U.S. patent application number 14/387609 was filed with the patent office on 2015-02-12 for polyamide acid and resin composition containing same.
This patent application is currently assigned to TORAY Industries, Inc.. The applicant listed for this patent is TORAY Industries, Inc.. Invention is credited to Daichi Miyazaki, Masao Tomikawa.
Application Number | 20150045502 14/387609 |
Document ID | / |
Family ID | 49260215 |
Filed Date | 2015-02-12 |
United States Patent
Application |
20150045502 |
Kind Code |
A1 |
Miyazaki; Daichi ; et
al. |
February 12, 2015 |
POLYAMIDE ACID AND RESIN COMPOSITION CONTAINING SAME
Abstract
The invention aims to provide polyamic acid that can form a
varnish with a low viscosity and serves to produce, through curing,
coat film with good mechanical characteristics and further aims to
produce cured coat film with good mechanical characteristics
regardless of whether the molar concentration of the acid anhydride
group in the acid dianhydride monomer and that of the amino group
in the multivalent amine compound or diamine compound are identical
to or different from each other. This objective is met by polyamic
acid including a structure as represented by chemical formula (1)
given below: (In chemical formula (1), .delta. represents an oxygen
or sulfur atom and W represents an electron-withdrawing group, and
R.sup.11 and R.sup.12 represent independently a hydrogen atom or a
hydrocarbon group having 1 to 10 carbon atoms.
Inventors: |
Miyazaki; Daichi; (Otsu-shi,
JP) ; Tomikawa; Masao; (Otsu-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
TORAY Industries, Inc. |
Tokyo |
|
JP |
|
|
Assignee: |
TORAY Industries, Inc.
Tokyo
JP
|
Family ID: |
49260215 |
Appl. No.: |
14/387609 |
Filed: |
March 28, 2013 |
PCT Filed: |
March 28, 2013 |
PCT NO: |
PCT/JP2013/059165 |
371 Date: |
September 24, 2014 |
Current U.S.
Class: |
524/600 ;
528/188 |
Current CPC
Class: |
C08G 73/1007 20130101;
C09D 179/08 20130101; C08G 73/1067 20130101; C08G 73/1071 20130101;
C08G 73/1075 20130101; C08G 73/101 20130101; C08G 73/1082 20130101;
C08G 2150/00 20130101; C08G 69/44 20130101 |
Class at
Publication: |
524/600 ;
528/188 |
International
Class: |
C08G 69/44 20060101
C08G069/44; C08G 73/10 20060101 C08G073/10; C09D 179/08 20060101
C09D179/08 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 29, 2012 |
JP |
2012-076500 |
Claims
1. Polyamic acid comprising a structure as represented by chemical
formula (1) given below: ##STR00020## wherein .delta. represents an
oxygen or sulfur atom and W represents an electron-withdrawing
group, and R.sup.11 and R.sup.12 represent independently a hydrogen
atom or a hydrocarbon group containing 1 to 10 carbon atoms.
2. Polyamic acid as described in claim 1, wherein the structure is
represented by chemical formula (2) or (3) given below:
##STR00021## wherein U and X represent a tetravalent
tetracarboxylic acid residue containing 2 or more carbon atoms, V
represents a tri- or higher-valent multivalent amine residue
containing 2 or more carbon atoms, Y represents a divalent diamine
residue containing 2 or more carbon atoms, Z represents a structure
represented by chemical formula (1) given above, k, m, and n each
represent a positive integer, and R.sup.1 to R.sup.4 represent
independently a hydrogen atom, a hydrocarbon group containing 1 to
10 carbon atoms, or an alkyl silyl group containing 1 to 10 carbon
atoms.
3. Polyamic acid as described in claim 1, wherein W in chemical
formula (1) is represented by any one of chemical formulae (4) to
(11): ##STR00022## wherein R.sup.21 to R.sup.28 are independently a
hydrocarbon group containing 1 to 10 carbon atoms or an organic
group containing 1 to 10 carbon atoms which comprises hydrogen and
carbon as essential elements and 1 to 10 other atoms of elements
selected from the group of boron, oxygen, sulfur, nitrogen,
phosphorus, silicon, and halogens.
4. Polyamic acid as described in claim 1, wherein the structure
represented by chemical formula (1) is represented by any one of
chemical formulae (12) to (14): ##STR00023##
5. A resin composition comprising: (a) polyamic acid as described
in claim 1 and (b) a solvent.
6. A production method for polyamic acid as described in claim 1
comprising: a step for reacting an amino group of a multivalent
amine compound containing 3 or more primary amino groups with a
compound that reacts with an amino group to form a structure as
represented by chemical formula (1) given above, to form a
multivalent amine derivative containing 2 or more primary amino
groups and a structure as represented by chemical formula (1) and a
step for polymerizing the multivalent amine derivative with
tetracarboxylic acid or a derivative thereof.
7. A production method for polyamic acid as described in claim 1
comprising: a step for reacting an amino group of a diamine
compound with a compound that reacts with an amino group to form a
structure as represented by chemical formula (1) given above, to
form a diamine derivative containing a primary amino group and a
structure as represented by chemical formula (1) and a step for
polymerizing the diamine derivative with tetracarboxylic acid or a
derivative thereof.
8. A production method for polyamic acid as described in claim 1
comprising: a step for polymerizing a diamine compound and
tetracarboxylic acid or a derivative thereof to produce polyamic
acid having an amino group at a chain end and a step for reacting
the amino group of the polyamic acid with a compound that reacts
with an amino group to form a structure as represented by chemical
formula (1), to thereby produce polyamic acid having a structure as
represented by chemical formula (1).
9. Polyimide film comprising polyimide produced by imidizing
polyamic acid as described in claim 1.
10. A production method for polyimide film comprising a step for
producing resin film containing polyamic acid from a resin
composition as described in claim 5 and a step for imidizing the
polyamic acid.
11. Polyamic acid as described in claim 2, wherein W in chemical
formula (1) is represented by any one of chemical formulae (4) to
(11): ##STR00024## wherein R.sup.21 to R.sup.28 are independently a
hydrocarbon group containing 1 to 10 carbon atoms or an organic
group containing 1 to 10 carbon atoms which comprises hydrogen and
carbon as essential elements and 1 to 10 other atoms of elements
selected from the group of boron, oxygen, sulfur, nitrogen,
phosphorus, silicon, and halogens.
12. Polyamic acid as described in claim 2, wherein the structure
represented by chemical formula (1) is represented by any one of
chemical formulae (12) to (14): ##STR00025##
13. Polyamic acid as described in claim 3, wherein the structure
represented by chemical formula (1) is represented by any one of
chemical formulae (12) to (14): ##STR00026##
14. A resin composition comprising: (a) polyamic acid as described
in claim 2 and (b) a solvent.
15. A resin composition comprising: (a) polyamic acid as described
in claim 3 and (b) a solvent.
16. A resin composition comprising: (a) polyamic acid as described
in claim 4 and (b) a solvent.
17. A production method for polyamic acid as described in claim 2
comprising: a step for reacting an amino group of a multivalent
amine compound containing 3 or more primary amino groups with a
compound that reacts with an amino group to form a structure as
represented by chemical formula (1) given above, to form a
multivalent amine derivative containing 2 or more primary amino
groups and a structure as represented by chemical formula (1) and a
step for polymerizing the multivalent amine derivative with
tetracarboxylic acid or a derivative thereof.
18. A production method for polyamic acid as described in claim 3
comprising: a step for reacting an amino group of a multivalent
amine compound containing 3 or more primary amino groups with a
compound that reacts with an amino group to form a structure as
represented by chemical formula (1) given above, to form a
multivalent amine derivative containing 2 or more primary amino
groups and a structure as represented by chemical formula (1) and a
step for polymerizing the multivalent amine derivative with
tetracarboxylic acid or a derivative thereof.
19. A production method for polyamic acid as described in claim 4
comprising: a step for reacting an amino group of a multivalent
amine compound containing 3 or more primary amino groups with a
compound that reacts with an amino group to form a structure as
represented by chemical formula (1) given above, to form a
multivalent amine derivative containing 2 or more primary amino
groups and a structure as represented by chemical formula (1) and a
step for polymerizing the multivalent amine derivative with
tetracarboxylic acid or a derivative thereof.
20. A production method for polyamic acid as described in claim 2
comprising: a step for reacting an amino group of a diamine
compound with a compound that reacts with an amino group to form a
structure as represented by chemical formula (1) given above, to
form a diamine derivative containing a primary amino group and a
structure as represented by chemical formula (1) and a step for
polymerizing the diamine derivative with tetracarboxylic acid or a
derivative thereof.
Description
TECHNICAL FIELD
[0001] The present invention relates to polyamic acid. More
specifically, the invention relates to polyamic acid that can be
used favorably as material for surface protect film and interlayer
insulation film of semiconductor elements, insulation layers and
spacer layers of organic electroluminescent elements (organic EL
elements), planarizing film of thin film transistor substrates,
insulation layers of organic transistors, flexible printed boards,
substrates for flexible display, substrates for flexible electronic
paper, substrates for flexible solar batteries, substrates for
flexible color filters, binders for electrodes of lithium ion
secondary batteries, and adhesives for semiconductors.
BACKGROUND ART
[0002] With good electrical insulating properties, heat resistance,
and mechanical characteristics, polyimides have been used in a
variety of fields including semiconductor production. Polyimides
generally tend to be insoluble in solvents and thermally infusible
and accordingly, difficult to mold or process directly. For film
formation, therefore, a solution (hereinafter, referred to as
varnish) containing polyamic acid as a precursor of a polyimide is
commonly used to form polyimide film through coating and curing
steps for conversion. Such a varnish may be a solution as obtained
from polymerization of polyamic acid or may be prepared by
dissolving polyamic acid in a solvent.
[0003] In general, mechanical characteristics (elongation
percentage and ultimate stress) of polyimide film can be improved
effectively by increasing the degree of polymerization of the
polyimide. As the degree of polymerization of polyamic acid
increases, however, the viscosity of the polymerization solution
increases, often causing troubles in the polymerization process. In
addition, it will be difficult to adjust the varnish to a viscosity
suitable for coating. The viscosity of a varnish can be adjusted
appropriately through control of the polymerization degree of
polyamic acid by changing the molar ratio between the acid
anhydride group in the acid dianhydride monomer used and the amino
group in the multivalent amine compound or diamine compound during
the polymerization of polyamic acid. However, polyimides produced
from this varnish have the same polymerization degree as the
polymerization degree of the original polyamic acid, making it
impossible to achieve high mechanical characteristics.
[0004] Accordingly, methods in which the polymerization degree is
controlled by adding water or alcohol during the polymerization of
polyamic acid to cap the acid anhydride end (Patent documents 1 and
2) and methods in which terminal amino groups are capped to control
the polymerization degree of polyamic acid (Patent document 3) have
been reported. If these methods are used, the end capping agent
will be removed during the curing step, allowing the acid anhydride
group and amino group to regenerate and take part in the
polymerization reaction again. As a result, the polymerization
degree of the resulting polyimide will increase, making it possible
to produce polyimide film with good mechanical characteristics.
[0005] Besides the above ones, methods in which an end capping
agent containing a thermally polymerizable group is used to
introduce a thermally polymerizable group into the polyamic acid
end have been reported (Non-patent documents 1 to 4). These methods
are intended to improve the mechanical characteristics of polyimide
film by causing reaction between the thermally polymerizable end
groups during the curing step.
PRIOR ART DOCUMENTS
Patent Documents
[0006] Patent document 1: Japanese Examined Patent Publication
(Kokoku) No. SHO-47-16980 [0007] Patent document 2: Japanese
Unexamined Patent Publication (Kokai) No. HEI-6-102667 [0008]
Patent document 3: Japanese Unexamined Patent Publication (Kokai)
No. 2009-109589
Non-Patent Documents
[0008] [0009] Non-patent document 1: K. J. Bowles, D. Jayne, and T.
A. Leonhard, SAMPE Quarterly, 24(2), p. 2 (1993) [0010] Non-patent
document 2: A. K. St Clair and T. St Clair, Polym. Eng. Sci., 22,
p. 9 (1982) [0011] Non-patent document 3: T. Takeichi, H. Date, and
Y. Takayama, J. Polym. Sci., Part A: Polym. Chem., 28, p. 3377
(1990) [0012] Non-patent document 4: T. Takekoshi and J. M. Terry,
Polymer, 35, p. 4874 (1994)
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0013] A polyimide with a high polymerization degree is produced as
a result of an increase in the polymerization degree of polyamic
acid, which is achieved by causing the terminal acid anhydride
group regenerated during curing to react with polyamic acid having
an amino group at the end in the methods described in Patent
documents 1 and 2 or by causing the terminal amino group
regenerated during curing to react with polyamic acid having an
acid anhydride group at the end in the method described in Patent
document 3. In order to obtain a polyimide that has a sufficiently
high polymerization degree by these methods, therefore, the
quantity of the capped terminal amino group and that of the
terminal acid anhydride group should be adjusted so that they
account for the same proportion. This means that the methods
described in Patent documents 1 to 3 have the disadvantage that the
acid anhydride group in the acid dianhydride monomer and the amino
group in the multivalent amine compound or diamine compound should
account for the same molar concentration or the intended
characteristics will not be achieved if their blending ratio is not
exactly one.
[0014] In Non-patent documents 1 to 4, on the other hand, either
the terminal acid anhydride group or terminal amino group is capped
with an end capping agent that contains a thermally polymerizable
group. In this case, the end capping agent is not removed and the
thermally polymerizable groups react with each other. Accordingly,
even if there are polyamic acid molecules having an acid anhydride
group or amino group at the end, they are left unreacted during
curing and fail to achieve a sufficiently high polymerization
degree and the polyimide film resulting from the curing step will
not have good mechanical characteristics.
[0015] An object of the present invention is to solve the above
problem. Specifically, the invention aims to provide polyamic acid
that can form a varnish with a low viscosity and serves to produce,
through curing, polyimide film with good mechanical characteristics
and further aims to provide polyimide film with good mechanical
characteristics regardless of whether the molar concentration of
the acid anhydride group in the acid dianhydride monomer and that
of the amino group in the multivalent amine compound or diamine
compound are the same or different from each other.
Means of Solving the Problems
[0016] The present invention provides polyamic acid containing a
structure as represented by chemical formula (1).
##STR00001##
(In chemical formula (1), .delta. is an oxygen or sulfur atom and W
is an electron-withdrawing group. R.sup.11 and R.sup.12 are
independently a hydrogen atom or a hydrocarbon group having 1 to 10
carbon atoms.)
Advantageous Effect of the Invention
[0017] The invention can provide polyamic acid that can form a
varnish with a low viscosity and serves to produce, through curing,
polyimide film with good mechanical characteristics.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 shows a 1H-NMR spectrum of the polymer prepared in
Example 12.
[0019] FIG. 2 shows a 1H-NMR spectrum of the polymer prepared in
Comparative example 13.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0020] The present invention provides polyamic acid containing a
structure as represented by chemical formula (1) given below.
##STR00002##
(In chemical formula (1), .delta. is an oxygen or sulfur atom and W
is an electron-withdrawing group. R.sup.11 and R.sup.12 are
independently a hydrogen atom or a hydrocarbon group having 1 to 10
carbon atoms.)
[0021] For the polyamic acid, W in the above chemical formula (1)
is preferably represented by any of chemical formula (4) to (11)
given below.
##STR00003##
(R.sup.21 to R.sup.28 are independently a hydrocarbon group
containing 1 to 10 carbon atoms or an organic group containing 1 to
10 carbon atoms which includes hydrogen and carbon as essential
elements and 1 to 10 other atoms of elements selected from the
group of boron, oxygen, sulfur, nitrogen, phosphorus, silicon, and
halogens.)
[0022] More preferably, the structure given by the above chemical
formula (1) is polyamic acid as represented by any one of chemical
formulae (12) to (14) given below.
##STR00004##
[0023] It is known that the structure given by the above chemical
formula (12) can be converted into an isocyanate by heating as
represented by chemical formula (21), as reported by, for example,
T. Mukaiyama, M. Tokizawa, H. Nohira, and H. Takei, J. Org. Chem.,
26, 4381 (1961).
##STR00005##
[0024] Furthermore, also in the case where .delta. in chemical
formula (1) is oxygen while W is a group as represented by any of
chemical formulae (4) to (11), the structure is expected to be
converted into an isocyanate when heated, as shown in chemical
formula (22) (when W is a group as represented by any of chemical
formulae (4) to (10)) or in chemical formula (23) (when W is a
group as represented by chemical formula (11), in the same way as
in chemical formula (21)). (Here, chemical formula (22) and
chemical formula (23) show reactions that occur when .delta. is
oxygen, but it is expected that thermal conversion into an
isothiocyanate also occurs through a similar reaction when .delta.
is sulfur.)
##STR00006##
(In chemical formula (22), a represents CR.sup.21 (in chemical
formula (4)), CR.sup.22 (in chemical formula (5)), CR.sup.23 (in
chemical formula (6)), SR.sup.25 (in chemical formula (7)), S(O)
R.sup.26 (in chemical formula (8)), PR.sup.27R.sup.28 (in chemical
formula (9)), or N.sup.+O.sup.- (in chemical formula (10)). .beta.
represents O (for chemical formulae (4) and (7) to (10)), S (for
chemical formula (5)), or NR.sup.24 (for chemical formula
(6)).)
[0025] If an isocyanate is reacted with an acid anhydride group, an
imide group will be formed as shown by chemical formula (24).
Accordingly, a polyimide with a high polymerization degree can be
produced through a reaction with a polyamic acid having an acid
anhydride group at, for example, a chain end. Furthermore, a
polyimide with a high polymerization degree can also be produced if
dimers or trimers are prepared through a reaction between
isocyanates as shown by chemical formula (25). (It should be noted
that reactions as given by chemical formula (24) and chemical
formula (25) can occur when the isocyanate is an isothiocyanate.)
As a result, it will be possible to obtain polyimide film with
improved mechanical characteristics.
##STR00007##
(In chemical formula (24), R denotes a divalent organic group.)
##STR00008##
[0026] Here, it is preferable for the polyamic acid according to
the present invention to contain a structure as shown by chemical
formula (2) or (3). In chemical formula (2), a structure as shown
by chemical formula (1) forms a side chain in a polyamic acid. In
chemical formula (3), a structure as shown by chemical formula (1)
is present at least at one end of a polyamic acid. Here, if k is 2
or larger in chemical formula (2), Zs may be bonded to different
atoms.
##STR00009##
(In chemical formulae (2) and (3), U and X denote a tetravalent
tetracarboxylic acid residue containing 2 or more carbon atoms, V
denotes a tri- or higher-valent multivalent amine residue
containing 2 or more carbon atoms, and Y denotes a divalent diamine
residue containing 2 or more carbon atoms. Z denotes a structure of
chemical formula (1) given above, and k, m, and n each show a
positive integer. R.sup.1 to R.sup.4 independently denote a
hydrogen atom, a hydrocarbon group containing 1 to 10 carbon atoms,
or an alkyl silyl group containing 1 to 10 carbon atoms.) U and X
are preferably a tetravalent hydrocarbon group containing 80 or
less carbon atoms and may be a tetravalent organic group containing
80 or less carbon atoms and including hydrogen and carbon as
essential elements and one or more other atoms of elements selected
from the group of boron, oxygen, sulfur, nitrogen, phosphorus,
silicon, and halogens. For each of boron, oxygen, sulfur, nitrogen,
phosphorus, silicon, and halogens, the number of atoms included is
preferably in the range of 20 or less, more preferably in the range
of 10 or less.
[0027] Examples of tetracarboxylic acid that can give U or X are as
follows. Examples of such aromatic tetracarboxylic acid include
monocyclic aromatic tetracarboxylic acid compounds such as
pyromellitic acid and 2,3,5,6-pyridine tetracarboxylic acid;
various isomers of biphenyl tetracarboxylic acid such as
3,3',4,4'-biphenyl tetracarboxylic acid, 2,3,3',4'-biphenyl
tetracarboxylic acid, 2,2',3,3'-biphenyl tetracarboxylic acid,
3,3',4,4'-benzophenone tetracarboxylic acid, and
2,2',3,3'-benzophenone tetracarboxylic acid; bis(dicarboxyphenyl)
compounds such as 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane,
2,2-bis(2,3-dicarboxyphenyl) hexafluoropropane,
2,2-bis(3,4-dicarboxyphenyl) propane, 2,2-bis(2,3-dicarboxyphenyl)
propane, 1,1-bis(3,4-dicarboxyphenyl) ethane,
1,1-bis(2,3-dicarboxyphenyl) ethane, bis(3,4-dicarboxyphenyl)
methane, bis(2,3-dicarboxyphenyl) methane, bis(3,4-dicarboxyphenyl)
sulfone, and bis(3,4-dicarboxyphenyl) ether; bis(dicarboxyphenoxy
phenyl) compounds such as
2,2-bis[4-(3,4-dicarboxyphenoxyl)phenyl]hexafluoropropane,
2,2-bis[4-(2,3-dicarboxyphenoxyl)phenyl]hexafluoropropane,
2,2-bis[4-(3,4-dicarboxyphenoxyl)phenyl]propane,
2,2-bis[4-(2,3-dicarboxyphenoxyl)phenyl]propane,
2,2-bis[4-(3,4-dicarboxyphenoxyl)phenyl]sulfone, and
2,2-bis[4-(3,4-dicarboxyphenoxyl)phenyl]ether; various isomers of
naphthalene or condensed polycyclic aromatic tetracarboxylic acid
such as 1,2,5,6-naphthalene tetracarboxylic acid,
1,4,5,8-naphthalene tetracarboxylic acid, 2,3,6,7-naphthalene
tetracarboxylic acid, 2,3,6,7-naphthalene tetracarboxylic acid, and
3,4,9,10-perylene tetracarboxylic acid; and bis(trimellitic acid
monoester acid anhydride) compounds such as p-phenylene
bis(trimellitic acid monoester acid anhydride), p-biphenylene
bis(trimellitic acid monoester acid anhydride), ethylene
bis(trimellitic acid monoester acid anhydride), and bisphenol A
bis(trimellitic acid monoester acid anhydride). Examples of such
aliphatic tetracarboxylic acid include chain aliphatic
tetracarboxylic acid compounds such as butane tetracarboxylic acid;
and alicyclic tetracarboxylic acid compounds such as cyclobutane
tetracarboxylic acid, 1,2,3,4-cyclopentane tetracarboxylic acid,
1,2,4,5-cyclohexane tetracarboxylic acid, bicyclo[2.2.1.]heptane
tetracarboxylic acid, bicyclo[3.3.1.]tetracarboxylic acid,
bicyclo[3.1.1.]hept-2-ene tetracarboxylic acid,
bicyclo[2.2.2.]octane tetracarboxylic acid, and adamantane
tetracarboxylic acid.
[0028] These acids may be used as they are or in the form of an
acid anhydride, active ester, or active amide. Two or more thereof
may be used in combination.
[0029] The use of a tetracarboxylic acid containing a silicon atom
such as dimethylsilane diphthalic acid and 1,3-bis(phthalic
acid)tetramethyl disiloxane can serve to increase the adhesion to a
support and the resistance to oxygen plasma used for cleaning and
the like and to UV ozone processing. It is preferable that these
tetracarboxylic acids containing a silicon atom account for 1 to 30
mol % of the total quantity of the acid components.
[0030] For the tetracarboxylic acids given above as examples, one
or more of the hydrogen atoms contained in a tetracarboxylic acid
residue may be replaced with a hydrocarbon group containing 1 to 10
carbon atoms such as methyl group and ethyl group; a fluoroalkyl
group containing 1 to 10 carbon atoms such as trifluoromethyl
group; or other groups such as F, Cl, Br, and I. Furthermore, if
they are replaced with an acidic group such as OH, COOH, SO.sub.3H,
CONH.sub.2, and SO.sub.2NH.sub.2, it is preferable in the case of
the use as a photosensitive resin composition as described later
because they serve to improve the solubility of the resin in an
aqueous alkali solution.
[0031] V is preferably a tri- or higher-valent hydrocarbon group
containing 80 or less carbon atoms and may be a tri- or
higher-valent organic group containing 80 or less carbon atoms and
including hydrogen and carbon as essential elements and one or more
other atoms of elements selected from the group of boron, oxygen,
sulfur, nitrogen, phosphorus, silicon, and halogens. For each of
boron, oxygen, sulfur, nitrogen, phosphorus, silicon, and halogens,
the number of atoms included is preferably in the range of 20 or
less, more preferably in the range of 10 or less.
[0032] Y is preferably a divalent hydrocarbon group containing 80
or less carbon atoms and may be a divalent organic group containing
80 or less carbon atoms and including hydrogen and carbon as
essential elements and one or more other atoms of elements selected
from the group of boron, oxygen, sulfur, nitrogen, phosphorus,
silicon, and halogens. For each of boron, oxygen, sulfur, nitrogen,
phosphorus, silicon, and halogens, the number of atoms included is
preferably in the range of 20 or less, more preferably in the range
of 10 or less.
[0033] Examples of such a multivalent amine compound or diamine
compound that give V or Y include the following. Examples of
multivalent amine compounds and diamine compounds containing an
aromatic ring include monocyclic aromatic diamine compounds such as
m-phenylene diamine, p-phenylene diamine, and 3,5-diaminobenzoic
acid; naphthalene or polycyclic aromatic diamine compounds such as
1,5-naphthalene diamine, 2,6-naphthalene diamine, 9,10-anthracene
diamine, and 2,7-diaminofluorene; bis(diaminophenyl) compounds or
various derivatives thereof such as 4,4'-diaminobenzanilide,
3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether,
3-carboxy-4,4'-diaminodiphenyl ether, 3-sulfonic
acid-4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl methane,
4,4'-diaminodiphenyl methane, 3,4'-diaminodiphenyl sulfone,
4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide,
4,4'-diaminodiphenyl sulfide, 4-aminobenzoic acid 4-aminophenyl
ester, and 9,9-bis(4-aminophenyl) fluorene; 4,4'-diaminobiphenyl or
various derivatives thereof such as 4,4'-diaminobiphenyl,
2,2'-dimethyl-4,4'-diaminobiphenyl,
2,2'-diethyl-4,4'-diaminobiphenyl,
3,3'-dimethyl-4,4'-diaminobiphenyl,
3,3'-diethyl-4,4'-diaminobiphenyl,
2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl,
3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, and 2,2'-di(trifluoro
methyl)-4,4'-diaminobiphenyl; bis(aminophenoxy) compounds such as
bis(4-aminophenoxy phenyl) sulfone, bis(3-aminophenoxy phenyl)
sulfone, bis(4-aminophenoxy) biphenyl,
bis[4-(4-aminophenoxyl)phenyl]ether,
2,2-bis[4-(4-aminophenoxyl)phenyl]propane,
2,2-bis[4-(4-aminophenoxyl)phenyl]hexafluoropropane,
1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, and
1,3-bis(4-aminophenoxy)benzene; bis(3-amino-4-hydroxyphenyl)
compounds such as bis(3-amino-4-hydroxyphenyl) hexafluoropropane,
bis(3-amino-4-hydroxyphenyl) sulfone, bis(3-amino-4-hydroxyphenyl)
propane, bis(3-amino-4-hydroxyphenyl)methylene,
bis(3-amino-4-hydroxyphenyl) ether, bis(3-amino-4-hydroxy)
biphenyl, and 9,9-bis(3-amino-4-hydroxyphenyl) fluorene;
bis(aminobenzoyl) compounds such as
2,2'-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]hexafluoropro-
pane,
2,2'-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]hexafluoropropan-
e, 2,2'-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane,
2,2'-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane,
bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone,
bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone,
9,9-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene,
9,9-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene,
N,N'-bis(3-aminobenzoyl)-2,5-diamino-1,4-dihydroxy benzene,
N,N'-bis(4-aminobenzoyl)-2,5-diamino-1,4-dihydroxy benzene,
N,N'-bis(3-aminobenzoyl)-4,4'-diamino-3,3-dihydroxy biphenyl,
N,N'-bis(4-aminobenzoyl)-4,4'-diamino-3,3-dihydroxy biphenyl,
N,N'-bis(3-aminobenzoyl)-3,3'-diamino-4,4-dihydroxy biphenyl, and
N,N'-bis(4-aminobenzoyl)-3,3'-diamino-4,4-dihydroxy biphenyl;
heterocyclic containing diamine compounds such as
2-(4-aminophenyl)-5-aminobenzoxazole,
2-(3-aminophenyl)-5-aminobenzoxazole,
2-(4-aminophenyl)-6-aminobenzoxazole,
2-(3-aminophenyl)-6-aminobenzoxazole,
1,4-bis(5-amino-2-benzoxazolyl)benzene,
1,4-bis(6-amino-2-benzoxazolyl)benzene,
1,3-bis(5-amino-2-benzoxazolyl)benzene,
1,3-bis(6-amino-2-benzoxazolyl)benzene,
2,6-bis(4-aminophenyl)benzobisoxazole,
2,6-bis(3-aminophenyl)benzobisoxazole,
2,2'-bis[(3-aminophenyl)-5-benzoxazolyl]hexafluoropropane,
2,2'-bis[(4-aminophenyl)-5-benzoxazolyl]hexafluoropropane,
bis[(3-aminophenyl)-5-benzoxazolyl],
bis[(4-aminophenyl)-5-benzoxazolyl],
bis[(3-aminophenyl)-6-benzoxazolyl], and
bis[(4-aminophenyl)-6-benzoxazolyl]; aromatic triamine compounds
such as 1,3,5-triamino benzene, tris(3-aminophenyl) methane,
tris(4-aminophenyl) methane, tris(3-aminophenyl)amine,
tris(4-aminophenyl)amine, tris(3-aminophenyl)benzene,
tris(4-aminophenyl)benzene, 1,3,5-tris(3-aminophenoxy)benzene,
1,3,5-tris(4-aminophenoxy)benzene,
1,3,5-tris(4-aminophenoxy)triazine, melamine, and 2,4,6-triamino
pyrimidine; aromatic tetraamine compounds such as
1,2,4,5-tetraaminobenzene, 3,3',4,4'-tetraaminobiphenyl,
3,3',4,4'-tetraaminodiphenyl sulfone, 3,3',4,4'-tetraaminodiphenyl
sulfide, 2,3,6,7-tetraaminonaphthalene, and
1,2,5,6-tetraaminonaphthalene; and compounds produced from these
multivalent amine compounds or diamine compounds by replacing one
or more of the hydrogen atoms bonded to their aromatic rings with
hydrocarbons or halogen atoms. Examples of aliphatic multivalent
amine compounds include aliphatic diamine compounds such as
ethylene diamine, propylene diamine, butane diamine, pentane
diamine, hexane diamine, octane diamine, nonane diamine, decane
diamine, undecane diamine, dodecane diamine, tetramethyl hexane
diamine, 1,12-(4,9-dioxa) dodecane diamine, and 1,8-(3,6-dioxa)
octane diamine; alicyclic diamine compounds such as cyclohexane
diamine, 4,4'-methylene bis(cyclohexyl amine), and isophorone
diamine; the polyoxyethylene amine and polyoxypropylene amine
products under the trade name of Jeffamine (manufactured by
Huntsman Corporation) and copolymer compounds thereof.
[0034] These multivalent amine compounds and diamine compounds may
be used as they are or in the form of trimethylsilylated
multivalent amine compounds or trimethylsilylated diamine compounds
produced therefrom. Two or more thereof may be used in combination.
For applications that require heat resistance, aromatic multivalent
amine compounds or aromatic diamine compounds are preferably used
in a quantity of 50 mol % or more of the total quantity of
multivalent amine compounds or diamine compounds.
[0035] The use of a diamine compound containing silicon, such as
1,3-bis(3-aminopropyl)tetramethyl disiloxane and
1,3-bis(4-anilino)tetramethyl disiloxane, as the multivalent amine
compound or diamine compound component can serve to increase the
adhesion to the support and the resistance to oxygen plasma used
for cleaning and the like and to UV ozone processing. These
silicon-containing diamine compounds are preferably added to 1 to
30 mol % of the total quantity of the multivalent amine compound or
diamine compound components.
[0036] For the multivalent amine compounds or diamine compounds
given above as examples, one or more of the hydrogen atoms
contained in the residue may be replaced with a hydrocarbon group
containing 1 to 10 carbon atoms such as methyl group and ethyl
group; a fluoroalkyl group containing 1 to 10 carbon atoms such as
trifluoromethyl group; or other groups such as F, Cl, Br, and I.
Furthermore, if they are replaced with an acidic group such as OH,
COOH, SO.sub.3H, CONH.sub.2, and SO.sub.2NH.sub.2, it is preferable
in the case of the use as a photosensitive resin composition as
described later because they serve to improve the solubility of the
resin in an aqueous alkali solution.
[0037] For the polyamic acid according to the present invention
that contains a structure as represented by chemical formula (2) or
chemical formula (3), the number of repetitions of the polyamic
acid unit is preferably 5 or more, more preferably 10 or more. In
addition, it is preferably 500 or less, more preferably 200 or
less. If it is in this range, the molecular weight can be
controlled in a preferable range. For m in chemical formula (2) and
n in chemical formula (3), it is only necessary to meet the
requirement for the preferable number of repetitions of the
polyamic acid units according to the present invention.
Accordingly, m and n are preferably 5 or more, more preferably 10
or more. In addition, it is preferably 500 or less, more preferably
200 or less.
[0038] Any structure in a polyamic acid as shown by chemical
formula (1) can be detected by the following methods. For example,
it can be detected by dissolving the polyamic acid in an acidic
solution to decompose them into the multivalent amine compound or
diamine compound and acid anhydride, i.e. the starting materials,
and analyzing them by gas chromatography or NMR. Alternatively, it
can also be detected by analyzing the polyamic acid directly by
NMR, gas chromatography, or infrared absorption spectrometry.
[0039] For the present invention, a resin composition of polyamic
acid can be prepared by mixing (a) the polyamic acid according to
the present invention and (b) a solvent. The use of this resin
composition makes it possible to produce polyimide film containing
a polyimide that is formed by imidizing the polyamic acid included
in the resin composition. Thus, the use of this resin composition
as a varnish makes it possible to produce polyimide film on various
supports as described later. Thus, polyimide film can be produced
by preparing resin film containing a polyamic acid and then
imidizing the polyamic acid. Solvents that can be used for this
include aprotic polar solvents such as N-methyl-2-pyrolidone,
.gamma.-butyrolactone, N,N-dimethyl formamide, N,N-dimethyl
acetamide, and dimethyl sulfoxide; ethers such as tetrahydrofuran,
dioxane, propylene glycol monomethyl ether, propylene glycol
monoethyl ether, diethylene glycol monomethyl ether, diethylene
glycol monoethyl ether diethylene glycol ethyl methyl ether, and
diethylene glycol dimethyl ether; ketones such as acetone, methyl
ethyl ketone, diisobutyl ketone, diacetone alcohol, and
cyclohexanone; esters such as ethyl acetate, propylene glycol
monomethyl ether acetate, and ethyl lactate; and aromatic
hydrocarbons such as toluene and xylene; which may be used singly
or in combination.
[0040] A varnish with a low viscosity can be obtained even if it
contains the polyamic acid according to the present invention at a
high concentration. Accordingly, there are no specific limitations
on the preferable content of the solvent, but it is preferably 50
parts by mass or more, more preferably 100 parts by mass or more,
and preferably 2,000 parts by mass or less, more preferably 1,500
parts by mass or less, per 100 parts by mass of the resin of
component (a). If it is in the range of 50 to 2,000 parts by mass,
a viscosity suitable for coating can be ensured to allow easy
production of a coat with an appropriately controlled
thickness.
[0041] The polyamic acid according to the present invention has a
polystyrene-based weight average molecular weight of preferably
100,000 or less, more preferably 80,000 or less, and still more
preferably 50,000 or less, as determined by gel permeation
chromatography. If it is in this range, an increase in viscosity of
a varnish can be depressed more effectively even if the varnish has
a high concentration. Furthermore, the weight average molecular
weight is preferably 2,000 or more, more preferably 3,000 or more,
and still more preferably 5,000 or more. If the weight average
molecular weight is 2,000 or more, it is possible to avoid
resulting in a varnish with an excessively low viscosity and ensure
good coatability.
[0042] The resin composition according to the present invention can
be converted into a photosensitive resin composition by adding a
photoacid generating agent. The inclusion of a photoacid generating
agent works to produce an acid in the irradiated portion so that
the irradiated portion increases in solubility in an aqueous alkali
solution, allowing a positive type relief pattern to be formed
after dissolution of the irradiated portion. The inclusion of an
epoxy compound or a thermal crosslinking agent as described later
along with the photoacid generating agent allows the acid formed in
the irradiated portion to serve for promotion of the crosslinking
reaction of the epoxy compound and the thermal crosslinking agent,
leading to the formation of a negative type relief pattern as a
result of insolubilization of the irradiated portion.
[0043] Examples of such a photoacid generating agent include
quinone diazide compounds, sulfonium salts, phosphonium salts,
diazonium salts, and iodonium salts. Two or more thereof may be
added to obtain a photosensitive resin composition with a high
sensitivity.
[0044] Examples of such a quinone diazide compound include
polyhydroxy compounds bonded to sulfonic acid of quinone diazide
through ester linkage, polyamino compounds bonded to sulfonic acid
of quinone diazide through sulfonamide linkage, and
polyhydroxypolyaminno compounds bonded to sulfonic acid of quinone
diazide through ester linkage and/or sulfonamide linkage. It is
preferable that 50 mol % or more of the functional groups in the
polyhydroxy compounds and polyamino compounds be replaced with
quinone diazide.
[0045] For the quinone diazide used for the present invention, both
5-naphthoquinone diazide sulfonyl group and 4-naphthoquinone
diazide sulfonyl group are preferred. A 4-naphthoquinone diazide
sulfonyl ester compound absorbs light in the i-line range of
mercury lamps, and therefore, it is suitable for i-line light
exposure. A 5-naphthoquinone diazide sulfonyl ester compound
absorbs light in a region including the g-line of mercury lamps,
and therefore, it is suitable for g-line light exposure. For the
present invention, it is preferable to adopt either a
4-naphthoquinone diazide sulfonyl ester compound or a
5-naphthoquinone diazide sulfonyl ester compound depending on the
wavelength of the light used for exposure. Furthermore, the agent
may contain a naphthoquinone diazide sulfonyl ester compound having
both a 4-naphthoquinone diazide sulfonyl group and a
5-naphthoquinone diazide sulfonyl group in one molecule, or the
resin composition to be used may contain both a 4-naphthoquinone
diazide sulfonyl ester compound and a 5-naphthoquinone diazide
sulfonyl ester compound.
[0046] Of the examples of photoacid generating agents, the
sulfonium salt, phosphonium salt, and diazonium salt are preferable
because they can stabilize moderately the acid component produced
by light exposure. The sulfonium salt is particularly preferable.
In addition, a sensitizing agent and the like may also be contained
as required.
[0047] For the present invention, the content of the photoacid
generating agent is preferably 0.01 to 50 parts by mass per 100
parts by mass of the resin of component (a) from the viewpoint of
increasing the sensitivity. Of these, the quinone diazide compound
preferably accounts for 3 to 40 parts by mass. The total content of
the sulfonium salt, phosphonium salt, and diazonium salt is
preferably 0.5 to 20 parts by mass.
[0048] The photosensitive resin composition according to the
present invention may contain a thermal crosslinking agent as shown
by chemical formula (31) given below or a thermal crosslinking
agent having a structure as shown by chemical formula (32) given
below (hereinafter, both are referred to as thermal crosslinking
agent). These thermal crosslinking agents can crosslink between
resin compounds that fall under component (a) or with other
additive components, thereby serving to produce polyimide film with
enhanced chemical resistance and hardness.
##STR00010##
(In the above chemical formula (31), R.sup.31 denotes a di- to
tetra-valent linking group. R.sup.32 denotes a monovalent
hydrocarbon group containing 1 to 20 carbon atoms, Cl, Br, I, or F.
R.sup.33 and R.sup.34 independently denote CH.sub.2OR.sup.36 (where
R.sup.36 is a hydrogen atom or a monovalent hydrocarbon containing
1 to 6 carbon atoms). R.sup.35 is a hydrogen atom, methyl group, or
ethyl group. Furthermore, s is an integer of 0 to 2, and t is an
integer of 2 to 4. If a plurality of R.sup.32s exist, they may be
identical to or different from each other. If a plurality of
R.sup.33s and R.sup.34s exist, they may be identical to or
different from each other. If a plurality of R.sup.35s exist, they
may be identical to or different from each other. Examples of the
linking group R.sup.31 are listed below.)
##STR00011##
(In the above formula, R.sup.41 to R.sup.60 denote a hydrogen atom
or a monovalent hydrocarbon group containing 1 to 20 carbon atoms
in which one or more of the hydrogen atoms may be replaced with Cl,
Br, I, or F.)
[Chemical formula 12]
*--N(CH.sub.2OR.sup.37).sub.u(H).sub.v (32)
(In the above chemical formula (32), R.sup.37 denotes a hydrogen
atom or a monovalent hydrocarbon containing carbon 1 to 6 atoms.
Further, u denotes 1 or 2 and v denotes 0 or 1. Here, u+v is equal
to 1 or 2)).
[0049] In the above formula (31), R.sup.33 and R.sup.34 denote
CH.sub.2OR.sup.36 (where R.sup.36 is a hydrogen atom or a
monovalent hydrocarbon containing 1 to 6 carbon atoms) which is a
thermally crosslinkable group. R.sup.36 is preferably a monovalent
hydrocarbon group containing 1 to 4 carbon atoms, more preferably a
methyl group or ethyl group, to allow the thermal crosslinking
agent of chemical formula (31) to maintain a moderate degree of
reactivity and high storage stability.
[0050] Preferable examples of thermal crosslinking agents
containing a structure as represented by chemical formula (31) are
listed below.
##STR00012##
[0051] In chemical formula (32), R.sup.37 denotes a hydrogen atom
or a monovalent hydrocarbon group containing 1 to 6 carbon atoms,
preferably a monovalent hydrocarbon group containing 1 to 4 carbon
atoms. Furthermore, from the viewpoint of stability of the compound
and storage stability of the resin composition, R.sup.37 is
preferably a methyl group or ethyl group and the compound
preferably contains 8 or less (CH.sub.2OR.sup.37) groups.
[0052] Preferable examples of thermal crosslinking agents
containing a group as represented by chemical formula (32) are
listed below.
##STR00013## ##STR00014##
[0053] The content of the thermal crosslinking agent is preferably
10 parts by mass or more and 100 parts by mass or less per 100
parts by mass of the resin of component (a). If the content of the
thermal crosslinking agent is 10 parts by mass or more and 100
parts by mass or less, a polyimide film with high strength and a
photosensitive resin composition with high storage stability will
be obtained.
[0054] The resin composition according to the present invention may
further contain a thermal acid-forming agent. A thermal
acid-forming agent works to generate an acid when heated after
development as described later, promote the crosslinking reaction
between the resin of component (a) and the thermal crosslinking
agent, and also promote the cyclization of imide rings in the resin
of component (a). This serves to provide polyimide film with an
improved chemical resistance and a reduced film loss. The acid
generated by the thermal acid-forming agent is preferably a strong
acid, which is preferably an aryl sulfonic acid such as p-toluene
sulfonic acid and benzene sulfonic acid or an alkyl sulfonic acid
such as methane sulfonic acid, ethane sulfonic acid, and butane
sulfonic acid. For the present invention, the thermal acid-forming
agent is preferably an aliphatic sulfonic acid compound as
represented by chemical formula (33) or (34), and two or more of
such compounds may be contained.
##STR00015##
[0055] In the chemical formulae (33) and (34), R.sup.61 to R.sup.63
may be identical to or different from each other and may have an
organic group containing 1 to 20 carbon atoms, which is preferably
a hydrocarbon group containing carbon atoms 1 to 20. They may be an
organic group containing 1 to 20 carbon atoms and including
hydrogen and carbon as essential elements and one or more atoms of
elements selected from the group of boron, oxygen, sulfur,
nitrogen, phosphorus, silicon, and halogens.
[0056] Specific examples of such compounds represented by chemical
formula (33) are listed below.
##STR00016##
[0057] Specific examples of such compounds represented by chemical
formula (34) are listed below.
##STR00017##
[0058] The content of the thermal acid-forming agent is preferably
0.5 part by mass or more and 10 parts by mass or less per 100 parts
by mass of the resin of component (a) from the viewpoint of
promoting the crosslinking reaction.
[0059] It may contain a compound having a phenolic hydroxyl group
as required to help the alkaline developer in developing the
photosensitive resin composition. Examples of such compounds with a
phenolic hydroxyl group include, for example, the products
available from Honshu Chemical Industry Co., Ltd., under the
following trade names: Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z,
BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ, Bis26X-CP,
BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ,
BisOTBP-CP, TekP-4HBPA (tetrakis P-DO-BPA), TrisP-HAP, TrisP-PA,
TrisP-PHBA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X,
BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP,
BisOCHP-OC, Bis236T-OCHP, methylenetris-FR-CR, BisRS-26X, and
BisRS-OCHP; the products available from Asahi Organic Chemicals
Industry Co., Ltd., under the following trade names: BIR-OC,
BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F,
and TEP-BIP-A; and others including 1,4-dihydroxy naphthalene,
1,5-dihydroxy naphthalene, 1,6-dihydroxy naphthalene, 1,7-dihydroxy
naphthalene, 2,3-dihydroxy naphthalene, 2,6-dihydroxy naphthalene,
2,7-dihydroxy naphthalene, 2,4-dihydroxy quinoline, 2,6-dihydroxy
quinoline, 2,3-dihydroxy quinoxaline, anthracene-1,2,10-triol,
anthracene-1,8,9-triol, and 8-quinolinol. If such a compound with a
phenolic hydroxyl group is contained, the resulting photosensitive
resin composition will be scarcely dissolved in an alkaline
developer before exposure, but will be easily dissolved in an
alkaline developer after exposure, leading to a decreased film loss
during development and ensuring rapid and easy development.
Accordingly, the sensitivity will improve easily.
[0060] Such a compound with a phenolic hydroxyl group preferably
accounts for 3 parts by mass or more and 40 parts by mass or less
per 100 parts by mass of the resin of component (a).
[0061] The photosensitive resin composition according to the
present invention may contain a contact improving agent. Examples
of such contact improving agents include silane coupling agents
such as vinyl trimethoxysilane, vinyl triethoxysilane, epoxy
cyclohexyl ethyl trimethoxysilane, 3-glycidoxy propyl
trimethoxysilane, 3-glycidoxy propyl triethoxysilane, p-styryl
trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl
triethoxysilane, and N-phenyl-3-aminopropyl trimethoxysilane, as
well as titanium chelate agents and aluminum chelate agents. There
are others including alkoxysilane-containing aromatic amine
compounds and alkoxysilane-containing aromatic amide compounds as
listed below.
##STR00018## ##STR00019##
[0062] Besides, compounds produced through a reaction between an
aromatic amine compound and an alkoxy-containing silicon compound
can also be used. Such compounds include, for example, those
produced by reacting an aromatic amine compound with an
alkoxysilane compound having a group reactive with an amino group
such as epoxy group and chloromethyl group. Two or more of the
above contact improving agents may be contained. If these contact
improving agents are contained, the photosensitive resin film can
come in stronger contact with the substrate material such as
silicon wafer, ITO, SiO.sub.2, and nitride silicon during the
development step. Besides, improved contact between the polyimide
film and the substrate material can increase the resistance to
oxygen plasma and UV ozone treatment performed for cleaning. The
content of the contact improving agent is preferably 0.01 to 10
parts by mass per 100 parts by mass of the resin of component
(a).
[0063] The resin composition according to the present invention may
contain inorganic particles with the aim of improving the heat
resistance. Materials of inorganic particles used for this aim
include metals such as platinum, gold, palladium, silver, copper,
nickel, zinc, aluminum, iron, cobalt, rhodium, ruthenium, tin,
lead, bismuth, and tungsten and metal oxides such as silicon oxide
(silica), titanium oxide, aluminum oxide, zinc oxide, tin oxide,
tungsten oxide, zirconium oxide, calcium carbonate, and barium
sulfate. There are no specific limitations on the shape of these
inorganic particles, and they may be spherical, elliptic,
flattened, rod-like, or fibrous. To prevent an increase in the
surface roughness of the polyimide film of a resin composition
containing these inorganic particles, the average particle diameter
of the inorganic particles is preferably 1 nm or more and 100 nm or
less, more preferably 1 nm or more and 50 nm or less, and still
more preferably 1 nm or more and 30 nm or less.
[0064] The content of the inorganic particles is preferably 3 parts
by mass or more, more preferably 5 parts by mass or more, and still
more preferably 10 parts by mass or more, and preferably 100 parts
by mass or less, more preferably 80 parts by mass or less, and
still more preferably 50 parts by mass or less, per 100 parts by
mass of the resin of component (a). The heat resistance will be
sufficiently high if the content of the inorganic particles is 3
parts by mass or more, and the polyimide film will have
sufficiently high toughness if it is 100 parts by mass or less.
[0065] The polyamic acid resin composition according to the present
invention may contain a surface active agent in order to improve
the coatability. Useful surface active agents include
fluorochemical surface active agents such as Fluorad (registered
trademark) manufactured by Sumitomo 3M, Megafac (registered
trademark) manufactured by DIC, Surflon (registered trademark)
manufactured by Asahi Glass Co., Ltd.; organic siloxane surface
active agents such as KP341 manufactured by Shin-Etsu Chemical Co.,
Ltd. DBE manufactured by Chisso Corporation, Polyflow (registered
trademark) and Glanol (registered trademark) manufactured by
Kyoeisha Chemical Co., Ltd., and BYK manufactured by BYK-Chemie;
and acrylic polymer surface active agents such as Polyflow
manufactured by Kyoeisha Chemical Co., Ltd. The content of the
surface active agent is preferably 0.01 to 10 parts by mass per 100
parts by mass of the resin of component (a).
[0066] Described below is the production method for the polyamic
acid according to the present invention. Polyamic acid can be
produced by reacting either a multivalent amine compound or a
diamine compound with either tetracarboxylic acid or a derivative
thereof, and the polyamic acid according to the present invention
that has a structure as shown by chemical formula (1) is preferably
produced by reacting either (i) a multivalent amine compound or
diamine compound that can serve as starting materials for producing
polyamic acid or (ii) an amino group derived from a multivalent
amine compound or diamine compound after the production of polyamic
acid, with a compound that reacts with an amino group to form a
structure as shown by the above-mentioned chemical formula (1).
[0067] Specifically, the following three methods can be applied
favorably.
(i-1) A production method including a step for reacting the amino
group of a multivalent amine compound containing 3 or more primary
amino groups with a compound that reacts with the amino group to
form a structure as shown by the above-mentioned chemical formula
(1) to form a multivalent amine derivative containing 2 or more
primary amino groups and a structure as shown by chemical formula
(1) and a step for polymerizing the multivalent amine derivative
and tetracarboxylic acid or a derivative thereof. (i-2) A
production method including a step for reacting the amino group of
a diamine compound with a compound that reacts with the amino group
to form a structure as shown by the above-mentioned chemical
formula (1) to form a diamine derivative containing a primary amino
group and a structure as shown by chemical formula (1) and a step
for polymerizing the diamine derivative and tetracarboxylic acid or
a derivative thereof. (ii) A production method including a step for
polymerizing a diamine compound and tetracarboxylic acid or a
derivative thereof to produce polyamic acid having an amino group
at a chain end and a step for reacting the amino group of the
polyamic acid with a compound that reacts with an amino group to
form a structure as represented by chemical formula (1), to thereby
produce a polyamic acid having a structure as shown by chemical
formula (1).
[0068] For these production method, examples of the compound that
reacts with an amino group to form a structure as shown by chemical
formula (1) include diketene, .beta.-keto acid, .beta.-thioketo
acid, .beta.-ketimino acid, .alpha.-sulfinyl carboxylic acid,
.alpha.-sulfonyl carboxylic acid, .alpha.-phosphinoyl carboxylic
acid, .alpha.-nitro carboxylic acid, .alpha.-cyano carboxylic acid,
and derivatives thereof. More specifically, such compounds include
diketene, acetoacetic acid, thioketene dimers, 1,2-benzo
isoxazole-3-acetic acid, methane sulfinyl acetic acid, methane
sulfonyl acetic acid, 2-(p-toluenesulfonyl) acetic acid, diphenyl
phosphinoyl acetic acid, nitro acetic acid, and cyanoacetic acid.
Of these, diketene, acetoacetic acid, 2-(p-toluenesulfonyl) acetic
acid, and cyano acetic acid are preferable.
[0069] Useful reaction solvents include aprotic polar solvents such
as N-methyl-2-pyrolidone, .gamma.-butyrolactone, N,N-dimethyl
formamide, N,N-dimethyl acetamide, and dimethyl sulfoxide; ethers
such as tetrahydrofuran, dioxane, propylene glycol monomethyl
ether, propylene glycol monoethyl ether, diethylene glycol
monomethyl ether, diethylene glycol monoethyl ether diethylene
glycol ethyl methyl ether, and diethylene glycol dimethyl ether;
ketones such as acetone, methyl ethyl ketone, diisobutyl ketone,
diacetone alcohol, and cyclohexanone; esters such as ethyl acetate,
propylene glycol monomethyl ether acetate, and ethyl lactate; and
aromatic hydrocarbons such as toluene, xylene, which may be used
singly or in combination with one or more thereof. Furthermore, if
the same solvent as solvent (b) contained in the resin composition
according to the present invention is used, the intended resin
composition can be obtained without isolating the resin after
production.
[0070] Moreover, the carboxyl group in the polyamic acid according
to the present invention may be esterified with a hydrocarbon group
containing 1 to 10 carbon atoms or an alkyl silyl group containing
1 to 10 carbon atoms.
[0071] Described below is the production method for the resin
composition according to the present invention. For example, a
resin composition can be produced by dissolving components (a) and
(b) described above, along with a photoacid generating agent,
dissolution adjusting agent, contact improving agent, inorganic
particles, surface active agent, etc., as required. This
dissolution can be carried out by stirring, heating, etc. If a
photoacid generating agent is contained, an appropriate heating
temperature is adopted in a range, commonly from room temperature
to 80.degree. C., where a photosensitive resin composition with
unimpaired performance is obtained. There are no specific
limitations on the order of dissolving these components, and for
example, the compound with the lowest solubility may be dissolved
first followed by others in the order of solubility. Alternatively,
the dissolution of those components that are likely to form bubbles
when dissolved by stirring, such as surface active agents and some
contact improving agents, may be postponed to the dissolution of
the other components so that the dissolution of the latter will not
be hindered by bubble formation.
[0072] The resulting resin composition is preferably filtrated
through a filter to remove dust and particles. Filters with a pore
size of, for example, 10 .mu.m, 3 .mu.m, 1 .mu.m, 0.5 .mu.m, 0.2
.mu.m, 0.1 .mu.m, 0.07 .mu.m, or 0.05 .mu.m are available, though
there are no specific limitations on the size. The filter to be
used for filtration may be of such a material as polypropylene
(PP), polyethylene (PE), nylon (NY), and polytetrafluoroethylene
(PTFE), of which polyethylene and nylon are preferable.
[0073] Described next is the production method for resin film
containing polyamic acid produced from the resin composition
according to the present invention. First, the resin composition
according to the present invention is spread over a support. There
are no specific limitations on the support, and useful ones include
wafer substrates of silicon, gallium arsenide, or the like; glass
substrates of sapphire glass, soda lime glass, alkali-free glass,
or the like; metal substrates of stainless steel, copper, or the
like, and others such as metal foil and ceramics substrate. Useful
resin composition coating methods include spin coating, slit
coating, dip coating, spray coating, and printing, which may be
used in combination. Before the coating step, the support may be
pre-treated with a contact improving agent as described above. For
example, a contact improving agent may be dissolved to 0.5 to 20 wt
% in a solvent such as isopropanol, ethanol, methanol, water,
tetrahydrofuran, propylene glycol monomethyl ether acetate,
propylene glycol monomethyl ether, ethyl lactate, and diethyl
adipate to prepare a solution, which is then used to treat the
support surface by an appropriate technique such as spin coating,
slit die coating, bar coating, dip coating, spray coating, and
steam processing. Vacuum drying may be carried out as required,
followed by heat treatment at 50.degree. C. to 300.degree. C. to
accelerate the reaction between the support and the contact
improving agent. In general, the coating step is followed by drying
the coating film of the resin composition to form resin film
containing polyamic acid. Useful drying methods include reduced
pressure drying methods, thermal drying methods, and combinations
thereof. The reduced pressure drying methods include, for example,
a process in which a support with a coating film formed on its
surface is put in a vacuum chamber, followed by reducing the
pressure in the vacuum chamber. Thermal drying is performed by
using a tool such as hot plate, oven, and infrared ray. When using
a hot plate, the coating film is put directly on the plate or held
on jigs such as proxy pins fixed on the plate while being dried by
heating. There are various proxy pins of different materials
including metals such as aluminum and stainless steel and synthetic
resins such as polyimide resin and Teflon (registered trademark),
but any types of proxy pins may work effectively if they have heat
resistance. An appropriate proxy pin height may be adopted
depending on the support size, type of the solvent used in the
polyamic acid resin composition, drying method used, etc., but it
is preferably about 0.1 to 10 mm. Depending on the type and purpose
of the solvent used in the polyamic acid resin composition, heating
is performed preferably at a temperature in the range of room
temperature to 180.degree. C. for 1 minute to several hours.
[0074] When the resin composition according to the present
invention contains a photoacid generating agent, a pattern can be
formed by processing the dried coat film by the method described
below. An actinic ray is applied to the coating film through a mask
of an intended pattern. Actinic rays available for exposure include
ultraviolet ray, visible light, electron beam, and X-ray, and the
i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury
lamp are preferred for the invention. If the film is positively
photosensitive, the exposed parts are dissolved by a developer. If
the film is negatively photosensitive, the exposed parts harden and
become insoluble in a developer.
[0075] After the exposure step, a developer is used to remove the
exposed parts of a positive film or unexposed parts of a negative
film to form an intended pattern. Regardless of whether the film is
positive or negative, preferable developers include an aqueous
solution of alkaline compounds such as tetramethyl ammonium,
diethanol amine, diethyl aminoethanol, sodium hydroxide, potassium
hydroxide, sodium carbonate, potassium carbonate, trimethyl amine,
diethyl amine, methyl amine, dimethyl amine, dimethylaminoethyl
acetate, dimethyl aminoethanol, dimethylaminoethyl methacrylate,
cyclohexyl amine, ethylene diamine, and hexamethylene diamine. In
some cases, polar solvents such as N-methyl-2-pyrolidone,
N,N-dimethyl formamide, N,N-dimethyl acetamide, dimethyl sulfoxide,
.gamma.-butyrolactone, and dimethyl acrylamide; alcohols such as
methanol, ethanol and isopropanol; esters such as ethyl lactate and
propylene glycol monomethyl ether acetate; and ketones such as
cyclopentanone, cyclohexaone, isobutyl ketone, and methyl isobutyl
ketone may be added singly or in combination to these aqueous
alkali solution. For negative films, it is also possible to use a
polar solvent as give above that contains no aqueous alkali
solution, or an alcohol, ester, or ketone, which may be added
singly or in combination. Commonly, rinsing in water is performed
after the development step. Here again, the water used for rinsing
may contain an alcohol such as ethanol and isopropyl alcohol, and
an ester such as ethyl lactate and propylene glycol monomethyl
ether acetate.
[0076] Finally, heat treatment is performed in the range of
180.degree. C. or more and 600.degree. C. or less to cure the
coating film. The polyamic acid contained in the resin film that
contains polyamic acid is imidized during this curing step to
produce polyimide film. Such polyimide film produced through the
imidization step can be used favorably as material for surface
protect film and interlayer insulation film of semiconductor
elements, insulation layers and spacer layers of organic
electroluminescent elements (organic EL elements), planarizing film
of thin film transistor substrates, insulation layers of organic
transistors, flexible printed boards, substrates for flexible
display, substrates for flexible electronic paper, substrates for
flexible solar batteries, substrates for flexible color filters,
binders for electrodes of lithium ion secondary batteries, and
adhesives for semiconductors.
Examples
[0077] The present invention will be illustrated below in greater
detail with reference to Examples, but it should be understood that
the invention is not construed as being limited thereto. With
respect to the number of measurements n, n=1 unless otherwise
specified.
(1) Measurement of Viscosity
[0078] A varnish was dissolved in N-methyl-2-pyrolidone to prepare
a 10 mass % solution and measurement was performed at 25.degree. C.
using a viscometer (TVE-22H, manufactured by Toki Sangyo Co.,
Ltd.).
(2) Measurement of Weight Average Molecular Weight
[0079] The polystyrene-based weight average molecular weight was
measured using a gel permeation chromatograph (Waters 2690,
manufactured by Nihon Waters K. K.). TOSOH TXK-GEL .alpha.-2500 and
.alpha.-4000 columns manufactured by Tosoh Corporation were used
along with a N-methyl-2-pyrolidone moving layer.
(3) Production of Polyimide Film
[0080] A varnish was subjected to filtration under pressure using a
1 .mu.m filter to remove foreign objects. Using a coater-developer
apparatus Mark-7 (manufactured by Tokyo Electron Ltd.), spin
coating was performed on a 6-inch silicon wafer in such a way that
the film thickness after pre-baking at 140.degree. C. for 4 minutes
would be 15 .mu.m, and then such pre-baking was carried out. The
pre-baked film was heat-treated at 350.degree. C. for 30 minutes in
a nitrogen air flow (oxygen concentration 20 .mu.m or less) in an
inert gas oven (INH-21CD, manufactured by Koyo Thermo Systems Co.,
Ltd.) to produce polyimide film. Subsequently, the polyimide film
was separated from the silicon wafer substrate by immersion in
hydrofluoric acid for 4 minutes and then it was air-dried. The
polyimide film thus obtained was used for measurement in paragraphs
(4) to (7).
(4) Measurement of Ultimate Tensile Elongation, Ultimate Tensile
Stress, Young's Modulus
[0081] Measurements were made using a Tensilon universal testing
machine (RTM-100, manufactured by Orientec Co., Ltd.) according to
Japanese Industrial Standard (JIS K 7127: 1999).
[0082] Measuring conditions were as follows: width of test piece 10
mm, chuck interval 50 mm, test speed 50 mm/min, number of
measurements n=10.
(5) Measurement of Glass Transition Temperature (Tg)
[0083] Measurements were made in a nitrogen air flow using a
thermomechanical analysis apparatus (EXSTAR6000 TMA/SS6100,
manufactured by SII NanoTechnology Inc.) Heating was performed
under the following conditions. A specimen was heated up to
200.degree. C. in the first stage to remove adsorbed water and
cooled to room temperature in the second stage. In the third stage,
measurements were made at a heating rate of 5.degree. C./min to
determine the glass transition temperature.
(6) Measurement of Coefficient of Thermal Expansion (CTE)
[0084] Measurements were made using the same apparatus and under
the same conditions as used for the measurement of glass transition
temperature to determine the average coefficient of linear
expansion in the range of 50 to 200.degree. C.
(7) Measurement of 5% Mass Decrease Temperature (Td5)
[0085] A thermal mass measuring apparatus (TGA-50, manufactured by
Shimadzu Corporation) was used to make measurements in a nitrogen
air flow. Heating was performed under the following conditions. A
specimen was heated up to 150.degree. C. in the first stage to
remove adsorbed water and cooled to room temperature in the second
stage. In the third stage, measurements were made at a heating rate
of 10.degree. C./min to determine the 5% mass decrease
temperature.
(8) Measurement of .sup.1H-NMR
[0086] A magnetic nuclear resonance apparatus (EX-270, manufactured
by JEOL Ltd.) was used along with deuterated dimethyl sulfoxide as
deuterated solvent to measure the 1H-NMR spectrum
[0087] Listed below are abbreviations of the compounds used in
Synthesis examples, Examples, and Comparative examples.
CHDA: trans-1,4-cyclohexane diamine DAE: 4,4'-diaminodiphenyl ether
PDA: p-phenylene diamine BPDA: 3,3',4,4'-biphenyl tetracarboxylic
dianhydride ODPA: bis(3,4-dicarboxyphenyl) ether dianhydride PMDA:
pyromellitic dianhydride TAM: tris(4-aminophenyl) methane TAB:
1,3,5-tris(4-aminophenoxy)benzene TsAcOH: 2-(p-toluenesulfonyl)
acetic acid DIBOC: di-tert-butyl dicarbonate MA: maleic anhydride
NMP: N-methyl-2-pyrolidone
Example 1
[0088] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 75 g of NMP
was added under a dry nitrogen flow. Subsequently, while stirring
was continued at room temperature, 10.01 g (50.00 mmol) of DAE was
added and washing was performed with 10 g of NMP. After confirming
the dissolution of DAE, the solution was cooled to 10.degree. C. or
below. After the cooling, a solution of 0.210 g (2.50 mmol) of
diketene diluted with 5 g of NMP was added by pouring over a period
of 1 minute and washing was performed with 5 g of NMP. After the
addition, the solution was heated to 40.degree. C. After the
heating, 10.91 g (50.00 mmol) of PMDA was added and washing was
performed with 10 g of NMP. After 2 hours, the solution was cooled
to provide a varnish.
Example 2
[0089] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 55 g of NMP
was added under a dry nitrogen flow. Subsequently, while stirring
was continued at room temperature, 12.01 g (60.00 mmol) of DAE was
added and washing was performed with 10 g of NMP. After confirming
the dissolution of DAE, the solution was cooled to 10.degree. C. or
below. After the cooling, a solution of 0.504 g (6.00 mmol) of
diketene diluted with 5 g of NMP was added by pouring over a period
of 1 minute and washing was performed with 5 g of NMP. After the
addition, the solution was heated to 40.degree. C. After the
heating, 13.09 g (60.00 mmol) of PMDA was added and washing was
performed with 10 g of NMP. After 2 hours, the solution was cooled
to provide a varnish.
Example 3
[0090] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 45 g of NMP
was added under a dry nitrogen flow. Subsequently, while stirring
was continued at room temperature, 12.01 g (60.00 mmol) of DAE was
added and washing was performed with 10 g of NMP. After confirming
the dissolution of DAE, the solution was cooled to 10.degree. C. or
below. After the cooling, a solution of 0.757 g (9.00 mmol) of
diketene diluted with 5 g of NMP was added by pouring over a period
of 1 minute and washing was performed with 5 g of NMP. After the
addition, the solution was heated to 40.degree. C. After the
heating, 13.09 g (60.00 mmol) of PMDA was added and washing was
performed with 10 g of NMP. After 2 hours, the solution was cooled
to provide a varnish.
Example 4
[0091] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 65 g of NMP
was added under a dry nitrogen flow. Subsequently, while stirring
was continued at room temperature, 12.01 g (60.00 mmol) of DAE was
added and washing was performed with 10 g of NMP. After confirming
the dissolution of DAE, the solution was cooled to 10.degree. C. or
below. After the cooling, a solution of 0.504 g (6.00 mmol) of
diketene diluted with 5 g of NMP was added by pouring over a period
of 1 minute and washing was performed with 5 g of NMP. After the
addition, the solution was heated to 40.degree. C. After the
heating, 12.43 g (57.00 mmol) of PMDA was added and washing was
performed with 10 g of NMP. After 2 hours, the solution was cooled
to provide a varnish.
Example 5
[0092] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 65 g of NMP
was added under a dry nitrogen flow, and the temperature was
elevated to 40.degree. C. After the temperature elevation, while
stirring was continued at room temperature, 12.01 g (60.00 mmol) of
DAE was added and washing was performed with 10 g of NMP. After
confirming the dissolution of DAE, 12.43 g (57.00 mmol) of PMDA was
added and washing was performed with 10 g of NMP. After 2 hours, a
solution of 0.504 g (6.00 mmol) of diketene diluted with 5 g of NMP
was added by pouring over a period of 1 minute and washing was
performed with 5 g of NMP. After 1 hour, the solution was cooled to
provide a varnish.
Example 6
[0093] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 65 g of NMP
was added under a dry nitrogen flow. Subsequently, while stirring
was continued at room temperature, 6.488 g (60.00 mmol) of PDA was
added and washing was performed with 10 g of NMP, followed by
elevating the temperature to 30.degree. C. After confirming the
dissolution of PDA, a solution of 0.504 g (6.00 mmol) of diketene
diluted with 5 g of NMP was added by pouring over a period of 1
minute and washing was performed with 5 g of NMP. After the
addition, the solution was heated to 60.degree. C. After the
heating, 17.65 g (60.00 mmol) of BPDA was added and washing was
performed with 10 g of NMP. After 4 hours, the solution was cooled
to provide a varnish.
Example 7
[0094] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 45 g of NMP
was added under a dry nitrogen flow. Subsequently, while stirring
was continued at room temperature, 5.710 g (50.00 mmol) of CHDA was
added and washing was performed with 10 g of NMP. After confirming
the dissolution of CHDA, the solution was cooled to 10.degree. C.
or below. After the cooling, a solution of 0.420 g (5.00 mmol) of
diketene diluted with 5 g of NMP was added by pouring over a period
of 1 minute and washing was performed with 5 g of NMP. After the
addition, the solution was heated to 60.degree. C. After the
heating, 10.30 g (35.00 mmol) of BPDA and 4.653 g (15.00 mmol) of
ODPA were added and washing was performed with 10 g of NMP. After 4
hours, the solution was cooled to provide a varnish.
Example 8
[0095] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 35 g of NMP
was added under a dry nitrogen flow. Subsequently, while stirring
was continued at room temperature, 1.157 g (4 mmol) of TAM was
added and washing was performed with 10 g of NMP. After confirming
the dissolution of TAM, the solution was cooled to 10.degree. C. or
below. After the cooling, a solution of 0.504 g (6.00 mmol) of
diketene diluted with 5 g of NMP was added by pouring over a period
of 1 minute and washing was performed with 5 g of NMP. After the
addition, the solution was heated to 40.degree. C. After the
heating, 6.808 g (34.00 mmol) of DAE was added and washing was
performed with 10 g of NMP. Subsequently, 8.725 g (40.00 mmol) of
PMDA was added and washing was performed with 10 g of NMP. After 2
hours, the solution was cooled to provide a varnish.
Example 9
[0096] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 35 g of NMP
was added under a dry nitrogen flow. Subsequently, while stirring
was continued at room temperature, 1.598 g (4 mmol) of TAB was
added and washing was performed with 10 g of NMP. After confirming
the dissolution of TAB, the solution was cooled to 10.degree. C. or
below. After the cooling, a solution of 0.504 g (6.00 mmol) of
diketene diluted with 5 g of NMP was added by pouring over a period
of 1 minute and washing was performed with 5 g of NMP. After the
addition, the solution was heated to 40.degree. C. After the
heating, 6.808 g (34.00 mmol) of DAE was added and washing was
performed with 10 g of NMP. Subsequently, 8.725 g (40.00 mmol) of
PMDA was added and washing was performed with 10 g of NMP. After 2
hours, the solution was cooled to provide a varnish.
Example 10
[0097] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 35 g of NMP
was added under a dry nitrogen flow. Subsequently, while stirring
was continued at room temperature, 0.425 g (5 mmol) of cyanoacetic
acid was added and washing was performed with 10 g of NMP. After
confirming the dissolution of cyanoacetic acid, the solution was
cooled to 10.degree. C. or below. After the cooling, 0.851 g (5.25
mmol) of carbonyl diimidazole was added and washing was performed
with 10 g of NMP. After the addition, stirring was continued
overnight at room temperature. On the next day, 10.01 g (50.00
mmol) of DAE was added and washing was performed with 10 g of NMP.
After the addition, stirring was additionally continued overnight
at room temperature. On the next day, after elevating the
temperature to 40.degree. C., 10.91 g (50.00 mmol) of PMDA was
added and washing was performed with 30 g of NMP. After 2 hours,
the solution was cooled to provide a varnish.
Example 11
[0098] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 35 g of NMP
was added under a dry nitrogen flow. Subsequently, while stirring
was continued at room temperature, 1.071 g (5 mmol) of TsAcOH was
added and washing was performed with 10 g of NMP. After confirming
the dissolution of TsAcOH, the solution was cooled to 10.degree. C.
or below. After the cooling, 0.851 g (5.25 mmol) of carbonyl
diimidazole was added and washing was performed with 10 g of NMP.
After the addition, stirring was continued overnight at room
temperature. On the next day, 10.01 g (50.00 mmol) of DAE was added
and washing was performed with 10 g of NMP. After the addition,
stirring was additionally continued overnight at room temperature.
On the next day, after elevating the temperature to 40.degree. C.,
10.91 g (50.00 mmol) of PMDA was added and washing was performed
with 30 g of NMP. After 2 hours, the solution was cooled to provide
a varnish.
Comparative Example 1
[0099] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 85 g of NMP
was added under a dry nitrogen flow, and the temperature was
elevated to 40.degree. C. After the temperature elevation, while
stirring is continued at room temperature, 6.007 g (30.00 mmol) of
DAE was added and washing was performed with 10 g of NMP. After
confirming the dissolution of DAE, 6.544 g (30.00 mmol) of PMDA was
added and washing was performed with 10 g of NMP. After 2 hours,
the solution was cooled to provide a varnish.
Comparative Example 2
[0100] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 85 g of NMP
was added under a dry nitrogen flow, and the temperature was
elevated to 40.degree. C. After the temperature elevation, while
stirring is continued at room temperature, 11.41 g (57.00 mmol) of
DAE was added and washing was performed with 10 g of NMP. After
confirming the dissolution of DAE, 13.09 g (60.00 mmol) of PMDA was
added and washing was performed with 10 g of NMP. After 2 hours,
the solution was cooled to provide a varnish.
Comparative Example 3
[0101] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 85 g of NMP
was added under a dry nitrogen flow, and the temperature was
elevated to 40.degree. C. After the temperature elevation, while
stirring is continued at room temperature, 12.01 g (60.00 mmol) of
DAE was added and washing was performed with 10 g of NMP. After
confirming the dissolution of DAE, 12.43 g (57.00 mmol) of PMDA was
added and washing was performed with 10 g of NMP. After 2 hours,
the solution was cooled to provide a varnish.
Comparative Example 4
[0102] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 60 g of NMP
was added under a dry nitrogen flow. Subsequently, while stirring
is continued at room temperature, 12.01 g (60.00 mmol) of DAE was
added and washing was performed with 10 g of NMP. After confirming
the dissolution of DAE, the solution was cooled to 10.degree. C. or
below. After the cooling, a solution of 1.31 g (6.00 mmol) of DIBOC
diluted with 5 g of NMP was added by pouring over a period of 1
minute and washing was performed with 5 g of NMP. After the
addition, the solution was heated to 40.degree. C. After the
heating, 12.43 g (57.00 mmol) of PMDA was added and washing was
performed with 10 g of NMP. After 2 hours, the solution was cooled
to provide a varnish.
Comparative Example 5
[0103] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 60 g of NMP
was added under a dry nitrogen flow. Subsequently, while stirring
is continued at room temperature, 12.01 g (60.00 mmol) of DAE was
added and washing was performed with 10 g of NMP. After confirming
the dissolution of DAE, the solution was cooled to 10.degree. C. or
below. After the heating, 0.588 g (6.00 mmol) of MA was added and
washing was performed with 10 g of NMP. After the addition, the
solution was heated to 40.degree. C. After the heating, 13.09 g
(60.00 mmol) of PMDA was added and washing was performed with 10 g
of NMP. After 2 hours, the solution was cooled to provide a
varnish.
Comparative Example 6
[0104] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 55 g of NMP
was added under a dry nitrogen flow. Subsequently, while stirring
is continued at room temperature, 12.01 g (60.00 mmol) of DAE was
added and washing was performed with 10 g of NMP. After confirming
the dissolution of DAE, the solution was cooled to 10.degree. C. or
below. After the cooling, a solution of 0.613 g (6.00 mmol) acetic
anhydride diluted with 5 g of NMP was added by pouring over a
period of 1 minute and washing was performed with 5 g of NMP. After
the addition, the solution was heated to 40.degree. C. After the
heating, 13.09 g (60.00 mmol) of PMDA was added and washing was
performed with 10 g of NMP. After 2 hours, the solution was cooled
to provide a varnish.
Comparative Example 7
[0105] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 85 g of NMP
was added under a dry nitrogen flow, and the temperature was
elevated to 60.degree. C. After the temperature elevation, while
stirring is continued at room temperature, 3.244 g (30.00 mmol) of
PDA was added and washing was performed with 10 g of NMP. After
confirming the dissolution of PDA, 8.827 g (30.00 mmol) of BPDA was
added and washing was performed with 10 g of NMP. After a period of
time, the viscosity of the polymerization solution increased,
making it impossible to continue stirring any longer.
Comparative Example 8
[0106] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 100 g of
NMP was added under a dry nitrogen flow, and the temperature was
elevated to 60.degree. C. After the temperature elevation, while
stirring is continued at room temperature, 6.164 g (57.00 mmol) of
PDA was added and washing was performed with 10 g of NMP. After
confirming the dissolution of PDA, 17.65 g (60.00 mmol) of BPDA was
added and washing was performed with 10 g of NMP. After 4 hours,
the solution was cooled to provide a varnish.
Comparative Example 9
[0107] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 60 g of NMP
was added under a dry nitrogen flow, and the temperature was
elevated to 60.degree. C. After the temperature elevation, while
stirring is continued at room temperature, 3.426 g (30.00 mmol) of
CHDA was added and washing was performed with 10 g of NMP. After
confirming the dissolution of CHDA, 6.179 g (21.00 mmol) of BPDA
and 2.792 g (9.00 mmol) of ODPA were added and washing was
performed with 10 g of NMP. After 4 hours, the solution was cooled
to provide a varnish.
Comparative Example 10
[0108] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 75 g of NMP
was added under a dry nitrogen flow, and the temperature was
elevated to 60.degree. C. After the temperature elevation, while
stirring is continued at room temperature, 5.424 g (47.50 mmol) of
CHDA was added and washing was performed with 10 g of NMP. After
confirming the dissolution of CHDA, 10.30 g (35.00 mmol) of BPDA
and 4.653 g (15.00 mmol) of ODPA were added and washing was
performed with 10 g of NMP. After 4 hours, the solution was cooled
to provide a varnish.
Comparative Example 11
[0109] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 85 g of NMP
was added under a dry nitrogen flow, and the temperature was
elevated to 40.degree. C. After the temperature elevation, while
stirring is continued at room temperature, 5.106 g (25.50 mmol) of
DAE and 0.868 g (3 mmol) of TAM were added and washing was
performed with 10 g of NMP. After confirming the dissolution of DAE
and TAM, 6.544 g (30.00 mmol) of PMDA was added and washing was
performed with 10 g of NMP. After a period of time, the
polymerization solution gelated, making it impossible to continue
stirring any longer.
Comparative Example 12
[0110] A thermometer and a stirring rod equipped with stirring
blades were fitted on a 200 mL four-necked flask. Then, 85 g of NMP
was added under a dry nitrogen flow, and the temperature was
elevated to 40.degree. C. After the temperature elevation, while
stirring was continued at room temperature, 5.106 g (25.50 mmol) of
DAE and 1.198 g (3 mmol) of TAB were added and washing was
performed with 10 g of NMP. After confirming the dissolution of DAE
and TAB, 6.544 g (30.00 mmol) of PMDA was added and washing was
performed with 10 g of NMP. After a period of time, the
polymerization solution gelated, making it impossible to continue
stirring any longer.
[0111] Tables 1 and 2 show results of evaluation of the varnish
specimens prepared in Examples 1 to 11 and Comparative examples 1
to 12 and measurements of the ultimate tensile elongation, ultimate
tensile stress, Young's modulus, coefficient of thermal expansion,
glass transition temperature, and 5% thermal mass decrease
temperature of the polyimide films produced from the varnish
specimens.
TABLE-US-00001 TABLE 1 Example 1 2 3 4*.sup.1 5*.sup.1 6 acid PMDA
molar 100 100 100 95 95 dianhydride BPDA ratio 100 ODPA diamine DAE
100 100 100 100 100 compound PDA 100 CHDA TAM TAB others diketene 5
10 15 10 10 10 cyanoacetic acid TsAcOH evaluation item unit weight
average molecular weight 61,700 35,800 27,100 45,700 52,700 26,200
viscosity (10 wt % NMP) mPa s 142 56 32 78 105 42 ultimate tensile
elongation % 99 102 102 109 105 19 ultimate tensile stress MPa 226
225 226 215 220 289 Young's modulus GPa 1.6 1.6 1.9 1.7 1.7 6.1
coefficient of thermal expansion ppm/.degree. C. 34 37 40 36 36 7.2
glass transition temperature .degree. C. 375 362 362 359 361 357 5%
heat weight loss temperature .degree. C. 586 580 572 577 578
>600 Example 7 8 9 10 11 acid PMDA molar 100 100 100 100
dianhydride BPDA ratio 70 ODPA 30 diamine DAE 85 85 100 100
compound PDA CHDA 100 TAM 10 TAB 10 others diketene 10 15 15
cyanoacetic 10 acid TsAcOH 10 evaluation item unit weight average
molecular weight 23,800 68,300 59,900 60,900 64,600 viscosity (10
wt % NMP) mPa s 42 122 145 128 150 ultimate tensile elongation % 10
46 66 115 118 ultimate tensile stress MPa 214 192 229 265 273
Young's modulus GPa 5.1 2.3 2.5 2.0 1.9 coefficient of thermal
expansion ppm/.degree. C. 27 35 37 36 36 glass transition
temperature .degree. C. 260 377 368 371 364 5% heat weight loss
temperature .degree. C. 492 569 581 591 584 *.sup.1Example 4 and
Example 5 use a different production method.
TABLE-US-00002 TABLE 2 Comparative example 1 2 3 4 5 6 acid PMDA
molar 100 100 95 95 100 100 dianhydride BPDA ratio ODPA diamine DAE
100 95 100 100 100 100 compound PDA CHDA TAM TAB others DIBOC 10 MA
10 acetic 10 anhydride evaluation item unit weight average
molecular weight 89,600 69,900 56,400 30,600 35,500 41,600
viscosity (10 wt % NMP) mPa s 2819 844 158 58 67 57 ultimate
tensile elongation % 101 52 65 82 102 23 ultimate tensile stress
MPa 228 128 141 153 180 127 Young's modulus GPa 1.6 2.0 1.6 1.6 1.8
2.0 coefficient of thermal expansion ppm/.degree. C. 32 35 38 36 38
37 glass transition temperature .degree. C. 372 366 359 361 370 366
5% heat weight loss temperature .degree. C. 590 589 584 582 585 584
Comparative example 7 8 9 10 11 12 acid PMDA molar 100 100
dianhydride BPDA ratio 100 100 70 70 ODPA 30 30 diamine DAE 85 85
compound PDA 100 95 CHDA 100 95 TAM 10 TAB 10 others DIBOC MA
acetic anhydride evaluation item unit weight average molecular
weight 102,600 26,000 74,600 29,200 N.D.*.sup.3 N.D.*.sup.3
viscosity (10 wt % NMP) mPa s >40000 122 580 62 N.D.*.sup.3
N.D.*.sup.3 ultimate tensile elongation % N.D.*.sup.1 8 13
N.D.*.sup.2 N.D.*.sup.3 N.D.*.sup.3 ultimate tensile stress MPa
N.D.*.sup.1 230 238 N.D.*.sup.2 N.D.*.sup.3 N.D.*.sup.3 Young's
modulus GPa N.D.*.sup.1 6.8 4.7 N.D.*.sup.2 N.D.*.sup.3 N.D.*.sup.3
coefficient of thermal expansion ppm/.degree. C. N.D.*.sup.1 6.3 20
N.D.*.sup.2 N.D.*.sup.3 N.D.*.sup.3 glass transition temperature
.degree. C. N.D.*.sup.1 364 262 N.D.*.sup.2 N.D.*.sup.3 N.D.*.sup.3
5% heat weight loss temperature .degree. C. N.D.*.sup.1 >600 500
N.D.*.sup.2 N.D.*.sup.3 N.D.*.sup.3 *.sup.1No data (Varnish was so
high in viscosity that coating could not be performed.) *.sup.2No
data (Cured film was so brittle that it was broken when separated
from silicon wafer.) *.sup.3No data (Varnish gelated to hinder
subsequent operations.)
Example 12
[0112] The varnish obtained in Example 2 was added to 2 L of water
while stirring to precipitate a polymer. After rinsing, the polymer
was recovered and dried overnight at 50.degree. C. The polymer thus
dried was subjected to .sup.1H-NMR measurement to confirm that a
structure as given by chemical formula (12) was present in the
polymer (FIG. 1).
Comparative Example 13
[0113] A polymer was produced from the varnish obtained in
Comparative example 1 in the same way as in Example 12. This
polymer was subjected to .sup.1H-NMR measurement (FIG. 2).
INDUSTRIAL APPLICABILITY
[0114] The present invention serves to produce polyamic acid that
can form a low-viscosity solution. After being cured, the resulting
coat film shows good physical properties and can be used favorably
as material for surface protect film and interlayer insulation film
of semiconductor elements, insulation layers and spacer layers of
organic electroluminescent elements (organic EL elements),
planarizing film of thin film transistor substrates, insulation
layers of organic transistors, flexible printed boards, substrates
for flexible display, substrates for flexible electronic paper,
substrates for flexible solar batteries, substrates for flexible
color filters, binders for electrodes of lithium ion secondary
batteries, and adhesives for semiconductors.
* * * * *