U.S. patent application number 11/362277 was filed with the patent office on 2007-01-11 for latent catalyst for epoxy resin, epoxy resin composition, and semiconductor device.
Invention is credited to Yoshiyuki Goh, Akihiro Horimoto.
Application Number | 20070010601 11/362277 |
Document ID | / |
Family ID | 34395573 |
Filed Date | 2007-01-11 |
United States Patent
Application |
20070010601 |
Kind Code |
A1 |
Horimoto; Akihiro ; et
al. |
January 11, 2007 |
Latent catalyst for epoxy resin, epoxy resin composition, and
semiconductor device
Abstract
The present invention provides a latent catalyst for epoxy
resin, comprising: a cation moiety having an activity of
accelerating curing reaction of epoxy resin; and a silicate anion
moiety of suppressing the curing reaction-accelerating activity.
Also disclosed are an epoxy resin composition comprising the latent
catalyst and a semiconductor device using the epoxy resin
composition.
Inventors: |
Horimoto; Akihiro; (Tokyo,
JP) ; Goh; Yoshiyuki; (Tokyo, JP) |
Correspondence
Address: |
SMITH, GAMBRELL & RUSSELL
SUITE 3100, PROMENADE II
1230 PEACHTREE STREET, N.E.
ATLANTA
GA
30307-3592
US
|
Family ID: |
34395573 |
Appl. No.: |
11/362277 |
Filed: |
February 24, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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10928618 |
Aug 27, 2004 |
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11362277 |
Feb 24, 2006 |
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Current U.S.
Class: |
523/451 ;
523/461; 523/466 |
Current CPC
Class: |
C08G 59/18 20130101;
Y10T 428/31511 20150401 |
Class at
Publication: |
523/451 ;
523/466; 523/461 |
International
Class: |
C08L 63/00 20060101
C08L063/00 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 29, 2003 |
JP |
P.2003-307700 |
Mar 19, 2004 |
JP |
P.2004-081581 |
Claims
1. A latent catalyst for epoxy resin, comprising: a cation moiety
having an activity of accelerating curing reaction of epoxy resin;
and a silicate anion moiety of suppressing the curing
reaction-accelerating activity.
2. The latent catalyst according to claim 1, wherein the cation
moiety contains a nitrogen cation or a phosphorus cation.
3. The latent catalyst according to claim 2, represented by the
following formula (1): ##STR25## wherein A.sup.1 represents a
nitrogen or phosphorous atom; R.sup.1, R.sup.2, R.sup.3 and R.sup.4
each represent an organic group having a substituted or
unsubstituted, aromatic or heterocyclic ring or represent a
substituted or unsubstituted aliphatic group, and R.sup.1, R.sup.2,
R.sup.3 and R.sup.4 may be the same or different from one another;
X.sup.1 represents an organic group that bonds to Y.sup.1 and
Y.sup.2; X.sup.2 represents an organic group that bonds to Y.sup.3
and Y.sup.4; Y.sup.1 and Y.sup.2 each represent a group resulting
from a proton-donating substituent through release of a proton, and
Y.sup.1 and Y.sup.2 bond to the silicon atom to form a chelate
structure; Y.sup.3 and Y.sup.4 each represent a group resulting
from a proton-donating substituent through release of a proton, and
Y.sup.3 and Y.sup.4 bond to the silicon atom to form a chelate
structure; X.sup.1 and X.sup.2 may be the same or different from
each other; Y.sup.1, Y.sup.2, Y.sup.3 and Y.sup.4 may be the same
or different from one another; and Z.sup.1 represents an organic
group having a substituted or unsubstituted, aromatic or
heterocyclic ring or represents a substituted or unsubstituted
aliphatic group.
4. The latent catalyst according to claim 3, wherein at least one
of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 in formula (1) is an
organic group having a substituted or unsubstituted aromatic
ring.
5. The latent catalyst according to claim 4, represented by the
following formula (2): ##STR26## wherein R.sup.5, R.sup.6 and
R.sup.7 each represent an organic group having a substituted or
unsubstituted, aromatic or heterocyclic ring or represent a
substituted or unsubstituted aliphatic group, and R.sup.5, R.sup.6
and R.sup.7 may be the same or different from one another; Ar
represents a substituted or unsubstituted aromatic group; X.sup.3
represents an organic group that bonds to Y.sup.5 and Y.sup.6;
X.sup.4 represents an organic group that bonds to Y.sup.7 and
Y.sup.8; Y.sup.5 and Y.sup.6 each represent a group resulting from
a proton-donating substituent through release of a proton, and
Y.sup.5 and Y.sup.6 bond to the silicon atom to form a chelate
structure; Y.sup.7 and Y.sup.8 each represent a group resulting
from a proton-donating substituent through release of a proton, and
Y.sup.7 and Y.sup.8 bond to the silicon atom to form a chelate
structure; X.sup.3 and X.sup.4 may be the same or different from
each other; Y.sup.5, Y.sup.6, Y.sup.7 and Y.sup.8 may be the same
or different from one another; and Z.sup.2 represents an organic
group having a substituted or unsubstituted, aromatic or
heterocyclic ring or represents a substituted or unsubstituted
aliphatic group.
6. The latent catalyst according to claim 5, represented by the
following formula (3): ##STR27## wherein R.sup.8, R.sup.9 and
R.sup.10 each represent one member selected from the group
consisting of a hydrogen atom, a methyl group, a methoxy group and
a hydroxyl group, and R.sup.8, R.sup.9 and R.sup.10 may be the same
or different from one another; X.sup.5 represents an organic group
that bonds to Y.sup.9 and Y.sup.10; Y.sup.9 and Y.sup.10 each
represent a group resulting from a proton-donating substituent
through release of a proton, and Y.sup.9 and Y.sup.10 may be the
same or different from each other, and Y.sup.9 and Y.sup.10 bond to
the silicon atom to form a chelate structure; and Z.sup.3
represents an organic group having a substituted or unsubstituted,
aromatic or heterocyclic ring or represents a substituted or
unsubstituted aliphatic group.
7. An epoxy resin composition comprising: (A) a compound having at
least two epoxy groups in one molecule; (B) a compound having at
least two phenolic hydroxyl groups in one molecule; and (C) the
latent catalyst for epoxy resin of any of claims 1 to 6.
8. The epoxy resin composition according to claim 7, which further
comprises (D) an inorganic filler.
9. The epoxy resin composition according to claim 8, wherein the
inorganic filler (D) is present in an amount of from 200 to 2400
parts by weight per 100 parts by weight of the sum of the compound
(A) and the compound (B).
10. A semiconductor device that comprises electronic parts
encapsulated by a cured product of the epoxy resin composition of
claim 9.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a latent catalyst for epoxy
resin, an epoxy resin composition, and a semiconductor device.
BACKGROUND OF THE INVENTION
[0002] For a method of producing semiconductor devices by
encapsulating semiconductor chips, such as IC or LSI, transfer
molding with an epoxy resin composition is suitable as it is
inexpensive and applicable to industrial mass production of the
devices, and is widely employed in the art. The properties and the
reliability of semiconductor devices are being improved by
improving epoxy resin and its curing agent, phenolic resin.
[0003] However, with the recent market tendency toward small-sized,
lightweight and high-performance electronic appliances, the degree
of integration of semiconductors for such appliances is increasing
year by year, and surface mounting of semiconductor devices is
promoted. Given that situation, the prerequisites for the epoxy
resin composition for use in encapsulating semiconductor chips are
being much severer. Accordingly, there have occurred some problems
that could not be solved by conventional epoxy resin
compositions.
[0004] These days the materials for encapsulating semiconductor
chips are required to have high flowability that is not detracted
from by the inorganic filler to be added thereto in a large amount
for improving the rapid curability thereof so as to improve the
production efficiency and for improving the heat resistance and the
reliability of encapsulated semiconductors.
[0005] An addition reaction product of a tertiary phosphine and a
quinone that has good rapid curability is added as a curing
accelerator to epoxy resin compositions for use in the filed of
electric and electronic materials, for the purpose of accelerating
the curing reaction of the curing resins (see, e.g., Patent
Document 1).
[0006] Regarding the temperature range thereof, the curing
accelerator of such a type may exhibit its curing acceleration
effect even at relatively low temperatures. Therefore, though
slightly, the curing reaction is accelerated even in the initial
stage thereof, and because of this reaction, the resin composition
shall have an increased molecular weight. The increased molecular
weight thereof causes an increase in the resin viscosity, and, as a
result, the resin composition that contains a large amount of a
filler for reliability improvement may be problematic in that its
flowability is poor and therefore its moldability is also poor.
[0007] For improving the flowability of resin compositions, various
trials have heretofore been made of using a curability-suppressing
component so as to protect the reactive substrate in the
compositions. For example, a study has been made for protecting the
active site of a curing accelerator with an ion pair to give a
latency, and latent catalysts having a salt structure of an organic
acid and a phosphonium ion are known (see, e.g., Patent Documents 2
and 3). However, since such ordinary salts contain the suppressing
component therein all the time from the initial stage to the end
stage of curing reaction, they could not attain sufficient
curability though could attain flowability. That is, conventional
latent catalysts could not satisfy both the two necessary
requirements of flowability and curability at the same time.
[0008] Patent Document 1: JP 10-025335 A (page 2)
[0009] Patent Document 2: JP 2001-098053 A (page 5)
[0010] Patent Document 3: U.S. Pat. No. 4,171,420 (pages 2-4)
SUMMARY OF THE INVENTION
[0011] An object of the invention is to provide a latent catalyst
useful for epoxy resin.
[0012] Another object of the invention is to provide an epoxy resin
composition of good curability, flowability and storability.
[0013] A still other object of the invention is to provide a
semiconductor device having excellent solder-cracking resistance
and excellent moisture-resistant reliability.
[0014] The present inventors made extensive studies so as to solve
the above-mentioned problems. As a result, the inventors obtained
the following findings (a) to (c) and have completed the present
invention based thereon.
[0015] (a) It was found that a latent catalyst, which has a site of
accelerating curing reaction of epoxy resin and a site of
suppressing the curing reaction-accelerating activity, and in which
the activity-suppressing site is dissociated under heat in curing
reaction of epoxy resin and loses the capability of suppressing the
curing reaction-accelerating activity, is extremely useful for
epoxy resin.
[0016] (b) It was found that, when the latent catalyst of such a
type as described above is mixed with an epoxy resin composition,
then the resulting epoxy resin composition satisfies good
storability, good flowability and good curability at the same
time.
[0017] (c) It was found that, even when semiconductor devices
manufactured by encapsulating electronic parts such as
semiconductor chips with a cured product of the epoxy resin
composition are exposed to high temperatures, they hardly have
defects such as cracking or delamination.
[0018] Specifically, the above-described objects of the present
invention have been achieved by providing the following (1) to
(10):
[0019] (1) A latent catalyst for epoxy resin, comprising:
[0020] a cation moiety having an activity of accelerating curing
reaction of epoxy resin; and
[0021] a silicate anion moiety of suppressing the curing
reaction-accelerating activity.
[0022] (2) The latent catalyst of above (1), wherein the cation
moiety contains a nitrogen cation or a phosphorus cation.
[0023] (3) The latent catalyst of above (2), represented by the
following formula (1): ##STR1## wherein A.sup.1 represents a
nitrogen or phosphorous atom;
[0024] R.sup.1, R.sup.2, R.sup.3 and R.sup.4 each represent an
organic group having a substituted or unsubstituted, aromatic or
heterocyclic ring or represent a substituted or unsubstituted
aliphatic group, and R.sup.1, R.sup.2, R.sup.3 and R.sup.4 may be
the same or different from one another;
[0025] X.sup.1 represents an organic group that bonds to Y.sup.1
and Y.sup.2;
[0026] X.sup.2 represents an organic group that bonds to Y.sup.3
and Y.sup.4;
[0027] Y.sup.1 and Y.sup.2 each represent a group resulting from a
proton-donating substituent through release of a proton, and
Y.sup.1 and Y.sup.2 bond to the silicon atom to form a chelate
structure;
[0028] Y.sup.3 and Y.sup.4 each represent a group resulting from a
proton-donating substituent through release of a proton, and
Y.sup.3 and Y.sup.4 bond to the silicon atom to form a chelate
structure;
[0029] X.sup.1 and X.sup.2 may be the same or different from each
other;
[0030] Y.sup.1, Y.sup.2, Y.sup.3 and Y.sup.4 may be the same or
different from one another; and
[0031] Z.sup.1 represents an organic group having a substituted or
unsubstituted, aromatic or heterocyclic ring or represents a
substituted or unsubstituted aliphatic group.
[0032] (4) The latent catalyst of above (3), wherein at least one
of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 in formula (1) is an
organic group having a substituted or unsubstituted aromatic
ring.
[0033] (5) The latent catalyst of above (4), represented by the
following formula (2): ##STR2## wherein R.sup.5, R.sup.6 and
R.sup.7 each represent an organic group having a substituted or
unsubstituted, aromatic or heterocyclic ring or represent a
substituted or unsubstituted aliphatic group, and R.sup.5, R.sup.6
and R.sup.7 may be the same or different from one another;
[0034] Ar represents a substituted or unsubstituted aromatic
group;
[0035] X.sup.3 represents an organic group that bonds to Y.sup.5
and Y.sup.6;
[0036] X.sup.4 represents an organic group that bonds to Y.sup.7
and Y.sup.8;
[0037] Y.sup.5 and Y.sup.6 each represent a group resulting from a
proton-donating substituent through release of a proton, and
Y.sup.5 and Y.sup.6 bond to the silicon atom to form a chelate
structure;
[0038] Y.sup.7 and Y.sup.8 each represent a group resulting from a
proton-donating substituent through release of a proton, and
Y.sup.7 and Y.sup.8 bond to the silicon atom to form a chelate
structure;
[0039] X.sup.3 and X.sup.4 may be the same or different from each
other;
[0040] Y.sup.5, Y.sup.6, Y.sup.7 and Y.sup.8 may be the same or
different from one another; and
[0041] Z.sup.2 represents an organic group having a substituted or
unsubstituted, aromatic or heterocyclic ring or represents a
substituted or unsubstituted aliphatic group.
[0042] (6) The latent catalyst of above (5), represented by the
following formula (3): ##STR3## wherein R.sup.8, R.sup.9 and
R.sup.10 each represent one member selected from the group
consisting of a hydrogen atom, a methyl group, a methoxy group and
a hydroxyl group, and R.sup.8, R.sup.9 and R.sup.10 may be the same
or different from one another;
[0043] X.sup.5 represents an organic group that bonds to Y.sup.9
and Y.sup.10;
[0044] Y.sup.9 and Y.sup.10 each represent a group resulting from a
proton-donating substituent through release of a proton, and
Y.sup.9 and Y.sup.10 may be the same or different from each other,
and Y.sup.9 and Y.sup.10 bond to the silicon atom to form a chelate
structure; and
[0045] Z.sup.3 represents an organic group having a substituted or
unsubstituted, aromatic or heterocyclic ring or represents a
substituted or unsubstituted aliphatic group.
[0046] (7) An epoxy resin composition comprising: [0047] (A) a
compound having at least two epoxy groups in one molecule; [0048]
(B) a compound having at least two phenolic hydroxyl groups in one
molecule; and [0049] (C) the latent catalyst for epoxy resin of any
of above (1) to (6).
[0050] (8) The epoxy resin composition of above (7), which further
comprises (D) an inorganic filler.
[0051] (9) The epoxy resin composition of above (8), wherein the
inorganic filler (D) is present in an amount of from 200 to 2400
parts by weight per 100 parts by weight of the sum of the compound
(A) and the compound (B).
[0052] (10) A semiconductor device that comprises electronic parts
encapsulated with a cured product of the epoxy resin composition of
above (9).
[0053] The latent catalyst of the invention is extremely useful for
epoxy resin curing acceleration, and when mixed in an epoxy resin
composition, an epoxy resin composition that satisfies all of good
flowability, good storability and good curability can be
obtained.
[0054] The semiconductor device of the invention has good
solder-cracking resistance and good moisture resistance, even when
exposed to high temperatures.
DETAILED DESCRIPTION OF THE INVENTION
[0055] Preferred embodiments of the latent catalyst, the epoxy
resin composition and the semiconductor device of the invention are
described below.
Latent Catalyst of the Invention
[0056] The latent catalyst of the invention has a cation moiety
capable of accelerating curing reaction of epoxy resin, and a
silicate anion moiety having the ability to suppress the curing
reaction-accelerating activity of the cation moiety. The silicate
anion is not dissociated in a temperature range lower than a
desired reaction temperature, and this makes it possible to
suppress the curing reaction-accelerating activity of the cation
moiety.
[0057] In the latent catalyst of the invention, the silicate anion
structure that has an extremely low nucleophilicity does not
readily initiate and accelerate curing reaction in a
low-temperature range, and therefore it can imparts both properties
of excellent flowability and excellent storage stability to epoxy
resin at the same time. Adducts of tertiary phosphine and
p-benzoquinone as in the related art, and intramolecular or
intermolecular salts of onium cation and phenoxide anion such as
ordinary onium-phenoxide salts readily induce curing acceleration
owing to the high nucleophilicity of the phenoxide anion therein,
and therefore they lower the flowability of resin compositions.
[0058] The silicate anion structure of extremely low
nucleophilicity cuts its chelate bond during curing reaction, for
example, under heat and dissociates itself, so that the silicate
moiety is taken in a resin and loses the function of suppressing
the curing reaction-accelerating activity of the cation moiety, and
as a result, the released cation moiety accelerates curing
reaction. Accordingly, the catalyst imparts both excellent
flowability and excellent curability of resin composition at the
same time. Intramolecular or intermolecular salts of onium cation
and borate anion such as ordinary borate salts in the related art
keep the borate anion of extremely low nucleophilicity therein all
the time during curing reaction, and therefore could not attain
satisfactory curability.
[0059] The structure (molecular form) of the latent catalyst of the
invention may be any so far as it comprises a cation moiety capable
of accelerating curing reaction of epoxy resin and an anion moiety
having the ability to suppress the curing reaction-accelerating
activity of the cation moiety, and examples thereof include, for
example, complexes or complex salts comprising an excess anion or
cation moiety coordinating therein, and other known molecular forms
formed through non-covalent bonding such as molecular compounds, as
well as simple salts comprising an anion moiety and a cation moiety
that bond to each other through ion-bonding at a ratio of 1/1.
[0060] In the latent catalyst of the invention, the cation moiety
includes, for example, a nitrogen atom, a phosphorus atom, a sulfur
atom or an iodine atom. From the aspect of the reaction activity,
the cation moiety preferably contains a nitrogen atom or a
phosphorus atom. For the cation moiety, employable are phosphines,
tertiary amines and onium salts that are used for accelerating
curing reaction of epoxy resin, and preferred are onium salts.
[0061] The latent catalyst of the invention is preferably an onium
silicate in which the cation moiety contains a nitrogen or
phosphorus atom, and the onium silicate includes those of formula
(1).
[0062] In formula (1), the atom A.sup.1 is a nitrogen or
phosphorous atom; and the substituents R.sup.1, R.sup.2, R.sup.3
and R.sup.4 bonding to the atom A.sup.1 each are an organic group
having a substituted or unsubstituted, aromatic or heterocyclic
ring or are a substituted or unsubstituted aliphatic group, and
they may be the same or different from one another. Examples of the
substituent on the organic group having an aromatic or heterocyclic
ring or on the aliphatic group include linear or branched
hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, butyl,
isobutyl and tert-butyl, aromatic hydrocarbon groups such as phenyl
and naphthyl, organic groups such as hydroxyl, nitro, sulfoxyl,
thiol and amino, and halogen groups such as fluoro, chloro and
bromo.
[0063] These substituents R.sup.1 to R.sup.4 include, for example,
phenyl, methylphenyl, methoxyphenyl, hydroxyphenyl, naphthyl,
hydroxynaphthyl, benzyl, methyl, ethyl, n-butyl, n-octyl and
cyclohexyl groups. From the aspect of the reaction activity and the
stability of the compound, preferred are substituted or
unsubstituted aromatic groups such as phenyl, methylphenyl,
methoxyphenyl, hydroxyphenyl and hydroxynaphthyl groups.
[0064] In formula (1), the substituent X.sup.1 is an organic group
that bonds to the substituents Y.sup.1 and Y.sup.2. Also, the
substituent X.sup.2 is an organic group that bonds to the
substituents Y.sup.3 and Y.sup.4 The substituents Y.sup.1 and
Y.sup.2 each are a group resulting from a proton-donating
substituent through release of a proton, and the substituents
Y.sup.1 and Y.sup.2 bond to the silicon atom to form a chelate
structure. Also, Y.sup.3 and Y.sup.4 each are a group resulting
from a proton-donating substituent through release of a proton, and
the substituents Y.sup.3 and Y.sup.4 bond to the silicon atom to
form a chelate structure. The substituents X.sup.1 and X.sup.2 may
be the same or different from each other; and the substituents
Y.sup.1, Y.sup.2, Y.sup.3 and Y.sup.4 may be the same or different
from one another.
[0065] The groups of Y.sup.1X.sup.1Y.sup.2 and
Y.sup.3X.sup.2Y.sup.4 in formula (1) result from divalent or more
polyvalent proton donors through release of two protons. The
divalent or more polyvalent proton donors include, for example,
catechol, pyrogallol, 1,2-dihydroxynaphthalene,
2,3-dihydroxynaphthalene, 2,2'-biphenol, 2,2'-binaphthol, salicylic
acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid,
chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol,
1,2-cyclohexanediol, 1,2-propanediol and glycerin. Of those,
preferred are catechol, 1,2-dihydroxynaphthalene and
2,3-dihydroxynaphthalene from the aspect of the storage stability
and the moisture-resistant reliability.
[0066] In formula (1), Z.sup.1 is an organic group having a
substituted or unsubstituted, aromatic or heterocyclic ring or is a
substituted or unsubstituted aliphatic group. Specific examples
thereof include aliphatic hydrocarbon groups such as methyl, ethyl,
propyl, butyl, hexyl and octyl groups; aromatic hydrocarbon groups
such as phenyl, benzyl, naphthyl, anthracenyl and biphenyl groups;
and reactive substituents such as glycidyloxypropyl,
mercaptopropyl, aminopropyl and vinyl groups. Of those, preferred
are methyl, phenyl, naphthyl and biphenyl groups from the aspect of
the heat stability. Examples of the substituent on the organic
group having an aromatic or heterocyclic ring or on the aliphatic
group include linear or branched hydrocarbon groups such as methyl,
ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, aromatic
hydrocarbon groups such as phenyl and naphthyl, organic groups such
as hydroxyl, nitro, sulfoxyl, thiol, amino and glycidyl ether, and
halogen groups such as fluoro, chloro and bromo.
[0067] These onium silicates as the latent catalyst according to
the invention are extremely superior to conventional curing
accelerators in the point of its properties as curing accelerators,
especially the curability, the flowability and the storability
thereof.
[0068] Of the onium silicates, more preferred latent catalysts
include those of formula (2) shown above having a phosphonium
cation.
[0069] In formula (2), the substituents R.sup.5, R.sup.6 and
R.sup.7 bonding to the phosphorus atom each are an organic group
having a substituted or unsubstituted, aromatic or heterocyclic
ring or are a substituted or unsubstituted aliphatic group, and
they may be the same or different from one another. Examples of the
substituent on the organic group having an aromatic or heterocyclic
ring or on the aliphatic group include linear or branched
hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, butyl,
isobutyl and tert-butyl, aromatic hydrocarbon groups such as phenyl
and naphthyl, organic groups such as hydroxyl, nitro, sulfoxyl,
thiol and amino, and halogen groups such as fluoro, chloro and
bromo.
[0070] These substituents R.sup.5 to R.sup.7 include, for example,
phenyl, methylphenyl, methoxyphenyl, hydroxyphenyl, naphthyl,
hydroxynaphthyl, benzyl, methyl, ethyl, n-butyl, n-octyl and
cyclohexyl groups. Specifically, as for the substituents R.sup.5,
R.sup.6 and R.sup.7 in formula (2), it is preferable that each of
substituents R.sup.5, R.sup.6 and R.sup.7 is a substituted or
unsubstituted aromatic group, such as phenyl, methylphenyl,
methoxyphenyl, hydroxyphenyl and hydroxynaphthyl groups. Latent
catalysts with such preferred substituents have especially
excellent reactivity of curing and stability of chemical
structure.
[0071] In formula (2), the substituent Ar is a substituted or
unsubstituted aromatic group. The substituent Ar includes, for
example, phenyl, methylphenyl, methoxyphenyl, hydroxyphenyl,
naphthyl and hydroxynaphthyl groups. Specifically, preferred
examples of the substituent Ar include phenyl, methylphenyl,
methoxyphenyl, hydroxyphenyl and hydroxynaphthyl groups. Latent
catalysts with such preferred substituents have especially
excellent reactivity of curing and stability of chemical structure.
Examples of the substituent on the organic group having an aromatic
or heterocyclic ring or on the aliphatic group include linear or
branched hydrocarbon groups such as methyl, ethyl, propyl,
isopropyl, butyl, isobutyl and tert-butyl, aromatic hydrocarbon
groups such as phenyl and naphthyl, organic groups such as
hydroxyl, nitro, sulfoxyl, thiol and amino, and halogen groups such
as fluoro, chloro and bromo.
[0072] In formula (2), the substituent X.sup.3 is an organic group
that bonds to the substituents Y.sup.5 and Y.sup.6. Also, the
substituent X.sup.4 is an organic group that bonds to the
substituents Y.sup.7 and Y.sup.8. The substituents Y.sup.5 and
Y.sup.6 each are a group resulting from a proton-donating
substituent through release of a proton, and the substituents
Y.sup.5 and Y.sup.6 bond to the silicon atom to form a chelate
structure. Also, the substituents Y.sup.7 and Y.sup.8 each are a
group resulting from a proton-donating substituent through release
of a proton, and the substituents Y.sup.7 and Y.sup.8 bond to the
silicon atom to form a chelate structure. The substituents X.sup.3
and X.sup.4 may be the same or different from each other; and
Y.sup.5, Y.sup.6, Y.sup.7 and Y.sup.8 may be the same or different
from one another.
[0073] The groups of Y.sup.5X.sup.3Y.sup.6 and
Y.sup.7X.sup.4Y.sup.8 in formula (2) result from divalent or more
polyvalent proton donors through release of two protons. The
divalent or more polyvalent proton donors include, for example,
catechol, pyrogallol, 1,2-dihydroxynaphthalene,
2,3-dihydroxynaphthalene, 2,2'-biphenol, 2,2'-binaphthol, salicylic
acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid,
chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol,
1,2-cyclohexanediol, 1,2-propanediol and glycerin. Of those,
preferred are catechol, 1,2-dihydroxynaphthalene and
2,3-dihydroxynaphthalene from the aspect of the storage stability
and the moisture-resistant reliability.
[0074] In formula (2), Z.sup.2 is an organic group having a
substituted or unsubstituted, aromatic or heterocyclic ring or is a
substituted or unsubstituted aliphatic group. Specific examples
thereof include aliphatic hydrocarbon groups such as methyl, ethyl,
propyl, butyl, hexyl and octyl groups; aromatic hydrocarbon groups
such as phenyl, benzyl, naphthyl, anthracenyl and biphenyl groups;
and reactive substituents such as glycidyloxypropyl,
mercaptopropyl, aminopropyl and vinyl groups. Of those, preferred
are methyl, phenyl, naphthyl and biphenyl groups from the aspect of
the heat stability. Examples of the substituent on the organic
group having an aromatic or heterocyclic ring or on the aliphatic
group include linear or branched hydrocarbon groups such as methyl,
ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, aromatic
hydrocarbon groups such as phenyl and naphthyl, organic groups such
as hydroxyl, nitro, sulfoxyl, thiol, amino and glycidyl ether, and
halogen groups such as fluoro, chloro and bromo.
[0075] Of the onium silicates, more preferred latent catalysts
include those of formula (3) shown above having a phosphonium
cation in which the organic groups bonding to the phosphorus atom
each are a substituted or unsubstituted phenyl group.
[0076] In formula (3), the substituents R.sup.8, R.sup.9 and
R.sup.10 on the phenyl groups are selected from a hydrogen atom, a
methyl group, a methoxy group and a hydroxyl group, and they may be
the same or different from each other.
[0077] In formula (3), the substituent X.sup.5 is an organic group
that bonds to the substituents Y.sup.9 and Y.sup.10. The
substituents Y.sup.9 and Y.sup.10 each are a group resulting from a
proton-donating substituent through release of a proton, and they
may be the same or different from each other, and the substituents
Y.sup.9 and Y.sup.10 bond to the silicon atom to form a chelate
structure.
[0078] The group of Y.sup.9X.sup.5Y.sup.10 in formula (3) results
from divalent or more polyvalent proton donors through release of
two protons. The divalent or more polyvalent proton donors include,
for example, catechol, pyrogallol, 1,2-dihydroxynaphthalene,
2,3-dihydroxynaphthalene, 2,2'-biphenol, 2,2'-binaphthol, salicylic
acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid,
chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol,
1,2-cyclohexanediol, 1,2-propanediol and glycerin. Of those,
preferred are catechol, 1,2-dihydroxynaphthalene and
2,3-dihydroxynaphthalene from the aspect of the storage stability
and the moisture-resistant reliability.
[0079] In formula (3), Z.sup.3 is an organic group having a
substituted or unsubstituted, aromatic or heterocyclic ring or is a
substituted or unsubstituted aliphatic group. Specific examples
thereof include aliphatic hydrocarbon groups such as methyl, ethyl,
propyl, butyl, hexyl and octyl groups; aromatic hydrocarbon groups
such as phenyl, benzyl, naphthyl, anthraceyl and biphenyl groups;
and reactive substituents such as glycidyloxypropyl,
mercaptopropyl, aminopropyl and vinyl groups. Of those, preferred
are methyl, phenyl, naphthyl and biphenyl groups from the aspect of
the heat stability. Examples of the substituent on the organic
group having an aromatic or heterocyclic ring or on the aliphatic
group include linear or branched hydrocarbon groups such as methyl,
ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, aromatic
hydrocarbon groups such as phenyl and naphthyl, organic groups such
as hydroxyl, nitro, sulfoxyl, thiol, amino and glycidyl ether, and
halogen groups such as fluoro, chloro and bromo.
[0080] The phosphonium silicates of formula (3) are preferred as
their synthesis can be made simple since the two proton-donating
substituents constituting the chelate are the same.
[0081] A method for synthesizing the latent catalyst of formula (1)
of the invention is described below.
[0082] As a synthesizing method of the latent catalyst of the
invention, it is preferable that contacting an onium salt compound
such as an onium halide with an alkali metal salt of a silicate.
The alkali metal salt of a silicate is obtained by neutralizing,
with an alkali hydroxide such as sodium hydroxide, a
trialkoxysilane (trialkoxysilane compound) and a proton donor that
can make a chelate bonding with a silicon atom. The synthesis
scheme is represented by the reaction formula shown below.
According to the synthesis method, the intended latent catalyst can
be easily synthesized at a high yield.
[0083] The trialkoxysilane (trialkoxysilane compound) includes, for
example, phenyltrimethoxysilane, phenyltriethoxysilane,
methyltrimethoxysilane, methyltriethoxysilane,
ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane
and hexyltriethoxysilane.
[0084] Examples of the onium salt compound include onium halide
compounds and onium hydroxide compounds. The onium halide compounds
include onium halide compounds having an organic group having an
optionally-substituted, aromatic or heterocyclic ring and those
having an optionally-substituted aliphatic group, while the onium
hydroxide compounds include onium hydroxide compounds having an
organic group having an optionally-substituted, aromatic or
heterocyclic ring and those having an optionally-substituted
aliphatic group. Specific examples thereof include sulfonium halide
compounds such as triphenylsulfonium bromide, ammonium halide
compounds such as methyltrioctylammonium bromide and
tetraphenylammonium bromide, and phosphonium halide compounds such
as tetrabutylphosphonium bromide, tetraphenylphosphonium bromide,
triphenyl(2-hydroxyphenyl)phosphonium bromide,
triphenyl(3-hydroxyphenyl)phosphonium bromide,
triphenyl(6-hydroxy-2-naphthalene)phosphonium bromide,
tris(4-methylphenyl)(2-hydroxyphenyl)phosphonium bromide and
tris(4-methoxyphenyl)(2-hydroxyphenyl)phosphonium bromide each of
which may be optionally substituted, and onium hydroxide compounds
such as tetraphenylphosphonium hydroxide and tetrabutylphosphonium
hydroxide, each of which may be optionally substituted. Of these,
the onium halide compounds are preferred because raw materials for
them are easily available at a low cost and they have excellent
chemical stability. ##STR4## wherein A represents a phosphorus or
nitrogen atom; R represents an organic group having a substituted
or unsubstituted, aromatic or heterocyclic ring or represents a
substituted or unsubstituted aliphatic group; X represents a
monovalent anion; R' represents an aliphatic group; and Y and Z
each represent a group resulting from a proton-donating substituent
through release of one proton; R'' represents an organic group that
bonds to the proton-donating substituents YH and ZH; R'''
represents an organic group having a substituted or unsubstituted,
aromatic or heterocyclic ring or represents a substituted or
unsubstituted aliphatic group.
[0085] In the above-mentioned reaction, the onium silicate can be
easily obtained by adding dropwise a solution of the onium salt
compound such as an onium halide compound to a solution of the
silicate complex that is formed by neutralizing a solution of the
trialkoxysilane (trialkoxysilane compound) and the proton donor
with an alkali such as sodium hydroxide, at room temperature.
[0086] The solvent for use in the reaction is, for example,
preferably an alcohol solvent such as methanol, ethanol or
propanol. For increasing the yield, the solvent may be optionally
mixed with a re-precipitation solvent such as water.
[0087] Another synthesizing method is to react the proton donor,
the trialkoxysilane compound and the onium salt compound in an
organic solvent in the presence of a metal alkoxide compound. More
specifically, the onium silicate can be prepared by a synthetic
route of mixing the proton donor that can make a chelate bonding
with a silicon atom and the trialkoxysilane compound in an organic
solvent such as alcohol which can dissolve therein these compounds;
adding a metal alkoxide compound in the solid form or adding
dropwise a solution obtained in advance by dissolving it in an
organic solvent to the resulting mixture; and then adding the onium
salt compound in the solid form or adding dropwise a solution
obtained in advance by dissolving it in an organic solvent. The
above-described preparation process enables synthesis at a high
yield.
[0088] In the present invention, the onium silicate can also be
synthesized by mixing the proton donor, the trialkoxysilane
compound and the onium salt compound in an organic solvent in the
presence of a metal alkoxide compound.
[0089] Examples of the alkoxide compound usable here include
alcoholate compounds of an alkali metal such as sodium methoxide,
sodium ethoxide, sodium-t-butoxide and potassium butoxide. Of
these, sodium methoxide is preferred from the aspect of its
cost.
[0090] The above-described reaction proceeds even in a solventless
manner, but it is preferably carried out in an organic solvent from
the aspects of the uniform reaction and yield. The reaction in an
alcohol solvent such as methanol, ethanol or propanol is more
preferred.
[0091] In the above-described reaction, the proton donor (M.sub.1)
and the trialkoxysilane compound (M.sub.2) are charged preferably
at a (M.sub.1)/(M.sub.2) molar ratio of from 0.5 to 5, with a range
of from 1.5 to 2.5 being more preferred from the standpoints of
yield and purity. The proton donor (M.sub.1) and the metal alkoxide
compound (M.sub.3) are charged preferably at a (M.sub.1)/(M.sub.3)
molar ratio of from 0.5 to 5, with a range of from 1.5 to 2.5 being
more preferred from the standpoints of yield and purity. The proton
donor (M.sub.1) and the onium salt compound (M.sub.4) are charged
preferably at a (M.sub.1)/(M.sub.4) molar ratio of from 0.5 to 5,
with a range of from 1.5 to 2.5 being more preferred from the
standpoints of yield and purity.
[0092] The above-described reaction proceeds sufficiently at room
temperature, but can also be effected under heating in order to
obtain a desired latent catalyst efficiently in a short time.
[0093] The product of the above-described reaction can have
improved purity by washing and purifying with an alcohol solvent
such as methanol or ethanol, an ether solvent such as diethyl ether
or tetrahydrofuran, or an aliphatic hydrocarbon solvent such as
n-hexane.
[0094] The above-mentioned synthetic route is one general method
for synthesizing the latent catalyst of formula (1), but the
invention is not limited thereto.
Epoxy Resin Composition of the Invention
[0095] The epoxy resin composition of the invention comprises (A) a
compound having at least two epoxy groups in one molecule, (B) a
compound having at least two phenolic hydroxyl groups in one
molecule, (C) the latent catalyst of the invention, and (c) an
inorganic filler, and optionally (D) an inorganic filler. The epoxy
resin composition has excellent curability, flowability and
storability.
[0096] The components of the epoxy resin composition of the
invention are described below.
Compound (A) Having at Least Two Epoxy Groups in One Molecule
[0097] The compound (A) having at least two epoxy groups in one
molecule for use in the invention may be any so far as it has at
least two epoxy groups in one molecule, and there is no particular
limitation posed thereon.
[0098] The compound (A) includes, for example, bisphenol-type epoxy
resins such as bisphenol A-type epoxy resins, bisphenol F-type
epoxy resins and bromobisphenol-type epoxy resins; biphenyl-type
epoxy resins, biphenylaralkyl-type epoxy resins, stilbene-type
epoxy resins, phenol-novolak-type epoxy resins, cresol-novolak-type
epoxy resins, naphthalene-type epoxy resins, dicyclopentadiene-type
epoxy resins, dihydroxybenzene-type epoxy resins; epoxy compounds
that are produced by reacting epichlorohydrin on the hydroxyl group
of phenols, phenolic resins or naphthols; epoxy resins produced
through oxidative epoxydation of olefins with peracids; glycidyl
ester-type epoxy resins and glycidylamine-type epoxy resins. These
compounds may be used either singly or in combination of two or
more thereof.
Compound (B) Having at Least Two Phenol Hydroxyl Groups in One
Molecule
[0099] The compound (B) for use in the invention has at least two
phenol hydroxyl groups in one molecule, and it acts or functions as
a curing agent for the compound (A).
[0100] The compound (B) includes phenol-novolak resins,
cresol-novolak resins, bisphenol resins, phenolaralkyl resins,
biphenylaralkyl resins, trisphenol resins, xylylene-modified
novolak resins, terpene-modified novolak resins and
dicyclopentadiene-modified phenol resins. These compounds may be
used either singly or in combination of two or more thereof.
Latent Catalyst (C)
[0101] The latent catalyst (C) for use in the epoxy resin
composition of the invention is the above-mentioned latent
catalyst. In particular, onium silicates are preferred, including,
for example, sulfonium silicate, ammonium silicate, pyridinium
silicate, phosphonium silicate, iodonium silicate, and selenium
silicate. These compounds may be used either singly or in
combination of two or more thereof.
Inorganic Filler (D)
[0102] The inorganic filler (D) may be blended with the epoxy resin
composition for the purpose of improving the solder resistance of
the resulting semiconductor devices. There is no particular
limitation posed on the kind thereof, and any of those generally
used in encapsulating materials may be used.
[0103] The inorganic filler (D) includes, for example, fused and
crushed silica, fused silica, crystalline silica, secondary
aggregated silica, alumina, titanium white, aluminium hydroxide,
talc, clay and glass fibers. They may be used either singly or in
combination of two or more thereof.
[0104] Though not particularly limited, the content (blending
amount) of the latent catalyst (C) in the epoxy resin composition
of the invention is preferably about 0.01 to 10% by weight, more
preferably about 0.1 to 5% by weight. Within the range, the epoxy
resin composition has well-balanced properties among curability,
flowability, storability, and properties of its cured products.
[0105] Also though not particularly limited, the blending ratio of
the compound (A) having at least two epoxy groups in one molecule
to the compound (B) having at least two phenolic hydroxyl groups in
one molecule is preferably such that the phenolic hydroxyl group of
the compound (B) is about 0.5 to 2 mol, more preferably about 0.7
to 1.5 mol per 1 mol of the epoxy group of the compound (A). Within
the range, the epoxy resin composition keep a suitable balance
among various properties, and the various properties are further
improved.
[0106] Also though not particularly limited, the content (blending
amount) of the inorganic filler (D) is preferably about 200 to 2400
parts by weight, more preferably about 400 to 1400 parts per 100
parts by weight of the sum of the compound (A) and the compound
(B). If the content thereof is less than the lower limit of the
range, then the inorganic filler (D) may have insufficient
reinforcing effect; on the other hand, if the content of the
inorganic filler (D) is more than the upper limit of the range,
then the flowability of the epoxy resin composition may lower and
may therefore cause filling insufficiency upon molding the epoxy
resin composition (for example, upon manufacturing semiconductor
devices).
[0107] When the content (blending amount) of the inorganic filler
(D) falls between 400 and 1400 parts by weight per 100 parts by
weight of the sum of the compound (A) and the compound (B), then
the moisture absorption of the cured products of the epoxy resin
composition becomes lower and the occurrence of solder cracks can
be prevented. The epoxy resin composition of this type has good
flowability upon heat-melting, and therefore the occurrence of wire
deformation inside semiconductor devices can be effectively
prevented.
[0108] The content (blending amount) of the inorganic filler (D) in
terms of parts by weight may be dealt with by converting it to % by
volume taking into account the specific gravity of the compound
(A), the compound (B) and the inorganic filler (D) itself.
[0109] Apart from the compounds (components) (A) to (D) mentioned
above, the epoxy resin composition of the invention may optionally
contain various additives of, for example, coupling agent such as
.gamma.-glycidoxypropyltrimethoxysilane, colorant such as carbon
black, flame retardant such as bromoepoxy resin, antimony oxide or
phosphorus compound, a low-stress component such as silicone oil or
silicone rubber, lubricant such as natural wax, synthetic wax,
higher fatty acid or its metal salt or paraffin, and
antioxidant.
[0110] To the extent that the properties of the latent catalyst (C)
that functions as a curing accelerator in the invention are not
impaired, the epoxy resin composition may contain any other known
catalyst such as triphenyl phosphine,
1,8-diazabicyclo(5.4.0)-7-undecene or 2-methylimidazole.
[0111] The epoxy resin composition of the invention may be obtained
by mixing the compounds (A) to (C) and optionally the compound (D)
along with any other additives by the use of a mixer at room
temperature, then heating and kneading the mixture with a hot roll,
a heating kneader or the like, and cooling and grinding the
resulting mixture.
[0112] The thus obtained epoxy resin composition for use as a
molding resin is molded and cured by a molding method such as
transfer molding, compression molding, injection molding or the
like to encapsulate electronic parts such as semiconductor
elements. In this way, a semiconductor device of the present
invention can be obtained.
[0113] The type of the semiconductor device of the invention is not
particularly limited. For example, it includes SIP (single inline
package), HSIP (SIP with heat sink), ZIP (zigzag inline package),
DIP (dual inline package), SDIP (shrink dual inline package), SOP
(small outline package), SSOP (shrink small outline package), TSOP
(thin small outline package), SOJ (small outline J-leaded package),
QFP (quad flat package), QFP(FP) (QFP fine pitch), TQFP (thin quad
flat package), QFJ(PLCC) (quad flat J-leaded package), BGA (ball
grid array), etc.
[0114] The thus obtained semiconductor device of the invention has
excellent solder-cracking resistance and excellent
moisture-resistant reliability.
[0115] The latent catalyst (C) of the invention, especially the
compound of formula (I) is thermally stable and the silicate anion
moiety therein is bulky. Accordingly, the ion mobility of the free
ion derived from the latent catalyst through dissociation during
curing reaction is low. This makes the solder-cracking resistance
and the moisture-resistant reliability of the semiconductor device
of the invention excellent.
[0116] In the foregoing embodiment, the epoxy resin composition of
the invention is used as an encapsulating material for
semiconductor devices. However, the application of the epoxy resin
composition of the invention is not limited thereto. Depending on
the use of the epoxy resin composition of the invention, the
addition of the inorganic filler may be omitted.
[0117] Although preferred embodiments of the latent catalyst, the
epoxy resin composition and the semiconductor device of the
invention have been illustrated above, the invention is not limited
to those embodiments.
EXAMPLES
[0118] The present invention will be illustrated in greater detail
with reference to the following Examples and Comparative Examples,
but the invention should not be construed as being limited
thereto.
[0119] Compounds C1 to C13 and triphenyl phosphine for use as a
latent catalyst were prepared.
Production of Compound C1
[0120] 7.92 g (0.040 mol) of phenyltrimethoxysilane, 8.81 g (0.080
mol) of catechol, a sodium hydroxide solution prepared by
dissolving 1.60 g (0.04 mol) of sodium hydroxide in 10 ml of
methanol, and 50 ml of methanol were put into a separable flask
(volume, 200 ml) equipped with a condenser and a stirrer, and
stirred and uniformly dissolved therein. A solution prepared by
dissolving 13.7 g (0.040 mol) of triphenylsulfonium bromide in 50
ml of methanol was gradually and dropwise added to the flask, and
then a crystal was precipitated. The crystal was taken out through
filtration, washed with water and dried in vacuum, thereby
obtaining 19.2 g of a pale whitish brown crystal.
[0121] This compound was taken as compound C1. The compound C1 was
analyzed through 1H-NMR, mass spectrometry and elementary analysis,
which confirmed that the compound C1 was the intended sulfonium
silicate of the following formula (5). The yield of the compound C1
was 82%. ##STR5## Production of Compound C2
[0122] 5.45 g (0.040 mol) of methyltrimethoxysilane, 12.82 g (0.080
mol) of 2,3-dihydroxynaphthalane, a sodium hydroxide solution
prepared by dissolving 1.60 g (0.040 mol) of sodium hydroxide in 10
ml of methanol, and 50 ml of methanol were put into a separable
flask (volume, 200 ml) equipped with a condenser and a stirrer, and
stirred and uniformly dissolved therein. A solution prepared by
dissolving 17.3 g (0.040 mol) of methyltrioctylammonium bromide in
50 ml of methanol was gradually and dropwise added to the flask,
and then a crystal was precipitated. The crystal was taken out
through filtration, washed with water and dried in vacuum, thereby
obtaining 21.0 g of a pale whitish yellow crystal.
[0123] This compound was taken as compound C2. The compound C2 was
analyzed through 1H-NMR, mass spectrometry and elementary analysis,
which confirmed that the compound C2 was the intended ammonium
silicate of the following formula (6). The yield of the compound C2
was 72%. ##STR6## Production of Compound C3
[0124] 7.92 g (0.040 mol) of phenyltrimethoxysilane, 8.81 g (0.080
mol) of catechol, a sodium hydroxide solution prepared by
dissolving 1.60 g (0.040 mol) of sodium hydroxide in 10 ml of
methanol, and 50 ml of methanol were put into a separable flask
(volume, 200 ml) equipped with a condenser and a stirrer, and
stirred and uniformly dissolved therein. A solution prepared by
dissolving 8.65 g (0.040 mol) of trimethylphenylammonium bromide in
25 ml of methanol was gradually and dropwise added to the flask,
and then a crystal was precipitated. The crystal was taken out
through filtration, washed with water and dried in vacuum, thereby
obtaining 13.7 g of a white crystal.
[0125] This compound was taken as compound C3. The compound C3 was
analyzed through 1H-NMR, mass spectrometry and elementary analysis,
which confirmed that the compound C3 is the intended ammonium
silicate of the following formula (7). The yield of the compound C3
was 75%. ##STR7## Production of Compound C4
[0126] 8.26 g (0.040 mol) of hexyltrimethoxysilane, 12.82 g (0.080
mol) of 2,3-dihydroxynaphthalane, a sodium hydroxide solution
prepared by dissolving 1.60 g (0.040 mol) of sodium hydroxide in 10
ml of methanol, and 50 ml of methanol were put into a separable
flask (volume, 200 ml) equipped with a condenser and a stirrer, and
stirred and uniformly dissolved therein. A solution prepared by
dissolving 13.6 g (0.040 mol) of tetrabutylphosphonium bromide in
25 ml of methanol was gradually and dropwise added to the flask,
and then a crystal was precipitated. The crystal was taken out
through filtration, washed with water and dried in vacuum, and it
gave 21.5 g of a pale whitish red crystal.
[0127] This compound was taken as compound C4. The compound C4 was
analyzed through 1H-NMR, mass spectrometry and elementary analysis,
which confirmed that the compound C4 is the intended phosphonium
silicate of the following formula (8). The yield of the compound C4
was 78%. ##STR8## Production of Compound C5
[0128] 5.45 g (0.040 mol) of methyltrimethoxysilane, 12.82 g (0.080
mol) of 2,3-dihydroxynaphthalane, a sodium hydroxide solution
prepared by dissolving 1.60 g (0.040 mol) of sodium hydroxide in 10
ml of methanol, and 50 ml of methanol were put into a separable
flask (volume, 200 ml) equipped with a condenser and a stirrer, and
stirred and uniformly dissolved therein. A solution prepared by
dissolving 16.8 g (0.040 mol) of tetraphenylphosphonium bromide in
25 ml of methanol was gradually and dropwise added to the flask,
and then a crystal was precipitated. The crystal was taken out
through filtration, washed with water and dried in vacuum, thereby
obtaining 21.8 g of a pale whitish red crystal.
[0129] This compound was taken as compound C5. The compound C5 was
analyzed through 1H-NMR, mass spectrometry and elementary analysis,
which confirmed that the compound C5 is the intended phosphonium
silicate of the following formula (9). The yield of the compound C5
was 78%. ##STR9## Production of Compound C6
[0130] 10.4 g (0.060 mol) of 2-bromophenol, 17.3 g (0.066 mol) of
triphenyl phosphine, 0.65 g (5 mmol) of nickel chloride, and 40 ml
of ethylene glycol were put into a separable flask (volume, 200 ml)
equipped with a condenser and a stirrer, and reacted with stirring
under heat at 160.degree. C. The reaction liquid was cooled, 40 ml
of pure water was dropwise added thereto, and the deposited crystal
was washed with toluene, taken out through filtration, and dried to
obtain triphenyl(2-hydroxyphenyl)phosphonium bromide.
[0131] Next, 3.96 g (0.020 mol) of phenyltrimethoxysilane, 6.40 g
(0.040 mol) of 2,3-dihydroxynaphthalane, a sodium hydroxide
solution prepared by dissolving 0.80 g (0.02 mol) of sodium
hydroxide in 10 ml of methanol, and 50 ml of methanol were put into
a separable flask (volume, 200 ml) equipped with a condenser and a
stirrer, and stirred and uniformly dissolved therein. A solution
prepared by dissolving 17.4 g (0.040 mol) of
triphenyl(2-hydroxyphenyl)phosphonium bromide that had been
prepared previously, in 25 ml of methanol was gradually and
dropwise added to the flask, and then a crystal was precipitated.
The crystal was taken out through filtration, washed with water and
dried in vacuum, thereby obtaining 16.7 g of a pale yellowish white
crystal.
[0132] This compound was taken as compound C6. The compound C6 was
analyzed through 1H-NMR, mass spectrometry and elementary analysis,
which confirmed that the compound C6 is the intended phosphonium
silicate molecular compound of the following formula (10). The
yield of the compound C6 was 81%. ##STR10## Production of Compound
C7
[0133] 10.4 g (0.060 mol) of 3-bromophenol, 17.3 g (0.066 mol) of
triphenyl phosphine, 0.65 g (5 mmol) of nickel chloride, and 40 ml
of ethylene glycol were put into a separable flask (volume, 200 ml)
equipped with a condenser and a stirrer, and reacted with stirring
under heat at 160.degree. C. The reaction liquid was cooled, 40 ml
of pure water was dropwise added thereto, and the deposited crystal
was washed with toluene, taken out through filtration, and dried to
obtain triphenyl(3-hydroxyphenyl)phosphonium bromide.
[0134] Next, 7.92 g (0.040 mol) of phenyltrimethoxysilane, 6.40 g
(0.040 mol) of 2,3-dihydroxynaphthalane, a sodium hydroxide
solution prepared by dissolving 1.60 g (0.04 mol) of sodium
hydroxide in 10 ml of methanol, and 50 ml of methanol were put into
a separable flask (volume, 200 ml) equipped with a condenser and a
stirrer, and stirred and uniformly dissolved therein. A solution
prepared by dissolving 17.4 g (0.040 mol) of
triphenyl(3-hydroxyphenyl)phosphonium bromide that had been
prepared previously, in 25 ml of methanol was gradually and
dropwise added to the flask, and then a crystal was precipitated.
The crystal was taken out through filtration, washed with water and
dried in vacuum, thereby obtaining 20.3 g of a pale reddish white
crystal.
[0135] This compound was taken as compound C7. The compound C7 was
analyzed through 1H-NMR, mass spectrometry and elementary analysis,
which confirmed that the compound C7 is the intended phosphonium
silicate of the following formula (11). The yield of the compound
C7 was 75%. ##STR11## Production of Compound C8
[0136] 13.4 g (0.060 mol) of 6-bromo-2-naphthol, 17.3 g (0.066 mol)
of triphenyl phosphine, 0.65 g (5 mmol) of nickel chloride, and 40
ml of ethylene glycol were put into a separable flask (volume, 200
ml) equipped with a condenser and a stirrer, and reacted with
stirring under heat at 160.degree. C. The reaction liquid was
cooled, 40 ml of pure water was dropwise added thereto, and the
deposited crystal was washed with toluene, taken out through
filtration, and dried to obtain
triphenyl(6-hydroxy-2-naphthalene)phosphonium bromide.
[0137] Next, 5.45 g (0.040 mol) of methyltrimethoxysilane, 2.8 g
(0.080 mol) of 2,3-dihydroxynaphthalane, a sodium hydroxide
solution prepared by dissolving 1.60 g (0.040 mol) of sodium
hydroxide in 10 ml of methanol, and 50 ml of methanol were put into
a separable flask (volume, 200 ml) equipped with a condenser and a
stirrer, and stirred and uniformly dissolved therein. A solution
prepared by dissolving 19.4 g (0.040 mol) of
triphenyl(6-hydroxy-2-naphthalene)phosphonium bromide that had been
prepared previously, in 25 ml of methanol was gradually and
dropwise added to the flask, and then a crystal was precipitated.
The crystal was taken out through filtration, washed with water and
dried in vacuum, thereby obtaining 20.8 g of a pale reddish white
crystal.
[0138] This compound was taken as compound C8. The compound C8 was
analyzed through 1H-NMR, mass spectrometry and elementary analysis,
which confirmed that the compound C8 is the intended phosphonium
silicate of the following formula (12). The yield of the compound
C8 was 73%. ##STR12## Production of Compound C9
[0139] 10.4 g (0.060 mol) of 2-bromophenol, 20.1 g (0.066 mol) of
tris(4-methylphenyl) phosphine, 0.65 g (5 mmol) of nickel chloride,
and 40 ml of ethylene glycol were put into a separable flask
(volume, 200 ml) equipped with a condenser and a stirrer, and
reacted with stirring under heat at 160.degree. C. The reaction
liquid was cooled, 40 ml of pure water was dropwise added thereto,
and the deposited crystal was washed with toluene, taken out
through filtration, and dried to obtain
tris(4-methylphenyl)(3-hydroxyphenyl) bromide.
[0140] Next, 6.01 g (0.040 mol) of ethyltriethoxysilane, 8.81 g
(0.080 mol) of catechol, a sodium hydroxide solution prepared by
dissolving 1.60 g (0.04 mol) of sodium hydroxide in 10 ml of
methanol, and 50 ml of methanol were put into a separable flask
(volume, 200 ml) equipped with a condenser and a stirrer, and
stirred and uniformly dissolved therein. A solution prepared by
dissolving 19.1 g (0.040 mol) of tris(4-methylphenyl)(3-
hydroxyphenyl)phosphonium bromide that had been prepared
previously, in 25 ml of methanol was gradually and dropwise added
to the flask, and then a crystal was precipitated. The crystal was
taken out through filtration, washed with water and dried in
vacuum, thereby obtaining 20.1 g of a pale reddish white
crystal.
[0141] This compound was taken as compound C9. The compound C9 was
analyzed through 1H-NMR, mass spectrometry and elementary analysis,
which confirmed that the compound C9 is the intended phosphonium
silicate of the following formula (13). The yield of the compound
C9 was 76%. ##STR13## Production of Compound C10
[0142] 10.4 g (0.060 mol) of 2-bromophenol, 23.20 g (0.066 mol) of
tris(4-methoxyphenyl) phosphine, 0.65 g (5 mmol) of nickel
chloride, and 40 ml of ethylene glycol were put into a separable
flask (volume, 200 ml) equipped with a condenser and a stirrer, and
reacted with stirring under heat at 160.degree. C. The reaction
liquid was cooled, 40 ml of pure water was dropwise added thereto,
and the deposited crystal was washed with toluene, taken out
through filtration, and dried to obtain
tris(4-methoxyphenyl)(2-hydroxyphenyl)phosphonium bromide.
[0143] Next, 7.93 g (0.040 mol) of phenyltrimethoxysilane, 15.1 g
(0.080 mol) of 3-hydroxy-2-naphthoic acid, a sodium hydroxide
solution prepared by dissolving 1.60 g (0.04 mol) of sodium
hydroxide in 10 ml of methanol, and 50 ml of methanol were put into
a separable flask (volume, 200 ml) equipped with a condenser and a
stirrer, and stirred and uniformly dissolved therein. A solution
prepared by dissolving 19.1 g (0.040 mol) of
tris(4-methoxyphenyl)(2-hydroxyphenyl)phosphonium bromide that had
been prepared previously, in 25 ml of methanol was gradually and
dropwise added to the flask, and then a crystal was precipitated.
The crystal was taken out through filtration, washed with water and
dried in vacuum, thereby obtaining 24.1 g of a pale yellowish white
crystal.
[0144] This compound was taken as compound C10. The compound C10
was analyzed through 1H-NMR, mass spectrometry and elementary
analysis, which confirmed that the compound C10 is the intended
phosphonium silicate of the following formula (14). The yield of
the compound C10 was 70%. ##STR14## Production of Compound C11
[0145] 6.49 g (0.060 mol) of benzoquinone, 17.3 g (0.066 mol) of
triphenyl phosphine, and 40 ml of acetone were put into a separable
flask (volume, 200 ml) equipped with a condenser and a stirrer, and
reacted with stirring at room temperature. The deposited crystal
was washed with acetone, taken out through filtration, and dried to
obtain triphenyl(2,5-dihydroxyphenyl)phosphobetaine.
[0146] Next, 7.92 g (0.040 mol) of phenyltrimethoxysilane, 12.8 g
(0.080 mol) of 2,3-dihydroxynaphthalene, a sodium hydroxide
solution prepared by dissolving 1.60 g (0.04 mol) of sodium
hydroxide in 10 ml of methanol, and 50 ml of methanol were put into
a separable flask (volume, 200 ml) equipped with a condenser and a
stirrer, and stirred and uniformly dissolved therein. A solution
prepared by dissolving 14.8 g (0.040 mol) of
triphenyl(2,5-dihydroxyphenyl)phosphobetaine that had been prepared
previously, in 200 ml of methanol was gradually and dropwise added
to the flask, and then a crystal was precipitated. The crystal was
taken out through filtration, washed with water and dried in
vacuum, thereby obtaining 20.0 g of a pale brownish white
crystal.
[0147] This compound was taken as compound C11. The compound C11
was analyzed through 1H-NMR, mass spectrometry and elementary
analysis, which confirmed that the compound C11 is the intended
phosphonium silicate of the following formula (15). The yield of
the compound C11 was 63%. ##STR15## Production of Compound C12
[0148] 32.0 g (0.20 mol) of 2,3-dihydroxynaphthalene, 19.8 g (0.10
mol) of phenyltrimethoxysilane and 150 ml of ethanol were put into
a separable flask (volume: 500 ml) equipped with a condenser and a
stirrer, and uniformly dissolved under stirring. A solution
prepared in advance by dissolving 5.40 g (0.10 mol) of sodium
methoxide in 20 ml of ethanol was added dropwise to the flask under
stirring, and then a solution obtained in advance by dissolving
4.19 g (0.10 ml) of tetraphenylphosphonium bromide in 100 ml of
ethanol was gradually added dropwise to the flask, whereby a
crystal was precipitated. The crystal thus precipitated was
collected by filtration, washed with water and dried in vacuum,
thereby obtaining a purified product.
[0149] The resulting compound was taken as compound C12. As a
result of analysis of the compound C12 through .sup.1H-NMR, mass
spectrometry and elementary analysis, it was confirmed that the
compound C12 is the intended phosphonium silicate represented by
the following formula (23). The yield of the compound C12 was 96%.
##STR16## Production of Compound C13
[0150] 8.26 g (0.040 mol) of hexyltrimethoxysilane, 8.81 g (0.080
mol) of catechol, a sodium hydroxide solution obtained in advance
by dissolving 1.60 g (0.040 mol) of sodium hydroxide in 10 ml of
methanol, and 50 ml of methanol were put into a separable flask
(volume: 200 ml) equipped with a condenser and a stirrer and the
mixture was stirred to yield a uniform solution. A solution
obtained in advance by mixing 27.7 g (0.040 mol) of a 40 wt. %
aqueous solution of tetrabutylphosphonium hydroxide with 25 ml of
methanol was gradually added dropwise to the flask to precipitate a
crystal. The crystal thus precipitated was collected by filtration,
washed with water and vacuum dried, whereby 19.1 g of a pale yellow
crystal was obtained.
[0151] The resulting compound was taken as compound C13. As a
result of analysis of the compound C13 through .sup.1H-NMR, mass
spectrometry and elementary analysis, it was confirmed that the
compound C13 is the intended phosphonium silicate represented by
the following formula (24). The yield of the compound C13 was 82%.
##STR17## Preparation of Epoxy Resin Composition and Manufacture of
Semiconductor Device
[0152] Epoxy resin compositions each containing any of the
above-mentioned compounds C1 to C13 and triphenyl phosphine were
prepared, and these were used in manufacturing semiconductor
devices.
Example 1
[0153] Biphenyl-type epoxy resin (YX-4000HK manufacture by Japan
Epoxy Resins Co., Ltd.) of the formula (16) shown below as the
compound (A); phenolaralkyl resin (XLC-LL manufactured by Mitsui
Chemicals Corp.) of the formula (17) shown below (in which the
number of repetitive units of 3 is a mean value) as the compound
(B); the compound C1 as the latent catalyst (C); fused spherical
silica (having a mean particle size of 15 .mu.m) as the inorganic
filler (D); carbon black, bromobisphenol A-type epoxy resin and
carnauba wax as the other additives were prepared. ##STR18##
Physical Data of Compound of Formula (16) [0154] Melting point:
105.degree. C. [0155] Epoxy equivalent: 193 [0156] ICI melt
viscosity at 150.degree. C.: 0.15 poises ##STR19## Physical Data of
Compound of Formula (17) [0157] Softening point: 77.degree. C.
[0158] Hydroxyl equivalent: 172 [0159] ICI melt viscosity at
150.degree. C.: 3.6 poises
[0160] Next, 52 parts by weight of the biphenyl-type epoxy resin,
48 parts by weight of the phenolaralkyl resin, 3.13 parts by weight
of the compound C1, 730 parts by weight of fused spherical silica,
2 parts by weight of carbon black, 2 parts by weight of
bromobisphenol A-type epoxy resin, and 2 parts by weight of
carnauba wax were mixed at room temperature, then kneaded with a
hot roll at 95.degree. C. for 8 minutes, and cooled and ground to
obtain an epoxy resin composition (thermosetting resin
composition).
[0161] 8 packages (semiconductor device) of 100-pin TQFP, and 15
packages (semiconductor device) of 16-pin DIP were manufactured,
using the epoxy resin composition as a molding resin.
[0162] 100-pin TQFP was manufactured in a mode of transfer molding
at a mold temperature of 175.degree. C. under an injection pressure
of 7.4 MPa and for a curing time of 2 minutes, followed by
post-curing at 175.degree. C. for 8 hours.
[0163] The package size of the 100-pin TQFP was 14.times.14 mm, its
thickness was 1.4 mm; the silicon chip (semiconductor chip) size
was 8.0.times.8.0 mm; and the lead frame was formed of
42-alloy.
[0164] 16-pin DIP was manufactured in a mode of transfer molding at
a mold temperature of 175.degree. C. under an injection pressure of
6.8 MPa and for a curing time of 2 minutes, followed by post-curing
at 175.degree. C. for 8 hours.
[0165] The package size of the 16-pin DIP was 6.4.times.19.8 mm,
its thickness was 3.5 mm; the silicon chip (semiconductor chip)
size was 3.5.times.3.5 mm; and the lead frame was formed of
42-alloy.
Example 2
[0166] Biphenylaralkyl-type epoxy resin (NC-3000P manufactured by
Nippon Kayaku Co., Ltd.) of the formula (18) shown below (in which
the number of repetitive units of 3 is a mean value) as the
compound (A); biphenylaralkyl-type phenol resin (MEH-7851SS
manufactured by Meiwa Kasei K.K.) of the formula (19) shown below
(in which the number of repetitive units of 3 is a mean value) as
the compound (B); the compound C1 as the latent catalyst (C); fused
spherical silica (having a mean particle size of 15 .mu.m) as the
inorganic filler (D); carbon black, bromobisphenol A-type epoxy
resin and carnauba wax as the other additives were prepared.
##STR20## Physical Data of Compound of Formula (18) [0167] Melting
point: 60.degree. C. [0168] Epoxy equivalent: 272 [0169] ICI melt
viscosity at 150.degree. C.: 1.3 poises ##STR21## Physical Data of
Compound of Formula (19) [0170] Softening point: 68.degree. C.
[0171] Hydroxyl equivalent: 199 [0172] ICI melt viscosity at
150.degree. C.: 0.9 poises
[0173] Next, 57 parts by weight of the biphenylaralkyl-type epoxy
resin, 43 parts by weight of the biphenylaralkyl-type phenol resin,
3.13 parts by weight of the compound C1, 650 parts by weight of
fused spherical silica, 2 parts by weight of carbon black, 2 parts
by weight of bromobisphenol A-type epoxy resin, and 2 parts by
weight of carnauba wax were mixed at room temperature, then kneaded
with a hot roll at 105.degree. C. for 8 minutes, and cooled and
ground to obtain an epoxy resin composition (thermosetting resin
composition).
[0174] Using the epoxy resin composition, packages (semiconductor
device) were manufactured in the same manner as in Example 1.
Example 3
[0175] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 1 except that 3.64
parts by weight of the compound C2 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 1.
Example 4
[0176] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 2 except that 3.64
parts by weight of the compound C2 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 2.
Example 5
[0177] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 1 except that 2.28
parts by weight of the compound C3 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 1.
Example 6
[0178] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 2 except that 2.28
parts by weight of the compound C3 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 2.
Example 7
[0179] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 1 except that 3.00
parts by weight of the compound C4 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 1.
Example 8
[0180] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 2 except that 3.00
parts by weight of the compound C4 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 2.
Example 9
[0181] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 1 except that 3.48
parts by weight of the compound C5 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 1.
Example 10
[0182] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 2 except that 3.48
parts by weight of the compound C5 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 2.
Example 11
[0183] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 1 except that 2.57
parts by weight of the compound C6 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 1.
Example 12
[0184] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 2 except that 2.57
parts by weight of the compound C6 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 2.
Example 13
[0185] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 1 except that 3.63
parts by weight of the compound C7 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 1.
Example 14
[0186] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 2 except that 3.63
parts by weight of the compound C7 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 2.
Example 15
[0187] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 1 except that 3.57
parts by weight of the compound C8 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 1.
Example 16
[0188] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 2 except that 3.57
parts by weight of the compound C8 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 2.
Example 17
[0189] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 1 except that 3.31
parts by weight of the compound C9 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 1.
Example 18
[0190] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 2 except that 3.31
parts by weight of the compound C9 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 2.
Example 19
[0191] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 1 except that 4.31
parts by weight of the compound C10 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 1.
Example 20
[0192] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 2 except that 4.31
parts by weight of the compound C10 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 2.
Example 21
[0193] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 1 except that 3.97
parts by weight of the compound C11 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 1.
Example 22
[0194] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 2 except that 3.97
parts by weight of the compound C11 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 2.
Example 23
[0195] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 1 except that 3.89
parts by weight of the compound C12 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 1.
Example 24
[0196] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 2 except that 3.89
parts by weight of the compound C12 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 2.
Example 25
[0197] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 1 except that 2.56
parts by weight of the compound C13 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 1.
Example 26
[0198] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 2 except that 2.56
parts by weight of the compound C13 was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 2.
Comparative Example 1
[0199] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 1 except that 1.85
parts by weight of triphenyl phosphine-benzoquinone adduct was used
in place of the compound C1. Using the epoxy resin composition,
packages (semiconductor device) were manufactured in the same
manner as in Example 1.
Comparative Example 2
[0200] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 2 except that 1.85
parts by weight of triphenyl phosphine-benzoquinone adduct was used
in place of the compound C1. Using the epoxy resin composition,
packages (semiconductor device) were manufactured in the same
manner as in Example 2.
Comparative Example 3
[0201] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 1 except that 1.00
part by weight of triphenyl phosphine was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 1.
Comparative Example 4
[0202] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 2 except that 1.00
part by weight of triphenyl phosphine was used in place of the
compound C1. Using the epoxy resin composition, packages
(semiconductor device) were manufactured in the same manner as in
Example 2.
Comparative Example 5
[0203] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 1 except that 2.57
parts by weight of C14 of the formula (20) shown below was used in
place of the compound C1. Using the epoxy resin composition,
packages (semiconductor device) were manufactured in the same
manner as in Example 1. ##STR22##
Comparative Example 6
[0204] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 2 except that 2.57
parts by weight of C14 was used in place of the compound C1. Using
the epoxy resin composition, packages (semiconductor device) were
manufactured in the same manner as in Example 2.
Comparative Example 7
[0205] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 1 except that 2.81
parts by weight of C15 of the formula (21) shown below was used in
place of the compound C1. Using the epoxy resin composition,
packages (semiconductor device) were manufactured in the same
manner as in Example 1. ##STR23##
Comparative Example 8
[0206] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 2 except that 2.81
parts by weight of C15 was used in place of the compound C1. Using
the epoxy resin composition, packages (semiconductor device) were
manufactured in the same manner as in Example 2.
Comparative Example 9
[0207] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 1 except that 3.29
parts by weight of C16 of the formula (22) shown below was used in
place of the compound C1. Using the epoxy resin composition,
packages (semiconductor device) were manufactured in the same
manner as in Example 1. ##STR24##
Comparative Example 10
[0208] An epoxy resin composition (thermosetting resin composition)
was prepared in the same manner as in Example 2 except that 3.29
parts by weight of C16 was used in place of the compound C1. Using
the epoxy resin composition, packages (semiconductor device) were
manufactured in the same manner as in Example 2.
Evaluation of Properties
[0209] The properties of the epoxy resin compositions obtained in
the Examples and the Comparative Examples were evaluated for items
(1) to (3) mentioned below, and the properties of the semiconductor
devices manufactured in the Examples and the Comparative Examples
were evaluated for items (4) and (5) mentioned below.
(1) Spiral Flow:
[0210] Using a mold for spiral flow determination according to
EMMI-I-66, each resin composition was examined at a mold
temperature of 175.degree. C. under an injection pressure of 6.8
MPa for a curing time of 2 minutes.
[0211] The spiral flow is a parameter of resin flowability. Larger
values indicate better flowability.
(2) Curing Torque:
[0212] Using a curelastmeter (Orientec's JSR Curelastmeter IV PS
Model), the torque of each resin composition was measured after 45
seconds at 175.degree. C.
[0213] Larger values of the curing torque indicate better
curability.
(3) Flow Retention:
[0214] The epoxy resin compositions were stored in air at
30.degree. C. for 1 week, and their spiral flow was measured in the
same manner as in the above item (1). The percentage (%) of the
spiral flow of the stored sample relative to that of the fresh
sample is obtained.
[0215] Larger values of the flow retention indicate better
storability.
(4) Solder-Cracking Resistance:
[0216] 100-pin TQFE was left in an atmosphere at 85.degree. C. and
85% RH for 168 hours, and then dipped in a solder bath at
260.degree. C. for 10 seconds.
[0217] Next, the samples were checked for external cracks. The
crack formation was expressed by percentage in accordance with the
formula: Crack Formation (%)=(number of cracked packages)/(number
of all packages).times.100.
[0218] In addition, the areal ratio of delamination of the silicon
chip from the cured epoxy resin composition was determined by the
use of a Scan Acoustic Tomograph. Delamination (%)=(delaminated
area)/(silicon chip area).times.100. The data of the tested 8
packages were averaged, and the mean value is expressed in terms of
percentage (%).
[0219] Smaller values of the crack formation and the delamination
indicate better solder-cracking resistance.
(5) Moisture-Resistant Reliability:
[0220] A voltage of 20 V was applied to 16-pin DIP in a water vapor
at 125.degree. C. and 100% RH, and the samples were checked for
interconnection failure. The time required until 8 of 15 packages
tested showed some interconnection failure was taken as the failure
time.
[0221] The test time was at most 500 hours. When the number of
failed packages was less than 8 at lapse of time of 500 hours, then
the failure time of the sample is indicated as over 500 hours
(>500).
[0222] Larger values of the failure time indicate better
moisture-resistant reliability.
[0223] The test data of (1) to (5) are given in Table 1 and Table
2. TABLE-US-00001 TABLE 1 Example 1 2 3 4 5 6 Composition Component
YX-4000HK 52 52 52 (wt. pts) (A) NC-3000 57 57 57 Component XLC-LL
48 48 48 (B) MEH-785155 43 43 43 Component C1 3.13 3.13 (C) C2 3.64
3.64 C3 2.28 2.28 C4 C5 C6 C7 C8 C9 C10 C11 Component Fused
spherical silica 730 650 730 650 730 650 (D) Carbon black 2 2 2 2 2
2 Bromobisphenol A-type epoxy 2 2 2 2 2 2 resin Carnauba wax 2 2 2
2 2 2 Properties Spiral flow (cm) 126 120 136 125 130 121 Curing
torque (N m) 7.79 7.91 7.05 7.13 7.24 7.35 90 Seconds torque
saturation (%) 90 91 89 90 88 90 Flow retention (%) 88 85 92 90 92
88 Solder resistance (number of external cracks, %) 0 0 0 0 0 0
Solder resistance (delamination, %) 0 0 0 0 0 0 Moisture-resistant
reliability >500 >500 >500 >500 >500 >500 Example
7 8 9 10 11 12 Composition Component YX-4000HK 52 52 52 (wt. pts)
(A) NC-3000 57 57 57 Component XLC-LL 48 48 48 (B) MEH-785155 43 43
43 Component C1 (C) C2 C3 C4 3.00 3.00 C5 3.45 3.48 C6 2.57 2.57 C7
C8 C9 C10 C11 Component Fused spherical silica 730 650 730 650 730
650 (D) Carbon black 2 2 2 2 2 2 Bromobisphenol A-type epoxy 2 2 2
2 2 2 resin Carnauba wax 2 2 2 2 2 2 Properties Spiral flow (cm)
133 126 123 115 120 111 Curing torque (N m) 7.25 7.25 7.66 7.86
7.33 7.50 90 Seconds torque saturation (%) 89 91 93 94 92 91 Flow
retention (%) 92 89 90 88 89 86 Solder resistance (number of
external cracks, %) 0 0 0 0 0 0 Solder resistance (delamination, %)
0 0 0 0 0 0 Moisture-resistant reliability >500 >500 >500
>500 >500 >500 Example 13 14 15 16 17 18 19 Composition
Component YX-4000HK 52 52 52 52 (wt. pts) (A) NC-3000 57 57 57
Component XLC-LL 48 48 48 48 (B) MEH-785155 43 43 43 Component C1
(C) C2 C3 C4 C5 C6 C7 3.63 3.63 C8 3.57 3.57 C9 3.31 3.31 C10 4.31
C11 C12 C13 Component Fused spherical silica 730 650 730 650 730
650 730 (D) Carbon black 2 2 2 2 2 2 2 Bromobisphenol A-type epoxy
2 2 2 2 2 2 2 resin Carnauba wax 2 2 2 2 2 2 2 Properties Spiral
flow (cm) 124 114 131 121 122 113 117 Curing torque (N m) 7.36 7.62
7.04 7.22 7.47 7.92 7.91 90 Seconds torque saturation (%) 90 89 88
87 89 88 88 Flow retention (%) 92 89 92 88 88 85 89 Solder
resistance (number of external cracks, %) 0 0 0 0 0 0 0 Solder
resistance (delamination, %) 0 0 0 0 0 0 0 Moisture-resistant
reliability >500 >500 >500 >500 >500 >500 >500
Example 20 21 22 23 24 25 26 Composition Component YX-4000HK 52 52
52 (wt. pts) (A) NC-3000 57 57 57 57 Component XLC-LL 48 48 48 (B)
MEH-785155 43 43 43 43 Component C1 (C) C2 C3 C4 C5 C6 C7 C8 C9 C10
4.31 C11 3.97 3.97 C12 3.89 3.89 C13 2.56 2.56 Component Fused
spherical silica 650 730 650 570 490 730 650 (D) Carbon black 2 2 2
2 2 2 2 Bromobisphenol A-type epoxy 2 2 2 2 2 2 2 resin Carnauba
wax 2 2 2 2 2 2 2 Properties Spiral flow (cm) 112 144 138 131 129
109 104 Curing torque (N m) 7.92 6.68 6.89 7.58 7.93 7.24 7.12 90
Seconds torque saturation (%) 87 86 84 92 93 93 91 Flow retention
(%) 86 93 94 92 93 90 87 Solder resistance (number of external
cracks, %) 0 0 0 0 0 0 0 Solder resistance (delamination, %) 0 0 0
0 0 0 0 Moisture-resistant reliability >500 >500 >500
>500 >500 >500 >500
[0224] TABLE-US-00002 TABLE 2 Comparative Example 1 2 3 4 5 6 7 8 9
10 Composition Component YX-4000HK 52 52 52 52 52 (wt. pts) (A)
NC-3000 57 57 57 57 57 Component XLC-LL 48 48 48 48 48 (B)
MEH-785155 43 43 43 43 43 Component Triphenyl 1.85 1.85 (C)
phosphine/p- benzoquinone adduct Ttriphenyl 1.00 1.00 phosphine C14
2.52 2.52 C15 2.81 2.81 C16 3.29 3.29 Component Fused spherical 730
650 730 650 730 650 730 650 730 650 (D) silica Carbon black 2 2 2 2
2 2 2 2 2 2 Bromobisphenol A- 2 2 2 2 2 2 2 2 2 2 type epoxy resin
Carnauba wax 2 2 2 2 2 2 2 2 2 2 Properties Spiral flow (cm) 105 99
77 65 84 81 146 140 144 139 Curing torque (N m) 7.00 7.15 3.90 4.33
7.75 7.90 5.02 6.10 4.24 5.01 90 Seconds torque saturation (%) 94
93 88 89 94 95 72 80 64 66 Flow retention (%) 86 83 78 76 86 84 86
87 90 89 Solder resistance (number of external 20 20 20 20 0 0 20
20 10 10 cracks, %) Solder resistance (delamination, %) 15 15 5 5 0
0 5 5 10 10 Moisture-resistant reliability 480 480 >500 >500
>500 >500 >500 >500 480 480
[0225] As shown in Table 1 and Table 2, the epoxy resin
compositions of Examples 1 to 26 (that are the epoxy resin
compositions of the invention) all had good curability and good
flowability, and, in addition, the packages of the Examples
encapsulated with the cured product of the resin composition (that
are the semiconductor devices of the invention) all had good
solder-cracking resistance and good moisture-resistant
reliability.
[0226] Contrary, the epoxy resin compositions of Comparative
Example 1 and Comparative Example 2 were both poor in flowability,
and the packages of these Comparative Examples were not resistant
to solder-cracking and their moisture-resistant reliability was
extremely low. The epoxy resin compositions of Comparative Example
3 and Comparative Example 4 both had remarkably poor curability and
flowability, and the packages of these Comparative Examples were
not resistant to solder-cracking. The epoxy resin compositions of
Comparative Example 5 and Comparative Example 6 were both poor in
flowability. The epoxy resin compositions of Comparative Example 7,
Comparative Example 8, Comparative Example 9 and Comparative
Example 10 were all deteriorated in curability, and could not bring
about good cracking resistance and reliability.
Examples 27 to 39, Comparative Example 11 to 15
[0227] Epoxy resin compositions (thermosetting resin compositions)
were produced in the same manner as in Examples 1, 3, 5, 7, 9, 11,
13, 15, 17, 19, 21, 23, 25 and Comparative Examples 1, 3, 5, 7, 9,
respectively, except that 26 parts by weight of the biphenyl-type
epoxy resin of formula (16) and 28.5 parts by weight of the
biphenylaralkyl-type epoxy resin of formula (18) were used as the
compound (A), and 45.5 parts by weight of the phenolaralkyl resin
of formula (17) was used as the compound (B). Using the epoxy resin
compositions, packages (semiconductor device) were
manufactured.
[0228] The epoxy resin compositions and the packages of these
Examples 27 to 39 and Comparative Examples 11 to 15 were tested and
evaluated in the same manner as above, and they gave almost the
same results as the corresponding data in Table 1 of the respective
base Example.
Examples 40 to 52, Comparative Examples 16 to 20
[0229] Epoxy resin compositions (thermosetting resin compositions)
were produced in the same manner as in Examples 1, 3, 5, 7, 9, 11,
13, 15, 17, 19, 21, 23, 25, and Comparative Examples 1, 3, 5, 7, 9,
respectively, except that 54.5 parts by weight of the biphenyl-type
epoxy resin of formula (16) was used as the compound (A), and 24
parts by weight of the phenolaralkyl resin of formula (17) and 21.5
parts by weight of the biphenylaralkyl-type phenol resin of formula
(19) were used as the compound (B). Using the epoxy resin
compositions, packages (semiconductor device) were
manufactured.
[0230] The epoxy resin compositions and the packages of these
Examples 40 to 52 and Comparative Examples 16 to 20 were tested and
evaluated in the same manner as above, and they gave almost the
same results as the corresponding data in Table 1 of the respective
base Example.
[0231] Using the latent catalyst of the invention, epoxy resin
compositions having good curability, flowability and storability
can be obtained. Similarly to epoxy resins, the latent catalyst is
suitable for thermosetting resin compositions that contains a
phosphine or phosphonium salt as a curing accelerator. The resin
composition of the invention is suitable for the field of electric
and electronic materials.
[0232] While the present invention has been described in detail and
with reference to specific embodiments thereof, it will be apparent
to one skilled in the art that various changes and modifications
can be made therein without departing from the spirit and scope
thereof.
[0233] The present application is based on Japanese patent
application Nos. 2003-307700 (filed Aug. 29, 2003) and 2004-081581
(filed Mar. 19, 2004), the contents thereof being herein
incorporated by reference.
* * * * *