably 3, and the upper limit
thereof is preferably 450, more preferably 400 and even more
preferably 350. m.sub.5c and m.sub.6c are respectively and
independently preferably 2 or more from the viewpoint of film
toughness after curing and preferably 450 or less from the
viewpoint of solubility in an aqueous alkaline solution. The sum of
m.sub.5c and m.sub.6c is preferably 2 or more, more preferably 4 or
more and even more preferably 6 or more from the viewpoint of film
toughness after curing, and preferably 200 or less, more preferably
175 or less and even more preferably 150 or less from the viewpoint
of solubility in an aqueous alkaline solution.
[0875] In the aforementioned phenol resin (A) having both a
structure represented by the aforementioned general formula (163)
and a structure represented by the aforementioned general formula
(164) in the same resin backbone, a higher molar ratio of the
structure represented by general formula (163) results in better
film properties after curing and superior heat resistance, while on
the other hand, a higher molar ratio of the structure represented
by general formula (164) results in better alkaline solubility and
superior pattern form after curing. Thus, the ratio
m.sub.5c/m.sub.6c of the structure represented by general formula
(163) to the structure represented by general formula (164) is
preferably 20/80 or more, more preferably 40/60 or more and
particularly preferably 50/50 or more from the viewpoint of film
properties after curing, and is preferably 90/10 or less, more
preferably 80/20 or less and even more preferably 70/30 or less
from the viewpoint of alkaline solubility and form of the cured
relief pattern.
[0876] A phenol resin having a repeating unit represented by the
aforementioned general formula (46) typically contains a phenol
compound and a copolymer component (and more specifically, one or
more types of compounds selected from the group consisting of a
copolymer component (and more specifically, a compound having an
aldehyde group (including a compound that forms an aldehyde
compound following decomposition in the manner of trioxane), a
compound having a ketone group, a compound having two methylol
groups in a molecule thereof, a compound having two alkoxymethyl
groups in a molecule thereof, and a compound having two haloalkyl
groups in a molecule thereof), and more typically, can be
synthesized by subjecting these monomer components to a
polymerization reaction. For example, a copolymer component such as
an aldehyde compound, ketone compound, methylol compound,
alkoxymethyl compound, diene compound or haloalkyl compound can be
polymerized with a phenol and/or phenol derivative like that
indicated below (to also be collectively referred to as a "phenol
compound") to obtain the phenol resin (A). In this case, the moiety
in the aforementioned general formula (46) represented by a
structure, in which an OH group and an arbitrary R.sub.12c group
are bound to an aromatic ring, is derived from the aforementioned
phenol compound, while the moiety represented by X.sub.C is derived
from the aforementioned copolymer component. The charged molar
ratio between the phenol compound and the aforementioned copolymer
component is such that (phenol compound):(copolymerization
component) is preferably 5:1 to 1.01:1 and more preferably 2.5:1 to
1.1:1 from the viewpoints of controlling the reaction and stability
of the resulting phenol resin (A) and photosensitive resin
composition.
[0877] The weight average molecular weight of the phenol resin
having a repeating unit represented by general formula (46) is
preferably 700 to 100,000, more preferably 1,500 to 80,000, and
even more preferably 2,000 to 50,000. The weight average molecular
weight is preferably 700 or more from the viewpoint of the
applicability to reflow treatment of the cured film, while on the
other hand, the weight average molecular weight is preferably
100,000 or less from the viewpoint of alkaline solubility of the
photosensitive resin composition.
[0878] Examples of phenol compounds that can be used to obtain a
phenol resin having a repeating unit represented by general formula
(46) include cresol, ethylcresol, propylphenol, butylphenol,
amylphenol, cyclohexylphenol, hydroxyphenol, benzylphenol,
nitrobenzylphenol, cyanobenzylphenol, adamantanephenol,
nitrophenol, fluorophenol, chlorophenol, bromophenol,
trifluoromethylphenol,
N-(hydroxyphenyl)-5-norbornene-2,3-dicarboximide,
N-(hydroxyphenyl-5-methyl-5-norbornene-2,3-dicarboximide,
trifluoromethylphenol, hydroxybenzoate, methyl hydroxybenzoate,
ethyl hydroxybenzoate, benzyl hydroxybenzoate, hydroxybenzamide,
hydroxybenzaldehyde, hydroxyacetophenone, hydroxybenzophenone,
hydroxybenzonitrile, resorcinol, xylenol, catechol, methyl
catechol, ethyl catechol, hexyl catechol, benzyl catechol,
nitrobenzyl catechol, methyl resorcinol, ethyl resorcinol, hexyl
resorcinol, benzyl resorcinol, nitrobenzyl resorcinol,
hydroquinone, caffeic acid, dihydroxybenzoate, methyl
dihydroxybenzoate, ethyl dihydroxybenzoate, butyl
dihydroxybenzoate, propyl dihydroxybenzoate, benzyl
dihydroxybenzoate, dihydroxybenzamide, dihydroxybenzaldehyde,
dihydroxyacetophenone, dihydroxybenzophenone,
dihydroxybenzonitrile,
N-(dihydroxyphenyl)-5-norbornene-2,3-dicarboximide,
N-(dihydroxyphenyl)-5-methyl-5-norbornene-2,3-dicarboximide,
nitrocatechol, fluorocatechol, chlorocatechol, bromocatechol,
trifluoromethylcatechol, nitroresorcinol, fluororesorcinol,
chlororesorcinol, bromoresorcinol, trifluoromethylresorcinol,
pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene,
trihydroxybenzoic acid, methyl trihydroxybenzoate, ethyl
trihydroxybenzoate, butyl trihydroxybenzoate, propyl
trihydroxybenzoate, benzyl trihydroxybenzoate, trihydroxybenzamide,
trihydroxybenzaldehyde, trihydroxyacetophenone,
trihydroxybenzophenone and trihydroxybenzonitrile.
[0879] Examples of the aforementioned aldehyde compound include
acetoaldehyde, propionaldehyde, pivalaldehyde, butylaldehyde,
pentanal, hexanal, trioxane, glyoxal, cyclohexylaldehyde,
diphenylacetoaldehyde, ethylbutylaldehyde, benzaldehyde, glyoxylic
acid, 5-norbornene-2-carboxyaldehyde, malondialdehyde,
succindialdehyde, glutaraldehyde, salicylaldehyde, naphthoaldehyde
and terephthalaldehyde.
[0880] Examples of the aforementioned ketone compound include
acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone,
dicyclohexyl ketone, dibenzyl ketone, cyclopentanone,
cyclohexanone, bicyclohexanone, cyclohexanedione, 3-butyn-2-one,
2-norbornanone, adamantanone and
2,2-bis(4-oxocyclohexyl)propane.
[0881] Examples of the aforementioned methylol compound include
2,6-bis(hydroxymethyl)-p-cresol,
2,6-bis(hydroxymethyl)-4-ethylphenol,
2,6-bis(hydroxymethyl)-4-propylphenol,
2,6-bis(hydroxymethyl)-4-n-butylphenol,
2,6-bis(hydroxymethyl)-4-t-butylphenol,
2,6-bis(hydroxymethyl)-4-methoxyphenol,
2,6-bis(hydroxymethyl)-4-ethoxyphenol,
2,6-bis(hydroxymethyl)-4-propoxyphenol,
2,6-bis(hydroxymethyl)-4-n-butoxyphenol,
2,6-bis(hydroxymethyl)-4-t-butoxyphenol,
1,3-bis(hydroxymethyl)urea, ribitol, arabitol, allitol,
2,2-bis(hydroxymethyl)butyric acid, 2-benzyloxy-1,3-propanediol,
2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol,
monoacetin, 2-methyl-2-nitro-1,3-propanediol,
5-norbornene-2,2-dimethanol, 5-norbornene-2,3-dimethanol,
pentaerythritol, 2-phenyl-1,3-propanediol, trimethylolethane,
trimethylolpropane, 3,6-bis(hydroxymethyl)durene,
2-nitro-p-xylylene glycol, 1,10-dihydroxydecane,
1,12-dihydroxydodecane, 1,4-bis(hydroxymethyl)cyclohexane,
1,4-bis(hydroxymethyl)cyclohexene,
1,6-bis(hydroxymethyl)adamantane, 1,4-benzenedimethanol,
1,3-benzenedimethanol, 2,6-bis(hydroxymethyl)-1,4-dimethoxybenzene,
2,3-bis(hydroxymethyl)naphthalene,
2,6-bis(hydroxymethyl)naphthalene,
1,8-bis(hydroxymethyl)anthracene, 2,2'-bis(hydroxymethyl)diphenyl
ether, 4,4'-bis(hydroxymethyl)diphenyl ether,
4,4'-bis(hydroxymethyl)diphenyl thioether,
4,4'-bis(hydroxymethyl)benzophenone,
4-hydroxymethylbenzoate-4'-hydroxymethylphenyl,
4-hydroxymethylbenzoate-4'-hydroxymethylanilide,
4,4'-bis(hydroxymethyl)phenyl urea, 4,4'-bis(hydroxymethyl)phenyl
urethane, 1,8-bis(hydroxymethyl)anthracene,
4,4'-bis(hydroxymethyl)biphenyl,
2,2'-dimethyl-4,4'-bis(hydroxymethyl)biphenyl,
2,2-bis(4-hydroxymethylphenyl)propane, ethylene glycol, diethylene
glycol, triethylene glycol, tetraethylene glycol, propylene glycol,
dipropylene glycol, tripropylene glycol and tetrapropylene
glycol.
[0882] Examples of the aforementioned alkoxymethyl compound include
2,6-bis(methoxymethyl)-p-cresol,
2,6-bis(methoxymethyl)-4-ethylphenol,
2,6-bis(methoxymethyl)-4-propylphenol,
2,6-bis(methoxymethyl)-4-n-butylphenol,
2,6-bis(methoxymethyl)-4-t-butylphenol,
2,6-bis(methoxymethyl)-4-methoxyphenol,
2,6-bis(methoxymethyl)-4-ethoxyphenol,
2,6-bis(methoxymethyl)-4-propoxyphenol,
2,6-bis(methoxymethyl)-4-n-butoxyphenol,
2,6-bis(methoxymethyl)-4-t-butoxyphenol, 1,3-bis(methoxymethyl)
urea, 2,2-bis(methoxymethyl) butyric acid,
2,2-bis(methoxymethyl)-5-norbornene,
2,3-bis(methoxymethyl)-5-norbornene,
1,4-bis(methoxymethyl)cyclohexane,
1,4-bis(methoxymethyl)cyclohexene,
1,6-bis(methoxymethyl)adamantane, 1,4-bis(methoxymethyl)benzene,
1,3-bis(methoxymethyl)benzene,
2,6-bis(methoxymethyl)-1,4-dimethoxybenzene,
2,3-bis(methoxymethyl)naphthalene,
2,6-bis(methoxymethyl)naphthalene,
1,8-bis(methoxymethyl)anthracene, 2,2'-bis(methoxymethyl)diphenyl
ether, 4,4'-bis(methoxymethyl)diphenyl ether,
4,4'-bis(methoxymethyl)diphenyl thioether,
4,4'-bis(methoxymethyl)benzophenone,
4-methoxymethylbenzoate-4'-methoxymethylphenyl,
4-methoxymethylbenzoate-4'-methoxymethylanilide,
4,4'-bis(methoxymethyl)phenyl urea, 4,4'-bis(methoxymethyl)phenyl
urethane, 1,8-bis(methoxymethyl)anthracene,
4,4'-bis(methoxymethyl)biphenyl,
2,2'-dimethyl-4,4'-bis(methoxymethyl)biphenyl,
2,2-bis(4methoxymethylphenyl)propane, ethylene glycol dimethyl
ether, diethylene glycol dimethyl ether, triethylene glycol
dimethyl ether, tetraethylene glycol dimethyl ether, propylene
glycol dimethyl ether, dipropylene glycol dimethyl ether,
tripropylene glycol dimethyl ether and tetrapropylene glycol
dimethyl ether.
[0883] Examples of the aforementioned diene compound include
butadiene, pentadiene, hexadiene, heptadiene, octadiene,
3-methyl-1,3-butadiene, 1,3-butanediol dimethacrylate,
2,4-hexadien-1-ol, methylcyclohexadiene, cyclopentadiene,
cyclohexadiene, cycloheptadiene, cyclooctadiene, dicyclopentadiene,
1-hydroxydicyclopentadiene, 1-methylcyclopentadiene,
methyldicyclopentadiene, diallyl ether, diallyl sulfide, diallyl
adipate, 2,5-norbornadiene, tetrahydroindene,
5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, triallyl
cyanurate, diallyl isocyanurate, triallyl isocyanurate and
diallylpropyl isocyanurate.
[0884] Examples of the aforementioned haloalkyl compound include
xylene dichloride, bis(chloromethyl)dimethoxybenzene,
bis(chloromethyl)durene, bis(chloromethyl)biphenyl,
bis(chloromethyl)biphenyl carboxylic acid,
bis(chloromethyl)biphenyl dicarboxylic acid,
bis(chloromethyl)methylbiphenyl, bis(chloromethyl)dimethylbiphenyl,
bis(chloromethyl)anthracene, ethylene glycol bis(chloroethyl)
ether, diethylene glycol bis(chloroethyl) ether, triethylene glycol
bis(chloroethyl) ether and tetraethylene glycol bis(chloroethyl)
ether.
[0885] Although the phenol resin (A) can be obtained by condensing
the previously described phenol compound and copolymer component by
dehydrating, dehydrohalogenating or dealcoholizing, or by
copolymerizing while cleaving unsaturated bonds, a catalyst may
also be used during polymerization. Examples of acid catalysts
include hydrochloric acid, sulfuric acid, nitric acid, phosphoric
acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic
acid, dimethyl sulfate, diethyl sulfate, acetic acid, oxalic acid,
1-hydroxyethylidene-1,1'-diphosphonic acid, zinc acetate, boron
trifluoride, boron trifluoride-phenol complex and boron
trifluoride-ether complex. On the other hand, examples of alkaline
catalysts include lithium hydroxide, sodium hydroxide, potassium
hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate,
triethylamine, pyridine, 4-N,N-dimoethylaminopyridine, piperidine,
piperazine, 1,4-diazabicyclo[2.2.2]octane,
1,8-diazabicyclo[5.4.0]-7-undecene,
1,5-diazabicyclo[4.3.0]-5-nonene, ammonia and
hexamethylenetetramine.
[0886] The amount of catalyst used to obtain a phenol resin having
a repeating structure represented by general formula (46) is
preferably within the range of 0.01 mol % to 100 mol % based on 100
mol % for the total number of moles of the copolymer component
(namely, component other than the phenol compound), and preferably
the total number of moles of an aldehyde compound, ketone compound,
methylol compound, alkoxymethyl compound, diene compound and
haloalkyl compound.
[0887] Normally, the reaction temperature during the synthesis
reaction of the phenol resin (A) is preferably within the range of
40.degree. C. to 250.degree. C. and more preferably 100.degree. C.
to 200.degree. C., while generally the reaction time is preferably
1 hour to 10 hours.
[0888] A solvent capable of adequately dissolving the resin can be
used as necessary.
[0889] Furthermore, the phenol resin having a repeating structure
represented by general formula (46) may also be that obtained by
further polymerizing a phenol compound that is not a raw material
of the structure represented by the aforementioned general formula
(46) within a range that does not impair the effects of the present
invention. A range that does not impair the effects of the present
invention refers to, for example, being 30% or less of the total
number of moles of phenol compound serving as raw material of
phenol resin (A).
[0890] (Phenol Resin Modified with Compound Having Unsaturated
Hydrocarbon Group Having 4 to 100 Carbon Atoms)
[0891] A phenol resin modified with a compound having an
unsaturated hydrocarbon group having 4 to 100 carbon atoms is the
reaction product of the reaction product of phenol or a derivative
thereof and a compound having an unsaturated hydrocarbon group
having 4 to 100 carbon atoms (which also may be simply referred to
as the "unsaturated hydrocarbon group-containing compound"
depending on the case) (and this reaction product may also be
referred to as the "unsaturated hydrocarbon group-modified phenol
derivative") and the polycondensation product with an aldehyde or a
phenol compound and an unsaturated hydrocarbon group-containing
compound.
[0892] A phenol derivative the same as that previously described as
a raw material of the phenol resin having a repeating unit
represented by general formula (46) can be used for the phenol
derivative.
[0893] The unsaturated hydrocarbon group of the unsaturated
hydrocarbon group-containing compound preferably contains two or
more unsaturated groups from the viewpoint of residual stress of
the cured film and applicability to reflow treatment. In addition,
the unsaturated hydrocarbon group preferably has 4 to 100 carbon
atoms, more preferably 8 to 80 carbon atoms, and even more
preferably 10 to 60 carbon atoms from the viewpoints of
compatibility when in the form of a resin composition and residual
stress of the cured film.
[0894] Examples of the unsaturated hydrocarbon group-containing
compound include unsaturated hydrocarbon groups having 4 to 100
carbon atoms, polybutadiene having a carboxyl group, epoxidated
polybutadiene, linoleyl alcohol, oleyl alcohol, unsaturated fatty
acids and unsaturated fatty acid esters. Preferable examples of
unsaturated fatty acids include crotonic acid, myristoleic acid,
palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic
acid, erucic acid, nervonic acid, linoleic acid, a-linolenic acid,
oleostearic acid, stearidonic acid, arachidonic acid,
eisocapentaenoic acid, clupanodonic acid and docosahexaenoic acid.
Among these, unsaturated fatty acid esters in the form of vegetable
oils are particularly preferable from the viewpoints of elongation
of the cured film and flexibility of the cured film.
[0895] Vegetable oils normally include esters of glycerin and
unsaturated fatty acids and consist of non-drying oils having an
iodine value of 100 or lower, semi-drying oils having an iodine
value of greater than 100 to less than 130, and drying oils having
an iodine value of 130 or higher. Examples of non-drying oils
include olive oil, morning glory seed oil, cashew nut oil, sasanqua
oil, camellia oil, castor oil and peanut oil. Examples of
semi-drying oils include corn oil, cottonseed oil and sesame oil.
Examples of drying oils include tung oil, linseed oil, soybean oil,
walnut oil, safflower oil, sunflower oil, perilla oil and mustard
oil. In addition, processed vegetable oils, obtained by processing
these vegetable oils, may also be used.
[0896] Among the aforementioned vegetable oils, a non-drying oil is
preferably used in the reaction between the phenol, phenol
derivative or phenol resin and the vegetable oil from the
viewpoints of improving yield and preventing gelation resulting
from the reaction proceeding excessively rapidly. On the other
hand, a drying oil is used preferably from the viewpoint of
improving adhesion with a resist pattern, mechanical properties and
thermal shock resistance. Among these drying oils, tung oil,
linseed oil, soybean oil, walnut oil or safflower oil is
preferable, and tung oil and linseed oil are more preferable, since
they allow the effects of the present invention to be demonstrated
more effectively and more reliably. One type of these oils is used
alone or two or more types are used in combination.
[0897] The reaction between the phenol or phenol derivative and the
unsaturated hydrocarbon group-containing compound is preferably
carried out at 50.degree. C. to 130.degree. C. The reaction ratio
between the phenol or phenol derivative and unsaturated hydrocarbon
group-containing compound is such that preferably 1 part by weight
to 100 parts by weight, and more preferably 5 parts by weigh to 50
parts by weight, of the unsaturated hydrocarbon group-containing
compound is used based on 100 parts by weight of the phenol or
phenol derivative from the viewpoint of lowering residual stress of
the cured film. If the amount of the unsaturated hydrocarbon
group-containing compound is less than 1 part by weight,
flexibility of the cured film tends to decrease, while if that
amount exceeds 100 parts by weight, heat resistance of the cured
film tends to decrease. In the aforementioned reaction, a catalyst
such as p-toluenesulfonic acid or trifluoromethanesulfonic acid may
be used as necessary.
[0898] A phenol resin modified by an unsaturated hydrocarbon
group-containing compound is formed by polycondensation of the
unsaturated hydrocarbon group-modified phenol derivative formed
according to the aforementioned reaction and an aldehyde. The
aldehyde is selected from, for example, formaldehyde,
acetoaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde,
methoxybenzaldehyde, hydroxyphenylacetoaldehyde,
methoxyphenylacetoaldehyde, crotonaldehyde, chloroacetoaldehyde,
chlorophenylacetoaldehyde, acetone, glyceraldehyde, glyoxylic acid,
methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate,
formyl acetate, methyl formyl acetate, 2-formylpropionate, methyl
2-formylpropionate, pyruvic acid, levulinic acid, 4-acetyl
butyrate, acetonedicarboxylic acid and 3,3',4,4'-benzophenone
tetracarboxylic acid. In addition, a precursor of formaldehyde,
such as paraformaldehyde or trioxane may also be used. One type of
these aldehydes is used alone or two or more types are used in
combination.
[0899] The reaction between the aforementioned aldehyde and the
aforementioned unsaturated hydrocarbon group-modified phenol
derivative is a polycondensation reaction, and conventionally known
conditions for synthesizing phenol resins can be used. The reaction
is preferably carried out in the presence of a catalyst such as an
acid or base, and an acid catalyst is used preferably from the
viewpoint of the degree of polymerization (molecular weight) of the
resin. Examples of acid catalysts include hydrochloric acid,
sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid and
oxalic acid. One type of these acid catalysts can be used alone or
two or more types can be used in combination.
[0900] The aforementioned reaction is preferably carried out at a
normal reaction temperature of 100.degree. C. to 120.degree. C. In
addition, although varying according to the type and amount of
catalyst used, the reaction time is normally 1 hour to 50 hours.
Following completion of the reaction, the reaction product is
subjected to vacuum dehydration at a temperature of 200.degree. C.
or lower to obtain a phenol resin modified by an unsaturated
hydrocarbon group-containing compound. Furthermore, a solvent such
as toluene, xylene or methanol can be used in the reaction.
[0901] The phenol resin modified by an unsaturated hydrocarbon
group-containing compound can also be obtained by polycondensing
the previously described unsaturated hydrocarbon group-modified
phenol derivative with an aldehyde together with a compound other
than phenol in the manner of m-xylene. In this case, the charged
molar ratio of the compound other than phenol to the compound
obtained by reacting the phenol derivative and unsaturated
hydrocarbon group-containing compound is preferably less than
0.5.
[0902] The phenol modified with an unsaturated hydrocarbon
group-containing compound can also be obtained by reacting a phenol
resin with an unsaturated hydrocarbon group-containing compound.
The phenol resin used in this case is a polycondensation product of
a phenol compound (namely, phenol and/or phenol derivative) and an
aldehyde. In this case, the same phenol derivatives and aldehydes
as those previously described can be used for the phenol derivative
and aldehyde, and phenol resin can be synthesized under
conventionally known conditions as previously described.
[0903] Specific examples of phenol resins obtained from a phenol
compound and aldehyde that are preferably used to form the phenol
resin modified with an unsaturated hydrocarbon group-containing
compound include phenol/formaldehyde novolac resin,
cresol/formaldehyde novolac resin, xylenol/formaldehyde novolac
resin, resorcinol/formaldehyde novolac resin and
phenol-naphthol/formaldehyde novolac resin.
[0904] The same unsaturated hydrocarbon group-containing compound
as that previously described with respect to producing an
unsaturated hydrocarbon group-modified phenol derivative that
reacts with an aldehyde can be used for the unsaturated hydrocarbon
group-containing compound that reacts with phenol resin.
[0905] Normally, the reaction between the phenol resin and
unsaturated hydrocarbon group-containing compound is preferably
carried out at 50.degree. C. to 130.degree. C. In addition, the
reaction ratio between the phenol resin and unsaturated hydrocarbon
group-containing compound is such that preferably 1 part by weight
to 100 parts by weight, more preferably 2 parts by weight to 70
parts by weight, and even more preferably 5 parts by weight to 50
parts by weight, are used with respect to 100 parts by weight of
phenol resin from the viewpoint of improving flexibility of the
cured film (resist pattern). If the amount of the unsaturated
hydrocarbon group-containing compound is less than 1 part by
weight, flexibility of the cured film tends to decrease, while if
that amount exceeds 100 parts by weight, the possibility of gelling
during the reaction tends to increase and heat resistance of the
cured film tends to decrease. A catalyst such as p-toluenesulfonic
acid or trifluoromethanesulfonic acid may be used during the
reaction between the phenol resin and unsaturated hydrocarbon
group-containing compound as necessary. Furthermore, although
subsequently described in detail, a solvent such as toluene,
xylene, methanol or tetrahydrofuran can be used in the
reaction.
[0906] An acid-modified phenol resin can also be used by allowing
polybasic acid anhydride to further react with phenolic hydroxyl
groups remaining in the phenol resin modified by an unsaturated
hydrocarbon group-containing compound formed according to the
method described below. Acid modification with a polybasic acid
anhydride results in the introduction of a carboxyl group, thereby
further improving solubility in an aqueous alkaline solution (used
as developer).
[0907] There are no particular limitations on the polybasic acid
anhydride provided it has an acid anhydride group formed by
dehydration condensation of the carboxyl groups of a polybasic acid
having a plurality of carboxyl groups. Examples of polybasic acid
anhydrides include dibasic acid anhydrides such as phthalic
anhydride, succinic anhydride, octenylsuccinic anhydride,
pentadodecenylsuccinic anhydride, maleic anhydride, itaconic
anhydride, tetrahydrophthalic anhydride, hexahydrophthalic
anhydride, methyl tetrahydrophthalic anhydride, methyl
hexahydrophthalic anhydride, nadic anhydride,
3,6-endomethylenetetrahydrophthalic anhydride, methyl
endomethylenetetrahydrophthalic anhydride, tetrabromophthalic
anhydride or trimellitic anhydride, and aromatic tetrabasic acid
dianhydrides such as biphenyltetracarboxylic dianhydride,
naphthalene tetracarboxylic dianhydride, diphenyl ether
tetracarboxylic dianhydride, butane tetracarboxylic dianhydride,
cyclopentane tetracarboxylic dianhydride, pyromellitic anhydride or
benzophenone tetracarboxylic dianhydride. One type of these
compounds may be used alone or two or more types may be used in
combination. Among these, the polybasic acid anhydride is
preferably a dibasic acid anhydride, and more preferably one or
more types selected from the group consisting tetrahydrophthalic
anhydride, succinic anhydride and hexahydrophthalic anhydride. In
this case, there is the advantage of allowing the formation of a
resist pattern having a more favorable form.
[0908] The reaction between a phenolic hydroxyl group and polybasic
acid anhydride can be carried out at 50.degree. C. to 130.degree.
C. In this reaction, preferably 0.10 moles to 0.80 moles, more
preferably 0.15 moles to 0.60 moles, and even more preferably 0.20
moles to 0.40 moles of the polybasic acid anhydride are reacted for
1 mole of phenolic hydroxyl groups. If the amount of the polybasic
acid anhydride is less than 0.10 moles, developability tends to
decrease, while if the amount exceeds 0.80 moles, the alkaline
resistance of unexposed portions tends to decrease.
[0909] Furthermore, in the aforementioned reaction, a catalyst may
be contained as necessary from the viewpoint of carrying out the
reaction rapidly. Examples of catalysts include tertiary amines
such as triethylamine, quaternary ammonium salts such as
triethylbenzyl ammonium chloride, imidazole compounds such as
2-ethyl-4-methylimidazole and phosphorous compounds such as
triphenylphosphine.
[0910] The acid value of the phenol resin further modified with a
polybasic acid anhydride is preferably 30 mgKOH/g to 200 mgKOH/g,
more preferably 40 mgKOH/g to 170 mgKOH/g, and even more preferably
50 mgKOH/g to 150 mgKOH/g. If the acid value is lower than 30
mgKOH/g, a longer amount of time tends to be required for alkaline
development in comparison with the case of the acid value being
within the aforementioned ranges, while if the acid value exceeds
200 mgKOH/g, resistance to developer of unexposed portions tends to
decrease in comparison with the case of the acid value being within
the aforementioned ranges.
[0911] The molecular weight of the phenol resin modified with the
unsaturated hydrocarbon group-containing compound is such that the
weight average molecular weight is preferably 1,000 to 100,000 and
more preferably 2,000 to 100,000 in consideration of solubility in
an aqueous alkaline solution and the balance between
photosensitivity and cured film properties.
[0912] The phenol resin (A) of the present embodiment is preferably
a mixture of at least one type of phenol resin selected from a
phenol resin having a repeating unit represented by the
aforementioned general formula (46) and a phenol resin modified
with the aforementioned compound having 4 to 100 carbon atoms and
an unsaturated hydrocarbon group (to be referred to as resin (a3)),
and a phenol resin selected from novolac resin and
polyhydroxystyrene (to be referred to as resin (a4)). The mixing
ratio between the resin (a3) and the resin (a4) in terms of the
weight ratio thereof is such that the ratio of (a3)/(a4) is within
the range of 5/95 to 95/5. This mixing ratio of (a3)/(a4) is
preferably 5/95 to 95/5, more preferably 10/90 to 90/10 and even
more preferably 15/85 to 85/15 from the viewpoints of solubility in
an aqueous alkaline solution, sensitivity and resolution when
forming a resist pattern, residual stress of the cured film, and
applicability to reflow treatment. Those resins indicated in the
previous sections describing novolac resin and polyhydroxystyrene
can be used for the novolac resin and polyhydroxystyrene of the
aforementioned resin (a4).
[0913] (B) Photosensitizer
[0914] The following provides an explanation of the photosensitizer
(B) used in the present invention. The photosensitizer (B) differs
according to whether the photosensitive resin composition of the
present invention is of the negative type in which a polyamic acid
ester is used for the resin (A), or is of the positive type in
which, for example, at least one type of novolac resin,
polyhydroxystyrene and phenol resin is mainly used for the resin
(A).
[0915] The incorporated amount of the photosensitizer (B) in the
photosensitive resin composition is 1 part by weight to 50 parts by
weight based on 100 parts by weight of the resin (A). The
aforementioned incorporated amount is 1 part by weight or more from
the viewpoint of photosensitivity or patterning properties, and is
50 parts by weight or less from the viewpoint curability of the
photosensitive resin composition or physical properties of the
photosensitive resin layer after curing.
[0916] First, an explanation is provided of the case of desiring a
negative type. In this case, a photopolymerization initiator and/or
photoacid generator is used for the photosensitizer (B), the
photopolymerization initiator is preferably a photo-radical
polymerization initiator, and preferable examples thereof include,
but are not limited to, photoacid generators in the manner of
benzophenone and benzophenone derivatives such as methyl o-benzoyl
benzoate, 4-benzoyl-4'-methyl diphenyl ketone, dibenzyl ketone or
fluorenone, acetophenone derivatives such as
2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone or
1-hydroxycyclohexyl phenyl ketone, thioxanthone and thioxanthone
derivatives such as 2-methylthioxanthone, 2-isopropylthioxanthone
or diethylthioxanthone, benzyl and benzyl derivatives such as
benzyldimethylketal or benzyl-.beta.-methoxyethylacetal,
[0917] benzoin and benzoin derivatives such as benzoin methyl
ether, oximes such as
1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime,
1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime,
1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime,
1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime,
1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime or
1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, N-arylglycines
such as N-phenylglycine, peroxides such as benzoyl perchloride,
aromatic biimidazoles, titanocenes or
.alpha.-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide. Among
the aforementioned photopolymerization initiators, oximes are more
preferable particularly from the viewpoint of photosensitivity.
[0918] In the case of using a photoacid generator for the
photosensitizer (B) in a negative-type photosensitive resin
composition, in addition to the photoacid generator demonstrating
acidity by irradiating with an active light beam in the manner of
ultraviolet light, due to that action, it has the effect of causing
a crosslinking agent to crosslink with a resin in the form of
component (A) or causing polymerization of crosslinking agents.
Examples of this photoacid generator used include diaryl sulfonium
salts, triaryl sulfonium salts, dialkyl phenacyl sulfonium salts,
diaryl iodonium salts, aryl diazonium salts, aromatic
tetracarboxylic acid esters, aromatic sulfonic acid esters,
nitrobenzyl esters, oxime sulfonic acid esters, aromatic
N-oxyimidosulfonates, aromatic sulfamides, haloalkyl
group-containing hydrocarbon-based compounds, haloalkyl
group-containing heterocyclic compounds and
naphthoquinonediazido-4-sulfonic acid esters. Two or more types of
these compounds can be used in combination or in combination with
other sensitizers as necessary. Among the aforementioned photoacid
generators, aromatic oxime sulfonic acid esters and aromatic
N-oxyimidosulfonates are more preferable from the viewpoint of
photosensitivity in particular.
[0919] The incorporated amount of these photosensitizers is 1 part
by weight to 50 parts by weight, and preferably 2 parts by weight
to 15 parts by weight from the viewpoint of photosensitivity, based
on 100 parts by weight of the resin (A). An incorporated amount of
1 part by weight or more based on 100 parts by weight of the resin
(A) results in superior photosensitivity, while an incorporated
amount of 50 parts by weight or less results in superior thick film
curability.
[0920] Next, an explanation is provided of the case of desired a
positive type. In this case, a photoacid generator is used for the
photosensitizer (B), and more specifically, although a compound
having a quinone diazide group, onium salt or halogen-containing
compound and the like can be used, a compound having a diazoquinone
structure is preferable from the viewpoints of solvent solubility
and storage stability.
[0921] Examples of compound (B) having a quinone diazide group (to
also be referred to as the "quinone diazide compound (B)") include
compounds having a 1,2-benzoquinone diazide structure and compounds
having a 1,2-naphthoaquinone diazide structure, and include known
substances described in, for example, U.S. Pat. Nos. 2,772,972,
2,797,213 and 3,669,658. The quinone diazide compound (B) is
preferably at least one type of compound selected from the group
consisting of 1,2-naphtoquinonediazido-4-sulfonic acid esters of
polyhydroxy compounds having a specific structure to be
subsequently described, and 1,2-naphthoquinonediazido-5-sulfonic
acid esters of those polyhydroxy compounds (to also be referred to
as "NQD compounds").
[0922] These NQD compounds are obtained by converting a
naphthoquinonediazidosulfonic acid compound to a sulfonyl chloride
with chlorosulfonic acid or thionyl chloride followed by subjecting
the resulting naphthoquinonediazidosulfonyl chloride to a
condensation reaction with a polyhydroxy compound. For example, an
NQD compound can be obtained by esterifying prescribed amounts of a
polyhydroxy compound and 1,2-naphthoquinonediazido-5-sulfonyl
chloride or 1,2-naphthoquinonediazido-4-sulfonyl chloride in the
presence of a base catalyst such as triethylamine and in a solvent
such as dioxane, acetone or tetrahydrofuran, followed by rinsing
the resulting product with water and drying.
[0923] In the present embodiment, the compound (B) having a quinone
diazide group is preferably a 1,2-naphthoquinonediazido-4-sulfonic
acid ester and/or 1,2-naphthoquinonediazido-5-sulfonic acid ester
of a hydroxy compound represented by the following general formulas
(120) to (124) from the viewpoint of sensitivity and resolution
when forming a resist pattern.
[0924] General formula (120) is indicated below:
##STR00197##
{wherein, X.sub.11 and X.sub.12 respectively and independently
represent a hydrogen atom or monovalent organic group having 1 to
60 carbon atoms (and preferably 1 to 30 carbon atoms), X.sub.13 and
X.sub.14 respectively and independently represent a hydrogen atom
or monovalent organic group having 1 to 60 carbon atoms (and
preferably 1 to 30 carbon atoms), r1, r2, r3 and r4 respectively
and independently represent an integer of 0 to 5, at least one of
r3 and r4 represents an integer of 1 to 5, (r1+r3).ltoreq.5 and
(r2+r4).ltoreq.5}.
[0925] General formula (121) is as indicated below:
##STR00198##
{wherein, Z represents a tetravalent organic group having 1 to 20
carbon atoms, X.sub.15, X.sub.16, X.sub.17 and X.sub.18
respectively and independently represent a monovalent organic group
having 1 to 30 carbon atoms, r6 represents an integer of 0 or 1,
r5, r7, r8 and r9 respectively and independently represent an
integer of 0 to 3, r10, r11, r12 and r13 respectively and
independently represent an integer of 0 to 2, and r10, r11, r12 and
r13 are not all 0}.
[0926] General Formula (122) is as indicated below:
##STR00199##
{wherein, r14 represents an integer of 1 to 5, r15 represents an
integer of 3 to 8, the (r14.times.r15) number of L respectively and
independently represent a monovalent organic group having 1 to 20
carbon atoms, the r15 number of T.sup.1 and the r15 number of
T.sup.2 respectively and independently represent a hydrogen atom or
monovalent organic group having 1 to 20 carbon atoms}.
[0927] General formula (123) is as indicated below:
##STR00200##
{wherein, A represents a divalent organic group containing an
aliphatic tertiary or quaternary carbon atom, and M represents a
divalent organic group and preferably represents a divalent group
selected from three groups represented by the following chemical
formulas}.
##STR00201##
[0928] Moreover, general formula (124) is as indicated below:
##STR00202##
{wherein, r17, r18, r19 and r20 respectively and independently
represent an integer of 0 to 2, at least one of r17, r18, r19 and
r20 is 1 or 2, X.sub.20 to X.sub.29 respectively and independently
represent a monovalent group selected from the group consisting of
a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy
group, allyl group and acyl group, and Y.sub.10, Y.sub.11 and
Y.sub.12 respectively and independently represent a divalent group
selected from the group consisting of a single bond, --O--, --S--,
--SO--, --SO.sub.2--, --CO--, --CO.sub.2--, cyclopentylidene group,
cyclohexylidene group, phenylene group and divalent organic group
having 1 to 20 carbon atoms}.
[0929] In still another embodiment, Y.sub.10 to Y.sub.12 in the
aforementioned general formula (124) are preferably respectively
and independently selected from three divalent organic groups
represented by the following general formulas:
##STR00203##
{wherein, X.sub.30 and X.sub.31 respectively and independently
represent at least one monovalent group selected from the group
consisting of a hydrogen atom, alkyl group, alkenyl group, aryl
group and substituted aryl group, X.sub.32, X.sub.33, X.sub.34 and
X.sub.35 respectively and independently represent a hydrogen atom
or alkyl group, r21 represents an integer of 1 to 5, and X.sub.36,
X.sub.37, X.sub.38 and X.sub.39 respectively and independently
represent a hydrogen atom or alkyl group}.
[0930] Examples of compounds represented by the aforementioned
general formula (120) include hydroxy compounds represented by the
following formulas (125) to (129).
##STR00204##
{wherein, r16 respectively and independently represent an integer
of 0 to 2, X.sub.40 respectively and independently represents a
hydrogen atom or monovalent organic group having 1 to 20 carbon
atoms, in the case a plurality of X.sub.40 are present, X.sub.40
may be mutually the same or different, and X.sub.40 is preferably a
monovalent organic group represented by the following general
formula:
##STR00205##
(wherein, r18 represents an integer of 0 to 2, X.sub.41 represents
a monovalent organic group selected from the group consisting of a
hydrogen atom, alkyl group and cycloalkyl group, and in the case
r18 is 2, the two X.sub.41 may be mutually the same or
different)},
[0931] general formula (126):
##STR00206##
{wherein, X.sub.42 represents a monovalent organic group selected
from the group consisting of an alkyl group having 1 to 20 carbon
atoms, alkoxy group having 1 to 20 carbon atoms, and cycloalkyl
group having 1 to 20 carbon atoms},
[0932] general formula (127):
##STR00207##
{wherein, r19 respectively and independently represents an integer
of 0 to 2 and X.sub.43 respectively and independently represents a
hydrogen or a monovalent organic group represented by the following
general formula:
##STR00208##
(wherein, r18 represents an integer of 0 to 2, X.sub.41 is selected
from the group consisting of a hydrogen atom, alkyl group and
cycloalkyl group, and in the case r18 is 2, X.sub.41 may be
mutually the same or different)}.
##STR00209##
[0933] A hydroxy compound represented by the following formulas
(130) to (132) is preferable as a compound represented by the
aforementioned general formula (120) since it has high sensitivity
when in the form of a NQD compound and demonstrates little
precipitation in a photosensitive resin composition.
[0934] The structures of formulas (130) to (132) are as indicated
below.
##STR00210##
[0935] A hydroxy compound represented by the following formula
(133) is preferable as a compound represented by the aforementioned
general formula (126) since it has high sensitivity when in the
form of a NQD compound and demonstrates little precipitation in a
photosensitive resin composition.
##STR00211##
[0936] A hydroxy compound represented by the following formulas
(134) to (136) is preferable as a compound represented by the
aforementioned general formula (127) since it has high sensitivity
when in the form of a NQD compound and demonstrates little
precipitation in a photosensitive resin composition.
[0937] The structures of formulas (134) to (136) are as indicated
below.
##STR00212##
[0938] In the aforementioned general formula (121), although there
are no particular limitations thereon provided it is a tetravalent
organic group having 1 to 20 carbon atoms, Z is preferably a
tetravalent group having a structure represented by the following
general formulas:
##STR00213##
[0939] Among compounds represented by the aforementioned general
formula (121), hydroxy compounds represented by the following
formulas (137) to (140) are preferable since they have high
sensitivity when in the form of a NQD compound and demonstrate
little precipitation in a photosensitive resin composition.
[0940] The structures of formulas (137) to (140) are as indicated
below.
##STR00214##
[0941] As the compound represented by general formula (122), a
hydroxy compound represented by the following formula (141):
##STR00215##
{wherein, r40 respectively and independently represents an integer
of 0 to 9} is preferable, since it has high sensitivity when in the
form of a NQD compound and demonstrates little precipitation in a
photosensitive resin composition.
[0942] Hydroxy compounds represented by the following formulas
(142) and (143) are preferable as compounds represented by the
aforementioned general formula (123) since they have high
sensitivity when in the form of a NQD compound and demonstrate
little precipitation in a photosensitive resin composition.
[0943] The structures of formulas (142) and (143) are as indicated
below.
##STR00216##
[0944] An NQD compound of a hydroxy compound represented by the
following formula (144) is specifically preferable as a compound
represented by the aforementioned general formula (124) since it
has high sensitivity and demonstrates little precipitation in a
photosensitive resin composition.
##STR00217##
[0945] In the case the compound (B) having a quinone diazide group
has a 1,2-naphtoquinonediazidosulfonyl group, this group may be any
of a 1,2-naphthoquinonediazido-5-sulfonyl group or
1,2-naphthoquinonediazido-4-sulfonyl group. Since a
1,2-naphthoquinonediazido-4-sulfonyl group absorbs in the i-line
region of a mercury lamp, it is suitable for exposure by i-line
irradiation. On the other hand, since a
1,2-naphthoquinonediazido-5-sulfonyl group is able to also absorb
in the g-line region of a mercury lamp, it is suitable for exposure
by g-line irradiation.
[0946] In the present embodiment, one or both of a
1,2-naphthoquinonediazido-4-sulfonic acid ester compound and
1,2-naphthoquinonediazido-5-sulfonic acid ester compound are
preferably selected corresponding to the wavelength used during
exposure. In addition, a 1,2-naphthoquinonediazidosulfonic acid
ester compound having a 1,2-naphthoquinonediazido-4-sulfonyl group
and 1,2-naphthoquinonediazido-5-sulfonyl group in the same molecule
can also be used, or a mixture of a
1,2-naphthoquinonediazido-4-sulfonic acid ester compound and a
1,2-naphthoquinonediazido-5-sulfonic acid ester compound can be
used by mixing.
[0947] In the compound (B) having a quinone diazide group, the
average esterification rate of the naphthoquinonediazidosulfonyl
ester of the hydroxy compound is preferably 10% to 100% and more
preferably 20% to 100% from the viewpoint of development
contrast.
[0948] Examples of preferable NQD compounds from the viewpoint of
sensitivity and cured film properties such as elongation include
those represented by the following group of general formulas:
##STR00218##
{wherein, Q represents a hydrogen atom or
naphthoquinonediazidosulfonic acid ester group represented by
either of the following formulas:
##STR00219##
provided that all Q are not simultaneously hydrogen atoms}.
[0949] In this case, a naphthoquinonediazidosulfonyl ester compound
having a 4-naphthoquinonediazidosulfonyl group and
5-naphthoquinonediazidosulfonyl group in the same molecule can be
used as an NQD compound, or 4-naphthoquinonediazidosulfonyl ester
compound and 5-naphthoquinonediazidosulfonyl ester compound can be
used as a mixture.
[0950] The aforementioned NQD compounds may be used alone or two or
more types may be mixed.
[0951] Examples of the aforementioned onium salt include iodonium
salts, sulfonium salts, phosiphonium salts, phosphonium salts and
diazonium salts, and is preferably an onium salt selected from the
group consisting of a diaryliodonium salt, triarylsulfonium salt
and trialkylsulfonium salt.
[0952] Examples of the aforementioned halogen-containing compound
include haloalkyl group-containing hydrocarbon compounds, and
trichloromethyltriazine is preferable.
[0953] The incorporated amount of these photoacid generators in the
case of a positive type is 1 part by weight to 50 parts by weight
and preferably 5 parts by weight to 30 parts by weight based on 100
parts by weight of the resin (A). Patterning properties of the
photosensitive resin composition are preferable if the incorporated
amount of the photoacid generator used for the photosensitizer (B)
is 1 part by weight or more, while the tensile elongation rate of a
film after curing the photosensitive resin composition is favorable
and development residue (scum) of exposed portions is low if the
incorporated amount is 50 parts by weight or less.
[0954] Other Components
[0955] The photosensitive resin composition of the present
invention may also contain components other than the aforementioned
components (A) and (B).
[0956] [Polyamic Acid Ester, Novolac Resin, Hydroxypolystyrene and
Phenol Resin]
[0957] A solvent can be contained in the negative-type resin
composition of the present embodiment in the form of the previously
described polyamic acid resin composition, or in the positive-type
photosensitive resin composition in the form of the novolac resin
composition, polyhydroxystyrene resin composition and phenol resin
composition, for the purpose of dissolving these resins.
[0958] Examples of solvents include amides, sulfoxides, ureas,
ketones, esters, lactones, ethers, halogenated hydrocarbons,
hydrocarbons and alcohols, and examples of which that can be used
include N-methyl-2-pyrrolidone, N,N-dimethylacetoamide,
N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, acetone,
methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone,
cyclohexanone, methyl acetate, ethyl acetate, butyl acetate,
diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate,
.gamma.-butyrolactone, propylene glycol monomethyl ether acetate,
propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol,
tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether,
diethylene glycol dimethyl ether, tetrahydrofuran, morpholine,
dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane,
chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane,
benzene, toluene, xylene and mesitylene. Among these, from the
viewpoint of resin solubility, resin composition stability and
adhesion to a substrate, N-methyl-2-pyrrolidone, dimethylsulfoxide,
tetramethylurea, butyl acetate, ethyl lactate,
.gamma.-butyrolactone, propylene glycol monomethyl ether acetate,
propylene glycol monomethyl ether, diethylene glycol dimethyl
ether, benzyl alcohol, phenyl glycol and tetrahydrofurfuryl alcohol
are preferable.
[0959] Among these solvents, those capable of completely dissolving
the polymer formed are particularly preferable, and examples
thereof include N-methyl-2-pyrroliodone, N,N-dimethylacetoamide,
N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea and
.gamma.-butyrolactone.
[0960] Examples of preferable solvents for the aforementioned
phenol resin include, but are not limited to, bis(2-methoxyethyl)
ether, methyl cellosolve, ethyl cellosolve, propylene glycol
monomethyl ether, propylene glycol monomethyl ether acetate,
diethylene glycol dimethyl ether, dipropylene glycol dimethyl
ether, cyclohexanone, cyclopentanone, toluene, xylene,
.gamma.-butyrolactone and N-methyl-2-pyrrolidone.
[0961] In addition, ketones, esters, lactones, ethers, hydrocarbons
and halogenated hydrocarbons may also be used as reaction solvents
depending on the case. More specifically, examples thereof include
acetone, methyl ethyl ketone, methyl isobutyl ketone,
cyclohexanone, methyl acetate, ethyl acetate, butyl acetate,
diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol
dimethyl ether, tetrahydrofuran, dichloromethane,
1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene,
o-dichlorobenzene, hexane, heptane, benzene, toluene and
xylene.
[0962] In the photosensitive resin composition of the present
invention, the amount of solvent used is preferably within the
range of 100 parts by weight to 1000 parts by weight, more
preferably 120 parts by weight to 700 parts by weight, and even
more preferably 125 parts by weight to 500 parts by weight based on
100 parts by weight of the resin (A).
[0963] In addition, in the case of forming a cured film on a
substrate composed of copper or copper alloy using the
photosensitive resin composition of the present invention, for
example, a nitrogen-containing heterocyclic compound such as an
azole compound or purine derivative can be optionally incorporated
to inhibit discoloration of the copper.
[0964] Examples of azole compounds include 1H-triazole,
5-methyl-1H-triazole, 5-ethyl-1H-triazole,
4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole,
4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole,
phenyltriazole, p-ethoxyphenyltriazole,
5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole,
hydroxyphenyltriazole, 1,5-dimethyltriazole,
4,5-diethyl-1H-triazole, 1H-benzotriazole,
2-(5-methyl-2-hydroxyphenyl)benzotriazole,
2-[2-hydroxy-3,5-bis(.alpha.,.alpha.-dimethylbenzyl)phenyl]benzotriazole,
2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole,
2-(3-t-butyl-5-methyl-2-hydroxyphenyl)benzotriazole,
2-(3,5-ti-t-amyl-2-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole,
hydroxyphenylbenzotriazole, tolyltriazole,
5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole,
4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole,
1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole,
5-amino-1H-tetrazole and 1-methyl-1H-tetrazole.
[0965] Particularly preferable examples include tolyltriazole,
5-methyl-1H-benzotriazole and 4-methyl-1H-benzotriazole. One type
of these azole compounds or a mixture of two or more types may be
used.
[0966] Specific examples of purine derivatives include purine,
adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine,
uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine,
2-hydroxyadenine, 2-methyladenine, 1-methyladenine,
N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine,
9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)
adenine, 8-aminoadenine, 6-amino-8-phenyl-9H-purine,
1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine,
N-methylguanine, 7-(2-hydroxyethyl)guanine,
N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine,
5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine,
8-azaxanthine, 8-azahypoxanthine and derivatives thereof.
[0967] The incorporated amount in the case the photosensitive resin
composition contains the aforementioned azole compound or purine
derivative is preferably 0.1 parts by weight to 20 parts by weight,
and more preferably 0.5 parts by weight to 5 parts by weight from
the viewpoint of photosensitivity, based on 100 parts by weight of
the resin (A). In the case the incorporated amount of the azole
compound based on 100 parts by weight of the resin (A) is 0.1 parts
by weight or more, discoloration of the copper or copper alloy
surface is inhibited in the case of having formed the
photosensitive resin composition of the present invention on copper
or copper alloy, while in the case the incorporated amount is 20
parts by weight or less, photosensitivity is superior.
[0968] A hindered phenol compound can be optionally incorporated in
order to inhibit discoloration of the copper surface. Examples of
hindered phenol compounds include, but are not limited to,
2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone,
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
4,4'-methylene-bis(2,6-di-t-butylphenol),
4,4'-thiobis(3-methyl-6-t-butylphenol),
4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylene
glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate],
1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxphenyl)propionate],
N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamide),
2,2'-methylene-bis(4-methyl-6-t-butylphenol),
2,2'-methylene-bis(4-ethyl-6-t-butylphenol),
[0969]
pentaerythryl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate-
], tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate,
1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene,
1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-
-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(-
1H,3H,5H)-trione,
1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(-
1H,3H,5H)-trione,
1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-
-2,4,6-(1H,3H,5H)-trione,
[0970]
1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tri-
azine-2,4,6-(1H,3H,5H)-trione,
1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1-
H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,-
6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-
-2,4,6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4-
,6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-
-2,4,6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-
-2,4,6-(1H,3H,5H)-trione,
[0971]
1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-
-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(-
1H,3H,5H)-trione, and
1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4-
,6-(1H,3H,5H)-trione. Among these,
1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(-
1H,3H,5H)-trione is particularly preferable.
[0972] The incorporated amount of the hindered phenol compound is
preferably 0.1 parts by weight to 20 parts by weight, and more
preferably 0.5 parts by weight to 10 parts by weight from the
viewpoint of photosensitivity, based on 100 parts by weight of the
resin (A). In the case the incorporated amount of the hindered
phenol compound based on 100 parts by weight of the resin (A) is
0.1 parts by weight or more, discoloration and corrosion of the
copper or copper alloy is prevented in the case of, for example,
having formed the photosensitive resin composition of the present
invention on copper or copper alloy, while in the case the
incorporated amount is 20 parts by weight or less, photosensitivity
is superior.
[0973] A crosslinking agent may also be contained in the
photosensitive resin composition of the present invention. The
crosslinking agent can be a crosslinking agent capable of
crosslinking the resin (A) or forming a crosslinked network by
itself when heat-curing a relief pattern formed using the
photosensitive resin composition of the present invention. The
crosslinking is further able to enhance heat resistance and
chemical resistance of a cured film formed from the photosensitive
resin composition.
[0974] Examples of crosslinking agents include compounds containing
a methylol group and/or alkoxymethyl group in the form of Cymel
(Registered Trade Mark) 300, 301, 303, 370, 325, 327, 701, 266,
267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170 or 1174, UFR 65 or
300, and Mycoat 102 or 105 (all manufactured by Mitsui-Cytec),
Nikalac (Registered Trade Mark) MX-270, -280 or -290, Nikalac MS-11
and Nikalac MW-30, -100, -300, -390 or -750 (all manufactured by
Sanwa Chemical Co., Ltd.), DML-OCHP, DML-MBPC, DML-BPC, DML-PEP,
DML-34X, DML-PSBP, DML-PTBP, DML-PCHP, DML-POP, DML-PFP, DML-MBOC,
BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT,
TMOM-BP, TMOM-BPA or TML-BPAF-MF (all manufactured by Honshu
Chemical Industry Co., Ltd.), benzenedimethanol,
bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene,
bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone,
hydroxymethylphenyl hydroxymethyl benzoate,
bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl,
bis(methoxymethyl)benzene, bis(methoxymethyl)cresol,
bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl
ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl
methoxymethyl benzoate, bis(methoxymethyl)biphenyl and
dimethylbis(methoxymethyl)biphenyl.
[0975] In addition, other examples include oxirane compounds in the
form of phenol novolac epoxy resin, cresol novolac epoxy resin,
bisphenol epoxy resin, trisphenol epoxy resin, tetraphenol epoxy
resin, phenol-xylylene epoxy resin, naphthol-xylylene epoxy resin,
phenol-naphthol epoxy resin, phenol-dicyclopentadiene epoxy resin,
alicyclic epoxy resin, aliphatic epoxy resin, diethylene glycol
diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol
diglycidyl ether, trimethylolpropane polyglycidyl ether,
1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether, glycerol
triglycidyl ether, ortho-secondary-butylphenyl glycidyl ether,
1,6-bis(2,3-epoxypropoxy)naphthalene, diglycerol polyglycidyl
ether, polyethylene glycol glycidyl ether, YDB-340, YDB-412,
YDF-2001, YDF-2004 (trade names, all manufactured by Nippon Steel
Chemical Co., Ltd.), NC-3000-H, EPPN-501H, EOCN-1020, NC-7000L,
EPPN-201L, XD-1000, EOCN-4600 (trade names, all manufactured by
Nippon Kayaku Co, Ltd.), Epikote (Registered Trade Mark) 1001,
Epikote 1007, Epikote 1009, Epikote 5050, Epikote 5051, Epikote
1031S, Epikote 180S65, Epikote 157H70, YX-315-75 (trade names, all
manufactured by Japan Epoxy Resins Co., Ltd.), EHPE3150, Placcel
G402, PUE101, PUE105 (trade names, all manufactured by Daicel
Chemical Industries, Ltd.), Epiclon (Registered Trade Mark) 830,
850, 1050, N-680, N-690, N-695, N-770, HP-7200, HP-820,
EXA-4850-1000 (trade names, all manufactured by DIC Corp.), Denacol
(Registered Trade Mark) EX-201, EX-251, EX-203, EX-313, EX-314,
EX-321, EX-411, EX-511, EX-512, EX-612, EX-614, EX-614B, EX-711,
EX-731, EX-810, EX-911, EM-150 (trade names, all manufactured by
Nagase Chemtex Corp.), Epolight (Registered Trade Mark) 70P and
Epolight 100MF (trade names, both manufactured by Kyoeisha Chemical
Co., Ltd.).
[0976] In addition, other examples include isocyanate compounds in
the form of 4,4'-diphenylmethane diisocyanate, tolylene
diisocyanate, 1,3-phenylene-bismethylene diisocyanate,
cyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate,
hexamethylene diisocyanate, Takenate (Registered Trade Mark) 500,
600, Cosmonate (Registered Trade Mark) NBDI, ND (trade names, all
manufactured by Mitsui Chemicals, Inc.), Duranate (Registered Trade
Mark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X and E402-B80T (trade
names, all manufactured by Asahi Kasei Chemicals Corp.).
[0977] In addition, although other examples include bismaleimide
compounds in the form of 4,4'-diphenylmethane bismaleimide,
phenylmethane maleimide, m-phenylene bismaleimide, bisphenol A
diphenyl ether bismaleimide,
3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide,
4-methyl-1,3-phenylene bismaleimide,
1,6'-bismaleimido-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether
bismaleimide, 4,4'-diphenylsulfide bismaleimide,
1,3-bis(3-maleimidophenoxy)benzene,
1,3-bis(4-maleimidophenoxy)benzene, BMI-1000, BMI-1100, BMI-2000,
BMI-2300, BMI-3000, BMI-4000, BMI-5100, BMI-7000, BMI-TMH, BMI-6000
and BMI-8000 (trade names, all manufactured by Daiwa Kasei Kogyo
Co., Ltd.), they are not limited thereto provided they are
compounds that demonstrate thermal crosslinking in the manner
described above.
[0978] The incorporated amount in the case of using a crosslinking
agent is preferably 0.5 parts by weight to 20 parts by weight and
more preferably 2 parts by weight to 10 parts by weight based on
100 parts by weight of the resin (A). In the case the incorporated
amount is 0.5 parts by weight or more, favorable heat resistance
and chemical resistance are demonstrated, while in the case the
incorporated amount is 20 parts by weight or less, storage
stability is superior.
[0979] The photosensitive resin composition of the present
invention may also contain an organic titanium compound. The
containing of an organic titanium compound allows the formation of
a photosensitive resin layer having superior chemical resistance
even in the case of having cured at a low temperature of about
250.degree. C.
[0980] Examples of organic titanium compounds able to be used for
the organic titanium compound include those in which an organic
chemical substance is bound to a titanium atom through a covalent
bond or ionic bond.
[0981] Specific examples of the organic titanium compound include
following I) to VII):
[0982] I) titanium chelate compounds: titanium chelate compounds
having two or more alkoxy groups are more preferable since they
allow the obtaining of storage stability of a negative-type
photosensitive resin composition as well as a favorable pattern,
and specific examples thereof include titanium
bis(triethanolamine)diisopropoxide, titanium
di(n-butoxide)bis(2,4-pentanedionate), titanium diisopropoxide
bis(2,4-pentanedionate), titanium diisopropoxide
bis(tetramethylheptanedionate) and titanium diisopropoxide
bis(ethylacetoacetate).
[0983] II) Tetraalkoxytitanium compounds: examples thereof include
titanium tetra(n-butoxide), titanium tetraethoxide, titanium
tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium
tetraisopropoxide, titanium tetramethoxide, titanium
tetramethoxypropoxide, titanium tetramethylphenoxide, titanium
tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium
tetrastearyloxide and titanium
tetrakis[bis{2,2-(allyloxymethyl)butoxide}].
[0984] III) Titanocene compounds: examples thereof include titanium
pentamethylcyclopentadienyl trimethoxide,
bis(.eta..sup.5-2,4-cyclopentadien-1-yl) bis(2,6-difluorophenyl)
titanium and bis(.eta..sup.5-2,4-cyclopentadien-1-yl)
bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) titanium.
[0985] IV) Monoalkoxy titanium compounds: examples thereof include
titanium tris(dioctylphosphate)isopropoxide and titanium
tris(dodecylbenzenesulfonate)isopropoxide.
[0986] V) Titanium oxide compounds: examples thereof include
titanium oxide bis(pentanedionate), titanium oxide
bis(tetramethylheptanedionate) and phthalocyanine titanium
oxide.
[0987] VI) Titanium tetraacetylacetonate compounds: examples
thereof include titanium tetraacetylacetonate.
[0988] VII) Titanate coupling agents: examples thereof include
isopropyltridecylbenzenesulfonyl titanate.
[0989] Among these, the organic titanium compound is preferably at
least one type of compound selected from the group consisting of
the aforementioned titanium chelate compounds (I),
tetraalkoxytitanium compounds (II) and titanocene compounds (III)
from the viewpoint of demonstrating more favorable chemical
resistance.
[0990] Titanium diisopropoxide bis(ethylacetoacetate), titanium
tetra(n-butoxide) and bis(.eta..sup.5-2,4-cyclopentadien-1-yl)
bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) titanium are
particularly preferable.
[0991] The incorporated amount in the case of incorporating the
organic titanium compound is preferably 0.05 parts by weight to 10
parts by weight and more preferably 0.1 parts by weight to 2 parts
by weight based on 100 parts by weight of the resin (A). In the
case the incorporated amount is 0.05 parts by weight or more,
favorable heat resistance and chemical resistance are demonstrated,
while in the case the incorporated amount is 10 parts by weight or
less, storage stability is superior.
[0992] Moreover, an adhesive assistant can be optionally
incorporated to improve adhesion between a substrate and a film
formed using the photosensitive resin composition of the present
invention. Examples of adhesive assistants include silane coupling
agents such as .gamma.-aminopropyldimethoxysilane,
N-(.beta.-aminoethyl)-.gamma.-aminopropylmethyldimethoxysilane,
.gamma.-glycidoxypropylmethyldimethoxysilane,
.gamma.-mercaptopropylmethyldimethoxysilane,
3-methacryloxypropyldimethoxymethylsilane,
3-methacryloxypropyltrimethoxysilane,
dimethoxymethyl-3-piperidinopropylsilane,
diethoxy-3-glycidoxypropylmethylsilane,
N-(3-diethoxymethylsilylpropyl)succinimide,
N-[3-(triethoxysilyl)propyl]phthalamic acid,
benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic
acid,
benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic
acid, 3-(triethoxysilyl)propylsuccinic anhydride,
N-phenylaminopropyltrimethoxysilane,
3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane or
3-(trialkoxysilyl)propyl succinic anhydride, and aluminum-based
adhesive assistants such as aluminum tris(ethylacetoacetate),
aluminum tris(acetylacetonate) or ethylacetylacetate aluminum
diisopropylate.
[0993] Among these adhesive assistants, silane coupling agents are
more preferable from the viewpoint of adhesive strength. In the
case the photosensitive resin composition contains an adhesive
assistant, the incorporated amount of the adhesive assistant is
preferably within the range of 0.5 parts by weight to 25 parts by
weight based on 100 parts by weight of the resin (A).
[0994] Examples of silane coupling agents include, but are not
limited to, 3-mercaptopropyltrimethoxysilane (KBM803: trade name,
manufactured by Shin-etsu Chemical Co., Ltd., Sila-Ace S810: trade
name, manufactured by Chisso Corp.),
3-mercaptopropyltriethoxysilane (SIM6475.0: trade name,
manufactured by Azmax Corp.), 3-mercaptopropylmethyldimethoxysilane
(LS1375: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.,
SIM6474.0: trade name, manufactured by Azmax Corp.),
mercaptomethyltrimethoxysilane (SIM6473.5C, trade name,
manufactured by Azmax Corp.), mercaptomethylmethyldimethoxysilane
(SIM6473.0, trade name, manufactured by Azmax Corp.),
3-mercaptopropyldiethoxymethoxysilane,
3-mercaptopropylethoxydimethoxysilane,
3-mercaptopropyltripropoxysilane,
3-mercaptopropyldiethoxypropoxysilane,
3-mercaptopropylethoxydipropoxysilane,
3-mercaptopropyldimethoxypropoxysilane,
3-mercaptopropylmethoxydipropoxysilane,
2-mercaptoethyltrimethoxysilane,
2-mercaptoethyldiethoxymethoxysilane,
2-mercaptoethylethoxydimethoxysilane,
2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane,
2-mercaptoethylethoxydipropoxysilane,
2-mercaptoethyldimethoxypropoxysilane,
2-mercaptoethylmethoxydipropoxysilane,
4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane,
4-mercaptobutyltripropoxysilane, N-(3-triethoxysilylpropyl)urea
(LS3610: trade name, Shin-Etsu Chemical Co., Ltd., SIU9055.0, trade
name, manufactured by Azmax Corp.), N-(3-trimethoxysilylpropyl)urea
(SIU9058.0: trade name, manufactured by Azmax Corp.),
N-(3-diethoxymethoxysilylpropyl)urea,
N-(3-ethoxydimethoxysilylpropyl)urea,
N-(3-tripropoxysilylpropyl)urea,
N-(3-diethoxypropoxysilylpropyl)urea,
N-(3-ethoxydipropoxysilylpropyl)urea,
N-(3-dimethoxypropoxysilylpropyl)urea,
N-(3-methoxydipropoxysilylpropyl)urea,
N-(3-trimethoxysilylethyl)urea,
N-(3-ethoxydimethoxysilylethyl)urea,
N-(3-tripropoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea,
N-(3-ethoxydipropoxysilylethyl)urea,
N-(3-dimethoxypropoxysilylethyl)urea,
N-(3-methoxydipropoxysilylethyl)urea,
N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea,
N-(3-tripropoxysilylbutyl)urea,
3-(m-aminophenoxy)propyltrimethoxysilane (SLA0598.0: manufactured
by Azmax Corp.), m-aminophenyltrimethoxysilane (SLA0599.0: trade
name, manufactured by Azmax Corp.), p-aminophenyltrimethoxysilane
(SLA0599.1: trade name, manufactured by Azmax Corp.),
aminophenyltrimethoxysilane (SLA0599.2 trade name, manufactured by
Azmax Corp.), 2-(trimethoxysilylethyl)pyridine (SIT8396.0: trade
name, manufactured by Azmax Corp.),
2-(triethoxysilylethyl)pyridine,
2-(dimethoxysilylmethylethyl)pyridine,
2-(diethoxysilylmethylethyl)pyridine,
(3-triethoxysilylpropyl)-t-butylcarbamate, (3-glycidoxypropyl)
triethoxysilane, tetramethoxysilane, tetraethoxysilane,
tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane,
tetra-i-butoxysilane, tetra-t-butoxysilane,
tetrakis(methoxyethoxysilane), tetrakis(methoxy-n-propoxysilane),
tetrakis(ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane),
bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane,
bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane,
bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane,
bis(triethoxysilyl)octadiene,
bis[3-(triethoxysilyl)propyl]disulfide,
bis[3-(triethoxysilyl)propyl]tetrasulfide,
di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane,
bis(pentadionate)titanium-O,O'-bis(oxyethyl)-aminopropyltriethoxysilane,
phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol,
n-propylphenylsilanediol, isopropylphenylsilanediol,
n-butylphenylsilanediol, isobutylphenylsilanediol,
tert-butylphenylsilanediol, diphenylsilanediol,
dimethoxydiphenylsilane, diethoxydiphenylsilane,
dimethoxy-di-p-tolylsilane, ethylmethylphenylsilanol,
n-propylmethylphenylsilanol, isopropylmethylphenylsilanol,
n-butylmethylphenylsilanol, isobutylmethylphenylsilanol,
tert-butylmethylphenylsilanol, ethyl-n-propylphenylsilanol,
ethylisopropylphenylsilanol, n-butylethylphenylsilanol,
isobutylethylphenylsilanol, tert-butylethylphenylsilanol,
methyldiphenylsilanol, ethyldiphenylsilanol,
n-propyldiphenylsilanol, isopropyldiphenylsilanol,
n-butyldiphenylsilanol, isobutyldiphenylsilanol,
tert-butyldiphenylsilanol and triphenylsilanol. These may be used
alone or in combination.
[0995] Among the aforementioned silane coupling agents,
phenylsilanetriol, trimethoxyphenylsilane,
trimethoxy(p-tolyl)silane, diphenylsilanediol,
dimethoxydiphenylsilane, diethoxydiphenylsilane,
dimethoxy-di-p-tolylsilane, triphenylsilane and silane coupling
agents represented by the following structures are particularly
preferable as silane coupling agents.
##STR00220##
[0996] 0.01 parts by weight to 20 parts by weight based on 100
parts by weight of the resin (A) is preferable for the incorporated
amount of silane coupling agent in the case of incorporating a
silane coupling agent.
[0997] The photosensitive resin composition of the present
invention may further include other components in addition to those
described above. Preferable examples of these components vary
according to whether a negative-type, using, for example, a
polyamic acid ester, or positive-type, using a phenol resin and the
like, is used for the resin (A).
[0998] A sensitizer for improving photosensitivity can be
optionally incorporated in the case of a negative-type using a
polyimide precursor and the like for the resin (A). Examples of
sensitizers include Michler's ketone,
4,4'-bis(diethylamino)benzophenone,
2,5-bis(4'-diethylaminobenzal)cyclopentane,
2,6-bis(4'-diethylaminobenzal)cyclohexanone,
2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone,
4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone,
p-diethylaminocinnamylidene indanone, p-dimethylaminobenzylidene
indanone, 2-(p-dimethylaminophenylbiphenylene)benzothiazole,
2-(p-dimethylaminophenylvinylene)benzothiazole,
2-(p-dimethylaminophenylvinylene)isonaphthothiazole,
1,3-bis(4'-dimethylaminobenzal)acetone,
1,3-bis(4'-diethylaminobenzal)acetone,
3,3'-carbonyl-bis(7-diethylaminocoumarin),
3-acetyl-7-dimethylaminocoumarin,
3-ethoxycarbonyl-7-dimethylaminocoumarin,
3-benzyloxycarbonyl-7-dimethylaminocoumarin,
3-methoxycarbonyl-7-diethylaminocoumarin,
3-ethoxycarbonyl-7-diethylaminocoumarin,
N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine,
N-p-tolyldiethanolamine, N-phenylethanolamine,
4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl
diethylaminobenzoate, 2-mercaptobenzimidazole,
1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole,
2-(p-dimethylaminostyryl)benzoxazole,
2-(p-dimethylaminostyryl)benzothiazole,
2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole and
2-(p-dimethylaminobenzoyl)styrene. These can be used alone or, for
example, 2 to 5 types can be used in combination.
[0999] The incorporated amount of the sensitizer in the case the
photosensitive resin composition contains a sensitizer for
improving photosensitivity is preferably 0.1 parts by weight to 25
parts by weight based on 100 parts by weight of the resin (A).
[1000] In addition, a monomer having a photopolymerizable
unsaturated bond can be optionally incorporated to improve
resolution of a relief pattern. The monomer is preferably a
(meth)acrylic compound that undergoes a radical polymerization
reaction by a photopolymerization initiator, and although not
limited to that indicated below, examples thereof include compounds
such as mono- or diacrylates and methacrylates of ethylene glycol
or polyethylene glycol such as diethylene glycol dimethacrylate or
tetraethylene glycol dimethacrylate, mono- or diacrylates and
methacrylates of propylene glycol or polypropylene glycol, mono-,
di- or triacrylates, methacrylates, cyclohexane diacrylates, and
dimethacrylates of glycerol, diacrylates and dimethacrylates of
1,4-butanediol, diacrylates and dimethacrylates of 1,6-hexanediol,
diacrylates and dimethacrylates of neopentyl glycol, mono- or
diacrylates, methacrylates, benzene trimethacrylates, isobornyl
acrylates and methacrylates, acrylamides and derivatives thereof,
methacrylamides and derivatives thereof and trimethylolpropane
triacrylates and methacrylates of bisphenol A, triacrylates and
methacrylates of glycerol, di- tri- or tetraacrylates and
methacrylates of pentaerythritol, and ethylene oxide or propylene
oxide adducts of these compounds.
[1001] In the case the photosensitive resin composition contains
the aforementioned monomer having a photopolymerizable unsaturated
bond in order to improve the resolution of a relief pattern, the
incorporated amount of the photopolymerizable monomer having an
unsaturated bond is preferably 1 part by weight to 50 parts by
weight based on 100 parts by weight of the resin (A).
[1002] In addition, in the case of a negative type using a polyamic
acid ester for the resin (A), a thermal polymerization inhibitor
can be optionally incorporated to improve viscosity and
photosensitivity stability of the photosensitive resin composition
when storing in a state of a solution containing a solvent in
particular. Examples of thermal polymerization inhibitors include
hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol,
phenothiazine, N-phenylnaphthylamine, ethyldiamine tetraacetic
acid, 1,2-cyclohexanediamine tetraacetic acid, glycol ether diamine
tetraacetic acid, 2,6-di-tert-butyl-p-methylphenol,
5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol,
2-nitroso-1-naphthol,
2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol,
N-nitroso-N-phenylhydroxylamine ammonium salt and
N-nitroso-N-(1-naphthyl) hydroxylamine ammonium salt.
[1003] The incorporated amount of the thermal polymerization
inhibitor in the case of incorporating in the photosensitive resin
composition is preferably within the range of 0.005 parts by weight
to 12 parts by weight based on 100 parts by weight of the resin
(A).
[1004] On the other hand, in the case of a positive type using a
phenol resin and the like for the resin (A) in the photosensitive
resin composition of the present invention, dyes, surfactants,
thermal acid generators, solubility enhancers and adhesive
assistants for enhancing adhesion with a base material
conventionally used as additives of photosensitive resin
compositions can be used as necessary in the photosensitive resin
composition to enhance adhesion with a substrate.
[1005] In providing an even more detailed description of the
aforementioned additives, examples of dyes include methyl violet,
crystal violet and malachite green. In addition, examples of
surfactants include nonionic surfactants composed of polyglycols or
derivatives thereof, such as polypropylene glycol or
polyoxyethylene lauryl ether, examples of which include
fluorine-based surfactants such as Fluorad (trade name, Sumitomo 3M
Ltd.), Megafac (trade name, Dainippon Ink & Chemicals, Inc.) or
Lumiflon (trade name, Asahi Glass Co., Ltd.), and organic siloxane
surfactants such as K2341 (trade name, Shin-Etsu Chemical Co.,
Ltd.), DBE (trade name, Chisso Corp.) or Granol (trade name,
Kyoeisha Chemical Co., Ltd.). Examples of adhesive assistants
include alkylimidazoline, butyric acid, alkyl acid,
polyhydroxystyrene, poly(vinyl methyl ether), t-butyl novolac
resin, epoxysilane and epoxy polymers, as well as various types of
silane coupling agents.
[1006] The incorporated amounts of the aforementioned dyes and
surfactants are preferably 0.1 parts by weight to 30 parts by
weight based on 100 parts by weight of the resin (A).
[1007] In addition, a thermal acid generator can be optionally
incorporated from the viewpoint of demonstrating favorable thermal
properties and mechanical properties of the cured product even in
the case of having lowered the curing temperature.
[1008] A thermal acid generator is preferably incorporated from the
viewpoint of demonstrating favorable thermal properties and
mechanical properties of the cured product even in the case of
having lowered the curing temperature.
[1009] Examples of thermal acid generators include salts formed
from strong acid and base such as onium salts or imidosulfonates
having a function that forms an acid as a result of heating.
[1010] Examples of onium salts include diaryliodonium salts such as
aryldiazonium salt or diphenyliodonium salt, di(alkylaryl)iodonium
salts such as di(t-butylphenyl)iodonium salt, trialkylsulfonium
salts such as trimethylsulfonium salt, dialkylmonoarylsulfonium
salts such as dimethylphenylsulfonium salt,
diarylmonoalkylsulfonium salts such as diphenylmethylsulfonium
salt, and triarylsulfonium salts.
[1011] Among these, di(t-butylphenyl)iodonium salt of
para-toluenesulfonic acid, di(t-butylphenyl)iodonium salt of
trifluoromethanesulfonic acid, trimethylsulfonium salt of
trifluoromethanesulfonic acid, dimethylphenylsulfonium salt of
trifluoromethanesulfonic acid, diphenylmethylsulfonium salt of
trifluoromethanesulfonic acid, di(t-butylphenyl)iodonium salt of
nonafluorobutanesulfonic acid, diphenyliodonium salt of
camphorsulfonic acid, diphenyliodonium salt of ethanesulfonic acid,
dimethylphenylsulfonium salt of benzenesulfonic acid and
dimethylphenylsulfonium salt of toluenesulfonic acid are
preferable.
[1012] In addition, salts such as pyridinium salts formed from
strong acids and bases as indicated below can also be used as salts
formed from strong acid and base in addition to the previously
described onium salts. Examples of strong acids include
arylsulfonic acids in the manner of p-toluenesulfonic acid or
benzenesulfonic acid, perfluoroalkylsulfonic acids in the manner of
camphorsulfonic acid, trifluoromethanesulfonic acid or
nonafluorobutanesulfonic acid, and alkylsulfonic acids in the
manner of methanesulfonic acid, ethanesulfonic acid or
butanesulfonic acid. Examples of bases include pyridines and
alkylpyridines in the manner of 2,4,6-trimethylpyridine, and
N-alkylpyridines and halogenated N-alkylpyridines in the manner of
2-chloro-N-methylpyridine.
[1013] Although imidosulfonates such as naphthoylimidosulfonate or
phthalimidosulfonate can be used as imidosulfonate, there are no
particular limitations thereon provided they are compounds capable
of generating acid in the presence of heat.
[1014] The incorporated amount in the case of using a thermal acid
generator is preferably 0.1 parts by weight to 30 parts by weight,
more preferably 0.5 parts by weight to 10 parts by weight, and even
more preferably 1 part by weight to 5 parts by weight, based on 100
parts by weight of the resin (A).
[1015] In the case of a positive-type photosensitive resin
composition, a solubility enhancer can be used to accelerate
removal of resin that is no longer required following
photosensitization. A compound having a hydroxyl group or carboxyl
group, for example, is preferable. Examples of compounds having a
hydroxyl group include ballast agents used in the previously
described naphthoquinone diazide compounds, along with
para-cumylphenol, bisphenols, resorcinols, linear phenol compounds
such as MtrisPC or MtetraPC, non-linear phenol compounds such
asTrisP-HAP, TrisP-PHBA or TrisP-PA (all manufactured by Honshu
Chemical Industry Co., Ltd.), diphenylmethane having 2 to 5 phenol
substituents, 3,3-diphenylpropane having 1 to 5 phenol
substituents, compounds obtained by reacting
2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane and
5-norbornene-2,3-dicarboxylic anhydride at a molar ratio of 1:2,
compounds obtained by reacting bis(3-amino-4-hydroxyphenyl)sulfone
and 1,2-cyclohexylcarboxylic anhydride at a molar ratio of 1:2,
N-hydroxysuccinimide, N-hydroxyphthalimide and
N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide. Examples of
compounds having a carboxyl group include 3-phenyllactic acid,
4-hydroxyphenyllactic acid, 4-hydroxymandelic acid,
3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid,
2-methoxy-2-(1-naphthyl)propionic acid, mandelic acid, atrolactic
acid, .alpha.-methoxyphenylacetic acid, 0-acetylmandelic acid and
itaconic acid.
[1016] The incorporated amount in the case of incorporating a
solubility enhancer is preferably 0.1 parts by weight to 30 parts
by weight based on 100 parts by weight of the resin (A).
[1017] <Method for Producing Cured Relief Pattern and
Semiconductor Device>
[1018] In addition, the present invention provides a method for
producing a cured relief pattern, comprising: (1) a step for
forming a resin layer on a substrate by coating the previously
described photosensitive resin composition of the present invention
on the substrate, (2) a step for exposing the resin layer to light,
(3) a step for forming a relief pattern by developing the resin
layer after exposing to light, and (4) a step for forming a cured
relief pattern by heat-treating the relief pattern by irradiating
with microwaves. The following provides an explanation of a typical
aspect of each step.
[1019] (1) Step for Forming a Resin Layer on a Substrate by Coating
the Photosensitive Resin Composition on the Substrate
[1020] In the present step, the photosensitive resin composition of
the present invention is coated onto a substrate followed by drying
as necessary to form a resin layer. A method conventionally used to
coat photosensitive resin compositions can be used, examples of
which include coating methods using a spin coater, bar coater,
blade coater, curtain coater or screen printer, and spraying
methods using a spray coater.
[1021] A coating film composed of the photosensitive resin
composition can be dried as necessary. A method such as air drying,
or heat drying or vacuum drying using an oven or hot plate, is used
for the drying method. More specifically, in the case of carrying
out air drying or heat drying, drying can be carried out under
conditions consisting of 1 minute to 1 hour at 20.degree. C. to
140.degree. C. The resin layer can be formed on a substrate in this
manner.
[1022] (2) Step for Exposing Resin Layer to Light
[1023] In the present step, the resin layer formed in the manner
described above is exposed to an ultraviolet light source and the
like either directly or through a photomask having a pattern or
reticle using an exposure device such as a contact aligner, mirror
projector or stepper.
[1024] Subsequently, post-exposure baking (PEB) and/or
pre-development baking may be carried out using an arbitrary
combination of temperature and time as necessary for the purpose of
improving photosensitivity and the like.
[1025] Although the range of baking conditions preferably consists
of a temperature of 40.degree. C. to 120.degree. C. and time of 10
seconds to 240 seconds, the range is not limited thereto provided
various properties of the photosensitive resin composition of the
present invention are not impaired.
[1026] (3) Step for Forming Relief Pattern by Developing Resin
Layer after Exposing to Light
[1027] In the present step, exposed portions or unexposed portions
of the photosensitive resin layer are developed and removed
following exposure. Unexposed portions are developed and removed in
the case of using a negative-type photosensitive resin composition
(such as in the case of using a polyamic acid ester for the resin
(A)), while exposed portions are developed and removed in the case
of using a positive-type photosensitive resin composition (such as
in the case of using a phenol resin for the resin (A)). An
arbitrary method can be selected and used for the development
method from among conventionally known photoresist development
methods, examples of which include the rotary spraying method,
paddle method and immersion method accompanying ultrasonic
treatment. In addition, post-development baking using an arbitrary
combination of temperature and time may be carried out as necessary
after development for the purpose of adjusting the form of the
relief pattern.
[1028] A good solvent with respect to the photosensitive resin
composition or a combination of this good solvent and a poor
solvent is preferable for the developer used for development. In
the case of a photosensitive resin composition that does not
dissolve in an aqueous alkaline solution, for example, preferable
examples of good solvents include N-methylpyrrolidone,
N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetoamide, cyclopentanone,
cyclohexanone, .gamma.-butyrolactone and
.alpha.-acetyl-.gamma.-butyrolactone, while preferable examples of
poor solvents include toluene, xylene, methanol, ethanol, isopropyl
alcohol, ethyl lactate, propylene glycol methyl ether acetate and
water. In the case of using a mixture of good solvent and poor
solvent, the proportion of poor solvent to good solvent is
preferably adjusted according to the solubility of polymer in the
photosensitive resin composition. In addition, two or more types of
each solvent, such as a combination of several types of each
solvent, can also be used.
[1029] On the other hand, in the case of a photosensitive resin
composition that dissolves in an aqueous alkaline solution, the
developer used for development dissolves and removes an aqueous
alkaline solution-soluble polymer, and typically is an aqueous
alkaline solution having an alkaline compound dissolved therein.
The alkaline compound dissolved in the developer may be either an
inorganic alkaline compound or organic alkaline compound.
[1030] Examples of inorganic alkaline compounds include lithium
hydroxide, sodium hydroxide, potassium hydroxide, diammonium
hydrogen phosphate, dipotassium hydrogen phosphate, disodium
hydrogen phosphate, lithium silicate, sodium silicate, potassium
silicate, lithium carbonate, sodium carbonate, potassium carbonate,
lithium borate, sodium borate, potassium borate and ammonia.
[1031] Examples of organic alkaline compounds include
tetramethylammonium hydroxide, tetraethylammonium hydroxide,
trimethylhydroxyethylammonium hydroxide, methylamine,
dimethylamine, trimethylamine, monoethylamine, diethylamine,
triethylamine, n-propylamine, di-n-propylamine, isopropylamine,
diisopropylamine, methyldiethylamine, dimethylethanolamine,
ethanolamine and triethanolamine.
[1032] Moreover. a water-soluble organic solvent such as methanol,
ethanol, propanol or ethylene glycol, surfactant, storage
stabilizer or resin dissolution inhibitor and the like can be added
in a suitable amount thereof to the aforementioned aqueous alkaline
solution as necessary. The relief pattern can be formed in the
above manner.
[1033] (4) Step for Forming Cured Relief Pattern by Heat-Treating
Relief Pattern by Irradiating with Microwaves
[1034] In the present step, the relief pattern obtained by
developing in the manner previously described is converted to a
cured relief pattern by heating by irradiating with microwaves.
There are no particular limitations on the frequency or output of
the radiated microwaves or on the radiation method. Heat curing is
required to be carried out in an oven capable of radiating
microwaves. Although heating can be carried out under conditions
consisting of, for example, 30 minutes to 5 hours at 180.degree. C.
to 400.degree. C., it is preferably carried out within a
temperature range of 180.degree. C. to 250.degree. C. Air may be
used for the atmospheric gas during heat curing, or an inert gas
such as nitrogen or argon can be used.
[1035] <Semiconductor Device>
[1036] The present invention also provides a semiconductor device
that contains a cured relief pattern obtained according to the
method for producing a cured relief pattern of the present
invention described above. The present invention also provides a
semiconductor device containing a semiconductor element in the form
of a base material and a cured relief pattern formed according to
the aforementioned method for producing a cured relief pattern on
the aforementioned base material. In addition, the present
invention can be applied to a method for producing a semiconductor
device that uses a semiconductor element for the base material and
contains the aforementioned method for producing a cured relief
pattern as a portion of the process thereof. The semiconductor
device of the present invention can be produced by combining with
known methods for producing semiconductor devices by forming the
cured relief pattern formed according to the aforementioned method
for producing a cured relief pattern as a surface protective film,
interlayer insulating film, rewiring insulating film, flip-chip
device protective film or protective film of a semiconductor device
having a bump structure.
[1037] The photosensitive resin composition is also useful in
applications such as the interlayer insulation of a multilayer
circuit, cover coating of a flexible copper-clad board,
solder-resistive film or liquid crystal alignment film in addition
to a semiconductor device as described above.
EXAMPLES
First Embodiment
[1038] The following provides an explanation of Examples 1 to 24
and Comparative Examples 1 to 6 as a first embodiment of the
present invention.
[1039] Although the following provides a detailed explanation of
the present invention using examples thereof, the present invention
is not limited thereto. In the examples, comparative examples and
production examples, physical properties of the photosensitive
resin composition were measured and evaluated in accordance with
the methods indicated below.
[1040] <Weight Average Molecular Weight>
[1041] The weight average molecular weight (Mw) of each resin was
measured by gel permeation chromatography (standard polystyrene
conversion). The Shodex 805M/806M serial columns (trade name)
manufactured by Showa Denko K.K. were used for measurement, Shodex
STANDARD SM-105 (trade name) manufactured by Showa Denko K.K. was
selected for the standard monodisperse polystyrene,
N-methyl-2-pyrrolidone was used for the developing solvent, and the
Shodex RI-930 (trade name) manufactured by Showa Denko K.K. was
used for the detector.
[1042] <Evaluation of Copper Adhesion of Cured Film>
[1043] Ti at a thickness of 200 nm and copper at a thickness of 400
nm were sequentially sputtered on a 6-inch silicon wafer (Fujimi
Inc., thickness: 625.+-.25 .mu.m) using a sputtering device (Model
L-440S-FHL, Canon Anelva Corp.). Continuing, a photosensitive
polyamic acid ester composition prepared according to the method to
be subsequently described was spin-coated on the wafer using a
coater developer (Model D-Spin60A, Sokudo Co., Ltd.) followed by
drying to form a coating film having a thickness of 10 .mu.m. This
coating film was then irradiated at an energy level of 300
mJ/cm.sup.2 with a parallel light mask aligner (Model PLA-501FA,
Canon Inc.) using a mask having a test pattern. Next, the wafer
having the coating film formed thereon was subjected to heat
treatment for 2 hours at 230.degree. C. in a nitrogen atmosphere
using a programmable curing oven (Model VF-2000, Koyo Lindberg
Ltd.) to obtain a cured relief pattern composed of polyimide resin
having a thickness of about 7 .mu.m on the copper. The resulting
cured film was treated for 100 hours under conditions of
120.degree. C., 2 atm and relative humidity of 100% with a pressure
cooker tester (Model PC-422R8D, Hirayama Manufacturing Corp.),
followed by making 11 cuts each in the vertical and horizontal
directions at 1 mm intervals in a grid pattern with a box knife to
form 100 independent films. Subsequently, a peel test was carried
out using Scotch tape (Registered Trade Mark) and the number of
films that peeled off was recorded in Table 1 to be subsequently
described. A smaller number of peeled films indicates favorable
reliability during use as a semiconductor.
[1044] <Chemical Resistance Test>
[1045] A photosensitive polyamic acid ester composition prepared
according to the method to be subsequently described was
spin-coated on a 6-inch silicon wafer (Fujimi Inc., thickness:
625.+-.25 .mu.m) using a coater developer (Model D-Spin60A, Sokudo
Co., Ltd.) followed by drying to form a coating film having a
thickness of 10 .mu.m. This coating film was then irradiated at an
energy level of 300 mJ/cm.sup.2 with a parallel light mask aligner
(Model PLA-501FA, Canon Inc.) using a mask having a test pattern.
Next, the wafer having the coating film formed thereon was
subjected to heat treatment for 2 hours at 230.degree. C. in a
nitrogen atmosphere using a programmable curing oven (Model
VF-2000, Koyo Lindberg Ltd.) to obtain a cured relief pattern
composed of polyimide resin having a thickness of about 7 .mu.m on
the silicon. The resulting cured film was treated for 1000 hours at
150.degree. C. with a pressure cooker tester (Model PC-422R8D,
Hirayama Manufacturing Corp.), followed by immersing for 60 minutes
in a chemical solution (1% by weight potassium
hydroxide/tetramethyl ammonium hydroxide solution) at 110.degree.
C. and observing the residual film rate and the presence of cracks.
Those cured films having a residual film rate of 90% or more and
observed to be free of cracks were evaluated as "A", while those
not satisfying either one of the above requirements were evaluated
as "B".
<Production Example 1> (Synthesis of Polymer 1)
[1046] 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride
(BPDA) were placed in a separable flask having a volume of 2 liters
followed by adding 131.2 g of 2-hydroxyethyl methacrylate (HEMA)
and 400 ml of .gamma.-butyrolactone, stirring at room temperature
and adding 81.5 g of pyridine while stirring to obtain a reaction
mixture. Following completion of generation of heat by the
reaction, the reaction mixture was allowed to cool to room
temperature and then allowed to stand for 16 hours.
[1047] Next, a solution obtained by dissolving 206.3 g of
dicyclohexylcarbodiimide (DCC) in 180 ml of .gamma.-butyrolactone
was added to the reaction mixture over the course of 40 minutes
while cooling with ice and stirring followed by adding a suspension
of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of
.gamma.-butyrolactone over the course of 60 minutes while stirring.
After further stirring for 2 hours at room temperature, 30 ml of
ethyl alcohol were added followed by stirring for 1 hour and then
adding 400 ml of .gamma.-butyrolactone. The precipitate that formed
in the reaction mixture was removed by filtration to obtain a
reaction liquid.
[1048] The resulting reaction liquid was added to 3 L of ethyl
alcohol to form a precipitate composed of a crude polymer. The
resulting crude polymer was filtered out and dissolved in 1.5 L of
tetrahydrofuran to obtain a crude polymer solution. The resulting
crude polymer solution was dropped into 28 L of water to
precipitate the polymer, and after filtering out the resulting
precipitate, the precipitate was vacuum-dried to obtain a powdered
polymer (Polymer 1). When the molecular weight of Polymer 1 was
measured by gel permeation chromatography (standard polystyrene
conversion), the weight average molecular weight (Mw) thereof was
22,000.
<Production Example 2> (Synthesis of Polymer 2)
[1049] A reaction was carried out in the same manner as the method
described in the aforementioned Production Example 1 with the
exception of using a mixture of a 54.5 g of pyromellitic anhydride
(PMDA) and 80.6 g of benzophenone-3,3',4,4'-tetracarboxylic
dianhydride (BTDA) instead of the 147.1 g of
3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) used in
Production Example 1 to obtain Polymer 2. When the molecular weight
of Polymer 2 was measured by gel permeation chromatography
(standard polystyrene conversion), the weight average molecular
weight (Mw) thereof was 22,000.
<Production Example 3> (Synthesis of Polymer 3)
[1050] A reaction was carried out in the same manner as the method
described in the aforementioned Production Example 1 with the
exception of using 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA)
instead of the 147.1 g of 3,3',4,4'-biphenyltetracarboxylic
dianhydride (BPDA) of Production Example 1 and using 50.2 g of
p-phenylenediamine (p-PD) instead of the 93.0 g of
4,4'-diaminodiphenyl ether (DADPE) to obtain Polymer 3. When the
molecular weight of Polymer 3 was measured by gel permeation
chromatography (standard polystyrene conversion), the weight
average molecular weight (Mw) thereof was 20,000.
<Production Example 4> (Synthesis of Polymer 4)
[1051] A reaction was carried out in the same manner as the method
described in the aforementioned Production Example 1 with the
exception of using 148.8 g of 2,2'-bis(trifluoromethyl)benzidine
instead of the 93.0 g of the 4,4'-diaminobiphenyl ether (DADPE)
used in Production Example 1 to obtain Polymer 4. When the
molecular weight of Polymer 4 was measured by gel permeation
chromatography (standard polystyrene conversion), the weight
average molecular weight (Mw) thereof was 20,000.
<Production Example 5> (Synthesis of Polymer 5)
[1052] A reaction was carried out in the same manner as the method
described in the aforementioned Production Example 1 with the
exception of using 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA)
instead of the 147.1 g of 3,3',4,4'-biphenyltetracarboxylic
dianhydride (BPDA) used in Production Example 1 to obtain Polymer
5. When the molecular weight of Polymer 5 was measured by gel
permeation chromatography (standard polystyrene conversion), the
weight average molecular weight (Mw) thereof was 22,000.
<Production Example 6> (Synthesis of Polymer 6)
[1053] A reaction was carried out in the same manner as the method
described in the aforementioned Production Example 1 with the
exception of using 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA)
instead of the 147.1 g of 3,3',4,4'-biphenyltetracarboxylic
dianhydride (BPDA) of Production Example 1 and using 105.5 g of
4,4'-diamino-3,3'-dimethylphenylmethane (MDT) instead of the 93.0 g
of 4,4'-diaminodiphenyl ether (DADPE) to obtain Polymer 6. When the
molecular weight of Polymer 6 was measured by gel permeation
chromatography (standard polystyrene conversion), the weight
average molecular weight (Mw) thereof was 22,000.
<Production Example 7> (Synthesis of Polymer 7)
[1054] A reaction was carried out in the same manner as the method
described in the aforementioned Production Example 1 with the
exception of using a mixture of a 54.5 g of pyromellitic anhydride
(PMDA) and 73.55 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride
(BPDA) instead of the 147.1 g of 3,3',4,4'-biphenyltetracarboxylic
dianhydride (BPDA) used in Production Example 1 to obtain Polymer
7. When the molecular weight of Polymer 7 was measured by gel
permeation chromatography (standard polystyrene conversion), the
weight average molecular weight (Mw) thereof was 21,000.
<Production Example 8> (Synthesis of Polymer 8)
[1055] A reaction was carried out in the same manner as the method
described in the aforementioned Production Example 1 with the
exception of using a mixture of a 54.5 g of pyromellitic anhydride
(PMDA) and 77.55 g of 4,4'-oxydiphthalic dianhydride (ODPA) instead
of the 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride
(BPDA) used in Production Example 1 to obtain Polymer 8. When the
molecular weight of Polymer 8 was measured by gel permeation
chromatography (standard polystyrene conversion), the weight
average molecular weight (Mw) thereof was 22,000.
<Production Example 9> (Synthesis of Polymer 9)
[1056] A reaction was carried out in the same manner as the method
described in the aforementioned Production Example 1 with the
exception of using 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA)
instead of the 147.1 g of 3,3',4,4'-biphenyltetracarboxylic
dianhydride (BPDA) of Production Example 1 and using a mixture of
46.5 g of DADPE and 25.11 g of p-phenylenediamine (p-PD) instead of
the 147.1 g of the 3,3',4,4'-biphenyltetracarboxylic dianhydride
(BPDA) used in Production Example 1 instead of the 93.0 g of
4,4'-diaminodiphenyl ether (DADPE) to obtain Polymer 9. When the
molecular weight of Polymer 9 was measured by gel permeation
chromatography (standard polystyrene conversion), the weight
average molecular weight (Mw) thereof was 23,000.
Example 1
[1057] A negative-type photosensitive resin composition was
prepared according to the method indicated below followed by
evaluation of the resulting photosensitive resin composition. 50 g
of a polyimide precursor in the form of Polymer 1 (corresponding to
resin (A1)), 50 g of Polymer 5 (corresponding to resin (A4)), 2 g
of TR-PBG-305 (trade name, Changzhou Tronly New Electronic
Materials Co., Ltd., corresponding to photosensitive component
(B)), 4 g of N-phenyldiethanolamine, 0.1 g of titanium
diisopropoxide bis(ethylacetoacetate) (corresponding to organic
titanium compound (E)), 10 g of tetraethylene glycol
dimethacrylate, 0.5 g of 5-methyl-1H-benzotriazole and 0.05 g of
2-nitroso-1-naphthol were dissolved in a mixed solvent composed of
160 g of .gamma.-butyrolactone (corresponding to solvent (C1), to
be referred to as "GBL") and 40 g of dimethylsulfoxide
(corresponding to solvent (C2)) to obtain a negative-type
photosensitive resin composition. The resulting resin composition
was evaluated in accordance with the previously described methods
and the results are shown in Table 1.
Example 2
[1058] A photosensitive resin composition was produced and
evaluated in the same manner as the method described in the
aforementioned Example 1 with the exception of using 20 g instead
of 50 g of the Polymer 1 and using 80 g instead of 50 g of the
Polymer 5 used in Example 1. The evaluation results are shown in
Table 1.
Example 3
[1059] A photosensitive resin composition was produced and
evaluated in the same manner as the method described in the
aforementioned Example 1 with the exception of using 80 g instead
of 50 g of the Polymer 1 and using 20 g instead of 50 g of the
Polymer 5 used in Example 1. The evaluation results are shown in
Table 1.
Example 4
[1060] A photosensitive resin composition was produced and
evaluated in the same manner as the method described in the
aforementioned Example 1 with the exception of using Polymer 2
instead of the Polymer 1 used in Example 1. The evaluation results
are shown in Table 1.
Example 5
[1061] A photosensitive resin composition was produced and
evaluated in the same manner as the method described in the
aforementioned Example 1 with the exception of using Polymer 3
instead of the Polymer 1 used in Example 1. The evaluation results
are shown in Table 1.
Example 6
[1062] A photosensitive resin composition was produced and
evaluated in the same manner as the method described in the
aforementioned Example 1 with the exception of using Polymer 4
instead of the Polymer 1 used in Example 1. The evaluation results
are shown in Table 1.
Example 7
[1063] A photosensitive resin composition was produced and
evaluated in the same manner as the method described in the
aforementioned Example 1 with the exception of using Polymer 5
instead of the Polymer 1 used in Example 1. The evaluation results
are shown in Table 1.
Example 8
[1064] A photosensitive resin composition was produced and
evaluated in the same manner as the method described in the
aforementioned Example 1 with the exception of using 200 g of GBL
instead of the 160 g used in Example 1 and omitting the DMSO. The
evaluation results are shown in Table 1.
Example 9
[1065] A photosensitive resin composition was produced and
evaluated in the same manner as the method described in the
aforementioned Example 1 with the exception of using 200 g of
N-methylpyrrolidone (NMP) instead of the GBL used in Example 1 and
omitting the DMSO. The evaluation results are shown in Table 1.
Example 10
[1066] A photosensitive resin composition was produced and
evaluated in the same manner as the method described in the
aforementioned Example 1 with the exception of using Polymer 3
instead of the Polymer 1 used in Example 1 and further using 200 g
of NMP instead of the GBL. The evaluation results are shown in
Table 1.
Example 11
[1067] A photosensitive resin composition was produced and
evaluated in the same manner as the method described in the
aforementioned Example 1 with the exception of omitting the GBL
used in Example 1 and using 200 g of NMP instead of the 40 g of
DMSO. The evaluation results are shown in Table 1.
Example 12
[1068] A photosensitive resin composition was produced and
evaluated in the same manner as the method described in the
aforementioned Example 1 with the exception of using NMP instead of
the GBL used in Example 1 and using ethyl lactate instead of the
DMSO. The evaluation results are shown in Table 1.
Example 13
[1069] A photosensitive resin composition was produced and
evaluated in the same manner as the method described in the
aforementioned Example 1 with the exception of using OXE-01 (trade
name, BASF Corp.) instead of the TR-PBG-305 used in Example 1. The
evaluation results are shown in Table 1.
Example 14
[1070] A photosensitive resin composition was produced and
evaluated in the same manner as the method described in the
aforementioned Example 1 with the exception of using
1-phenyl-1,2-propanedione-2-(0-ethoxycarbonyl) oxime (Initiator A)
instead of the TR-PBG-305 used in Example 1. The evaluation results
are shown in Table 1.
Comparative Examples 1 to 5
[1071] Evaluations were carried out in the same manner as Example 1
with the exception of changing the compositions to those shown in
Table 1. The evaluation results are shown in Table 1.
TABLE-US-00001 TABLE 1 Ex.1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex.
8 Ex. 9 Ex. 10 Resin (A1) Polymer 1 50 20 80 50 50 50 (g) Polymer 2
50 (g) Resin (A2) Polymer 3 50 50 (g) Resin (A3) Polymer 4 50 (g)
Resin (A4) Polymer 5 50 80 20 50 50 50 50 50 50 (g) Polymer 6 50
(g) Photosensitive TR-PBG-305 2 2 2 2 2 2 2 2 2 2 Component (B) (g)
OXE-01 Initiator A (g) Solvent (C1) GBL (g) 160 160 160 160 160 160
160 200 NMP (g) 200 200 Solvent (C2) DMSO (g) 40 40 40 40 40 40 40
Other Solvent Ethyl Lactate (g) Copper 0/100 0/100 10/100 0/100
0/100 0/100 10/100 30/100 30/100 30/100 adhesion Comp. Comp. Comp.
Comp. Comp. Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex.
5 Resin (A1) Polymer 1 50 50 50 50 (g) Polymer 2 (g) Resin (A2)
Polymer 3 (g) Resin (A3) Polymer 4 (g) Resin (A4) Polymer 5 50 50
50 50 100 100 100 100 (g) Polymer 6 100 (g) Photosensitive
TR-PBG-305 2 2 2 2 2 Component (B) (g) OXE-01 2 2 Initiator 4 2 A
(g) Solvent (C1) GBL (g) 160 160 160 160 160 160 NMP (g) 160 200
Solvent (C2) DMSO (g) 200 40 40 40 40 40 40 Other Solvent Ethyl 40
Lactate (g) Copper 40/100 30/100 0/100 20/100 70/100 80/100 90/100
70/100 80/100 adhesion
[1072] Based on the results shown in Table 1, Examples 1 to 14 were
indicated to yield resin films demonstrating favorable adhesion of
the cured film to copper wiring in comparison with Comparative
Examples 1 to 5.
Examples 15 to 21
[1073] Negative-type photosensitive resin compositions were
produced and evaluated using the same method as Example 1 with the
exception of using the proportions shown in Table 2.
Examples 22 to 24 and Comparative Example 6
[1074] Negative-type photosensitive resin compositions were
produced and evaluated using the same method as Example 1 with the
exception of using the proportions shown in Table 3.
TABLE-US-00002 TABLE 2 Ex. 15 Ex. 16 Ex. 17 Ex. 18 Ex. 19 Ex. 20
Ex. 21 Resin (A1) Polymer 1 (g) 50 50 50 50 50 50 50 Polymer 2 (g)
Resin (A2) Polymer 3 (g) Resin (A3) Polymer 4 (g) Resin (A4)
Polymer 5 (g) 50 50 50 50 50 50 50 Polymer 6 (g) Photosensitive
TR-PBG-305 (g) 2 2 2 2 2 2 2 Component (B) OXE-01 (g) Initiator A
(g) Solvent (C1) GBL (g) 160 160 160 160 160 160 160 Solvent (C2)
Tetrahydrofurfuryl alcohol (g) 40 Ethyl acetoacetate (g) 40
Dimethyl succinate (g) 40 Dimethyl malonate (g) 40
N,N-dimethylacetoamide (g) 40 .gamma.-butyrolactone (g) 40
1,3-dimethyl-2-imidazolinone (g) 40 Copper 25/100 25/100 25/100
25/100 20/100 20/100 20/100 Adhesion
TABLE-US-00003 TABLE 3 Comp. Ex. 22 Ex. 23 Ex. 24 Ex. 6 Resin (A)
Polymer 5 100 (g) Polymer 7 100 (g) Polymer 8 100 (g) Polymer 9 100
(g) Photosensitive TR-PBG-305 2 2 2 2 Component (B) (g) OXE-01 (g)
Initiator A Solvent (C1) GBL (g) 160 160 160 160 Solvent (C2) DMSO
(g) 40 40 40 40 Chemical A A A B Resistance Copper 15/100 10./100
10/100 70/100 Adhesion
Second Embodiment
[1075] The following provides an explanation of Examples 25 to 44
and Comparative Examples 7 and 8 as a second embodiment of the
present invention. In the examples and comparative examples,
physical properties of the photosensitive resin composition were
measured and evaluated in accordance with the methods indicated
below.
[1076] (1) Weight Average Molecular Weight
[1077] The weight average molecular weight (Mw) of each polyimide
precursor was determined in the same manner as the previously
described first embodiment.
[1078] (2) Fabrication of Rounded Out Concave Relief Patterns and
Evaluation of Focus Margin
[1079] <Steps (1) and (2)>
[1080] Ti at a thickness of 200 nm and copper at a thickness of 400
nm were sequentially sputtered on a 6-inch silicon wafer (Fujimi
Inc., thickness: 625.+-.25 .mu.m) using a sputtering device (Model
L-440S -FHL, Canon Anelva Corp.) to prepare sputtered Cu wafer
substrates.
[1081] A photosensitive resin composition was spin-coated on the
aforementioned sputtered Cu wafer substrates using a spin coating
device (Model D-Spin60A, Sokudo Co., Ltd.) followed by heating and
drying for 270 seconds at 110.degree. C. to prepare a spin-coated
film having a film thickness of 13 .mu.m.+-.0.2 .mu.m.
[1082] <Steps (3) and (4)>
[1083] The spin-coated film was irradiated at an energy level of
300 mJ/cm.sup.2 to 700 mJ/cm.sup.2 in 100 mJ/cm.sup.2 increments
with the Prisma GHI S/N 5503 equal-magnification projection
exposure device (Ultratech, Inc.) using a test pattern reticule
having a circular pattern of a mask size of 8 .mu.m in diameter. At
this time, the focus was moved 2 .mu.m at a time towards the bottom
of the film for each exposure level using the surface of the
spin-coated film as a reference.
[1084] Next, the coating film formed on the sputtered Cu wafer was
spray-developed with a developing machine (Model D-SPIN636,
Dainippon Screen Mfg. Co., Ltd.) using cyclopentanone to obtain a
rounded out concave relief pattern of a polyamic acid ester by
rinsing with propylene glycol methyl ether acetate. Furthermore,
the duration of spray development for the above-mentioned 13 .mu.m
spin-coated film was defined as the amount of time equal to 1.4
times the minimum amount of time for developing unexposed portions
of the resin composition.
[1085] <Step (5)>
[1086] The sputtered Cu wafer having the rounded out concave relief
pattern formed thereon was subjected to heat treatment by heating
to 230.degree. C. at a heating rate of 5.degree. C./min in a
nitrogen atmosphere using a programmable curing oven (Model
VF-2000, Koyo Lindberg Ltd.) and holding at 230.degree. C. for 2
hours to obtain a polyimide rounded out concave relief pattern
having a mask size of 8 .mu.m on the sputtered Cu wafer substrate.
Each of the resulting patterns was observed for pattern form and
pattern width with a light microscope followed by determination of
focus margin.
[1087] <Evaluation of Focus Margin>
[1088] The propriety of openings in the rounded out concave relief
pattern having a mask size of 8 .mu.m obtained by going through
steps (1) to (5) in order was judged to be acceptable if it
satisfied either of the following criteria (I) and (II).
[1089] (I) Area of the pattern openings is equal to 1/2 of more the
opening area of the corresponding pattern mask.
[1090] (II) The pattern cross-section does not demonstrating
tailing and there is no occurrence of undercutting, swelling or
bridging.
[1091] <Evaluation of Opening Pattern Cross-Sectional
Angle>
[1092] The following provides an explanation of the method used to
evaluate the cross-sectional angle of a relief pattern obtained by
going through steps (1) to (5) in order. A sputtered Cu wafer
obtained by going through steps (1) to (5) in order was immersed in
liquid nitrogen and a portion consisting of a line and space (1:1)
having a width of 50 .mu.m was fractured in the vertical direction
relative to the line. The resulting cross-section was observed with
a scanning electron microscope (SEM, Model S-4800, Hitachi
High-Technologies Corp.). Cross-sectional angle was evaluated
according to the method described in the following steps a to e
with reference to FIGS. 1A to 1E:
[1093] a. lines are drawn on the upper side and lower side of the
opening (FIG. 1A);
[1094] b. the height of the opening is determined (FIG. 1B);
[1095] c. a straight line parallel to the upper side and lower side
that passes through the midpoint of height (center line) is drawn
(FIG. 1C);
[1096] d. the intersection between the center line and opening
pattern (center point) is determined (FIG. 1D); and,
[1097] e. A line is drawn on the center line that is tangent to the
slope of the pattern, and the angle formed by that tangent line and
the lower side is treated as the cross-sectional angle (FIG.
1E).
[1098] <Evaluation of Electrical Properties>
[1099] The following provides an explanation of the method used to
evaluate electrical properties of a semiconductor device produced
using a varnish of the resulting photosensitive polyimide
precursor. A silicon nitride layer (PD-220NA, Samco Inc.) was
formed on a 6-inch silicon wafer (Fujimi Inc., thickness: 625.+-.25
.mu.m). The photosensitive resin compositions obtained in Examples
1 to 15 and Comparative Examples 1 to 5 were coated onto the
silicon nitride layer with a spin coating device (Model D-Spin60A,
Sokudo Co., Ltd.) to obtain a resin film of a photosensitive
polyimide precursor. A prescribed pattern was formed using the
Prisma GHI S/N 5503 equal-magnification projection exposure device
(Ultratech, Inc.). Next, the resin film formed on the wafer was
spray-developed with a developing machine (Model D-SPIN636,
Dainippon Screen Mfg. Co., Ltd.) using cyclopentanone to obtain a
prescribed relief pattern of a polyamic acid ester by rinsing with
propylene glycol methyl ether acetate. The resulting wafer was
subjected to heat treatment for 2 hours at a temperature of
230.degree. C. in a nitrogen atmosphere using a programmable curing
oven (Model VF-2000, Koyo Lindberg Ltd.) to obtain an interlayer
insulating film. Next, metal wiring was formed on the
aforementioned interlayer insulating film so as to form a
prescribed pattern to obtain a semiconductor device. The degree of
wiring delay was compared between the semiconductor device obtained
in this manner and a semiconductor device having a silicon oxide
insulating film employing the same configuration as this
semiconductor device. The signal delay time determined by
converting from the oscillation frequency of a ring oscillator was
used for the evaluation reference. Both of the semiconductor
devices were compared and evaluated for acceptability according to
the criteria indicated below.
[1100] Acceptable: Semiconductor device has a smaller signal delay
than the semiconductor device obtained using a silicon oxide
insulating film.
[1101] Unacceptable: Semiconductor device has a larger signal delay
than the semiconductor device obtained using a silicon oxide
insulating film.
<Production Example 1a> (Synthesis of Polyimide Precursor
(A)-1)
[1102] 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) were placed
in a separable flask having a volume of 2 liters followed by adding
131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of
.gamma.-butyrolactone, stirring at room temperature, and adding
81.5 g of pyridine while stirring to obtain a reaction mixture.
Following completion of generation of heat by the reaction, the
reaction mixture was allowed to cool to room temperature and then
allowed to stand for 16 hours.
[1103] Next, a solution obtained by dissolving 206.3 g of
dicyclohexylcarbodiimide (DCC) in 180 ml of .gamma.-butyrolactone
was added to the reaction mixture over the course of 40 minutes
while cooling with ice and stirring followed by adding a suspension
of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of
.gamma.-butyrolactone over the course of 60 minutes while stirring.
After further stirring for 2 hours at room temperature, 30 ml of
ethyl alcohol were added followed by stirring for 1 hour and then
adding 400 ml of .gamma.-butyrolactone. The precipitate that formed
in the reaction mixture was removed by filtration to obtain a
reaction liquid.
[1104] The resulting reaction liquid was added to 3 L of ethyl
alcohol to form a precipitate composed of a crude polymer. The
resulting crude polymer was filtered out and dissolved in 1.5 L of
tetrahydrofuran to obtain a crude polymer solution. The resulting
crude polymer solution was dropped into 28 L of water to
precipitate the polymer, and after filtering out the resulting
precipitate, the precipitate was vacuum-dried to obtain a powdered
polymer (Polyimide Precursor (A)-1). When the molecular weight of
Polyimide Precursor (A)-1 was measured by gel permeation
chromatography (standard polystyrene conversion), the weight
average molecular weight (Mw) thereof was 20,000.
<Production Example 2a> (Synthesis of Polyimide Precursor
(A)-2)
[1105] A reaction was carried out in the same manner as the method
described in the previously described Production Example 1 with the
exception of using 147.1 g of 3,3',4,4'-biphenyltetracarboxylic
dianhydride (BPDA) instead of the 155.1 g of 4,4'-oxydiphthalic
dianhydride (ODPA) used in Production Example 1a to obtain Polymer
(A)-2). When the molecular weight of Polymer (A)-2 was measured by
gel permeation chromatography (standard polystyrene conversion),
the weight average molecular weight (Mw) thereof was 22,000.
<Production Example 3a> (Synthesis of Polyimide Precursor
(A)-3)
[1106] A reaction was carried out in the same manner as the method
described in the previously described Production Example 1 with the
exception of using 98.6 g of 2,2'-dimethylbiphenyl-4,4'-diamine
(m-TB) instead of the 93.0 g of 4,4'-diaminodiphenyl ether (DADPE)
used in Production Example 1a to obtain Polymer (A)-3. When the
molecular weight of Polymer (A)-3 was measured by gel permeation
chromatography (standard polystyrene conversion), the weight
average molecular weight (Mw) thereof was 21,000.
<Production Example 4a> (Synthesis of Polyimide Precursor
(A)-4)
[1107] A reaction was carried out in the same manner as the method
described in the previously described Production Example 1 with the
exception of using 147.1 g of 3,3',4,4'-biphenyltetracarboxylic
dianhydride (BPDA) instead of the 155.1 g of 4,4'-oxydiphthalic
dianhydride (ODPA) used in Production Example 1a and using 98.6 g
of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) instead of the 93.0 g
of 4,4'-diaminodiphenyl ether (DADPE) to obtain Polymer (A)-4. When
the molecular weight of Polymer (A)-4 was measured by gel
permeation chromatography (standard polystyrene conversion), the
weight average molecular weight (Mw) thereof was 21,000.
<Production Example 5a> (Synthesis of Polyimide Precursor
(A)-5)
[1108] A reaction was carried out in the same manner as the method
described in the previously described Production Example 1 with the
exception of using 109.1 g of pyromellitic anhydride (PMDA) instead
of the 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) used in
Production Example 1a and using 148.7 g of
2,2'-bis(trifluoromethyl)benzidine (TFMB) instead of the 93.0 g of
4,4'-diaminodiphenyl ether (DADPE) to obtain Polymer (A)-5. When
the molecular weight of Polymer (A)-5 was measured by gel
permeation chromatography (standard polystyrene conversion), the
weight average molecular weight (Mw) thereof was 21,000.
<Production Example 6a> (Synthesis of Polyimide Precursor
(A)-6)
[1109] A reaction was carried out in the same manner as the method
described in the previously described Production Example 1 with the
exception of using 148.7 g of 2,2'-bis(trifluoromethyl)benzidine
(TFMB) instead of the 93.0 g of 4,4'-diaminodiphenyl ether (DADPE)
used in Production Example 1a to obtain Polymer (A)-6. When the
molecular weight of Polymer (A)-6 was measured by gel permeation
chromatography (standard polystyrene conversion), the weight
average molecular weight (Mw) thereof was 22,000.
<Production Example 7a> (Synthesis of Polyimide Precursor
(A)-7)
[1110] A reaction was carried out in the same manner as the method
described in the previously described Production Example 1 with the
exception of using a mixture of 77.6 g of 4,4'-oxydiphthalic
dianhydride (ODPA) and 73.6 g of 3,3',4,4'-biphenyltetracarboxylic
dianhydride (BPDA) instead of the 155.1 g of 4,4'-oxydiphthalic
dianhydride (ODPA) used in Production Example 1a to obtain Polymer
(A)-7. When the molecular weight of Polymer (A)-7 was measured by
gel permeation chromatography (standard polystyrene conversion),
the weight average molecular weight (Mw) thereof was 21,000.
Example 25
[1111] A photosensitive resin composition was prepared according to
the method indicated below using Polyimide Precursor (A)-1 followed
by evaluation of the focus margin and electrical properties
thereof. 100 g of Polyimide Precursor (A)-1, 2 g of TR-PBG-305
((B)-1, trade name, Changzhou Tronly New Electronic Materials Co.,
Ltd.), 12 g of tetraethylene glycol dimethacrylate ((C)-2), 0.2 g
of 2,6-di-tert-butyl-p-cresol ((D)-1) and 4 g of
2,2'-(phenylimino)diethanol ((E)-1) were dissolved in a mixed
solvent composed of 80 g of N-methyl-2-pyrrolidone (NMP) and 20 g
of ethyl lactate. The viscosity of the resulting solution was
adjusted to about 35 poise by further adding a small amount of the
aforementioned mixed solvent to obtain a photosensitive resin
composition.
[1112] A polyimide rounded out concave relief pattern was produced
on a sputtered Cu wafer substrate using this composition according
to the aforementioned steps (1) to (5), and when focus margin was
determined according to the method described in the previous
section on "Evaluation of Focus Margin", the focus margin was 16
.mu.m.
[1113] In addition, when cross-sectional angle was determined
according to the method described in the previous section on
"Evaluation of Opening Pattern Cross-Sectional Angle",
cross-sectional angle was 83.degree.. Moreover, when electrical
properties were evaluated according to the method described in the
previous section on "Evaluation of Electrical Properties", the
composition was judged to be acceptable.
Example 26
[1114] Focus margin, cross-sectional angle and electrical
properties were evaluated in the same manner as Example 25 with the
exception of changing component (B)-1 used in the aforementioned
Example 25 to 2 g of TR-PBG-3057 ((B)-2, trade name, Changzhou
Tronly New Electronic Materials Co., Ltd.) and changing the amount
of (E)-1 to 8 g. As a result, focus margin was 16 .mu.m,
cross-sectional angle was 78.degree., and electrical properties
were acceptable.
Example 27
[1115] Focus margin, cross-sectional angle and electrical
properties were evaluated in the same manner as Example 25 with the
exception of changing component (B)-1 used in the aforementioned
Example 25 to 2 g of 1,2-octandione, 1-{4-(phenylthio)-,
2-(O-benzoyloxime)} ((B)-3), Irgacure OXE01, trade name, BASF
Corp.). As a result, focus margin was 16 .mu.m, cross-sectional
angle was 77.degree., and electrical properties were
acceptable.
Example 28
[1116] Focus margin, cross-sectional angle and electrical
properties were evaluated in the same manner as Example 25 with the
exception of changing component (B)-1 used in the aforementioned
Example 25 to 2 g of a compound represented by formula (66) ((B)-4)
and changing the amount of (E)-1 to 8 g. As a result, focus margin
was 14 .mu.m, cross-sectional angle was 70.degree., and electrical
properties were acceptable.
Example 29
[1117] Focus margin, cross-sectional angle and electrical
properties were evaluated in the same manner as Example 25 with the
exception of changing the added amount of component (B)-1 used in
the aforementioned Example 25 to 4 g. As a result, focus margin was
12 .mu.m, cross-sectional angle was 85.degree., and electrical
properties were acceptable.
Example 30
[1118] Focus margin, cross-sectional angle and electrical
properties were evaluated in the same manner as Example 25 with the
exception of changing component (C)-1 used in the aforementioned
Example 25 to 12 g of nonaethylene glycol dimethacrylate ((C)-2).
As a result, focus margin was 8 .mu.m, cross-sectional angle was
83.degree., and electrical properties were acceptable.
Example 31
[1119] Focus margin, cross-sectional angle and electrical
properties were evaluated in the same manner as Example 25 with the
exception of changing component (C)-1 used in the aforementioned
Example 25 to 12 g of diethylene glycol dimethacrylate ((C)-3). As
a result, focus margin was 12 .mu.m, cross-sectional angle was
83.degree., and electrical properties were acceptable.
Example 32
[1120] Focus margin, cross-sectional angle and electrical
properties were evaluated in the same manner as Example 25 with the
exception of changing component (A)-1 used in the aforementioned
Example 25 to 100 g of (A)-2 and changing the added amount of
component (E)-1 to 12 g. As a result, focus margin was 16 .mu.m,
cross-sectional angle was 68.degree., and electrical properties
were acceptable.
Example 33
[1121] Focus margin, cross-sectional angle and electrical
properties were evaluated in the same manner as Example 25 with the
exception of changing component (A)-1 used in the aforementioned
Example 25 to 100 g of (A)-3. As a result, focus margin was 10
.mu.m, cross-sectional angle was 85.degree., and electrical
properties were acceptable.
Example 34
[1122] Focus margin, cross-sectional angle and electrical
properties were evaluated in the same manner as Example 25 with the
exception of changing component (A)-1 used in the aforementioned
Example 25 to 100 g of (A)-4. As a result, focus margin was 10
.mu.m, cross-sectional angle was 85.degree., and electrical
properties were acceptable.
Example 35
[1123] Focus margin, cross-sectional angle and electrical
properties were evaluated in the same manner as Example 25 with the
exception of changing component (A)-1 used in the aforementioned
Example 25 to 100 g of (A)-5. As a result, focus margin was 8
.mu.m, cross-sectional angle was 75.degree., and electrical
properties were acceptable.
Example 36
[1124] Focus margin, cross-sectional angle and electrical
properties were evaluated in the same manner as Example 25 with the
exception of changing component (A)-1 used in the aforementioned
Example 25 to 100 g of (A)-6. As a result, focus margin was 14
.mu.m, cross-sectional angle was 70.degree., and electrical
properties were acceptable.
Example 37
[1125] Focus margin, cross-sectional angle and electrical
properties were evaluated in the same manner as Example 25 with the
exception of changing component (A)-1 used in the aforementioned
Example 25 to a mixture of 50 g of (A)-1) and 50 g of (A)-2 and
changing the added amount of component (E)-1 to 8 g. As a result,
focus margin was 14 .mu.m, cross-sectional angle was 80.degree.,
and electrical properties were acceptable.
Example 38
[1126] Focus margin, cross-sectional angle and electrical
properties were evaluated in the same manner as Example 25 with the
exception of changing the added amount of component (D)-1 used in
the aforementioned Example 25 to 1 g. As a result, focus margin was
10 .mu.m, cross-sectional angle was 75.degree., and electrical
properties were acceptable.
Example 39
[1127] Focus margin, cross-sectional angle and electrical
properties were evaluated in the same manner as Example 25 with the
exception of changing the solvent used in the aforementioned
Example 25 from NMP to a mixture of 80 g of .gamma.-butyrolactone
and 20 g of dimethylsulfoxide. As a result, focus margin was 12
.mu.m, cross-sectional angle was 85.degree., and electrical
properties were acceptable.
Example 40
[1128] Focus margin, cross-sectional angle and electrical
properties were evaluated in the same manner as Example 25 with the
exception of changing (D)-1 used in the aforementioned Example 25
to (D)-2 in the form of p-methoxyphenol. As a result, focus margin
was 16 .mu.m, cross-sectional angle was 82.degree., and electrical
properties were acceptable.
Example 41
[1129] Focus margin, cross-sectional angle and electrical
properties were evaluated in the same manner as Example 25 with the
exception of changing (D)-1 used in the aforementioned Example 25
to (D)-3 in the form of 4-t-butylpyrocatechol. As a result, focus
margin was 16 .mu.m, cross-sectional angle was 80.degree., and
electrical properties were acceptable.
Example 42
[1130] Focus margin, cross-sectional angle and electrical
properties were evaluated in the same manner as Example 25 with the
exception of changing (D)-1 used in the aforementioned Example 25
to (D)-4 in the form of N,N-diphenylnitrosoamide. As a result,
focus margin was 16 .mu.m, cross-sectional angle was 78.degree.,
and electrical properties were acceptable.
Example 43
[1131] Focus margin, cross-sectional angle and electrical
properties were evaluated in the same manner as Example 25 with the
exception of changing (D)-1 used in the aforementioned Example 25
to (D)-5 in the form of ammonium N-nitrosophenylhydroxylamine. As a
result, focus margin was 16 .mu.m, cross-sectional angle was
80.degree., and electrical properties were acceptable.
Example 44
[1132] Focus margin, cross-sectional angle and electrical
properties were evaluated in the same manner as Example 25 with the
exception of changing component (A)-1 used in the aforementioned
Example 25 to 100 g of (A)-7. As a result, focus margin was 10
.mu.m, cross-sectional angle was 82.degree., and electrical
properties were acceptable.
Comparative Example 7
[1133] Focus margin, cross-sectional angle and electrical
properties were evaluated in the same manner as Example 25 with the
exception of changing component (B)-1 used in the aforementioned
Example 25 to 2 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)
oxime ((B)-5). As a result, focus margin was 4 .mu.m,
cross-sectional angle was 88.degree., and electrical properties
were unacceptable.
Comparative Example 8
[1134] Focus margin, cross-sectional angle and electrical
properties were evaluated in the same manner as Example 25 with the
exception of changing (D)-1 used in the aforementioned Example 25
to (D)-5 in the form of 1,1-diphenyl-2-picrylhydrazyl free radical.
As a result, focus margin was 4 .mu.m, cross-sectional angle was
92.degree., and electrical properties were unacceptable.
[1135] The results for Examples 25 to 44 and Comparative Examples 7
and 8 are collectively shown in Table 4.
TABLE-US-00004 TABLE 4 Ex. 25 Ex. 26 Ex. 27 Ex. 28 Ex. 29 Ex. 30
Ex. 31 Ex. 32 Ex. 33 Ex. 34 Ex. 35 Polymer (A)-1 100 100 100 100
100 100 100 Component (A) (A)-2 100 (A)-3 100 (A)-4 100 (A)-5 100
(A)-6 (A)-7 Initiator (B)-1 2 4 2 2 2 2 2 2 Component (B) (B)-2 2
(B)-3 2 (B)-4 2 (B)-5 Monomer (C)-1 12 12 12 12 12 12 12 12 12
Component (C) (C)-2 12 (C)-3 12 Polymerization (D)-1 0.2 0.2 0.2
0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Inhibitor (D-2) (D)-3 (D)-4 (D)-5
(D)-6 Intensifier (E)-1 4 8 4 8 4 4 4 12 4 4 4 Solvent NMP 100 100
100 100 100 100 100 100 100 100 100 GBL DMSO Focus Margin 16 .mu.m
16 .mu.m 16 .mu.m 14 .mu.m 12 .mu.m 8 .mu.m 12 .mu.m 16 .mu.m 10
.mu.m 10 .mu.m 8 .mu.m Cross-Sectional 83 78 77 70 85 83 83 68 85
85 75 Angle Electrical Accept- Accept- Accept- Accept- Accept-
Accept- Accept- Accept- Accept- Accept- Accept- Properties able
able able able able able able able able able able Comp. Comp. Ex.
36 Ex. 37 Ex. 38 Ex. 39 Ex. 40 Ex. 41 Ex. 42 Ex. 43 Ex. 44 Ex. 7
Ex. 8 Polymer (A)-1 50 100 100 100 100 100 100 100 100 Component
(A) (A)-2 50 (A)-3 (A)-4 (A)-5 (A)-6 100 (A)-7 100 Initiator (B)-1
2 2 2 2 2 2 2 2 2 2 Component (B) (B)-2 (B)-3 (B)-4 (B)-5 2 Monomer
(C)-1 12 12 12 12 12 12 12 12 12 12 12 Component (C) (C)-2 (C)-3
Polymerization (D)-1 0.2 0.2 1 0.2 0.2 0.2 Inhibitor (D-2) 0.2
(D)-3 0.2 (D)-4 0.2 (D)-5 0.2 (D)-6 0.2 Intensifier (E)-1 4 8 4 4 4
4 4 4 4 4 4 Solvent NMP 100 100 100 100 100 100 100 100 100 100 GBL
80 DMSO 20 Focus Margin 14 .mu.m 14 .mu.m 10 .mu.m 12 .mu.m 16
.mu.m 16 .mu.m 16 .mu.m 16 .mu.m 10 .mu.m 4 .mu.m 4 .mu.m
Cross-Sectional 70 80 75 85 82 80 78 80 82 88 92 Angle Electrical
Accept- Accept- Accept- Accept- Accept- Accept- Accept- Accept-
Accept- Un- Un- Properties able able able able able able able able
able Accept- Accept- able able
Third Embodiment
[1136] The following provides an explanation of Examples 45 to 51
and Comparative Examples 9 and 10 as a third embodiment of the
present invention. In the examples and comparative examples,
physical properties of the photosensitive resin composition were
measured and evaluated in accordance with the methods indicated
below.
[1137] (1) Weight Average Molecular Weight
[1138] The weight average molecular weight (Mw) of each polyamic
acid ester synthesized according to the previously described method
was measured using gel permeation chromatography by standard
polystyrene conversion. GPC analysis conditions are indicated
below.
[1139] Column: Shodex 805M/806M serial columns (trade name, Showa
Denko K.K.)
[1140] Standard monodisperse polystyrene: Shodex STANDARD SM-105
(trade name,
[1141] Showa Denko K.K.)
[1142] Eluent: N-methyl-2-pyrrolidone, 40.degree. C.
[1143] Flow rate: 1.0 ml/min
[1144] Detector: Shodex RI-930 (trade name, Showa Denko K.K.)
[1145] (2) Production of Cured Film on Cu
[1146] Ti at a thickness of 200 nm and copper at a thickness of 400
nm were sequentially sputtered on a 6-inch silicon wafer (Fujimi
Inc., thickness: 625.+-.25 .mu.m) using a sputtering device (Model
L-440S -FHL, Canon Anelva Corp.). Continuing, a photosensitive
resin composition prepared according to the method to be
subsequently described was spin-coated on the wafer using a coater
developer (Model D-Spin60A, Sokudo Co., Ltd.) followed by drying to
form a coating film having a thickness of about 15 .mu.m. The
entire surface of this coating film was then irradiated at an
energy level of 900 mJ/cm.sup.2 with a parallel light mask aligner
(Model PLA-501FA, Canon Inc.). Next, coating film was
spray-developed with a coater developer (Model D-Spin60A, Sokudo
Co., Ltd.) using cyclopentanone for the developer followed by
rinsing with propylene glycol methyl ether acetate to obtain a
developed film on Cu.
[1147] The wafer having the developed film on Cu was subjected to
heat treatment for 2 hours at the temperature described in each
example in a nitrogen atmosphere using a programmable curing oven
(Model VF-2000, Koyo Lindberg Ltd.) to obtain a cured film composed
of a polyimide resin having a thickness of about 10 .mu.m to 15
.mu.m on the Cu.
[1148] (3) Measurement of Peel Strength of Cured Film on Cu
[1149] After affixing adhesive step (thickness: 500 .mu.m) to the
cured film formed on the Cu, cut portions having a width of 5 mm
were made in the cured film with a box knife, and the cut portions
were measured for 180.degree. peel strength based on JIS K 6854-2.
The conditions for the tensile test at that time were as indicated
below.
[1150] Load cell: 50 N
[1151] Pulling speed: 50 mm/min
[1152] Travel: 60 mm
<Production Example 1b> (Synthesis of Photosensitive
Polyimide Precursor (A)
[1153] (Polymer A-1))
[1154] 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) were placed
in a separable flask having a volume of 2 liters followed by the
addition of 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400
ml of .gamma.-butyrolactone and adding 79.1 g of pyridine while
stirring at room temperature to obtain a reaction mixture.
Following completion of generation of heat by the reaction, the
reaction mixture was allowed to cool to room temperature and then
allowed to stand undisturbed for 16 hours.
[1155] Next, a solution obtained by dissolving 206.3 g of
dicyclohexylcarbodiimide (DCC) in 180 ml of .gamma.-butyrolactone
was added to the reaction mixture over the course of 40 minutes
while cooling with ice and stirring followed by adding a suspension
of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of
.gamma.-butyrolactone over the course of 60 minutes while stirring.
After further stirring for 2 hours at room temperature, 30 ml of
ethyl alcohol were added followed by stirring for 1 hour and then
adding 400 ml of .gamma.-butyrolactone. The precipitate that formed
in the reaction mixture was removed by filtration to obtain a
reaction liquid.
[1156] The resulting reaction liquid was added to 3 L of ethyl
alcohol to form a precipitate composed of a crude polymer. The
resulting crude polymer was filtered out and dissolved in 1.5 L of
tetrahydrofuran to obtain a crude polymer solution. The resulting
crude polymer solution was dropped into 28 L of water to
precipitate the polymer, and after filtering out the resulting
precipitate, the precipitate was vacuum-dried to obtain a powdered
polymer A-1.
[1157] When the weight average molecular weight (Mw) of this
Polymer A-1 was measured, the weight average molecular weight (Mw)
thereof was 20,000.
<Production Example 2b> (Synthesis of Photosensitive
Polyimide Precursor (A)
[1158] (Polymer A-2))
[1159] Polymer A-2 was obtained by carrying out a reaction in the
same manner as the method described in Production Example 1b with
the exception of using 147.1 g of 3,3',4,4'-biphenyltetracarboxylic
dianhydride instead of the 155.1 g of 4,4'-oxydiphthalic
dianhydride used in the aforementioned Production Example 1b. When
the weight average molecular weight (Mw) of Polymer A-2 was
measured, the weight average molecular weight (Mw) thereof was
22,000.
<Production Example 3b> (Synthesis of Photosensitive
Polyimide Precursor (A)
[1160] (Polymer A-3))
[1161] Polymer A-3 was obtained by carrying out a reaction in the
same manner as the method described in Production Example 1b with
the exception of using 147.8 g of
2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB) instead of
the 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) used in the
aforementioned Production Example 1b. When the weight average
molecular weight (Mw) of Polymer A-3 was measured, the weight
average molecular weight (Mw) thereof was 21,000.
Example 45
[1162] Component (A) in the form of 50 g of Polymer A-1 and 50 g of
Polymer A-2, 2 g of Component (B) in the form of TR-PBG-346 (trade
name, Changzhou Tronly New Electronic Materials Co., Ltd.), 8 g of
Component (C) in the form of tetraethylene glycol dimethacrylate,
0.05 g of 2-nitroso-1-naphthol, 4 g of N-phenyldiethanolamine, 0.5
g of N-(3-(triethoxysilyl)propyl)phthalamic acid and 0.5 g of
benzophenone-3,3'-bis(N-(3-triethoxysilyl)propylamide)-4,4'-dicarboxylic
acid were dissolved in a mixed solvent of N-methylpyrrolidone and
ethyl lactate (mixing ratio 8:2), and viscosity was adjusted to
about 35 poise by adjusting the amount of solvent to obtain a
photosensitive resin composition solution.
[1163] After coating, exposing and developing this composition on
Cu according to the previously described methods, the composition
was cured at 230.degree. C. to produce a cured film on a Cu layer,
and measurement of the peel strength thereof yielded a value of
0.63 N/mm.
Example 46
[1164] A photosensitive resin composition solution was prepared in
the same manner as Example 45 with the exception of changing the
amount of TR-PBG-346 added as Component (B) in the aforementioned
Example 45 to 4 g.
[1165] After coating, exposing and developing this composition on
Cu according to the previously described methods, the composition
was cured at 230.degree. C. to produce a cured film on a Cu layer,
and measurement of the peel strength thereof yielded a value of
0.61 N/mm.
Example 47
[1166] A photosensitive resin composition solution was prepared in
the same manner as Example 45 with the exception of changing the
amount of TR-PBG-346 added as Component (B) in the aforementioned
Example 45 to 1 g.
[1167] After coating, exposing and developing this composition on
Cu according to the previously described methods, the composition
was cured at 230.degree. C. to produce a cured film on a Cu layer,
and measurement of the peel strength thereof yielded a value of
0.60 N/mm.
Example 48
[1168] A photosensitive resin composition solution was prepared in
the same manner as Example 45. After coating, exposing and
developing this composition on Cu according to the previously
described methods, the composition was cured at 350.degree. C. to
produce a cured film on a Cu layer, and measurement of the peel
strength thereof yielded a value of 0.58 N/mm.
Example 49
[1169] A photosensitive resin composition solution was prepared in
the same manner as Example 45 with the exception of using 100 g of
Polymer A-1 instead of the mixture of 50 g of Polymer A-1 and 50 g
of Polymer A-2 used as Component (A) in the aforementioned Example
45.
[1170] After coating, exposing and developing this composition on
Cu according to the previously described methods, the composition
was cured at 230.degree. C. to produce a cured film on a Cu layer,
and measurement of the peel strength thereof yielded a value of
0.66 N/mm.
Example 50
[1171] A photosensitive resin composition solution was prepared in
the same manner as Example 45 with the exception of using 100 g of
Polymer A-1 instead of the mixture of 50 g of Polymer A-1 and 50 g
of Polymer A-2 used as Component (A) in the aforementioned Example
45, and changing the solvent used as Component (C) from the mixed
solvent of N-methylpyrrolidone and ethyl lactate (mixing ratio 8:2)
to .gamma.-butyrolactone and dimethylsulfoxide (mixing ratio
85:15).
[1172] After coating, exposing and developing this composition on
Cu according to the previously described methods, the composition
was cured at 230.degree. C. to produce a cured film on a Cu layer,
and measurement of the peel strength thereof yielded a value of
0.65 N/mm.
Example 51
[1173] A photosensitive resin composition solution was prepared in
the same manner as Example 45 with the exception of using 100 g of
Polymer A-3 instead of the mixture of 50 g of Polymer A-1 and 50 g
of Polymer A-2 used as Component (A) in the aforementioned Example
45.
[1174] After coating, exposing and developing this composition on
Cu according to the previously described methods, the composition
was cured at 350.degree. C. to produce a cured film on a Cu layer,
and measurement of the peel strength thereof yielded a value of
0.50 N/mm.
Comparative Example 9
[1175] A photosensitive resin composition solution was prepared in
the same manner as Example 45 with the exception of using 2 g of
TR-PBG-304 (trade name, Changzhou Tronly New Electronic Materials
Co., Ltd.) instead of Component (B) in the aforementioned Example
45.
[1176] After coating, exposing and developing this composition on
Cu according to the previously described methods, the composition
was cured at 230.degree. C. to produce a cured film on a Cu layer,
and measurement of the peel strength thereof yielded a value of
0.41 N/mm.
Comparative Example 10
[1177] A photosensitive resin composition solution was prepared in
the same manner as Example 45 with the exception of using 2 g of
TR-PBG-304 (trade name, Changzhou Tronly New Electronic Materials
Co., Ltd.) instead of Component (B) in the aforementioned Example
45.
[1178] After coating, exposing and developing this composition on
Cu according to the previously described methods, the composition
was cured at 350.degree. C. to produce a cured film on a Cu layer,
and measurement of the peel strength thereof yielded a value of
0.38 N/mm.
[1179] The results of evaluating peel strength of the adhesive film
from the Cu for the photosensitive resin compositions of Examples
45 to 51 and Comparative Examples 9 and 10 are shown in Table 5.
Since PBG-304 (b-1) does not demonstrate absorbance in the g-line
and h-line regions, peel strength of the cured film obtained by
using PBG-304, from Cu, was lower in comparison with PBG-346 (B-1)
that demonstrates absorbance in the g-line and h-line regions.
TABLE-US-00005 TABLE 5 Ratio of Number of Parts Added of
Alternative Component (B)/ Curing Cu Peel Component (A) Component
(B) Component Component (A) Temperature .degree. C. Strength N/mm
Example 45 Polymer A-1/ B-1 2/100 230 0.63 Polymer A-2 Example 46
Polymer A-1/ B-1 4/100 230 0.61 Polymer A-2 Example 47 Polymer A-1/
B-1 1/100 230 0.60 Polymer A-2 Example 48 Polymer A-1/ B-1 2/100
230 0.58 Polymer A-2 Example 49 Polymer A-1/ B-1 2/100 350 0.66
Polymer A-2 Example 50 Polymer A-1 B-1 2/100 230 0.65 Example 51
Polymer A-3 B-1 2/100 350 0.50 Comparative Polymer A-1/ b-1 2/100
230 0.41 Example 9 Polymer A-2 Comparative Polymer A-1/ b-1 2/100
350 0.38 Example 10 Polymer A-2
[1180] Explanation of abbreviations used in Table 5:
[1181] (Component B)
[1182] B-1: TR-PBG-346 (trade name, Changzhou Tronly New Electronic
Materials Co., Ltd.)
##STR00221##
[1183] b-1: TR-PBG-304 (trade name, Changzhou Tronly New Electronic
Materials Co., Ltd.)
##STR00222##
Fourth Embodiment
[1184] The following provides an explanation of Examples 52 to 67
and Comparative Examples 11 to 13 as a fourth embodiment of the
present invention. In the examples and comparative examples,
physical properties of the photosensitive resin composition were
measured and evaluated in accordance with the methods indicated
below.
[1185] (1) Weight Average Molecular Weight
[1186] The weight average molecular weight (Mw) of each polyimide
precursor was determined in the same manner as the previously
described first embodiment.
[1187] (2) Production of Cured Relief Pattern on Cu Subjected to
Surface Treatment
[1188] A photosensitive resin composition prepared according to the
method to be subsequently described was spin-coated on Cu subjected
to surface treatment using a coater developer (Model D-Spin60A,
Sokudo Co., Ltd.) followed by drying to form a coating film having
a thickness of 10 .mu.m. This coating film was then irradiated at
an energy level of 300 mJ/cm.sup.2 with a parallel light mask
aligner (Model PLA-501FA, Canon Inc.) using a mask having a test
pattern. Next, this coating film was spray-developed with a coater
developer (Model D-Spin60A, Sokudo Co., Ltd.) using cyclopentanone
in the case of a negative type or using 2.38% TMAH in the case of a
positive type followed by rinsing with propylene glycol methyl
ether acetate in the case of a negative type or pure water in the
case of a positive type to obtain a relief pattern on Cu.
[1189] The wafer having the relief pattern formed on Cu was
subjected to heat treatment for 2 hours at the temperature
indicated in each example in a nitrogen atmosphere using a
programmable curing oven (Model VF-2000, Koyo Lindberg Ltd.) to
obtain a cured relief pattern composed of resin having a thickness
of about 6 .mu.m to 7 .mu.m on Cu.
[1190] (3) High Temperature Storage Test of Cured Relief Pattern on
Cu Subjected to
[1191] Surface Treatment and Subsequent Evaluation
[1192] A wafer having a relief pattern formed on Cu subjected to
surface treatment was subjected to heat treatment for 168 hours at
150.degree. C. in air using a programmable curing oven (Model
VF-2000, Koyo Lindberg Ltd.). Continuing, the resin layer on the Cu
was completely removed by plasma etching using a plasma surface
treatment device (Model EXAM, Shinko Seiki Co., Ltd.). The plasma
etching conditions are indicated below.
[1193] Output: 133 W
[1194] Gas types and flow rates: O.sub.2: 40 ml/min and CF.sub.4: 1
ml/min
[1195] Gas pressure: 50 Pa
[1196] Mode: Hard mode
[1197] Etching time: 1800 sec
[1198] The surface of the Cu from which the resin layer had been
completely removed was observed with a field emission scanning
electron microscope (FE-SEM, Model S-4800, Hitachi
High-Technologies Corp.), and the ratio of the surface area
occupied by voids to the total surface area of the Cu layer was
calculated using image analysis software (A-ZO Kun, Asahi Kasei
Corp.).
<Production Example 1> (Synthesis of Polymer A as Polyimide
Precursor)
[1199] 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) were placed
in a separable flask having a volume of 2 liters followed by adding
131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of
.gamma.-butyrolactone, stirring at room temperature, and adding
81.5 g of pyridine while stirring to obtain a reaction mixture.
Following completion of generation of heat by the reaction, the
reaction mixture was allowed to cool to room temperature and then
allowed to stand for 16 hours.
[1200] Next, a solution obtained by dissolving 206.3 g of
dicyclohexylcarbodiimide (DCC) in 180 ml of .gamma.-butyrolactone
was added to the reaction mixture over the course of 40 minutes
while cooling with ice and stirring followed by adding a suspension
of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of
.gamma.-butyrolactone over the course of 60 minutes while stirring.
After further stirring for 2 hours at room temperature, 30 ml of
ethyl alcohol were added followed by stirring for 1 hour and then
adding 400 ml of .gamma.-butyrolactone. The precipitate that formed
in the reaction mixture was removed by filtration to obtain a
reaction liquid.
[1201] The resulting reaction liquid was added to 3 L of ethyl
alcohol to form a precipitate composed of a crude polymer. The
resulting crude polymer was filtered out and dissolved in 1.5 L of
tetrahydrofuran to obtain a crude polymer solution. The resulting
crude polymer solution was dropped into 28 L of water to
precipitate the polymer, and after filtering out the resulting
precipitate, the precipitate was vacuum-dried to obtain a powdered
polymer (Polymer A). When the molecular weight of Polymer A was
measured by gel permeation chromatography (standard polystyrene
conversion), the weight average molecular weight (Mw) thereof was
20,000.
[1202] Furthermore, the weight average molecular weights of the
resins obtained in each production example were measured under the
following conditions using gel permeation chromatography (GPC), and
weight average molecular weight was determined by standard
polystyrene conversion.
[1203] Pump: JASCO PU-980
[1204] Detector: JASCO RI-930
[1205] Column oven: JASCO CO-965, 40.degree. C.
[1206] Column: Two Shodex KD-806M columns connected in series
[1207] Mobile phase: 0.1 mol/1 LiBr/NMP
[1208] Flow rate: 1 ml/min
<Production Example 2> (Synthesis of Polymer B as Polyimide
Precursor (A))
[1209] A reaction was carried out in the same manner as the method
described in the previously described Production Example 1 with the
exception of using 147.1 g of 3,3'4,4'-biphenyltetracarboxylic
dianhydride (BPDA) instead of the 155.1 g of 4,4'-oxydiphthalic
dianhydride (ODPA) used in Production Example 1 to obtain Polymer
B. When the molecular weight of Polymer B was measured by gel
permeation chromatography (standard polystyrene conversion), the
weight average molecular weight (Mw) thereof was 22,000.
<Production Example 3> (Synthesis of Polymer C as Polyimide
Precursor (A))
[1210] A reaction was carried out in the same manner as the method
described in the previously described Production Example 1 with the
exception of using 147.8 g of
2,2-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB) instead of the
93.0 g of 4,4'-diaminodiphenyl ether (DADPE) used in Production
Example 1 to obtain Polymer C. When the molecular weight of Polymer
C was measured by gel permeation chromatography (standard
polystyrene conversion), the weight average molecular weight (Mw)
thereof was 21,000.
<Production Example 4> (Synthesis of Polymer D as Polyimide
Precursor (A))
[1211] (Synthesis of Blocked Phthalic Acid Compound AIPA-MO)
[1212] 543.5 g of 5-aminoisophthalic acid (AIPA) and 1700 g of
N-methyl-2-pyrrolidone were placed in a separable flask having a
volume of 5 liters followed by mixing, stirring and heating to
50.degree. C. with a water bath. 512.0 g (3.3 mol) of
2-methacryloyloxyethyl isocyanate diluted with 500 g of
.gamma.-butyrolactone were dropped therein with a dropping funnel,
followed by stirring for about 2 hours at 50.degree. C.
[1213] After confirming completion of the reaction (disappearance
of 5-aminoisophthalic acid) by low molecular weight gel permeation
chromatography (to be referred to as "low molecular weight GPC"),
the reaction liquid was added to 15 liters of ion exchange water
followed by stirring, allowing to stand undisturbed, filtering out
the crystalline precipitate of the reaction product, suitably
rinsing with water and finally vacuum-drying for 48 hours at
40.degree. C. to obtain AIPA-MO obtained by a reaction of the amino
group of the 5-aminoisophthalic acid with the isocyanate group of
the 2-methacryloxyethyl isocyanate. The low molecular weight GPC
purity of the resulting AIPA-MO was about 100%.
[1214] (Synthesis of Polymer D)
[1215] 100.89 g (0.3 mol) of the resulting AIPA-MO, 71.2 g (0.9
mol) of pyridine and 400 g of GBL were placed in a separable flask
having a volume of 2 liters followed by mixing and cooling to
5.degree. C. with an ice bath. A solution obtained by dissolving
and diluting 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC)
in 125 g of GBL was dropped therein over the course of about 20
minutes while cooling with ice followed by dropping in a solution
obtained by dissolving 103.16 g (0.28 mol) of
4,4'-bis(4-aminophenoxy)biphenyl (BAPB) in 168 g of NMP over the
course of 20 minutes and then stirring for 3 hours in an ice bath
while holding at a temperature below 5.degree. C. followed by
removing from the ice bath and stirring for 5 hours at room
temperature. The precipitate that formed in the reaction mixture
was removed by filtration to obtain a reaction liquid.
[1216] A mixture of 840 g of water and 560 g of isopropanol was
dropped into the resulting reaction liquid followed by
re-dissolving in 560 g of NMP. The resulting crude polymer solution
was dropped into 5 liters of water, and after filtering out the
resulting precipitate, the precipitate was vacuum-dried to obtain a
powdered polymer (Polymer D). When the molecular weight of Polymer
D was measured by gel permeation chromatography (standard
polystyrene conversion), the weight average molecular weight (Mw)
thereof was 34,700.
<Production Example 5 (Synthesis of Polymer E as Polyoxazole
Precursor (A))
[1217] 183.1 g of 2,2-bis(3-amino-4-hydroxyphenyl)
hexafluoropropane, 640.9 g of N,N-dimethylacetoamide (DMAc) and
63.3 g of pyridine were mixed and stirred in a separable flask
having a volume of 3 liters at room temperature (25.degree. C.) to
obtain a homogeneous solution. A solution obtained by dissolving
118.0 g of 4,4'-diphenyl ether dicarbonyl chloride in 354 g of
diethylene glycol dimethyl ether (DMDG) was dropped therein with a
dropping funnel. At this time, the separable flask was cooled with
a water bath at 15.degree. C. to 20.degree. C. The time required
for dropping was 40 minutes and the reaction temperature was a
maximum of 30.degree. C.
[1218] 3 hours after completion of dropping, 30.8 g (0.2 mol) of
1,2-cyclohexyldicarboxylic anhydride were added to the reaction
liquid, followed by stirring and allowing to stand for 15 hours at
room temperature to block 99% of all terminal amino groups of the
polymer chain with carboxycyclohexylamide groups. The reaction rate
at this time can be easily calculated by monitoring the residual
amount of 1,2-cyclohexyldicarboxylic anhydride added by
high-performance liquid chromatography (HPLC). Subsequently, the
aforementioned reaction liquid was dropped into 2 liters of water
while stirring rapidly to precipitate the polymer, and the polymer
was then recovered, suitably rinsed with water and dehydrated
followed by vacuum-drying to obtain a crude polybenzoxazole
precursor having a weight average molecular weight as measured by
gel permeation chromatography (GPC) of 9,000 (as polystyrene).
[1219] The crude polybenzoxazole precursor obtained in the above
manner was re-dissolved in .gamma.-butyrolactone (GBL) followed by
treating this with a cation exchange resin and anion exchange
resin, adding the resulting solution to ion exchange water,
filtering out the precipitated polymer, rinsing with water and
vacuum-drying to obtain a purified polybenzoxazole precursor
(Polymer E).
<Production Example 6> (Synthesis of Polymer F as Polyimide
(A))
[1220] A condenser tube equipped with a Dean-Stark trap was
attached to a glass, 4-neck separable flask equipped with a Teflon
(Registered Trade Mark) paddle stirrer. The aforementioned flask
was immersed in a silicon oil bath and agitated while passing
nitrogen gas there through.
[1221] 72.28 g (280 mmol) of
2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP, Clariant Japan K.K.),
70.29 g (266 mmol) of
5-(2,5-dioxotetrahydro-3-furanyl)-3-methylcyclohexene-1,2-dicarboxylic
anhydride (MCTC, Tokyo Chemical Industry Co., Ltd.), 254.6 g of
.gamma.-butyrolactone and 60 g of toluene were added, and after
stirring for 4 hours at 100 rpm at room temperature, 4.6 g (28
mmol) of 5-norbornene-2,3-dicarboxylic anhydride (Tokyo Chemical
Industry Co., Ltd.) were added followed by heating and stirring for
8 hours at 100 rpm and silicon bath temperature of 50.degree. C.
while allowing nitrogen gas to pass through. Subsequently, the
temperature of the silicon bath was raised to 180.degree. C.
followed by stirring for 2 hours at 100 rpm. Toluene and water
distillates that formed during the reaction were removed. The
reaction liquid was returned to room temperature following
completion of the imidization reaction.
[1222] Subsequently, the aforementioned reaction liquid was dropped
into 3 liters of water while stirring rapidly to dispersed and
precipitate a polymer, after which the polymer was recovered,
suitably rinsed with water and vacuum-dried to obtain a crude
polyimide (Polymer F) having a weight average molecular weight as
measured by gel permeation chromatography (GPC) of 23,000 (as
polystyrene).
<Production Example 7> (Synthesis of Polymer G as Phenol
Resin (A))
[1223] 128.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate, 121.2 g
(0.5 mol) of 4,4'-bis(methoxymethyl)biphenyl (BMMB), 3.9 g (0.025
mol) of diethyl sulfate and 140 g of diethylene glycol dimethyl
ether were mixed and stirred at 70.degree. C. in separable flask
having a volume of 0.5 liters equipped with a Dean-Stark apparatus
to dissolve the solids.
[1224] The mixed solution was heated to 140.degree. C. with an oil
bath and methanol was confirmed to be generated from the reaction
liquid. The reaction liquid was then stirred for 2 hours at
140.degree. C.
[1225] Next, the reaction vessel was cooled in air followed by the
separate addition of 100 g of tetrahydrofuran and stirring. The
aforementioned diluted reaction liquid was dropped into 4 liters of
water while stirring rapidly to disperse and precipitate the resin
followed by recovering the resin, suitably rinsing with water,
dehydrating and then vacuum-drying to obtain a copolymer (Polymer
G) composed of methyl 3,5-dihydroxybenzoate and BMMB at a yield of
70%. The weight average molecular weight of this Polymer G as
determined by standard polystyrene conversion using GPC was
21,000.
<Production Example 8> (Synthesis of Polymer H as Phenol
Resin (A))
[1226] The air inside a separable flask having a volume of 1.0
liter equipped with a Dean-Stark apparatus was replaced with
nitrogen, followed by mixing and stirring 81.3 g (0.738 mol) of
resorcinol, 84.8 g (0.35 mol) of BMMB, 3.81 g (0.02 mol) of
p-toluenesulfonic acid and 116 g of propylene glycol monomethyl
ether (PGME) at 50.degree. C. to dissolve the solids.
[1227] The mixed solution was heated to 120.degree. C. with an oil
bath and methanol was confirmed to be generated from the reaction
liquid. The reaction liquid was then stirred for 3 hours at
120.degree. C.
[1228] Next, 24.9 g (0.150 mol) of 2,6-bis(hydroxymethyl)-p-cresol
and 249 g of PGME were mixed and stirred in a separate vessel, and
the uniformly dissolved solution was dropped into the separable
flask using a dropping funnel over the course of 1 hour, followed
by additionally stirring for 2 hours after dropping.
[1229] Following completion of the reaction, treatment was carried
out in the same manner as Production Example 7 to obtain a
copolymer (Polymer H) composed of resorcinol, BMMB and
2,6-bis(hydroxymethyl)-P-cresol at a yield of 77%. The weight
average molecular weight of this Polymer H as determined by
standard polystyrene conversion using GPC was 9,900.
Example 52
[1230] 50 g each of the polyimide precursors in the form of Polymer
A and Polymer B (corresponding to resin (A) as the polyimide
precursor) were dissolved in a mixed solvent composed of 80 g of
N-methyl-2-pyrrolidone (NMP) and 20 g of ethyl lactate together
with 4 g of 1-phenyl-1,2-propanedione-2-(0-ethoxycarbonyl) oxime
(abbreviated as PDO in Table 6) (corresponding to Photosensitizer
(B)), 8 g of tetraethylene glycol dimethacrylate and 1.5 g of
N-[3-(triethoxysilyl)propyl]phthalamic acid. The viscosity of the
resulting was adjusted to about 35 poise by further adding a small
amount of the aforementioned mixed solvent to obtain a
negative-type photosensitive resin composition.
[1231] After having coated the aforementioned composition onto a
6-inch silicon wafer (Fujimi Inc., thickness: 625.+-.25 .mu.m), a
cured film of the aforementioned composition was formed by
exposing, developing and curing the coating film. Ti at a thickness
of 200 nm and Cu at a thickness of 400 nm were then sequentially
sputtered thereon using a sputtering device (Model L-440S-FHL,
Canon Anelva Corp.), and a Cu layer having a thickness of 5 .mu.m
was formed by electrolytic copper plating by using this sputtered
Cu layer as a seed layer. Continuing, the substrate was immersed in
an etching solution containing cupric chloride, acetic acid and
ammonium acetate to form surface irregularities having a maximum
height of 1 .mu.m on the surface thereof.
[1232] A cured relief pattern was produced on the Cu layer
subjected to this surface treatment using the aforementioned
composition by curing at 230.degree. C. according to the previously
described method, and after carrying out a high-temperature storage
test, the ratio of the surface area occupied by voids to the total
surface area of the Cu layer was evaluated, yielding a result of
5.7%.
Example 53
[1233] A silicon wafer was produced having a Cu layer formed
thereon in the same manner as the aforementioned Example 52
followed by carrying out surface treatment by etching in the same
manner as Example 52 with the exception of making the maximum
height following microetching of the Cu layer to be 2 .mu.m.
[1234] A cured relief pattern was produced on the Cu layer
subjected to this surface treatment using the same composition as
Example 52 by curing at 230.degree. C. according to the previously
described method, and after carrying out a high-temperature storage
test, the ratio of the surface area occupied by voids to the total
surface area of the Cu layer was evaluated, yielding a result of
5.1%.
Example 54
[1235] A silicon wafer was produced having a Cu layer formed
thereon in the same manner as the aforementioned Example 52
following by substituting a portion of the surface Cu layer with
tin by carrying out electroless tin plating. Continuing, the wafer
was immersed in a 1% by weight aqueous solution of
3-glycidoxypropyltrimethoxysilane to form a silane coupling agent
on the surface thereof.
[1236] A cured relief pattern was produced on the Cu layer
subjected to this surface treatment using the same composition as
Example 52 by curing at 230.degree. C. according to the previously
described method, and after carrying out a high-temperature storage
test, the ratio of the surface area occupied by voids to the total
surface area of the Cu layer was evaluated, yielding a result of
5.8%.
Example 55
[1237] A Cu layer was formed that was subjected to surface
treatment in the same manner as Example 52 with the exception of
changing the 6-inch silicon wafer used in Example 52 to a glass
substrate measuring 20 cm on a side.
[1238] A cured relief pattern was produced on the Cu layer
subjected to this surface treatment using the same composition as
Example 52 by curing at 230.degree. C. according to the previously
described method, and after carrying out a high-temperature storage
test, the ratio of the surface area occupied by voids to the total
surface area of the Cu layer was evaluated, yielding a result of
5.6%.
Example 56
[1239] A Cu layer was formed that was subjected to surface
treatment in the same manner as Example 52 with the exception of
changing the 6-inch silicon wafer used in Example 52 to a 4-inch
SiC wafer.
[1240] A cured relief pattern was produced on the Cu layer
subjected to this surface treatment using the same composition as
Example 52 by curing at 230.degree. C. according to the previously
described method, and after carrying out a high-temperature storage
test, the ratio of the surface area occupied by voids to the total
surface area of the Cu layer was evaluated, yielding a result of
5.3%.
Example 57
[1241] A Cu layer was formed that was subjected to surface
treatment in the same manner as Example 52 with the exception of
changing the 6-inch silicon wafer used in Example 52 to an FR4
substrate measuring 20 cm on a side.
[1242] A cured relief pattern was produced on the Cu layer
subjected to this surface treatment using the same composition as
Example 52 by curing at 230.degree. C. according to the previously
described method, and after carrying out a high-temperature storage
test, the ratio of the surface area occupied by voids to the total
surface area of the
[1243] Cu layer was evaluated, yielding a result of 5.5%.
Example 58
[1244] A Cu layer was formed that was subjected to surface
treatment in the same manner as Example 52 with the exception of
changing the 6-inch silicon wafer used in Example 25 to an 8-inch
molded resin substrate obtained by embedding a singulated chip and
then flattening the surface by CMP.
[1245] A cured relief pattern was produced on the Cu layer
subjected to this surface treatment using the same composition as
Example 52 by curing at 230.degree. C. according to the previously
described method, and after carrying out a high-temperature storage
test, the ratio of the surface area occupied by voids to the total
surface area of the Cu layer was evaluated, yielding a result of
5.7%.
Example 59
[1246] A Cu layer was produced that was subjected to surface
treatment in the same manner as Example 52 and a relief pattern was
produced on the surface-treated Cu layer using the same composition
as Example 52 by curing at 350.degree. C. according to the
previously described method, and after carrying out a
high-temperature storage test, the ratio of the surface area
occupied by voids to the total surface area of the Cu layer was
evaluated, yielding a result of 5.5%.
Example 60
[1247] A negative-type photosensitive resin composition solution
was prepared in the same manner as the aforementioned Example 52
with the exception of changing resin (A) in the form of the 50 g of
Polymer A and 50 g of Polymer B used in the Example 52 to 100 g of
Polymer A, and changing component (B) in the form of the 4 g of PDO
to 2.5 g of 1,2-octanedione, 1-{4-(phenylthio)-,
2-(O-benzoyloxime)} (Irgacure OXE01, trade name, BASF Corp.).
[1248] A Cu layer was produced that was subjected to surface
treatment in the same manner as Example 52 and a relief pattern was
produced on the surface-treated Cu layer using the aforementioned
composition by curing at 230.degree. C. according to the previously
described method, and after carrying out a high-temperature storage
test, the ratio of the surface area occupied by voids to the total
surface area of the Cu layer was evaluated, yielding a result of
5.4%.
Example 61
[1249] A negative-type photosensitive resin composition solution
was prepared in the same manner as the aforementioned Example 52
with the exception of changing resin (A) in the form of the 50 g of
Polymer A and 50 g of Polymer B used in Example 52 to 100 g of
Polymer A, and changing component (B) in the form of the 4 g of PDO
to 2.5 g of 1,2-octanedione, 1-{4-(phenylthio)-,
2-(0-benzoyloxime)} (Irgacure OXE01, trade name, BASF Corp.) and
further changing the solvent to 85 g of .gamma.-butyrolactone and
15 g of dimethylsulfoxide.
[1250] A Cu layer was produced that was subjected to surface
treatment in the same manner as Example 52 and a relief pattern was
produced on the surface-treated Cu layer using the aforementioned
composition by curing at 230.degree. C. according to the previously
described method, and after carrying out a high-temperature storage
test, the ratio of the surface area occupied by voids to the total
surface area of the Cu layer was evaluated, yielding a result of
5.4%.
Example 62
[1251] A negative-type photosensitive resin composition solution
was prepared in the same manner as the aforementioned Example 52
with the exception of changing resin (A) in the form of the 50 g of
Polymer A and 50 g of Polymer B used in Example 52 to 100 g of
Polymer C.
[1252] A Cu layer was produced that was subjected to surface
treatment in the same manner as Example 52 and a relief pattern was
produced on the surface-treated Cu layer using the aforementioned
composition by curing at 350.degree. C. according to the previously
described method, and after carrying out a high-temperature storage
test, the ratio of the surface area occupied by voids to the total
surface area of the Cu layer was evaluated, yielding a result of
4.9%.
Example 63
[1253] A negative-type photosensitive resin composition solution
was prepared in the same manner as the aforementioned Example 52
with the exception of changing resin (A) in the form of the 50 g of
Polymer A and 50 g of Polymer B used in Example 52 to 100 g of
Polymer D.
[1254] A Cu layer was produced that was subjected to surface
treatment in the same manner as Example 52 and a relief pattern was
produced on the surface-treated Cu layer using the aforementioned
composition by curing at 250.degree. C. according to the previously
described method, and after carrying out a high-temperature storage
test, the ratio of the surface area occupied by voids to the total
surface area of the Cu layer was evaluated, yielding a result of
5.6%.
Example 64
[1255] A positive-type photosensitive resin composition was
prepared according to the following method using Polymer E followed
by evaluation of the prepared photosensitive resin composition. 100
g of a polyoxazole precursor in the form of Polymer E
(corresponding to resin (A)) were dissolved in 100 g of
.gamma.-butyrolactone (as solvent) together with 15 g of a
photosensitive diazoquinone compound (B1) (Toyo Gosei Co., Ltd.,
equivalent to photosensitizer (B)), obtained by esterifying 77% of
the phenolic hydroxyl groups represented by the following formula
(146):
##STR00223##
with naphthoquinonediazido-4-sulfonic acid, and 6 g of
3-t-butoxycarbonylaminopropyltriethoxysilane. The viscosity of the
resulting solution was adjusted to about 20 poise by further adding
a small amount of .gamma.-butyrolactone to obtain a positive-type
photosensitive resin composition.
[1256] A Cu layer was produced that was subjected to surface
treatment in the same manner as Example 52 and a relief pattern was
produced on the surface-treated Cu layer using the aforementioned
composition by curing at 350.degree. C. according to the previously
described method, and after carrying out a high-temperature storage
test, the ratio of the surface area occupied by voids to the total
surface area of the Cu layer was evaluated, yielding a result of
5.3%.
Example 65
[1257] A positive-type photosensitive resin composition solution
was prepared in the same manner as the aforementioned Example 64
with the exception of changing resin (A) in the form of the 100 g
of Polymer E used in Example 64 to 100 g of Polymer F.
[1258] A Cu layer was produced that was subjected to surface
treatment in the same manner as Example 52 and a relief pattern was
produced on the surface-treated Cu layer using the aforementioned
composition by curing at 250.degree. C. according to the previously
described method, and after carrying out a high-temperature storage
test, the ratio of the surface area occupied by voids to the total
surface area of the Cu layer was evaluated, yielding a result of
5.2%.
Example 66
[1259] A positive-type photosensitive resin composition solution
was prepared in the same manner as the aforementioned Example 64
with the exception of changing resin (A) in the form of the 100 g
of Polymer used in Example 64 to 100 g of Polymer G.
[1260] A Cu layer was produced that was subjected to surface
treatment in the same manner as Example 52 and a relief pattern was
produced on the surface-treated Cu layer using the aforementioned
composition by curing at 220.degree. C. according to the previously
described method, and after carrying out a high-temperature storage
test, the ratio of the surface area occupied by voids to the total
surface area of the Cu layer was evaluated, yielding a result of
5.6%.
Example 67
[1261] A positive-type photosensitive resin composition solution
was prepared in the same manner as the aforementioned Example 64
with the exception of changing resin (A) in the form of the 100 g
of Polymer E used in Example 64 to 100 g of Polymer H.
[1262] A Cu layer was produced that was subjected to surface
treatment in the same manner as Example 52 and a relief pattern was
produced on the surface-treated Cu layer using the aforementioned
composition by curing at 220.degree. C. according to the previously
described method, and after carrying out a high-temperature storage
test, the ratio of the surface area occupied by voids to the total
surface area of the Cu layer was evaluated, yielding a result of
5.5%.
Comparative Example 11
[1263] A Cu layer was produced in the same manner as Example 52
with the exception of not carrying out surface treatment, a relief
pattern was produced on the Cu layer using the same composition as
Example 52 by curing at 230.degree. C. according to the previously
described method, and after carrying out a high-temperature storage
test, the ratio of the surface area occupied by voids to the total
surface area of the Cu layer was evaluated. The ratio was 14.3%
since the Cu was not subjected to surface treatment.
Comparative Example 12
[1264] A Cu layer was produced in the same manner as Example 52
with the exception of not carrying out surface treatment, a relief
pattern was produced on the Cu layer using the same composition as
Example 60 by curing at 350.degree. C. according to the previously
described method, and after carrying out a high-temperature storage
test, the ratio of the surface area occupied by voids to the total
surface area of the Cu layer was evaluated. The ratio was 14.9%
since the Cu was not subjected to surface treatment
Comparative Example 13
[1265] A Cu layer was produced in the same manner as Example 52
with the exception of not carrying out surface treatment, a relief
pattern was produced on the Cu layer using the same composition as
Example 62 by curing at 350.degree. C. according to the previously
described method, and after carrying out a high-temperature storage
test, the ratio of the surface area occupied by voids to the total
surface area of the Cu layer was evaluated. The ratio was 14.6%
since the Cu was not subjected to surface treatment.
TABLE-US-00006 TABLE 6 Ex. 52 Ex. 53 Ex. 54 Ex. 55 Ex. 56 Ex. 57
Ex. 58 Ex. 59 Ex. 60 Ex. 61 Component Polymer A 50 50 50 50 50 50
50 50 100 100 (A) Polymer B 50 50 50 50 50 50 50 50 Polymer C
Polymer D Polymer E Polymer F Polymer G Polymer H Component PDO 4 4
4 4 4 4 4 4 (B) OXE01 2.5 2.5 B1 Silicon Max surface with with with
with wafer irregularity height 1 .mu.m Max surface with
irregularity height 2 .mu.m Treatment of Silane done coupling agent
Glass Max surface with substrate irregularity height 1 .mu.m SiC
Max surface with wafer irregularity height 1 .mu.m FR4 Max surface
with substrate irregularity height 1 .mu.m Molded Max surface with
substrate irregularity height 1 .mu.m Solvent N-methyl pyrrolidone
80 80 80 80 80 80 80 80 80 Ethyl lactate 20 20 20 20 20 20 20 20 20
.gamma.-butyrolactone 85 Dimethyl sulfoxide 15 Curing temp.
(.degree. C.) 230 230 230 230 230 230 230 350 230 230 Void surface
area ratio (%) 5.7 5.1 5.8 5.6 5.3 5.5 5.7 5.5 5.4 5.4 Comp. Comp.
Comp. Ex. 62 Ex. 63 Ex. 64 Ex. 65 Ex. 66 Ex. 67 Ex. 11 Ex. 12 Ex.
13 Component Polymer A 50 (A) Polymer B 50 Polymer C 100 100
Polymer D 100 Polymer E 100 100 Polymer F 100 Polymer G 100 Polymer
H 100 Component PDO 4 4 4 4 (B) OXE01 B1 15 15 15 15 15 Silicon Max
surface with with with with with with wafer irregularity height 1
.mu.m Max surface irregularity height 2 .mu.m Treatment of Silane
coupling agent Glass Max surface substrate irregularity height 1
.mu.m SiC Max surface wafer irregularity height 1 .mu.m FR4 Max
surface substrate irregularity height 1 .mu.m Molded Max surface
substrate irregularity height 1 .mu.m Solvent N-methyl pyrrolidone
80 80 80 80 Ethyl lactate 20 20 20 20 .gamma.-butyrolactone 100 100
100 100 100 Dimethyl sulfoxide Curing temp. (.degree. C.) 350 250
350 250 220 220 230 350 350 Void surface area ratio (%) 4.9 5.6 5.3
5.2 5.6 5.5 14.3 14.9 14.6
Fifth Embodiment
[1266] The following provides an explanation of Examples 68 to 73
and Comparative Examples 14 to 18 as a fifth embodiment of the
present invention. In the examples and comparative examples,
physical properties of the photosensitive resin composition were
measured and evaluated in accordance with the methods indicated
below.
[1267] (1) Weight Average Molecular Weight
[1268] The weight average molecular weight (Mw) of each polyimide
precursor was determined in the same manner as the previously
described first embodiment.
[1269] (2) Production of Cured Film on Cu
[1270] Ti at a thickness of 200 nm and copper at a thickness of 400
nm were sequentially sputtered on a 6-inch silicon wafer (Fujimi
Inc., thickness: 625.+-.25 .mu.m) using a sputtering device (Model
L-440S-FHL, Canon Anelva Corp.). Continuing, a photosensitive resin
composition prepared according to the method to be subsequently
described was spin-coated on the wafer using a coater developer
(Model D-Spin60A, Sokudo Co., Ltd.) followed by drying to form a
coating film having a thickness of about 15 .mu.m. The entire
surface of this coating film was then irradiated at an energy level
of 900 mJ/cm.sup.2 with a parallel light mask aligner (Model
PLA-501FA, Canon Inc.). Next, this coating film was spray-developed
with a coater developer (Model D-Spin60A, Sokudo Co., Ltd.) using
cyclopentanone in the case of a negative type or using 2.38% TMAH
in the case of a positive type followed by rinsing with propylene
glycol methyl ether acetate in the case of a negative type or pure
water in the case of a positive type to obtain a developed film on
the Cu.
[1271] The wafer having the developed film formed on Cu was
irradiated with microwaves at 500 W and 7 GHz in a nitrogen
atmosphere using a microwave continuous heating oven (Micro Denshi
Co., Ltd.) while heating for 2 hours at the temperature described
in each example to obtain a cured film having a thickness of about
10 .mu.m to 15 .mu.m on the Cu.
[1272] (3) Measurement of Peel Strength of Cured Film on Cu
[1273] After affixing adhesive step (thickness: 500 .mu.m) to the
cured film formed on the Cu, cut portions having a width of 5 mm
were made in the cured film with a box knife, and the cut portions
were measured for 180.degree. peel strength based on JIS K 6854-2.
The conditions for the tensile test at that time were as indicated
below.
[1274] Load cell: 50 N
[1275] Pulling speed: 50 mm/min
[1276] Travel: 60 mm
<Production Example 1d (Synthesis of Polymer A as Polyamic Acid
Ester (A))
[1277] 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) were placed
in a separable flask having a volume of 2 liters followed by the
addition of 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400
ml of .gamma.-butyrolactone, stirring at room temperature, and
adding 81.5 g of pyridine while stirring to obtain a reaction
mixture. Following completion of generation of heat by the
reaction, the reaction mixture was allowed to cool to room
temperature and then allowed to stand for 16 hours.
[1278] Next, a solution obtained by dissolving 206.3 g of
dicyclohexylcarbodiimide (DCC) in 180 ml of .gamma.-butyrolactone
was added to the reaction mixture over the course of 40 minutes
while cooling with ice and stirring followed by adding a suspension
of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of
.gamma.-butyrolactone over the course of 60 minutes while stirring.
After further stirring for 2 hours at room temperature, 30 ml of
ethyl alcohol were added followed by stirring for 1 hour and then
adding 400 ml of .gamma.-butyrolactone. The precipitate that formed
in the reaction mixture was removed by filtration to obtain a
reaction liquid.
[1279] The resulting reaction liquid was added to 3 L of ethyl
alcohol to form a precipitate composed of a crude polymer. The
resulting crude polymer was filtered out and dissolved in 1.5 L of
tetrahydrofuran to obtain a crude polymer solution. The resulting
crude polymer solution was dropped into 28 L of water to
precipitate the polymer, and after filtering out the resulting
precipitate, the precipitate was vacuum-dried to obtain a powdered
polymer (Polymer A). When the weight average molecular weight (Mw)
of this Polymer A was measured by gel permeation chromatography
(standard polystyrene conversion), the weight average molecular
weight (Mw) thereof was 20,000.
[1280] Furthermore, the weight average molecular weights of the
resins obtained in each production example were measured under the
following conditions using gel permeation chromatography (GPC), and
weight average molecular weight was determined by standard
polystyrene conversion.
[1281] Pump: JASCO PU-980
[1282] Detector: JASCO RI-930
[1283] Column oven: JASCO CO-965, 40.degree. C.
[1284] Column: Two Shodex KD-806M columns connected in series
[1285] Mobile phase: 0.1 mol/1 LiBr/NMP
[1286] Flow rate: 1 ml/min
<Production Example 2d> (Synthesis of Polymer B as Polyamic
Acid Ester (A))
[1287] A reaction was carried out in the same manner as the method
described in the previously described Production Example 1 with the
exception of using 147.1 g of 3,3'4,4'-biphenyltetracarboxylic
dianhydride (BPDA) instead of the 155.1 g of 4,4'-oxydiphthalic
dianhydride (ODPA) used in Production Example 1 to obtain Polymer
B. When the molecular weight of Polymer B was measured by gel
permeation chromatography (standard polystyrene conversion), the
weight average molecular weight (Mw) thereof was 22,000.
<Production Example 3d> (Synthesis of Polymer C as Polyamic
Acid Precursor (A))
[1288] A reaction was carried out in the same manner as the method
described in the previously described Production Example 1 with the
exception of using 147.8 g of
2,2-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB) instead of the
93.0 g of 4,4'-diaminodiphenyl ether (DADPE) used in Production
Example 1 to obtain Polymer C. When the molecular weight of Polymer
C was measured by gel permeation chromatography (standard
polystyrene conversion), the weight average molecular weight (Mw)
thereof was 21,000.
<Production Example 4d> (Synthesis of Polymer D as Phenol
Resin (A))
[1289] 128.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate, 121.2 g
(0.5 mol) of 4,4'-bis(methoxymethyl)biphenyl (BMMB), 3.9 g (0.025
mol) of diethyl sulfate and 140 g of diethylene glycol dimethyl
ether were mixed and stirred at 70.degree. C. in separable flask
having a volume of 0.5 liters equipped with a Dean-Stark apparatus
to dissolve the solids.
[1290] The mixed solution was heated to 140.degree. C. with an oil
bath and methanol was confirmed to be generated from the reaction
liquid. The reaction liquid was then stirred for 2 hours at
140.degree. C.
[1291] Next, the reaction vessel was cooled in air followed by the
separate addition of 100 g of tetrahydrofuran and stirring. The
aforementioned diluted reaction liquid was dropped into 4 liters of
water while stirring rapidly to disperse and precipitate the resin
followed by recovering the resin, suitably rinsing with water,
dehydrating and then vacuum-drying to obtain a copolymer (Polymer
D) composed of methyl 3,5-dihydroxybenzoate and BMMB at a yield of
70%. The weight average molecular weight of this Polymer D as
determined by standard polystyrene conversion using GPC was
21,000.
<Production Example 5d> (Synthesis of Polymer E as Phenol
Resin (A))
[1292] The air inside a separable flask having a volume of 1.0
liter equipped with a Dean-Stark apparatus was replaced with
nitrogen followed by mixing and stirring 81.3 g (0.738 mol) of
resorcinol, 84.8 g (0.35 mol) of BMMB, 3.81 g (0.02 mol) of
p-toluenesulfonic acid and 116 g of propylene glycol monomethyl
ether (PGME) at 50.degree. C. to dissolve the solids.
[1293] The mixed solution was heated to 120.degree. C. with an oil
bath and methanol was confirmed to be generated from the reaction
liquid. The reaction liquid was then stirred for 3 hours at
120.degree. C.
[1294] Next, 24.9 g (0.150 mol) of 2,6-bis(hydroxymethyl)-p-cresol
and 249 g of PGME were mixed and stirred in a separate vessel and
the uniformly dissolved solution was dropped into the separable
flask using a dropping funnel over the course of 1 hour followed by
additionally stirring for 2 hours after dropping.
[1295] Following completion of the reaction, treatment was carried
out in the same manner as Production Example 4 to obtain a
copolymer (Polymer E) composed of resorcinol, BMMB and
2,6-bis(hydroxymethyl)-P-cresol at a yield of 77%. The weight
average molecular weight of this Polymer E as determined by
standard polystyrene conversion using GPC was 9,900.
<Comparative Production Exampled 1d> (Synthesis of Polymer F
as Polyamic Acid)
[1296] 93.0 g of diaminodiphenyl ether (DADPE) were placed in a
2-liter separable flask followed by the addition of 400 ml of
N-methyl-2-pyrrolidone and stirring to dissolve. 155.1 g of
4,4'-oxydiphthalic anhydride were added thereto while still in
solid form followed by stirring the solution to allow the
components to react and dissolve, and continuing to stir for 2
hours at 80.degree. C. to obtain a solution of Polymer F. The
weight average molecular weight of this Polymer F as determined by
standard polystyrene conversion using GPC was 20,000.
<Comparative Production Example 2d> (Synthesis of Polymer G
as Polyamic Acid)
[1297] A reaction was carried out in the same manner as the method
described in the previously described Comparative Production
Example 1d with the exception of using 147.1 g of
3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) instead of the
155.1 g of 4,4'-oxydiphthalic anhydride (ODPA) used in Comparative
Production Example 1 to obtain a solution of Polymer G. The weight
average molecular weight (Mw) of this Polymer G as measured by gel
permeation chromatography (standard polystyrene conversion) was
22,000.
<Comparative Production Example 3d (Synthesis of Polymer H as
Polyamic Acid)
[1298] A reaction was carried out in the same manner as the method
described in the previously described Comparative Production
Example 1d with the exception of using 147.8 g of
2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB) instead of
the 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) used in Production
Example 1 to obtain Polymer H. The weight average molecular weight
(Mw) of this Polymer H as measured by gel permeation chromatography
(standard polystyrene conversion) was 21,000.
Example 68
[1299] A negative-type photosensitive resin composition was
prepared according to the method indicated below using Polymers A
and B followed by evaluation of the prepared photosensitive resin
composition. A polyamic acid ester in the form of 50 g of Polymer A
and 50 g of Polymer B (equivalent to resin (A)) was dissolved in a
mixed solvent composed of 80 g of N-methyl-2-pyrrolidone (NMP) and
20 g of ethyl lactate together with 4 g of
1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl) oxime (abbreviated
as PDO in Table 7) (corresponding to photosensitive agent (B)), 8 g
of tetraethylene glycol dimethacrylate and 1.5 g of
N-[3-(triethoxysilyl)propyl]phthalamic acid. The viscosity of the
resulting solution was adjusted to about 35 poise by further adding
a small amount of the aforementioned mixed solvent to obtain a
negative-type photosensitive resin composition.
[1300] After coating, exposing and developing this composition on
Cu according to the previously described methods, the composition
was cured at 230.degree. C. while irradiating with microwaves to
produce a cured film on a Cu layer, and measurement of the peel
strength thereof yielded a value of 0.69 N/mm.
Example 69
[1301] A negative-type photosensitive resin composition solution
was prepared in the same manner as the aforementioned Example 68
with the exception of changing resin (A) in the form of 50 g of
Polymer A and 50 g of Polymer B used in Example 68 to 100 g of
Polymer A.
[1302] After coating, exposing and developing this composition on
Cu according to the previously described methods, the composition
was cured at 230.degree. C. while irradiating with microwaves to
produce a cured film on a Cu layer, and measurement of the peel
strength thereof yielded a value of 0.68 N/mm.
Example 70
[1303] A negative-type photosensitive resin composition solution
was prepared in the same manner as the aforementioned Example 68
with the exception of changing resin (A) in the form of the 50 g of
Polymer A and 50 g of Polymer B used in Example 68 to 100 g of
Polymer A, changing the component (C) in the form of 4 g of PDO to
2.5 g of 1,2-octanedione, 1-{4-(phenylthio)-, 2-(0-benzoyloxime)}
(Irgacure OXE01, trade name, BASF Corp.), and further changing the
solvent to 85 g of .gamma.-butyrolactone and 15 g of
dimethylsulfoxide.
[1304] After coating, exposing and developing this composition on
Cu according to the previously described methods, the composition
was cured at 230.degree. C. while irradiating with microwaves to
produce a cured film on a Cu layer, and measurement of the peel
strength thereof yielded a value of 0.68 N/mm.
Example 71
[1305] A negative-type photosensitive resin composition solution
was prepared in the same manner as the aforementioned Example 68
with the exception of changing resin (A) in the form of 50 g of
Polymer A and 50 g of Polymer B used in Example 68 to 100 g of
Polymer C.
[1306] After coating, exposing and developing this composition on
Cu according to the previously described methods, the composition
was cured at 230.degree. C. while irradiating with microwaves to
produce a cured film on a Cu layer, and measurement of the peel
strength thereof yielded a value of 0.65 N/mm.
Example 72
[1307] A positive-type photosensitive resin composition was
prepared according to the following method using Polymer D followed
by evaluation of the prepared photosensitive resin composition. 100
g of a phenol resin in the form of Polymer D (corresponding to
resin (A)) were dissolved in 100 g of .gamma.-butyrolactone (as
solvent) together with 15 g of a photosensitive diazoquinone
compound (B1) (Toyo Gosei Co., Ltd., equivalent to photosensitizer
(B)), obtained by esterifying 77% of the phenolic hydroxyl groups
represented by the following formula (146):
##STR00224##
with naphthoquinonediazido-4-sulfonic acid, and 6 g of
3-t-butoxycarbonylaminopropyltriethoxysilane. The viscosity of the
resulting solution was adjusted to about 20 poise by further adding
a small amount of .gamma.-butyrolactone to obtain a positive-type
photosensitive resin composition.
[1308] After coating, exposing and developing this composition on
Cu according to the previously described methods, the composition
was cured at 220.degree. C. while irradiating with microwaves to
produce a cured film on a Cu layer, and measurement of the peel
strength thereof yielded a value of 0.70 N/mm.
Example 73
[1309] A positive-type photosensitive resin composition solution
was prepared in the same manner as the aforementioned Example 72
with the exception of changing resin (A) in the form of the 100 g
of Polymer D used in Example 72 to 100 g of Polymer E.
[1310] After coating, exposing and developing this composition on
Cu according to the previously described methods, the composition
was cured at 220.degree. C. while irradiating with microwaves to
produce a cured film on a Cu layer, and measurement of the peel
strength thereof yielded a value of 0.70 N/mm.
Comparative Example 14
[1311] A negative-type photosensitive resin composition was
prepared in the same manner as Example 68 and the composition was
evaluated in the same manner as Example 68 with the exception of
not irradiating with microwaves during curing. At this time, the
peel strength was 0.43 N/mm.
Comparative Example 15
[1312] A negative-type photosensitive resin composition was
prepared in the same manner as Example 68 with the exception of
changing the 50 g of Polymer A and the 50 g of Polymer B used in
Example 68 to 50 g of Polymer F and 50 g of Polymer G, followed by
evaluating the composition in the same manner as Example 68. At
this time, the peel strength was 0.47 N/mm.
Comparative Example 16
[1313] A negative-type photosensitive resin composition was
prepared in the same manner as Example 71 and the composition was
evaluated in the same manner as Example 71 with the exception of
not irradiating with microwaves during curing. At this time, the
peel strength was 0.42 N/mm.
Comparative Example 17
[1314] A negative-type photosensitive resin composition was
prepared in the same manner as Example 71 with the exception of
changing the 100 g of Polymer C used in Example 71 to 100 g of
Polymer H, followed by evaluating the composition in the same
manner as Example 68. At this time, the peel strength was 0.41
N/mm.
Comparative Example 18
[1315] A negative-type photosensitive resin composition was
prepared in the same manner as Example 73 and the composition was
evaluated in the same manner as Example 73 with the exception of
not irradiating with microwaves during curing. At this time, the
peel strength was 0.46 N/mm.
[1316] The results for Examples 68 to 73 and Comparative Examples
14 to 18 are summarized in Table 7.
TABLE-US-00007 TABLE 7 Ex. Ex. Ex. Ex. Ex. Ex. Comp. Comp. Comp.
Comp. Comp. 68 69 70 71 72 73 Ex. 14 Ex. 15 Ex. 16 Ex. 17 Ex. 18
Component (A) Polymer A 50 100 100 50 Polymer B 50 50 Polymer C 100
100 Polymer D 100 Polymer E 100 100 Polymer F 50 Polymer G 50
Polymer H 100 Component (B) PDO 4 4 4 4 4 4 OXE01 2.5 2.5 B1 15 15
15 Microwave irradiation Yes Yes Yes Yes Yes Yes No Yes No Yes No
Solvent N-methylpyrrolidone 80 80 80 80 80 80 80 Ethyl lactate 20
20 20 20 20 20 20 .gamma.-butyrolactone 85 100 100 100
Dimethylsulfoxide 15 Curing temperature (.degree. C.) 230 230 230
230 220 220 230 230 230 230 220 Peel strength (N/mm) 0.69 0.68 0.69
0.65 0.70 0.70 0.43 0.47 0.42 0.41 0.46
INDUSTRIAL APPLICABILITY
[1317] The photosensitive resin composition of the present
invention can be preferably used in the field of photosensitive
materials useful for the production of, for example, electrical and
electronic materials of semiconductor devices and multilayer wiring
boards.
* * * * *