U.S. patent application number 15/743189 was filed with the patent office on 2019-04-25 for epoxy resin composition, process for producing same, and uses of said composition.
This patent application is currently assigned to SUMITOMO SEIKA CHEMICALS CO., LTD.. The applicant listed for this patent is SUMITOMO SEIKA CHEMICALS CO., LTD.. Invention is credited to Noriaki FUKUDA, Ryota HARISAKI, Nobukatsu NEMOTO, Katsumasa YAMAMOTO.
Application Number | 20190119434 15/743189 |
Document ID | / |
Family ID | 57757015 |
Filed Date | 2019-04-25 |
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United States Patent
Application |
20190119434 |
Kind Code |
A1 |
FUKUDA; Noriaki ; et
al. |
April 25, 2019 |
EPOXY RESIN COMPOSITION, PROCESS FOR PRODUCING SAME, AND USES OF
SAID COMPOSITION
Abstract
The present invention provides an epoxy resin composition that
can produce a cured product maintaining good dielectric
characteristics (low dielectric constant and low dielectric loss
tangent), and having high adhesion strength to metal; and also
provides a process for producing the same, a cured product obtained
by curing the epoxy resin composition, and use thereof. The present
invention includes an epoxy resin composition comprising an epoxy
resin, an acid anhydride-based curing agent, and a curing
accelerator, the epoxy resin being represented by the formula (1):
##STR00001## wherein X is a divalent group obtained by removing two
hydrogen atoms from a hydrocarbon ring, or a divalent group
represented by the formula (2): ##STR00002## wherein Y is a bond, a
C.sub.1-6 alkylene group, etc.; R.sup.1 is the same or different,
and is a C.sub.1-18 alkyl group, etc., R.sup.2 is the same or
different, and is a C.sub.1-18 alkylene group, etc., R.sup.3 is the
same or different, and is a C.sub.1-18 alkyl group, etc., and n is
the same or different, and is an integer of 0 to 3. The present
invention also includes a process for producing the same, a cured
product of the epoxy resin composition, and use thereof.
Inventors: |
FUKUDA; Noriaki; (Kako-gun,
JP) ; HARISAKI; Ryota; (Kako-gun, JP) ;
YAMAMOTO; Katsumasa; (Kako-gun, JP) ; NEMOTO;
Nobukatsu; (Koriyama-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SUMITOMO SEIKA CHEMICALS CO., LTD. |
Kako-gun, Hyogo |
|
JP |
|
|
Assignee: |
SUMITOMO SEIKA CHEMICALS CO.,
LTD.
Kako-gun, Hyogo
JP
|
Family ID: |
57757015 |
Appl. No.: |
15/743189 |
Filed: |
July 7, 2016 |
PCT Filed: |
July 7, 2016 |
PCT NO: |
PCT/JP2016/070158 |
371 Date: |
January 9, 2018 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01L 23/31 20130101;
C08G 59/4284 20130101; C09K 3/1018 20130101; H01L 23/293 20130101;
C08G 59/4215 20130101; C08G 59/306 20130101; C09J 11/06 20130101;
C08G 2190/00 20130101; C08G 59/4238 20130101; C08G 59/686 20130101;
C09J 163/00 20130101 |
International
Class: |
C08G 59/30 20060101
C08G059/30; C08G 59/42 20060101 C08G059/42; C08G 59/68 20060101
C08G059/68; C09J 163/00 20060101 C09J163/00; C09K 3/10 20060101
C09K003/10 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 10, 2015 |
JP |
2015-139146 |
Oct 9, 2015 |
JP |
2015-201380 |
Claims
1-10. (canceled)
11. An epoxy resin composition comprising an epoxy resin, an acid
anhydride-based curing agent, and a curing accelerator, the epoxy
resin being represented by the formula (1): ##STR00012## wherein X
is a divalent group obtained by removing two hydrogen atoms from a
hydrocarbon ring, or a divalent group represented by the formula
(2): ##STR00013## wherein Y is a bond, a C.sub.1-6 alkylene group,
an oxygen atom (--O--), or a group represented by the formula:
--S(O).sub.m-- wherein m is 0, 1, or 2; R.sup.1 is the same or
different, and is a C.sub.1-18 alkyl group, a C.sub.2-9 alkenyl
group, a cycloalkyl group, an aryl group, or an aralkyl group,
wherein one or more carbon atoms of these groups may be replaced by
at least one atom selected from the group consisting of an oxygen
atom and a nitrogen atom; R.sup.2 is the same or different, and is
a C.sub.1-18 alkylene group, wherein one or more carbon atoms of
this group other than a carbon atom directly bonded to a silicon
atom may be replaced by at least one atom selected from the group
consisting of an oxygen atom and a nitrogen atom; R.sup.3 is the
same or different, and is a C.sub.1-18 alkyl group, a C.sub.2-9
alkenyl group, a cycloalkyl group, an aryl group, or an aralkyl
group, wherein one or more carbon atoms of these groups may be
replaced by at least one atom selected from the group consisting of
an oxygen atom and a nitrogen atom; and n is the same or different,
and is an integer of 0 to 3.
12. The epoxy resin composition according to claim 11, wherein the
curing accelerator is a nitrogen-containing curing accelerator.
13. The epoxy resin composition according to claim 12, wherein the
nitrogen-containing curing accelerator is a tertiary amine compound
or an imidazole compound.
14. The epoxy resin composition according to claim 12, wherein the
nitrogen-containing curing accelerator is an imidazole
compound.
15. The epoxy resin composition according to claim 12, wherein the
nitrogen-containing curing accelerator is a tertiary amine
compound.
16. The epoxy resin composition according to claim 11, wherein the
epoxy resin is represented by the formula (1a): ##STR00014##
wherein X is a divalent group obtained by removing two hydrogen
atoms from a hydrocarbon ring, or a divalent group represented by
the formula (2a): ##STR00015## wherein Y is a bond, a C.sub.1-6
alkylene group, an oxygen atom (--O--), or a group represented by
the formula: --S(O).sub.m-- wherein m is 0, 1, or 2; R.sup.1 is the
same or different, and is a C.sub.1-18 alkyl group, a C.sub.2-9
alkenyl group, a cycloalkyl group, an aryl group, or an aralkyl
group, wherein one or more carbon atoms of these groups may be
replaced by at least one atom selected from the group consisting of
an oxygen atom and a nitrogen atom; R.sup.2 is the same or
different, and is a C.sub.1-18 alkylene group, wherein one or more
carbon atoms of this group other than a carbon atom directly bonded
to a silicon atom may be replaced by at least one atom selected
from the group consisting of an oxygen atom and a nitrogen atom;
R.sup.3 is the same or different, and is a C.sub.1-18 alkyl group,
a C.sub.2-9 alkenyl group, a cycloalkyl group, an aryl group, or an
aralkyl group, wherein one or more carbon atoms of these groups may
be replaced by at least one atom selected from the group consisting
of an oxygen atom and a nitrogen atom; and n is the same or
different, and is an integer of 0 to 3.
17. The epoxy resin composition according to claim 11, wherein the
epoxy resin is represented by the formula (1a): ##STR00016##
wherein all R.sup.1 are C.sub.1-3 alkyl groups, both n are 0, both
R.sup.2 are dimethylene groups, and X is a 1,4-phenylene group.
18. The epoxy resin composition according to claim 11, wherein the
acid anhydride-based curing agent is at least one member selected
from the group consisting of cyclic aliphatic acid anhydrides,
aromatic acid anhydrides, and aliphatic acid anhydrides.
19. The epoxy resin composition according to claim 11, wherein the
acid anhydride-based curing agent is at least one member selected
from the group consisting of hexahydrophthalic anhydride,
3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic
anhydride, 1-methylnorbornane-2,3-dicarboxylic anhydride,
5-methylnorbornane-2,3-dicarboxylic anhydride,
norbornane-2,3-dicarboxylic anhydride, 1-methylnadic anhydride,
5-methylnadic anhydride, nadic anhydride, phthalic anhydride,
tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride,
4-methyltetrahydrophthalic anhydride, and dodecenylsuccinic
anhydride.
20. A process for producing the epoxy resin composition according
to claim 11, the process comprising mixing an epoxy resin
represented by the formula (1), an acid anhydride-based curing
agent, and a curing accelerator.
21. A cured product of the epoxy resin composition according to
claim 11.
22. A semiconductor sealing material, a liquid sealing material, a
potting material, a sealing material, a printed circuit board
material, or a composite material, each of which uses the epoxy
resin composition according to claim 11 or a cured product thereof.
Description
TECHNICAL FIELD
[0001] The present invention relates to an epoxy resin composition,
a process for producing the same, and use of the composition.
BACKGROUND ART
[0002] Epoxy resins, which are a type of thermosetting resin, are
used in various fields, such as electric and electronic materials,
coating compositions, adhesives, and composite materials, because
cured products thereof have excellent heat resistance, electrical
insulating properties, and like characteristics. Particularly in
the field of electric and electronic materials, epoxy resins are
used in semiconductor sealing materials, printed circuit board
materials, etc.
[0003] The frequency of transmission signals has recently increased
along with an increase in the performance of electronic devices and
a reduction in the weight and size thereof. In accordance with the
increased frequency, materials used in printed circuit boards and
semiconductor sealing materials are strongly required to have a
lower dielectric constant in the high frequency region.
[0004] Epoxy resins satisfy performance requirements for electrical
insulating properties and heat resistance; however, highly polar
hydroxyl groups are generated due to the reaction between epoxy
group and active hydrogen, thereby increasing relative dielectric
constant. Thus, satisfactory dielectric characteristics (low
dielectric constant, etc.) are not obtained.
[0005] Accordingly, for the purpose of improving the dielectric
characteristics (achieving low dielectric constant and low
dielectric loss tangent) of epoxy resins, resin compositions
comprising an epoxy resin in combination with a phenol novolak
resin or the like are reported (PTL 1 to PTL 5, etc.).
[0006] Moreover, in copper wiring used in substrate materials, the
development of low-roughness copper foil and copper plating
corresponding to the increased frequency of transmission signals
has been advanced. However, if the surface roughness of copper
wiring is low, the anchor effect of copper and epoxy resin is
reduced, thereby making it difficult to ensure adhesion strength.
For this reason, there is a demand for epoxy resins having
sufficient adhesion to copper wiring that has low surface roughness
and a small anchor effect.
[0007] PTL 6 reports a photocurable composition comprising a
silicon-containing epoxy resin. Further, PTL 7 reports that a cured
product is obtained using a silicon-containing epoxy resin and a
curing agent.
CITATION LIST
Patent Literature
[0008] PTL 1: JP1995-157540A
[0009] PTL 2: JP2005-187800A
[0010] PTL 3: JP2009-227992A
[0011] PTL 4: JPH06-192393A
[0012] PTL 5: JPH08-325355A
[0013] PTL 6: JP2012-001668A
[0014] PTL 7: GB123960
SUMMARY OF INVENTION
Technical Problem
[0015] In the compositions of PTL 1 to PTL 5, the content ratio of
epoxy resin is reduced by using the epoxy resin in combination with
other components, such as a phenol novolak resin, thereby improving
the dielectric characteristics (achieving low dielectric constant
and low dielectric loss tangent) of cured products of these
compositions. However, there was a problem such that sufficient
adhesion strength to metal, such as copper and aluminum, was not
achieved.
[0016] Accordingly, an object of the present invention is to
provide an epoxy resin composition that can produce a cured product
maintaining good dielectric characteristics (low dielectric
constant and low dielectric loss tangent), and having high adhesion
strength to metal; and to also provide a process for producing the
same.
[0017] Another object of the present invention is to provide a
cured product obtained by curing the epoxy resin composition, and
use thereof (e.g., as a semiconductor sealing material, a printed
circuit board material, a composite material, etc.).
Solution to Problem
[0018] As a result of extensive research to solve the above
problem, the present inventor found that the above problem can be
solved by an epoxy resin composition comprising a specific epoxy
resin, an acid anhydride-based curing agent, and a curing
accelerator, the epoxy resin containing a silicon atom having an
alicyclic epoxy group. The present invention has been completed
upon further studies based on this finding.
[0019] The present invention includes an epoxy resin composition
comprising a specific epoxy resin, an acid anhydride-based curing
agent, and a curing accelerator, as well as a process for producing
the same, and use thereof described below.
[0020] Item 1. An epoxy resin composition comprising an epoxy
resin, an acid anhydride-based curing agent, and a curing
accelerator, the epoxy resin being represented by the formula
(1):
##STR00003##
wherein X is a divalent group obtained by removing two hydrogen
atoms from a hydrocarbon ring, or a divalent group represented by
the formula (2):
##STR00004##
wherein Y is a bond, a C.sub.1-6 alkylene group, an oxygen atom
(--O--), or a group represented by the formula: --S(O).sub.m--
wherein m is 0, 1, or 2; [0021] R.sup.1 is the same or different,
and is a C.sub.1-18 alkyl group, a C.sub.2-9 alkenyl group, a
cycloalkyl group, an aryl group, or an aralkyl group, wherein one
or more carbon atoms of these groups may be replaced by at least
one atom selected from the group consisting of an oxygen atom and a
nitrogen atom; [0022] R.sup.2 is the same or different, and is a
C.sub.1-18 alkylene group, wherein one or more carbon atoms of this
group other than a carbon atom directly bonded to a silicon atom
may be replaced by at least one atom selected from the group
consisting of an oxygen atom and a nitrogen atom; [0023] R.sup.3 is
the same or different, and is a C.sub.1-18 alkyl group, a C.sub.2-9
alkenyl group, a cycloalkyl group, an aryl group, or an aralkyl
group, wherein one or more carbon atoms of these groups may be
replaced by at least one atom selected from the group consisting of
an oxygen atom and a nitrogen atom; and [0024] n is the same or
different, and is an integer of 0 to 3.
[0025] Item 2. The epoxy resin composition according to claim 1,
wherein the curing accelerator is a nitrogen-containing curing
accelerator.
[0026] Item 3. The epoxy resin composition according to Item 2,
wherein the nitrogen-containing curing accelerator is a tertiary
amine compound or an imidazole compound.
[0027] Item 4. The epoxy resin composition according to Item 2 or
3, wherein the nitrogen-containing curing accelerator is an
imidazole compound.
[0028] Item 5. The epoxy resin composition according to Item 2 or
3, wherein the nitrogen-containing curing accelerator is a tertiary
amine compound.
[0029] Item 6. A process for producing the epoxy resin composition
according to Item 1, the process comprising mixing an epoxy resin
represented by the formula (1), an acid anhydride-based curing
agent, and a curing accelerator.
[0030] Item 7. A cured product of the epoxy resin composition
according to any one of Items 1 to 5.
[0031] Item 8. A semiconductor sealing material, a liquid sealing
material, a potting material, a sealing material, a printed circuit
board material, or a composite material, each of which uses the
epoxy resin composition according to any one of Items 1 to 5 or a
cured product thereof (the cured product of the epoxy resin
composition according to Item 7).
[0032] Item 9. The epoxy resin composition according to any one of
Items 1 to 5 for use in a semiconductor sealing material, a liquid
sealing material, a potting material, a sealing material, a printed
circuit board material, or a composite material.
[0033] Item 10. Use of the epoxy resin composition according to any
one of Items 1 to 5 for producing a semiconductor sealing material,
a liquid sealing material, a potting material, a sealing material,
a printed circuit board material, or a composite material.
Advantageous Effects of Invention
[0034] The epoxy resin composition of the present invention can
produce a cured product maintaining good dielectric characteristics
(low dielectric constant and low dielectric loss tangent) and
having high adhesion strength to metal. Therefore, the epoxy resin
composition of the present invention can be suitably used for
applications, such as semiconductor sealing material, liquid
sealing materials, potting materials, sealing materials, printed
circuit board materials, and composite materials.
DESCRIPTION OF EMBODIMENTS
[0035] In the present specification, the phrase `"containing" or
"comprising" a component` means that the component is contained,
and that any other components may also be contained. In addition,
this phrase includes the concept of "consisting of," which means
that only the component is contained, as well as the concept of
"consisting essentially of," which means that the component is
essentially contained.
[0036] The present invention is described in detail below.
[0037] The epoxy resin composition of the present invention
characteristically comprises an epoxy resin represented by the
formula (1), an acid anhydride-based curing agent, and a curing
accelerator.
[0038] The epoxy resin used in the present invention has a
structure represented by the formula (1). In the formula (1),
R.sup.1 is the same or different, and is a C.sub.1-18 alkyl group,
a C.sub.2-9 alkenyl group, a cycloalkyl group, an aryl group, or an
aralkyl group, wherein one or more carbon atoms of these groups may
be replaced by at least one atom selected from the group consisting
of an oxygen atom and a nitrogen atom. The one or more carbon atoms
is preferably a carbon atom that is not directly bonded to the
silicon atom. The one or more carbon atoms that may be replaced may
be one or plural (e.g., 2, 3, 4, 5, or 6) carbon atoms, and
preferably one carbon atom. In terms of ease of synthesis, etc., it
is preferable that R.sup.1 bonded to the same silicon atom be the
same, and it is more preferable that all R.sup.1 be the same.
[0039] The C.sub.1-18 alkyl group represented by R.sup.1 is, for
example, a linear or branched alkyl group. Examples include a
methyl group, an ethyl group, an n-propyl group, an isopropyl
group, an n-butyl group, an isobutyl group, a tert-butyl group, an
n-pentyl group, a neopentyl group, a tert-pentyl group, an n-hexyl
group, an n-heptyl group, a 2,2,4-trimethylpentyl group, an n-octyl
group, an isooctyl group, an n-nonyl group, an n-decyl group, an
n-dodecyl group, and the like. Preferable is a C.sub.1-10 alkyl
group, more preferable is a C.sub.1-6 alkyl group, even more
preferable is a C.sub.1-3 alkyl group, and particularly preferable
is a methyl group.
[0040] The C.sub.2-9 alkenyl group represented by R.sup.1 is, for
example, a linear or branched alkenyl group. Examples include a
vinyl group, an allyl croup, a 2-propenyl group, a butenyl group, a
pentenyl group, a hexenyl group, a heptenyl group, an octenyl
group, a nonenyl group, and the like. Preferable is a C.sub.2-4
alkenyl group.
[0041] The cycloalkyl group represented by R.sup.1 is, for example,
a 3- to 8-membered-ring cycloalkyl group. Examples include a
cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a
methylcyclohexyl group, and the like.
[0042] The aryl group represented by R.sup.1 is, for example, a
monocyclic or bicyclic aryl group. Examples include a phenyl group,
a tolyl group, a xylyl group, an ethyl phenyl group, a naphthyl
group, and the like. Preferable among them is a phenyl group.
[0043] The aralkyl group represented by R.sup.1 is, for example, a
C.sub.1-4 alkyl group substituted with an aryl group (particularly
a phenyl group). Examples include a benzyl group, an
.alpha.-phenethyl group, a .beta.-phenethyl group, a
.beta.-methylphenethyl group, and the like.
[0044] R.sup.1 is preferably a C.sub.1-3 alkyl group, and more
preferably a methyl group.
[0045] In the formula (1), R.sup.3 is the same or different, and is
a C.sub.1-18 alkyl group, a C.sub.2-9 alkenyl group, a cycloalkyl
group, an aryl group, or an aralkyl group, wherein one or more
carbon atoms of these groups may be replaced by at least one atom
selected from the group consisting of an oxygen atom and a nitrogen
atom. The one or more carbon atoms that may be replaced may be one
or plural (e.g., 2, 3, 4, 5, or 6) carbon atoms, and preferably one
carbon atom. When R.sup.3 is directly bonded to the oxirane ring,
the one or more carbon atoms is preferably a carbon atom that is
not directly bonded to the oxirane ring.
[0046] Examples of the C.sub.1-18 alkyl group, a C.sub.2-9 alkenyl
group, cycloalkyl group, aryl group, and aralkyl group represented
by R.sup.3 include the same corresponding substituents represented
by R.sup.1 described above.
[0047] R.sup.3 is preferably a C.sub.1-3 alkyl group, and more
preferably a methyl group.
[0048] In the formula (1), n is the same or different, and is an
integer of 0 to 3 (0, 1, 2, or 3). n is preferably 0 or 1, and more
preferably 0. n represents the number of R.sup.3 bonded to one
alicyclic epoxy group contained in the formula (1).
[0049] The formula (1) includes two alicyclic epoxy groups bonded
to R.sup.2 and represented by:
##STR00005##
When R.sup.3 bonded to one of the alicyclic epoxy groups is
regarded as R.sup.3a, whereas R.sup.3 bonded to the other alicyclic
epoxy group is regarded as R.sup.3b, that is, when the formula (1)
is the following formula (1'):
##STR00006##
wherein R.sup.1, R.sup.2, X, and n are as defined in the formula
(1), each of R.sup.3a may be the same or different, each of
R.sup.3b may also be the same or different, and .sup.3a and
R.sup.3b may be the same or different. In this case, n of
(R.sup.3a).sub.n and n of (R.sup.3b).sub.n may also be the same or
different. The formula (1) also includes the embodiment of the
formula (1').
[0050] The alicyclic epoxy group is preferably:
##STR00007##
In this group, it is particularly preferable that n be 1 or 0. The
alicyclic epoxy group is particularly preferably:
##STR00008##
It is even more preferable that n be 0.
[0051] In the formula (1), R.sup.2 is the same or different, and is
a C.sub.1-18 alkylene group, or a linear or branched alkylene
group. Examples include a methylene group, a methylmethylene group,
an ethylmethylene group, a dimethylmethylene group, a
diethylmethylene group, a dimethylene group (--CH.sub.2CH.sub.2--),
a trimethylene group (--CH.sub.2CH.sub.2CH.sub.2--), a
tetramethylene group, a pentamethylene group, a hexamethylene
group, a heptamethylene group, an octamethylene group, a
nonamethylene group, a decamethylene group, an undecamethylene
group, a dodecamethylene group, a tridecamethylene group, and the
like. Preferable is a C.sub.2-10 alkylene group, more preferable is
a C.sub.2-4 alkylene group, even more preferable is a C.sub.2 or
C.sub.3 alkylene group, (particularly a dimethylene group or a
trimethylene group), and particularly preferable is a C.sub.2
alkylene group (particularly a dimethylene group).
[0052] In the C.sub.1-18 alkylene group, one or more carbon atoms
other than the carbon atom directly bonded to the silicon atom may
be replaced by at least one atom selected from the group consisting
of an oxygen atom and a nitrogen atom. When R.sup.2 is directly
bonded to the oxirane ring, the one or more carbon atoms is
preferably a carbon atom that is not directly bonded to the oxirane
ring.
[0053] It is preferable that R.sup.2 and R.sup.3 be bonded to
different carbon atoms in the alicyclic epoxy group.
[0054] In the formula (1), the "hydrocarbon ring" of the divalent
group represented by X obtained by removing two hydrogen atoms from
a hydrocarbon ring is a monocyclic or polycyclic (particularly
bicyclic or tricyclic) aliphatic hydrocarbon ring, or a monocyclic
or polycyclic aromatic hydrocarbon ring. Examples include a
cyclopentane ring, a cyclohexane ring, a tetralin ring, a
decahydronaphthalene ring, a 1,2,3,4,5,6,7,8-octahydronaphthalene
ring, a norbornene ring, an adamantane ring, a benzene ring, a
toluene ring, a xylene ring, a naphthalene ring, a phenanthrene
ring, an anthracene ring, a pyrene ring, a triphenylene ring, and
the like. Preferable are a cyclohexane ring and a benzene ring. The
divalent group represented by X is preferably a
cyclohexane-1,4-diyl group or a 1,4-phenylene group; and more
preferably a 1,4-phenylene group.
[0055] In the formula (2), the C.sub.1-6 alkylene group represented
by Y is, for example, a chain or branched alkylene group. Examples
include a methylene group, a methylmethylene group, an
ethylmethylene group, a dimethylmethylene group, a diethylmethylene
group, a dimethylene group (--CH2CH.sub.2--), a trimethylene group
(--CH.sub.2CH.sub.2CH.sub.2--), and the like.
[0056] In the formula (2), m is 0, 1, or 2; and preferably 0 or
2.
[0057] Y is preferably a bond, an oxygen atom, a methylene group, a
dimethylmethylene group, --S--, or --SO.sub.2--; and more
preferably a bond, a dimethylmethylene group, an oxygen atom, or
--SO.sub.2--.
[0058] Preferable among the divalent groups represented by the
formula (2) is a group represented by the formula (2a):
##STR00009##
wherein Y is as defined above.
[0059] In the formula (2a), Y is preferably a bond, a
dimethylmethylene group, an oxygen atom, or --SO.sub.2--.
[0060] Preferable among the epoxy resins represented by the formula
(1) is a compound represented by the formula (1a):
##STR00010##
wherein each symbol is as defined above.
[0061] It is preferable that in the formula (1a), all R.sup.1 are
C.sub.1-3 , alkyl groups (particularly methyl groups), both n are
0, both R.sup.2 are dimethylene groups, and X is a 1,4-phenylene
group.
[0062] The epoxy resin represented by the formula (1) (including
the epoxy resins represented by the formulas (1') and (1a)) can be
produced by a known method, for example, based on or according to
the disclosures of PTL 6 and PTL 7. As a specific example, the
epoxy resin can be produced by the following reaction formula.
##STR00011##
wherein R.sup.2A is a C.sub.1-18 alkylidene group or a C.sub.2-18
alkenyl group, and other symbols are as defined above.
[0063] The C.sub.1-18 alkylidene group represented by R.sup.2A is,
for example, a linear or branched alkylidene group. Examples
include a methylidene group, a propylidene group, an isopropylidene
group, a butylidene group, an isobutylidene group, a sec-butylidene
group, a pentylidene group, an isopentylidene group, an octylidene
group, an isooctylidene group, and the like. Preferable is a
C.sub.1-10 alkylidene group, more preferable is a C.sub.1-4
alkylidene group, even more preferable is a C.sub.1-3 alkylidene
group, and particularly preferable is a methylidene group or an
ethylidene group.
[0064] The C.sub.2-18 alkenyl group represented by R.sup.2A is, for
example, a linear or branched alkenyl group. Examples include a
vinyl group, an allyl group, a propenyl group, a butenyl group, a
pentenyl group, a hexenyl group, a heptenyl group, an octenyl
group, a norbornenyl group, a cyclohexenyl group, and the like.
Preferable is a C.sub.2-10 alkenyl group, more preferable is a
C.sub.2-4 alkenyl group, even more preferable is a C.sub.2 or
C.sub.3 alkenyl group, and particularly preferable is a vinyl group
or an allyl group.
[0065] The epoxy resin can be produced by hydrosilylation of the
compound represented by the formula (3) and the compound
represented by the formula (4). Hydrosilylation can be generally
performed in the presence of a catalyst in the presence or absence
of a solvent.
[0066] The catalyst used in hydrosilylation may be a known
catalyst. Examples include platinum-based catalysts, such as
platinum carbon, chloroplatinic acid, olefin complexes of platinum,
alkenylsiloxane complexes of platinum, and carbonyl complexes of
platinum; rhodium-based catalysts, such as
tris(triphenylphosphine)rhodium; and iridium-based catalysts, such
as bis(cyclooctadienyl)dichloroiridium. These catalysts may be in
the form of solvates (e.g., hydrates, alcoholates, etc.). Further,
the catalyst may be used in the form of a solution obtained by
dissolving the catalyst in an alcohol (e.g., ethanol) when
used.
[0067] The amount of the catalyst used may be an effective amount
as the catalyst, and is not particularly limited. The amount of the
catalyst used is generally 0.00001 to 20 parts by mass, and
preferably 0.0005 to 5 parts by mass, based on the total amount of
100 parts by mass of the compound represented the formula (3) and
the compound represented by the formula (4).
[0068] Although hydrosilylation proceeds without use of a solvent,
the reaction can be carried out under milder conditions by using a
solvent. Examples of solvents include aromatic hydrocarbon
solvents, such as toluene and xylene; aliphatic hydrocarbon
solvents, such as hexane and octane; ether solvents, such as
tetrahydrofuran and dioxane; alcohol solvents, such as ethanol and
isopropanol; and the like. These may be used singly or in
combination of two or more.
[0069] The amount of the compound represented by the formula (4) is
generally 0.5 to 2 mol, preferably 0.6 to 1.5 mol, and more
preferably 0.8 to 1.2 mol, per mol of the Si--H group in the
compound represented by the formula (3).
[0070] The reaction temperature is 20.degree. C. to 150.degree. C.,
and preferably 50.degree. C. to 120.degree. C. The reaction time is
about 1 hour to 24 hours.
[0071] After completion of the reaction, for example, the solvent
is distilled off from the reaction mixture, thereby obtaining an
epoxy resin represented by the formula (1).
[0072] The epoxy resin composition of the present invention may
contain an epoxy resin other than the epoxy resin represented by
the formula (1) within a range in which the effects of the present
invention can be exhibited. Examples include bisphenol A epoxy
resins, bisphenol F epoxy resins, phenol novolak epoxy resins,
cresol novolak epoxy resins, cycloaliphatic epoxy resins,
brominated epoxy resins, nitrogen-containing ring epoxy resins such
as triglycidyl isocyanurate- and hydantoin-type epoxy resins,
hydrogenated bisphenol A epoxy resins, aliphatic epoxy resins,
glycidyl ether epoxy resins, bisphenol S epoxy resins, biphenyl
epoxy resins, dicyclo epoxy resins, naphthalene epoxy resins, and
the like. These epoxy resins may be used singly or in combination
of two or more.
[0073] The acid anhydride-based curing agent used in the present
invention may be a known acid anhydride-based curing agent.
Examples include cyclic aliphatic acid anhydrides, aromatic acid
anhydrides, aliphatic acid anhydrides, and the like. Specific
examples include hexahydrophthalic anhydride,
3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic
anhydride, 1-methylnorbornane-2,3-dicarboxylic anhydride,
5-methylnorbornane-2,3-dicarboxylic anhydride,
norbornane-2,3-dicarboxylic anhydride, 1-methylnadic anhydride,
5-methylnadic anhydride, nadic anhydride, phthalic anhydride,
tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride,
4-methyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride,
and the like. Preferable are cyclic aliphatic acid anhydrides, such
as hexahydrophthalic anhydride, 3-methylhexahydrophthalic
anhydride, and 4-methylhexahydrophthalic anhydride. These curing
agents may be used singly or in combination of two or more.
[0074] The amount of acid anhydride-based curing agent used is not
particularly limited; however, the amount of the active group (acid
anhydride group) in the curing agent reactive with the epoxy group
is preferably 0.5 to 1.5 equivalents, and more preferably 0.7 to
1.2 equivalents, per equivalent of the epoxy group in the epoxy
resin composition.
[0075] The epoxy resin composition of the present invention may
contain a curing agent other than the acid anhydride-based curing
agent within a range in which the effects of the present invention
can be exhibited. Examples include aliphatic polyamines, such as
triethylenetetramine; polyaminoamide; polymercaptans; aromatic
polyamines, such as diaminodiphenylmethane; phenol novolak resin;
dicyandiamide; and the like.
[0076] The acid anhydride-based curing agent used in the epoxy
resin composition of the present invention has a long pot life and
low toxicity; however, the curing reaction may proceed relatively
slowly, and curing may require a high temperature and a long period
of time. Accordingly, it is preferable to use a curing accelerator
in combination.
[0077] Examples of curing accelerators include tertiary amine
compounds, such as benzyldimethylamine, cyclohexyldimethylamine,
pyridine, triethanolamine, 2-(dimethylaminomethyl)phenol,
dimethylpiperazine, 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU),
1,5-diazabicyclo[4.3.0]non-5-ene (DEN),
1,4-diazabicyclo[2.2.2]octane (DABCO), and
2,4,6-tris(dimethylaminomethyl)phenol; imidazole compounds, such as
2-methylimidazole, 2-ethylimidazole, 2-n-heptylimidazole,
2-n-undecylimidazole, 2-phenylimidazole,
2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole,
1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole,
2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-methylimidazole,
1-(2-cyanoethyl)-2-n-undecylimidazole,
1-(2-cyanoethyl)-2-phenylimidazole,
1-(2-cyanoethyl)-2-ethyl-4-methylimidazole,
2-phenyl-4-methyl-5-hydroxymethylimidazole,
2-phenyl-4,5-di(hydroxymethyl)imidazole,
1-(2-cyanoethyl)-2-phenyl-4,5-di((2'-cyanoethoxy)methyl)imidazole,
1-(2-cyanoethyl)-2-n-undecyl imidazolium trimellitate,
1-(2-cyanoethyl)-2-phenyl imidazolium trimellitate,
1-(2-cyanoethyl)-2-ethyl-4-methyl imidazolium trimellitate,
2,4-diamino-6-(2'-methylimidazolyl-(1'))ethyl-s-triazine,
2,4-diamino-6-(2'-n-undecylimidazolyl)ethyl-s-triazine,
2,4-diamino-6-(2'-ethyl-4'-methylimidazolyl-(1'))ethyl-s-triazine,
isocyanuric acid adducts of 2-methylimidazole, isocyanuric acid
adducts of 2-phenylimidazole, and isocyanuric acid adducts of
2,4-diamino-6-(2'-methylimidazolyl-(1'))ethyl-s-triazine; phosphine
compounds, such as triphenylphosphine; phosphonium salts, such as
tetraphenyl phosphonium tetraphenyl borate; metal compounds, such
as tin octylate; and the like. These may be used singly or in
combination of two or more.
[0078] Among these, a curing accelerator containing a nitrogen atom
is preferably used. When a nitrogen-containing curing accelerator
is used, an epoxy resin composition having better metal adhesion
can be obtained.
[0079] It is more preferable to use a tertiary amine compound or an
imidazole compound as a curing accelerator, thereby obtaining an
epoxy resin composition having good heat resistance and metal
adhesion.
[0080] The amount of the nitrogen-containing curing accelerator is
not particularly limited; however, the amount of the
nitrogen-containing curing accelerator is preferably 0.1 to 5 parts
by mass, and more preferably 0.5 to 2 parts by mass, based on 100
parts by mass of the epoxy resin in the epoxy resin composition,
because an epoxy resin composition that can produce a cured product
having good heat resistance and metal adhesion is obtained.
[0081] The specific epoxy resins, acid anhydride-based curing
agents, and curing accelerators mentioned above can be used in any
combination. Although it is not particularly limited, it is
preferable to use the epoxy resin represented by the formula (1)
(including the epoxy resins represented by the formulas (1') and
(1a)) in combination with a cyclic aliphatic acid anhydride as an
acid anhydride-based curing agent, and a tertiary amine compound or
an imidazole compound as a curing accelerator (a
nitrogen-containing curing accelerator). Further, it is more
preferable to use the epoxy resin represented by the formula (1) in
combination with at least one acid anhydride-based curing agent
selected from the group consisting of hexahydrophthalic anhydride,
3-methylhexahydrophthalic anhydride, and 4-methylhexahydrophthalic
anhydride, and at least one curing accelerator selected from the
group consisting of 2-ethyl-4-methylimidazole,
2,4,6-tris(dimethylaminomethyl)phenol,
1,4-diazabicyclo[2.2.2]octane, and
1,8-diazabicyclo[5.4.0]undec-7-ene.
[0082] The epoxy resin composition of the present invention may
optionally contain additives within a range that does not impair
the objects and effects of the present invention. Examples of
additives include inorganic fillers, fibrous reinforcing agents,
antioxidants, inorganic fluorescent substances, lubricants,
ultraviolet absorbers, heat light stabilizers, dispersants,
antistatic agents, polymerization inhibitors, antifoaming agents,
solvents, anti-aging agents, radical inhibitors, adhesion-improving
agents, flame retardants, surfactants, storage stability-improving
agents, ozone aging inhibitors, thickeners, plasticizers,
radiation-blocking agents, nucleating agents, coupling agents,
conductivity-imparting agents, phosphorus-based
peroxide-decomposing agents, pigments, metal deactivators, physical
property-controlling agents, and the like.
[0083] The epoxy resin composition of the present invention can be
produced by mixing the epoxy resin represented by the formula (1),
an acid anhydride-based curing agent, and a curing accelerator, and
further optionally other components. The mixing method is not
particularly limited, as long as it allows uniform mixing.
[0084] A cured product can be obtained by curing the epoxy resin
composition of the present invention. The curing method is not
particularly limited; for example, the composition can be cured by
heating. Moreover, the epoxy resin composition can be dissolved in
a solvent (e.g., toluene, acetone, etc.) to prepare a varnish, and
then the varnish can be applied to a substrate (e.g., copper foil,
aluminum foil, a polyimide film, etc.), followed by heating,
thereby obtaining a film-like cured product. The curing temperature
is generally room temperature to 200.degree. C. The curing time
varies depending on the composition liquid, and can be generally
widely set from 30 minutes to 1 week.
[0085] A cured product obtained by curing the epoxy resin
composition of the present invention has good dielectric
characteristics (low dielectric constant and low dielectric loss
tangent) and high adhesion strength to metal, such as copper and
aluminum; therefore, for example, the cured product can be suitably
used for applications, such as semiconductor sealing materials,
liquid sealing materials, potting materials, sealing materials,
printed circuit board materials, and composite materials.
Furthermore, the present invention includes a semiconductor sealing
material, a liquid sealing material, a potting material, a sealing
material, a printed circuit board material, and a composite
material, each of which uses the epoxy resin composition or a cured
product thereof.
EXAMPLES
[0086] The present invention is described in more detail below with
reference to Examples; however, the present invention is not
limited to only these Examples.
Production Example 1 (Production of Epoxy Resin A)
[0087] 1,2-Epoxy-4-vinylcyclohexane (25 g), 0.25 g of 2 wt %
ethanol solution of hexachloroplatinic acid hexahydrate, and 250 g
of toluene were placed in a 500-mL four-necked flask equipped with
a stirrer, a thermometer, and a condenser in a nitrogen atmosphere.
After the temperature was raised to 70.degree. C., 20 g of
1,4-bis(dimethylsilyl)benzene was slowly added dropwise, and the
mixture was then stirred at 90.degree. C. for 4 hours. After the
toluene was concentrated, 42 g of slightly yellow liquid (epoxy
resin A:
[0088] 1,4-di[2-(3,4-epoxycyclohexylethyl)dimethylsilyl]benzene)
was obtained.
Examples 1 to 4 and Comparative Examples 1 and 2
[0089] Components in amounts (mass ratio) shown in Table 1 were
uniformly mixed, and the mixture was then sufficiently degassed,
thereby preparing epoxy resin compositions.
[0090] The components in Table 1 are as follows. [0091] Epoxy resin
B: Bis-A epoxy resin (JER Grade 828, produced by Mitsubishi
Chemical Corporation) [0092] Acid anhydride-based curing agent:
4-methylhexahydrophthalic anhydride/hexahydrophthalic
anhydride=70/30 (RIKACID MH-700, produced by New Japan Chemical
Co., Ltd.) [0093] Curing accelerator A: 2-ethyl-4-methylimidazole
(2E4MZ, produced by Mitsubishi Chemical Corporation) [0094] Curing
accelerator B: 2,4,6-tris(dimethylaminomethyl)phenol (DMP, produced
by Tokyo Chemical Industry Co., Ltd.) [0095] Curing accelerator C:
1,4-diazabicyclo[2.2.2]octane (DABCO, produced by Tokyo Chemical
Industry Co., Ltd.) [0096] Curing accelerator D:
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, produced by Tokyo Chemical
Industry Co., Ltd.)
Test Example 1
(1) Tensile Shear Adhesion Strength to Aluminum
[0097] The epoxy resin compositions obtained in Examples 1 to 4 and
Comparative Examples 1 and 2 were each applied to an aluminum plate
(JIS A1050P) (size: 2.times.25.times.100 mm) so that the adhesive
part had a rectangular shape (12.5.times.25 mm). Then, another
aluminum plate was bonded thereto, and cured by heating at
100.degree. C. for 1 hour, 120.degree. C. for 2 hours, and
150.degree. C. for 2 hours. Thus, tensile shear adhesion test
pieces were obtained.
[0098] The obtained adhesion test pieces were each subjected to a
tensile shear adhesion test using a tensile tester (AGS-X, produced
by Shimadzu Corp.) with a clamp distance of 100 mm at a test rate
of 5 mm/min, and the tensile shear adhesion strength was calculated
from the measured maximum breaking strength and the adhesion area.
Table 1 shows the results.
(2) Maintenance Rate of Tensile Shear Adhesion Strength to Aluminum
After High-Temperature High-Humidity Test
[0099] The epoxy resin compositions obtained in Examples 1 to 4 and
Comparative Examples 1 and 2 were each applied to an aluminum plate
(JIS A1050P) (size: 2.times.25.times.100 mm) so that the adhesive
part had a rectangular shape (12.5.times.25 mm). Then, another
aluminum plate was bonded thereto, and cured by heating at
100.degree. C. for 1 hour, 120.degree. C. for 2 hours, and
150.degree. C. for 2 hours. Thus, tensile shear adhesion test
pieces were obtained.
[0100] The obtained adhesion test pieces were allowed to stand in
an atmosphere at 85.degree. C. with 85% RH for 168 hours.
Subsequently, the test pieces were each subjected to a tensile
shear adhesion test using a tensile tester (AGS-X, produced by
Shimadzu Corp.) with a clamp distance of 100 mm at a test rate of 5
mm/min, and the tensile shear adhesion strength was calculated from
the measured maximum breaking strength and the adhesion area.
[0101] The maintenance rate (%) of tensile shear adhesion strength
to aluminum after the high-temperature high-humidity test was
calculated by dividing the tensile shear adhesion strength to
aluminum after the high-temperature high-humidity test by the
tensile shear adhesion strength to aluminum before the
high-temperature high-humidity test. Table 1 shows the results.
(3) Tensile Shear Adhesion Strength to Copper
[0102] The epoxy resin compositions obtained in Examples 1 to 4 and
Comparative Examples 1 and 2 were each applied to an oxygen-free
copper plate (JIS C1020P) (size: 2.times.25.times.100 mm) so that
the adhesive part had a rectangular shape (12.5.times.25 mm). Then,
another oxygen-free copper plate was bonded thereto, and cured by
heating at 100.degree. C. for 1 hour, 120.degree. C. for 2 hours,
and 150.degree. C. for 2 hours. Thus, tensile shear adhesion test
pieces were obtained.
[0103] The obtained adhesion test pieces were each subjected to a
tensile shear adhesion test using a tensile tester (AGS-X, produced
by Shimadzu Corp.) with a clamp distance of 100 mm at a test rate
of 5 mm/min, and the tensile shear adhesion strength was calculated
from the measured maximum breaking strength and the adhesion area.
Table 1 shows the results.
(4) Maintenance Rate of Tensile Shear Adhesion Strength to Copper
After High-Temperature High-Humidity Test
[0104] The epoxy resin compositions obtained in Examples 1 to 4 and
Comparative Examples 1 and 2 were each applied to an oxygen-free
copper plate (JIS C1020P) (size: 2.times.25.times.100 mm) so that
the adhesive part had a rectangular shape (12.5.times.25 mm). Then,
another oxygen-free copper plate was bonded thereto, and cured by
heating at 100.degree. C. for 1 hour, 120.degree. C. for 2 hours,
and 150.degree. C. for 2 hours. Thus, tensile shear adhesion test
pieces were obtained.
[0105] The obtained adhesion test pieces were allowed to stand in
an atmosphere at 85.degree. C. with 85% RH for 168 hours.
Subsequently, the test pieces were each subjected to a tensile
shear adhesion test using a tensile tester (AGS-X, produced by
Shimadzu Corp.) with a clamp distance of 100 mm at a test rate of 5
mm/min, and the tensile shear adhesion strength was calculated from
the measured maximum breaking strength and the adhesion area.
[0106] The maintenance rate (5) of tensile shear adhesion strength
to copper after the high-temperature high-humidity test was
calculated by dividing the tensile shear adhesion strength to
copper after the high-temperature high-humidity test by the tensile
shear adhesion strength to copper before the high-temperature
high-humidity test. Table 1 shows the results.
(5) Electric Characteristics (Dielectric Characteristics)
[0107] The epoxy resin compositions obtained in Examples 1 to 4 and
Comparative Examples 1 and 2 were each poured into a resin mold
(thickness: 2 mm), and cured by heating at 100.degree. C. for 1
hour, 120.degree. C. for 2 hours, and 150.degree. C. for 2 hours.
Thus, test pieces for dielectric measurement were obtained.
[0108] The obtained test pieces were each calibrated with PTFE
using a dielectric constant measuring device (Impedance Analyzer,
produced by Agilent), and then the relative dielectric constant (1
GHz) and the dielectric loss tangent (1 GHz) were measured. Table 1
shows the results.
(6) Glass Transition Temperature
[0109] The epoxy resin compositions obtained in Examples 1 to 4 and
Comparative Examples 1 and 2 were each poured into a resin mold,
and cured by heating at 100.degree. C. for 1 hour, 120.degree. C.
for 2 hours, and 150.degree. C. for 2 hours. Thus, test pieces for
glass transition temperature measurement were obtained.
[0110] The glass transition temperature of the obtained test pieces
was measured using a thermomechanical analyzer (SSC5200, produced
by SII Nanotechnology Inc.) in compressed mode at a load of 50 mN
at 5.degree. C./min. Table 1 shows the results.
(7) Changes in Test Pieces After Heat Resistance Test
[0111] The epoxy resin compositions obtained in Examples 1 to 4 and
Comparative Examples 1 and 2 were each poured into a resin mold,
and cured by heating at 100.degree. C. for 1 hour, 120.degree. C.
for 2 hours, and 150.degree. C. for 2 hours. After the glass
transition temperature of the cured test pieces was measured, the
test pieces after measurement were observed, and the presence of
cracks was evaluated based on their appearance.
TABLE-US-00001 TABLE 1 Comparative Comparative Example 1 Example 2
Example 3 Example 4 Example 1 Example 2 Epoxy resin A 100 100 100
100 0 0 Epoxy resin B 0 0 0 0 100 100 Acid anhydride-based curing
agent 76 76 76 76 88 88 Curing accelerator A 1 0 0 0 1 0 Curing
accelerator B 0 1 0 0 0 0 Curing accelerator C 0 0 1 0 0 0 Curing
accelerator D 0 0 0 1 0 1 Tensile shear adhesion strength 5.0 4.8
4.0 4.5 4.4 4.2 (MPa) to aluminum Maintenance rate (%) of tensile
shear 96 92 92 93 27 25 adhesion strength to aluminum after
high-temperature high-humidity test Tensile shear adhesion strength
8.0 7.7 6.9 7.5 4.9 7.0 (MPa) to copper Maintenance rate (%) of
tensile shear 99 100 98 99 65 54 adhesion strength to copper after
high-temperature high-humidity test Relative dielectric constant (1
GHz) 2.6 2.6 2.6 2.6 2.8 2.9 Dielectric loss tangent (1 GHz) 0.005
0.006 0.006 0.005 0.010 0.010 Glass transition temperature
(.degree. C.) 162 160 160 161 162 159 Cracks after heat resistance
test None None None None Observed Observed
[0112] The epoxy resin compositions obtained in Examples 1 to 4
have high adhesion strength to metal. In particular, even after the
high-temperature high-humidity test, they can maintain high
adhesion strength and have adhesion reliability. Furthermore, they
have good dielectric characteristics and heat resistance.
[0113] In contrast, the epoxy resin compositions obtained in
Comparative Examples 1 and 2 have a certain degree of initial
adhesion strength to metal; however, their adhesion was rapidly
reduced after the high-temperature high-humidity test. In addition,
it was confirmed that their dielectric characteristics and heat
resistance were inferior to those of the epoxy resin compositions
obtained in Examples 1 to 4.
* * * * *