U.S. patent application number 17/248005 was filed with the patent office on 2021-07-08 for method for manufacturing electronic component, resin composition for temporary fixing, resin film for temporary fixing, and resin film sheet for temporary fixing.
The applicant listed for this patent is Showa Denko Materials Co., Ltd.. Invention is credited to Manabu Ishii, Tatsuya Makino, Shogo Sobue, Takahiro Tokuyasu.
Application Number | 20210206149 17/248005 |
Document ID | / |
Family ID | 1000005464458 |
Filed Date | 2021-07-08 |
United States Patent
Application |
20210206149 |
Kind Code |
A1 |
Makino; Tatsuya ; et
al. |
July 8, 2021 |
METHOD FOR MANUFACTURING ELECTRONIC COMPONENT, RESIN COMPOSITION
FOR TEMPORARY FIXING, RESIN FILM FOR TEMPORARY FIXING, AND RESIN
FILM SHEET FOR TEMPORARY FIXING
Abstract
A method for manufacturing an electronic component, includes: a
step of temporarily fixing onto a support body a workpiece to
become a member constituting an electronic component, via a
film-like temporary fixing material; a step of processing the
workpiece which is temporarily fixed onto the support body; and a
step of separating the processed workpiece from the support body
and the film-like temporary fixing material, and the film-like
temporary fixing material contains an (meth)acrylic copolymer (A)
having a not unevenly distributed reactive functional group.
Inventors: |
Makino; Tatsuya; (Tokyo,
JP) ; Sobue; Shogo; (Tokyo, JP) ; Tokuyasu;
Takahiro; (Tokyo, JP) ; Ishii; Manabu; (Tokyo,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Showa Denko Materials Co., Ltd. |
Tokyo |
|
JP |
|
|
Family ID: |
1000005464458 |
Appl. No.: |
17/248005 |
Filed: |
January 5, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
15778775 |
May 24, 2018 |
10913248 |
|
|
PCT/JP2016/084800 |
Nov 24, 2016 |
|
|
|
17248005 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01L 2221/68381
20130101; H01L 2225/06541 20130101; H01L 2221/68327 20130101; C08L
2203/20 20130101; C09D 133/066 20130101; H01L 2224/03002 20130101;
C09D 133/08 20130101; C08K 5/14 20130101; B32B 2037/1253 20130101;
H01L 21/02057 20130101; H01L 2221/68386 20130101; C08K 5/0025
20130101; H01L 2225/06513 20130101; H01L 2224/94 20130101; B32B
27/308 20130101; B32B 37/12 20130101; C08L 83/04 20130101; H01L
2224/05009 20130101; C08K 5/3445 20130101; B32B 38/10 20130101;
B32B 27/08 20130101; H01L 2225/06565 20130101; H01L 21/6835
20130101; H01L 2225/06517 20130101; H01L 21/304 20130101; H01L
21/683 20130101; C08L 33/10 20130101; B32B 2309/02 20130101 |
International
Class: |
B32B 27/08 20060101
B32B027/08; H01L 21/02 20060101 H01L021/02; H01L 21/304 20060101
H01L021/304; C09D 133/08 20060101 C09D133/08; C09D 133/06 20060101
C09D133/06; H01L 21/683 20060101 H01L021/683; B32B 27/30 20060101
B32B027/30; C08K 5/3445 20060101 C08K005/3445; C08L 33/10 20060101
C08L033/10; C08L 83/04 20060101 C08L083/04 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 26, 2015 |
JP |
2015-230594 |
Nov 26, 2015 |
JP |
2015-230597 |
Claims
1. A method for manufacturing an electronic component, comprising:
a step of temporarily fixing onto a support body a workpiece to
become a member constituting an electronic component, via a
film-like temporary fixing material; a step of processing the
workpiece which is temporarily fixed onto the support body; and a
step of separating the processed workpiece from the support body
and the film-like temporary fixing material, wherein the film-like
temporary fixing material contains an (meth)acrylic copolymer (A)
having a not unevenly distributed reactive functional group.
2. The method for manufacturing an electronic component according
to claim 1, wherein the film-like temporary fixing material is
provided by laminating a resin film for temporary fixing containing
the (meth)acrylic copolymer (A) having a not unevenly distributed
reactive functional group on the workpiece or the support body.
3. The method for manufacturing an electronic component according
to claim 1, wherein the (meth)acrylic copolymer (A) having a not
unevenly distributed reactive functional group contains a
(meth)acrylic monomer (a-1) in which a glass transition temperature
of an homopolymer is higher than or equal to 50.degree. C., a
(meth)acrylic monomer (a-2) in which a glass transition temperature
of an homopolymer is lower than or equal to 0.degree. C., and a
(meth)acrylic monomer (a-3) having an reactive functional group, as
a copolymer component.
4. The method for manufacturing an electronic component according
to claim 3, wherein the (meth)acrylic monomer (a-2) in which the
glass transition temperature of the homopolymer is lower than or
equal to 0.degree. C. is a (meth)acrylic monomer having an alkyl
group of which the number of carbon atoms is 6 to 20.
5. The method for manufacturing an electronic component according
to claim 1 wherein the reactive functional group is an epoxy
group.
6. The method for manufacturing an electronic component according
to claim 5, wherein the film-like temporary fixing material further
contains an epoxy curing agent (B).
7. The method for manufacturing an electronic component according
to claim 6, wherein the epoxy curing agent (B) is an
imidazole-based curing agent.
8. The method for manufacturing an electronic component according
to claim 1, wherein the film-like temporary fixing material further
contains a silicone compound (C).
9. The method for manufacturing an electronic component according
to claim 8, wherein the silicone compound (C) is a silicone
modified alkyd resin.
10. The method for manufacturing an electronic component according
to claim 1, wherein the film-like temporary fixing material is
formed of two or more layers, and at least a layer in contact with
the workpiece contains the (meth)acrylic copolymer (A) having a not
unevenly distributed reactive functional group.
11.-23. (canceled)
Description
TECHNICAL FIELD
[0001] The present invention relates to a method for manufacturing
an electronic component, and more specifically, relates to a method
for manufacturing an electronic component including a step of
processing a workpiece which is temporarily fixed onto a support
body by using a temporary fixing material. In addition, the present
invention relates to a resin composition for temporary fixing, a
resin film for temporary fixing, and a resin film sheet for
temporary fixing, which are used at the time of manufacturing an
electronic component.
BACKGROUND ART
[0002] In the field of the electronic component, the growth of a
technology relevant to a package referred to as a system in package
(SIP) in which a plurality of semiconductor elements are stacked is
remarkable. In the SIP type package, a plurality of semiconductor
elements are laminated, and thus, the thickness of the
semiconductor element is required to be maximally small Such a
semiconductor element, for example, is preferably by building an
integrated circuit in a semiconductor wafer having a constant
thickness, and then, by segmenting the semiconductor wafer which is
thinned by grinding a rear surface of the semiconductor wafer. The
semiconductor wafer is processed by temporarily fixing the
semiconductor wafer onto the support body with the temporary fixing
material (for example, refer to Patent Literature 1).
[0003] A wire bonding method of the related art is a mainstream in
the connection of the semiconductor element, but recently, a
connection method referred to as a silicon through electrode (TSV)
has attracted attention and has been actively studied. In the case
of preparing a semiconductor element including a through electrode,
the semiconductor wafer is thinned, and then, a process of forming
the through electrode is further performed. In this case, a high
temperature process of heating the semiconductor wafer up to
approximately 300.degree. C., is performed.
[0004] In addition, a method of preparing a wafer level package by
flip chip mounting a semiconductor chip on the thinned
semiconductor wafer has also attracted attention. In a flip chip
mounting process, it is necessary to perform heating up to higher
than or equal to 260.degree. C., in order to melt a solder.
CITATION LIST
Patent Literature
[0005] Patent Literature 1: International Publication No.
2008/045669 Pamphlet
SUMMARY OF INVENTION
Technical Problem
[0006] For this reason, the temporary fixing material which is used
in a manufacturing step described above is required to have
adhesiveness of rigidly fixing the semiconductor wafer onto the
support body at the time of grinding the semiconductor wafer and of
mounting the semiconductor wafer onto the semiconductor wafer, and
heat resistance in the high temperature process. On the other hand,
the temporary fixing material is required to have peeling
properties capable of easily separating the semiconductor wafer
after processing, from the support body. In particular, it is
required that the semiconductor wafer can be separated from the
support body at a maximally low temperature such that damage and
warpage do not occur on the semiconductor chip, and the temporary
fixing material does not remain on the semiconductor wafer.
[0007] The temporary fixing material described in Patent Literature
1 tends to have insufficient heat resistance with respect to the
high temperature process at the time of forming the through
electrode on the semiconductor wafer and the high temperature
process at the time of connecting the semiconductor wafers
together, on which the through electrode is formed. In a case where
the heat resistance of the temporary fixing material is not
sufficient, the temporary fixing material is thermally decomposed
in the high temperature process, and the semiconductor wafer is
easily peeled off from the support body.
[0008] It is considered that a resin having excellent general heat
resistance, such as polyimide having a high glass transition
temperature (Tg), is used. However, in a case where the temporary
fixing material is formed into the shape of a film in order to
easily ensure flatness at the time of processing, the glass
transition temperature of the resin is high, and thus, it is
necessary to perform pasting at a high temperature in order to
sufficiently fix the semiconductor wafer onto the support body, and
there is a possibility that damage occurs on the semiconductor
wafer. For this reason, the film-like temporary fixing material is
required to have low temperature pasting properties capable of
embedding a difference on the semiconductor wafer without a gap
even in the case of being pasted at a low temperature, and of
sufficiently fixing the semiconductor wafer onto the support
body.
[0009] In consideration of the circumstances described above, an
object of the present invention is to provide a resin composition
for temporary fixing capable of forming a film-like temporary
fixing material which has excellent low temperature pasting
properties and sufficient heat resistance, is capable of
sufficiently fixing a workpiece such as a semiconductor chip or a
semiconductor wafer onto a support body, and is capable of easily
separating the workpiece after processing from the support body and
the temporary fixing material, and a resin film for temporary
fixing and a resin film sheet for temporary fixing using the resin
composition for temporary fixing.
[0010] In addition, another object of the present invention is to
provide a method for manufacturing an electronic component using a
film-like temporary fixing material which has sufficient heat
resistance, is capable of sufficiently fixing a workpiece such as a
semiconductor chip or a semiconductor wafer onto a support body,
and is capable of easily separating the workpiece after processing
from the support body and the temporary fixing material.
Solution to Problem
[0011] The present invention provides a first method for
manufacturing an electronic component, including: a step of
temporarily fixing onto a support body a workpiece to become a
member constituting an electronic component, via a film-like
temporary fixing material; a step of processing the workpiece which
is temporarily fixed onto the support body; and a step of
separating the processed workpiece from the support body and the
film-like temporary fixing material, in which the film-like
temporary fixing material contains an (meth)acrylic copolymer (A)
having a not unevenly distributed reactive functional group.
[0012] In the present invention, the (meth)acrylic copolymer having
a not unevenly distributed reactive functional group indicates a
(meth)acrylic copolymer in which the reactive functional group
contained in the (meth)acrylic copolymer is not unevenly
distributed in a polymer chain. Furthermore, in a (meth)acrylic
monomer having a reactive functional group other than a
(meth)acryloyl group, a reaction rate is fast, and thus, the
(meth)acrylic monomer is preferentially subjected to a reaction at
the time of performing copolymerization, and as a result thereof,
the reactive group is unevenly distributed in the polymer chain.
The present inventors have found that a strength of the film-like
temporary fixing material is improved, and heat resistance and
peeling properties are improved by using the (meth)acrylic
copolymer in which the reactive functional group is not unevenly
distributed, compared to the case of a (meth)acrylic copolymer
obtained by a synthesis method of the related art, in which a
reactive group is unevenly distributed.
[0013] The film-like temporary fixing material described above
contains the (meth)acrylic copolymer (A) having a not unevenly
distributed reactive functional group, and thus, has sufficient
heat resistance, is capable of sufficiently fixing the workpiece
such as a semiconductor chip or a semiconductor wafer onto the
support body, and is capable of easily separating the workpiece
after processing from the support body and the temporary fixing
material. Accordingly, it is possible to efficiently process the
workpiece such as a semiconductor chip or a semiconductor wafer.
The method for manufacturing an electronic component according to
the present invention, using such a film-like temporary fixing
material, is capable of efficiently manufacturing an electronic
component such as an SIP type package.
[0014] In addition, the present invention provides a second method
for manufacturing an electronic component, including: a step of
temporarily fixing onto a support body a workpiece to become a
member constituting an electronic component, via a film-like
temporary fixing material; a step of processing the workpiece which
is temporarily fixed onto the support body; and a step of
separating the processed workpiece from the support body and the
film-like temporary fixing material, in which the film-like
temporary fixing material contains (i) a (meth)acrylic copolymer
(i) obtained by performing living radical polymerization with
respect to a polymerizable composition containing a (meth)acrylic
monomer (a-1) in which a glass transition temperature of an
homopolymer is higher than or equal to 50.degree. C., a
(meth)acrylic monomer (a-2) in which a glass transition temperature
of an homopolymer is lower than or equal to 0.degree. C., and a
(meth)acrylic monomer (a-3) having an reactive functional group, or
(ii) a (meth)acrylic copolymer (ii) obtained by performing
polymerization while adding the (meth)acrylic monomer (a-3) having
the reactive functional group into a polymerizable composition
containing the (meth)acrylic monomer (a-1) in which the glass
transition temperature of the homopolymer is higher than or equal
to 50.degree. C., and the (meth)acrylic monomer (a-2) in which the
glass transition temperature of the homopolymer is lower than or
equal to 0.degree. C.
[0015] The film-like temporary fixing material contains the
(meth)acrylic copolymer (i) or the (meth)acrylic copolymer (ii),
and thus, has sufficient heat resistance, is capable of
sufficiently fixing the workpiece such as a semiconductor chip or a
semiconductor wafer onto the support body, and is capable of easily
separating the workpiece after processing from the support body and
the temporary fixing material. Accordingly, it is possible to
efficiently process the workpiece such as a semiconductor chip or a
semiconductor wafer.
[0016] In the first or second method for manufacturing an
electronic component according to the present invention, the
film-like temporary fixing material can be provided by laminating
the (meth)acrylic copolymer (A) having a not unevenly distributed
reactive functional group, or the resin film for temporary fixing
containing the (meth)acrylic copolymer (i) or the (meth)acrylic
copolymer (ii) on the workpiece or the support body.
[0017] Here, using a resin having excellent general heat
resistance, such as polyimide having a high glass transition
temperature (Tg), is considered as a method of improving heat
resistance of the temporary fixing material. However, in a case
where the temporary fixing material is formed into the shape of a
film in order to easily ensure flatness at the time of processing,
the glass transition temperature of the resin is high, and thus, it
is necessary to perform pasting at a high temperature in order to
sufficiently fix the semiconductor wafer onto the support body, and
there is a possibility that damage occurs on the semiconductor
wafer. In contrast, the resin film for temporary fixing described
above contains the (meth)acrylic copolymer (A) having a not
unevenly distributed reactive functional group, or the
(meth)acrylic copolymer (i) or the (meth)acrylic copolymer (ii),
and thus, is capable of having low temperature pasting properties
capable of embedding a difference on the semiconductor wafer
without a gap even in the case of being pasted at a low
temperature, and of sufficiently fixing the semiconductor wafer
onto the support body, and is capable of making heat resistance and
low temperature pasting properties compatible in a high level. By
using such a resin film for temporary fixing, it is possible to
more efficiently manufacture the electronic component such as an
SIP type package.
[0018] In the first method for manufacturing of an electronic
component according to the present invention, it is preferable that
the (meth)acrylic copolymer (A) having a not unevenly distributed
reactive functional group contained in the film-like temporary
fixing material, contains a (meth)acrylic monomer (a-1) in which a
glass transition temperature of an homopolymer is higher than or
equal to 50.degree. C., a (meth)acrylic monomer (a-2) in which a
glass transition temperature of an homopolymer is lower than or
equal to 0.degree. C., and a (meth)acrylic monomer (a-3) having an
reactive functional group, as a copolymer component, from the
viewpoint of improving heat resistance and peeling properties.
[0019] In the first or second method for manufacturing an
electronic component according to the present invention, it is
preferable that the (meth)acrylic monomer (a-2) in which the glass
transition temperature of the homopolymer is lower than or equal to
0.degree. C., is a (meth)acrylic monomer having an alkyl group of
which the number of carbon atoms is 6 to 20, from the viewpoint of
improving peeling properties.
[0020] In the first or second method for manufacturing an
electronic component according to the present invention, it is
preferable that the reactive functional group contained in the
(meth)acrylic copolymer (A) having a not unevenly distributed
reactive functional group, or the reactive functional group of the
(meth)acrylic monomer (a-3) having the reactive functional group is
an epoxy group, from the viewpoint of improving heat
resistance.
[0021] In this case, the film-like temporary fixing material
described above is capable of further containing an epoxy curing
agent (B), from the viewpoint of improving curing properties, heat
resistance, and peeling properties.
[0022] It is preferable that the epoxy curing agent (B) described
above is an imidazole-based curing agent, from the viewpoint of
further improving the curing properties.
[0023] In the first or second method for manufacturing an
electronic component according to the present invention, the
film-like temporary fixing material described above is capable of
further containing a silicone compound (C), from the viewpoint of
improving peeling properties of the film-like temporary fixing
material. In this case, it is possible to easily separate the
workpiece after processing from the support body and the temporary
fixing material without using a solvent.
[0024] It is preferable that the silicone compound (C) described
above is a silicone modified alkyd resin, from the viewpoint of
improving compatibility with respect to the component (A), or the
component (i) or the component (ii), and heat resistance and
peeling properties of the film-like temporary fixing material.
[0025] In the first or second method for manufacturing an
electronic component according to the present invention, the
film-like temporary fixing material described above can be formed
of two or more layers, and at least a layer in contact with the
workpiece is capable of containing the component (A) described
above, or the component (i) described above or the component (ii)
described above. In this case, it is possible to have a difference
in a peeling strength or an elastic modulus on each layer, and
thus, it is possible to selectively peel off a peeling
interface.
[0026] In addition, the present invention provides a first resin
composition for temporary fixing for forming a film-like temporary
fixing material which is used for manufacturing an electronic
component, in which a method for manufacturing the electronic
component includes a step of temporarily fixing onto a support body
a workpiece to become a member constituting an electronic
component, via the film-like temporary fixing material, a step of
processing the workpiece which is temporarily fixed onto the
support body, and a step of separating the processed workpiece from
the support body and the film-like temporary fixing material, and
the film-like temporary fixing material contains an (meth)acrylic
copolymer (A) having a not unevenly distributed reactive functional
group.
[0027] In addition, the present invention provides a second resin
composition for temporary fixing for forming a film-like temporary
fixing material which is used for manufacturing an electronic
component, in which a method for manufacturing the electronic
component includes a step of temporarily fixing onto a support body
a workpiece to become a member constituting an electronic
component, via the film-like temporary fixing material, a step of
processing the workpiece which is temporarily fixed onto the
support body, and a step of separating the processed workpiece from
the support body and the film-like temporary fixing material, and
the resin composition for temporary fixing contains, (i) a
(meth)acrylic copolymer (i) obtained by performing living radical
polymerization with respect to a polymerizable composition
containing a (meth)acrylic monomer (a-1) in which a glass
transition temperature of an homopolymer is higher than or equal to
50.degree. C., a (meth)acrylic monomer (a-2) in which a glass
transition temperature of an homopolymer is lower than or equal to
0.degree. C., and a (meth)acrylic monomer (a-3) having an reactive
functional group, or (ii) a (meth)acrylic copolymer (ii) obtained
by performing polymerization while adding the (meth)acrylic monomer
(a-3) having the reactive functional group into a polymerizable
composition containing the (meth)acrylic monomer (a-1) in which the
glass transition temperature of the homopolymer is higher than or
equal to 50.degree. C., and the (meth)acrylic monomer (a-2) in
which the glass transition temperature of the homopolymer is lower
than or equal to 0.degree. C.
[0028] According to the first and second resin compositions for
temporary fixing according to the present invention, it is possible
to form a film-like temporary fixing material which has excellent
low temperature pasting properties and sufficient heat resistance,
and is capable of sufficiently fixing the workpiece such as a
semiconductor chip or a semiconductor wafer onto the support body.
The film-like temporary fixing material is capable of easily
separating the workpiece after processing from the support body,
and of being easily peeled off from the workpiece after processing,
and thus, it is possible to easily separate the workpiece after
processing from the support body and the temporary fixing
material.
[0029] In the first resin composition for temporary fixing
according to the present invention, it is preferable that the
(meth)acrylic copolymer (A) having a not unevenly distributed
reactive functional group contains a (meth)acrylic monomer (a-1) in
which a glass transition temperature of an homopolymer is higher
than or equal to 50.degree. C., a (meth)acrylic monomer (a-2) in
which a glass transition temperature of an homopolymer is lower
than or equal to 0.degree. C., and a (meth)acrylic monomer (a-3)
having an reactive functional group, as a copolymer component, from
the viewpoint of improving heat resistance and peeling
properties.
[0030] In the first or second resin composition for temporary
fixing according to the present invention, it is preferable that
the (meth)acrylic monomer (a-2) in which the glass transition
temperature of the homopolymer is lower than or equal to 0.degree.
C., is a (meth)acrylic monomer having an alkyl group of which the
number of carbon atoms is 6 to 20, from the viewpoint of improving
peeling properties.
[0031] In the first or second resin composition for temporary
fixing according to the present invention, it is preferable that
the reactive functional group contained in the (meth)acrylic
copolymer (A) having a not unevenly distributed reactive functional
group, or the reactive functional group of the (meth)acrylic
monomer (a-3) having the reactive functional group is an epoxy
group, from the viewpoint of improving heat resistance.
[0032] The first or second resin composition for temporary fixing
according to the present invention is capable of further containing
an epoxy curing agent (B), from the viewpoint of improving curing
properties, heat resistance, and peeling properties.
[0033] It is preferable that the epoxy curing agent (B) described
above is an imidazole-based curing agent, from the viewpoint of
further improving the curing properties.
[0034] The first or second resin composition for temporary fixing
according to the present invention is capable of further containing
a silicone compound (C), from the viewpoint of improving peeling
properties of the film-like temporary fixing material to be formed.
In this case, it is possible to easily separate the workpiece after
processing from the support body and the temporary fixing material
without using a solvent.
[0035] It is preferable that the silicone compound (C) described
above is a silicone modified alkyd resin, from the viewpoint of
improving compatibility with respect to the component (A), or the
component (i) or the component (ii), and heat resistance and
peeling properties of the film-like temporary fixing material to be
formed.
[0036] In addition, the present invention provides a resin film for
temporary fixing configured by forming first or second resin
composition for temporary fixing according to the present invention
into the shape of a film. By using such a resin film for temporary
fixing, it is possible to efficiently process the workpiece such as
a semiconductor chip or a semiconductor wafer. Accordingly, it is
possible to efficiently manufacture an electronic component such as
an SIP type package.
[0037] In addition, the present invention provides a first resin
film sheet for temporary fixing, including: a support film; and the
first or the second resin film for temporary fixing according to
the present invention, which is disposed on the support film.
According to the first resin film sheet for temporary fixing
according to the present invention, it is possible to easily
transfer the resin film for temporary fixing according to the
present invention onto the workpiece or the support body, and to
efficiently process the workpiece.
[0038] In addition, the present invention provides a second resin
film sheet for temporary fixing, including: a support film; a first
thermoplastic resin layer configured by forming the first or the
second resin composition for temporary fixing according to the
present invention, which is disposed on the support film, into the
shape of a film; and a second thermoplastic resin layer disposed on
the first thermoplastic resin layer. According to the second resin
film sheet for temporary fixing according to the present invention,
it is possible to have a difference in a peeling strength or an
elastic modulus on each layer, and thus, it is possible to
selectively peel off a peeling interface.
Advantageous Effects of Invention
[0039] According to the present invention, it is possible to
provide a method for manufacturing an electronic component using a
film-like temporary fixing material which has sufficient heat
resistance, is capable of sufficiently fixing the workpiece such as
a semiconductor chip or a semiconductor wafer onto the support
body, and is capable of easily separating the workpiece after
processing from the support body and the temporary fixing
material.
[0040] In addition, according to the present invention, it is
possible to provide a resin composition for temporary fixing for
forming a film-like temporary fixing material, which has excellent
low temperature pasting properties and sufficient heat resistance,
is capable of sufficiently fixing the workpiece such as a
semiconductor chip or a semiconductor wafer onto the support body,
and is capable of easily separating the workpiece after processing
from the support body and the temporary fixing material, and a
resin film for temporary fixing and a resin film sheet for
temporary fixing using the resin composition for temporary
fixing.
BRIEF DESCRIPTION OF DRAWINGS
[0041] FIG. 1A, FIG. 1B, and FIG. 1C are schematic sectional views
for illustrating one embodiment of a processing method of a
semiconductor wafer according to the present invention, and FIG. 1D
is a top view illustrating a semiconductor wafer after
processing.
[0042] FIG. 2A, FIG. 2B, and FIG. 2C are a schematic sectional view
for illustrating one embodiment of a manufacturing method of a
separating step of separating the processed semiconductor wafer
according to the present invention from a support body and a
film-like temporary fixing material.
[0043] FIG. 3A and FIG. 3B are a schematic sectional view for
illustrating one embodiment of a method for manufacturing an
electronic component according to the present invention.
[0044] FIG. 4A is a top view illustrating one embodiment of a resin
film sheet for temporary fixing, and FIG. 4B is a schematic
sectional view along line I-I of FIG. 4A.
[0045] FIG. 5A is a top view illustrating another embodiment of the
resin film sheet for temporary fixing, and FIG. 5B is a schematic
sectional view along line II-II of FIG. 5A.
[0046] FIG. 6 is a schematic sectional view illustrating another
embodiment of the resin film sheet for temporary fixing.
DESCRIPTION OF EMBODIMENTS
[0047] Hereinafter, preferred embodiments of the present invention
will be described in detail with reference to the drawings.
Furthermore, in the drawings, the same reference numerals will be
applied to the same or the corresponding portions, and the repeated
description will be omitted. In addition, a dimension ratio of the
drawings is not limited to the illustrated ratio.
[0048] A method for manufacturing an electronic component of this
embodiment, includes: a step of temporarily fixing onto a support
body a workpiece to become a member constituting an electronic
component, via a film-like temporary fixing material; a step of
processing the workpiece which is temporarily fixed onto the
support body; and a step of separating the processed workpiece from
the support body and the film-like temporary fixing material.
[0049] [Semiconductor Wafer Processing Method]
[0050] A processing method of a semiconductor wafer will be
described below, as an example of the method for manufacturing an
electronic component according to this embodiment. The processing
method of the semiconductor wafer of this embodiment broadly
includes four steps described below. The processing method includes
(a) a temporary fixing step of temporarily fixing a semiconductor
wafer onto a support body via a film-like temporary fixing
material, (b) a processing step of processing the semiconductor
wafer which is temporarily fixed onto the support body, (c) a
separating step of separating the processed semiconductor wafer
from the support body and the film-like temporary fixing material,
and (d) a washing step of performing washing in a case where there
is residual dross on the semiconductor wafer.
[0051] FIG. 1A, FIG. 1B, and FIG. 1C are schematic sectional views
for illustrating one embodiment of the processing method of the
semiconductor wafer, and FIG. 1D is a top view illustrating the
semiconductor wafer after processing.
[0052] <(a) Temporary Fixing Step>
[0053] FIG. 1A illustrates a step of interposing a film-like
temporary fixing material 40 formed of the resin composition for
temporary fixing or the resin film for temporary fixing according
to this embodiment, between a support body 50 and a semiconductor
wafer 60, and of temporarily fixing the semiconductor wafer 60 onto
the support body 50.
[0054] The thickness of the semiconductor wafer 60 is not
particularly limited, and can be 600 .mu.m to 800 .mu.m.
[0055] In the case of using the resin composition for temporary
fixing, the film-like temporary fixing material 40 can be formed on
an element formation surface of the semiconductor wafer 60
according to a method such as spin coating or on the support body.
In a case where the resin composition for temporary fixing is
diluted by an organic solvent, the organic solvent is removed by
heating and drying, according to a volatilization condition of the
solvent, after spin coating, and thus, the film-like temporary
fixing material 40 is formed.
[0056] The resin film for temporary fixing is laminated on the
element formation surface of the semiconductor wafer 60 or on the
support body by using the resin film for temporary fixing formed of
the resin composition for temporary fixing (for example, a resin
film 20 for temporary fixing in resin film sheets 1 and 2 for
temporary fixing illustrated in FIGS. 4A, 4B, 5A, and 5B described
below), and by using a roll laminator, a vacuum laminator, and the
like, and thus, the film-like temporary fixing material 40 can be
disposed, from the viewpoint of an efficiency.
[0057] Next, the semiconductor wafer 60 on which the film-like
temporary fixing material 40 is formed, is set on a wafer bonding
device or a vacuum laminator, and the support body 50 is pressed by
a press, and is pasted. Furthermore, in a case where the film-like
temporary fixing material 40 is formed on the support body 50 side,
the support body 50 on which the film-like temporary fixing
material 40 is disposed, is set on the wafer bonding device or the
vacuum laminator, and the semiconductor wafer 60 is pressed by a
press, and is pasted.
[0058] In the case of using the wafer bonding device, for example,
the semiconductor wafer 60 is temporarily fixed onto the support
body 50 via the film-like temporary fixing material 40 at an
atmospheric pressure of less than or equal to 1 hPa, a crimping
pressure of 1 MPa, and a crimping temperature of 60.degree. C. to
200.degree. C., for retaining time of 100 seconds to 300 seconds,
by using a vacuum pressing machine EVG520IS (Product Name),
manufactured by EV Group.
[0059] In the case of using the vacuum laminator, for example, the
semiconductor wafer 60 is temporarily fixed onto the support body
50 via the film-like temporary fixing material 40 at an atmospheric
pressure of less than or equal to 1 hPa, a crimping temperature of
40.degree. C. to 180.degree. C., of preferably 60.degree. C. to
150.degree. C., and a lamination pressure of 0.01 MPa to 0.5 MPa,
of preferably 0.1 MPa to 0.5 MPa, for retaining time of 1 second to
600 seconds, or preferably 30 seconds to 300 seconds, by using a
vacuum laminator LM-50.times.50-S (Product Name), manufactured by
NPC Incorporated., and a vacuum laminator V130 (Product Name),
manufactured by Nichigo Morton Co., Ltd.
[0060] The semiconductor wafer 60 is temporarily fixed onto the
support body 50 via the film-like temporary fixing material 40, and
then, heating is performed at 100.degree. C. to 200.degree. C. for
5 minutes to 120 minutes, and thus, thermal curing of the film-like
temporary fixing material 40 is performed.
[0061] A material of the support body of this embodiment is not
particularly selected, and substrate such as a silicon wafer, a
glass wafer, and a quartz wafer can be used.
[0062] The support body of this embodiment may be subjected to a
peeling treatment, or as illustrated in FIG. 1A, the entire front
surface of a part of the front surface of the support body 50 is
subjected to the peeling treatment, and thus, a peeling layer 52
can be formed. A peeling agent used for the peeling treatment is
not particularly limited, and for example, a surface modifier
having a fluorine element, polyolefin-based wax and silicone oil,
silicone oil having an epoxy group, and a silicone modified alkyd
resin are preferable, from the viewpoint of excellent peeling
properties.
[0063] In the case of using the film-like temporary fixing material
according to this embodiment described below, the semiconductor
wafer can be processed at a high temperature by using the support
body, and the resin composition for temporary fixing can be peeled
off from the semiconductor wafer and the support body at a room
temperature, after processing, without an adhesive deposit.
[0064] <(b) Processing Step>
[0065] The processing step includes grinding used at a wafer level,
electrode formation, metal wiring formation, protective film
formation, and the like. A grinding method is not particularly
limited, and a known grinding method can be used. It is preferable
that the grinding is performed while cooling the semiconductor
wafer and a grinding stone (diamond or the like) with water.
[0066] For example, as illustrated in FIG. 1B, a rear surface of a
semiconductor wafer 80, that is, a surface of the semiconductor
wafer 80 on a side opposite to a side in contact with a film-like
temporary fixing material 70 is ground by a grinder 90, and for
example, a thickness of approximately 700 .mu.m is thinned to be
less than or equal to 100 .mu.m.
[0067] For example, DGP-8761 (Product Name), manufactured by DISCO
Corporation, or the like is exemplified as a device performing
grinding processing, and in this case, a cutting condition can be
arbitrarily selected according to a desired thickness and a
grinding state of the semiconductor wafer.
[0068] Specifically, the other step includes a known process such
as metal sputtering for forming an electrode or the like, wet
etching for etching a metal sputtering layer, pattern formation
according to coating, exposure, and development of a resist for
metal wiring formation, resist peeling, dry etching, metal plating
formation, silicon etching for TSV formation, and oxide film
formation on a silicon front surface. Further, a step of laminating
another semiconductor chip or wafer on the temporarily fixed
semiconductor wafer, and a step of sealing the temporarily fixed
semiconductor wafer by using a sealing material can also be
included in the other step.
[0069] FIG. 1C illustrates an example in which the rear surface
side of the thinned semiconductor wafer 80 is subjected to
processing such as dry ion etching or a Bosch process, and a
through hole is formed, and then, a treatment such as copper
plating is performed, and thus, a through electrode 82 is
formed.
[0070] Thus, the semiconductor wafer 80 is subjected to
predetermined processing. FIG. 1D is a top view of the
semiconductor wafer 80 after processing. The through electrode 82
is formed on the processed semiconductor wafer 80, and the
semiconductor wafer 80 is diced along a dicing line 84, and thus,
is segmented into a semiconductor element.
[0071] <(c) Separating Step>
[0072] FIGS. 2A, 2B, and 2C are a schematic sectional view for
illustrating one embodiment of the separating step of separating
the processed semiconductor wafer from the support body and the
film-like temporary fixing material. The separating step according
to this embodiment includes a first peeling step of peeling off the
semiconductor wafer from the support body, and a second peeling
step of peeling off the film-like temporary fixing material from
the semiconductor wafer. The first peeling step is a step of
peeling off the semiconductor wafer which is processed in the
processing step, from the support body, that is, a step of
performing various processings with respect to the thinned
semiconductor wafer, and then, of peeling off the semiconductor
wafer from the support body before dicing. A method of separating
the semiconductor wafer and the support body from each other by
sliding the semiconductor wafer and the support body in opposite
directions along a horizontal direction while mainly heating the
semiconductor wafer and the support body (preferably 200.degree. C.
to 250.degree. C.), a method of horizontally fixing one of the
semiconductor wafer of the support body and the support body, and
of lifting the other one from the horizontal direction at a
constant angle, and a method of pasting a protective film onto the
ground surface of the ground semiconductor wafer, and of peeling
off the semiconductor wafer and the protective film from the
support body in a peeling manner, and the like are exemplified as a
peeling method, and can be adopted without any particular
limitation.
[0073] All of the peeling methods can be applied to this
embodiment, but the method of horizontally fixing one of the
semiconductor wafer 80 of the support body and the support body 50
as illustrated in FIG. 1A, and of lifting the other one from the
horizontal direction at a constant angle, and a method of pasting
the protective film onto the ground surface of the ground
semiconductor wafer, and of peeling off the semiconductor wafer and
the protective film in the peeling manner are more preferable. In
general, such peeling methods are performed at a room temperature,
or may be performed at a temperature of approximately 40.degree. C.
to 100.degree. C. where damage does not occur on the semiconductor
wafer. When decomposition is mechanically performed, for example,
De-Bonding device EVG805EZD manufactured by EV Group, can be
used.
[0074] In the second peeling step, for example, as illustrated in
FIG. 2B, the semiconductor wafer 80 is horizontally fixed, and an
end of the film-like temporary fixing material 70 are lifted from
the horizontal direction at a constant angle, and thus, the
semiconductor wafer 80 from which the film-like temporary fixing
material is peeled off, can be obtained (refer to FIG. 2C). In this
embodiment, the film-like temporary fixing material is formed by
using a resin composition for temporary fixing according to this
embodiment described below, and thus, it is possible to easily
obtain the processed semiconductor wafer in which residual dross
such as an adhesive deposit is sufficiently reduced.
[0075] In this embodiment, in the first peeling step, separation
may be performed between the semiconductor wafer and the film-like
temporary fixing material.
[0076] <(d) Cleaning Step>
[0077] A part of the temporary fixing material easily remains on a
circuit formation surface of the semiconductor wafer. In a case
where a part of the temporary fixing material remains on the
circuit formation surface of the peeled semiconductor wafer, the
washing step for removing the remaining temporary fixing material
can be provided. The temporary fixing material can be removed, for
example, by washing the semiconductor wafer.
[0078] A washing liquid to be used is not particularly limited,
insofar as being a washing liquid capable of removing the remaining
temporary fixing material, and for example, the organic solvent
described above, which can be used for diluting the resin
composition for temporary fixing, is exemplified. Only one type or
two or more types of such organic solvents can be used in
combination.
[0079] In addition, in a case where it is difficult to remove the
remaining temporary fixing material, bases and acids may be added
to the organic solvent. Amines such as ethanol amine, diethanol
amine, triethanol amine, triethyl amine, and ammonia; and ammonium
salts such as tetramethyl ammonium hydroxide can be used as an
example of the bases. An organic acid such as an acetic acid, an
oxalic acid, a benzene sulfonic acid, and a dodecyl benzene
sulfonic acid can be used as the acids. It is preferable that an
additive amount is 0.01 mass % to 10 mass % at a concentration in
the washing liquid. In addition, in order to improve removability
of the residue, the existing surfactant may be added.
[0080] A washing method is not particularly limited, and for
example, a method of performing washing with a paddle by using the
washing liquid described above, a washing method with spray
atomization, and a method of performing dipping in a washing liquid
bath are exemplified. A temperature is preferably 10.degree. C. to
80.degree. C., and is more preferably 15.degree. C. to 65.degree.
C., and finally, water washing or alcohol washing is performed, and
a drying treatment is performed, and thus, a thin semiconductor
wafer 80 is obtained.
[0081] Furthermore, according to the resin composition for
temporary fixing according to this embodiment, it is possible to
sufficiently reduce residual dross such as an adhesive deposit, and
thus, it is possible to omit the washing step.
[0082] As described above, the through electrode 82 is formed on
the processed semiconductor wafer 80, and the semiconductor wafer
80 is segmented into a semiconductor element along the dicing line
84 (refer to FIG. 1D).
[0083] In this embodiment, the obtained semiconductor element is in
contact with the other semiconductor element or a substrate for
mounting a semiconductor element, and thus, it is possible to
manufacture a semiconductor device.
[0084] FIGS. 3A and 3B are a schematic sectional view for
illustrating one embodiment of a method for manufacturing a
semiconductor device. First, according to the method described
above, a through electrode 86 is formed, and a segmented
semiconductor element 100 is prepared (FIG. 3A). Then, a plurality
of semiconductor elements 100 are laminated on a wiring substrate
110, and thus, it is possible to obtain a semiconductor device 120
(FIG. 3B).
[0085] [Resin Composition for Temporary Fixing]
[0086] The resin composition for temporary fixing according to this
embodiment is a resin composition for temporary fixing for forming
a film-like temporary fixing material which is used in the method
for manufacturing an electronic component of this embodiment,
described above, and contains an (meth)acrylic copolymer (A) having
a not unevenly distributed reactive functional group (also referred
to as an component (A)). The resin composition for temporary fixing
of this embodiment can be cured by heating.
[0087] Furthermore, herein, (meth)acryl indicates any one of acryl
and methacryl.
[0088] It is preferable that the (meth)acrylic copolymer (A) having
a not unevenly distributed reactive functional group contains a
(meth)acrylic monomer (a-1) in which a glass transition temperature
of an homopolymer is higher than or equal to 50.degree. C., a
(meth)acrylic monomer (a-2) in which a glass transition temperature
of an homopolymer is lower than or equal to 0.degree. C., and a
(meth)acrylic monomer (a-3) having an reactive functional group, as
a copolymer component. It is possible to make heat resistance of
the film-like temporary fixing material formed of the resin
composition for temporary fixing excellent by containing the
(meth)acrylic monomer (a-1) in which the glass transition
temperature of the homopolymer is higher than or equal to
50.degree. C., it is possible to make low temperature pasting
properties and peeling properties excellent by containing the
(meth)acrylic monomer (a-2) in which the glass transition
temperature of the homopolymer is lower than or equal to 20.degree.
C., and it is possible to make heat resistance excellent by
containing the (meth)acrylic monomer (a-3) having the reactive
functional group.
[0089] The glass transition temperature of the homopolymer is known
from various literatures, catalogs, and the like, and for example,
is described in J. Brandup, E. H. Immergut, E. A. Grulke: Polymer
Handbook. 4th Ed., John Wiley & Sons, 2003. A value measured by
differential scanning calorimetry (DSC) or the like can be used for
a monomer not described in various literatures.
[0090] For example, methyl methacrylate (105.degree. C.), ethyl
methacrylate (65.degree. C.), t-butyl methacrylate (107.degree.
C.), cyclohexyl methacrylate (66.degree. C.), adamantyl acrylate
(153.degree. C.), adamantyl methacrylate (183.degree. C.),
isobornyl acrylate (94.degree. C.), isobornyl methacrylate
(180.degree. C.), dicyclopentanyl acrylate (120.degree. C.),
dicyclopentanyl methacrylate (175.degree. C.), benzyl methacrylate
(54.degree. C.), tetrahydrofurfuryl methacrylate (60.degree. C.),
and the like are exemplified as the (meth)acrylic monomer (a-1) in
which the glass transition temperature of the homopolymer is higher
than or equal to 50.degree. C. Only one type or two or more types
of such compounds can be used in combination. Furthermore, the
temperature in parentheses indicates the glass transition
temperature of the homopolymer.
[0091] A (meth)acrylic monomer in which a glass transition
temperature of a homopolymer is higher than or equal to 70.degree.
C., is more preferable, and a (meth)acrylic monomer in which a
glass transition temperature of a homopolymer is higher than or
equal to 90.degree. C., is even more preferable, as the
(meth)acrylic monomer (a-1) in which the glass transition
temperature of the homopolymer is higher than or equal to
50.degree. C., from the viewpoint of heat resistance.
[0092] The (meth)acrylic copolymer (A) having a not unevenly
distributed reactive functional group contains the (meth)acrylic
monomer (a-1) in which the glass transition temperature of the
homopolymer is higher than or equal to 50.degree. C., by preferably
5 mass % to 70 mass %, more preferably 10 mass % to 60 mass %, and
even more preferably 15 mass % to 50 mass %, on the basis of the
total amount of the copolymerization component, as the
copolymerization component. In a case where the content of the
(meth)acrylic monomer (a-1) in which the glass transition
temperature of the homopolymer is higher than or equal to
50.degree. C., is greater than or equal to 5 mass %, it is possible
to make heat resistance of the film-like temporary fixing material
formed of the resin composition for temporary fixing excellent, and
in a case where the content is less than or equal to 70 mass %, it
is possible to make the low temperature pasting properties more
excellent.
[0093] For example, ethyl acrylate (-22.degree. C.), propyl
acrylate (-37.degree. C.), isopropyl acrylate (-3.degree. C.),
butyl acrylate (-49.degree. C.), isobutyl acrylate (-24.degree.
C.), s-butyl acrylate (-22.degree. C.), hexyl acrylate (-57.degree.
C.), hexyl methacrylate (-5.degree. C.), heptyl acrylate
(-60.degree. C.), octyl acrylate (-65.degree. C.), 2-ethyl hexyl
acrylate (-50.degree. C.), 2-ethyl hexyl methacrylate (-10.degree.
C.), isooctyl acrylate (-58.degree. C.), nonyl acrylate
(-58.degree. C.), isononyl acrylate (-58.degree. C.), decyl
methacrylate (-70.degree. C.), isodecyl methacrylate (-41.degree.
C.), lauryl acrylate (-3.degree. C.), lauryl methacrylate
(-65.degree. C.), isostearyl acrylate (-18.degree. C.), 2-methoxy
ethyl acrylate (-50.degree. C.), tetrahydrofurfuryl acrylate
(-12.degree. C.), and the like are exemplified as the (meth)acrylic
monomer (a-2) in which the glass transition temperature of the
homopolymer is lower than or equal to 0.degree. C. Only one type or
two or more types of such compounds can be used in combination.
Furthermore, the temperature in parentheses indicates the glass
transition temperature of the homopolymer.
[0094] A (meth)acrylic monomer in which a glass transition
temperature of a homopolymer is lower than or equal to -10.degree.
C., is preferable, and a (meth)acrylic monomer in which a glass
transition temperature of a homopolymer is lower than or equal to
-20.degree. C., is more preferable, as the (meth)acrylic monomer
(a-2) in which the glass transition temperature of the homopolymer
is less than or equal to 0.degree. C., from the viewpoint of low
temperature pasting properties and peeling properties.
[0095] Further, it is preferable that the (meth)acrylic monomer
(a-2) in which the glass transition temperature of the homopolymer
is less than or equal to 0.degree. C., is a (meth)acrylic monomer
having an alkyl group of which the number of carbon atoms is 6 to
20, from the viewpoint of improving peeling properties. For
example, hexyl acrylate (-57.degree. C.), hexyl methacrylate
(-5.degree. C.), heptyl acrylate (-60.degree. C.), octyl acrylate
(-65.degree. C.), 2-ethyl hexyl acrylate (-50.degree. C.), 2-ethyl
hexyl methacrylate (-10.degree. C.), isooctyl acrylate (-58.degree.
C.), nonyl acrylate (-58.degree. C.), isononyl acrylate
(-58.degree. C.), decyl methacrylate (-70.degree. C.), isodecyl
methacrylate (-41.degree. C.), lauryl acrylate (-3.degree. C.),
lauryl methacrylate (-65.degree. C.), isostearyl acrylate
(-18.degree. C.), and the like are exemplified as such a monomer.
Only one type or two or more types of such compounds can be used in
combination. Furthermore, the temperature in parentheses indicates
the glass transition temperature of the homopolymer.
[0096] The (meth)acrylic copolymer (A) having a not unevenly
distributed reactive functional group contains the (meth)acrylic
monomer (a-2) in which the glass transition temperature of the
homopolymer is less than or equal to 0.degree. C., by preferably 20
mass % to 90 mass %, more preferably 30 mass % to 85 mass %, and
even more preferably 40 mass % to 70 mass %, on the basis of the
total amount of the copolymerization component, as the
copolymerization component. In a case where the content of the
(meth)acrylic monomer (a-2) in which the glass transition
temperature of the homopolymer is less than or equal to 0.degree.
C. is greater than or equal to 20 mass %, it is possible to make
low temperature pasting properties and peeling properties of the
film-like temporary fixing material formed of the resin composition
for temporary fixing excellent, and in a case where the content is
less than or equal to 90 mass %, it is possible to make the heat
resistance more excellent.
[0097] For example, an epoxy group, an oxetanyl group, a carboxyl
group, a hydroxy group, an amide group, an amino group, and the
like are exemplified as the reactive functional group contained in
the (meth)acrylic monomer (a-3) having the reactive functional
group. Among them, the epoxy group, the carboxyl group, and the
hydroxy group are preferable, and the epoxy group is more
preferable, from the viewpoint of improving heat resistance. Only
one type or two or more types of such functional groups can be used
in combination.
[0098] For example, glycidyl (meth)acrylate, 4-hydroxy butyl
(meth)acrylate glycidyl ether, and 3,4-epoxy cyclohexyl methyl
(meth)acrylate are exemplified as a (meth)acrylic monomer having an
epoxy group. Only one type or two or more types of such compounds
can be used in combination. Among them, it is preferable that the
(meth)acrylic monomer having an epoxy group is glycidyl
(meth)acrylate, from the viewpoint of heat resistance.
[0099] It is preferable that the (meth)acrylic copolymer (A) having
a not unevenly distributed reactive functional group contains the
(meth)acrylic monomer (a-3) having the reactive functional group by
3 mass % to 50 mass %, on the basis of the total amount of the
copolymerization component, as the copolymerization component. The
content of the (meth)acrylic monomer (a-3) having the reactive
functional group is preferably 5 mass % to 40 mass %, and is more
preferably 10 mass % to 30 mass %, on the basis of the total amount
of the copolymerization component. In a case where the content of
the (meth)acrylic monomer (a-3) having the reactive functional
group is greater than or equal to 3 mass %, it is possible to make
heat resistance of the film-like temporary fixing material formed
of the resin composition for temporary fixing excellent, and in a
case where the content is less than or equal to 50 mass %, it is
possible to suppress a reaction between the reactive functional
groups during the preservation of the resin composition for
temporary fixing, and thus, it is possible to obtain sufficient
preservation stability.
[0100] Radical polymerization can be used for synthesizing the
(meth)acrylic copolymer (A) having a not unevenly distributed
reactive functional group. For example, a solution polymerization
method, a suspension polymerization method, a bulk polymerization
method, and the like are exemplified as a radical polymerization
method, and the suspension polymerization method is more
preferable. In the solution polymerization method, it is difficult
to increase the molecular weight, and in the bulk polymerization
method, it is not industrially easy to perform thermal control.
[0101] In order to obtain the (meth)acrylic copolymer without
having an unevenly distributed reactive functional group, it is
preferable to use living radical polymerization in the radical
polymerization. Accordingly, a copolymer is obtained in which a
(meth)acrylic monomer having a reactive functional group with a
high reaction rate is not unevenly distributed, compared to general
radical polymerization. In this case, it is more preferable that
the (meth)acrylic monomer having a reactive functional group with a
high reaction rate is added later. Accordingly, the copolymer is
more easily obtained in which the (meth)acrylic monomer having a
reactive functional group with a high reaction rate is not unevenly
distributed.
[0102] In the living radical polymerization, atom transfer radical
polymerization (ATRP polymerization), reversible
addition-fragmentation chain transfer polymerization (RAFT
polymerization), and the like are known, and any method can be
used, but it is preferable to perform polymerization by the RAFT
polymerization.
[0103] In the RAFT polymerization, a polymerization initiator and a
reversible addition-fragmentation chain transfer agent
(hereinafter, referred to as an RAFT agent) are used. Such
polymerization is excellent in productivity, compared to the other
living radical polymerization, from the viewpoint that the
polymerization can be applied to various monomers, and can be
applied to a wide range of reaction conditions.
[0104] Dithiocarbonates such as O-ethyl-S-(1-phenyl ethyl)
dithiocarbonate, O-ethyl-S-(2-propoxy ethyl) dithiocarbonate, and
O-ethyl-S-(1-cyano-1-methyl ethyl) dithiocarbonate, dithioesters
such as cyanoethyl dithiopropionate, benzyl dithiopropionate,
benzyl dithiobenzoate, and acetoxy ethyl dithiobenzoate,
dithiocarbamates such as S-benzyl-N,N-dimethyl dithiocarbamate and
benzyl-1-pyrrol carbodithioate, and trithiocarbonates such as
dibenzyl trithiocarbonate and S-cyanomethyl-S-dodecyl
trithiocarbonate are exemplified as the RAFT agent.
[0105] It is preferable that an optimal RAFT agent is selected
according to reactivity of a monomer, as the RAFT agent to be used,
and in particular, dithiocarbamates and dithiocarbonates are
preferable for polymerization of acrylic acid ester, and
dithioesters are preferable for polymerization of methacrylic acid
ester.
[0106] A use amount of the RAFT agent is preferably 0.01 parts by
mass to 10 parts by mass, and is more preferably 0.05 parts by mass
to 3 parts by mass, with respect to 100 parts by mass of the total
amount of the monomer. In a case where the use amount is greater
than or equal to 0.01 parts by mass, it is easy to control the
reaction, and in a case where the use amount is less than or equal
to 10 parts by mass, the molecular weight does not excessively
decrease.
[0107] In the case of using the suspension polymerization method in
order to obtain the (meth)acrylic copolymer without having an
unevenly distributed reactive functional group, the (meth)acrylic
monomer having a reactive functional group with a high reaction
rate may be added and polymerized while heating and stirring a
dispersion liquid obtained by adding a (meth)acrylic monomer, a
polymerization initiator, and water, in order for the (meth)acrylic
monomer having a reactive functional group with a high reaction
rate not to be unevenly distributed. The addition may be
continuously performed while performing heating and stirring, or
may be performed by being divided into several times, at
intervals.
[0108] For example, organic peroxide such as benzoyl peroxide,
lauroyl peroxide, di-t-butyl peroxyhexahydroterephthalate, t-butyl
peroxy-2-ethyl hexanoate, 1,1-t-butyl peroxy-3,3,5-trimethyl
cyclohexane, and t-butyl peroxyisopropyl carbonate, and an azo
compound such as azobisisobutyronitrile,
azobis-4-methoxy-2,4-dimethyl valeronitrile,
azobiscyclohexanone-1-carbonitrile, and azodibenzoyl are
exemplified as a radical polymerization initiator.
[0109] The polymerization initiator is used in a range of
preferably 0.01 parts by mass to 10 parts by mass, more preferably
0.05 parts by mass to 5 parts by mass, and even more preferably 0.1
parts by mass to 3 parts by mass, with respect to 100 parts by mass
of the total amount of (meth)acrylic monomer, as a compounding
amount of the polymerization initiator. In a case where the
compounding amount of the polymerization initiator is greater than
or equal to 0.01 parts by mass, the polymerization sufficiently
progresses, and in a case where the compounding amount is less than
or equal to 10 parts by mass, the molecular weight does not
excessively decrease.
[0110] In the case of using the suspension polymerization method, a
suspension agent may be added into an aqueous medium. For example,
a water-soluble polymer such as polyvinyl alcohol, methyl
cellulose, and polyacryl amide, and a poorly-soluble inorganic
substance such as calcium phosphate and magnesium pyrophosphate are
exemplified as the suspension agent, and among them, a non-ionic
water-soluble polymer such as polyvinyl alcohol is preferable. In
the case of using an ionic water-soluble polymer or the
poorly-soluble inorganic substance, a great amount of ionic
impurities tend to remain in the obtained resin composition. It is
preferable that the water-soluble polymer is used by 0.01 parts by
mass to 1 part by mass, with respect to 100 parts by mass of the
total amount of a monomer mixture.
[0111] A mercaptan-based compound, thioglycol, carbon
tetrachloride, and an .alpha.-methyl styrene dimer can be added as
a molecular weight modifier to be used for the suspension
polymerization, as necessary.
[0112] Even in the case of using the solution polymerization method
in order to obtain the (meth)acrylic copolymer without having an
unevenly distributed reactive functional group, as with the
suspension polymerization method described above, the (meth)acrylic
monomer having a reactive functional group with a high reaction
rate may be added and polymerized, in order for the (meth)acrylic
monomer having a reactive functional group with a high reaction
rate not to be unevenly distributed. The addition may be
continuously performed while performing heating and stirring, or
may be performed by being divided into several times, at
intervals.
[0113] For example, a ketone-based organic solvent such as acetone,
methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; an
ester-based organic solvent such as ethyl acetate, butyl acetate,
methyl lactate, ethyl lactate, and .gamma.-butyrolactone; a
polyhydric alcohol alkyl ether-based organic solvent such as
ethylene glycol monoethyl ether, ethylene glycol monobutyl ether,
ethylene glycol dimethyl ether, ethylene glycol diethyl ether,
propylene glycol monomethyl ether, propylene glycol dimethyl ether,
diethylene glycol monomethyl ether, diethylene glycol monobutyl
ether, and diethylene glycol dimethyl ether; polyhydric alcohol
alkyl ether acetate such as ethylene glycol monomethyl ether
acetate, propylene glycol monomethyl ether acetate, and diethylene
glycol monomethyl ether acetate; an amide-based organic solvent
such as N,N-dimethyl formamide, N,N-dimethyl acetoamide, and
N-methyl pyrrolidone, and the like are exemplified as a solvent
used in the solution polymerization. Only one type or two or more
types of such organic solvents can be used in combination.
[0114] A concentration of a (meth)acrylic monomer mixture at the
time of initiating the solution polymerization is preferably 40
mass % to 70 mass %, and is more preferably 50 mass % to 60 mass %.
In a case where the concentration of the (meth)acrylic monomer
mixture is greater than or equal to 40 mass %, the molecular weight
easily increases.
[0115] It is preferable that a glass transition temperature of the
(meth)acrylic copolymer (A) having a not unevenly distributed
reactive functional group is -50.degree. C. to 50.degree. C. In a
case where the glass transition temperature is higher than or equal
to -50.degree. C., it is not possible to increase fluidity and
pressure-sensitive adhesiveness of the resin composition for
temporary fixing, and thus, it is possible to make handleability
and peeling properties of the film-like temporary fixing material
to be formed excellent, and in a case where the glass transition
temperature is lower than or equal to 50.degree. C., it is possible
to ensure fluidity and pressure-sensitive adhesiveness of the resin
composition for temporary fixing, and thus, it is possible to make
low temperature pasting properties of the film-like temporary
fixing material to be formed and embedding properties in a case
where there is a projection such as a bump on a front surface of
the workpiece excellent. From the same viewpoint, the glass
transition temperature of the (meth)acrylic copolymer (A) having a
not unevenly distributed reactive functional group is more
preferably -40.degree. C. to 40.degree. C., and is even more
preferably -30.degree. C. to 30.degree. C.
[0116] The glass transition temperature of the (meth)acrylic
copolymer (A) having a not unevenly distributed reactive functional
group is a midpoint glass transition temperature measured by using
DSC. Specifically, the glass transition temperature is a midpoint
glass transition temperature obtained by measuring a change in a
heat amount in a condition of a temperature increasing rate of
10.degree. C./minute, a measurement temperature of -80.degree. C.
to 80.degree. C., and by being calculated by a method based on JIS
K 7121.
[0117] It is preferable that a weight average molecular weight of
the (meth)acrylic copolymer (A) having a not unevenly distributed
reactive functional group is 100,000 to 3,000,000. In a case where
the weight average molecular weight is greater than or equal to
100,000, it is possible to make heat resistance and peeling
properties of the film-like temporary fixing material formed of the
resin composition for temporary fixing excellent, and in a case
where the weight average molecular weight is less than or equal to
3,000,000, it is possible to ensure fluidity of the resin
composition for temporary fixing, and to make embedding properties
in a case where there is a projection such as a bump on the front
surface of the workpiece, excellent. From the same viewpoint, the
weight average molecular weight of the (meth)acrylic copolymer (A)
having a not unevenly distributed reactive functional group is more
preferably 150,000 to 2,000,000, and is even more preferably
200,000 to 1,000,000. Furthermore, the weight average molecular
weight is a value in terms of polystyrene using a calibration curve
according to standard polystyrene in gel permeation chromatography
(GPC).
[0118] In a case where the reactive functional group of the
(meth)acrylic copolymer (A) having a not unevenly distributed
reactive functional group is an epoxy group, as necessary, a resin
composition for temporary fixing according to this embodiment is
capable of containing a epoxy curing agent (B).
[0119] The epoxy curing agent (B) used in this embodiment may be an
epoxy curing agent obtained by a reaction with respect to an epoxy
group of a component (A), and for example, a phenolic curing agent,
an acid anhydride-based curing agent, an amine-based curing agent,
an imidazole-based curing agent, an imidazoline-based curing agent,
a triazine-based curing agent, a phosphine-based curing agent, and
the like are exemplified as the epoxy curing agent (B). Among them,
the imidazole-based curing agent which can be expected to reduce
processing time and to improve workability, is preferable, from the
viewpoint of rapid-curing properties, heat resistance, and peeling
properties. Only one type or two or more types of such compounds
can be used in combination.
[0120] For example, 2-methyl imidazole, 2-undecyl imidazole,
2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl
imidazole, 2-phenyl imidazole, 2-phenyl-4-methyl imidazole,
1-benzyl-2-methyl imidazole, 1-benzyl-2-phenyl imidazole,
1-cyanoethyl-2-methyl imidazole, 1-cyanoethyl-2-undecyl imidazole,
1-cyanoethyl-2-ethyl-4-methyl imidazole, 1-cyanoethyl-2-phenyl
imidazole, 1-cyanoethyl-2-undecyl imidazolium trimellitate,
1-cyanoethyl-2-phenyl imidazolium trimellitate,
2,4-diamino-6-[2'-methyl imidazolyl-(1')]-ethyl-s-triazine,
2,4-diamino-6-[2'-undecyl imidazolyl-(1')]-ethyl-s-triazine,
2,4-diamino-6-[2'-ethyl-4'-methyl
imidazolyl-(1')]-ethyl-s-triazine, a 2,4-diamino-6-[2'-methyl
imidazolyl-(1')]-ethyl-s-triazine isoisocyanuric acid adduct, a
2-phenyl imidazole isoisocyanuric acid adduct,
2-phenyl-4,5-dihydroxy methyl imidazole,
2-phenyl-4-methyl-5-hydroxy methyl imidazole,
2,3-dihydro-1H-pyrrolo [1,2-a]benzimidazole, and
1-dodecyl-2-methyl-3-benzyl imidazolium chloride are exemplified as
the imidazole-based curing agent. Among them,
1-cyanoethyl-2-undecyl imidazole, 1-cyanoethyl-2-phenyl imidazole,
2,4-diamino-6-[2'-methyl imidazolyl-(1')]-ethyl-s-triazine,
2,4-diamino-6-[2'-undecyl imidazolyl-(1')]-ethyl-s-triazine,
2,4-diamino-6-[2'-ethyl-4'-methyl
imidazolyl-(1')]-ethyl-s-triazine,
2,4-diamino-6-[2'-ethyl-4'-methyl
imidazolyl-(1')]-ethyl-s-triazine, the 2,4-diamino-6-[2'-methyl
imidazolyl-(1')]-ethyl-s-triazine isoisocyanuric acid adduct,
2-phenyl-4,5-dihydroxy methyl imidazole, and
2-phenyl-4-methyl-5-hydroxy methyl imidazole are preferable, from
the viewpoint of preservation stability of the resin composition
for temporary fixing. Only one type or two or more types of such
compounds can be used in combination.
[0121] It is preferable that a compounding amount of the epoxy
curing agent (B) in the resin composition for temporary fixing
according to this embodiment is 0.01 parts by mass to 50 parts by
mass, with respect to 100 parts by mass of the (meth)acrylic
copolymer (A) having a not unevenly distributed reactive functional
group. In a case where the compounding amount is greater than or
equal to 0.01 parts by mass, it is possible to make curing
properties and heat resistance of the film-like temporary fixing
material formed of the resin composition for temporary fixing
excellent, and thus, it is possible to expect to reduce a
processing time and to improve workability, and in a case where the
compounding amount is less than or equal to 50 parts by mass, it is
possible to make preservation stability of the resin composition
for temporary fixing excellent. From the same viewpoint, the
content of the epoxy curing agent (B) is more preferably 0.05 parts
by mass to 30 parts by mass, and is particularly preferably 0.1
parts by mass to 10 parts by mass, with respect to 100 parts by
mass of the (meth)acrylic copolymer (A) having a not unevenly
distributed reactive functional group.
[0122] The resin composition for temporary fixing according to this
embodiment is capable of containing a silicone compound (C) and the
other components, as necessary, in addition to the (meth)acrylic
copolymer (A) having a not unevenly distributed reactive functional
group.
[0123] The resin composition for temporary fixing according to this
embodiment contains the silicone compound (C), and thus, when the
film-like temporary fixing material to be formed is peeled off from
the semiconductor wafer or the support body, it is possible to
easily peel off the film-like temporary fixing material without
using a solvent at a low temperature of lower than or equal to
100.degree. C.
[0124] The silicone compound (C) may be a compound including a
siloxane portion, and for example, organopolysiloxane not having a
reactive functional group, organopolysiloxane having a reactive
functional group, a silicone modified polyimide resin, a silicone
modified polyamide imide resin, a silicone modified alkyd resin,
straight silicone oil, non-reactive modified silicone oil, reactive
modified silicone oil, and the like are exemplified as the silicone
compound (C). Among them, the silicone modified alkyd resin is
preferable, from the viewpoint of heat resistance, peeling
properties, and compatibility with respect to the (meth)acrylic
copolymer (A) having a not unevenly distributed reactive functional
group of the film-like temporary fixing material formed of the
resin composition for temporary fixing. Only one type or two or
more types of such compounds can be used in combination.
[0125] For example, a silicone modified alkyd resin obtained by
allowing organopolysiloxane having a hydroxyl group to react as an
alcohol component at the same time when polyhydric alcohol, an
aliphatic acid, a polybasic acid, or the like reacts, a silicone
modified alkyd resin obtained by allowing organopolysiloxane having
a reactive functional group to react with a general alkyd resin
synthesized in advance, and the like are exemplified as the
silicone modified alkyd resin.
[0126] For example, dihydric alcohol such as ethylene glycol,
diethylene glycol, triethylene glycol, propylene glycol,
trimethylene glycol, tetramethylene glycol, and neopentyl glycol,
trihydric alcohol such as glycerin, trimethylol ethane, and
trimethylol propane, and tetrahydric or more polyhydric alcohol
such as diglycerin, triglycerin, pentaerythritol,
dipentaerythritol, mannitol, and sorbit are exemplified as
polyhydric alcohol used as a raw material of the alkyd resin. Only
one type of such components may be independently used, and two or
more types thereof may be used in combination.
[0127] For example, an aromatic polybasic acid such as a phthalic
anhydride, a terephthalic acid, an isophthalic acid, and a
trimellitic anhydride, an aliphatic saturated polybasic acid such
as a succinic acid, an adipic acid, and a sebacic acid, an
aliphatic unsaturated polybasic acid such as a maleic acid, a
maleic anhydride, a fumaric acid, an itaconic acid, and a
citraconic anhydride, a polybasic acid according to a Diels-Alder
reaction, such as a cyclopentadiene-maleic anhydride adduct, a
terpene-maleic anhydride adduct, and a rosin-maleic anhydride
adduct, and the like are exemplified as a polybasic acid used as a
raw material of the alkyd resin. Only one type of such components
may be independently used, and two or more types thereof may be
used in combination.
[0128] The alkyd resin may further contain a modifier or a
cross-linking agent.
[0129] For example, an octyl acid, a lauric acid, a palmitic acid,
a stearic acid, an oleic acid, a linoleic acid, a linolenic acid,
an eleostearic acid, a ricinoleic acid, a dehydrated ricinoleic
acid, or coconut oil, linseed oil, tung oil, castor oil, dehydrated
castor oil, soybean oil, safflower oil, and aliphatic acids
thereof, and the like can be used as the modifier. Only one type of
such components may be independently used, and two or more types
thereof may be used in combination.
[0130] In a case where the resin composition for temporary fixing
according to this embodiment contains the silicone modified alkyd
resin, it is preferable to further contain a cross-linking agent
capable of thermal cross-linking the silicone modified alkyd resin,
or a cross-linking agent and a catalyst. An amino resin such as a
melamine resin and a urea resin is exemplified as such a
cross-linking agent. In this case, it is possible to further
improve the heat resistance and the peeling properties of the
film-like temporary fixing material formed of the resin composition
for temporary fixing.
[0131] An amino resin such as a melamine resin and a urea resin, an
urethane resin, an epoxy resin, and a phenolic resin can be
exemplified as the cross-linking agent. Among them, it is
preferable to use the amino resin, since an aminoalkyd resin which
is cross-linked by the amino resin, is obtained. For example,
TESFINE 319 and TA31-209E (all are manufactured by Hitachi Kasei
Polymer Co., Ltd., Product Name, TESFINE: Registered Trademark) is
exemplified as such a silicone modified alkyd resin. Only one type
of such cross-linking agents may be independently used, and two or
more types thereof may be used in combination.
[0132] In the silicone modified alkyd resin, an acidic catalyst can
be used as a curing catalyst. The acidic catalyst is not
particularly limited, and any acidic catalyst can be suitably
selected from known acidic catalysts and can be used as a
cross-linking reaction catalyst of the alkyd resin. For example, an
organic-based acidic catalyst such as a p-toluene sulfonic acid and
a methane sulfonic acid is preferable as such an acidic catalyst.
Only one type of such acidic catalysts may be independently used,
and two or more types thereof may be used in combination. In
addition, a compounding amount of the acidic catalyst is selected
in a range of generally 0.1 parts by mass to 40 parts by mass,
preferably 0.5 parts by mass to 30 parts by mass, and more
preferably 1 part by mass to 20 parts by mass, with respect to 100
parts by mass of the total amount of the alkyd resin and the
cross-linking agent.
[0133] It is preferable that surface free energy of the silicone
modified alkyd resin is 15 mN/m to 30 mN/m. When the surface free
energy of the silicone modified alkyd resin is in such a range, it
is possible to make heat resistance and peeling properties of the
film-like temporary fixing material formed of the resin composition
for temporary fixing compatible. Further, it is more preferable
that the resin composition for temporary fixing contains a silicone
modified alkyd resin of which surface free energy is 15 mN/m to 27
mN/m, and it is even more preferable that the resin composition for
temporary fixing contains a silicone modified alkyd resin of which
surface free energy is 15 mN/m to 24 mN/m, from the viewpoint of
heat resistance. Furthermore, a silicone modified alkyd resin is
applied onto a PET film, and then, a contact angle of water,
ethylene glycol, and methyl iodide is measured by using a contact
angle meter (CA-X type, manufactured by Kyowa Interface Science
Co., LTD.), with respect to a film having a thickness of 0.3 .mu.m,
which is obtained by drying the silicone modified alkyd resin at
150.degree. C. for 3 seconds, and thus, surface free energy can be
calculated by surface free energy analysis software (EG-2,
manufactured by Kyowa Interface Science Co., LTD.).
[0134] It is preferable that a compounding amount of the silicone
compound (C) is 0.1 parts by mass to 100 parts by mass, with
respect to 100 parts by mass of the (meth)acrylic copolymer (A)
having a not unevenly distributed reactive functional group. In a
case where the compounding amount is greater than or equal to 0.1
parts by mass, it is possible to make peeling properties of the
film-like temporary fixing material formed of the resin composition
for temporary fixing excellent, and in a case where the compounding
amount is less than or equal to 100 parts by mass, it is possible
to rigidly fix the semiconductor wafer onto the support body, and
to suppress peeling at the time of grinding or the like the
semiconductor wafer. From the same viewpoint, the compounding
amount of the silicone compound (C) is more preferably 0.5 parts by
mass to 90 parts by mass, and is particularly preferably 1 part by
mass to 80 parts by mass, with respect to 100 parts by mass of the
(meth)acrylic copolymer (A) having a not unevenly distributed
reactive functional group.
[0135] The resin composition for temporary fixing according to this
embodiment is capable of further containing a thermosetting
component such as an epoxy resin, from the viewpoint of improving
heat resistance.
[0136] The epoxy resin is not particularly limited insofar as
having a heat resistance effect by curing. A difunctional epoxy
resin such as bisphenol A type epoxy, a novolac type epoxy resin
such as a phenol novolac type epoxy resin and a cresol novolac type
epoxy resin can be used as the epoxy resin. In addition, generally
known epoxy resin such as a polyfunctional epoxy resin, a glycidyl
amine type epoxy resin, a heterocyclic contain epoxy resin, an
alicyclic epoxy resin can be applied as the epoxy resin. Only one
type or two or more types of such epoxy resins can be used in
combination.
[0137] It is preferable that a compounding amount of the
thermosetting component (for example, the epoxy resin) is 1 part by
mass to 100 parts by mass, with respect to 100 parts by mass of the
(meth)acrylic copolymer (A) having a not unevenly distributed
reactive functional group. In a case where the compounding amount
is greater than or equal to 1 part by mass, it is possible to make
heat resistance of the film-like temporary fixing material formed
of the resin composition for temporary fixing excellent, and in a
case where the compounding amount is less than or equal to 100
parts by mass, it is possible to ensure fluidity of the film-like
temporary fixing material formed of the resin composition for
temporary fixing, and thus, it is possible to make embedding
properties in a case where there is a projection such as a bump on
the front surface of the workpiece excellent. From the same
viewpoint, the compounding amount of the thermosetting component
(for example, the epoxy resin) is more preferably 2 parts by mass
to 80 parts by mass, and particularly preferably 3 parts by mass to
60 parts by mass, with respect to 100 parts by mass of the
(meth)acrylic copolymer (A) having a not unevenly distributed
reactive functional group.
[0138] The resin composition for temporary fixing according to this
embodiment is capable of further containing an inorganic filler,
from the viewpoint of improving heat resistance.
[0139] For example, insulating fine particles, whisker, and the
like are exemplified as the inorganic filler. For example, glass,
silica, alumina, titanium oxide, carbon black, mica, and boron
nitride are exemplified as the insulating fine particles. Among
them, silica, alumina, titanium oxide, and boron nitride are
preferable, and silica, alumina, and boron nitride are more
preferable, from the viewpoint of handleability. For example,
aluminum borate, aluminum titanate, zinc oxide, calcium silicate,
magnesium sulfate, and boron nitride are exemplified as the
whisker. Only one type or two or more types of such compounds can
be used in combination.
[0140] It is preferable that the inorganic filler has an organic
group on a front surface. The front surface of the inorganic filler
is modified by the organic group, and thus, it is easy to improve
dispersibility with respect to an organic solvent at the time of
preparing the resin composition for temporary fixing, and adhesion
properties and heat resistance of the film-like temporary fixing
material formed of the resin composition for temporary fixing.
[0141] It is preferable that an average particle diameter of the
inorganic filler is 0.01 .mu.m to 10 .mu.m. In a case where the
average particle diameter is greater than or equal to 0.01 .mu.m,
it is possible to ensure fluidity of the film-like temporary fixing
material formed of the resin composition for temporary fixing, and
thus, it is possible to make embedding properties in a case where
there is a projection such as a bump on the front surface of the
workpiece excellent, and in a case where the average particle
diameter is less than or equal to 10 .mu.m, it is possible to
prevent the inorganic filler from being precipitated in the resin
composition for temporary fixing. From the same viewpoint, the
average particle diameter of the inorganic filler is more
preferably 0.05 .mu.m to 5 .mu.m, and is particularly preferably
0.1 .mu.m to 3 .mu.m.
[0142] It is preferable that a compounding amount of the inorganic
filler is 1 part by mass to 100 parts by mass, with respect to 100
parts by mass of the (meth)acrylic copolymer (A) having a not
unevenly distributed reactive functional group. In a case where the
compounding amount is greater than or equal to 1 part by mass, it
is possible to make heat resistance of the film-like temporary
fixing material formed of the resin composition for temporary
fixing excellent, and in a case where the compounding amount is
less than or equal to 100 parts by mass, it is possible to ensure
fluidity of the film-like temporary fixing material formed of the
resin composition for temporary fixing, and thus, it is possible to
make embedding properties in a case where there is a projection
such as a bump on the front surface of the workpiece excellent.
From the same viewpoint, the compounding amount of the inorganic
filler is more preferably 3 parts by mass to 70 parts by mass, and
is particularly preferably 5 parts by mass to 50 parts by mass,
with respect to 100 parts by mass of the (meth)acrylic copolymer
(A) having a not unevenly distributed reactive functional
group.
[0143] An organic filler can be further compounded in the resin
composition for temporary fixing according to this embodiment. For
example, carbon, a rubber-based filler, silicone-based fine
particles, polyamide fine particles, polyimide fine particles, and
the like are exemplified as the organic filler. A compounding
amount of the organic filler is preferably less than or equal to 50
parts by mass, is more preferably less than or equal to 40 parts by
mass, and is even more preferably less than or equal to 30 parts by
mass, with respect to 100 parts by mass of the (meth)acrylic
copolymer (A) having a not unevenly distributed reactive functional
group.
[0144] A so-called additive such as an antioxidant, an
anti-yellowing agent, a coloring agent, a plasticizer, and a
stabilizer, may be further added to the resin composition for
temporary fixing according to this embodiment, at a ratio not
negatively affecting the effect of the present invention, as
necessary.
[0145] The resin composition for temporary fixing of this
embodiment may be diluted by further using an organic solvent, as
necessary. The organic solvent is not particularly limited insofar
as being capable of dissolving the resin composition, and for
example, a ketone-based organic solvent such as acetone, methyl
ethyl ketone, methyl isobutyl ketone, and cyclohexanone; an
ester-based organic solvent such as ethyl acetate, butyl acetate,
methyl lactate, ethyl lactate, and .gamma.-butyrolactone; a
polyhydric alcohol alkyl ether-based organic solvent such as
ethylene glycol monoethyl ether, ethylene glycol monobutyl ether,
ethylene glycol dimethyl ether, ethylene glycol diethyl ether,
propylene glycol monomethyl ether, propylene glycol dimethyl ether,
diethylene glycol monomethyl ether, diethylene glycol monobutyl
ether, and diethylene glycol dimethyl ether; polyhydric alcohol
alkyl ether acetate such as ethylene glycol monomethyl ether
acetate, propylene glycol monomethyl ether acetate, and diethylene
glycol monomethyl ether acetate; and an amide-based organic solvent
such as N,N-dimethyl formamide, N,N-dimethyl acetoamide, and
N-methyl pyrrolidone are exemplified as the organic solvent. Only
one type or two or more types of such organic solvents can be used
in combination.
[0146] It is preferable that a solid content concentration of the
resin composition for temporary fixing according to this embodiment
is 10 mass % to 80 mass %.
[0147] The resin composition for temporary fixing of this
embodiment can be prepared by mixing and kneading the (meth)acrylic
copolymer (A) having a not unevenly distributed reactive functional
group, and as necessary, the epoxy curing agent (B), the silicone
compound (C), the organic solvent, and the other components. The
mixing and kneading can be performed by suitably combining general
dispersers such as a stirrer, a stone mill, a three-roll mill, and
a bead mill.
[0148] As another embodiment of the resin composition for temporary
fixing, instead of the component (A) in the resin composition for
temporary fixing described above, (i) a (meth)acrylic copolymer (i)
obtained by performing living radical polymerization with respect
to a polymerizable composition containing the (meth)acrylic monomer
(a-1) in which the glass transition temperature of the homopolymer
is higher than or equal to 50.degree. C., the (meth)acrylic monomer
(a-2) in which the glass transition temperature of the homopolymer
is less than or equal to 0.degree. C., and the (meth)acrylic
monomer (a-3) having the reactive functional group (also referred
to as an component (i)), or (ii) a (meth)acrylic copolymer (ii)
obtained by performing polymerization while adding the
(meth)acrylic monomer (a-3) having the reactive functional group
into a polymerizable composition containing the (meth)acrylic
monomer (a-1) in which the glass transition temperature of the
homopolymer is higher than or equal to 50.degree. C. and the
(meth)acrylic monomer (a-2) in which the glass transition
temperature of the homopolymer is less than or equal to 0.degree.
C. (also referred to as a component (ii)).
[0149] The monomers of (a-1), (a-2), and (a-3) described above, and
polymerization methods, compounding amounts, and the like thereof
can be identical to those of the component (A) described above. In
addition, glass transition temperatures and weight average
molecular weights of the component (i) and the component (ii) may
be in a preferred range of the component (A) described above.
[0150] [Resin Film for Temporary Fixing]
[0151] The resin film for temporary fixing according to this
embodiment is configured by forming the resin composition for
temporary fixing according to this embodiment into the shape of a
film.
[0152] The resin film for temporary fixing according to this
embodiment, for example, can be easily manufactured by applying the
resin composition for temporary fixing onto a support film. In
addition, in a case where the resin composition for temporary
fixing is diluted by the organic solvent, the resin composition is
applied onto the support film, and the organic solvent is removed
by heating and drying, and thus, the resin film for temporary
fixing can be manufactured.
[0153] A protective film can be pasted onto the resin film for
temporary fixing disposed on the support film, as necessary. In
this case, it is possible to obtain a resin film sheet for
temporary fixing having a three-layer structure formed of the
support film, the resin film for temporary fixing, and the
protective film, described below.
[0154] The resin film sheet for temporary fixing obtained as
described above, for example, can be easily preserved by being
wound into the shape of a roll. In addition, the roll-like film can
be preserved by being cut into a preferable size to be in the shape
of a sheet.
[0155] FIG. 4A is a top view illustrating one embodiment of the
resin film sheet for temporary fixing of this embodiment, and FIG.
4B is a schematic sectional view along line I-I of FIG. 4A.
[0156] A resin film sheet 1 for temporary fixing illustrated in
FIGS. 4A and 4B, includes a support film 10, the resin film 20 for
temporary fixing, which is disposed on the support film 10, and a
protective film 30 which is disposed on a side of the resin film 20
for temporary fixing, opposite to the support film 10.
[0157] The support film 10 is not particularly limited, and for
example, polyethylene terephthalate, polybutylene terephthalate,
polyethylene naphthalate, polyethylene, polypropylene, polyamide,
polyimide, and the like are exemplified as the support film 10.
Among them, polyethylene terephthalate, polybutylene terephthalate,
polyethylene naphthalate, polypropylene, polyamide, and polyimide
are preferable, from the viewpoint of flexibility and toughness. In
addition, it is preferable that the support film 10 has
releasability, and it is preferable that a film subjected to a
release treatment by a silicone-based compound, a fluorine-based
compound, and the like is used as the support film, from the
viewpoint of improving peeling properties with respect to the resin
film for temporary fixing (a resin layer).
[0158] The thickness of the support film 10 may be suitably changed
according to desired flexibility, and is preferably 3 .mu.m to 250
.mu.m. In a case where the thickness is greater than or equal to 3
.mu.m, a film strength is sufficient, and in a case where the
thickness is less than or equal to 250 .mu.m, sufficient
flexibility is obtained. From such a viewpoint, the thickness of
the support film 10 is more preferably 5 .mu.m to 200 .mu.m, and is
particularly preferably 7 .mu.m to 150 .mu.m.
[0159] The thickness of the resin film 20 for temporary fixing of
this embodiment is not particularly limited, but is preferably 5
.mu.m to 300 .mu.m, in the thickness after drying. In a case where
the thickness is greater than or equal to 5 .mu.m, the thickness is
sufficient, and thus, a strength of a film or a cured material of
the film is sufficient, and in a case where the thickness is less
than or equal to 300 .mu.m, it is easy to reduce the amount of
remaining solvent in the film by sufficient drying, and thus, it is
possible to reduce foam formation at the time of heating the cured
material of the film.
[0160] In a case of manufacturing a thick film, a film having a
thickness of less than or equal to 100 .mu.m, which is formed in
advance, may be pasted. By using the pasted film as described
above, it is possible to reduce the remaining solvent at the time
of preparing a thick film.
[0161] The protective film 30 is not particularly limited, and for
example, polyethylene terephthalate, polybutylene terephthalate,
polyethylene naphthalate, polyethylene, polypropylene, and the like
are exemplified as the protective film 30. Among them, polyethylene
terephthalate, polyethylene, and polypropylene are preferable, from
the viewpoint of flexibility and toughness. In addition, it is
preferable that the film subjected to the release treatment by the
silicone-based compound, the fluorine-based compound, and the like,
is used as the protective film, from the viewpoint of improving
peeling properties with respect to the resin film for temporary
fixing (the resin layer).
[0162] The thickness of the protective film 30 can be suitably set
according to desired flexibility, and is preferably 10 .mu.m to 250
.mu.m. In a case where the thickness is greater than or equal to 10
.mu.m, a film strength is sufficient, and in a case where the
thickness is less than or equal to 250 .mu.m, sufficient
flexibility is obtained. From such a viewpoint, the thickness of
the protective film 30 is more preferably 15 .mu.m to 200 .mu.m,
and is particularly preferably 20 .mu.m to 150 .mu.m.
[0163] FIG. 5A is a top view illustrating another embodiment of the
resin film sheet for temporary fixing according to the present
invention, and FIG. 5B is a schematic sectional view along line
II-II of FIG. 5A.
[0164] A resin film sheet 2 for temporary fixing illustrated in
FIGS. 5A and 5B has the same configuration as that of the resin
film sheet 1 for temporary fixing, except that the resin film 20
for temporary fixing and the protective film 30 are cut in advance
according to the shape of a member to be temporarily fixed.
Furthermore, in FIGS. 5A and 5B, an outer edge portion of the cut
resin film 20 for temporary fixing and the cut protective film 30
is removed, but a slit may be formed on the resin film for
temporary fixing and the protective film according to the shape of
the member to be temporarily fixed, and thus, the outer edge
portion may remain.
[0165] In the present invention, the film-like temporary fixing
material and the resin film for temporary fixing described above
are capable of having a configuration of two or more layers. In
this case, it is preferable that at least a layer in contact with
the workpiece is capable of containing the component (A) described
above, or the component (i) described above or the component (ii)
described above, and formed of the resin composition for temporary
fixing according to this embodiment. Accordingly, it is possible to
have a difference in a peeling strength or an elastic modulus on
each layer, and thus, it is possible to selectively peel off a
peeling interface.
[0166] A resin film sheet 3 for temporary fixing illustrated in
FIG. 6 includes the support film 10, a first thermoplastic resin
layer 22 configured by forming the resin composition for temporary
fixing of this embodiment into the shape of a film, which is
disposed on the support film 10, and a second thermoplastic resin
layer 24 disposed on the first thermoplastic resin layer 22. In the
resin film sheet 3 for temporary fixing of this embodiment, a resin
film 26 for temporary fixing is formed of the first thermoplastic
resin layer 22 and the second thermoplastic resin layer 24, and the
protective film 30 is disposed on the second thermoplastic resin
layer 24.
[0167] The support film 10 and the protective film 30 described
above can be used.
[0168] The first thermoplastic resin layer 22 can be formed by
applying the resin composition for temporary fixing onto the
support film 10. In addition, in a case where the resin composition
for temporary fixing is diluted by the organic solvent, the resin
composition is applied onto the support film, and the organic
solvent is removed by heating and drying, and thus, the first
thermoplastic resin layer 22 can be formed.
[0169] The thickness of the first thermoplastic resin layer 22 can
be 10 .mu.m to 350 .mu.m.
[0170] The same material as that of the first thermoplastic resin
layer 22 can be used as a material configuring the second
thermoplastic resin layer 24, and for example, the (meth)acrylic
copolymer, the epoxy curing agent, and the silicone compound,
described above, are exemplified as the material. Further, as
necessary, an epoxy resin, an inorganic filler, an organic filler,
and various additives can be included as the material.
[0171] The second thermoplastic resin layer 24 can be formed by
applying a coating liquid containing the material described above
onto the first thermoplastic resin layer 22. In a case where the
coating liquid is diluted by the organic solvent, the organic
solvent can be removed by heating and drying.
[0172] In addition, the second thermoplastic resin layer formed on
the support film or the protective film may be pasted onto the
first thermoplastic resin layer.
[0173] The thickness of the second thermoplastic resin layer 24 can
be 10 .mu.m to 350 .mu.m.
[0174] It is preferable that the resin film sheet 3 for temporary
fixing of this embodiment is used such that the first thermoplastic
resin layer 22 is in contact with the workpiece.
EXAMPLES
[0175] Hereinafter, the present invention will be described in more
detail by examples and comparative examples, but the present
invention is not limited to the following examples.
Synthesis Example 1
[0176] [Synthesis of (Meth)Acrylic Copolymer A-1 Having not
Unevenly Distributed Reactive Functional Group]
[0177] 0.04 parts by mass of polyvinyl alcohol and 200 parts by
mass of ion exchange water were added into a flask provided with a
stirrer, a cooler, a gas introduction pipe, and a thermometer, and
a mixture of 20 parts by mass of methyl methacrylate as (a-1), 65
parts by mass of butyl acrylate as (a-2), 15 parts by mass of
glycidyl methacrylate as (a-3), 0.4 parts by mass of lauroyl
peroxide, and 0.1 parts by mass of O-ethyl-S-(1-phenyl ethyl)
dithiocarbonate as an RAFT agent was added while being stirred. A
liquid temperature increased while introducing nitrogen gas, and
polymerization was performed at 60.degree. C. for 10 hours, and
then, at 90.degree. C. for 2 hours, and thus, resin particles were
obtained. Such resin particles were filtered, and were washed with
ion exchange water, and then, were dried at 40.degree. C. for 8
hours by using a vacuum dryer, and thus, a (meth)acrylic copolymer
A-1 having a not unevenly distributed epoxy group was obtained.
[0178] [Measurement of Weight Average Molecular Weight]
[0179] A weight average molecular weight of A-1 (in terms of
standard polystyrene) was measured in a condition of an eluent flow
rate of 1 mL/minute and a column temperature of 40.degree. C., by
using GPC (HLC-8320GPC, manufactured by Tosoh Corporation), and as
a result thereof, the weight average molecular weight was
31.times.10.sup.4. Furthermore, tetrahydrofuran was used as an
eluent, and Gelpack GL-A150-S/GL-A160-S, manufactured by Hitachi
Chemical Company, Ltd. was used as a column. The weight average
molecular weight is a value in terms of polystyrene using a
calibration curve according to standard polystyrene.
[0180] [Measurement of Glass Transition Temperature]
[0181] A glass transition temperature of A-1 was measured in a
condition of a temperature increasing rate of 10.degree. C./minute
and a measurement temperature of -80 to 80.degree. C., by using DSC
(DSC8230, manufactured by Rigaku Corporation), and as a result
thereof, the glass transition temperature was -14.degree. C.
Furthermore, in this case, the glass transition temperature is a
midpoint glass transition temperature calculated by a method based
on JIS K 7121 from a change in a heat amount.
Synthesis Example 2
[0182] [Synthesis of (Meth)Acrylic Copolymer A-2 Having not
Unevenly Distributed Reactive Functional Group]
[0183] 0.04 parts by mass of polyvinyl alcohol and 200 parts by
mass of ion exchange water were added into a flask provided with a
stirrer, a cooler, a gas introduction pipe, and a thermometer, and
a mixture of 20 parts by mass of methyl methacrylate as (a-1), 65
parts by mass of butyl acrylate as (a-2), 0.4 parts by mass of
lauroyl peroxide, and 0.075 parts by mass of n-octyl mercaptan was
added while being stirred. A liquid temperature increased to
60.degree. C. while introducing nitrogen gas, and 15 parts by mass
of glycidyl methacrylate as (a-3) was continuously dropped for 4
hours. After that, polymerization was performed at 60.degree. C.
for 2 hours, and then, at 90.degree. C. for 2 hours, and thus,
resin particles were obtained. Such resin particles were filtered,
and were washed with ion exchange water, and then, were dried at
40.degree. C. for 8 hours by using a vacuum dryer, and thus, a
(meth)acrylic copolymer A-2 having a not unevenly distributed epoxy
group was obtained. A weight average molecular weight and a glass
transition temperature of A-2 were measured by the same method as
that of Synthesis Example 1, and as a result thereof, the weight
average molecular weight and the glass transition temperature were
30.times.10.sup.4 and -13.degree. C., respectively.
Synthesis Example 3
[0184] [Synthesis of (Meth)Acrylic Copolymer A-3 Having not
Unevenly Distributed Reactive Functional Group]
[0185] 0.04 parts by mass of polyvinyl alcohol and 200 parts by
mass of ion exchange water were added into a flask provided with a
stirrer, a cooler, a gas introduction pipe, and a thermometer, and
a mixture of 21 parts by mass of methyl methacrylate as (a-1), 64
parts by mass of 2-ethyl hexyl acrylate as (a-2), 15 parts by mass
of glycidyl methacrylate as (a-3), 0.4 parts by mass of lauroyl
peroxide, and 0.06 parts by mass of O-ethyl-S-(1-phenyl ethyl)
dithiocarbonate as an RAFT agent was added while being stirred. A
liquid temperature increased while introducing nitrogen gas, and
polymerization was performed at 60.degree. C. for 10 hours, and
then, at 90.degree. C. for 2 hours, and thus, resin particles were
obtained. Such resin particles were filtered, and were washed with
ion exchange water, and then, were dried at 40.degree. C. for 8
hours by using a vacuum dryer, and thus, a (meth)acrylic copolymer
A-3 was obtained. A weight average molecular weight and a glass
transition temperature of A-3 were measured by the same method as
that of Synthesis Example 1, and as a result thereof, the weight
average molecular weight and the glass transition temperature were
47.times.10.sup.4 and -11.degree. C., respectively.
Synthesis Example 4
[0186] [Synthesis of (Meth)Acrylic Copolymer A-4 Having not
Unevenly Distributed Reactive Functional Group]
[0187] 0.04 parts by mass of polyvinyl alcohol and 200 parts by
mass of ion exchange water were added into a flask provided with a
stirrer, a cooler, a gas introduction pipe, and a thermometer, and
a mixture of 21 parts by mass of methyl methacrylate as (a-1), 64
parts by mass of 2-ethyl hexyl acrylate as (a-2), 0.4 parts by mass
of lauroyl peroxide, and 0.045 parts by mass of n-octyl mercaptan
was added while being stirred. A liquid temperature increased to
60.degree. C. while introducing nitrogen gas, and 15 parts by mass
of glycidyl methacrylate as (a-3) was continuously dropped for 4
hours. After that, polymerization was performed at 60.degree. C.
for 2 hours, and then, at 90.degree. C. for 2 hours, and thus,
resin particles were obtained. Such resin particles were filtered,
and were washed with ion exchange water, and then, were dried at
40.degree. C. for 8 hours by using a vacuum dryer, and thus, a
(meth)acrylic copolymer A-4 having a not unevenly distributed epoxy
group was obtained. A weight average molecular weight and a glass
transition temperature of A-4 were measured by the same method as
that of Synthesis Example 1, and as a result thereof, the weight
average molecular weight and the glass transition temperature were
45.times.10.sup.4 and -12.degree. C., respectively.
Synthesis Example 5
[0188] [Synthesis of (Meth)Acrylic Copolymer A-5 Having not
Unevenly Distributed Reactive Functional Group]
[0189] 0.04 parts by mass of polyvinyl alcohol and 200 parts by
mass of ion exchange water were added into a flask provided with a
stirrer, a cooler, a gas introduction pipe, and a thermometer, and
a mixture of 18 parts by mass of methyl methacrylate as (a-1), 67
parts by mass of isooctyl acrylate as (a-2), 0.4 parts by mass of
lauroyl peroxide, and 0.045 parts by mass of n-octyl mercaptan was
added while being stirred. A liquid temperature increased to
60.degree. C. while introducing nitrogen gas, and 15 parts by mass
of glycidyl methacrylate as (a-3) was continuously dropped for 4
hours. After that, polymerization was performed at 60.degree. C.
for 2 hours, and then, at 90.degree. C. for 2 hours, and thus,
resin particles were obtained. Such resin particles were filtered,
and were washed with ion exchange water, and then, were dried at
40.degree. C. for 8 hours by using a vacuum dryer, and thus, a
(meth)acrylic copolymer A-5 having a not unevenly distributed epoxy
group was obtained. A weight average molecular weight and a glass
transition temperature of A-5 were measured by the same method as
that of Synthesis Example 1, and as a result thereof, the weight
average molecular weight and the glass transition temperature were
47.times.10.sup.4 and -16.degree. C., respectively.
Synthesis Example 6
[0190] [Synthesis of (Meth)Acrylic Copolymer C-1 not Having
Reactive Functional Group]
[0191] 0.04 parts by mass of polyvinyl alcohol and 200 parts by
mass of ion exchange water were added into a flask provided with a
stirrer, a cooler, a gas introduction pipe, and a thermometer, and
a mixture of 32 parts by mass of methyl methacrylate as (a-1), 68
parts by mass of butyl acrylate as (a-2), 0.4 parts by mass of
lauroyl peroxide, and 0.06 parts by mass of n-octyl mercaptan was
added while being stirred. A liquid temperature increased while
introducing nitrogen gas, and polymerization was performed at
60.degree. C. for 6 hours, and then, at 90.degree. C. for 2 hours,
and thus, resin particles were obtained. Such resin particles were
filtered, and were washed with ion exchange water, and then, were
dried at 40.degree. C. for 8 hours by using a vacuum dryer, and
thus, a (meth)acrylic copolymer C-1 not having a reactive
functional group was obtained. A weight average molecular weight
and a glass transition temperature of C-1 were measured by the same
method as that of Synthesis Example 1, and as a result thereof, the
weight average molecular weight and the glass transition
temperature were 42.times.10.sup.4 and -13.degree. C.,
respectively.
Synthesis Example 7
[0192] [Synthesis of (Meth)Acrylic Copolymer C-2 Having Unevenly
Distributed Reactive Functional Group]
[0193] 0.04 parts by mass of polyvinyl alcohol and 200 parts by
mass of ion exchange water were added into a flask provided with a
stirrer, a cooler, a gas introduction pipe, and a thermometer, and
a mixture of 20 parts by mass of methyl methacrylate as (a-1), 65
parts by mass of butyl acrylate as (a-2), 15 parts by mass of
glycidyl methacrylate as (a-3), 0.4 parts by mass of lauroyl
peroxide, and 0.075 parts by mass of n-octyl mercaptan was added
while being stirred. A liquid temperature increased while
introducing nitrogen gas, and polymerization was performed at
60.degree. C. for 6 hours, and then, at 90.degree. C. for 2 hours,
and thus, resin particles were obtained. Such resin particles were
filtered, and were washed with ion exchange water, and then, were
dried at 40.degree. C. for 8 hours by using a vacuum dryer, and
thus, a (meth)acrylic copolymer C-2 having an unevenly distributed
epoxy group was obtained. A weight average molecular weight and a
glass transition temperature of C-2 were measured by the same
method as that of Synthesis Example 1, and as a result thereof, the
weight average molecular weight and the glass transition
temperature were 33.times.10.sup.4 and -9.degree. C.,
respectively.
Examples 1 to 5 and Comparative Examples 1 and 2
[0194] [Preparation of Varnish (Resin Composition for Temporary
Fixing)]
[0195] The (meth)acrylic copolymer, the epoxy curing agent (B), the
silicone compound (C), and an organic solvent were compounded
according to a compounding ratio shown in Table 1, and thus,
varnishes V-1 to V-7 were prepared.
[0196] [Preparation of Resin Film for Temporary Fixing]
[0197] The varnishes V-1 to V-7 prepared at the compounding ratio
shown in Table 1, were applied onto a release treatment surface of
a release PET film (A31, manufactured by Teijin Dupont Films
Limited, a thickness of 38 .mu.m), was dried at 90.degree. C. for 5
minutes and at 140.degree. C. for 5 minutes, and thus, resin films
F-1 to F-7 for temporary fixing were obtained. At this time, the
thickness of the resin layer can be arbitrarily adjusted, and in
this example, a film thickness after drying was adjusted to be 40
.mu.m.
TABLE-US-00001 TABLE 1 Comparative Comparative Item Unit Example 1
Example 2 Example 3 Example 4 Example 5 Example 1 Example 2 Varnish
-- V-1 V-2 V-3 V-4 V-5 V-6 V-7 (Meth)Acrylic A-1 Parts by 100 -- --
-- -- -- -- Copolymer A-2 Mass -- 100 -- -- -- -- -- A-3 -- -- 100
-- -- -- -- A-4 -- -- -- 100 -- -- -- A-5 -- -- -- -- 100 -- -- C-1
-- -- -- -- -- 100 -- C-2 -- -- -- -- -- -- 100 (B) Epoxy 2PZ-CN
Parts by 1 1 1 1 1 1 1 Curing Agent Mass (C) Silicone TA31-209E
Parts by 22.2 22.2 11.1 11.1 11.1 11.1 22.2 Compound Mass (solid
(solid (solid (solid (solid (solid (solid content 10) content 10)
content 5) content 5) content 5) content 5) content 10) SH550 3 3 2
2 2 2 3 5H3773M 5 5 3 3 3 3 5 Organic Cyclohexanone Parts by 300
300 300 300 350 300 300 Solvent Mass Resin Film for Temporary --
F-1 F-2 F-3 F-4 F-5 F-6 F-7 Fixing Material
[0198] The details of each component in Table 1 are as follows.
[0199] 2PZ-CN: Imidazole-Based Epoxy Curing Agent (manufactured by
SHIKOKU CHEMICALS CORPORATION) [0200] TA31-209E: Silicone Modified
Alkyd Resin (manufactured by Hitachi Kasei Polymer Co., Ltd.)
[0201] SH550: Phenyl Modified Silicone Oil (manufactured by Toray
Dow Corning Corporation) [0202] SH3773M: Polyether Modified
Silicone Oil (manufactured by Toray Dow Corning Corporation)
[0203] Various evaluations of the resin films for temporary fixing
obtained as described above were performed in the following
procedure. Evaluation results are shown in Table 2.
[0204] [Evaluation of Low Temperature Pasting Properties]
[0205] The resin film for temporary fixing was laminated on an
element formation surface of a semiconductor wafer, in a condition
of an atmospheric pressure of less than or equal to 1 hPa, a
crimping temperature of 120.degree. C., a lamination pressure of
0.1 MPa, and retaining time of 15 seconds, by using a vacuum
laminator (a vacuum laminator LM-50.times.50-S, manufactured by NPC
Incorporated). After that, a support film (A31) was removed, and
thus, a semiconductor wafer with the resin film for temporary
fixing was obtained. A sample in which air bubbles or the like due
to insufficient embedding did not occur on the element formation
surface of the semiconductor wafer after lamination, was evaluated
as "A", and a sample in which air bubbles or the like occurred, was
evaluated as "C".
[0206] [Crimping with Respect to Support Body]
[0207] The semiconductor wafer with the resin film for temporary
fixing described above and a support body (a silicon wafer) were
crimped, in a condition of an atmospheric pressure of less than or
equal to 1 hPa, a crimping temperature of 120.degree. C., a
lamination pressure of 0.1 MPa, and retaining time of 15 seconds,
by using a vacuum laminator (a vacuum laminator LM-50.times.50-S,
manufactured by NPC Incorporated), and thus, a lamination sample
was obtained in which the semiconductor wafer described above was
temporarily fixed onto the support body via the resin film for
temporary fixing. After that, heating was performed at 110.degree.
C. for 30 minutes, and then, at 170.degree. C. for 1 hour, and
thermal curing of the resin film for temporary fixing was
performed.
[0208] [Evaluation of Back Grinding Properties]
[0209] In the lamination sample, a surface of the semiconductor
wafer on a side opposite to a side in contact with the resin film
for temporary fixing was ground by using a full automatic
grinder/polisher (DGP-8761, manufactured by DISCO Inc.). In a
wheel, a first axis of GF01-SDC320-BT300-50, a second axis of
IF-01-1-4/6-B K09, and a third axis of DPEG-GA0001 were
respectively used. The number of rotations of a chuck table was 300
min.sup.-1, the number of rotations of the wheel was set such that
the first axis of 3,200 min.sup.-1, the second axis of 3,400
min.sup.-1, and the third axis of 1,400 min.sup.-1, and grinding
was performed by a crossfeed method. The grinding was performed
until the thickness became 142 .mu.m by the first axis, and then,
the grinding was performed until the thickness became 102 .mu.m by
the second axis, and until the thickness became 100 .mu.m by the
third axis. A sample in which a crack or the like did not occur
when the grinding was ended, was evaluated as "A", and a sample in
which a crack or the like occurred, was evaluated as "C".
[0210] [Evaluation of Heat Resistance]
[0211] A state of the resin film for temporary fixing in the
lamination sample was confirmed by using an ultrasonic microscope
(Insight-300, manufactured by Insight Co., Ltd.). After that, the
lamination sample was heated at 200.degree. C. for 30 minutes, and
then, at 260.degree. C. for 10 minutes, and the state of the resin
film for temporary fixing was confirmed again by using the
ultrasonic microscope. A sample in which foam formation did not
occur on the resin film for temporary fixing even in the heating
treatment, was evaluated as "A", and a sample in which foam
formation occurred, was evaluated as "C".
[0212] [Evaluation of Peeling Properties from Support Body]
[0213] A pair of tweezers having sharp tip ends were put between
the support body and the resin film for temporary fixing in the
lamination sample, and the pair of tweezers were moved along the
outer edge. At this time, a sample in which the support body was
capable of being peeled off without having any crack on the
semiconductor wafer, was evaluated as "A", and a sample in which
the support body was not capable of being peeled off, was evaluated
as "C".
[0214] [Evaluation of Peeling Properties from Semiconductor
Wafer]
[0215] In the lamination sample in which an evaluation value in the
evaluation of peeling properties from the support body was "A",
which an end portion of the film for temporary fixing, which was
pasted onto the semiconductor wafer, was lifted by the pair of
tweezers. At this time, a sample in which the resin layer for
temporary fixing was capable of being peeled off from the
semiconductor wafer, was evaluated as "A", a sample in which the
resin layer for temporary fixing was capable of being peeled off
from the semiconductor wafer, but residual dross occurred, was
evaluated as "B", and a sample in which the resin layer for
temporary fixing was not capable of being peeled off from the
semiconductor wafer, was evaluated as "C". Furthermore, a case
where the semiconductor wafer was not capable of being peeled off
from the support body in [Evaluation of Peeling Properties from
Support Body], was evaluated as "Unevaluable".
TABLE-US-00002 TABLE 2 Comparative Comparative Item Example 1
Example 2 Example 3 Example 4 Example 5 Example 1 Example 2 Resin
Film for Temporary F-1 F-2 F-3 F-4 F-5 F-6 F-7 Fixing Material
Evaluation Evaluation of A A A A A A A Result Low Temperature
Pasting Properties Evaluation of A A A A A A A Back Grinding
Properties Evaluation of A A A A A C A Heat Resistance Evaluation
of A A A A A C A Peeling Properties from Support Body Evaluation of
A A A A A Unevaluable B Peeling Properties from Semiconductor
Wafer
[0216] In a manufacturing method using the resin films F-1 to F-5
for temporary fixing using the (meth)acrylic copolymers A-1 to A-5
having a not unevenly distributed reactive functional group
(Examples 1 to 5), it is possible to efficiently manufacture an
electronic component having sufficient low temperature pasting
properties and flatness, in which excellent back grinding
properties can be obtained even in a case where the resin film for
temporary fixing was pasted onto the semiconductor wafer in a
condition of lower than or equal to 160.degree. C., and excellent
heat resistance and peeling properties.
[0217] In contrast, in a manufacturing method using the resin film
F-6 for temporary fixing using the (meth)acrylic copolymer C-1 not
having a reactive functional group (Comparative Example 1), heat
resistance and peeling properties of the resin film for temporary
fixing were degraded, compared to the example described above, and
in a manufacturing method using the resin film F-7 for temporary
fixing using the (meth)acrylic copolymer C-2 having an unevenly
distributed reactive functional group (Comparative Example 2),
peeling properties of the resin film for temporary fixing were
degraded, compared to the example described above, and thus, a
manufacturing efficiency of an electronic component was degraded,
compared to the example described above.
[0218] [Preparation of Two-Layer Resin Film for Temporary
Fixing]
Example 6
[0219] The varnish V-1 was prepared as with Example 1, and the
varnish V-1 was applied onto a release treatment surface of a
polyethylene terephthalate film subjected to a release treatment
(A31, manufactured by Teijin Dupont Films Limited, a thickness of
38 .mu.m), and was heated and dried at 90.degree. C. for 5 minutes,
and at 140.degree. C. for 5 minutes, and thus, a first
thermoplastic resin layer was formed. After that, a polyethylene
terephthalate film subjected to a release treatment (A31,
manufactured by Teijin Dupont Films Limited, a thickness of 38
.mu.m) was pasted onto the first thermoplastic resin layer as the
protective film, and thus, a first resin sheet was obtained.
[0220] On the other hand, a varnish V-8 having a composition shown
in Table 3 described below was prepared, the varnish V-8 was
applied onto a release treatment surface of a polyethylene
terephthalate film subjected to a release treatment (A31,
manufactured by Teijin Dupont Films Limited, a thickness of 38
.mu.m), was heated and dried at 90.degree. C. for 5 minutes, and at
140.degree. C. for 5 minutes, and thus, a second thermoplastic
resin layer was formed. After that, a polyethylene terephthalate
film subjected to a release treatment (A31, manufactured by Teijin
Dupont Films Limited, a thickness of 38 .mu.m) was pasted onto the
second thermoplastic resin layer as the protective film, and thus,
a second resin sheet was obtained.
[0221] (Composition of Varnish V-8)
TABLE-US-00003 TABLE 3 Item Unit V-8 (Meth) Acrylic A-1 Parts by
Mass 100 Copolymer (B) Epoxy 2PZ-CN Parts by Mass 1 Curing Agent
(C) Silicone TA31-209E Parts by Mass 2.2 (solid content 1) Compound
5H550 2 SH3773M 2 Organic Solvent Cyclohexanone Parts by Mass
300
[0222] The protective film was peeled off from each of the first
resin sheet and the second resin sheet, and the first thermoplastic
resin layer and the second thermoplastic resin layer were pasted at
60.degree. C. by roll lamination, and thus, a two-layer resin film
F-8 for temporary fixing was obtained.
Example 7
[0223] A two-layer resin film F-9 for temporary fixing was obtained
as with Example 6, except that the varnish V-2 prepared as with
Example 2, was used instead of the varnish V-1.
[0224] The resin films F-8 and F-9 for temporary fixing obtained as
described above were subjected to various evaluations described
above. Furthermore, the first resin sheet side was pasted onto the
semiconductor wafer. Evaluation results are shown in Table 4.
TABLE-US-00004 TABLE 4 Item Example 6 Example 7 Resin Film for
Temporary Fixing Material F-8 F-9 Evaluation Evaluation of Low
Temperature Result Pasting Properties A A Evaluation of Back
Grinding A A Properties Evaluation of Heat Resistance A A
Evaluation of Peeling Properties A A from Support Body Evaluation
of Peeling Properties A A from Semiconductor Wafer
REFERENCE SIGNS LIST
[0225] 1: resin film sheet for temporary fixing, 2, 3: resin film
sheet for temporary fixing, 10: support film, 20, 26: resin film
for temporary fixing, 22: first thermoplastic resin layer, 24:
second thermoplastic resin layer, 30: protective film, 40:
temporary fixing material, 50: support body, 52: peeling layer, 60:
semiconductor wafer, 70: temporary fixing material, 80:
semiconductor wafer, 82: through electrode, 84: dicing line, 86:
through electrode, 90: grinder, 100: semiconductor element, 110:
wiring substrate, 120: semiconductor device.
* * * * *