U.S. patent application number 15/769189 was filed with the patent office on 2018-11-08 for curable resin film and first protective film forming sheet.
The applicant listed for this patent is LINTEC Corporation. Invention is credited to Akinori SATO, Masanori YAMAGISHI.
Application Number | 20180320029 15/769189 |
Document ID | / |
Family ID | 58662774 |
Filed Date | 2018-11-08 |
United States Patent
Application |
20180320029 |
Kind Code |
A1 |
YAMAGISHI; Masanori ; et
al. |
November 8, 2018 |
CURABLE RESIN FILM AND FIRST PROTECTIVE FILM FORMING SHEET
Abstract
A curable resin film of the present invention forms a first
protective film (1a) by attaching the curable resin film containing
an epoxy-based thermosetting component having a weight-average
molecular weight of 200 to 4,000 to a surface (5a) of a
semiconductor wafer (5) having a plurality of bumps (51) with an
average peak height (h1) of 50 to 400 .mu.m, an average diameter of
60 to 500 .mu.m, and an average pitch of 100 to 800 .mu.m, heating
the attached curable resin film at 100.degree. C. to 200.degree. C.
for 0.5 to 3 hours, and curing the heated curable resin film, and
when longitudinal sections thereof are observed by a scanning
electron microscope, a ratio (h3/h1) of an average thickness (h3)
of the first protective film (1a) at a center position between the
bumps (51) to an average peak height (h1) of the bumps (51), and a
ratio (h2/h1) of an average thickness (h2) of the first protective
film (1a) at a position being in contact with the plurality of
bumps (51) to the average peak height (h1) satisfy a relationship
represented by the following expression of
[{(h2/h1)-(h3/h1)}.ltoreq.0.1].
Inventors: |
YAMAGISHI; Masanori;
(Phoenix, AZ) ; SATO; Akinori; (Saitama-shi,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
LINTEC Corporation |
Tokyo |
|
JP |
|
|
Family ID: |
58662774 |
Appl. No.: |
15/769189 |
Filed: |
November 2, 2016 |
PCT Filed: |
November 2, 2016 |
PCT NO: |
PCT/JP2016/082505 |
371 Date: |
April 18, 2018 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09D 133/04 20130101;
C09J 7/25 20180101; H01L 2224/11515 20130101; C09J 2203/326
20130101; C09J 7/38 20180101; C09J 7/30 20180101; C09J 163/00
20130101; H01L 24/26 20130101; C09J 7/20 20180101; C08L 33/00
20130101; C09J 4/06 20130101; C09J 2463/00 20130101; C09J 2433/00
20130101; C09J 133/00 20130101; C08L 63/00 20130101; C08L 2203/16
20130101; C08L 2203/20 20130101; H01L 2224/11 20130101; C09D 133/04
20130101; C08L 63/00 20130101 |
International
Class: |
C09J 7/25 20060101
C09J007/25; C09J 7/38 20060101 C09J007/38; C08L 63/00 20060101
C08L063/00; H01L 23/00 20060101 H01L023/00 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 4, 2015 |
JP |
2015-217111 |
Claims
1. A curable resin film for forming a first protective film on a
surface having a plurality of bumps in a semiconductor wafer by
being attached to the surface and being cured, wherein the curable
resin film contains an epoxy-based thermosetting component having a
weight-average molecular weight of 200 to 4,000 as a curable
component, and wherein the first protective film that protects the
plurality of bumps is formed by attaching the curable resin film to
a surface of the semiconductor wafer having the plurality of bumps
with an average peak height h1 of 50 to 400 .mu.m, an average
diameter D of 60 to 500 .mu.m in a plan view, and an average pitch
P of 100 to 800 .mu.m, heating the attached curable resin film at
100.degree. C. to 200.degree. C. for 0.5 to 3 hours, and curing the
heated curable resin film, and when longitudinal sections of the
first protective film and the semiconductor wafer having the
plurality of bumps are observed by a scanning electron microscope,
a ratio (h3/h1) of an average thickness h3 of the first protective
film at a center position between the plurality of bumps to the
average peak height h1 of the plurality of bumps, and a ratio
(h2/h1) of an average thickness h2 of the first protective film at
a position being in contact with the plurality of bumps to the
average peak height h1 satisfy a relationship represented by the
following Expression (1). {(h2/h1)-(h3/h1)}.ltoreq.0.1 (1)
2. A curable resin film for forming a first protective film on a
surface having a plurality of bumps in a semiconductor wafer by
being attached to the surface and being cured, wherein the curable
resin film contains an energy ray-curable component having a
weight-average molecular weight of 200 to 4,000 as a curable
component, and wherein the first protective film that protects the
plurality of bumps is formed by attaching the curable resin film to
a surface of the semiconductor wafer having the plurality of bumps
with an average peak height h1 of 50 to 400 .mu.m, an average
diameter D of 60 to 500 .mu.m in a plan view, and an average pitch
P of 100 to 800 .mu.m, irradiating the attached curable resin film
with energy rays under a condition of illuminance of 50 to 500
mW/cm.sup.2, and light intensity of 100 to 2,000 mJ/cm.sup.2, and
curing the irradiated curable resin film, and when longitudinal
sections of the first protective film and the semiconductor wafer
having the plurality of bumps are observed by a scanning electron
microscope, a ratio (h3/h1) of an average thickness h3 of the first
protective film at a center position between the plurality of bumps
to the average peak height h1 of the plurality of bumps, and a
ratio (h2/h1) of an average thickness h2 of the first protective
film at a position being in contact with the plurality of bumps to
the average peak height h1 satisfy a relationship represented by
the following Expression (1). {(h2/h1)-(h3/h1)}.ltoreq.0.1 (1)
3. The curable resin film according to claim 1 which contains 5% to
80% by mass of filler having an average particle diameter of 5 to
1,000 nm.
4. A first protective film forming sheet comprising the curable
resin film according to claim 1 on one surface of a first
supporting sheet.
Description
TECHNICAL FIELD
[0001] The present invention relates to a curable resin film and a
first protective film forming sheet provided with the curable resin
film.
[0002] Priority is claimed on Japanese Patent Application No.
2015-217111, filed on Nov. 4, 2015, the content of which is
incorporated herein by reference.
BACKGROUND ART
[0003] In the related art, in a case in which a multi-pin LSI
package, which is used in MPU or a gate array, is mounted on a
printed wiring board, a flip chip mounting method in which a
semiconductor chip in which convex electrodes (bumps) made of
eutectic solder, high-temperature solder, metal, or the like are
formed in connection pad portions is used, and these bumps are made
to face, brought into contact with, and melting/diffusion-joined to
the corresponding terminal portions on a chip mounting substrate
using a so-called face down method has been employed.
[0004] The semiconductor chip that is used in this mounting method
is obtained by, for example, dividing a semiconductor wafer having
bumps formed on a circuit surface by grinding a surface opposite to
the circuit surface or dicing the semiconductor wafer. In the
process of obtaining the above-described semiconductor chip,
generally, for the purpose of protecting a circuit surface and a
bump of the semiconductor wafer, a curable resin film is attached
to a bump-formed surface, and this film is cured so as to form a
protective film on the bump-formed surface. As such a curable resin
film, those containing a thermosetting component that is cured by
heating are widely used. As a protective film forming sheet
including the above-described curable resin film, a protective film
forming sheet formed by stacking a thermoplastic resin layer having
a predetermined thermal elastic modulus on the film and further
stacking a thermoplastic resin layer which is not plastic at
25.degree. C. on the uppermost layer of the thermoplastic resin
layer has been disclosed (for example, refer to Patent Document 1).
According to Patent Document 1, this protective film forming sheet
is excellent in terms of the bump filling property of the
protective film, the wafer workability, the electric connection
reliability after resin sealing, and the like.
CITATION LIST
Patent Literature
[0005] [Patent Document 1] Japanese Unexamined Patent Application,
First Publication No. 2005-028734
SUMMARY OF INVENTION
Technical Problem
[0006] On the other hand, when manufacturing a semiconductor chip
by using a protective film forming sheet provided with a curable
resin film as described above, after a protective film is formed on
a bump-formed surface of a semiconductor wafer by thermally curing
the curable resin film, this protective film is greatly distorted
in a concave shape at the position between the bumps in some cases
(refer to FIG. 6). In FIG. 6, a protective film 101a formed on a
surface 105a, which is a surface, on which a bump 151 is formed on
a semiconductor wafer 105, by thermally curing a thermosetting
resin film is greatly distorted concavely on a side of the surface
105a. Such a large distortion in a concave shape of the protective
film 101a is considered to occur due to contraction or the like
when the curable resin film is cured on the surface 105a of the
semiconductor wafer 105.
[0007] In this way, if the large distortion in the concave shape
occurs on the protective film 101a on the semiconductor wafer 105,
for example, when performing inspection of the circuit surface in a
manufacturing step of the semiconductor wafer, there is a
possibility that deviation occurs in alignment between an
inspection apparatus and the semiconductor wafer, so that it is
difficult to perform accurate inspection. In addition, when the
large distortion in the concave shape occurs on the protective film
101a, at the time of dicing the semiconductor wafer 105 in chip
units using a dicing apparatus, there is a possibility that
deviation occurs in alignment between a dicing saw provided in the
dicing apparatus and the semiconductor wafer, so that it is
difficult to perform accurate dicing. As a cause of the deviation
of the alignment as described above, it is considered that the
protective film 101a is largely distorted in the concave shape, and
thus a lens action occurs in this concave portion, and the shape of
the surface 105a which is a circuit surface of the semiconductor
wafer 105, for example, the shape of a pattern 152 or the position
thereof cannot be accurately detected.
[0008] Therefore, in the related art, in a case where the large
distortion in the concave shape occurs on the protective film 101a
on the semiconductor wafer 105, yield of the semiconductor chip is
lowered or the reliability as a semiconductor package is
deteriorated, which is a serious problem.
[0009] The present invention has been made in view of the above
problems, and an object of the present invention is to provide a
curable resin film and a first protective film forming sheet, which
are capable of suppressing occurrence of large distortion in a
concave shape on a first protective film when the first protective
film is formed on a bump-formed surface of the semiconductor
wafer.
Solution to Problem
[0010] In order to solve the above-mentioned problems, the
inventors of the present invention have extensively studied
experiments and studies. As a result, it has been found that after
optimizing the weight-average molecular weight of the curable
component contained in the curable resin film used for forming the
first protective film, when a dimensional relationship between of
the first protective film cured under predetermined conditions and
the bump is appropriately defined, on a semiconductor wafer having
a plurality of bumps of a predetermined dimensional shape and
arrangement condition, the occurrence of the large distortion in
the concave shape on the first protective film disposed between the
bumps can be suppressed, and thereby the present invention has been
completed.
[0011] That is, according to the present invention, there is
provided a curable resin film for forming the first protective film
on a surface having a plurality of bumps on the semiconductor wafer
by being attached to the surface and being cured, in which the
curable resin film contains an epoxy-based thermosetting component
having a weight-average molecular weight of 200 to 4,000 as a
curable component, a first protective film that protects the
plurality of bumps is formed by attaching the curable resin film to
a surface of the semiconductor wafer having the plurality of bumps
with an average peak height h1 of 50 to 400 .mu.m, an average
diameter D of 60 to 500 .mu.m in a plan view, and an average pitch
P of 100 to 800 .mu.m, heating the attached curable resin film at
100.degree. C. to 200.degree. C. for 0.5 to three hours, and curing
the heated curable resin film, and when longitudinal sections of
the first protective film and the semiconductor wafer having the
plurality of bumps are observed by a scanning electron microscope,
a ratio (h3/h1) of an average thickness h3 of the first protective
film at a center position between the plurality of bumps to the
average peak height h1 of the plurality of bumps, and a ratio
(h2/h1) of an average thickness h2 of the first protective film at
a position being in contact with the plurality of bumps to the
average peak height h1 satisfy a relationship represented by the
following Expression (1).
{(h2/h1)-(h3/h1)}.ltoreq.0.1 (1)
[0012] In addition, according to the present invention, there is
provided a curable resin film for forming the first protective film
on a surface having a plurality of bumps on the semiconductor wafer
by being attached to the surface and being cured, in which the
curable resin film contains an energy ray-curable component having
a weight-average molecular weight of 200 to 4,000 as a curable
component, a first protective film that protects the plurality of
bumps is formed by attaching the curable resin film to a surface of
the semiconductor wafer having the plurality of bumps with an
average peak height h1 of 50 to 400 .mu.m, an average diameter D of
60 to 500 .mu.m in a plan view, and an average pitch P of 100 to
800 .mu.m, irradiating the attached curable resin film with energy
rays under a condition of illuminance of 50 to 500 mW/cm.sup.2, and
light intensity of 100 to 2,000 mJ/cm.sup.2, and curing the
irradiated curable resin film, and when longitudinal sections of
the first protective film and the semiconductor wafer having the
plurality of bumps are observed by a scanning electron microscope,
a ratio (h3/h1) of an average thickness h3 of the first protective
film at a center position between the plurality of bumps to the
average peak height h1 of the plurality of bumps, and a ratio
(h2/h1) of an average thickness h2 of the first protective film at
a position being in contact with the plurality of bumps to the
average peak height h1 satisfy a relationship represented by the
following Expression (1).
{(h2/h1)-(h3/h1)}.ltoreq.0.1 (1)
[0013] In the above configuration, it is more preferable that the
curable resin film of the present invention contains 5% to 80% by
mass of filler having an average particle diameter of 5 to 1,000
nm.
[0014] In addition, according to the present invention, there is
provided a first protective film forming sheet including the
curable resin film having any configuration described above on one
surface of a first supporting sheet.
Advantageous Effects of Invention
[0015] According to the present invention, the curable resin film
and the first protective film forming sheet provided with the
curable resin film, after optimizing the weight-average molecular
weight of the curable component contained in the curable resin film
used for forming the first protective film, when a dimensional
relationship between of the first protective film cured under
predetermined conditions and the bump is appropriately defined, on
a semiconductor wafer having a plurality of bumps of a
predetermined dimensional shape and arrangement condition. With
this, it is possible to suppress the occurrence of the large
distortion in the concave shape the first protective film disposed
between the bumps. As a result, for example, the inspection in a
step of manufacturing a semiconductor wafer and the alignment
accuracy in a step of dicing the semiconductor wafer into a chip
improve. Therefore, the inspection accuracy and the dicing accuracy
in the manufacturing step improve, and a semiconductor package
excellent in the reliability can be manufactured.
BRIEF DESCRIPTION OF DRAWINGS
[0016] FIG. 1A is a sectional view schematically showing an example
of procedure of forming a first protective film on a bump-formed
surface of a semiconductor wafer by using a curable resin film
according to the present invention, and is a diagram showing a
state in which the curable resin film is attached to the
bump-formed surface of the semiconductor wafer.
[0017] FIG. 1B is a sectional view schematically showing an example
of procedure of forming a first protective film on the bump-formed
surface of the semiconductor wafer by using the curable resin film
according to the present invention, and is a diagram showing a
state in which the first protective film is formed by thermally
curing the curable resin film.
[0018] FIG. 2 is a plan view schematically showing an example of a
state in which the first protective film is formed on the
bump-formed surface of the semiconductor wafer by using the curable
resin film according to the present invention.
[0019] FIG. 3 is a sectional view schematically showing an example
of a layer structure of the curable resin film and the first
protective film forming sheet according to the present
invention.
[0020] FIG. 4 is a sectional view schematically showing another
example of a layer structure of the curable resin film and the
first protective film forming sheet according to the present
invention.
[0021] FIG. 5 is a sectional view schematically showing still
another example of a layer structure of the curable resin film and
the first protective film forming sheet according to the present
invention.
[0022] FIG. 6 is a diagram showing a state in which the protective
film is formed on the bump-formed surface of the semiconductor
wafer by using the curable resin film in the related art.
DESCRIPTION OF EMBODIMENTS
[0023] Hereinafter, embodiments of a curable resin film of the
present invention and a first protective film forming sheet using
the same will be described in detail with reference to the drawings
of FIGS. 1 to 5 of the present invention and the drawing of FIG. 6
of the related art, as necessary. FIGS. 1A and 1B are sectional
views schematically showing an example of procedure of forming the
first protective film on the bump-formed surface of the
semiconductor wafer by using the curable resin film according to
the present invention, and FIG. 2 is a plan view of the
semiconductor wafer shown in FIG. 1B. In addition, FIGS. 3 to 5 are
sectional views schematically showing each example of the layer
structure of the curable resin film and the first protective film
forming sheet. Further, FIG. 6 is a diagram showing an example in
which the first protective film is formed on the bump-formed
surface of the semiconductor wafer by using the curable resin film
in the related art. Note that, in the drawings used in the
following description, for the sake of easy understanding of the
features of the present invention, and for the sake of convenience,
a portion serving as a main part is sometimes enlarged and the
dimensional ratio and the like of each component may be different
from the actual one. Further, in the present specification, the
above-described "film" may be referred to as "layer" in some
cases.
[0024] The curable resin film 1 according to the present invention
as shown in FIGS. 3 to 5 are for forming a first protective film 1a
that protects a plurality of bumps 51 on a semiconductor wafer 5 as
shown in FIGS. 1A and 1B, and FIG. 2. That is, the curable resin
film 1 of the present invention is used to form a first protective
film 1a on the surface 5a by being attached to the surface 5a
having the plurality of bumps 51 on the semiconductor wafer 5 as
shown in FIG. 1A, and being cured as shown in FIG. 1B.
[0025] In addition, a first protective film forming sheet 1A
according to the present invention is provided with the curable
resin film 1 on one surface 11a of the first supporting sheet 11,
as shown in FIG. 3. That is, before attaching the curable resin
film 1 on the semiconductor wafer 5, the first protective film
forming sheet 1A transports the curable resin film 1 as a product
package, for example, or stably supports and protects the curable
resin film 1 by the first supporting sheet 11 when transporting the
curable resin film 1 in the process.
[0026] Hereinafter, configurations of the curable resin film 1 of
the present invention and the first protective film forming sheet
1A are specifically described in order.
[0027] <<Curable Resin Film>>
[0028] As described above, the curable resin film of the present
invention is a layer (film) for protecting the plurality of bumps
51 on the surface 5a of the semiconductor wafer 5, and the first
protective film 1a is formed by heating or curing with energy ray
irradiation.
[0029] <Curable Resin Film Containing Thermosetting
Component>
[0030] The curable resin film 1 of the present invention is
configured to contain an epoxy-based thermosetting component having
a weight-average molecular weight of 200 to 4,000 as a curable
component.
[0031] In addition, the curable resin film 1 of the present
invention is used to form the first protective film by being
attached to the semiconductor wafer 5 having the plurality of bumps
51 on the surface 5a as shown in FIGS. 1A and 1B.
[0032] The curable resin film 1 of the present invention forms the
first protective film 1a that protects the plurality of bumps 51
and the surface 5a by attaching the curable resin film onto the
semiconductor wafer 5 having the plurality of bumps 51 with an
average peak height h1 of 50 to 400 .mu.m, an average diameter D of
60 to 500 .mu.m in a plan view, and an average pitch P of 100 to
800 .mu.m, and heating the attached curable resin film at
100.degree. C. to 200.degree. C. for 0.5 to 3 hours, and curing the
heated curable resin film, and when longitudinal sections of the
first protective film 1a and the semiconductor wafer 5 are observed
by a scanning electron microscope, a ratio (h3/h1) of an average
thickness h3 of the first protective film 1a at a center position
between the plurality of bumps 51 to an average peak height h1 of
the plurality of bumps 51, and a ratio (h2/h1) of an average
thickness h2 of the first protective film 1a at a position being in
contact with the plurality of bumps 51 to the average peak height
h1 satisfy a relationship represented by the following Expression
(1).
{(h2/h1)-(h3/h1)}.ltoreq.0.1 (1)
[0033] The "average thickness h3 of the first protective film 1a at
a center position between the plurality of bumps 51" defined in the
present invention substantially means a portion in which the
thickness of the first protective film 1a in the vicinity of the
center between the plurality of bumps 51 is substantially the
thinnest.
[0034] Also, the "average pitch P" in "the plurality of bumps 51
having the plurality of bumps 51 with average pitch P of 100 to 800
.mu.m" defined in the present invention means the average pitch
between the center lines of each bump 51. Note that, the average
peak height h1 of the plurality of bumps, average thickness h2 of
the first protective film at the position being in contact with the
plurality of bumps, the average thickness h3 of the first
protective film at the center position between the plurality of
bumps, the average pitch P, and the average diameter D can be
measured by image analysis using a scanning electron
microscope.
[0035] As described above, the curable resin film 1 of the present
invention is used by being attached to the surface 5a having the
bump 51 in the semiconductor wafer 5. Then, the curable resin film
1 after attachment has an increase in fluidity by heating, spreads
between the plurality of bumps 51 so as to cover the bumps 51, is
close contact with the surface (circuit surface) 5a, and embeds the
bump 51 while covering the surface 51a of the bump 51,
particularly, the vicinity of the surface 5a of the semiconductor
wafer 5. The curable resin film 1 in such a state is thermally
cured by being further heated so as to finally form the first
protective film 1a and protects the bump 51 in a state of being in
close contact with the surface Ma on the surface 5a. The
semiconductor wafer 5 to which the curable resin film 1 is attached
is detached and removed from a first supporting sheet (refer to the
first supporting sheet 11 provided in the first protective film
forming sheet 1A as shown in FIG. 3) after grinding the surface
(the back surface 5b) on the side opposite to the surface 5a which
is the circuit surface. Subsequently, embedding of the bumps 51 and
formation of the first protective film 1a are performed by heating
the curable resin film 1, and finally, the semiconductor wafer is
incorporated into a semiconductor device (not shown) in a state
where this first protective film 1a is provided.
[0036] The plurality of the bumps 51 are provided on surface 5a
which is the circuit surface of the semiconductor wafer 5. The bump
51 has, for example, a shape of a sphere a part of which is cut out
along a flat surface, and a flat surface corresponding to a portion
exposed by cutting out the above-described part is in contact with
the surface 5a of the semiconductor wafer 5.
[0037] The first protective film 1a is formed with the curable
resin film 1 of the present invention, covers the surface 5a of the
semiconductor wafer 5, and further covers the top surface and the
surface 51a other than the vicinity thereof among the bump 51. In
this way, the first protective film 1a is close contact with the
top surface of the bumps 51 and the area other than the vicinity
thereof among the surfaces 51a of the bumps 51, and is also close
contact with the surface (circuit surface) 5a the semiconductor
wafer 5 so as to embed the bump 51. In the examples as shown in
FIGS. 1A and 1B, the bumps have substantially spherical shapes
(shapes in which a part of the spheres are cut out by planes) as
described above, but the shape of the bump that can be protected by
the first protective film 1a formed from the curable resin film 1
according to the present invention is not limited thereto. Examples
of preferred bumps include a bump having a shape obtained by
stretching the bump having a substantially spherical shape as shown
in FIGS. 1A and 1B, in a height direction (direction orthogonal to
the surface 5a of the semiconductor wafer 5 in FIGS. 1A and 1B),
that is, a shape of a spheroid which is substantially long
spherical (a shape in which a portion including one end in the
major axis direction of a spheroid which is long spherical is cut
out by a plane), and a bump having a shape obtained by crushing the
bump having a substantially spherical shape in a height direction,
that is, a shape of a spheroid which is substantially oblate (a
shape in which a portion including one end in the minor axis
direction of a spheroid which is substantially oblate is cut out by
a plane). The first protective film 1a formed by the curable resin
film 1 according to the present invention can be applied to the
bumps having any other shapes, and particularly, in a case where
the shape of the bump is a spherical shape including a spherical
shape or an elliptical shape as described above, the effect of
protecting the surface of the semiconductor wafer and the bump is
remarkably obtained.
[0038] In addition, as described above, the curable resin film 1 of
the present invention employs a configuration in which after
optimizing the weight-average molecular weight of the curable
component contained in the curable resin film 1, when a dimensional
relationship between of the first protective film 1a cured under
predetermined conditions and the plurality of bumps 51 are
appropriately defined, on the semiconductor wafer 5 having the
plurality of bumps 51 of a predetermined dimensional shape and
arrangement condition. With this, it is possible to suppress the
occurrence of the large distortion in the concave shape the first
protective film 1a formed and disposed between the plurality of
bumps 51. With this, for example, it is possible to obtain an
effect of improving the inspection in a step of manufacturing a
semiconductor wafer and the alignment accuracy in a step of dicing
the semiconductor wafer into a chip.
[0039] More specifically, regarding the curable resin film 1, as
shown in FIG. 1B, in the first protective film 1a cured under the
predetermined heating conditions, the ratio (h3/h1) of the average
thickness h3 of the first protective film 1a at the center position
A between the plurality of bumps 51 to the average peak height h1
of the plurality of bumps 51, and the ratio (h2/h1) of the average
thickness h2 of the first protective film 1a at the position B
being in contact with the plurality of bumps 51 satisfy the
relationship represented by the following expression
{{(h2/h1)-(h3/h1)}.ltoreq.0.1}. That is, in the first protective
film 1a formed by thermally curing the curable resin film 1, as
represented by the above expression, the average thickness h2 at
the position B being in contact with the plurality of bumps 51 and
the average thickness h3 at the center position A between the
plurality of bumps 51 are defined in a relationship in which the
average thickness h2 is thicker and the difference between both is
minimized. That is, according to one aspect of the present
invention, examples thereof include a curable resin film and a
first protective film forming sheet which have the properties
satisfying the above relationship.
[0040] In addition, as shown in FIGS. 1A and 1B, and FIG. 2, the
first protective film 1a formed of the curable resin film 1
according to the present invention is prevented from shrinking in
the film during curing, and thus it is possible to effectively
suppress the occurrence of the large distortion in a concave shape.
For example, in FIG. 1B and FIG. 2, the large distortion does not
occur in the first protective film 1a and fluoroscopic defects due
to a lens effect or the like do not occur, so that a circuit
pattern 52 on the surface 5 of the semiconductor wafer 5 can be
clearly recognized. With this, it is possible to accurately detect
the arrangement shape and the like of the circuit pattern 52 on the
surface 5a of the semiconductor wafer 5, and therefore, for
example, various inspections in the manufacturing step of the
semiconductor wafer 5, and the alignment accuracy between the
inspection apparatus, the manufacturing apparatus, the
semiconductor wafer 5 in a step of dicing the semiconductor wafer 5
in a chip shape improve. Therefore, the inspection accuracy and the
dicing accuracy improve, and a semiconductor package excellent in
the reliability can be manufactured.
[0041] In the present invention, the curable component contained in
the curable resin film 1 is configured to contain an epoxy-based
thermosetting component having a weight-average molecular weight of
200 to 4,000. When the curable resin film 1 contains the
epoxy-based thermosetting component within the above range, it is
possible to minimize the occurrence of deformation due to thermal
shrinkage or the like in the first protective film 1a after
thermally curing. With this, it is possible to suppress the
occurrence of the large distortion in the concave shape on the
thermally-cured first protective film 1a. Meanwhile, in the present
embodiment, unless particularly otherwise described, the
weight-average molecular weight refers to a polystyrene-equivalent
value measured using gel permeation chromatography (GPC).
[0042] Further, in the present invention, from the viewpoint of
more remarkably obtaining the above action and effect, the
weight-average molecular weight of the epoxy-based thermosetting
component contained in the curable resin film 1 is more preferably
250 to 3,500, and particularly preferably 300 to 3,000.
[0043] Detailed components of the epoxy-based thermosetting
component will be described later.
[0044] In the present invention, the curable resin film 1 may
further contain a filler (D) which will be described in detail
later. In this case, the average particle diameter and the amount
of the filler (D) are not particularly limited, and for example,
the filler having the average particle diameter of 5 to 1,000 nm is
preferably contained in the curable resin film 1 by 5% to 80% by
mass of the entire mass of the thermosetting resin composition
forming the curable resin film 1. When the average particle
diameter and the amount of the filler (D) contained in the curable
resin film 1 are limited to the above-mentioned range, it is
possible to obtain an effect in which the occurrence of the large
distortion in a concave shape in the cured first protective film 1a
as described above can be more remarkably suppressed. It is
considered that the reason for this is that when a certain
percentage of the filler (D) contained in the curable resin film 1
is limited to those having an average particle diameter in a
predetermined range, shrinkage or the like which is likely to occur
at the time of curing the curable resin film 1 can be effectively
suppressed.
[0045] Note that, the average particle diameter of the filler (D)
is more preferably 5 to 500 nm, and particularly preferably 10 to
300 nm, from the viewpoint that the above action and effect can be
more remarkably obtained. Here, the above average particle diameter
is obtained by measuring the outer diameter of one particle at
several places and calculating the average value thereof.
[0046] In addition, the amount of the filler (D) in the curable
resin film 1 is more preferably 7% to 60% by mass of the entire
mass of the thermosetting resin composition forming the curable
resin film 1 after limiting the average particle diameter to the
above range.
[0047] Detailed components of the filler (D) will be described
later.
[0048] The thickness of the first protective film 1a after curing
is not particularly limited, and the entire average thickness may
be set within the range of the dimensional relationship represented
by the above Expression (1). On the other hand, when considering of
the protection function of the surface 5a and the bump 51 of the
semiconductor wafer 5, the average thickness h3 of the first
protective film 1a at the center position A between the plurality
of bumps 51 is preferably set to be about 10 to 400 .mu.m, and the
average thickness h2 of the first protective film 1a at the
position B being in contact with the bump 51 is preferably set to
be about 1 to 350 .mu.m.
[0049] Here, FIG. 6 schematically shows a cross section in a state
where the protective film 101a is formed on the surface 105a which
is the bump-formed surface of the semiconductor wafer 105 through
the method by using the conventional curable resin film. As shown
in FIG. 6, in a case of forming the protective film 101a using the
conventional curable resin film in which a dimensional relationship
between the weight-average molecular weight of the curable
component contained in the curable resin film, the protective film
101a cured under the predetermined conditions, and the bump 151 is
not appropriately set, protective film 101a has a large distortion
in a concave shape at a position between the bumps 151 due to the
shrinkage or the like occurring at the time of curing the curable
resin film.
[0050] As shown in FIG. 6, in a case where the large distortion in
a concave shape occurs on the protective film 101a on the
semiconductor wafer 105, a lens action occurs in the concave
portion, and thereby it is difficult to accurately detect the shape
on the surface 105a which is the circuit surface of the
semiconductor wafer 105 in some cases. For this reason, for
example, when performing inspection of the circuit surface in a
manufacturing step of the semiconductor wafer, there is a
possibility that deviation occurs in alignment between an
inspection apparatus and the semiconductor wafer, so that it is
difficult to perform accurate inspection. In addition, in the case
where the large distortion in the concave shape occurs on the
protective film 101a, at the time of dicing the semiconductor wafer
105 in chip units, there is a possibility that deviation occurs in
alignment between a dicing saw provided in the dicing apparatus and
the semiconductor wafer, so that it is difficult to perform
accurate dicing. Therefore, in a case where the protective film
101a is formed on the semiconductor wafer 105 by using a method of
using the conventional curable resin film, yield of the
semiconductor chip to be obtained is lowered or the reliability as
a semiconductor package is deteriorated, which is a serious
problem.
[0051] In contrast, according to the curable resin film 1 of the
present invention, as described above, the weight-average molecular
weight of the curable component contained in the curable resin film
used for forming the first protective film 1, and a dimensional
relationship between the first protective film 1a cured under
predetermined conditions and the plurality of bumps 51 on the
semiconductor wafer 5 having the plurality of bumps 51 of a
predetermined dimensional shape and arrangement condition are
appropriately defined. With this, it is possible to suppress the
occurrence of the large distortion in the concave shape the first
protective film 1a disposed between the bumps 51. Accordingly, the
alignment accuracy in the step of performing the inspection step
and the dicing step of the manufacturing step improves, and thus
the inspection accuracy and the dicing accuracy improve, thereby
manufacturing a semiconductor package excellent in the
reliability.
[0052] <Curable Resin Film Containing Energy Ray-Curable
Component>
[0053] The curable component contained in the curable resin film 10
of the present invention is configured to contain an energy
ray-curable component having a weight-average molecular weight of
200 to 4,000, with respect to the curable resin film 1 containing
the thermosetting component as described above.
[0054] Similar to the curable resin film 1 containing the
above-described thermosetting component, the curable resin film 10
of the present invention is used to form the first protective film
by being attached to the semiconductor wafer 5 having the plurality
of bumps 51 on the surface 5a as shown in FIGS. 1A and 1B.
[0055] The curable resin film 10 of the present invention forms the
first protective film 1a that protects the plurality of bumps 51
and the surface 5a by attaching the curable resin film onto the
semiconductor wafer 5 having the plurality of bumps 51 with an
average peak height h1 of 50 to 400 .mu.m, an average diameter D of
60 to 500 .mu.m in a plan view, and an average pitch P of 100 to
800 .mu.m, and irradiating the attached curable resin film with
energy rays under conditions of illuminance of 50 to 500
mW/cm.sup.2, and light intensity of 100 to 2,000 mJ/cm.sup.2 and
curing the irradiated curable resin film, and when longitudinal
sections of the first protective film 1a and the semiconductor
wafer 5 are observed by a scanning electron microscope, a ratio
(h3/h1) of an average thickness h3 of the first protective film 1a
at a center position between the plurality of bumps 51 to an
average peak height h1 of the plurality of bumps 51, and a ratio
(h2/h1) of an average thickness h2 of the first protective film 1a
at a position being in contact with the plurality of bumps 51 to
the average peak height h1 satisfy a relationship represented by
the following Expression (1).
{(h2/h1)-(h3/h1)}.ltoreq.0.1 (1)
[0056] That is, the curable resin film 10 of the present invention
is common to the above-described curable resin film 1 from the
viewpoint of a dimensional shape and an arrangement condition of
the plurality of bumps 51 on the semiconductor wafer 5, and each
condition of a dimensional relationship between the cured first
protective film 1a and the plurality of bumps 51. On the other
hand, the curable resin film 10 of the present invention is
different from the above-described curable resin film 1 from the
viewpoint that the curable resin film 10 contains an energy
ray-curable component as a curable component, and is cured by being
irradiated with energy rays under curing conditions with the
illuminance of 50 to 500 mW/cm.sup.2, and the light intensity of
100 to 2000 mJ/cm.sup.2.
[0057] In the present invention, the curable component contained in
the curable resin film 10 is configured to contain an energy
ray-curable component having a weight-average molecular weight of
200 to 4,000. When the curable resin film 10 contains the energy
ray-curable component within the above range, it is possible to
minimize the occurrence of deformation due to thermal shrinkage or
the like in the first protective film 1a after curing by energy ray
irradiation. With this, it is possible to suppress the occurrence
of the large distortion in the concave shape on the cured first
protective film 1a.
[0058] Note that, in the present invention, "energy rays" refer to
rays having energy quanta in electromagnetic waves or charged
particle radiation, and examples thereof include ultraviolet rays,
electron beams, and the like.
[0059] Ultraviolet rays can be radiated using, for example, a
high-pressure mercury lamp, a fusion lamp, a xenon lamp, LED, or
the like as an ultraviolet ray source. As the electron beams,
electron beams generated using an electron beam accelerator or the
like can be radiated.
[0060] In the present invention, "being energy ray-curable" refers
to a property of being cured by being irradiated with energy rays,
and "being non-energy ray-curable" refers to a property of not
being cured by being irradiated with energy rays.
[0061] Further, in the present invention, from the viewpoint of
more remarkably obtaining the above action and effect, the
weight-average molecular weight of the energy ray-curable component
contained in the curable resin film 10 is more preferably 200 to
4,000, and particularly preferably 300 to 4,000.
[0062] Detailed components of the energy ray-curable component will
be described later.
[0063] <<First Protective Film Forming Sheet (Curable Resin
Film)>>
[0064] Hereinafter, the configurations of curable resin films 1 and
10 having the above-described configuration, and the first
protective film forming sheet 1A in which any one of the above
curable resin films is provided on the first supporting sheet are
further described in detail.
[0065] <First Supporting Sheet>
[0066] The first supporting sheet 11 provided with first protective
film forming sheet 1A may be a sheet made of a single layer
(monolayer) or a sheet made of a plurality of layers of two or more
layers. In a case in which the first supporting sheet 11 is made of
a plurality of layers, the constituent materials and the
thicknesses of the plurality of layers may be identical to or
different from one another, and the combination of the plurality of
layers is not particularly limited as long as the effects of the
present invention are not impaired.
[0067] Meanwhile, in the present embodiment, the sentence
"component materials of a plurality of layers and the thickness may
be identical to or different from one another" means that "all of
the layers may be identical to one another, all of the layers may
be different from one another, or only some of the layers may be
identical to one another", which will be true not only for the
first supporting sheet but also for other elements. Furthermore,
the sentence "a plurality of layers is different from one another"
means that "at least one of the constituent materials and the
thicknesses of the respective layers are different from one
another".
[0068] Examples of a preferred the first supporting sheet 11
include a structure formed by stacking a first pressure-sensitive
adhesive layer on a first base material, a structure formed by
stacking a first interlayer on the first base material and stacking
the first pressure-sensitive adhesive layer on the first
interlayer, and a structure formed of the first base material.
[0069] An example of the first protective film forming sheet
according to the present invention will be described with reference
to FIGS. 3 to 5 for each kind of such first supporting sheet.
[0070] FIG. 3 is a sectional view schematically showing an example
of the first protective film forming sheet of the present
invention. In the first protective film forming sheet 1A as shown
in FIG. 3, the first supporting sheet 11 is formed by stacking the
first pressure-sensitive adhesive layer 13 on the first base
material 12. That is, the first protective film forming sheet 1A is
configured to include the first pressure-sensitive adhesive layer
13 on the first base material 12, and the curable resin film 1
including the thermosetting component on the first
pressure-sensitive adhesive layer 13. The first supporting sheet 11
is a stacked body of the first base material 12 and the first
pressure-sensitive adhesive layer 13, in which the curable resin
film 1 is provided on one surface 11a of the first supporting sheet
11, that is, on one surface 13a of the first pressure-sensitive
adhesive layer 13.
[0071] In the first protective film forming sheet 1A, as described
above, the curable resin film 1 is used to be attached to the
bump-formed surface of the semiconductor wafer, and is obtained by
appropriately regulating a dimensional relationship between of the
first protective film 1a cured under predetermined conditions and
the plurality of bumps 51, on a semiconductor wafer 5 having the
plurality of bumps 51 of on the semiconductor wafer 5 having the
plurality of bumps 51 having the weight-average molecular weight, a
predetermined dimensional shape and arrangement condition of the
curable component to be e contained.
[0072] FIG. 4 is a sectional view schematically showing another
example of the first protective film forming sheet of the present
invention. Meanwhile, in FIG. 4, the same constituent element as in
FIG. 3 is given the same reference sign as in FIG. 3 and will not
be described in detail, and the same is true for FIG. 5.
[0073] The first protective film forming sheet 1B as shown in FIG.
4 uses the first supporting sheet obtained by stacking the first
interlayer on the first base material, and stacking the first
pressure-sensitive adhesive layer on the first interlayer. That is,
the first protective film forming sheet 1B is configured to include
the first interlayer 14 on the first base material 12, the first
pressure-sensitive adhesive layer 13 on the first interlayer 14,
and the curable resin film 1 on the first pressure-sensitive
adhesive layer 13. The first supporting sheet 11A is a stacked body
obtained by stacking the first base material 12, the first
interlayer 14, and the first pressure-sensitive adhesive layer 13
in this order, in which the curable resin film 1 is provided on one
surface 11a of the first supporting sheet 11A, that is, on one
surface 13a of the first pressure-sensitive adhesive layer 13.
[0074] In other words, the first protective film forming sheet 1B
is further provided with the first interlayer 14 between the first
base material 12 and the first pressure-sensitive adhesive layer 13
in the first protective film forming sheet 1A as shown in FIG.
3.
[0075] In the first protective film forming sheet 1B, as described
above, the curable resin film 1 is used to be attached to the
bump-formed surface of the semiconductor wafer, and is obtained by
appropriately regulating a dimensional relationship between of the
first protective film 1a cured under predetermined conditions and
the plurality of bumps 51, on a semiconductor wafer 5 having the
plurality of bumps 51 of on the semiconductor wafer 5 having the
plurality of bumps 51 having the weight-average molecular weight, a
predetermined dimensional shape and arrangement condition of the
curable component to be e contained.
[0076] FIG. 5 is a sectional view schematically showing still
another example of the first protective film forming sheet of the
present invention.
[0077] In the first protective film forming sheet 1C as shown in
FIG. 5, the first supporting sheet is formed of only the first base
material. That is, the first protective film forming sheet 1C is
configured to include curable resin film 1 on the first base
material 12.
[0078] The first supporting sheet 11B is formed of only the first
base material 12, the curable resin film 1 is provided in direct
contact with on one surface 11a of the first supporting sheet 11B,
that is, one surface 12a of the first base material 12. In other
words, the first protective film forming sheet 1C is formed by
removing the first pressure-sensitive adhesive layer 13 in the
first protective film forming sheet 1A as shown in FIG. 3.
[0079] In the first protective film forming sheet 1C, as described
above, the curable resin film 1 is used to be attached to the
bump-formed surface of the semiconductor wafer, and is obtained by
appropriately regulating a dimensional relationship between of the
first protective film 1a cured under predetermined conditions and
the plurality of bumps 51, on a semiconductor wafer 5 having the
plurality of bumps 51 of on the semiconductor wafer 5 having the
plurality of bumps 51 having the weight-average molecular weight, a
predetermined dimensional shape and arrangement condition of the
curable component to be e contained.
[0080] Hereinafter, each configuration of the first supporting
sheet will be described in detail.
[0081] [First Base Material]
[0082] The first base material provided with the first supporting
sheet is a sheet-form or film-form base material, and examples of a
constituent material thereof include the following various
resins.
[0083] Examples of the resins forming the first base material
include polyethylene such as low-density polyethylene (LDPE),
linear low-density polyethylene (LLDPE), and high-density
polyethylene (HDPE); polyolefin other than polyethylene such as
polypropylene, polybutene, polybutadiene, polymethylpentene, and
norbornene resins; ethylene-based copolymers (copolymers obtained
using ethylene as monomers) such as ethylene-vinyl acetate
copolymers, ethylene-(meth)acrylate copolymers,
ethylene-(meth)acrylic acid ester copolymers, and
ethylene-norbornene copolymers; vinyl chloride-based resins (resins
obtained using vinyl chloride as monomers) such as polyvinyl
chloride and vinyl chloride copolymers; polystyrene;
polycycloolefin; polyesters such as polyethylene terephthalate,
polyethylene naphthalate, polybutylene terephthalate, polyethylene
isophthalate, polyethylene-2,6-naphthalene dicarboxylate, and
wholly aromatic polyesters in which all constituent units have an
aromatic cyclic group; copolymers of two or more polyester
described above; poly(meth)acrylic acid esters; polyurethane;
polyurethane acrylate; polyimide; polyamide; polycarbonate;
fluororesin; polyacetal; modified polyphenylene oxides;
polyphenylene sulfides; polysulfone; polyether ketones; and the
like.
[0084] In addition, examples of the resins constituting the first
base material also include polymer alloys such as mixtures of the
polyester and other resin are also exemplary examples. The polymer
alloys of the polyester and other resin are preferably polymer
alloys in which the amount of the resin other than the polyester is
relatively small.
[0085] In addition, examples of the resins constituting the first
base material also include crosslinked resins in which one or more
resins described as exemplary examples above are crosslinked with
each other; modified resins such as ionomers for which one or more
resins described as exemplary examples above are used; and the
like.
[0086] Meanwhile, in the present embodiment, "(meth)acrylic acid"
refers to both "acrylic acid" and "methacrylic acid". What has been
described above is also true for terminologies similar to
(meth)acrylic acid, for example, "(meth)acrylate" refers to both
"acrylate" and "methacrylate", and "a (meth)acryloyl group" refers
to both "an acryloyl group" and "a methacryloyl group".
[0087] The forming the first base material may be constituted of
only one type or two or more types of the resins. In a case in
which the first base material has two or more types of resins, the
combination and ratio thereof can be arbitrarily selected.
[0088] The first base material may be a single layer (monolayer) or
a plurality of two or more layers. In a case in which the first
base material is a plurality of layers, the respective layers in
the plurality of layers may be identical to or different from one
another, and the combination of the plurality of layers is not
particularly limited.
[0089] The thickness of the first base material is preferably 5 to
1,000 .mu.m, more preferably 10 to 500 .mu.m, still more preferably
15 to 300 .mu.m, and particularly preferably 20 to 150 .mu.m.
[0090] Here, "the thickness of the first base material" refers to
the thickness of the entire first base material, and, for example,
the thickness of the first base material made up of a plurality of
layers refers to the total thickness of all of the layers
constituting the first base material.
[0091] The first base material is preferably a first base material
having a high accuracy in thickness, that is, a first base material
in which the variation of the thickness is suppressed throughout
the entire portion. Among the above-described constituent
materials, examples of materials having a high accuracy in
thickness that can be used to constitute the above-described first
base material include polyethylene, polyolefin other than
polyethylene, polyethylene terephthalate, ethylene-vinyl acetate
copolymers, and the like.
[0092] The first base material may also contain, in addition to the
main constituent material such as the resin, a variety of
well-known additives such as a filler, a colorant, an antistatic
agent, an antioxidant, an organic lubricant, a catalyst, and a
softening agent (plasticizer).
[0093] The first base material may be transparent or opaque and may
be colored depending on the purpose. In addition, other layers may
be deposited on the first base material.
[0094] In addition, in a case in which the first pressure-sensitive
adhesive layer described below or the curable resin layer is energy
ray-curable, the first base material preferably transmits energy
rays.
[0095] The first base material can be manufactured using a
well-known method. For example, the first base material containing
the resin can be manufactured by forming a resin composition
containing the resin.
[0096] [First Pressure-Sensitive Adhesive Layer]
[0097] The first pressure-sensitive adhesive layer has a sheet form
or a film form and contains a pressure-sensitive adhesive.
[0098] Examples of the pressure-sensitive adhesive include
pressure-sensitive adhesive resins such as acrylic resins
(pressure-sensitive adhesives made of a resin having a
(meth)acryloyl group), urethane-based resins (pressure-sensitive
adhesives made of a resin having a urethane bond), rubber-based
resins (pressure-sensitive adhesives made of a resin having a
rubber structure), silicone-based resins (pressure-sensitive
adhesives made of a resin having a siloxane bond), epoxy-based
resins (pressure-sensitive adhesives made of a resin having an
epoxy group), polyvinyl ethers, and polycarbonate, and acrylic
resins are preferred.
[0099] Meanwhile, in the present invention, "pressure-sensitive
adhesive resins" refer to both resins having a pressure-sensitive
adhesiveness and resins having an adhesiveness, and examples
thereof include not only resins having an adhesiveness for
themselves but also resins exhibiting a pressure-sensitive
adhesiveness when jointly used with other components such as
additives, resins exhibiting an adhesiveness due to the presence of
a trigger such as heat or water, and the like.
[0100] The first pressure-sensitive adhesive layer may be a single
layer (monolayer) or a plurality of two or more layers. In a case
in which the first pressure-sensitive adhesive layer is a plurality
of layers, the respective layers in the plurality of layers may be
identical to or different from one another, and the combination of
the plurality of layers is not particularly limited.
[0101] The thickness of the first pressure-sensitive adhesive layer
is preferably 1 to 1,000 .mu.m, more preferably 5 to 500 .mu.m, and
particularly preferably 10 to 100 .mu.m.
[0102] Here, "the thickness of the first pressure-sensitive
adhesive layer" refers to the thickness of the entire first
pressure-sensitive adhesive layer, and, for example, the thickness
of the first pressure-sensitive adhesive layer made up of a
plurality of layers refers to the total thickness of all of the
layers constituting the first pressure-sensitive adhesive
layer.
[0103] The first pressure-sensitive adhesive layer may be a first
pressure-sensitive adhesive layer formed using an energy
ray-curable pressure-sensitive adhesive or a first
pressure-sensitive adhesive layer formed using a non-energy
ray-curable pressure-sensitive adhesive. For the first
pressure-sensitive adhesive layer formed using an energy
ray-curable pressure-sensitive adhesive, it is possible to easily
adjust the properties before curing and after curing.
[0104] {{First Pressure-Sensitive Adhesive Composition}}
[0105] The first pressure-sensitive adhesive layer can be formed
using a first pressure-sensitive adhesive composition containing a
pressure-sensitive adhesive. For example, the first
pressure-sensitive adhesive layer can be formed at an intended
portion by applying the first pressure-sensitive adhesive
composition to a target surface on which the first
pressure-sensitive adhesive layer is to be formed and drying the
first pressure-sensitive adhesive composition as necessary. A more
specific method for forming the first pressure-sensitive adhesive
layer will be described below in detail together with methods for
forming other layers. The ratio between the amounts of components,
which do not gasify at normal temperature, in the first
pressure-sensitive adhesive composition is, generally, identical to
the ratio between the amounts of the above-described components in
the first pressure-sensitive adhesive layer. Meanwhile, in the
present embodiment, "normal temperature" refers to a temperature
that is not particularly cooled or heated, that is, a temperature
in an ordinary state, and examples thereof include a temperature of
15.degree. C. to 25.degree. C. and the like.
[0106] The first pressure-sensitive adhesive composition may be
applied using a well-known method, and examples thereof include
methods in which a variety of coaters such as an air knife coater,
a blade coater, a bar coater, a gravure coater, a roll coater, a
roll knife coater, a curtain coater, a die coater, a knife coater,
a screen coater, a Mayer bar coater, and a kiss coater are
used.
[0107] The drying conditions of the first pressure-sensitive
adhesive composition are not particularly limited; however, in a
case in which the first pressure-sensitive adhesive composition
contains a solvent described below, the first pressure-sensitive
adhesive composition is preferably heated and dried, and, in this
case, the first pressure-sensitive adhesive composition is
preferably dried under conditions of, for example, 70.degree. C. to
130.degree. C. and 10 seconds to 5 minutes.
[0108] In a case in which the first pressure-sensitive adhesive
layer is energy ray-curable, examples of the first
pressure-sensitive adhesive composition containing an energy
ray-curable pressure-sensitive adhesive, that is, an energy
ray-curable first pressure-sensitive adhesive composition include a
first pressure-sensitive adhesive composition (I-1) containing a
non-energy ray-curable pressure-sensitive adhesive resin (I-1a)
(hereinafter, in some cases, abbreviated as "the pressure-sensitive
adhesive resin (I-1a)") and an energy ray-curable compound; a first
pressure-sensitive adhesive composition (I-2) containing an energy
ray-curable pressure-sensitive adhesive resin (I-2a) in which an
unsaturated group is introduced into a side chain of the non-energy
ray-curable pressure-sensitive adhesive resin (I-1a) (hereinafter,
in some cases, abbreviated as "the pressure-sensitive adhesive
resin (I-2a)"); a first pressure-sensitive adhesive composition
(I-3) containing the pressure-sensitive adhesive resin (I-2a) and
an energy ray-curable low-molecular-weight compound; and the
like.
[0109] {First Pressure-Sensitive Adhesive Composition (I-1)}
[0110] As described above, the first pressure-sensitive adhesive
composition (I-1) contains the non-energy ray-curable
pressure-sensitive adhesive resin (I-1a) and an energy ray-curable
compound.
[0111] (Pressure-Sensitive Adhesive Resin (I-1a))
[0112] The pressure-sensitive adhesive resin (I-1a) is preferably
an acrylic resin.
[0113] Examples of the acrylic resin include acrylic polymers
having at least a constituent unit derived from an alkyl
(meth)acrylate.
[0114] The acrylic resin may have only one type or two or more
types of constituent units, and in a case of two or more types, the
combination and ratio thereof can be arbitrarily selected.
[0115] Examples of the alkyl (meth)acrylate include alkyl
(meth)acrylates in which the number of carbon atoms in an alkyl
group constituting the alkyl ester is 1 to 20, and the alkyl group
is preferably a linear alkyl group or a branched alkyl group.
[0116] More specific examples of the alkyl (meth)acrylate include
methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl
(meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate,
isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl
(meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl
(meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl
(meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate,
isononyl (meth)acrylate, decyl (meth)acrylate, undecyl
(meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate),
tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl
(meth)acrylate), pentadecyl (meth)acrylate, hexadecyl
(meth)acrylate (palmityl (meth)acrylate), heptadecyl
(meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate),
nonadecyl (meth)acrylate, (meth)acrylate, and the like.
[0117] The acrylic polymer preferably has a constituent unit
derived from an alkyl (meth)acrylate in which the number of carbon
atoms in the alkyl group is four or more from the viewpoint that
the pressure-sensitive adhesive force of the first
pressure-sensitive layer improves. In addition, the
pressure-sensitive adhesive force of the first pressure-sensitive
adhesive layer further improves, the number of carbon atoms in the
alkyl group is preferably 4 to 12 and more preferably 4 to 8 from
the viewpoint that the pressure-sensitive adhesive force of the
first pressure-sensitive adhesive layer further improves. In
addition, the alkyl (meth)acrylate in which the number of carbon
atoms in the alkyl group is four or more is preferably alkyl
acrylate.
[0118] The acrylic polymer preferably further has, in addition to
the constituent unit derived from the alkyl (meth)acrylate, a
constituent unit derived from a functional group-containing
monomer.
[0119] Examples of the functional group-containing monomer include
monomers in which the functional group reacts with a crosslinking
agent described below and thus serves as a starting point of
crosslinking or the functional group reacts with an unsaturated
group in an unsaturated group-containing compound and thus enables
the introduction of the unsaturated group into a side chain of the
acrylic polymer.
[0120] Examples of the functional group in the functional
group-containing monomer include a hydroxyl group, a carboxy group,
an amino group, an epoxy group, and the like.
[0121] That is, examples of the functional group-containing monomer
include hydroxyl group-containing monomers, carboxy
group-containing monomers, amino group-containing monomers, epoxy
group-containing monomers, and the like.
[0122] Examples of the hydroxyl group-containing monomers include
hydroxyalkyl (meth)acrylates such as hydroxymethyl (meth)acrylate,
2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate,
3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate,
3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate;
non-(meth)acrylic unsaturated alcohols such as vinyl alcohol and
allyl alcohol (unsaturated alcohols not having a (meth)acryloyl
skeleton); and the like.
[0123] Examples of the carboxy group-containing monomers include
ethylenic unsaturated monocarboxylic acids such as (meth)acrylic
acid and crotonic acid (monocarboxylic acids having an ethylenic
unsaturated bond); ethylenic unsaturated dicarboxylic acids such as
fumaric acid, itaconic acid, maleic acid, and citraconic acid
(dicarboxylic acids having an ethylenic unsaturated bond);
anhydrides of the ethylenic unsaturated dicarboxylic acid;
carboxyalkyl (meth)acrylates such as 2-carboxyethyl methacrylate;
and the like.
[0124] The functional group-containing monomer is preferably the
hydroxyl group-containing monomer or the carboxy group-containing
monomer and more preferably the hydroxyl group-containing
monomer.
[0125] The acrylic polymer may be constituted of only one type or
two or more types of the functional group-containing monomers. In a
case in which the acrylic polymer is constituted of two or more
types of the functional group-containing monomers, the combination
and ratio thereof can be arbitrarily selected.
[0126] In the acrylic polymer, the amount of the constituent unit
derived from the functional group-containing monomer is preferably
1% to 35% by mass, more preferably 3% to 32% by mass, and
particularly preferably 5% to 30% by mass of the mass of the
constituent units.
[0127] The acrylic polymer may further have, in addition to the
constituent unit derived from the alkyl (meth)acrylate and the
constituent unit derived from the functional group-containing
monomer, a constituent unit derived from a different monomer.
[0128] The different monomer is not particularly limited as long as
the monomer can be copolymerized with the alkyl (meth)acrylate or
the like.
[0129] Examples of the different monomer include styrene,
.alpha.-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate,
acrylonitrile, acrylamide, and the like.
[0130] The different monomer constituting the acrylic polymer may
be constituted of only one type or two or more types of the
functional group-containing monomers. In a case in which the
different monomer constituting the acrylic polymer is constituted
of two or more types of the functional group-containing monomers,
the combination and ratio thereof can be arbitrarily selected.
[0131] The acrylic polymer can be used as the non-energy
ray-curable pressure-sensitive adhesive resin (I-1a).
[0132] Meanwhile, a substance obtained by causing an unsaturated
group-containing compound having an energy ray-polymerizable
unsaturated group (energy ray-polymerizable group) to react with
the functional group in the acrylic polymer can be used as the
energy ray-curable pressure-sensitive adhesive resin (I-2a).
[0133] Meanwhile, in the present invention, "being energy
ray-polymerizable" refers to a property of being polymerized by
being irradiated with energy rays.
[0134] The first pressure-sensitive adhesive composition (I-1) may
contain only one type or two or more types of the
pressure-sensitive adhesive resin (I-1a). In a case in which the
first pressure-sensitive adhesive composition (I-1) contains two or
more types of the pressure-sensitive adhesive resins (I-1a), the
combination and ratio thereof can be arbitrarily selected.
[0135] In the first pressure-sensitive adhesive composition (I-1),
the amount of the pressure-sensitive adhesive resin (I-1a) is
preferably 5% to 99% by mass, more preferably 10% to 95% by mass,
and particularly preferably 15% to 90% by mass of the total mass of
the first pressure-sensitive adhesive composition (I-1).
[0136] (Energy Ray-Curable Compounds)
[0137] Examples of the energy ray-curable compound contained in the
first pressure-sensitive adhesive composition (I-1) include
monomers or oligomers which have an energy ray-polymerizable
unsaturated group and can be cured by being irradiated with energy
rays.
[0138] Among the energy ray-curable compounds, examples of monomers
include polyhydric (meth)acrylates such as trimethylol propane
tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol
tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate,
1,4-butylene glycol di(meth)acrylate, and 1,6-hexanediol
(meth)acrylate; urethane (meth)acrylate; polyether (meth)acrylate;
polyether (meth)acrylate; epoxy (meth)acrylate; and the like.
[0139] Among the energy ray-curable compounds, examples of
oligomers include oligomers obtained by polymerizing the monomers
described as exemplary examples above.
[0140] The energy ray-curable compound is preferably urethane
(meth)acrylate or a urethane (meth)acrylate oligomer since the
molecular weight is relatively great and the storage elastic
modulus of the first pressure-sensitive adhesive layer is not
easily decreased.
[0141] The first pressure-sensitive adhesive composition (I-1) may
contain only one type or two or more types of the energy
ray-curable compounds. In a case in which the first
pressure-sensitive adhesive composition (I-1) contains two or more
types of the energy ray-curable compounds, the combination and
ratio thereof can be arbitrarily selected.
[0142] In the first pressure-sensitive adhesive composition (I-1),
the amount of the energy ray-curable compound is preferably 1% to
95% by mass, more preferably 5% to 90% by mass, and particularly
preferably 10% to 85% by mass of the entire mass of the first
pressure-sensitive adhesive composition (I-1).
[0143] (Crosslinking Agent)
[0144] In a case in which the acrylic polymer further having, in
addition to the constituent unit derived from the alkyl
(meth)acrylate, the constituent unit derived from the functional
group-containing monomer as the pressure-sensitive adhesive resin
(I-1a), the first pressure-sensitive adhesive composition (I-1)
preferably further contains a crosslinking agent.
[0145] The crosslinking agent is, for example, a substance that
reacts with the functional group and thus crosslinks the
pressure-sensitive adhesive resins (I-1a).
[0146] Examples of the crosslinking agent include isocyanate-based
crosslinking agents (crosslinking agents having an isocyanate
group) such as tolylene diisocyanate, hexamethylene diisocyanate,
xylylene diisocyanate, and adduct bodies of the above-described
diisocyanate; epoxy-based crosslinking agents (crosslinking agents
having a glycidyl group) such as ethylene glycol glycidyl ether;
aziridine-based crosslinking agents (crosslinking agents having an
aziridinyl group) such as
hexa[1-(2-methyl)-aziridinyl]triphosphatriazine; metal
chelate-based crosslinking agents (crosslinking agents having a
metal chelate structure) such as aluminum chelates;
isocyanurate-based crosslinking agents (crosslinking agents having
an isocyanuric acid skeleton); and the like.
[0147] The crosslinking agent is preferably the isocyanate-based
crosslinking agent since the isocyanate-based crosslinking agent
improves the cohesive force of the pressure-sensitive adhesive so
as to improve the pressure-sensitive adhesive force of the first
pressure-sensitive adhesive layer, is easily procurable, and the
like.
[0148] The first pressure-sensitive adhesive composition (I-1) may
contain only one type or two or more types of the crosslinking
agents. In a case in which the first pressure-sensitive adhesive
composition (I-1) contains two or more types of the crosslinking
agents, the combination and ratio thereof can be arbitrarily
selected.
[0149] In the first pressure-sensitive adhesive composition (I-1),
the amount of the crosslinking agent is preferably 0.01 to 50 parts
by mass, more preferably 0.1 to 20 parts by mass, and particularly
preferably 1 to 10 parts by mass of the amount (100 parts by mass)
of the pressure-sensitive adhesive resin (I-1a).
[0150] (Photopolymerization Initiator)
[0151] The first pressure-sensitive adhesive composition (I-1) may
also further contain a photopolymerization initiator. The first
pressure-sensitive adhesive composition (I-1) containing the
photopolymerization initiator sufficiently proceeds with a curing
reaction even in a case of being irradiated with energy rays having
a relatively low energy such as ultraviolet rays.
[0152] Examples of the photopolymerization initiator include
benzoin compounds such as benzoin, benzoin methyl ether, benzoin
ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether,
benzoin benzoate, methyl benzoin benzoate, and benzoin dimethyl
ketal; acetophenone compounds such as
2-hydroxy-2-methyl-1-phenyl-propane-1-one, and
2,2-dimethoxy-1,2-diphenylethane-1-one; acylphosphine oxide
compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide;
sulfide compounds such as benzylphenyl sulfide and
tetramethylthiuram monosulfide; .alpha.-ketol compounds such as
1-hydroxycyclohexyl phenyl ketone; azo compounds such as
azobisisobutyronitrile; titanocene compounds such as titanocene;
thioxanthone compounds such as thioxanthone; peroxide compounds;
diketone compounds such as diacetyle; dibenzyl, and the like.
[0153] In addition, as the photopolymerization initiator, for
example, a quinone compound such as 1-chloroanthraquinone; a
photosensitizer such as amine; or the like can also be used.
[0154] The first pressure-sensitive adhesive composition (I-1) may
contain only one type or two or more types of the
photopolymerization initiators. In a case in which the first
pressure-sensitive adhesive composition (I-1) contains two or more
types of the photopolymerization initiators, the combination and
ratio thereof can be arbitrarily selected.
[0155] In the first pressure-sensitive adhesive composition (I-1),
the amount of the photopolymerization initiator is preferably 0.01
to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and
particularly preferably 0.05 to 5 parts by mass of the amount (100
parts by mass) of the energy ray-curable compound.
[0156] (Other Additives)
[0157] The first pressure-sensitive adhesive composition (I-1) may
also contain other additives which do not correspond to any of the
above-described components as long as the effects of the present
invention are not impaired.
[0158] Examples of the other additives include a variety of
well-known additives such as an antistatic agent, an antioxidant, a
softening agent (plasticizer), a filler (filler), an antirust
agent, a colorant (a pigment or a dye), a sensitizer, a tackifier,
a reaction retardant, and a crosslinking accelerator
(catalyst).
[0159] Meanwhile, the reaction retardant is a substance that
suppresses the progress of an unintended crosslinking reaction in
the first pressure-sensitive adhesive composition (I-1) under
storage due to, for example, the action of the catalyst mixed into
the first pressure-sensitive adhesive composition (I-1). Examples
of the reaction retardant include reaction retardants that form a
chelate complex due to a chelate with respect to the catalyst, and
more specific examples thereof include substances having two or
more carbonyl groups (--C(.dbd.O)--) in one molecule.
[0160] The first pressure-sensitive adhesive composition (I-1) may
contain only one type or two or more types of other additives. In a
case in which the first pressure-sensitive adhesive composition
(I-1) contains two or more types of other additives, the
combination and ratio thereof can be arbitrarily selected.
[0161] In the first pressure-sensitive adhesive composition (I-1),
the amount of the other additives is not particularly limited and
may be appropriately selected depending on the type of the
additives.
[0162] (Solvent)
[0163] The first pressure-sensitive adhesive composition (I-1) may
also contain a solvent. When the first pressure-sensitive adhesive
composition (I-1) contains a solvent, the coating aptitude to a
coating target surface improves.
[0164] The solvent is preferably an organic solvent, and examples
of the organic solvent include ketones such as methyl ethyl ketone
and acetone; esters (carboxylic acid esters) such as ethyl acetate;
ethers such as tetrahydrofuran and dioxane; aliphatic hydrocarbons
such as cyclohexane and n-hexane; aromatic hydrocarbons such as
toluene and xylene; alcohols such as 1-propanol and 2-propanol; and
the like.
[0165] As the solvent, a solvent used during the manufacturing of
the pressure-sensitive adhesive resin (I-1a) may be used in the
first pressure-sensitive adhesive composition (I-1) without being
removed from the pressure-sensitive adhesive resin (I-1a).
Alternatively, as the solvent, a solvent of the same type as or a
different type from the solvent used during the manufacturing of
the pressure-sensitive adhesive resin (I-1a) may be separately
added during the manufacturing of the first pressure-sensitive
adhesive composition (I-1).
[0166] The first pressure-sensitive adhesive composition (I-1) may
contain only one type or two or more types of the solvents. In a
case in which the first pressure-sensitive adhesive composition
(I-1) contains two or more types of the solvents, the combination
and ratio thereof can be arbitrarily selected.
[0167] In the first pressure-sensitive adhesive composition (I-1),
the amount of the solvent is not particularly limited and may be
appropriately adjusted.
[0168] {First Pressure-Sensitive Adhesive Composition (I-2)}
[0169] As described above, the first pressure-sensitive adhesive
composition (I-2) contains an energy ray-curable pressure-sensitive
adhesive resin (I-2a) in which an unsaturated group is introduced
into a side chain of the non-energy ray-curable pressure-sensitive
adhesive resin (I-1a).
[0170] (Pressure-Sensitive Adhesive Resin (I-2a))
[0171] The pressure-sensitive adhesive resin (I-2a) can be obtained
by, for example, causing an unsaturated group-containing compound
having an energy ray-polymerizable unsaturated group to react with
the functional group in the pressure-sensitive adhesive resin
(I-1a).
[0172] The unsaturated group-containing compound is a compound
further having, in addition to the energy ray-polymerizable
unsaturated group, a group that can be bonded with the
pressure-sensitive adhesive resin (I-1a) by reacting with the
functional group in the pressure-sensitive adhesive resin
(I-1a).
[0173] Examples of the energy ray-polymerizable unsaturated group
include a (meth)acryloyl group, a vinyl group (ethenyl group), an
allyl group (2-propenyl group), and the like, and a (meth)acryloyl
group is preferred.
[0174] Examples of the group that can be bonded with the functional
group in the pressure-sensitive adhesive resin (I-1a) include
isocyanate groups and glycidyl groups that can be bonded with a
hydroxyl group or an amino group, hydroxyl groups and amino groups
that can be bonded with a carboxy group or an epoxy group, and the
like.
[0175] Examples of the unsaturated group-containing compound
include (meth)acryloyloxyethyl isocyanate, (meth)acryloyl
isocyanate, glycidyl (meth)acrylate, and the like.
[0176] The first pressure-sensitive adhesive composition (I-2) may
contain only one type or two or more types of the
pressure-sensitive adhesive resin (I-2a). In a case in which the
first pressure-sensitive adhesive composition (I-2) contains two or
more types of the pressure-sensitive adhesive resins (I-2a), the
combination and ratio thereof can be arbitrarily selected.
[0177] In the first pressure-sensitive adhesive composition (I-2),
the amount of the pressure-sensitive adhesive resin (I-2a) is
preferably 5% to 99% by mass, more preferably 10% to 95% by mass,
and particularly preferably 10% to 90% by mass of the total mass of
the first pressure-sensitive adhesive composition (I-2).
[0178] (Crosslinking Agent)
[0179] In a case in which, as the pressure-sensitive adhesive resin
(I-2a), for example, the acrylic polymer having the constituent
unit derived from the functional group-containing monomer, which is
the same as that in the pressure-sensitive adhesive resin (I-1a) is
used, the first pressure-sensitive adhesive composition (I-2) may
further contain a crosslinking agent.
[0180] Examples of the crosslinking agent in the first
pressure-sensitive adhesive composition (I-2) include the same
crosslinking agents as those in the first pressure-sensitive
adhesive composition (I-1).
[0181] The first pressure-sensitive adhesive composition (I-2) may
contain only one type or two or more types of the crosslinking
agents. In a case in which the first pressure-sensitive adhesive
composition (I-2) contains two or more types of the crosslinking
agents, the combination and ratio thereof can be arbitrarily
selected.
[0182] In the first pressure-sensitive adhesive composition (I-2),
the amount of the crosslinking agent is preferably 0.01 to 50 parts
by mass, more preferably 0.1 to 20 parts by mass, and particularly
preferably 1 to 10 parts by mass of the amount (100 parts by mass)
of the pressure-sensitive adhesive resin (I-2a).
[0183] (Photopolymerization Initiator)
[0184] The first pressure-sensitive adhesive composition (I-2) may
also further contain a photopolymerization initiator. The first
pressure-sensitive adhesive composition (I-2) containing the
photopolymerization initiator sufficiently proceeds with a curing
reaction even in a case of being irradiated with energy rays having
a relatively low energy such as ultraviolet rays.
[0185] Examples of the photopolymerization initiator in the first
pressure-sensitive adhesive composition (I-2) include the same
photopolymerization initiators as those in the first
pressure-sensitive adhesive composition (I-1).
[0186] The first pressure-sensitive adhesive composition (I-2) may
contain only one type or two or more types of the
photopolymerization initiators. In a case in which the first
pressure-sensitive adhesive composition (I-2) contains two or more
types of the photopolymerization initiators, the combination and
ratio thereof can be arbitrarily selected.
[0187] In the first pressure-sensitive adhesive composition (I-2),
the amount of the photopolymerization initiator is preferably 0.01
to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and
particularly preferably 0.05 to 5 parts by mass of the amount (100
parts by mass) of the pressure-sensitive adhesive resin (I-2a).
[0188] (Other Additives)
[0189] The first pressure-sensitive adhesive composition (I-2) may
also contain other additives which do not correspond to any of the
above-described components as long as the effects of the present
invention are not impaired.
[0190] Examples of the other additives in the first
pressure-sensitive adhesive composition (I-2) include the same
other additives as those in the first pressure-sensitive adhesive
composition (I-1).
[0191] The first pressure-sensitive adhesive composition (I-2) may
contain only one type or two or more types of other additives. In a
case in which the first pressure-sensitive adhesive composition
(I-2) contains two or more types of other additives, the
combination and ratio thereof can be arbitrarily selected.
[0192] In the first pressure-sensitive adhesive composition (I-2),
the amount of the other additives is not particularly limited and
may be appropriately selected depending on the type of the
additives.
[0193] (Solvent)
[0194] The first pressure-sensitive adhesive composition (I-2) may
also contain a solvent for the same purpose as in the case of the
first pressure-sensitive adhesive composition (I-1).
[0195] Examples of the solvent in the first pressure-sensitive
adhesive composition (I-2) include the same solvents as those in
the first pressure-sensitive adhesive composition (I-1).
[0196] The first pressure-sensitive adhesive composition (I-2) may
contain only one type or two or more types of the solvents. In a
case in which the first pressure-sensitive adhesive composition
(I-2) contains two or more types of the solvents, the combination
and ratio thereof can be arbitrarily selected.
[0197] In the first pressure-sensitive adhesive composition (I-2),
the amount of the solvent is not particularly limited and may be
appropriately adjusted.
[0198] {First Pressure-Sensitive Adhesive Composition (I-3)}
[0199] As described above, the first pressure-sensitive adhesive
composition (I-3) contains the pressure-sensitive adhesive resin
(I-2a) and an energy ray-curable low-molecular-weight compound.
[0200] In the first pressure-sensitive adhesive composition (I-3),
the amount of the pressure-sensitive adhesive resin (I-2a) is
preferably 5% to 99% by mass, more preferably 10% to 95% by mass,
and particularly preferably 15% to 90% by mass of the total mass of
the first pressure-sensitive adhesive composition (I-3).
[0201] (Energy Ray-Curable Low-Molecular-Weight Compound)
[0202] Examples of the energy ray-curable low-molecular-weight
compound contained in the first pressure-sensitive adhesive
composition (I-3) include monomers or oligomers which have an
energy ray-polymerizable unsaturated group and can be cured by
being irradiated with energy rays and include the same energy
ray-curable compounds as that in the first pressure-sensitive
adhesive composition (I-1).
[0203] The first pressure-sensitive adhesive composition (I-3) may
contain only one type or two or more types of the energy
ray-curable low-molecular-weight compounds. In a case in which the
first pressure-sensitive adhesive composition (I-3) contains two or
more types of the energy ray-curable low-molecular-weight
compounds, the combination and ratio thereof can be arbitrarily
selected.
[0204] In the first pressure-sensitive adhesive composition (I-3),
the amount of the energy ray-curable low-molecular-weight compound
is preferably 0.01 to 300 parts by mass, more preferably 0.03 to
200 parts by mass, and particularly preferably 0.05 to 100 parts by
mass of the amount (100 parts by mass) of the pressure-sensitive
adhesive resin (I-2a).
[0205] (Photopolymerization Initiator)
[0206] The first pressure-sensitive adhesive composition (I-3) may
also further contain a photopolymerization initiator. The first
pressure-sensitive adhesive composition (I-3) containing the
photopolymerization initiator sufficiently proceeds with a curing
reaction even when irradiated with energy rays having a relatively
low energy such as ultraviolet rays.
[0207] Examples of the photopolymerization initiator in the first
pressure-sensitive adhesive composition (I-3) include the same
photopolymerization initiators as those in the first
pressure-sensitive adhesive composition (I-1).
[0208] The first pressure-sensitive adhesive composition (I-3) may
contain only one type or two or more types of the
photopolymerization initiators. In a case in which the first
pressure-sensitive adhesive composition (I-3) contains two or more
types of the photopolymerization initiators, the combination and
ratio thereof can be arbitrarily selected.
[0209] In the first pressure-sensitive adhesive composition (I-3),
the amount of the photopolymerization initiator is preferably 0.01
to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and
particularly preferably 0.05 to 5 parts by mass of the total amount
(100 parts by mass) of the pressure-sensitive adhesive resin (I-2a)
and the energy ray-curable low-molecular-weight compound.
[0210] (Other Additives)
[0211] The first pressure-sensitive adhesive composition (I-3) may
also contain other additives which do not correspond to any of the
above-described components as long as the effects of the present
invention are not impaired.
[0212] Examples of the other additives include the same other
additives as those in the first pressure-sensitive adhesive
composition (I-1).
[0213] The first pressure-sensitive adhesive composition (I-3) may
contain only one type or two or more types of other additives. In a
case in which the first pressure-sensitive adhesive composition
(I-3) contains two or more types of other additives, the
combination and ratio thereof can be arbitrarily selected.
[0214] In the first pressure-sensitive adhesive composition (I-3),
the amount of the other additives is not particularly limited and
may be appropriately selected depending on the type of the
additives.
[0215] (Solvent)
[0216] The first pressure-sensitive adhesive composition (I-3) may
also contain a solvent for the same purpose as in the case of the
first pressure-sensitive adhesive composition (I-1).
[0217] Examples of the solvent in the first pressure-sensitive
adhesive composition (I-3) include the same solvents as those in
the first pressure-sensitive adhesive composition (I-1).
[0218] The first pressure-sensitive adhesive composition (I-3) may
contain only one type or two or more types of the solvents. In a
case in which the first pressure-sensitive adhesive composition
(I-3) contains two or more types of the solvents, the combination
and ratio thereof can be arbitrarily selected.
[0219] In the first pressure-sensitive adhesive composition (I-3),
the amount of the solvent is not particularly limited and may be
appropriately adjusted.
[0220] {First Pressure-Sensitive Adhesive Compositions Other Than
First Pressure-Sensitive Adhesive Compositions (I-1) to (I-3)}
[0221] Hitherto, the first pressure-sensitive adhesive composition
(I-1), the first pressure-sensitive adhesive composition (I-2), and
the first pressure-sensitive adhesive composition (I-3) have been
mainly described, but the substances described as the contained
components thereof can also be used in the same manner in general
first pressure-sensitive adhesive compositions other than the
above-described three types of first pressure-sensitive adhesive
compositions (in the present embodiment, referred to as the first
pressure-sensitive adhesive compositions other than the first
pressure-sensitive adhesive compositions (I-1) to (I-3)).
[0222] Examples of the first pressure-sensitive adhesive
compositions other than the first pressure-sensitive adhesive
compositions (I-1) to (I-3) include, in addition to, the first
energy ray-curable pressure-sensitive adhesive compositions, a
first non-energy ray-curable pressure-sensitive adhesive
composition.
[0223] Examples of the first non-energy ray-curable
pressure-sensitive adhesive compositions include non-energy
ray-curable pressure-sensitive adhesive compositions containing a
pressure-sensitive adhesive resin such as an acrylic resin (a resin
having a (meth)acryloyl group), an urethane-based resin (a resin
having a urethane bond), a rubber-based resin (a resin having a
rubber structure), a silicone-based resin (a resin having a
siloxane bond), an epoxy-based resin (a resin having an epoxy
group), a polyvinyl ether, or a polycarbonate, and non-energy
ray-curable pressure-sensitive adhesive compositions containing an
acrylic resin are preferred.
[0224] The first pressure-sensitive adhesive compositions other
than the first pressure-sensitive adhesive compositions (I-1) to
(I-3) preferably contain one or more types of crosslinking agents,
and the amount thereof can be set to be the same as that in the
case of the above-described first pressure-sensitive adhesive
composition (I-1) or the like.
[0225] <Method for Manufacturing First Pressure-Sensitive
Adhesive Composition>
[0226] The first pressure-sensitive adhesive compositions such as
the first pressure-sensitive adhesive compositions (I-1) to (I-3)
can be obtained by blending individual components for constituting
the first pressure-sensitive adhesive compositions such as the
pressure-sensitive adhesive, components other than the
pressure-sensitive adhesive as necessary, and the like.
[0227] The addition order during the blending of the respective
components is not particularly limited, and two or more types of
components may be added at the same time.
[0228] In a case in which the solvent is used, the solvent may be
used by mixing the solvent with all of the blending components
other than the solvent so as to dilute these blending components in
advance or may be used by mixing the solvent with the blending
components without diluting all of the blending components other
than the solvent in advance.
[0229] A method for mixing the respective components during
blending is not particularly limited and may be appropriately
selected from well-known methods such as a method in which the
components are mixed together by rotating a stirring stick, a
stirring blade, or the like; a method in which the components are
mixed together using a mixer, and a method in which the components
are mixed together by applying ultrasonic waves thereto.
[0230] The temperature and the time during the addition and mixing
of the respective components are not particularly limited as long
as the respective blending components do not deteriorate and may be
appropriately adjusted, but the temperature is preferably
15.degree. C. to 30.degree. C.
[0231] [First Interlayer]
[0232] The first interlayer has a sheet form or a film form, and a
constituent material thereof may be appropriately selected
depending on the purpose and is not particularly limited.
[0233] For example, in a case in which the purpose is to suppress
the deformation of the first protective film by reflecting the
shape of bumps present on a semiconductor surface in the first
protective film that covers the semiconductor surface, examples of
a preferred constituent material of the first interlayer include
urethane (meth)acrylate and the like from the viewpoint of further
improving the attachment property of the first interlayer.
[0234] The first interlayer may be a single layer (monolayer) or a
plurality of two or more layers. In a case in which the first
interlayer is a plurality of layers, the respective layers in the
plurality of layers may be identical to or different from one
another, and the combination of the plurality of layers is not
particularly limited.
[0235] The thickness of the first interlayer can be appropriately
adjusted depending on the height of bumps on the semiconductor
surface which is a protection target, but is preferably 50 to 600
.mu.m, more preferably 70 to 500 .mu.m, and particularly preferably
80 to 400 .mu.m since it is possible to relatively easily absorb
the influence of bumps having a relatively high height.
[0236] Here, "the thickness of the first interlayer" refers to the
thickness of the entire first interlayer, and, for example, the
thickness of the first interlayer made up of a plurality of layers
refers to the total thickness of all of the layers constituting the
first interlayer.
[0237] {{First Interlayer Forming Composition}}
[0238] The first interlayer can be formed using a first interlayer
forming composition containing the constituent material.
[0239] For example, the first interlayer can be formed at an
intended portion by applying the first interlayer forming
composition to a target surface on which the first interlayer is to
be formed and drying the first interlayer forming composition or
curing the first interlayer forming composition by being irradiated
with energy rays as necessary. A more specific method for forming
the first interlayer will be described below in detail together
with methods for forming other layers. The ratio between the
amounts of components, which do not gasify at normal temperature,
in the first interlayer forming composition is, generally,
identical to the ratio between the amounts of the above-described
components in the first interlayer. Here, "normal temperature" is
as described above.
[0240] The first interlayer forming composition may be applied
using a well-known method, and examples thereof include methods in
which a variety of coaters such as an air knife coater, a blade
coater, a bar coater, a gravure coater, a roll coater, a roll knife
coater, a curtain coater, a die coater, a knife coater, a screen
coater, a Mayer bar coater, and a kiss coater are used.
[0241] The drying conditions of the first interlayer forming
composition are not particularly limited; however, in a case in
which the first interlayer forming composition contains a solvent
described below, the first interlayer forming composition is
preferably heated and dried, and, in this case, the first
interlayer forming composition is preferably dried under conditions
of, for example, 70.degree. C. to 130.degree. C. and 10 seconds to
5 minutes.
[0242] In a case in which the first interlayer forming composition
is energy ray-curable, the first interlayer forming composition is
preferably further cured by being irradiated with energy rays after
drying.
[0243] Examples of the first interlayer forming composition include
a first interlayer forming composition containing urethane
(meth)acrylate (II-1) and the like.
[0244] {First Interlayer Forming Composition (II-1)}
[0245] As described above, the first interlayer forming composition
(II-1) contains urethane (meth)acrylate.
[0246] (Urethane (Meth)acrylate)
[0247] The urethane (meth)acrylate is a compound having at least a
(meth)acryloyl group and a urethane bond in one molecule and is
energy ray-polymerizable.
[0248] The urethane (meth)acrylate may be a monofunctional urethane
(meth)acrylate (urethane (meth)acrylate having only one
(meth)acryloyl group in one molecule) or may be a di- or
higher-functional urethane (meth)acrylate (urethane (meth)acrylate
having two or more (meth)acryloyl groups in one molecule), that is,
a multifunctional urethane (meth)acrylate, but urethane
(meth)acrylate having at least one (meth)acryloyl group is
preferably used.
[0249] Examples of the urethane (meth)acrylate contained in the
first interlayer forming composition include urethane
(meth)acrylate obtained by further causing a (meth)acrylic compound
having a hydroxyl group and a (meth)acryloyl group to react with a
terminal isocyanate urethane prepolymer obtained by reacting a
polyol compound and a polyhydric isocyanate compound. Here, "the
terminal isocyanate urethane prepolymer" refers to a prepolymer
having a urethane bond and having an isocyanate group at a terminal
portion of the molecule.
[0250] The first interlayer forming composition (II-1) may contain
only one type or two or more types of the urethane (meth)acrylate.
In a case in which the first interlayer forming composition (II-1)
contains two or more types of the urethane (meth)acrylate, the
combination and ratio thereof can be arbitrarily selected.
[0251] (A) Polyol Compound
[0252] The polyol compound is not particularly limited as long as
the compound has two or more hydroxyl groups in one molecule.
[0253] One type of the polyol compound may be used singly or two or
more types of the polyol compounds may be used in combination. In a
case in which two or more types of the polyol compounds are used in
combination, the combination and ratio thereof can be arbitrarily
selected.
[0254] Examples of the polyol compound include alkylenediol,
polyether-type polyols, polyester-type polyols, polycarbonate-type
polyols, and the like.
[0255] The polyol compound may be any one of a difunctional diol, a
trifunctional triol, and tetra- or higher-functional polyols, but a
diol is preferred since the diol can be easily procured and is
excellent in terms of versatility, reactivity, and the like.
[0256] Polyether-Type Polyol
[0257] The polyether-type polyol is not particularly limited, but
is preferably a polyether-type diol, and examples of the
polyether-type diol include compounds represented by General
Formula (1).
HO R--O .sub.nH (1)
[0258] (Here, in Formula (1), n represents an integer of 2 or more;
R represents a divalent hydrocarbon group, and a plurality of R's
may be identical to or different from one another)
[0259] In Formula (1), n represents the number of repeating units
of a group represented by General Formula "--R--O--" and is not
particularly limited as long as n is an integer of 2 or more. Among
these, n is preferably 10 to 250, more preferably 25 to 205, and
particularly preferably 40 to 185.
[0260] In Formula (1), R is not particularly limited as long as R
is a divalent hydrocarbon group, but is preferably an alkylene
group, more preferably an alkylene group having 1 to 6 carbon
atoms, still more preferably an ethylene group, a propylene group,
or a tetramethylene group, and particularly preferably a propylene
group or a tetramethylene group.
[0261] The compound represented by Formula (1) is preferably
polyethylene glycol, polypropylene glycol or polytetramethylene
glycol and more preferably polypropylene glycol or
polytetramethylene glycol.
[0262] When the polyether-type diol and the polyhydric isocyanate
compound are reacted with each other, urethane (meth)acrylate
having an ether bond portion represented by General Formula (1a) as
the terminal isocyanate urethane prepolymer can be obtained. In
addition, when the above-described terminal isocyanate urethane
prepolymer is used, the urethane (meth)acrylate has the ether bond
portion, that is, has a constituent unit derived from the
polyether-type diol.
R--O .sub.n (1a)
[0263] (Here, in Formula (1a), R and n are the same as described
above)
[0264] Polyester-Type Polyol
[0265] The polyester-type polyol is not particularly limited, and
examples thereof include polyols obtained by causing an
esterification reaction using a polybasic acid or a derivative
thereof, and the like. Meanwhile, in the present embodiment, unless
particularly otherwise described, "a derivative" refers to a
compound in which one or more groups are substituted with other
groups (substituents). Here, "a group" refers not only to an atomic
group formed by bonding a plurality of atoms but also to one
atom.
[0266] Examples of the polybasic acid or the derivative thereof
include polybasic acids that are ordinarily used as a manufacturing
raw material of polyesters and derivatives thereof.
[0267] Examples of the polybasic acids include saturated aliphatic
polybasic acids, unsaturated aliphatic polybasic acids, aromatic
polybasic acids, and the like, and dimers corresponding to any of
the above-described polybasic acids may also be used.
[0268] Examples of the saturated aliphatic polybasic acids include
saturated aliphatic dibasic acids such as oxalic acid, malonic
acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
suberic acid, azelaic acid, and sebacic acid, and the like.
[0269] Examples of the unsaturated aliphatic polybasic acids
include unsaturated aliphatic dibasic acids such as maleic acid and
fumaric acid.
[0270] Examples of the aromatic polybasic acids include aromatic
dibasic acids such as phthalic acid, isophthalic acid, terephthalic
acid, and 2,6-naphthalenedicarboxylic acid; aromatic tribasic acids
such as trimellitic acid; aromatic tetrabasic acids such as
pyromellitic acid; and the like.
[0271] Examples of the derivatives of the polybasic acids include
acid anhydrides of the saturated aliphatic polybasic acids, the
unsaturated aliphatic polybasic acids, and the aromatic polybasic
acids described above, hydrogenated dimer acids, and the like.
[0272] One type of the polybasic acid or a derivative thereof may
be used singly or two or more types of the polyol compounds may be
used in combination. In a case in which two or more types of the
polybasic acid or the derivative are used in combination, the
combination and ratio thereof can be arbitrarily selected.
[0273] The polybasic acid is preferably the aromatic polybasic acid
since the aromatic polybasic acid is suitable for the formation of
coated films having an appropriate hardness.
[0274] In the esterification reaction for obtaining the
polyester-type polyol, a well-known catalyst may also be used as
necessary.
[0275] Examples of the catalyst include tin compounds such as
dibutyltin oxide and stannous octanoate; alkoxy titanium such as
tetrapropyl titanate; and the like.
[0276] Polycarbonate-Type Polyol
[0277] The polycarbonate-type polyol is not particularly limited,
and examples thereof include polycarbonates obtained by reacting
the same glycol as the compound represented by Formula (1) and
alkylene carbonate, and the like.
[0278] Here, one type of glycol and alkylene carbonate may be used
singly or two or more types thereof may be used in combination. In
a case in which two or more types of the glycol and alkylene
carbonate are used in combination, the combination and ratio
thereof can be arbitrarily selected.
[0279] The number-average molecular weight computed from the
hydroxyl value of the polyol compound is preferably 1,000 to
10,000, more preferably 2,000 to 9,000, and particularly preferably
3,000 to 7,000. When the number-average molecular weight is 1,000
or more, the excess generation of urethane bonds is suppressed, and
it becomes easier to suppress the viscoelastic characteristic of
the first interlayer. In addition, when the number-average
molecular weight is 10,000 or less, the excess softening of the
first interlayer is suppressed.
[0280] The number-average molecular weight computed from the
hydroxyl value of the polyol compound refers to a value computed
from the following expression.
[The number-average molecular weight of the polyol compound]=[the
number of functional groups in the polyol
compound].times.56.11.times.1,000/[the hydroxyl value of the polyol
compound (unit: mgKOH/g)]
[0281] The polyol compound is preferably the polyether-type polyol
and more preferably a polyether-type diol.
[0282] (B) Polyhydric Isocyanate Compound
[0283] The polyhydric isocyanate compound that is reacted with the
polyol compound is not particularly limited as long as the
polyhydric isocyanate compound has two or more isocyanate
groups.
[0284] One type of the polyhydric isocyanate compound may be used
singly or two or more types of the polyhydric isocyanate compounds
may be used in combination. In a case in which two or more types of
the polyhydric isocyanate compounds are used in combination, the
combination and ratio thereof can be arbitrarily selected.
[0285] Examples of the polyhydric isocyanate compound include
chain-like diisocyanates such as tetramethylene diisocyanate,
hexamethylene diisocyanate, and trimethylhexamethylene
diisocyanate; cyclic aliphatic diisocyanates such as isophorone
diisocyanate, norbornane diisocyanate,
dicyclohexylmethane-4,4'-diisocyanate,
dicyclohexylmethane-2,4'-diisocyanate, and
.omega.,.omega.'-diisocyanate dimethylcyclohexane; aromatic
diisocyanates such as 4,4'-diphenylmethane diisocyanate, tolylene
diisocyanate, xylylene diisocyanate, tolylene diisocyanate,
tetramethylene xylylene diisocyanate, and
naphthalene-1,5-diisocyanate; and the like.
[0286] Among these, the polyhydric isocyanate compound is
preferably isophorone diisocyanate, hexamethylene diisocyanate, or
xylylene diisocyanate from the viewpoint of the handling
property.
[0287] (C) (Meth)acrylic Compound
[0288] The (meth)acrylic compound that is reacted with the terminal
isocyanate urethane prepolymer is not particularly limited as long
as the compound has at least a hydroxyl group and a (meth)acryloyl
group in one molecule.
[0289] One type of the (meth)acrylic compound may be used singly or
two or more types of the (meth)acrylic compounds may be used in
combination. In a case in which two or more types of the
(meth)acrylic compounds are used in combination, the combination
and ratio thereof can be arbitrarily selected.
[0290] Examples of the (meth)acrylic compound include hydroxyl
group-containing (meth)acrylic acid esters such as 2-hyroxyethyle
(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl
(meth)acrylate, 2-hyroxybutyl (meth)acrylate, 3-hyroxybuyl
(meth)acrylate, 4-hydroxybutyl (meth)acrylate, 4-hydroxycyclohexyl
(meth)acrylate, 5-hydroxycyclooxtyl (meth)acrylate,
2-hydroxy-3-phenyloxypropyl (meth)acrylate, pentaerythritol
tri(meth)acrylate, polyethylene glycol mono(meth)acrylate, and
polypropylene glycol mono(meth)acrylate; hydroxyl group-containing
(meth)acrylamides such as N-methylol (meth)acrylamide; reactants
obtained by reacting (meth)acrylic acid with vinyl alcohol, vinyl
phenol, or bisphenol A glycidyl ether; and the like.
[0291] Among these, the (meth)acrylic compound is preferably the
hydroxyl group-containing (meth)acrylic acid ester, more preferably
a hydroxyl group-containing alkyl (meth)acrylate, and particularly
preferably 2-hydroxyethyl (meth)acrylate.
[0292] The reaction between the terminal isocyanate urethane
prepolymer and the (meth)acrylic compound may be caused using a
solvent, a catalyst, and the like as necessary.
[0293] Conditions during the reaction between the terminal
isocyanate urethane prepolymer and the (meth)acrylic compound may
be appropriately adjusted, and, for example, the reaction
temperature is preferably 60.degree. C. to 100.degree. C., and the
reaction time is preferably one to four hours.
[0294] The urethane (meth)acrylate may be any of an oligomer, a
polymer and a mixture of an oligomer and a polymer and is
preferably an oligomer.
[0295] For example, the weight-average molecular weight of the
urethane (meth)acrylate is preferably 1,000 to 100,000, more
preferably 3,000 to 80,000, and particularly preferably 5,000 to
65,000. When the weight-average molecular weight of the
weight-average molecular weight of the urethane (meth)acrylate is
1,000 or more, it becomes easy to optimize the hardness of the
first interlayer due to the intermolecular force between structures
derived from the urethane (meth)acrylate in polymers of the
urethane (meth)acrylate and a polymerizable monomer described
below.
[0296] (Polymerizable Monomer)
[0297] The first interlayer forming composition (II-1) may also
contain, in addition to the urethane (meth)acrylate, a
polymerizable monomer from the viewpoint of further improving the
film-forming property.
[0298] The polymerizable monomer refers to polymerizable monomers
except for oligomers and polymers which are energy
ray-polymerizable and have a weight-average molecular weight of
1,000 or more and is preferably a compound having at least one
(meth)acryloyl group in one molecule.
[0299] Examples of the polymerizable monomer include alkyl
(meth)acrylates in which an alkyl group constituting the alkyl
ester has 1 to 30 carbon atoms and has a chain-like shape;
functional group-containing (meth)acrylic compounds having a
functional group such as a hydroxyl group, an amide group, an amino
group, or an epoxy group; (meth)acrylic acid esters having an
aliphatic cyclic group; (meth)acrylic acid esters having an
aromatic hydrocarbon group; (meth)acrylic acid esters having a
heterocyclic group; compounds having a vinyl group; compounds
having an allyl group; and the like.
[0300] Examples of the alkyl (meth)acrylates having a chain-like
alkyl group having 1 to 30 carbon atoms include methyl
(meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate,
isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl
(meth)acrylate, sec-butyl (meth)acrylate, tert-butyl
(meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl
(meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate,
2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl
(meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate,
dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl
(meth)acrylate, tetradecyl (meth)acrylate (myristyl
(meth)acrylate), pentadecyl (meth)acrylate, hexadecyl
(meth)acrylate (palmityl (meth)acrylate), heptadecyl
(meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate),
isooctadecyl (meth)acrylate (isostearyl (meth)acrylate), nonadecyl
(meth)acrylate, icosyl (meth)acrylate, and the like.
[0301] Examples of functional group-containing (meth)acrylic
derivatives include hydroxyl group-containing (meth)acrylic acid
esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl
(meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl
(meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl
(meth)acrylate; (meth)acrylamides such as (meth)acrylamide,
N,N-dimethyl (meth)acrylamide, N-butyl (meth)acrylamide, N-methylol
(meth)acrylamide, N-methylolpropane (meth)acrylamide,
N-methoxymethyl (meth)acrylamide, and N-butoxymethyl
(meth)acrylamide and derivatives thereof; (meth)acrylic acid esters
having an amino group (hereinafter, in some cases, referred to as
"the amino group-containing (meth)acrylic acid esters");
(meth)acrylic acid esters having a monosubstituted amino group
which are formed by substituting one hydrogen atom in an amino
group with a group other than a hydrogen atom (hereinafter, in some
cases, referred to as "the monosubstituted amino group-containing
(meth)acrylic acid esters"); (meth)acrylic acid esters having a
disubstituted amino group which are formed by substituting two
hydrogen atoms in an amino group with groups other than a hydrogen
atom (hereinafter, in some cases, referred to as "the disubstituted
amino group-containing (meth)acrylic acid esters"); (meth)acrylic
acid esters having an epoxy group such as glycidyl (meth)acrylate
and methyl glycidyl (meth)acrylate (hereinafter, in some cases,
referred to as "the epoxy group-containing (meth)acrylic acid
esters"); and the like.
[0302] Here, "the amino group-containing (meth)acrylic acid ester"
refers to a compound formed by substituting one or more hydrogen
atoms in a (meth)acrylic acid ester with an amino group
(--NH.sub.2). Similarly, "the monosubstituted amino
group-containing (meth)acrylic acid ester" refers to a compound
formed by substituting one or more hydrogen atoms in a
(meth)acrylic acid ester with a monosubstituted amino group, and
"the disubstituted amino group-containing (meth)acrylic acid ester"
refers to a compound formed by substituting one or more hydrogen
atoms in a (meth)acrylic acid ester with a disubstituted amino
group.
[0303] Examples of the group other than a hydrogen atom which
substitutes the hydrogen atom (that is, the substituent) in "the
monosubstituted amino group" and "the disubstituted amino group"
include alkyl groups and the like.
[0304] Examples of the (meth)acrylic acid esters having an
aliphatic cyclic group include isobornyl (meth)acrylate,
dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate,
dicyclopentenyloxyethyl (meth)acrylate, cyclohexyl (meth)acrylate,
adamantyl (meth)acrylate, and the like.
[0305] Examples of the (meth)acrylic acid esters having an aromatic
hydrocarbon group include phenyl hydroxypropyl (meth)acrylate,
benzyl (meth)acrylate, 2-hyroxy-3-phenoxypropyl (meth)acrylate, and
the like.
[0306] The heterocyclic group in the (meth)acrylic acid ester
having a heterocyclic group may be any of an aromatic heterocyclic
group and an aliphatic heterocyclic group.
[0307] Examples of the (meth)acrylic acid esters having the
heterocyclic group include tetrahydrofurfuryl (meth)acrylate,
(meth)acryloyl morpholine, and the like.
[0308] Examples of the compounds having a vinyl group include
styrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether,
N-vinylformamide, N-vinylpyrrolidone, N-vinylcaprolactam, and the
like.
[0309] Examples of the compounds having an allyl group include
allyl glycidyl ethers and the like.
[0310] The polymerizable monomer preferably has a group having a
relatively large volume since the compatibility with the urethane
(meth)acrylate is favorable. Examples of the polymerizable monomer
include (meth)acrylic acid esters having an aliphatic cyclic group,
(meth)acrylic acid esters having an aromatic hydrocarbon group, and
(meth)acrylic acid esters having a heterocyclic group, and
(meth)acrylic acid esters having an aliphatic cyclic group are more
preferred.
[0311] The first interlayer forming composition (II-1) may contain
only one type or two or more types of the polymerizable monomers.
In a case in which the first interlayer forming composition (II-1)
contains two or more types of the polymerizable monomers, the
combination and ratio thereof can be arbitrarily selected.
[0312] In the first interlayer forming composition (II-1), the
amount of the polymerizable monomer is preferably 10% to 99% by
mass, more preferably 15% to 95% by mass, still more preferably 20%
to 90% by mass, and particularly preferably 25% to 80% by mass of
the total mass of the first interlayer forming composition
(II-1).
[0313] (Photopolymerization Initiator)
[0314] The first interlayer forming composition (II-1) may also
contain, in addition to the urethane (meth)acrylate and the
polymerizable monomer, a photopolymerization initiator. The first
interlayer forming composition (II-1) containing the
photopolymerization initiator sufficiently proceeds with a curing
reaction even in a case of being irradiated with energy rays having
a relatively low energy such as ultraviolet rays.
[0315] Examples of the photopolymerization initiator include
benzoin compounds such as benzoin, benzoin methyl ether, benzoin
ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether,
benzoin benzoate, methyl benzoin benzoate, and benzoin dimethyl
ketal; acetophenone compounds such as
2-hydroxy-2-methyl-1-phenyl-propane-1-one, and
2,2-dimethoxy-1,2-diphenylethane-1-one; acylphosphine oxide
compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide;
sulfide compounds such as benzylphenyl sulfide and
tetramethylthiuram monosulfide; .alpha.-ketol compounds such as
1-hydroxycyclohexyl phenyl ketone; azo compounds such as
azobisisobutylonitrile; titanocene compounds such as titanocene;
thioxanthone compounds such as thioxanthone; peroxide compounds;
diketone compounds such as diacetyle; dibenzyl, and the like.
[0316] In addition, as the photopolymerization initiator, for
example, a quinone compound such as 1-chloroanthraquinone; a
photosensitizer such as amine; or the like can also be used.
[0317] The first interlayer forming composition (II-1) may contain
only one type or two or more types of the photopolymerization
initiators. In a case in which the first interlayer forming
composition (II-1) contains two or more types of the
photopolymerization initiators, the combination and ratio thereof
can be arbitrarily selected.
[0318] In the first interlayer forming composition (II-1), the
amount of the photopolymerization initiator is preferably 0.01 to
20 parts by mass, more preferably 0.03 to 10 parts by mass, and
particularly preferably 0.05 to 5 parts by mass of the total amount
(100 parts by mass) of the urethane (meth)acrylate and the
polymerizable monomer.
[0319] (Resin Components Other than Urethane (Meth)Acrylate)
[0320] The first interlayer forming composition (II-1) may also
contain resin components other than the urethane (meth)acrylate as
long as the effects of the present invention are not impaired.
[0321] The types of the resin components and the amount thereof in
the first interlayer forming composition (II-1) may be
appropriately selected depending on the purpose and are not
particularly limited.
[0322] (Other Additives)
[0323] The first interlayer forming composition (II-1) may also
contain other additives which do not correspond to any of the
above-described components as long as the effects of the present
invention are not impaired.
[0324] Examples of the other additives include a variety of
well-known additives such as a crosslinking agent, an antistatic
agent, an antioxidant, a chain transfer, a softening agent
(plasticizer), a filler, an antirust agent, and a colorant (a
pigment or a dye).
[0325] Examples of the chain transfer include thiol compounds
having at least one thiol group (mercapto group) in one
molecule.
[0326] Examples of the thiol compounds include nonyl mercaptan,
1-dodecanethiol, 1,2-ethanedithiol, 1,3-propandithiol,
triazinethiol, triazinedithiol, triazinetrithiol,
1,2,3-propanetrithiol, tetraethylene glycol
bis(3-mercaptopropionate), trimethylolpropane
tris(3-mercaptopropionate), pentaerythritol
tetrakis(3-mercaptopropionate), pentaerythritol
tetrakisthioglycolate, dipentaerythritol
hexakis(3-mercaptopropionate),
tris[(3-mercaptopropioniloxy)-ethyl]-isocyanurate,
1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol
tetrakis(3-mercaptobutylate),
1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trion-
e, and the like.
[0327] The first interlayer forming composition (II-1) may contain
only one type or two or more types of other additives. In a case in
which the first interlayer forming composition (II-1) contains two
or more types of the other additives, the combination and ratio
thereof can be arbitrarily selected.
[0328] In the first interlayer forming composition (II-1), the
amount of the other additives is not particularly limited and may
be appropriately selected depending on the type of the
additives.
[0329] (Solvent)
[0330] The first interlayer forming composition (II-1) may also
contain a solvent. When the first interlayer forming composition
(II-1) contains a solvent, the coating aptitude to a coating target
surface improves.
[0331] {{Method for Manufacturing First Interlayer Forming
Composition}}
[0332] The first interlayer forming composition such as the first
interlayer forming composition (II-1) can be obtained by blending
individual components for constituting the first interlayer forming
composition.
[0333] The addition order during the blending of the respective
components is not particularly limited, and two or more types of
components may be added at the same time.
[0334] In a case in which the solvent is used for the first
interlayer forming composition, the solvent may be used by mixing
the solvent with all of the blending components other than the
solvent so as to dilute these blending components in advance or may
be used by mixing the solvent with the blending components without
diluting all of the blending components other than the solvent in
advance.
[0335] A method for mixing the respective components during
blending is not particularly limited and may be appropriately
selected from well-known methods such as a method in which the
components are mixed together by rotating a stirring stick, a
stirring blade, or the like; a method in which the components are
mixed together using a mixer, and a method in which the components
are mixed together by applying ultrasonic waves thereto.
[0336] The temperature and the time during the addition and mixing
of the respective components are not particularly limited as long
as the respective blending components do not deteriorate and may be
appropriately adjusted, but the temperature is preferably
15.degree. C. to 30.degree. C.
[0337] <Curable Resin Film>
[0338] As described above, the curable resin film of the present
invention is a layer for protecting the plurality of bumps 51 on
the surface 5a of the semiconductor wafer 5, and the first
protective film 1a is formed by heating or curing with energy ray
irradiation.
[0339] As described above, the curable resin film 1 of the present
invention contains an epoxy-based thermosetting component having a
weight-average molecular weight of 200 to 4,000 as the curable
component, and is used to form the first protective film 1a by
being attached to the surface 5a of the semiconductor wafer 5
having the plurality of bumps 51. The curable resin film 1 forms
the first protective film 1a by being attached to the surface 5a of
the semiconductor wafer 5 having the bumps 51 with an average peak
height h1 of 50 to 400 .mu.m, an average diameter D of 60 to 500
.mu.m, and an average pitch P of 100 to 800 .mu.m, heating the
attached curable resin film at 100.degree. C. to 200.degree. C. for
0.5 to 3 hours, and curing the heated curable resin film, and when
longitudinal sections of the first protective film 1a and the
semiconductor wafer 5 are observed by a scanning electron
microscope, a ratio (h3/h1) of an average thickness h3 of the first
protective film 1a at a center position between the bumps 51 to an
average peak height h1 of the plurality of bumps 51, and a ratio
(h2/h1) of an average thickness h2 of the first protective film 1a
at a position being in contact with the bumps 51 to the average
peak height h1 satisfy a relationship represented by the following
expression [{(h2/h1)-(h3/h1)}.ltoreq.0.1].
[0340] In addition, the curable resin film 10 of the present
invention is common to the curable resin film 1 in terms of the
conditions of the dimensional relationship between the cured first
protective film 1a and the plurality of bumps 51, but is different
from the curable resin film 1 from the viewpoint of containing the
energy ray-curable component having a weight-average molecular
weight of 200 to 4,000 as the thermosetting component, and forming
the first protective film 1a by being cured and irradiated with
energy rays under the curing conditions of illuminance of 50 to 500
mW/cm.sup.2, and light intensity of 100 to 2,000 mJ/cm.sup.2.
[0341] The curable resin film 1 can be formed using the
thermosetting resin composition containing a constituent material
thereof. The thermosetting resin composition contains the
epoxy-based thermosetting component having the weight-average
molecular weight of 200 to 4,000.
[0342] The physical properties such as viscoelasticity and the like
of such a curable resin film 1 can be adjusted by adjusting one or
both of the type and amount of the components contained in the
thermosetting resin composition. In addition, the weight-average
molecular weight of the epoxy-based thermosetting component can
also be adjusted to be within the above range by adjusting one or
both of the type and amount of the component.
[0343] The thermosetting resin composition and a method of
manufacturing thereof will be described in detail.
[0344] For example, among the contained components of the
thermosetting resin composition, particularly, by increasing and
decreasing the amount in the composition of the thermosetting
component, physical properties such as viscosity of the curable
resin film 1 can be adjusted within the preferable range.
[0345] Examples of a preferred curable resin film 1 include
thermosetting resin layers containing a polymer component (A) and a
thermosetting component (B). The polymer component (A) is a
component considered to be formed by a polymerization reaction of a
polymerizable compound. In addition, the thermosetting component
(B) is a component capable of a curing (polymerization) reaction
using heat as a trigger of the reaction. Meanwhile, in the present
invention, a polycondensation reaction is also considered as the
polymerization reaction.
[0346] On the other hand, the curable resin film 10 can be formed
using an energy ray-curable resin composition containing a
constituent material thereof. The energy ray-curable resin
composition contains the energy ray-curable component having the
weight-average molecular weight of 200 to 4,000.
[0347] The physical properties such as viscoelasticity and the like
of such a curable resin film 10 can be adjusted by adjusting one or
both of the type and amount of the components contained in the
energy ray-curable resin composition. In addition, the
weight-average molecular weight of the energy ray-curable component
can also be adjusted to be within the above range by adjusting one
or both of the type and amount of the component.
[0348] The curable resin films 1 and 10 may be a sheet made of a
single layer (monolayer) or a sheet made of a plurality of layers
of two or more layers. In a case in which the curable resin films 1
and 10 is a plurality of layers, the respective layers in the
plurality of layers may be identical to or different from one
another, and the combination of the plurality of layers is not
particularly limited.
[0349] In a case where the curable resin films 1 and 10 is made of
the plurality of layers, all the layers constituting the curable
resin films 1 and 10 may satisfy the conditions of the above
constituent component.
[0350] The thickness of the curable resin films 1 and 10 is not
particularly limited, and for example, is preferably 1 to 100
.mu.m, more preferably 5 to 75 .mu.m, particularly preferably 5 to
50 .mu.m. When the thickness of the curable resin film 1 is equal
to or more than the lower limit value, it is possible to form a
first protective film 1a having a higher protection function.
[0351] Here, "the thickness of the curable resin film" refers to
the thickness of the entire curable resin films 1 and 10, and, for
example, the thickness of the curable resin films 1 and 10 made up
of a plurality of layers refers to the total thickness of all of
the layers constituting the curable resin films 1 and 10.
[0352] [Thermosetting Resin Composition]
[0353] The curable resin film 1 can be formed using the
thermosetting resin composition containing a constituent material
thereof, that is, the thermosetting resin composition containing at
least the thermosetting component. For example, the curable resin
film 1 can be formed at an intended portion by applying the
thermosetting resin composition to a target surface on which the
curable resin film 1 is to be formed and drying the thermosetting
resin composition as necessary. The ratio between the amounts of
components, which do not gasify at normal temperature, in the
thermosetting resin composition is, generally, identical to the
ratio between the amounts of the above-described components in the
curable resin film 1. Here, "normal temperature" is as described
above.
[0354] The thermosetting resin composition may be applied using a
well-known method, and examples thereof include methods in which a
variety of coaters such as an air knife coater, a blade coater, a
bar coater, a gravure coater, a roll coater, a roll knife coater, a
curtain coater, a die coater, a knife coater, a screen coater, a
Mayer bar coater, and a kiss coater are used.
[0355] The drying conditions of the thermosetting resin composition
are not particularly limited; however, in a case in which the
thermosetting resin composition contains a solvent described below,
the thermosetting resin composition is preferably heated and dried,
and, in this case, the thermosetting resin composition is
preferably dried under conditions of, for example, 70.degree. C. to
130.degree. C. and 10 seconds to 5 minutes.
[0356] {Thermosetting Resin Composition (III-1)}
[0357] Examples of a thermosetting resin composition include the
thermosetting resin composition (III-1) (in the present embodiment,
simply abbreviated as "thermosetting resin composition (III-1)")
containing a polymer component (A) and a thermosetting component
(B).
[0358] (Polymer Component (A))
[0359] The polymer component (A) is a polymer compound for
imparting a film-forming property, flexibility, and the like to the
curable resin film 1.
[0360] The thermosetting resin composition (III-1) and the curable
resin film 1 may contain only one type or two or more types of the
polymer components (A). In a case in which the polymer component
(A) contains two or more types of the thermosetting resin
composition (III-1) and the curable resin film 1, the combination
and ratio thereof can be arbitrarily selected.
[0361] Examples of the polymer component (A) include acrylic resins
(resins having a (meth)acryloyl group), polyesters, urethane-based
resins (resins having a urethane bond), acrylic urethane resins,
silicone-based resins (resin having a siloxane bond), rubber-based
resins (resins having a rubber structure), phenoxy resins,
thermosetting polyimides, and the like, and acrylic resins are
preferred.
[0362] Examples of the acrylic resin in the polymer component (A)
include well-known acrylic polymers.
[0363] The weight-average molecular weight (Mw) of the acrylic
resin is preferably 10,000 to 2,000,000 and more preferably 100,000
to 1,500,000. When the weight-average molecular weight of the
acrylic resin is equal to or more than the lower limit value, the
shape stability (aging stability during storage) of the curable
resin film 1 improves. In addition, when the weight-average
molecular weight of the acrylic resin is equal to or less than the
upper limit value, it becomes easy for the curable resin film 1 to
follow the uneven surfaces of adherends, and for example, an effect
of further suppressing the generation of voids and the like between
an adherend and the curable resin film 1 can be obtained.
[0364] The glass transition temperature (Tg) of the acrylic resin
is preferably -60.degree. C. to 70.degree. C. and more preferably
-30.degree. C. to 50.degree. C. When the Tg of the acrylic resin is
equal to or higher than the lower limit value, the adhesive force
between the first protective film 1a and the first supporting sheet
is suppressed, and thus the peeling property of the first
supporting sheet improves. In addition, when the Tg of the acrylic
resin is equal to or lower than the upper limit value, the adhesive
force of the adherend of the curable resin film 1 and the first
protective film 1a improves.
[0365] Examples of the acrylic resin include polymers of one or
more type of (meth)acrylic acid esters; copolymers of two or more
types of monomers selected from (meth)acrylic acid, itaconic acid,
vinyl acetate, acrylonitrile, styrene, N-methylol acrylamide, and
the like; and the like.
[0366] Examples of the (meth)acrylic acid esters constituting the
acrylic resin include alkyl (meth)acrylic acid esters in which an
alkyl group constituting the alkyl ester has 1 to 18 carbon atoms
and has a chain-like shape such as methyl (meth)acrylate, ethyl
(meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate,
n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl
(meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate,
hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl
(meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate,
n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl
(meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate
(lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl
(meth)acrylate (myristyl (meth)acrylate), pentadecyl
(meth)acrylate, hexadecyl (meth)acrylate (palmityl (meth)acrylate),
heptadecyl (meth)acrylate, and octadecyl (meth)acrylate (stearyl
(meth)acrylate), and the like;
[0367] cycloalkyl (meth)acrylic acid esters such as isobornyl
(meth)acrylate and dicyclopentanyl (meth)acrylate;
[0368] aralkyl (meth)acrylic acid esters such as benzyl
(meth)acrylate;
[0369] cycloalkenyl (meth)acrylic acid esters such as
dicyclopentenyl (meth)acrylate;
[0370] cycloalkenyloxy alkyl (meth)acrylic acid esters such as
dicyclopentenyloxyethyl (meth)acrylate;
[0371] imide (meth)acrylate;
[0372] glycidyl group-containing (meth)acrylic acid esters such as
glycidyl (meth)acrylate;
[0373] hydroxyl group-containing (meth)acrylic acid esters such as
hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate,
2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate,
2-hydorybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and
4-hydroxybutyl (meth)acrylate; and
[0374] substituted amino group-containing (meth)acrylic acid esters
such as N-methylaminoethyl (meth)acrylate; and the like. Here, "the
substituted amino group" refers to a group formed by substituting
one or two hydrogen atoms in an amino group with a group other than
a hydrogen atom.
[0375] The acrylic resin may be, for example, in addition to the
(meth)acrylic acid ester, a resin formed by the copolymerization of
one or more types of monomers selected from (meth)acrylic acid,
itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylol
acrylamide, and the like.
[0376] The acrylic resin may contain only one type or two or more
types of the monomers. In a case in which the acrylic resin has two
or more types of monomers, the combination and ratio thereof can be
arbitrarily selected.
[0377] The acrylic resin may also have a functional group capable
of bonding to other compounds such as a vinyl group, a
(meth)acryloyl group, an amino group, a hydroxyl group, a carboxy
group, or an isocyanate group. The functional group in the acrylic
resin may be bonded to other compounds through a crosslinking agent
(F) described below or may be directly bonded to other compounds
without the crosslinking agent (F). When the acrylic resin is
bonded to other compounds through the functional group, there is a
tendency that the reliability of packages obtained using the
curable resin film 1 improves.
[0378] In the present invention, as the polymer component (A), a
thermoplastic resin other than the acrylic resin (hereinafter, in
some cases, simply abbreviated as "the thermoplastic resin") may be
used singly without using the acrylic resin or may be jointly used
with the acrylic resin. When the thermoplastic resin is used, there
are cases in which the peeling property of the first protective
film 1a from the first supporting sheet 11 improves, it becomes
easy for the curable resin film 1 to follow the uneven surfaces of
adherends, and the generation of voids and the like between an
adherend and the curable resin film 1 is further suppressed.
[0379] The weight-average molecular weight of the thermoplastic
resin is preferably 1,000 to 100,000 and more preferably 3,000 to
80,000.
[0380] The glass transition temperature (Tg) of the thermoplastic
resin is preferably -30.degree. C. to 150.degree. C. and more
preferably -20.degree. C. to 120.degree. C.
[0381] Examples of the thermoplastic resin include polyesters,
polyurethanes, phenoxy resins, polybutene, polybutadienes,
polystyrenes, and the like.
[0382] The thermosetting resin composition (III-1) and the curable
resin film 1 may contain only one type or two or more types of the
thermoplastic resin. In a case in which the thermoplastic resin
contains two or more types of the thermosetting resin composition
(III-1) and the curable resin film 1, the combination and ratio
thereof can be arbitrarily selected.
[0383] In the thermosetting resin composition (III-1), the ratio of
the amount of the polymer component (A) (that is, the amount of the
polymer component (A) in the curable resin film 1) to the total
amount of all of the components other than the solvent is
preferably 5% to 85% by mass and more preferably 5% to 80% by mass
of the entire mass of the thermosetting resin composition (III-1),
regardless of the type of the polymer component (A).
[0384] There are cases in which the polymer component (A)
corresponds to the thermosetting component (B). In the present
invention, in a case in which the thermosetting resin composition
(III-1) contains components corresponding both the polymer
component (A) and the thermosetting component (B) as described
above, the thermosetting resin composition (III-1) is considered to
contain the polymer component (A) and the thermosetting component
(B).
[0385] (Thermosetting Component (B))
[0386] The thermosetting component (B) is a component for curing
the curable resin film 1 so as to form a rigid first protective
film 1a.
[0387] The thermosetting resin composition (III-1) and the curable
resin film 1 may contain only one type or two or more types of the
thermosetting component (B). In a case in which the thermosetting
component (B) contains two or more types of the thermosetting resin
composition (III-1) and the curable resin film 1, the combination
and ratio thereof can be arbitrarily selected.
[0388] Examples of the thermosetting component (B) include
epoxy-based thermosetting resins, thermosetting polyimides,
polyurethanes, unsaturated polyesters, silicone resins, and the
like, and epoxy-based thermosetting resins are preferred.
[0389] (A) Epoxy-Based Thermosetting Resin
[0390] The epoxy-based thermosetting resin is made up of an epoxy
resin (B1) and a thermal curing agent (B2).
[0391] The thermosetting resin composition (III-1) and the curable
resin film 1 may contain only one type or two or more types of the
epoxy-based thermosetting resin. In a case in which the epoxy-based
thermosetting resin contains two or more types of the thermosetting
resin composition (III-1) and the curable resin film 1, the
combination and ratio thereof can be arbitrarily selected.
[0392] Epoxy Resin (B1)
[0393] As the epoxy resin (B1), well-known epoxy resins are
exemplary examples. Examples thereof include polyfunctional epoxy
resins, biphenyl compounds, bisphenol A diglycidyl ethers and
hydrogenated substances thereof, orthocresol novolac epoxy resins,
dicyclopentadiene-type epoxy resins, biphenyl-type epoxy resins,
bisphenol A-type epoxy resins, bisphenol F-type epoxy resins,
phenylene skeleton-type epoxy resins, and the like, and di- or
higher-functional epoxy compounds.
[0394] As the epoxy resin (B1), an epoxy resin having an
unsaturated hydrocarbon group may also be used. The epoxy resin
having an unsaturated hydrocarbon group has more favorable
compatibility with acrylic resins than epoxy resins not having an
unsaturated hydrocarbon group. Therefore, when the epoxy resin
having an unsaturated hydrocarbon group is used, the reliability of
packages obtained using the curable resin film improves.
[0395] Examples of the epoxy resin having an unsaturated
hydrocarbon group include compounds formed by converting a part of
epoxy groups in a polyfunctional epoxy resin to groups having an
unsaturated hydrocarbon group. The above-described compound can be
obtained by, for example, an addition reaction of (meth)acrylic
acid or a derivative thereof to an epoxy group.
[0396] In addition, examples of the epoxy resin having an
unsaturated hydrocarbon group include compounds in which a group
having an unsaturated hydrocarbon group is directly bonded to an
aromatic ring or the like constituting an epoxy resin and the
like.
[0397] The unsaturated hydrocarbon group is a polymerizable
unsaturated group, and specific examples thereof include ethenyl
groups (vinyl groups), 2-propenyl group (allyl group),
(meth)acryloyl groups, (meth)acrylamide groups, and the like, and
acryloyl groups are preferred.
[0398] The number-average molecular weight of the epoxy resin (B1)
is not particularly limited, but is preferably 300 to 30,000, more
preferably 400 to 10,000, and particularly preferably 500 to 3,000
from the viewpoint of the curing property of the curable resin film
1 and the strength and thermal resistance of the first protective
film 1a after curing.
[0399] The epoxy equivalent of the epoxy resin (B1) is preferably
100 to 1,000 g/eq and more preferably 300 to 800 g/eq.
[0400] One type of the epoxy resin (B1) may be used singly or two
or more types thereof may be jointly used. In a case in which two
or more types of the epoxy resin (B1) are jointly used, the
combination and ratio thereof can be arbitrarily selected.
[0401] Thermal Curing Agent (B2)
[0402] The thermal curing agent (B2) functions as a curing agent of
the epoxy resin (B1).
[0403] Examples of the thermal curing agent (B2) include compounds
having two or more functional groups capable of reacting with an
epoxy group in one molecule. Examples of the functional group
include phenolic hydroxyl groups, alcoholic hydroxyl groups, an
amino group, a carboxy group, groups in which an acid group is
turned into an anhydride, and the like, phenolic hydroxyl groups,
amino groups, or groups in which an acid group is turned into an
anhydride are preferred, and phenolic hydroxyl groups or amino
groups are more preferred.
[0404] As the thermal curing agent (B2), examples of phenolic
curing agents having a phenolic hydroxyl group include
polyfunctional phenolic resins, biphenol, novolac-type phenolic
resins, dicyclopentadiene-based phenolic resins, aralkylphenolic
resins, and the like.
[0405] As the thermal curing agent (B2), examples of amine-based
curing agents having an amino group include dicyandiamide
(hereinafter, in some cases, abbreviated as "DICY"), and the
like.
[0406] The thermal curing agent (B2) may also have an unsaturated
hydrocarbon group.
[0407] Examples of the thermal curing agent (B2) having an
unsaturated hydrocarbon group include compounds formed by
substituting a part of hydroxyl groups in a phenolic resin with
groups having an unsaturated hydrocarbon group, compounds formed by
directly bonding a group having an unsaturated hydrocarbon group to
an aromatic ring of a phenolic resin, and the like.
[0408] The unsaturated hydrocarbon group in the thermal curing
agent (B2) is identical to the unsaturated hydrocarbon group in the
above-described epoxy resin having an unsaturated hydrocarbon
group.
[0409] In a case in which a phenolic curing agent is used as the
thermal curing agent (B2), the thermal curing agent (B2) preferably
has a high softening point or glass transition temperature since
the peeling property from the first supporting sheet of the first
protective film 1a improves.
[0410] The number-average molecular weight of the resin component
such as a polyfunctional phenolic resin, a novolac-type phenolic
resin, a dicyclopentadiene-based phenolic resin, or an
aralkylphenolic resin as the thermal curing agent (B2) is
preferably 300 to 30,000, more preferably 400 to 10,000, and
particularly preferably 500 to 3,000.
[0411] The molecular weight of a non-resin component, for example,
biphenol or dicyandiamide as the thermal curing agent (B2) is not
particularly limited, and is preferably, for example, 60 to
500.
[0412] One type of the thermal curing agent (B2) may be used singly
or two or more types of the polyol compounds may be used in
combination. In a case in which two or more types of the thermal
curing agents (B2) are used in combination, the combination and
ratio thereof can be arbitrarily selected.
[0413] In the thermosetting resin composition (III-1) and the
curable resin film 1, the amount of the thermal curing agent (B2)
is preferably 0.1 to 500 parts by mass, more preferably 1 to 200
parts by mass of the amount (100 parts by mass) of the epoxy resin
(B1). When the amount of the thermal curing agent (B2) is equal to
or more than the lower limit value, it becomes easier for the
curing of the curable resin film 1 to proceed. In addition, when
the amount of the thermal curing agent (B2) is equal to or less
than the upper limit value, the moisture absorptivity of the
curable resin film 1 decreases, and thus the reliability of
packages obtained using the curable resin film 1 further
improves.
[0414] In the thermosetting resin composition (III-1) and the
curable resin film 1, the amount of the thermosetting component
(B), for example, the total amount of the epoxy resin (B1) and the
thermal curing agent (B2) is preferably 50 to 1,000 parts by mass,
more preferably 100 to 900 parts by mass, and particularly
preferably 150 to 800 parts by mass of the amount (100 parts by
mass) of the polymer component (A). When the amount of the
thermosetting component (B) is in the above-described range, the
adhesive force between the first protective film 1a and the first
supporting sheet is suppressed, and thus the peeling property of
the first supporting sheet improves.
[0415] (Curing Accelerator (C))
[0416] The thermosetting resin composition (III-1) and the curable
resin film 1 may also contain a curing accelerator (C). The curing
accelerator (C) is a component for adjusting the speed of curing
the thermosetting resin composition (III-1).
[0417] Examples of preferred curing accelerators (C) include
tertiary amines such as triethylene diamine, benzyldimethylamine,
triethanolamine, dimethylaminoethanol, and
tris(dimethylaminomethyl)phenol; imidazoles (imidazoles in which
one or more hydrogen atoms are substituted with groups other than a
hydrogen atom) such as 2-methylimidazole, 2-phenyl imidazole,
2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole,
and 2,-phenyl-4-methyl-5-hydroxymethylimidazole; organic phosphines
(phosphines in which one or more hydrogen atoms are substituted
with organic groups) such as tributyl phosphine, diphenyl
phosphine, and triphenyl phosphine; tetraphenyl boron salts such as
tetraphenyl phosphonium tetraphenyl borate and triphenyl phosphine
tetraphenyl borate; and the like.
[0418] The thermosetting resin composition (III-1) and the curable
resin film 1 may contain only one type or two or more types of the
curing accelerator (C). In a case in which the curing accelerator
(C) contains two or more types of the thermosetting resin
composition (III-1) and the curable resin film 1, the combination
and ratio thereof can be arbitrarily selected.
[0419] In a case in which the curing accelerator (C) is used, in
the thermosetting resin composition (III-1) and the curable resin
film 1, the amount of the curing accelerator (C) is preferably 0.01
to 10 parts by mass and more preferably 0.1 to 5 parts by mass of
the amount (100 parts by mass) of the thermosetting component (B).
When the amount of the curing accelerator (C) is equal to or more
than the lower limit value, the effects of the use of the curing
accelerator (C) can be more significantly obtained. When the amount
of the curing accelerator (C) is equal to or less than the upper
limit value, for example, an effect of suppressing a highly polar
curing accelerator (C) migrating toward the adhesion interface with
adherends in the curable resin film 1 under high temperature and
high humidity conditions and segregating becomes significant, and
the reliability of packages obtained using the curable resin film 1
further improves.
[0420] (Filler (D))
[0421] The thermosetting resin composition (III-1) and the curable
resin film 1 may also contain a filler (D). When curable resin film
1 contains the filler (D), it is easy to adjust the coefficient of
thermal expansion of the first protective film 1a obtained by
curing the curable resin film 1 to be within the above range, and,
when this coefficient of thermal expansion is optimized for a
subject on which the first protective film 1a is to be formed, the
reliability of packages obtained using the curable resin film
further improves. In addition, when the curable resin film 1
contains the filler (D), it is also possible to decrease the
moisture absorptivity of the first protective film 1a or improving
the heat dissipation property.
[0422] Further, in the present invention, when the curable resin
film 1 contains the filler (D), as described above, it is possible
to obtain an effect which can remarkably suppress the large
distortion in the concave shape on the cured first protective film
1a.
[0423] The filler (D) may be any one of an organic filler and an
inorganic filler, but is preferably an inorganic filler.
[0424] Examples of preferred inorganic fillers include powder of
silica, alumina, talc, calcium carbonate, titanium white,
colcothar, silicon carbide, boron nitride, and the like; beads
obtained by spherodizing this inorganic filler; surface-modified
products of these inorganic fillers; single crystal fibers of these
inorganic fillers; glass fibers; and the like.
[0425] Among these, the inorganic filler is preferably silica or
alumina.
[0426] The thermosetting resin composition (III-1) and the curable
resin film 1 may contain only one type or two or more types of the
filler (D). In a case in which the filler (D) contains two or more
types of the thermosetting resin composition (III-1) and the
curable resin film 1, the combination and ratio thereof can be
arbitrarily selected.
[0427] In a case in which the filler (D) is used, in the
thermosetting resin composition (III-1), the ratio of the amount of
the filler (D) (that is, the amount of the filler (D) in the
curable resin film 1) to the total amount of all of the components
other than the solvent is preferably 5% to 80% by mass and more
preferably 7% to 60% by mass. When the amount of the filler (D) is
in the above-described range, the adjustment of the coefficient of
thermal expansion becomes easier.
[0428] In addition, when the thermosetting resin composition
(III-1) and the curable resin film 1 contain the filler (D) having
an average particle diameter of 5 to 1,000 nm in the curable resin
film 1 which is 5% to 80% of the entire mass of the thermosetting
resin composition (III-1), it is possible to obtain an effect which
can remarkably suppress the large distortion in the concave shape
on the cured first protective film 1a.
[0429] (Coupling Agent (E))
[0430] The thermosetting resin composition (III-1) and the curable
resin film 1 may also contain a coupling agent (E). When a coupling
agent having a functional group capable of reacting with an
inorganic compound or an organic compound is used as the coupling
agent (E), it is possible to improve the adhesiveness and adhesion
of the curable resin film 1 to adherends. In addition, when the
coupling agent (E) is used, the first protective film 1a obtained
by curing the curable resin film 1 is not impaired in the thermal
resistance and is improved in terms of the water resistance.
[0431] The coupling agent (E) is preferably a compound having a
functional group capable of reacting with the functional group in
the polymer component (A), the thermosetting component (B), or the
like and more preferably a silane coupling agent.
[0432] Examples of preferred silane coupling agents include
3-glycidyloxypropyltrimethoxysilane,
3-glycidyloxypropylmethyldiethoxysilane,
3-glycidyloxypropyltriethoxysilane,
3-glycidyloxymethyldiethoxysilane,
epoxycyclohexyl)ethyltrimethoxysilane,
3-methacryloyloxypropyltrimethoxysilane,
3-aminopropyltrimethoxysilane,
3-(2-aminoethylamino)propyltrimethoxysilane,
3-(2-aminoethylamino)propylmethyldiethoxysilane,
3-(phenylamino)propyltrimethoxysilane,
3-anilinopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane,
3-mercaptopropyltrimethoxysilane,
3-mercaptopropylmethyldimethoxysilane,
bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane,
methyltriethoxysilane, vinyltrimethoxysilane,
vinyltriacetoxysilane, imidazolesilane, and the like.
[0433] The thermosetting resin composition (III-1) and the curable
resin film 1 may contain only one type or two or more types of the
coupling agent (E). In a case in which the coupling agent (E)
contains two or more types of the thermosetting resin composition
(III-1) and the curable resin film 1, the combination and ratio
thereof can be arbitrarily selected.
[0434] In a case where the coupling agent (E) is used, in the
thermosetting resin composition (III-1) and the curable resin film
1, the amount of the coupling agent (E) is preferably 0.03 to 20
parts by mass, more preferably 0.05 to 10 parts by mass, and
particularly preferably 0.1 to 5 parts by mass of the total amount
(100 parts by mass of the polymer component (A) and the
thermosetting component (B)). When the amount of the coupling agent
(E) is equal to or more than the lower limit value, the effects of
the use of the coupling agent (E) such as the improvement of the
dispersibility of the filler (D) in resins and the improvement of
the adhesiveness of the curable resin film 1 to adherends can be
significantly obtained.
[0435] In addition, when the amount of the coupling agent (E) is
equal to or less than the upper limit value, the generation of
outgas is further suppressed.
[0436] (Crosslinking Agent (F))
[0437] In a case in which a polymer component having a functional
group such as a vinyl group which is capable of bonding to other
compounds, a (meth)acryloyl group, an amino group, a hydroxyl
group, a carboxy group, or an isocyanate group which is capable of
reacting with other compounds such as the above-described acrylic
resin is used as the polymer component (A), the thermosetting resin
composition (III-1) and the curable resin film 1 may also contain a
crosslinking agent (F) for bonding and crosslinking the functional
group to other compounds. When the functional group is crosslinked
to other compound using the crosslinking agent (F), it is possible
to adjust the initial adhesive force and the agglomerative force of
the curable resin film 1.
[0438] Examples of the crosslinking agent (F) include organic
polyhydric isocyanate compounds, organic polyhydric imine
compounds, metal chelate-based crosslinking agents (crosslinking
agents having a metal chelate structure), aziridine-based
crosslinking agents (crosslinking agents having an aziridinyl
group), and the like.
[0439] Examples of the organic polyhydric isocyanate compounds
include aromatic polyhydric isocyanate compounds, aliphatic
polyhydric isocyanate compounds, and alicyclic polyhydric
isocyanate compounds (hereinafter, in some cases, these compounds
will be collectively abbreviated as "aromatic polyhydric isocyanate
compounds and the like"); timers, isocyanurate bodies, and adduct
bodies of the aromatic polyhydric isocyanate compounds and the
like; terminal isocyanate urethane prepolymers obtained by reacting
the aromatic polyhydric isocyanate compounds and the like and a
polyol compound. The "adduct body" refers to a reactant of the
aromatic polyhydric isocyanate compound, the aliphatic polyhydric
isocyanate compound, or the alicyclic polyhydric isocyanate
compound and a low-molecular-weight active hydrogen-containing
compound such as ethylene glycol, propylene glycol, neopentyl
glycol, trimethylolpropane, or castor oil, and examples thereof
include xylylene diisocyanate adducts of trimethylolpropane as
described below and the like. In addition, "the terminal isocyanate
urethane prepolymer" is as described above.
[0440] More specific examples of the organic polyhydric isocyanate
compound include 2,4-tolylene diisocyanate; 2,6-tolylene
diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylylene diisocyanate;
diphenylmethane-4,4'-diisocyanate;
diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane
diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate;
dicyclohexylmethane-4,4'-diisocyanate;
dicyclohexylmethane-2,4'-diisocyanate; compounds obtained by adding
any one or more types of tolylene diisocyanate, hexamethylene
diisocyanate, and xylylene diisocyanate to all or some of hydroxyl
groups in a polyol such as trimethylolpropane; lysine diisocyanate;
and the like.
[0441] Examples of the organic polyhydric imine compounds include
N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide),
trimethylolpropane tri-.beta.-aziridinylpropionate,
tetramethylolmethane-tri-.beta.-aziridinylpropionate,
N,N'-toluene-2,4-bis(1-aziridinecarboxamide) triethylene melamine,
and the like.
[0442] In a case in which the organic polyhydric isocyanate
compound is used as the crosslinking agent (F), a hydroxyl
group-containing polymer is preferably used as the polymer
component (A). In a case in which the crosslinking agent (F) has an
isocyanate group and the polymer component (A) has a hydroxyl
group, it is possible to simply introduce a crosslinking structure
into the curable resin film 1 by a reaction between the
crosslinking agent (F) and the polymer component (A).
[0443] The thermosetting resin composition (III-1) and the curable
resin film 1 may contain only one type of the crosslinking agent
(F). In addition, thermosetting resin composition (III-1) and the
curable resin film 1 may contain two or more types of the
crosslinking agents (F), and in this case, the combination and
ratio thereof can be arbitrarily selected.
[0444] In a case in which the crosslinking agent (F) is used, in
the thermosetting resin composition (III-1), the amount of the
crosslinking agent (F) is preferably 0.01 to 20 parts by mass, more
preferably 0.1 to 10 parts by mass, and particularly preferably 0.5
to 5 parts by mass of the amount (100 parts by mass) of the polymer
component (A). When the amount of the crosslinking agent (F) is
equal to or more than the lower limit value, the effects of the use
of the crosslinking agent (F) can be significantly obtained. In
addition, when the amount of the crosslinking agent (F) is equal to
or less than the upper limit value, the excess use of the
crosslinking agent (F) is suppressed.
[0445] (Energy Ray-Curable Resin (G))
[0446] The thermosetting resin composition (III-1) and the curable
resin film 1 may contain an energy ray-curable resin (G). When the
curable resin film 1 contains the energy ray-curable resin (G), it
is possible to change the characteristics by being irradiated with
energy rays.
[0447] The energy ray-curable resin (G) is obtained by polymerizing
(curing) an energy ray-curable compound.
[0448] Examples of the energy ray-curable compound include
compounds having at least one polymerizable double bond in the
molecule, and acrylate-based compounds having a (meth)acryloyl
group are preferred.
[0449] Examples of the acrylate-based compounds include chain-like
aliphatic skeleton-containing (meth)acrylates such as
trimethylolpropane tri(meth)acrylate, tetramethylolmethane
tetra(meth)acrylate, pentaerythritol tri(meth)acrylate,
pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxy
penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate,
1,4-butylene glycol di(meth)acrylate, and 1,6-hexanediol
di(meth)acrylate; cyclic aliphatic skeleton-containing
(meth)acrylates such as dicyclopentanyl di(meth)acrylate;
polyalkylene glycol (meth)acrylates such as polyethylene glycol
di(meth)acrylate; oligo ester (meth)acrylates; urethane
(meth)acrylate oligomers; epoxy-modified (meth)acrylates; polyether
(meth)acrylates other than the above-described polyalkylene glycol
(meth)acrylates; itaconic acid oligomers; and the like.
[0450] The weight-average molecular weight of the energy
ray-curable compound is preferably 100 to 30,000 and more
preferably 300 to 10,000.
[0451] Only one type or two or more types of the energy ray-curable
compounds may be used for polymerization. In a case in which two or
more types of the energy ray-curable compounds are used for
polymerization, the combination and ratio thereof can be
arbitrarily selected.
[0452] The thermosetting resin composition (III-1) may contain only
one type or two or more types of the energy ray-curable resins (G).
In a case in which the thermosetting resin composition (III-1)
contains two or more types of the energy ray-curable resins (G),
the combination and ratio thereof can be arbitrarily selected.
[0453] The amount of the energy ray-curable resin (G) in the
thermosetting resin composition (III-1) is preferably 1% to 95% by
mass, more preferably 5% to 90% by mass, and particularly
preferably 10% to 85% by mass, of the entire mass of the
thermosetting resin composition (III-1).
[0454] (Photopolymerization Initiator (H))
[0455] In the case of containing the energy ray-curable resin (G),
the thermosetting resin composition (III-1) may also contain a
photopolymerization initiator (H) in order to cause the
polymerization reaction of the energy ray curable resin (G) to more
efficiently proceed.
[0456] Examples of the photopolymerization initiator (H) include
benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin
ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether,
benzoin benzoic acid, benzoin benzoate methyl, benzoin dimethyl
ketal, 2,4-diethylthioxanthone, 1-hydroxycyclohexyl phenyl ketone,
benzyl diphenyl sulfide, tetramethylthiuram monosulfide,
azobisisobutyronitrile, benzyl, dibenzyl, diacetyl,
1,2-diphenylmethane, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)
phenyl] propanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide,
and 2-chloroanthraquinone.
[0457] The thermosetting resin composition (III-1) may contain only
one type or two or more types of the photopolymerization initiators
(H). In a case in which the thermosetting resin composition (III-1)
contains two or more types of the photopolymerization initiators
(H), the combination and ratio thereof can be arbitrarily
selected.
[0458] The amount of the photopolymerization initiators (H) in the
thermosetting resin composition (III-1) is preferably 0.1 to 20
parts by mass, more preferably 1 to 10 parts by mass, and
particularly preferably 2 to 5 parts by mass of the amount (100
parts by mass) of the energy ray-curable resin (G).
[0459] (Versatile Additive (I)) The thermosetting resin composition
(III-1) and the curable resin film 1 may also contain a versatile
additive (I) as long as the effects of the present invention are
not impaired.
[0460] The versatile additive (I) may be a well-known versatile
additive, can be arbitrarily selected depending on the purpose, and
is not particularly limited, and examples of preferred versatile
additives include a plasticizer, an antistatic agent, an
antioxidant, a colorant (a pigment or a dye), a gettering agent,
and the like.
[0461] The thermosetting resin composition (III-1) and the curable
resin film 1 may contain only one type or two or more types of the
versatile additive (I). In a case in which the thermosetting resin
composition (III-1) and the curable resin film 1 contain two or
more types of the versatile additive (I), the combination and ratio
thereof can be arbitrarily selected.
[0462] The amount of the versatile additive (I) in the
thermosetting resin composition (III-1) and the curable resin film
1 is not particularly limited and may be appropriately selected
depending on the purpose.
[0463] (Solvent) The thermosetting resin composition (III-1)
preferably further contains a solvent. The thermosetting resin
composition (III-1) containing a solvent improves in terms of the
handling property.
[0464] The solvent is not particularly limited, but preferred
examples thereof include hydrocarbons such as toluene and xylyene;
alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol
(2-methyl propane-1-ol), and 1-butanol; esters such as ethyl
acetate; ketones such as acetone and methyl ethyl ketone; ethers
such as tetrahydrofuran; amides (compounds having an amide bond)
such as dimethyl formamide and N-methyl pyrrolidone, and the
like.
[0465] The thermosetting resin composition (III-1) may contain only
one type or two or more types of the solvents. In a case in which
the thermosetting resin composition (III-1) contains two or more
types of the solvents, the combination and ratio thereof can be
arbitrarily selected.
[0466] The solvent contained in the thermosetting resin composition
(III-1) is preferably methyl ethyl ketone or the like since it is
possible to more uniformly mix the components contained in the
thermosetting resin composition (III-1).
[0467] {{Method of Manufacturing Thermosetting Resin
Composition}}
[0468] The thermosetting resin composition such as the
thermosetting resin composition (III-1) can be obtained by blending
individual components for constituting the thermosetting resin
composition.
[0469] The addition order during the blending of the respective
components is not particularly limited, and two or more types of
components may be added at the same time.
[0470] In a case in which the solvent is used, the solvent may be
used by mixing the solvent with all of the blending components
other than the solvent so as to dilute these blending components in
advance or may be used by mixing the solvent with the blending
components without diluting all of the blending components other
than the solvent in advance.
[0471] A method for mixing the respective components during
blending is not particularly limited and may be appropriately
selected from well-known methods such as a method in which the
components are mixed together by rotating a stirring stick, a
stirring blade, or the like; a method in which the components are
mixed together using a mixer, and a method in which the components
are mixed together by applying ultrasonic waves thereto.
[0472] The temperature and the time during the addition and mixing
of the respective components are not particularly limited as long
as the respective blending components do not deteriorate and may be
appropriately adjusted, but the temperature is preferably
15.degree. C. to 30.degree. C.
[0473] [Energy Ray-Curable Resin Composition]
[0474] Hereinafter, an energy ray-curable resin composition forming
the curable resin film 10 of the present invention will be
described in detail. The curable resin film 10 can be formed using
an energy ray-curable resin composition containing a constituent
material thereof. For example, the curable resin film 1 can be
formed at an intended portion by applying the energy ray-curable
resin composition to a target surface on which the curable resin
film 1 is to be formed and drying the curable resin composition as
necessary. The ratio between the amounts of components, which do
not gasify at normal temperature, in the energy ray-curable resin
composition is, generally, identical to the ratio between the
amounts of the above-described components in the curable resin
film. Here, "normal temperature" is as described above.
[0475] The energy ray-curable resin composition contains an energy
ray-curable component (a).
[0476] The energy ray-curable component (a) is preferably uncured
and is preferably pressure-sensitive adhesive and more preferably
uncured and pressure-sensitive adhesive. Here, "energy rays" and
"being energy ray-curable" are as described above.
[0477] The curable resin film 10 formed of the energy ray-curable
resin composition may be a sheet made of a single layer (monolayer)
or a sheet made of a plurality of layers of two or more layers. In
a case in which the curable resin film 10 formed of the energy
ray-curable resin composition is a plurality of layers, the
respective layers in the plurality of layers may be identical to or
different from one another, and the combination of the plurality of
layers is not particularly limited.
[0478] The thickness of the curable resin film 10 is preferably 1
to 100 .mu.m, more preferably 5 to 75 .mu.m, and particularly
preferably 5 to 50 .mu.m When the thickness of the curable resin
film 10 formed of the energy ray-curable resin composition is equal
to or more than the lower limit value, it is possible to form a
first protective film 1a having a higher protection function. In
addition, when the thickness of the curable resin film 10 is equal
to or less than the upper limit value, excessive thickness is
suppressed.
[0479] Here, "the thickness of the curable resin film 10" refers to
the thickness of the entire curable resin film 10 formed of the
energy ray-curable resin composition, and, for example, the
thickness of the curable resin film 10 made up of a plurality of
layers refers to the total thickness of all of the layers
constituting the curable resin film 10.
[0480] The energy ray-curable resin composition may be applied
using a well-known method, and examples thereof include methods in
which a variety of coaters such as an air knife coater, a blade
coater, a bar coater, a gravure coater, a roll coater, a roll knife
coater, a curtain coater, a die coater, a knife coater, a screen
coater, a Mayer bar coater, and a kiss coater are used.
[0481] The drying conditions of the energy ray-curable resin
composition are not particularly limited; however, in a case in
which the energy ray-curable resin composition contains a solvent
described below, the energy ray-curable resin layer forming
composition is preferably heated and dried, and, in this case, the
curable resin composition is preferably dried under conditions of,
for example, 70.degree. C. to 130.degree. C. and 10 seconds to five
minutes.
[0482] {{Energy Ray-Curable Resin Composition (IV-1)}}
[0483] Examples of the energy ray-curable resin composition include
an energy ray-curable resin composition (IV-1) containing an energy
ray-curable component (a).
[0484] {Energy Ray-Curable Component (a)}
[0485] The energy ray-curable component (a) is a component that is
cured by being irradiated with energy rays and is a component for
imparting a film-forming property, flexibility, and the like to the
curable resin film 10.
[0486] Examples of the energy ray-curable component (a) include a
polymer (a1) which has an energy ray-curable group and a
weight-average molecular weight of 80,000 to 2,000,000 and a
compound (a2) which has an energy ray-curable group and a molecular
weight of 100 to 80,000. The polymer (a1) may be a polymer at least
a part of which is crosslinked with a crosslinking agent or a
polymer which is not crosslinked.
[0487] (Polymer Having Energy Ray-Curable Group and Weight-Average
Molecular Weight of 80,000 to 2,000,000 (a1))
[0488] Examples of the polymer (a1) which has an energy ray-curable
group and a weight-average molecular weight of 80,000 to 2,000,000
include an acrylic resin (a1-1) formed by polymerizing an acrylic
polymer (a11) having a functional group capable of reacting with
groups in other compounds and an energy ray-curable compound (a12)
having a group that reacts with the functional group and an energy
ray-curable group such as an energy ray-curable double bond.
[0489] Examples of the functional group capable of reacting with
groups in other compounds include a hydroxyl group, a carboxy
group, an amino group, a substituted amino group (a group formed by
substituting one or two hydrogen atoms in an amino group with a
group other than a hydrogen atom), an epoxy group, and the like.
Here, the functional group is preferably a group other than a
carboxy group from the viewpoint of preventing the corrosion of
circuits such as semiconductor wafers or semiconductor chips.
[0490] Among these, the functional group is preferably a hydroxyl
group.
[0491] Acrylic Polymer Having Functional Group (a11)
[0492] Examples of the acrylic polymer (a11) having the functional
group include acrylic polymers formed by copolymerizing an acrylic
monomer having the above-described functional group and an acrylic
monomer not having the above-described functional group, and the
acrylic polymer may be an acrylic polymer formed by copolymerizing
the above-described monomers and, furthermore, a monomer other than
acrylic monomers (non-acrylic monomer).
[0493] In addition, the acrylic polymer (a11) may be a random
copolymer or a block copolymer.
[0494] Examples of the acrylic monomer having the functional group
include hydroxyl group-containing monomers, carboxy
group-containing monomers, amino group-containing monomers,
substituted amino group-containing monomers, epoxy group-containing
monomers, and the like.
[0495] Examples of the hydroxyl group-containing monomers include
hydroxyalkyl (meth)acrylates such as hydroxymethyl (meth)acrylate,
2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate,
3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate,
3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate;
non-(meth)acrylic unsaturated alcohols such as vinyl alcohol and
allyl alcohol (unsaturated alcohols not having a (meth)acryloyl
skeleton); and the like.
[0496] Examples of the carboxy group-containing monomers include
ethylenic unsaturated monocarboxylic acids such as (meth)acrylic
acid and crotonic acid (monocarboxylic acids having an ethylenic
unsaturated bond); ethylenic unsaturated dicarboxylic acids such as
fumaric acid, itaconic acid, maleic acid, and citraconic acid
(dicarboxylic acids having an ethylenic unsaturated bond);
anhydrides of the ethylenic unsaturated dicarboxylic acid;
carboxyalkyl (meth)acrylates such as 2-carboxyethyl methacrylate;
and the like.
[0497] The acrylic monomer having the functional group is
preferably the hydroxyl group-containing monomer or the carboxy
group-containing monomer and more preferably the hydroxyl
group-containing monomer.
[0498] The acrylic polymer (a11) may be constituted of only one
type or two or more types of the acrylic monomers having the
functional group. In a case in which the acrylic polymer (a11) is
constituted of two or more types of the acrylic monomers having the
functional group, the combination and ratio thereof can be
arbitrarily selected.
[0499] Examples of the acrylic monomer not having the functional
group include alkyl (meth)acrylates in which an alkyl group
constituting the alkyl ester has 1 to 18 carbon atoms and has a
chain-like shape such as methyl (meth)acrylate, ethyl
(meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate,
n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl
(meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate,
hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl
(meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate,
n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl
(meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate
(lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl
(meth)acrylate (myristyl (meth)acrylate), pentadecyl
(meth)acrylate, hexadecyl (meth)acrylate (palmityl (meth)acrylate),
heptadecyl (meth)acrylate, and octadecyl (meth)acrylate (stearyl
(meth)acrylate) and the like.
[0500] In addition, examples of the acrylic monomer not having the
functional group also include alkoxyalkyl group-containing
(meth)acrylic acid esters such as methoxymethyl (meth)acrylate,
methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, and
ethoxyethyl (meth)acrylate; (meth)acrylic acid esters having an
aromatic group which includes (meth)acrylic acid aryl ester such as
phenyl (meth)acrylate or the like; non-crosslinkable
(meth)acrylamides and derivatives thereof; (meth)acrylic acid
esters having a non-crosslinkable tertiary amino group such as
N,N-dimethyl aminoethyl (meth)acrylate and N,N-dimethyl aminopropyl
(meth)acrylate; and the like.
[0501] The acrylic polymer (a11) may be constituted of only one
type or two or more types of the acrylic monomers not having the
functional group. In a case in which the acrylic polymer (a11) is
constituted of two or more types of the acrylic monomers not having
the functional group, the combination and ratio thereof can be
arbitrarily selected.
[0502] Examples of the non-acrylic monomer include olefins such as
ethylene and norbornene; vinyl acetate; styrene; and the like.
[0503] The acrylic polymer (a11) may be constituted of only one
type or two or more types of the non-acrylic monomers. In a case in
which the acrylic polymer (a11) is constituted of two or more types
of the non-acrylic monomers, the combination and ratio thereof can
be arbitrarily selected.
[0504] The ratio (amount of a constituent unit derived from the
acrylic monomer having the functional group to the entire mass of
constituent units constituting the acrylic polymer (a11) is
preferably 0.1% to 50% by mass, more preferably 1% to 40% by mass,
and particularly preferably 3% to 30% by mass. When the ratio is in
the above-described range, in the acrylic resin (a1-1) obtained by
polymerization between the acrylic polymer (a11) and the energy
ray-curable compound (a12), it becomes possible to easily adjust
the degree of curing of the first protective film to a preferred
range with the amount of the energy ray-curable group.
[0505] The acrylic polymer (a11) may be constituted of only one
type or two or more types of the acrylic resins (a1-1). In a case
in which the acrylic polymer (a11) is constituted of two or more
types of the acrylic resins (a1-1), the combination and ratio
thereof can be arbitrarily selected.
[0506] In the energy ray-curable energy ray-curable resin
composition (IV-1), the amount of the acrylic resin (a1-1) is
preferably 1% to 60% by mass, more preferably 3% to 50% by mass,
and particularly preferably 5% to 40% by mass of the entire mass of
the energy ray-curable resin composition (IV-1).
[0507] Energy Ray-Curable Compound (a12)
[0508] The energy ray-curable compound (a12) is preferably an
energy ray-curable compound having one or more types of groups
selected from the group consisting of an isocyanate group, an epoxy
group, and a carboxy group as the group capable of reacting with
the functional group in the acrylic polymer (a11) and more
preferably an energy ray-curable compound having an isocyanate
group as the above-described group. For example, in a case in which
the energy ray-curable compound (a12) has an isocyanate group as
the above-described group, this isocyanate group easily reacts with
a hydroxyl group in the acrylic polymer (a11) having the hydroxyl
group as the functional group.
[0509] The number of the energy ray-curable groups in one molecule
of the energy ray-curable compound (a12) is preferably 1 to 5 and
more preferably 1 or 2.
[0510] Examples of the energy ray-curable compound (a12) include
2-methacryloyloxyethyl isocyanate,
methaisopropenyl-.alpha.,.alpha.-dimethylbenzyl isocyanate,
methacryloyl isocyanate, ally isocyanate,
1,1-(bisacryloyloxymethyl)ethyl isocyanate;
[0511] acryloyl monoisocyanate compounds obtained by a reaction
between a diisocyante compound or a polyisocyanate compound and
hydroxyethyl (meth)acrylate; and
[0512] acryloyl monoisocyanate compounds obtained from a reaction
among a diisocyante compound or a polyisocyanate compound, a polyol
compound, and hydroxyethyl (meth)acrylate; and the like.
[0513] Among these, the energy ray-curable compound (a12) is
preferably 2-methacryloyloxyethyl isocyanate.
[0514] The energy ray-curable compound (a12) may be constituted of
only one type or two or more types of the acrylic resins (a1-1). In
a case in which the energy ray-curable compound (a12) is
constituted of two or more types of the acrylic resins (a1-1), the
combination and ratio thereof can be arbitrarily selected.
[0515] The ratio of the amount of an energy ray-curable group
derived from the energy ray-curable compound (a12) to the amount of
the functional group derived from the acrylic polymer (a11) in the
acrylic resin (a1-1) is preferably 20 to 120 mol %, more preferably
35 to 100 mol %, and particularly preferably 50 to 100 mol %. When
the ratio of the amount is in the above-described range, the
adhesive force of the first protective film after curing becomes
stronger. Meanwhile, in a case in which the energy ray-curable
compound (a12) is a monofunctional compound (having one group in
one molecule), the upper limit value of the ratio of the amount
becomes 100 mol %; however, in a case in which the energy
ray-curable compound (a12) is a polyfunctional compound (having two
or more groups in one molecule), the upper limit value of the ratio
of the amount exceeds 100 mol % in some cases.
[0516] The weight-average molecular weight (Mw) of the polymer (a1)
is preferably 100,000 to 2,000,000 and more preferably 300,000 to
1,500,000.
[0517] Here, "the weight-average molecular weight" is as described
above.
[0518] In a case in which at least a part of the polymer (a1) is
crosslinked with a crosslinking agent, the polymer (a1) may be a
polymer that is formed by polymerizing monomers which do not
correspond to any of the monomers described above as the monomers
constituting the acrylic polymer (a11) and have a group that reacts
with the crosslinking agent and is crosslinked in the group that
reacts with the crosslinking agent or may be a polymer crosslinked
in a group which is derived from the energy ray-curable compound
(a12) and reacts with the functional group.
[0519] The energy ray-curable resin composition (IV-1) and the
curable resin film 10 may contain only one type or two or more
types of the polymers (a1). In a case in which the energy
ray-curable resin composition (IV-1) and the curable resin film 10
contain two or more types of the polymers (a1), the combination and
ratio thereof can be arbitrarily selected.
[0520] (Compound Having Energy Ray-Curable Group and Weight-Average
Molecular Weight of 100 to 80,000 (a2))
[0521] Examples of the energy ray-curable group having the compound
(a2) which has an energy ray-curable group and a weight-average
molecular weight of 100 to 80,000 include groups having an energy
ray-curable double bond, and preferred examples thereof include a
(meth)acryloyl group, a vinyl group, and the like.
[0522] The compound (a2) is not particularly limited as long as the
compound satisfies the above-described conditions, and examples
thereof include low-molecular-weight compounds having an energy
ray-curable group, epoxy resins having an energy ray-curable group,
phenolic resins having an energy ray-curable group, and the
like.
[0523] Among the compound (a2), examples of the
low-molecular-weight compounds having an energy ray-curable group
include polyfunctional monomers, oligomers, and the like, and
acrylate-based compounds having a (meth)acryloyl group are
preferred.
[0524] Examples of the acrylate compounds include difunctional
(meth)acrylates such as 2-hydroxy-3-(meth)acryloyloxypropoyl
methacrylate, polyethylene glycol di(meth)acrylate, propoxylated
ethoxylated bisphenol A di(meth)acrylate,
2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated
bisphenol A di(meth)acrylate,
2,2-bis[4-((meth)acryloxydiethoxy)phenyl]propane,
9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene,
2,2-bis[4-((meth)acryloxypolypropoxy)phenyl]propane,
tricyclodecanedimethanol di(meth)acrylate, 1,10-decanediol
di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol
di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene
glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate,
polytetramethylene glycol di(meth)acrylate, ethylene glycol
di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene
glycol di(meth)acrylate,
2,2-bis[4-((meth)acryloylethoxy)phenyl]propane, neopentyl glycol
di(meth)acrylate, ethoxylated polypropylene glycol
di(meth)acrylate, and 2-hydroxy-1,3-di(meth)acryloxypropane;
[0525] polyfunctional (meth)acrylates such as
tris(2-(meth)acryloxyethyl) isocyanurate,
.epsilon.-caprolacton-modified tris-(2-(meth)acryloxyethyl)
isocyanurate, ethoxylated glycerin tri(meth)acrylate,
pentaerythritol tri(meth)acrylate, trimethylolpropane
tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate,
ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol
tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, and
dipentaerythritol hexa(meth)acrylate;
[0526] polyfunctional (meth)acrylate oligomers such as urethane
(meth)acrylate oligomers; and the like.
[0527] Among the compound (a2), as the epoxy resins having an
energy ray-curable group, the phenolic resins having an energy
ray-curable group, for example, the epoxy resins described in
Paragraph 0043 and the like of "Japanese Unexamined Patent
Application, First Publication No. 2013-194102" can be used. These
resins also correspond to resins constituting a thermosetting
component described below; however, in the present invention, the
resins will be handled as the compound (a2).
[0528] The weight-average molecular weight of the compound (a2) is
preferably 100 to 30,000 and more preferably 300 to 10,000.
[0529] The energy ray-curable resin composition (IV-1) and the
curable resin film 10 may contain only one type or two or more
types of the compounds (a2). In a case in which the energy
ray-curable resin composition (IV-1) and the curable resin film 10
contain two or more types of the compounds (a2), the combination
and ratio thereof can be arbitrarily selected.
[0530] {Polymer not Having Energy Ray-Curable Group (b)}
[0531] In the case where the energy ray-curable resin composition
(IV-1) and the curable resin film 10 contain the compound (a2) as
the energy ray-curable component (a), the energy ray-curable resin
composition (IV-1) and the energy ray-curable resin layer
preferably further contain a polymer (b) not having any energy
ray-curable groups.
[0532] The polymer (b) may be a polymer at least a part of which is
crosslinked with a crosslinking agent or a polymer which is not
crosslinked.
[0533] Examples of the polymer (b) not having any energy
ray-curable group include acrylic polymers, phenoxy resins,
urethane resins, polyesters, rubber-based resins, acrylic urethane
resins, and the like.
[0534] Among these, the polymer (b) is preferably an acrylic
polymer (hereinafter, in some cases, abbreviated as "the acrylic
polymer (b-1)").
[0535] The acrylic polymer (b-1) may be a well-known acrylic
polymer, and, for example, the acrylic polymer may be a homopolymer
of one type of acrylic monomer, a copolymer of two or more types of
acrylic monomers. In addition, the acrylic polymer (b-1) may be a
copolymer of one or more types of acrylic monomers and one or more
types of monomers other than acrylic monomers (non-acrylic
monomers).
[0536] Examples of the acrylic monomer constituting the acrylic
polymer (b-1) include alkyl (meth)acrylates, (meth)acrylic acid
ester having a cyclic skeleton, glycidyl group-containing
(meth)acrylic acid ester, hydroxyl group-containing (meth)acrylic
acid esters, and substituted amino group-containing (meth)acrylic
acid esters. Here, "substituted amino group" is as described
above.
[0537] Examples of the alkyl (meth)acrylates include alkyl
(meth)acrylates in which an alkyl group constituting the alkyl
ester has 1 to 18 carbon atoms and has a chain-like shape such as
methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl
(meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate,
isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl
(meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl
(meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl
(meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate,
isononyl (meth)acrylate, decyl (meth)acrylate, undecyl
(meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate),
tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl
(meth)acrylate), pentadecyl (meth)acrylate, hexadecyl
(meth)acrylate (palmityl (meth)acrylate), heptadecyl
(meth)acrylate, and octadecyl (meth)acrylate (stearyl
(meth)acrylate) and the like.
[0538] Examples of the (meth)acrylic acid esters having a cyclic
skeleton include cycloalkyl (meth)acrylic acid esters such as
isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate;
[0539] aralkyl (meth)acrylic acid esters such as benzyl
(meth)acrylate;
[0540] cycloalkenyl (meth) acrylic acid esters such as
dicyclopentenyl (meth) acrylic acid esters;
[0541] cycloalkenyloxy alkyl (meth) acrylic acid esters such as
dicyclopentenyloxyethyl (meth) acrylic acid esters; and the
like.
[0542] Examples of the glycidyl group-containing (meth)acrylic acid
esters include glycidyl (meth)acrylate and the like.
[0543] Examples of the hydroxyl group-containing (meth)acrylic acid
esters include hydroxymethyl (meth)acrylate, 2-hydroxyethyl
(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl
(meth)acrylate, 2-hydorybutyl (meth)acrylate, 3-hydroxybutyl
(meth)acrylate, 4-hydroxybutyl (meth)acrylate, and the like.
[0544] Examples of the substituted amino group-containing
(meth)acrylic acid esters include N-methylaminoethyl (meth)acrylate
and the like.
[0545] Examples of the non-acrylic monomer constituting the acrylic
polymer (b-1) include olefins such as ethylene and norbornene;
vinyl acetate; styrene; and the like.
[0546] Examples of the polymer (b) at least a part of which is
crosslinked with a crosslinking agent and which does not have the
energy ray-curable group include polymers in which a reactive
functional group in the polymer (b) reacts with a crosslinking
agent.
[0547] The reactive functional group may be appropriately selected
depending on the type and the like of the crosslinking agent and is
not particularly limited. For example, in a case in which the
crosslinking agent is a polyisocyanate compound, examples of the
reactive functional group include a hydroxyl group, a carboxy
group, an amino group, and the like, and, among these, the hydroxyl
group that is highly reactive with isocyanate groups is preferred.
In addition, in a case in which the crosslinking agent is an
epoxy-based compound, examples of the reactive functional group
include a carboxy group, an amino group, an amide group, and the
like, and, among these, the carboxy group that is highly reactive
with epoxy groups is preferred. Here, the reactive functional group
is preferably a group other than a carboxy group from the viewpoint
of preventing the corrosion of circuits such as semiconductor
wafers or semiconductor chips.
[0548] Examples of the polymer (b) which has the reactive
functional group but does not have any energy ray-curable groups
include polymers obtained by polymerizing monomers having at least
the reactive functional group. In the case of the acrylic polymer
(b-1), as any one or both of the acrylic monomer and the
non-acrylic monomer that have been exemplified as the monomers
constituting the acrylic polymer, monomers having the reactive
functional group may be used. For example, examples of the polymer
(b) having a hydroxyl group as the reactive functional group
include polymers obtained by polymerizing hydroxyl group-containing
(meth)acrylic acid ester and also include polymers obtained by
polymerizing monomers formed by substituting one or more hydrogen
atoms in the previously exemplary examples of an acrylic monomer or
non-acrylic monomer with the reactive functional group.
[0549] In the polymer (b) having the reactive functional group, the
ratio (amount) of the amount of a constituent unit derived from a
monomer having the reactive functional group is preferably 1 to 20%
by mass and more preferably 2 to 10% by mass of the entire mass of
constituent units constituting the polymer. When the ratio is in
the above-described range, in the polymer (b), the degree of
crosslinking is in a more preferred range.
[0550] The weight-average molecular weight (Mw) of the polymer (b)
not having any energy ray-curable groups is preferably 10,000 to
2,000,000 and more preferably 100,000 to 1,500,000 since the
film-forming property of the energy ray curable resin composition
(IV-1) becomes more preferable.
[0551] Here, "the weight-average molecular weight" is as described
above.
[0552] The energy ray curable resin composition (IV-1) energy
ray-curable resin composition (IV-1) and the curable resin film 10
may contain only one type or two or more types of the polymers (b)
not having any energy ray-curable groups. In a case in which the
energy ray curable resin composition (IV-1) and the curable resin
film 10 contain two or more types of the polymers (b) not having
any energy ray-curable groups, the combination and ratio thereof
can be arbitrarily selected.
[0553] Examples of the energy ray-curable resin composition (IV-1)
include compositions containing any one or both of the polymer (a1)
and the compound (a2). In the case of containing the compound (a2),
the energy ray-curable resin composition (IV-1) preferably further
contains a polymer (b) not having an energy ray-curable group, and
in this case, the polymer (a1) is further preferably contained. In
addition, the energy ray-curable resin composition (IV-1) may
contain the polymer (a1) and the polymer (b) not having any energy
ray-curable groups without containing the compound (a2).
[0554] In a case where the energy ray-curable resin composition
(IV-1) contains the polymer (a1), the compound (a2), and the
polymer (b) not having any energy ray-curable groups, in the energy
ray-curable resin composition (IV-1), the amount of the compound
(a2) is preferably 10 to 400 parts by mass, and more preferably 30
to 350 parts by mass of the total amount (100 parts by mass) of the
polymer (a1) and the polymer (b) not having any energy ray-curable
groups.
[0555] In the energy ray-curable resin composition (IV-1), the
ratio of the total amount of the energy ray-curable component (a)
and the polymer (b) not having any energy ray-curable groups (that
is, the total amount of the energy ray-curable component (a) and
the polymer (b) not having any energy ray-curable groups in the
curable resin film 10) to the total amount of the components other
than the solvent is preferably 5% to 90% by mass, more preferably
10% to 80% by mass, and particularly preferably 20% to 70% by mass.
When the ratio of the amount of the energy ray-curable component is
in the above-described range, the energy ray-curing property of the
curable resin film 10 becomes more favorable.
[0556] The energy ray-curable resin composition (IV-1) may also
contain, in addition to the energy ray-curable component, one or
more types of elements selected from the group consisting of a
thermosetting component, a photopolymerization initiator, a filler,
a coupling agent, a crosslinking agent, and a versatile additive
depending on the purpose. For example, when the energy ray-curable
resin composition (IV-1) containing the energy ray-curable
component and a thermosetting component is used, the adhesive force
of the curable resin film 10 to be formed to adherends improves by
heating, and the strength of the first protective film 1a formed of
this curable resin film 10 also improves.
[0557] As the thermosetting component, the photopolymerization
initiator, the filler, the coupling agent, the crosslinking agent,
and the versatile additive in the energy ray-curable resin
composition (IV-1), it is possible to exemplify those which are the
same as the thermosetting component (B), the photopolymerization
initiator (H), the filler (D), the coupling agent (E), the
crosslinking agent (F), and the versatile additive (I) in the
energy ray-curable resin composition (III-1).
[0558] In the energy ray-curable resin composition (IV-1), one type
of each of the thermosetting component, the photopolymerization
initiator, the filler, the coupling agent, the crosslinking agent,
and the versatile additive may be used singly or two or more types
thereof may be jointly used, and, in a case in which two or more
types thereof are used, the combination and ratio thereof can be
arbitrarily selected.
[0559] The amounts of the thermosetting component, the
photopolymerization initiator, the filler, the coupling agent, the
crosslinking agent, and the versatile additive in the energy
ray-curable resin composition (IV-1) may be appropriately adjusted
depending on the purpose and are not particularly limited.
[0560] From the viewpoint that the handling property of the energy
ray-curable resin composition (IV-1) improves by dilution, it is
preferable that the energy ray-curable resin composition (IV-1)
further contains a solvent.
[0561] Examples of the solvent contained in the energy ray-curable
resin composition (IV-1) include the same solvent as that in the
energy ray-curable resin composition (III-1).
[0562] The energy ray-curable resin composition (IV-1) may contain
only one type or two or more types of the solvents.
[0563] {{Other Components}}
[0564] In the energy ray-curable resin composition used for the
curable resin film 10 of the present invention, in addition to the
above-described energy ray-curable component, similar to the case
of the curable resin film 1 containing the thermosetting component
described above, the components other than the curable component,
that is, an appropriate amount of a curing accelerator (C), a
filler (D), a coupling agent (E) and the like can be contained.
[0565] In addition, even in the curable resin film 10 formed of the
energy ray-curable resin composition, the same action as that of
the curable resin film 1 can be obtained by containing components
other than the above-described energy ray-curable component.
[0566] {{Method of Manufacturing of Energy Ray-Curable Resin
Composition}}
[0567] The energy ray-curable resin composition such as energy
ray-curable resin composition (IV-1) can be obtained by blending
individual components for constituting the first interlayer forming
composition.
[0568] The addition order during the blending of the respective
components is not particularly limited, and two or more types of
components may be added at the same time.
[0569] In a case in which the solvent is used, the solvent may be
used by mixing the solvent with all of the blending components
other than the solvent so as to dilute these blending components in
advance or may be used by mixing the solvent with the blending
components without diluting all of the blending components other
than the solvent in advance.
[0570] A method for mixing the respective components during
blending is not particularly limited and may be appropriately
selected from well-known methods such as a method in which the
components are mixed together by rotating a stirring stick, a
stirring blade, or the like; a method in which the components are
mixed together using a mixer, and a method in which the components
are mixed together by applying ultrasonic waves thereto.
[0571] The temperature and the time during the addition and mixing
of the respective components are not particularly limited as long
as the respective blending components do not deteriorate and may be
appropriately adjusted, but the temperature is preferably
15.degree. C. to 30.degree. C.
[0572] <<Method for Manufacturing First Protective Film
Forming Sheet>>
[0573] The first protective film forming sheets 1A and 10A can be
manufactured by sequentially stacking the respective layers
described above so as to obtain the corresponding positional
relationship. The methods for forming the respective layers are as
described above.
[0574] For example, in the manufacturing of the first supporting
sheet 11, in a case in which the first pressure-sensitive adhesive
layer or the first interlayer is stacked on the first base
material, the first pressure-sensitive adhesive layer or the first
interlayer can be stacked by applying the first pressure-sensitive
adhesive composition or the first interlayer forming composition
described above onto the first base material and drying the
composition or irradiating the composition with energy rays as
necessary.
[0575] Meanwhile, for example, in a case in which the curable resin
film is further stacked on the first pressure-sensitive adhesive
layer that has been stacked on the first base material, the curable
resin film can be directly formed by applying the thermosetting
resin composition or the energy ray-curable protective film forming
composition on the first pressure-sensitive adhesive layer.
Similarly, in a case in which the first pressure-sensitive adhesive
layer is further stacked on the first interlayer that has been
stacked on the first base material, the first pressure-sensitive
adhesive layer can be directly formed by applying the first
pressure-sensitive adhesive composition onto the first interlayer.
As described above, in a case in which a stacking structure of two
continuous layers is formed using any compositions, it is possible
to newly form a layer by further applying the composition onto a
layer formed of the above-described composition. Here, the stacking
structure of two continuous layers is preferably formed by forming,
between these two layers, the layer which is stacked from the back
on a separate peeling film in advance using the above-described
composition and attaching the exposed surface opposite to the
surface of the already-formed layer in contact with the peeling
film to the exposed surface of the other layer that has been
formed. At this time, the above-described composition is preferably
applied onto a peeling-treated surface of the peeling film. The
peeling film may be removed as necessary after the formation of the
stacking structure.
[0576] For example, in a case in which the first protective film
forming sheets (the first protective film forming sheet in which
the first supporting sheet 11 is a stacked substance of the first
base material and the first pressure-sensitive adhesive layer) 1A
and 10A formed by stacking the first pressure-sensitive adhesive
layer on the first base material and stacking the curable resin
layer on the first pressure-sensitive adhesive layer are
manufactured, first, the first pressure-sensitive adhesive
composition is applied onto the first base material and the applied
first base material is dried as necessary or being irradiated with
energy rays so as to stack the first pressure-sensitive adhesive
layer on the first base material in advance. In addition, the first
protective film forming sheets 1A and 10A can be obtained by,
separately, applying the thermosetting resin composition or the
energy ray-curable protective film forming composition onto the
peeling film and drying the applied peeling film as necessary so as
to form the curable resin film 1 containing thermosetting
components on the peeling film, and attaching the exposed surface
of the curable resin film 1 to the exposed surface of the first
pressure-sensitive adhesive layer that has been stacked on the
first base material so as to stack the curable resin films 1 and 10
on the first pressure-sensitive adhesive layer.
[0577] Further, for example, in a case where the first supporting
sheet 11 is manufactured by stacking the first interlayer on the
first base material, and stacking the first pressure-sensitive
adhesive layer on the first interlayer, first, the first interlayer
forming composition is applied on the first base material, and
dried as necessary so as to stack the first interlayer on the first
base material. In addition, separately, the first supporting sheet
11 can be obtained by applying the first pressure-sensitive
adhesive composition onto the peeling film, drying or irradiating
the first pressure-sensitive adhesive composition with energy rays
as necessary so that the first pressure-sensitive adhesive layer is
formed on the peeling film, and then attaching the exposed surface
of the first pressure-sensitive adhesive layer to the exposed
surface of the first interlayer that has been stacked on the first
base material so as to stack the first pressure-sensitive adhesive
layer on the first interlayer. In this case, the first protective
film forming sheets 1A and 10A can be obtained by, for example,
separately, further applying the thermosetting resin composition or
the energy ray-curable protective film forming composition onto the
peeling film and drying the thermosetting resin composition or the
energy ray-curable protective film forming composition as necessary
so as to form the curable resin film 1 containing the thermosetting
component on the peeling film and attaching the exposed surface of
the curable resin layer to the exposed surface of the first
pressure-sensitive adhesive layer that has been stacked on the
first interlayer so as to stack the curable resin films 1 and 10 on
the first pressure-sensitive adhesive layer.
[0578] Meanwhile, in a case in which the first pressure-sensitive
adhesive layer or the first interlayer is stacked on the first base
material, as described above, the first pressure-sensitive adhesive
layer or the first interlayer may be stacked on the first base
material by, instead of applying the first pressure-sensitive
adhesive composition or the first interlayer forming composition
onto the first base material, applying the first pressure-sensitive
adhesive composition or the first interlayer forming composition
onto the peeling film and drying the composition as necessary so as
to form the first pressure-sensitive adhesive layer or the first
interlayer on the peeling film and attaching the exposed surface of
this layer to one surface of the first base material so as to stack
the first pressure-sensitive adhesive layer or the first interlayer
on the first base material.
[0579] In any of the methods, the peeling film may be removed at an
arbitrary timing after the formation of the intended stacking
structure.
[0580] As described above, all of the layers other than the first
base material which constitute the first protective film forming
sheets 1A and 10A can be stacked using a method in which the layers
are formed on the peeling film in advance and attached on a surface
of an intended layer, and thus the first protective film forming
sheets 1A and 10A may be manufactured by appropriately selecting
layers for which the above-described steps are employed as
necessary.
[0581] Meanwhile, the first protective film forming sheets 1A and
10A is, generally, stored in a state in which the peeling film is
attached to the surface of the outermost layer (for example, the
curable resin films 1 and 10) on the opposite side to the first
supporting sheet 11. Therefore, the first protective film forming
sheets 1A and 10A can also be obtained by applying a composition
for forming a layer constituting the outermost layer such as
thermosetting resin composition or the energy ray-curable
protective film forming composition onto the peeling film
(preferably the peeling-treated surface thereof) and drying the
applied peeling film as necessary so as to form the layer
constituting the outermost layer on the peeling film, stacking the
remaining layers on the exposed surface on the opposite side to the
surface of the layer in contact with the peeling film using any of
the above-described methods, and leaving the layers in the attached
state without removing the peeling film.
[0582] <<Action and Effect>>
[0583] As described above, according to the present invention, the
curable resin film and the first protective film forming sheet
provided with the curable resin film, after optimizing the
weight-average molecular weight of the curable component contained
in the curable resin film used in for forming the first protective
film, when a dimensional relationship between of the first
protective film cured under predetermined conditions and the
plurality of bumps on a semiconductor wafer having a plurality of
bumps of a predetermined dimensional shape and arrangement
condition, and thereby the occurrence of the large distortion in
the concave shape on the first protective film disposed between the
bumps can be suppressed are appropriately defined.
[0584] With this, for example, the inspection in a step of
manufacturing a semiconductor wafer and the alignment accuracy in a
step of dicing the semiconductor wafer into a chip improve.
[0585] Therefore, the inspection accuracy and the dicing accuracy
in the manufacturing step improve, and a semiconductor package
excellent in the reliability can be manufactured.
EXAMPLES
[0586] Next, the present invention will be described in more detail
by describing examples and comparative examples.
[0587] The scope of the present invention is not limited to the
examples, and the curable resin film and the first protective film
forming sheet according to the present invention can be performed
by appropriately changing and modifying within the range without
changing the gist of the present invention.
[0588] The components used for manufacturing the thermosetting
resin composition are indicated below.
[0589] Polymer Component
[0590] Polymer component (A)-1: An acrylic resin (having a
weight-average molecular weight of 800,000 and a glass transition
temperature of -28.degree. C.) obtained by copolymerizing butyl
acrylate (hereinafter, abbreviated as "BA") (55 parts by mass),
methyl acrylate (hereinafter, abbreviated as "MA") (10 parts by
mass), glycidyl methacrylate (hereinafter, abbreviated as "GMA")
(20 parts by mass), and 2-hydroxyethyl acrylate (hereinafter,
abbreviated as "HEA") (15 parts by mass). The mixing ratio of the
respective components are indicated in the following Table 1.
[0591] Epoxy Resin
[0592] Epoxy resin (B1)-1: A liquid bisphenol F type epoxy resin
("YL 983 U" manufactured by Mitsubishi Chemical Corporation);
weight-average molecular weight=340
[0593] Epoxy resin (B1)-2: A polyfunctional aromatic type epoxy
resin ("EPPN-502H" manufactured by Nippon Kayaku Co., Ltd.);
weight-average molecular weight=1,000
[0594] Epoxy resin (B1)-3: A dicyclopentadiene type epoxy resin
("EPICLON HP-7200" manufactured by DIC Corporation); weight-average
molecular weight=600
[0595] Thermal Curing Agent
[0596] Thermal curing agent (B2)-1: A novolac-type phenolic resin
("BRG-556" manufactured by Showa Denko KK)
[0597] Curing Accelerator
[0598] Curing accelerator (C)-1:
2-phenyl-4,5-dihydroxymethylimidazole ("Curezol 2 PHZ-PW"
manufactured by Shikoku Chemicals Corporation)
[0599] Filler
[0600] Filler (D)-1: A spherical silica modified with an epoxy
group ("Admanano YA 050 C-MKK" manufactured by Admatechs); 0.05
.mu.m (average particle diameter); 19% by mass (content ratio in
thermosetting resin composition)
Example 1
[0601] <Manufacturing of First Protective Film Forming Sheet
(Curable Resin Film)>
[0602] (Manufacturing of Thermosetting Resin Composition)
[0603] The polymer component (A)-1, the epoxy resin (B1)-1, the
epoxy resin (B1)-2, the epoxy resin (B1)-3, the thermal curing
agent (B2)-1, the curing accelerator (C)-1, and the filler (D)-1
were dissolved and dispersed in methyl ethyl ketone such that the
ratio of the amount to the total amount of all components other
than the solvent is the value indicated in the following Table 1
(described as "content ratio" in Table 1), and stirred at
23.degree. C. so as to obtain a thermosetting resin composition
(III-1) having a solid content concentration of 55% by mass as a
thermosetting resin composition.
[0604] (Manufacturing of Pressure-Sensitive Adhesive Resin
(I-2a))
[0605] 2-ethylhexyl acrylate (hereinafter, abbreviated as "2EHA")
(80 parts by mass) and HEA (20 parts by mass) were set as raw
materials of a copolymer, and then a polymerization reaction was
performed so as to obtain an acrylic polymer.
[0606] 2-methacryloyloxyethyl isocyanate (hereinafter, abbreviated
as "MOI") (22 parts by mass, approximately 80 mol % to HEA) was
added to the acrylic polymer, and an addition reaction was
performed at 50.degree. C. for 48 hours in an air stream so as to
obtain a target pressure-sensitive adhesive resin (I-2a).
[0607] (Manufacturing of First Pressure-Sensitive Adhesive
Composition)
[0608] As an isocyanate crosslinking agent, a tolylene diisocyanate
trimer adduct of trimethylolpropane was added to the
pressure-sensitive adhesive resin (I-2a) (100 parts by mass)
obtained above, ("Coronate L" manufactured by Tosoh Corporation)
(0.5 parts by mass) and stirred at 23.degree. C. so as to obtain a
first pressure-sensitive adhesive composition (I-2) having a solid
content concentration of 30% by mass, as the first
pressure-sensitive adhesive composition. Note that, the number of
compounding parts in this "Manufacturing of First
Pressure-Sensitive Adhesive Composition" is all in terms of solid
content.
[0609] (Manufacturing of First Protective Film Forming Sheet)
[0610] The above-obtained first pressure-sensitive adhesive
composition was applied onto a peeling-treated surface of a peeling
film ("SP-PET381031" manufactured by Lintec Corporation, thickness:
38 .mu.m) obtained by carrying out a peeling treatment on a single
surface of a polyethylene terephthalate film with a silicone
treatment and was heated and dried at 120.degree. C. for 2 minutes,
thereby forming a 100 .mu.m-thick first pressure-sensitive adhesive
layer.
[0611] Next, a 105 .mu.m-thick stacked film formed by stacking a
polyolefin film (thickness: 25 .mu.m), an adhesive layer
(thickness: 2.5 .mu.m), a polyethylene terephthalate film
(thickness: 50 .mu.m), an adhesive layer (thickness: 2.5 .mu.m),
and a polyolefin film (thickness: 25 .mu.m) in this order was
attached as a first base material to an exposed surface of the
first pressure-sensitive adhesive layer in one pressure-sensitive
adhesive sheet, thereby obtaining a first supporting sheet.
[0612] The above-obtained thermosetting resin composition was
applied onto a peeling-treated surface of a peeling film
("SP-PET381031" manufactured by Lintec Corporation, thickness: 38
.mu.m) obtained by carrying out a peeling treatment on a single
surface of a polyethylene terephthalate film with a silicone
treatment and was dried at 100.degree. C. for 2 minute, thereby
forming a 40 .mu.m-thick thermosetting curable resin film.
[0613] Next, the peeling film was removed from the first
pressure-sensitive adhesive layer of the above-obtained first
supporting sheet, an exposed surface of the curable resin film
obtained above was attached to an exposed surface of the first
pressure-sensitive adhesive layer, thereby obtaining the first
protective film forming sheet formed by stacking the first base
material, the first pressure-sensitive adhesive layer, the curable
resin film, and the peeling film in this order in the thickness
direction.
[0614] <Evaluation of Semiconductor Wafer after Forming
Protective Film>
[0615] (Confirmation of Distortion after Curing Curable Resin Film
to Form Protective Film)
[0616] The first protective film is formed on the bump-formed
surface of the semiconductor wafer by using the curable resin film
(the first protective film forming sheet) obtained above
description.
[0617] That is, first, the back surface protective film was
attached to the back surface side of the semiconductor wafer
provided with the plurality of bumps on the surface, the first
protective film forming sheet was attached to the surface side, and
the back surface protective film, the semiconductor wafer, and the
first protective film forming sheet (curable resin film) were
sequentially stacked so as to manufacture a stacked body.
[0618] Next, the first pressure-sensitive adhesive layer was
exposed by peeling the first supporting sheet from the back surface
protective sheet, and the first supporting sheet was attached to an
upper surface of a ring frame for wafer dicing such that a stacked
body (semiconductor wafer) was fixed and the first supporting sheet
was peeled from the first protective film forming sheet.
[0619] Subsequently, while applying a pressure of 0.5 MPa to the
curable resin film on the semiconductor wafer fixed to the ring
frame for wafer dicing, using a pressure and thermal curing
apparatus ("RAD-9100" manufactured by Lintec Corporation), the
curable resin film was heated at a set temperature of 180.degree.
C. for one hour so as to be softened and then cured so as to form
the first protective film.
[0620] In addition, when the longitudinal section of the
semiconductor wafer after forming the protective film was observed
by the scanning electron microscope, and as shown in FIGS. 1A and
1B, the average peak height h1 of the plurality of bumps, the
average thickness h2 of the first protective film at the position
being in contact with the plurality of bumps, and the average
thickness h3 of the first protective film at the center position
between the plurality of bumps were measured by image analysis with
the scanning electron microscope. Further, from these h1 to h3,
"the ratio (h3/h1) of the average thickness h3 of the first
protective film at the center position between the plurality of
bumps to the average peak height h1 of the plurality of bumps" and
"the ratio (h2/h1) of the average thickness h2 of the first
protective film at the position being in contact with the plurality
of bumps to the average peak height h1 of the plurality of bumps"
were calculated, and the results are indicated in Table 2.
[0621] As indicated in the following Table 2, in Example 1, it was
possible to confirmed that after forming the first protective film
by curing the curable resin film, the ratio (h3/h1) of the average
thickness h3 of the first protective film at the center position
between the plurality of bumps to the average peak height h1 of the
plurality of bumps, and the ratio (h2/h1) of the average thickness
h2 of the first protective film at the position being in contact
with the plurality of bumps satisfied the relationship represented
by the following expression {{(h2/h1)-(h3/h1)}.ltoreq.0.1}. In
Example 1, it was possible to confirm that the value calculated on
the left side of the above expression was 0.06, and a flat-like
first protective film in which the distortion is suppressed was
formed.
Manufacture and Evaluation of First Protective Film Forming
Sheet
Example 2 and Comparative Examples
[0622] A first protective film forming sheet of Example 2 was
manufactured by using the same method as that used in Example 1
except that the thickness of the first pressure-sensitive adhesive
layer on the first protective film forming sheet was set to be 80
.mu.m, and the thickness of the curable resin film was set to be 60
.mu.m, and the evaluation was performed as described above. The
results are indicated in Table 2.
[0623] Further, a first protective film forming sheet of
Comparative Example 1 was manufactured by using the same method as
that used in Example 1 except that the thickness of the first
pressure-sensitive adhesive layer on the first protective film
forming sheet was set to be 60 .mu.m, and the thickness of the
curable resin film was set to be 80 .mu.m, and the evaluation was
performed as described above. The results are indicated in Table
2.
[0624] As indicated in the following Table 2, in Example 2, it was
possible to confirmed that after forming the first protective film
by curing the curable resin film, the ratio (h3/h1) of the average
thickness h3 of the first protective film at the center position
between the plurality of bumps to the average peak height h1 of the
plurality of bumps, and the ratio (h2/h1) of the average thickness
h2 of the first protective film at the position being in contact
with the plurality of bumps satisfied the relationship represented
by the following expression {{(h2/h1)-(h3/h1)}.ltoreq.0.1}. In
addition, in Example 2, it was possible to confirm that the value
calculated on the left side of the above expression was 0.09, and
the first protective film on which a large distortion in a concave
shape was suppressed was formed.
[0625] In contrast, in comparative examples, the above-described
(h3/h1) and (h2/h1) did not satisfy the next expression
{{(h2/h1)-(h3/h1)}.ltoreq.0.1}. In the comparative examples, it was
possible to confirm that the value calculated on the left side of
the above expression was 0.19, and a large distortion in a concave
shape occurred.
TABLE-US-00001 TABLE 1 Examples 1, 2, Comparative Example Contained
component (ratio of the content Polymer component (A)-1 100 (parts
by mass)) of thermosetting resin Epoxy resin (B1)-1 135 composition
(B1)-2 90 (B1)-3 150 Thermal curing agent (B2)-1 180 Curing
accelerator (C)-1 1 Filler (D)-1 160
TABLE-US-00002 TABLE 2 Examples Comparative 1 2 Example First
protective film Curable resin film Thickness (.mu.m) 40 60 80
forming sheet Weight-average molecular 340~1,000 340~1,000
340~1,000 weight of curable component Average particle diameter of
0.05 0.05 0.05 filler (D) (.mu.m) Amount of filler (D) (% by mass)
19 19 19 First supporting sheet Thickness (.mu.m) 105 105 105 First
pressure-sensitive adhesive Thickness (.mu.m) 100 80 60 layer
Evaluation results Height h1 of bump (.mu.m) 200 200 200 Average
thickness h2 of first protective film at position being 116 144 176
in contact with a plurality of bumps (.mu.m) Average thickness h3
of first protective film at center 104 126 138 position between
with a plurality of bumps (.mu.m) (h2/h1) - (h3/h1) 0.06 0.09
0.19
[0626] From the results of the above-described examples, as defined
in the present invention, after optimizing the weight-average
molecular weight of the curable component contained in the curable
resin film used in for forming the first protective film, when a
dimensional relationship between of the first protective film cured
under predetermined conditions and the plurality of bumps on a
semiconductor wafer having the plurality of bumps of a
predetermined dimensional shape and arrangement condition are
appropriately set, and thereby the occurrence of the large
distortion in the concave shape on the first protective film
disposed between the bumps can be suppressed. Therefore, it is
possible to improve the inspection accuracy and the dicing accuracy
in the manufacturing step and to manufacture a semiconductor
package excellent in the reliability.
INDUSTRIAL APPLICABILITY
[0627] The present invention can be used for manufacturing a
semiconductor chip or the like having a bump at a connection pad
portion used in a flip chip mounting method.
REFERENCE SIGNS LIST
[0628] 1,10 . . . CURABLE RESIN FILM [0629] 1a . . . FIRST
PROTECTIVE FILM [0630] 1A, 1B, 1C . . . FIRST PROTECTIVE FILM
FORMING SHEET, [0631] 11, 11A, 11B . . . FIRST SUPPORTING SHEET
[0632] 11a . . . ONE SURFACE (FIRST SUPPORTING SHEET) [0633] 12 . .
. FIRST BASE MATERIAL, [0634] 12a . . . SURFACE (FIRST BASE
MATERIAL) [0635] 13 . . . FIRST PRESSURE-SENSITIVE ADHESIVE LAYER,
[0636] 13a . . . SURFACE (FIRST PRESSURE-SENSITIVE ADHESIVE LAYER),
[0637] 14 . . . FIRST INTERLAYER, [0638] 5 . . . SEMICONDUCTOR
WAFER, [0639] 5a . . . SURFACE (BUMP-FORMED SURFACE: CIRCUIT
SURFACE), [0640] 5b . . . BACK SURFACE [0641] 51 . . . BUMP, [0642]
51a . . . SURFACE (SURFACE OF BUMP)
* * * * *