U.S. patent application number 14/024077 was filed with the patent office on 2014-01-09 for inclusion complex containing epoxy resin composition for semiconductor encapsulation.
This patent application is currently assigned to NIPPON SODA CO., LTD.. The applicant listed for this patent is NIPPON SODA CO., LTD.. Invention is credited to Natsuki AMANOKURA, Masami KANEKO, Kazuo ONO.
Application Number | 20140011326 14/024077 |
Document ID | / |
Family ID | 40467688 |
Filed Date | 2014-01-09 |
United States Patent
Application |
20140011326 |
Kind Code |
A1 |
ONO; Kazuo ; et al. |
January 9, 2014 |
INCLUSION COMPLEX CONTAINING EPOXY RESIN COMPOSITION FOR
SEMICONDUCTOR ENCAPSULATION
Abstract
A solid semiconductor sealing composition that includes (A) an
epoxy resin, and (B) a clathrate complex. The clathrate complex
contains (b1) at least one of 5-hydroxyisophthalic acid and
5-nitroisophthalic acid; and (b2) at least one of
2-ethyl-4-methylimidazole and
2-phenyl-4-methyl-5-hydroxymethylimidazole. A method of sealing a
solid semiconductor using the sealing composition.
Inventors: |
ONO; Kazuo; (Ichihara,
JP) ; KANEKO; Masami; (Ichihara, JP) ;
AMANOKURA; Natsuki; (Ichihara, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
NIPPON SODA CO., LTD. |
Tokyo |
|
JP |
|
|
Assignee: |
NIPPON SODA CO., LTD.
Tokyo
JP
|
Family ID: |
40467688 |
Appl. No.: |
14/024077 |
Filed: |
September 11, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
12733462 |
Mar 3, 2010 |
|
|
|
PCT/JP2008/002603 |
Sep 19, 2008 |
|
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14024077 |
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Current U.S.
Class: |
438/127 ;
523/400 |
Current CPC
Class: |
C08G 59/686 20130101;
H01L 2924/0002 20130101; C09J 163/00 20130101; C08G 59/621
20130101; C08G 59/4014 20130101; H01L 2924/00 20130101; H01L 23/293
20130101; H01L 2924/0002 20130101 |
Class at
Publication: |
438/127 ;
523/400 |
International
Class: |
H01L 23/29 20060101
H01L023/29 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 21, 2007 |
JP |
2007-245404 |
Jul 11, 2008 |
JP |
2008-181659 |
Claims
1. A method of sealing a semiconductor comprising: applying to the
semiconductor a composition comprising: (A) an epoxy resin; and (B)
a clathrate complex comprising: (b1) at least one of
5-hydroxyisophthalic acid and 5-nitroisophthalic acid, and (b2) at
least one of 2-ethyl-4-methylimidazole and
2-phenyl-4-methyl-5-hydroxymethylimidazole.
2. A solid semiconductor sealing composition comprising: (A) an
epoxy resin; (B) a clathrate complex comprising: (b1) at least one
of 5-hydroxyisophthalic acid and 5-nitroisophthalic acid; and (b2)
at least one of 2-ethyl-4-methylimidazole and
2-phenyl-4-methyl-5-hydroxymethylimidazole; and (C) an inorganic
filler.
3. The solid semiconductor sealing composition according to claim
2, wherein the inorganic filler is present in an amount of 70 to 95
wt % with respect to a total weight of the sealing composition.
Description
[0001] This is a Continuation of application Ser. No. 12/733,462
filed Mar. 3, 2010, which in turn is a U.S. national stage
application of International Application No. PCT/JP2008/002603
filed Sep. 19, 2008. The disclosure of the prior applications is
hereby incorporated by reference herein in its entirety.
[0002] The present invention relates to an epoxy resin composition
for sealing a semiconductor, wherein a clathrate complex is used as
a curing agent and/or curing accelerator.
BACKGROUND ART
[0003] Epoxy resin compositions comprising epoxy resin, curing
agent, curing accelerator and other additives are used as a sealant
of semiconductor devices or electrical parts such as transistor,
IC, LSI, etc. Conventionally, amine compounds or imidazole
compounds, etc. were used as curing agent or curing accelerator,
while there were problems for the storage stability of epoxy resin
compositions. Recently, in order to improve the storage stability,
it has been proposed to use a clathrate complex comprising
imidazole compounds or amine compounds as guest compounds and
1,1',2,2'-tetrakis(4-hydroxyphenyl)ethane as host, as curing
accelerator (see patent document 1). However, when
1,1',2,2'-tetrakis(4-hydroxyphenyl)ethane includes imidazole
compounds or amine compounds, the storage stability of sealant at
normal temperature can be improved compared with when these
compounds are used alone or in combination, while it was not
sufficient to satisfy the sealant composition with respect to fine
specs of semiconductors which has progressed significantly in
recent years. [0004] Patent document 1: Japanese Laid-Open Patent
Application No. 2004-307545
DISCLOSURE OF THE INVENTION
Object to be Solved by the Invention
[0005] The object of the present invention is to improve the
storage stability of a sealant, to retain the flowability of the
sealant when sealing, and to achieve an efficient curing rate of
the sealant by heating to be applicable as a sealant for delicate
semiconductors.
Means to Solve the Object
[0006] The present inventors made a keen study to solve the above
objects, and found out that the above objects can be solved by
using a clathrate complex comprising at least an aromatic
carboxylic acid compound and an imidazole compound, as a curing
agent and/or curing accelerator of epoxy resin. The present
invention has been thus completed.
[0007] Specifically, the present invention relates to:
[1] an epoxy resin composition for sealing a semiconductor
comprising the following component (A) and component (B) (A) an
epoxy resin (B) a clathrate complex comprising (b1) an aromatic
carboxylic acid compound, and (b2) at least one imidazole compound
represented by formula (II)
##STR00001##
(wherein R.sub.2 represents a hydrogen atom, C1-C10 alkyl group,
phenyl group, benzyl group or cyanoethyl group; R.sub.3 to R.sub.5
represent a hydrogen atom, nitro group, halogen atom, C1-C20 alkyl
group, phenyl group, benzyl group, hydroxymethyl group or C1-C20
acyl group).
[0008] Further, the present invention relates to:
[2] a solid epoxy resin composition for sealing a semiconductor
comprising the following components (A) to (C): (A) an epoxy resin
(B) a clathrate complex comprising (b1) an aromatic carboxylic acid
compound; and (b2) at least one imidazole compound represented by
formula (II)
##STR00002##
(wherein R.sub.2 represents a hydrogen atom, C1-C10 alkyl group,
phenyl group, benzyl group or cyanoethyl group, and R.sub.3 to
R.sub.5 represent a hydrogen atom, nitro group, halogen atom,
C1-C20 alkyl group, phenyl group, benzyl group, hydroxymethyl group
or C1-C20 acyl group) (C) an inorganic filler.
[0009] Further, the present invention relates to:
[3] the epoxy resin composition according to [1] or [2], wherein
the aromatic carboxylic acid compound of (b1) is a compound
represented by formula (I-1)
##STR00003##
[0010] (wherein n1 represents any integer of 1 to 4, n2 represents
any integer of 0 to 4; R.sub.1 represents a C1-6 alkyl group, nitro
group, or hydroxy group);
or by formula (I-2)
##STR00004##
[0011] (wherein m1 represents any integer of 1 to 4; m2 represents
any integer of 0 to 2; R.sup.11 represents C1-6 alkyl group, nitro
group, hydroxy group, or a compound represented by the following
formula
##STR00005##
[0012] (wherein q represents an integer of 1 or 2; * shows a
binding position).
[4] the epoxy resin composition according to [1] or [2], wherein
the aromatic carboxylic acid compound of (b1) is at least one
selected from the group consisting of 3,5-dihydroxybenzoic acid,
isophthalic acid, terephthalic acid, 5-t-butyl isophthalic acid,
5-nitroisophthalic acid, 5-hydroxyisophthalic acid, trimellitic
acid, trimesic acid, pyromellitic acid, 2,6-naphthalene
dicarboxylic acid, 1,4-naphthalene dicarboxylic acid and
benzophenone-4,4'-dicarboxylic acid; [5] the epoxy resin
composition according to any one of [1] to [4], wherein the
clathrate complex of (B) is a clathrate complex of (b1) at least
one aromatic carboxylic acid compound selected from the group
consisting of 3,5-dihydroxybenzoic acid, isophthalic acid,
terephthalic acid, 5-t-butyl isophthalic acid, 5-nitroisophthalic
acid, 5-hydroxyisophthalic acid, trimellitic acid, trimesic acid,
pyromellitic acid, 2,6-naphthalene dicarboxylic acid,
1,4-naphthalene dicarboxylic acid and
benzophenone-4,4'-dicarboxylic acid; and (b2) at least one
imidazole compound selected from the group consisting of
2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole
and 2-phenyl-4-methyl-5-hydroxymethylimidazole.
[0013] Further, the present invention relates to:
[6] a clathrate complex comprising at least one selected from the
group consisting of trimesic acid, 2,6-naphthalene dicarboxylic
acid, 1,4-naphthalene dicarboxylic acid and
benzophenone-4,4'-dicarboxylic acid; and
[0014] at least one imidazole compound represented by formula
(II)
##STR00006##
[0015] (wherein R.sub.2 represents a hydrogen atom, C1-C10 alkyl
group, phenyl group, benzyl group or cyanoethyl group; R.sub.3 to
R.sub.5 represent a hydrogen atom, nitro group, halogen atom,
C1-C20 alkyl group, phenyl group, benzyl group, hydroxymethyl group
or C1-C20 acyl group).
BEST MODE OF CARRYING OUT THE INVENTION
[0016] The epoxy resin composition for sealing a semiconductor of
the present invention is not particularly limited as long as it
comprises
(A) an epoxy resin; and (B) a clathrate complex comprising (b1) an
aromatic carboxylic acid compound, and (b2) at least one imidazole
compound represented by formula (II)
##STR00007##
[0017] (wherein, R.sub.2 represents a hydrogen atom, C1-C10 alkyl
group, phenyl group, benzyl group or cyanoethyl group; R.sub.3 to
R.sub.5 represent a hydrogen atom, nitro group, halogen atom,
C1-C20 alkyl group, phenyl group, benzyl group, hydroxymethyl group
or C1-C20 acyl group).
[0018] As an epoxy resin of component (A), various
conventionally-known polyepoxy compounds can be used, and examples
include: aromatic glycidylether compounds such as
bis(4-hydroxyphenyl)propane diglycidylether,
bis(4-hydroxy-3,5-dibromophenyl)propane diglycidylether,
bis(4-hydroxyphenyl)ethane diglycidylether,
bis(4-hydroxyphenyl)methane diglycidylether, resorcinol
diglycidylether, phloroglucinol triglycidylether, trihydroxy
biphenyl triglycidylether, tetraglycidyl benzophenone,
bisresorcinol tetraglycidylether, tetramethyl bisphenol A
diglycidylether, bisphenol C diglycidylether, bisphenol
hexafluoropropane diglycidylether,
1,3-bis[1-(2,3-epoxypropaxy)-1-trifluoromethyl-2,2,2-trifluoroethyl]benze-
ne,
1,4-bis[1-(2,3-epoxypropaxy)-1-trifluoromethyl-2,2,2-trifluoromethyl]b-
enzene, 4,4'-bis(2,3-epoxypropoxy)octafluoro biphenyl, phenol
novolac-type bisepoxy compound, etc.; alicyclic polyepoxy compounds
such as alicyclic diepoxyacetal, alicyclic diepoxyadipate,
alicyclic diepoxycarboxylate, vinylcyclohexene dioxide, etc.;
glycidyl ester compounds such as diglycidyl phthalate, diglycidyl
tetrahydrophtalate, diglycidyl hexahydrophtalate, dimethyl
glycidylphtalate, dimethyl glycidyl hexahydrophtalate,
diglycidyl-p-oxybenzoate, diglycidyl
cyclopentane-1,3-dicarboxylate, dimer acid glycidylester, etc.;
glycidyl amine compounds such as diglycidylaniline,
diglycidyltoluidine, triglycidylaminophenol, tetraglycidyl
diaminodiphenylmethane, diglycidyl tribromoaniline, etc.; and
heterocyclic epoxy compounds such as diglycidylhydantoin, glycidyl
glycid oxyalkylhydantoin, triglycidyl isocyanurate, etc.
[0019] Component (B) is not particularly limited as long as it is a
clathrate complex comprising at least an aromatic carboxylic acid
compound, and an imidazole compound represented by formula (II)
##STR00008##
(wherein R.sub.2 represents a hydrogen atom, C1-C10 alkyl group,
phenyl group, benzyl group or cyanoethyl group, R.sub.3 to R.sub.5
represent a hydrogen atom, nitro group, halogen atom, C1-C20 alkyl
group, phenyl group, benzyl group, hydroxymethyl group or C1-C20
acyl group), and it may comprise a third component such as a
solvent, etc.
[0020] Herein, a "clathrate complex" relates to a compound wherein
2 or more molecules are bound via a bond other than a covalent
bond. More preferably, it is a crystalline compound wherein 2 or
more molecules are bound via a bond other than a covalent bond. The
compound to include is called a host compound, and the compound to
be included is called a guest compound. Further, salts are
encompassed in the herein-mentioned clathrate complex.
[0021] The ratio of the above-mentioned aromatic carboxylic acid
compound and the imidazole compound is not particularly limited as
long as it can form a clathrate complex. However, it is preferred
that the imidazole compound is 0.1 to 5.0 mol with respect to 1 mol
of the aromatic carboxylic acid compound, and more preferably 0.5
to 4.0 mol.
[0022] When a third component is contained, it is preferred that
the third component is 40 mol % or less with respect to the total
amount of the composition, more preferably 10 mol % or less.
Particularly, it is most preferred that the third component is not
contained.
[0023] The aromatic carboxylic acid compound is not particularly
limited, and the following can be exemplified:
[0024] benzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid,
4-methylbenzoic acid, 2-ethylbenzoic acid, 3-ethylbenzoic acid,
4-ethylbenzoic acid, 2-n-propylbenzoic acid, 3-n-propylbenzoic
acid, 4-n-propylbenzoic acid, 2-butylbenzoic acid, 3-butylbenzoic
acid, 4-butylbenzoic acid, 2-isopropyl benzoic acid, 3-isopropyl
benzoic acid, 4-isopropyl benzoic acid, 2-isobutyl benzoic acid,
3-isobutyl benzoic acid, 4-isobutyl benzoic acid, 2-hydroxybenzoic
acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2-nitrobenzoic
acid, 3-nitrobenzoic acid, 4-nitrobenzoic acid,
methyl-2-nitrobenzoate, methyl-3-nitrobenzoate,
methyl-4-nitrobenzoate, ethyl-2-nitrobenzoate,
ethyl-3-nitrobenzoate, ethyl-4-nitrobenzoate,
propyl-2-nitrobenzoate, propyl-3-nitrobenzoate,
propyl-4-nitrobenzoate, butyl-2-nitrobenzoate,
butyl-3-nitrobenzoate, butyl-4-nitrobenzoate, 2,3-dimethylbenzoic
acid, 2,4-dimethylbenzoic acid, 2,5-dimethylbenzoic acid,
2,6-dimethylbenzoic acid, 3,4-dimethylbenzoic acid,
3,5-dimethylbenzoic acid, 3,6-dimethylbenzoic acid,
4,5-dimethylbenzoic acid, 4,6-dimethylbenzoic acid,
2,3-diethylbenzoic acid, 2,4-diethylbenzoic acid,
2,5-diethylbenzoic acid, 2,6-diethylbenzoic acid,
3,4-diethylbenzoic acid, 3,5-diethylbenzoic acid,
3,6-diethylbenzoic acid, 4,5-diethylbenzoic acid,
4,6-diethylbenzoic acid, 2,3-dihydroxybenzoic acid,
2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid,
2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid,
3,5-dihydroxybenzoic acid, 3,6-dihydroxybenzoic acid,
4,5-dihydroxybenzoic acid, 4,6-dihydroxybenzoic acid;
[0025] phthalic acid, 3-methylphthalic acid, 4-methylphthalic acid,
5-methylphthalic acid, 6-methylphthalic acid, 3-ethylphthalic acid,
4-ethylphthalic acid, 5-ethylphthalic acid, 6-ethylphthalic acid,
3-n-propylphthalic acid, 4-n-propylphthalic acid,
5-n-propylphthalic acid, 6-n-propylphthalic acid, 3-butylphthalic
acid, 4-butylphthalic acid, 5-butylphthalic acid, 6-butylphthalic
acid, 3-isopropylphthalic acid, 4-isopropylphthalic acid,
5-isopropylphthalic acid, 6-isopropylphthalic acid,
3-isobutylphthalic acid, 4-isobutylphthalic acid,
5-isobutylphthalic acid, 6-isobutylphthalic acid, 3-hydroxyphthalic
acid, 4-hydroxyphthalic acid, 5-hydroxyphthalic acid,
6-hydroxyphthalic acid, 3,4-dihydroxyphthalic acid,
3,5-dihydroxyphthalic acid, 3,6-dihydroxyphthalic acid,
4,5-dihydroxyphthalic acid, 4,6-dihydroxyphthalic acid,
3-nitrophthalic acid, 4-nitrophthalic acid, 5-nitrophthalic acid,
6-nitrophthalic acid, 3,4-dimethylphthalic acid,
3,5-dimethylphthalic acid, 3,6-dimethylphthalic acid,
4,5-dimethylphthalic acid, 4,6-dimethylphthalic acid;
[0026] isophthalic acid, 2-methylisophthalic acid,
4-methylisophthalic acid, 5-methylisophthalic acid,
6-methylisophthalic acid, 2-ethylisophthalic acid,
4-ethylisophthalic acid, 5-ethylisophthalic acid,
6-ethylisophthalic acid, 2-n-propylisophthalic acid,
4-n-propylisophthalic acid, 5-n-propylisophthalic acid,
6-n-propylisophthalic acid, 2-isopropylisophthalic acid,
4-isopropylisophthalic acid, 5-isopropylisophthalic acid,
6-isopropylisophthalic acid, 2-butyl isophthalic acid, 4-butyl
isophthalic acid, 5-butyl isophthalic acid, 6-butyl isophthalic
acid, 2-isobutyl isophthalic acid, 4-isobutyl isophthalic acid,
5-isobutyl isophthalic acid, 6-isobutyl isophthalic acid, 4-t-butyl
isophthalic acid, 5-t-butyl isophthalic acid, 6-t-butyl isophthalic
acid, 2-hydroxyisophthalic acid, 4-hydroxyisophthalic acid,
5-hydroxyisophthalic acid, 6-hydroxyisophthalic acid,
2,4-dihydroxyisophthalic acid, 2,5-dihydroxyisophthalic acid,
2,6-dihydroxyisophthalic acid, 4,5-dihydroxyisophthalic acid,
4,6-dihydroxyisophthalic acid, 5,6-dihydroxyisophthalic acid,
2,4-dimethylisophthalic acid, 2,5-dimethylisophthalic acid,
2,6-dimethylisophthalic acid, 4,5-dimethylisophthalic acid,
4,6-dimethylisophthalic acid, 5,6-dimethylisophthalic acid,
2-nitroisophthalic acid, 4-nitroisophthalic acid,
5-nitroisophthalic acid, 6-nitroisophthalic acid,
2-methylterephthalic acid, 2-ethylterephthalic acid,
2-n-propylterephthalic acid, 2-isopropylterephthalic acid,
2-butylterephthalic acid, 2-isobutylterephthalic acid,
2-hydroxyterephthalic acid, 2,6-dihydroxyterephthalic acid,
2,6-dimethylterephthalic acid, 2-nitroterephthalic acid,
1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid
(trimellitic acid), 1,2,5-benzenetricarboxylic acid,
1,3,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid
(trimesic acid), 4-hydroxy-1,2,3-benzenetricarboxylic acid,
5-hydroxy-1,2,3-benzenetricarboxylic acid,
3-hydroxy-1,2,4-benzenetricarboxylic acid,
5-hydroxy-1,2,4-benzenetricarboxylic
6-hydroxy-1,2,4-benzenetricarboxylic acid,
1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid);
[0027] 1-naphthoic acid, 2-naphthoic acid, 2-methyl-1-naphthoic
acid, 3-methyl-1-naphthoic acid, 4-methyl-1-naphthoic acid,
5-methyl-1-naphthoic acid, 6-methyl-1-naphthoic acid,
7-methyl-1-naphthoic acid, 8-methyl-1-naphthoic acid,
1-methyl-2-naphthoic acid, 3-methyl-2-naphthoic acid,
4-methyl-2-naphthoic acid, 5-methyl-2-naphthoic acid,
6-methyl-2-naphthoic acid, 7-methyl-2-naphthoic acid,
8-methyl-2-naphthoic acid, 1,2-naphthalene dicarboxylic acid,
1,3-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic
acid, 1,5-naphthalene dicarboxylic acid, 1,6-naphthalene
dicarboxylic acid, 1,7-naphthalene dicarboxylic acid,
1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic
acid, 2,4-naphthalene dicarboxylic acid, 2,5-naphthalene
dicarboxylic acid, 2,6-naphthalene dicarboxylic acid,
2,7-naphthalene dicarboxylic acid, 2,8-naphthalene dicarboxylic
acid, 2-hydroxy-1-naphthoic acid, 3-hydroxy-1-naphthoic acid,
4-hydroxy-1-naphthoic acid, 5-hydroxy-1-naphthoic acid,
6-hydroxy-1-naphthoic acid, 7-hydroxy-1-naphthoic acid,
8-hydroxy-1-naphthoic acid, 1-hydroxy-2-naphthoic acid,
3-hydroxy-2-naphthoic acid, 4-hydroxy-2-naphthoic acid,
5-hydroxy-2-naphthoic acid, 6-hydroxy-2-naphthoic acid,
7-hydroxy-2-naphthoic acid, 8-hydroxy-2-naphthoic acid,
1,2,4,5-naphthalene tetracarboxylic acid, 2,3-dihydroxy-1-naphthoic
acid, 2,4-dihydroxy-1-naphthoic acid, 2,5-dihydroxy-1-naphthoic
acid, 2,6-dihydroxy-1-naphthoic acid, 2,7-dihydroxy-1-naphthoic
acid, 2,8-dihydroxy-1-naphthoic acid, 3,4-dihydroxy-1-naphthoic
acid, 3,5-dihydroxy-1-naphthoic acid, 3,6-dihydroxy-1-naphthoic
acid, 3,7-dihydroxy-1-naphthoic acid, 3,8-dihydroxy-1-naphthoic
acid, 4,5-dihydroxy-1-naphthoic acid, 4,6-hydroxy dihydroxy
naphthoic acid, 4,7-dihydroxy-1-naphthoic acid,
4,8-dihydroxy-1-naphthoic acid, 5,6-dihydroxy-1-naphthoic acid,
5,7-dihydroxy-1-naphthoic acid, 5,8-dihydroxy-1-naphthoic acid,
6,7-dihydroxy-1-naphthoic acid, 6,8-dihydroxy-1-naphthoic acid,
7,8-dihydroxy-1-naphthoic acid, 1,3-dihydroxy-2-naphthoic acid,
1,4-dihydroxy-2-naphthoic acid, 1,5-dihydroxy-2-naphthoic acid,
1,6-dihydroxy-2-naphthoic acid, 1,7-dihydroxy-2-naphthoic acid,
1,8-dihydroxy-2-naphthoic acid, 3,4-dihydroxy-2-naphthoic acid,
3,5-dihydroxy-2-naphthoic acid, 3,6-dihydroxy-2-naphthoic acid,
3,8-dihydroxy-2-naphthoic acid, 4,5-dihydroxy-2-naphthoic acid,
4,6-dihydroxy-2-naphthoic acid, 4,7-dihydroxy-2-naphthoic acid,
4,8-dihydroxy-2-naphthoic acid, 5,6-dihydroxy-2-naphthoic acid,
5,7-dihydroxy-2-naphthoic acid, 5,8-dihydroxy-2-naphthoic acid,
6,7-dihydroxy-2-naphthoic acid, 6,8-dihydroxy-2-naphthoic acid,
7,8-dihydroxy-2-naphthoic acid, cyclohexanecarboxylic acid,
1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,
1,4-cyclohexanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid,
1,2-decahydronaphthalene dicarboxylic acid,
1,3-decahydronaphthalene dicarboxylic acid,
1,4-decahydronaphthalene dicarboxylic acid,
1,5-decahydronaphthalene dicarboxylic acid,
1,6-decahydronaphthalene dicarboxylic acid,
1,7-decahydronaphthalene dicarboxylic acid,
1,8-decahydronaphthalene dicarboxylic acid, etc.
[0028] These aromatic carboxylic acid compounds may be used alone
or by combining two or more kinds.
[0029] Among these, it is preferred to be an aromatic carboxylic
acid compound represented by formula (I-1)
##STR00009##
[0030] (wherein n1 represents any integer of 1 to 4; n2 represents
any integer of 0 to 4; R.sub.1 represents C1-6 alkyl group, nitro
group or hydroxy group);
or formula (I-2)
##STR00010##
[0031] (wherein m1 represents any integer of 1 to 4; m2 represents
any integer of 0 to 2; R.sub.11 represents C1-6 alkyl group, nitro
group, hydroxy group or the following formula
##STR00011##
[0032] (wherein q represents an integer of 1 or 2; * represents a
binding position).
[0033] Examples of C1-6 alkyl group of R.sub.1 and R.sub.11 include
a methyl group, ethyl group, propyl group, isopropyl group,
cyclopropyl group, butyl group, isobutyl group, s-butyl group,
t-butyl group, cyclobutyl group, cyclopropylmethyl group, pentyl
group, isopentyl group, 2-methylbutyl group, neopentyl group,
1-ethylpropyl group, hexyl group, isohexyl group, 4-methylpentyl
group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl
group, 3,3-dimethylbutyl group, 2,2-dimethylbutyl group, etc.
[0034] Further, among these, it is preferred to be at least one
selected from the group consisting of 3,5-dihydroxybenzoic acid,
isophthalic acid, terephthalic acid, 5-t-butyl isophthalic acid,
5-nitroisophthalic acid, 5-hydroxyisophthalic acid, trimellitic
acid, trimesic acid, pyromellitic acid, 2,6-naphthalene
dicarboxylic acid, 1,4-naphthalene dicarboxylic acid and
benzophenone-4,4'-dicarboxylic acid.
[0035] The imidazole compound is not particularly limited as long
as it is a compound represented by formula (II)
##STR00012##
(wherein R.sub.2 represents a hydrogen atom, C1-C10 alkyl group,
phenyl group, benzyl group or cyanoethyl group; R.sub.3 to R.sub.5
represent a hydrogen atom, nitro group, halogen atom, C1-C20 alkyl
group, phenyl group, benzyl group, hydroxymethyl group or C1-C20
acyl group).
[0036] Examples of C1-C10 alkyl group of R.sub.2 include a methyl
group, ethyl group, propyl group, isopropyl group, cyclopropyl
group, butyl group, isobutyl group, s-butyl group, t-butyl group,
cyclobutyl group, cyclopropylmethyl group, pentyl group, isopentyl
group, 2-methylbutyl group, neopentyl group, 1-ethylpropyl group,
hexyl group, isohexyl group, 4-methylpentyl group, 3-methylpentyl
group, 2-methylpentyl group, 1-methylpentyl group,
3,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,1-dimethylbutyl
group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group,
2,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group,
octyl group, nonyl group, decyl group, etc.
[0037] Examples of C1-C20 alkyl group of R.sub.3 to R.sub.5 include
an undecyl group, lauryl group, palmityl group, stearyl group, etc.
besides those exemplified for alkyl group of R.sub.2.
[0038] Examples of C1-C20 acyl group of R.sub.3 to R.sub.5 include
a formyl group, acetyl group, propionyl group, butyryl group,
isobutyryl group, valeryl group, pivaloyl group, hexanoyl group,
octanoyl group, decanoyl group, lauroyl group, myristoyl group,
palmitoyl group, stearoyl group, etc.
[0039] Examples of imidazole compounds specifically include
imidazole, 1-methylimidazole, 2-methylimidazole, 3-methylimidazole,
4-methylimidazole, 5-methylimidazole, 1-ethylimidazole,
2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole,
5-ethylimidazole, 1-n-propylimidazole, 2-n-propylimidazole,
1-isopropylimidazole, 2-isopropylimidazole, 1-n-butylimidazole,
2-n-butylimidazole, 1-isobutylimidazole, 2-isobutylimidazole,
2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole,
1,2-dimethylimidazole, 1,3-dimethylimidazole,
2,4-dimethylimidazole, 2-ethyl-4-methylimidazole,
1-phenylimidazole, 2-phenyl-1H-imidazole,
4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole,
1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole,
1-cyanoethyl-2-methylimidazole,
1-cyanoethyl-2-ethyl-4-methylimidazole,
1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole,
2-phenylimidazole isocyanurate adduct, 2-methylimidazole
isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole,
2-phenyl-4-methyl-5-hydroxymethylimidazole,
1-cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy)methylimidazole,
1-dodecyl-2-methyl-3-benzylimidazolium chloride,
1-benzyl-2-phenylimidazole hydrochloride, etc.
[0040] Among these, an imidazole compound which is at least one
selected from the group consisting of 2-methylimidazole,
2-ethyl-4-methylimidazole, 2-undecylimidazole and
2-phenyl-4-methyl-5-hydroxymethylimidazole is preferred.
[0041] As for the clathrate complex of the above-mentioned aromatic
carboxylic acid compound and the imidazole compound, the
combination thereof is not limited as long as it is within the
above scope. However, a clathrate complex of an aromatic carboxylic
acid compound which is at least one selected from the group
consisting of 3,5-dihydroxybenzoic acid, isophthalic acid,
terephthalic acid, 5-t-butyl isophthalic acid, 5-nitroisophthalic
acid, 5-hydroxyisophthalic acid, trimellitic acid, trimesic acid,
pyromellitic acid, 2,6-naphthalene dicarboxylic acid,
1,4-naphthalene dicarboxylic acid and
benzophenone-4,4'-dicarboxylic acid; and an imidazole compound
which is at least one selected from the group consisting of
2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole
and 2-phenyl-4-methyl-5-hydroxymethylimidazole is more
preferred.
(Novel Clathrate Complex)
[0042] In the present invention, a clathrate complex of at least
one selected from the group consisting of trimesic acid,
2,6-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic
acid and benzophenone-4,4'-dicarboxylic acid; and at least one
imidazole compound represented by formula (II)
##STR00013##
(wherein R.sub.2 represents a hydrogen atom, C1-C10 alkyl group,
phenyl group, benzyl group or cyanoethyl group, R.sub.3 to R.sub.5
represent a hydrogen atom, nitro group, halogen atom, C1-C20 alkyl
group, phenyl group, benzyl group, hydroxymethyl group or C10-C20
acyl group) is a novel clathrate complex.
[0043] As for the method for producing a clathrate complex of
component (B), it can be obtained by mixing directly the
above-mentioned aromatic carboxylic acid compound and the imidazole
compound, or by mixing them in a solvent. Further, in case of a
material with a low boiling point, or a material with a high steam
pressure, the intended clathrate complex can be obtained by
allowing to act the steam of these materials on the above-mentioned
aromatic carboxylic acid compound. Further, by allowing to react
two or more kinds of imidazole compounds with the above-mentioned
aromatic carboxylic acid compound, a clathrate complex consisted of
plural components of 3 components or more can be obtained.
Moreover, the intended clathrate complex can be obtained by first
generating a clathrate complex of the above-mentioned aromatic
carboxylic acid compound and an imidazole compound, and then
allowing to react this clathrate complex with another imidazole
compound by a method such as mentioned in the above.
[0044] The structure of the obtained clathrate complex can be
confirmed by thermal analysis (TG and DTA), infrared absorption
spectrometry (IR), X-ray diffraction pattern, solid
[0045] NMR spectrum, etc. Further, the composition of the clathrate
complex can be confirmed by thermal analysis, .sup.1H-NMR
spectrometry, high performance liquid chromatography (HPLC),
element analysis, etc.
[0046] The 50% particle diameter of the clathrate complex of
component (B) is not particularly limited, and it is usually within
about 0.01 to 80 .mu.m, preferably about 0.01 to 30 .mu.m, and more
preferably about 0.1 to 20 .mu.m. Those which average particle
diameter exceeds about 80 .mu.m are not preferred, as the clathrate
complex particle cannot get in between the wirings of a
semiconductor when sealing.
[0047] The 50% particle diameter is the particle diameter in .mu.m
when the cumulative curve calculated by setting the particle
population as 100% is 50%.
[0048] The epoxy resin composition of the present invention
suffices to contain the above component (A) and component (B), and
it may be a solid epoxy resin composition for sealing a
semiconductor comprising an inorganic filler (C), in addition to
component (A) and component (B).
[0049] The inorganic filler (C) of the solid epoxy resin
composition for sealing a semiconductor of the present invention is
not particularly limited, and examples include silica glass,
spherical silica obtained by flame melting, spherical silica
produced by zol-gel method, etc. crystalline silica, alumina, tarc,
ammonium nitrate, silicon nitrate, magnesia, magnesium silicate,
etc. These may be used alone or by combining 2 or more kinds.
[0050] In the epoxy resin composition of the present invention,
component (B) is used as a curing agent or a curing accelerator.
When component (B) is a curing accelerator, it may further contain
a curing agent. The curing agent is not particularly limited as
long as it is a compound that cures epoxy resin by reacting with
the epoxy group in epoxy resin. As such curing agents, any of those
commonly used as a conventional curing agent of epoxy resin can be
selected and used. Examples include amine compounds such as
aliphatic amines, alicyclic and heterocyclic amines, aromatic
amines, and denatured amines; imidazole compounds, imidazoline
compounds, amide compounds, ester compounds, phenol compounds,
alcohol compounds, thiol compounds, ether compounds, thioether
compounds, urea compounds, thiourea compounds, Lewis acid
compounds, phosphorus compounds, acid-anhydride compounds, onium
salt compounds, active silicon compound-aluminum complex, etc.
[0051] As for curing agent and curing accelerator, the following
compounds can be specifically exemplified.
[0052] Examples of aliphatic amines include ethylenediamine,
trimethylenediamine, triethylenediamine, tetramethylenediamine,
hexamethylenediamine, diethylenetriamine, triethylenetetramine,
tetraethylene pentamine, dipropylene diamine,
dimethylaminopropylamine, diethylaminopropylamine,
trimethylhexamethylenediamine, pentanediamine,
bis(2-dimethylaminoethyl)ether, pentamethyldiethylenetriamine,
alkyl-t-monoamine,
1,4-diazabicyclo(2,2,2)octane(triethylenediamine),
N,N,N',N'-tetramethylhexamethylenediamine,
N,N,N',N'-tetramethylpropylenediamine,
N,N,N',N'-tetramethylethylenediamine, N,N-dimethylcyclohexylamine,
dibutylaminopropylamine, dimethylaminoethoxyethoxyethanol,
triethanolamine, dimethylaminohexanol, etc.
[0053] Examples of alicyclic and heterocyclic amines include
piperidine, piperazine, menthanediamine, isophorone diamine,
methylmorpholine, ethylmorpholine,
N,N',N''-tris(dimethylaminopropyl)hexahydro-s-triazine,
3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxyspiro(5,5)undecane adduct,
N-aminoethylpiperazine, trimethylaminoethylpiperazine,
bis(4-aminocyclohexyl)methane, N,N'-dimethylpiperazine,
1,8-diazabicyclo(4,5,0)undecene-7, etc.
[0054] Examples of aromatic amines include o-phenylenediamine,
m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane,
diaminodiphenylsulfone, benzylmethylamine, dimethylbenzylamine,
m-xylylenediamine, pyridine, picoline,
.alpha.-methylbenzylmethylamine, etc.
[0055] Examples of denatured amines include epoxy compound-added
polyamine, Michael added-polyamine, Mannich added-polyamine,
thiourea-added polyamine, ketone blocked polyamine, dicyandiamide,
guanidine, organic acid hydrazide, diamino maleonitrile,
amineimide, boron trifluoride-piperidine complex, boron
trifluoride-monoethylamine complex, etc.
[0056] Examples of imidazole compounds include imidazole,
1-methylimidazole, 2-methylimidazole, 3-methylimidazole,
4-methylimidazole, 5-methylimidazole, 1-ethylimidazole,
2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole,
5-ethylimidazole, 1-n-propylimidazole, 2-n-propylimidazole,
1-isopropylimidazole, 2-isopropylimidazole, 1-n-butylimidazole,
2-n-butylimidazole, 1-isobutylimidazole, 2-isobutylimidazole,
2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole,
1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4-dimethyl
imidazole, 2-ethyl-4-methylimidazole, 1-phenylimidazole,
2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole,
2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole,
1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole,
1-cyanoethyl-2-ethyl-4-methylimidazole,
1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole,
2-phenylimidazole isocyanurate adduct, 2-methylimidazole
isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole,
2-phenyl-4-methyl-5-hydroxymethylimidazole,
1-cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy)methylimidazole,
1-dodecyl-2-methyl-3-benzylimidazolium chloride,
1-benzyl-2-phenylimidazole hydrochloride, etc.
[0057] Examples of imidazoline compounds include
2-methylimidazoline, 2-phenylimidazoline, etc.
[0058] Examples of amide compounds include a polyamide obtained by
a condensation of a dimer acid, polyamine, etc.
[0059] Examples of ester compounds include active carbonyl
compounds such as aryl ester and thioaryl ester of carboxylic acid,
etc.
[0060] Examples of phenol compounds, alcohol compounds, thiol
compounds, ether compounds and thioether compounds include as
phenol resin curing agent, aralkyl-type phenol resin such as phenol
aralkyl resin and naphtol aralkyl resin, novolac-type phenol resin
such as phenol novolac resin, cresol novolac resin, denatured resin
thereof such as, for example epoxlylated or butylated novolac-type
phenol resin etc., dicyclopentadiene denatured phenol resin,
paraxylene denatured phenol resin, triphenol alkan-type phenol
resin, multifunctional-type phenol resin, etc. Further,
tri-2-ethylhexyl hydrochloride such as polyol, polymercaptan,
polysulphide, 2-(dimethylaminomethylphenol),
2,4,6-tris(dimethylaminomethyl)phenol,
2,4,6-tris(dimethylaminomethyl)phenol, etc. can be exemplified.
[0061] Examples of urea compound, thiourea compound, Lewis acid
compounds include butylated urea, butylated melamine, butylated
thiourea, boron trifluoride, etc.
[0062] Examples of phosphorous compounds include organic phosphine
compounds including primary phosphine such as alkyl phosphine
including ethyl phosphine and butyl phosphine, phenyl phosphine,
etc.; secondary phosphine such as dialkyl phosphine including
dimethyl phosphine and dipropylphospine, diphenyl phosphine,
methylethyl phosphine, etc.; tertiary phosphine such as trimethyl
phosphine, triethyl phosphine, triphenyl phosphine, etc.
[0063] Examples of acid anhydride compounds include phthalic
anhydride, tetrahydrophthalic anhydride, hexahydrophthalic
anhydride, methyltetrahydrophthalic anhydride,
methylhexahydrophthalic anhydride, endomethylene tetrahydrophthalic
anhydride, methylendomethylene tetrahydrophthalic anhydride, maleic
anhydride, tetramethylene maleic anhydride, trimellitic anhydride,
chlorendic anhydride, pyromellitic anhydride, dodecenyl succinic
anhydride, benzophenonetetracarboxylic anhydride, ethyleneglycol
bis(anhydrotrimellitate), glyceroltris(anhydrotrimellitate),
methylcyclohexene tetracarboxylic anhydride, polyazelaic anhydride,
etc.
[0064] Further, examples of onium salt compound and active silicon
compound-aluminum complex include aryl diazonium salt, diaryl
iodonium salt, triaryl sulfonium salt, triphenyl silanol-aluminum
complex, triphenyl methoxysilane-aluminum complex,
silylperoxide-aluminum complex, triphenyl silanol-tris(salicyl
aldehydate)aluminum complex, etc.
[0065] As for the above-mentioned curing agent, it is preferred to
use particularly an amine compound, imidazole compound and phenol
compound. Among the phenol compounds, it is more preferred to use a
phenol resin curing agent.
[0066] As for the method for producing the epoxy resin composition
for sealing a semiconductor of the present invention, it can be
produced by melting and kneading the mixture comprising each of the
above components and other additives in a given amount with the use
of kneader, roller, extrusion molding machine, etc. at a
temperature and time with which no gelatinization occurs,
subsequently cooling the resultant, and then grinding and remolding
the same. Further, in the method for producing the epoxy resin
composition for sealing a semiconductor of the present invention,
the step of melting and kneading by heating may be omitted.
[0067] The produced epoxy resin composition may be a solid or in a
liquid state, depending on its composition and producing method,
and it is preferred to be a solid. When using as a solid, it is
preferred that the content of the inorganic filler is 70 to 95%
with respect to the total epoxy resin composition.
[0068] The amount of the clathrate complex to be used may be
similar to the amount used for usual curing agent and curing
accelerator, and depends on the curing method. In case of an
addition-type curing agent, wherein a curing agent molecule is
always integrated in the cured resin by reacting with the epoxy
group, while it depends on the desired property of the resin, the
clathrate complex is generally used so that the included imidazole
compound (curing agent and/or curing accelerator) becomes 0.3 to
1.0 mol with respect to 1 mol of the epoxy group. Further, in a
case of a polymerization-type curing agent or photoinitiation-type
curing agent wherein the curing agent molecule catalytically
induces ring-opening of the epoxy group without being integrated in
the resin, and causes addition polymerization reaction between
oligomers, or in case of using as a curing accelerator, the
clathrate complex suffices to be 1.0 mol or less with respect to 1
mol of epoxy group. These clathrate complexes may be used alone or
by mixing two or more kinds.
[0069] Other additives may be added to the epoxy resin composition
for sealing a semiconductor of the present invention according to
need. Examples of the other additives include the following: silane
coupling agents such as vinyltrimethoxysilane,
vinyltriethoxysilane, .gamma.-glycidoxypropyltrimethoxysilane,
.gamma.-glycidoxypropyltriethoxysilane,
.gamma.-methacryloxypropyltrimethoxysilane,
.gamma.-methacryloxypropyltriethoxysilane,
.gamma.-aminopropyltrimethoxysilane,
.gamma.-aminopropyltriethoxysilane, N-.beta.
(aminoethyl).gamma.-aminopropyltrimethoxysilane, N-.beta.
(aminoethyl) .gamma.-aminopropyltriethoxysilane,
N-phenyl-.gamma.-aminopropyltrimethoxysilane,
N-phenyl-.gamma.-aminopropyltriethoxysilane,
.gamma.-mercaptopropyltrimethoxysilane,
.gamma.-mercaptopropyltriethoxysilane, etc.; fillers such as
calcium bicarbonate, light calcium bicarbonate, natural silica,
synthetic silica, molten silica, kaolin, clay, titanium oxide,
barium sulfate, zinc oxide, aluminum hydroxide, magnesium
hydroxide, talc, mica, wollastonite, potassium titanate, aluminum
borate, sepiolite, xonotolite, etc.; elastomer denaturing agents
such as NBR, polybutadiene, chloroprene rubber, silicone,
crosslinked NBR, crosslinked BR, acryls, core-shell acryl, urethane
rubber, polyester elastomer, functional group containing-liquid
NBR, liquid polybutadiene, liquid polyester, liquid polysulfide,
denatured silicone, urethane prepolymers, etc.;
[0070] Flame retardants such as hexabromocyclodecane,
bis(dibromopropyl)tetrabromobisphenol A,
tris(dibromopropyl)isocyanurate, tris(tribromoneopentyl)phosphate,
decabromodiphenyl oxide, bis(pentabromo)phenylethane,
tris(tribromophenoxy)triazine, ethylenebistetrabromophthalimide,
polybromophenylindane, brominated polystyrene, tetrabromobisphenol
A polycarbonate, brominated phenylene ethylene oxide,
polypentabromobenzylacrylate, triphenylphosphate,
tricresylphosphate, trixynilphosphate, cresyldiphenylphosphate,
xylyldiphenylphosphate, cresylbis(di-2,6-xylenyl)phosphate,
2-ethylhexyldiphenylphosphate, resorcinolbis(diphenyl)phosphate,
bisphenol A bis(diphenyl)phosphate, bisphenol A
bis(dicresyl)phosphate, resorcinolbis(di-2,6-xylenyl)phosphate,
tris(chloroethyl)phosphate, tris(chloropropyl)phosphate,
tris(dichloropropyl)phosphate, tris(tribromopropyl)phosphate,
diethyl-N,N-bis(2-hydroxyethyl)aminomethylphosphonate, aluminum
hydroxide treated with oxalate anion, aluminum hydroxide treated
with nitrate, aluminum hydroxide treated with high-temperature hot
water, hydrated metal compound surface-treated with stannic acid,
magnesium hydroxide surface-treated with nickel compound, magnesium
hydroxide surface-treated with silicone polymer, procobite,
multilayer surface-treated hydrated metal compound, magnesium
hydroxide treated with cation polymer, etc.; engineering plastics
such as high density polyethylene, polypropylene, polystyrene,
polymethyl methacrylate, polyvinyl chloride, nylon-6,6, polyacetal,
polyethersulphone, polyetherimide, polybutylene terephtalate,
polyether etherketone, polycarbonate, polysulphone, etc.;
plasticizers; diluents such as n-butylglycidylether,
phenylglycidylether, styrene oxide, t-butylphenylglycidylether,
dicyclopentadiene diepoxide, phenol, cresol, t-butylphenol, etc.;
extender; strengthening agent; coloring agent; thickening agent;
mold lubricant such as higher fatty acid, higher fatty acid ester,
higher fatty acid calcium, etc., including carnauba wax and
polyethylene wax, etc. The compounding amount of these additives is
not particularly limited, and the compounding amount can be
appropriately determined within the limit that the effect of the
present invention may be obtained.
[0071] Further, the epoxy resin composition for sealing a
semiconductor of the present invention can contain other resins,
besides epoxy resin. Examples of other resins include polyester
resin, acryl resin, silicon resin, polyurethane resin, etc.
EXAMPLES
[0072] Examples are shown in the following, while the present
invention is not limited to these Examples.
[Preparation of Clathrate Complex]
[0073] Clathrate complexes were prepared with the combinations
shown in the following Tables 1 to 5. Preparation of each clathrate
complex was performed by the methods shown in Example 2, Example 3
and Example 17, and similar methods.
Example 2
[0074] To a 3 L-three neck flask, 180.0 g of 5-tert butyl
isophthalic acid and 107.1 g of 2-ethyl-4-methylimidazole, and 810
ml of methanol were added, stirred and heated at reflux for 3
hours. After cooling, by performing filtration and vacuum drying,
201.3 g of the clathrate complex of 5-tert-butyl isophthalic
acid/2-ethyl-4-methylimidazole (1:1) was obtained. The clathration
of the obtained clathrate complex was confirmed by .sup.1H-NMR,
TG-DTA and XRD.
[0075] Clathrate complexes of Examples 5, 9, 12, 13, 14, 18, 23,
28, 29, 31, 33, 34, 35, 36, 38, 39, 40, 43, 44 and 45 were prepared
in the same manner.
Example 3
[0076] To a 500 ml-three neck flask, 49.8 g of isophthalic acid and
300 ml of acetone were added and stirred. Thereto, 33.1 g of
2-ethyl-4-methylimidazole dissolved separately with 60 ml of
acetone was dropped by heating. After dropping, the resultant was
heated at reflux for 3 hours, cooled, and then subjected to suction
filtration. By performing vacuum drying, 79.2 of the clathrate
complex of isophthalic acid/2-ethyl-4-methylimidazole (1:1) was
obtained. The clathration of the obtained clathrate complex was
confirmed by .sup.1H-NMR, TG-DTA and XRD.
[0077] Clathrate complexes of Examples 1, 8, 10, 11, 19, 21, 30, 37
and 46 were prepared in the same manner.
Example 17
[0078] To a 3 L-three neck flask, 43.2 g of
1,4-naphthalenedicarboxylic acid and 44.5 g of 2-undecylimidazole,
and 1000 ml of ethyl acetate were added, stirred and heated at
reflux for 3 hours. After cooling, by performing filtration and
vacuum drying, 85.9 of the clathrate complex of
1,4-naphthalenedicarboxylic acid/2-undecylimidazole (1:1) was
obtained. The obtained clathrate complex was subjected to
.sup.1H-NMR, TG-DTA and XRD to confirm the clathration.
[0079] Clathrate complexes of Examples 4, 20, 22, 27, 32 and 41
were prepared in the same manner.
[0080] In Tables 1 to 5, "2E4MZ" denotes 2-ethyl-4-methylimidazole,
"2MZ" denotes 2-methylimidazole, "C11Im" denotes
2-undecylimidazole, "2P4 MHZ" denotes
2-phenyl-4-methyl-5-hydroxymethylimidazole, and "C17Im" denotes
2-heptadecylimidazole.
TABLE-US-00001 TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7
No. S1 S2 S3 S4 S5 S6 S7 imidazole 2E4MZ 2E4MZ 2E4MZ 2E4MZ 2E4MZ
2E4MZ 2E4MZ Aromatic 2,6- 5-tert butyl isophthalic benzophenone- 5-
terephthalic 3,5- carboxylic acid naphthalene isophthalic acid
4,4'-dicarboxylic nitroisophthalic acid dihydroxy-2- dicarboxylic
acid acid acid naphthoic acid acid Host:imidazole 1:1 1:1 1:1 2:3
1:1 1:1 1:1 Carboxylic acid 400 810 300 144 800 200 200 (mmol)
Imidazole 400 972 300 288 960 200 200 (mmol) Solvent acetone
methanol acetone ethyl acetate methanol methanol methanol Solvent
amount 400 810 360 315 1200 150 150 (ml) Obtained 121.2 201.3 79.2
55.9 225.7 46.7 46.7 amount (g)
TABLE-US-00002 TABLE 2 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex.
14 Ex. 15 Ex. 16 No. S8 S9 S10 S11 S12 S13 S14 S15 S16 imidazole
2MZ 2MZ 2MZ 2MZ 2MZ 2MZ 2MZ 2MZ 2MZ Aromatic 2,6-naphthalene 5-
5-tert-butyl benzophenone- isophthalic 3,5- trimesic 5-hydroxy
terephthalic carboxylic dicarboxylic nitroisophthalic isophthalic
4,4'-dicarboxylic acid dihydroxy- acid isophthalic acid acid acid
acid acid benzoic acid acid acid Host:imidazole 1:1 1:2 1:1 2:3 1:1
1:1 1:1 1:1 1:1 Carboxylic 320 400 200 161 375 300 250 100 240 acid
(mmol) Imidazole 320 800 200 322 375 300 250 100 360 (mmol) Solvent
acetone methanol acetone acetone methanol methanol methanol
methanol methanol Solvent 800 1000 390 210 500 600 500 100 170
amount (ml) Obtained 94.1 133.2 57.4 63.0 78.4 54.3 69.1 21.0 41.5
amount (g)
TABLE-US-00003 TABLE 3 Ex. 17 Ex. 18 Ex. 19 Ex. 20 Ex. 21 Ex. 22
Ex. 23 No. S17 S18 S19 S20 S21 S22 S23 imidazole C11Im C11Im C11Im
C11Im C11Im C11Im C11Im Aromatic 1,4- trimesic acid 5-tert-
isophthalic trimellic acid 5- pyromellitic carboxylic acid
naphthalene butyl acid nitroisophthalic acid dicarboxylic
isophthalic acid acid acid Host:imidazole 1:1 2:3 1:1 1:1 1:1 1:1
1:1 Carboxylic acid 400 120 250 200 160 150 250 (mmol) Imidazole
200 180 250 200 160 150 250 (mmol) Solvent ethyl methanol acetone
ethyl acetone ethyl acetate methanol acetate acetate Solvent amount
1000 320 250 1000 1000 750 1000 (ml) Obtained 85.9 56.5 108.0 68.1
64.8 62.9 92.2 amount (g) Ex. 24 Ex. 25 Ex. 26 No. S24 S25 S26
imidazole C11Im C11Im C11Im Aromatic carboxylic acid benzophenone-
3,5-dihydroxy 5-hydroxy 4,4' benzoic acid isophthalic dicarboxylic
acid acid Host:imidazole 1:1 1:1 1:1 Carboxylic acid 14.8 150 100
(mmol) Imidazole 14.8 150 100 (mmol) Solvent ethyl acetate acetone
methanol Solvent amount (ml) 30 250 50 Obtained amount (g) 7.0 51.5
23.5
TABLE-US-00004 TABLE 4 Ex. 27 Ex. 28 Ex. 29 Ex. 30 Ex. 31 No. S27
S28 S29 S30 S31 imidazole 2P4MHZ 2P4MHZ 2P4MHZ 2P4MHZ 2P4MHZ
Aromatic carboxylic acid 1-4,naphthalene 2,6- 5-nitro- 5-tert-butyl
isophthalic dicarboxylic naphthalene isophthalic isophthalic acid
acid dicarboxylic acid acid acid Host:imidazole 1:2 1:2 1:2 1:1 1:2
Carboxylic acid (mmol) 200 100 200 150 180 Imidazole (mmol) 400 200
400 150 360 Solvent ethyl acetate methanol methanol acetone
methanol Solvent amount (ml) 850 200 600 750 500 Obtained amount
(g) 117.4 54.7 113.9 56.5 85.9 Ex. 32 Ex. 33 Ex. 34 Ex. 35 Ex. 36
No. S32 S33 S34 S35 S36 imidazole 2P4MHZ 2P4MHZ 2P4MHZ 2P4MHZ
2P4MHZ Aromatic carboxylic acid benzophenone- terephthalic
trimellic trimesic pyromellic 4,4'- acid acid acid acid
dicarboxylic acid Host:imidazole 2:1 1:1 1 :1 1:1 1:2 Carboxylic
acid (mmol) 112 200 220 220 200 Imidazole (mmol) 56 200 220 220 400
Solvent ethyl acetate methanol methanol methanol methanol Solvent
amount (ml) 35 400 1330 1200 1000 Obtained amount (g) 39.9 59.5
79.1 61.5 125.0
TABLE-US-00005 TABLE 5 Ex. 37 Ex. 38 Ex. 39 Ex. 40 Ex. 41 Ex. 42
No. S37 S38 S39 S40 S41 S42 imidazole 2P4MHZ 2P4MHZ 2MZ 2MZ 2MZ
2E4MZ Aromatic 3,5- 5-hydroxy pyromellic trimellic 1,4- 3,5-
carboxylic acid dihydroxy isophthalic acid acid naphthalene
dihyrdroxy benzoic acid acid dicarboxylic benzoic acid acid
Host:imidazole 2:3 1:1 1:1 1:1 1:1 1:1 Carboxylic acid 200 200 300
240 200 250 (mmol) Imidazole 200 200 300 240 200 500 (mmol) Solvent
acetone methanol methanol methanol ethyl acetate acetone + methanol
Solvent amount 600 230 500 300 600 1000 + 100 (ml) Obtained amount
55.0 64.6 95.5 58.4 55.2 54.3 (g) Ex. 43 Ex. 44 Ex. 45 Ex. 46 Ex.
47 Ex. 48 No. S43 S44 S45 S46 S47 S48 imidazole 2E4MZ 2E4MZ 2E4MZ
2E4MZ C17Im C17Im Aromatic trimesic pyromellic trimellic 1-4-
isophthalic trimellic carboxylic acid acid acid acid naphthalene
acid acid dicarboxylilc acid Host:imidazole 1:1 1:2 1:1 1:1 1:1 1:1
Carboxylic acid 480 200 300 200 100 20 (mmol) Imidazole 480 400 300
200 100 20 (mmol) Solvent methanol methanol methanol acetone
methanol methanol Solvent amount 800 200 200 650 200 40 (ml)
Obtained amount 128.0 86.6 72.4 63.1 39.3 8.9 (g)
[Production of Epoxy Resin Composition]
[0081] The clathrate complexes of the Examples were used as curing
catalyst, and compounded at a composition rate shown in Tables 6 to
11, respectively, and the mixture was heated at reflux at
100.degree. C. for 5 minutes, cooled and ground to produce the
epoxy resin composition for sealing a semiconductor. The
compounding amount of each composition in the Tables is shown by
part by weight.
[0082] Further, as comparative examples, imidazole compounds that
are not clathrate complex were used to produce similarly a epoxy
resin composition for sealing a semiconductor at a composition rate
shown in Table 12.
(Spiral Flow Test)
[0083] The epoxy resin composition of each Example was tableted, to
mold tablets. These tablets were subjected to injection molding by
using Archimedes spiral mold and transfer molding machine, under a
condition of 175.degree. C. at a pressure of 70 Kgf/cm.sup.2 for 3
minutes, and their length was measured. The spiral flow levels were
measured for the initiation level and the level after 96 hours at
30.degree. C., and the retention rate (%) was calculated from these
levels.
(Gelation Time)
[0084] It was measured using a gelation test apparatus at
175.degree. C.
[0085] ESCN195LL epoxy equivalent 195 (Sumitomo Chemical Co., Ltd.)
was used for o-cresol novolac epoxy resin, PSM-42610H equivalent
103 (Gunei Chemical Industry, Co. Ltd.) was used for novolac
phenol, refined granular carnauba (Toakasei Co., Ltd.) was used as
mold lubricant, KBM-403 (Shin-Etsu Chemical Co., Ltd.) was used as
coupling agent, and DENKA FB-940A spherical silica (Denki Kagaku
Kogyo K.K) was used as silica.
TABLE-US-00006 TABLE 6 Ex. 49 Ex. 50 Ex. 51 Ex. 52 Clathrate
complex No. S1 S2 S4 S5 o-cresol novolac epoxy 100 100 100 100
Novolac phenol 50 50 50 50 Mold lubricant 2 2 2 2 Coupling agent 5
5 5 5 Silica 900 900 900 900 Curing catalyst 5.926 6.035 5.405
5.834 Spiral flow level 117.5 127.2 117.7 155 (initial value) [cm]
Spiral flow level 67.8 85.8 61.2 146.5 (30.degree. C. .times. after
96 h) [cm] Retention rate 96 h 57.7% 67.5% 52.0% 94.5% after spiral
flow Gelation time [s] 22 22.6 26.1 28.7
TABLE-US-00007 TABLE 7 Ex. 53 Ex. 54 Ex. 55 Ex. 56 Ex. 57 Ex. 58
Clathrate S8 S9 S10 S11 S13 S14 complex No. o-cresol 100 100 100
100 100 100 novolac epoxy Novolac 50 50 50 50 50 50 phenol Mold
lubricant 2 2 2 2 2 2 Coupling 5 5 5 5 5 5 agent Silica 900 900 900
900 900 900 Curing 7.267 4.572 7.414 5.97 5.754 7.119 catalyst
Spiral flow 43.7 68.7 72.3 75.2 99.8 170.0 level (initial value)
[cm] Spiral flow 33.2 29.8 54.2 36.5 76.3 170.5 level (30.degree.
C. .times. after 96 h) [cm] Retention rate 76.0% 43.4% 75.0% 48.5%
76.5% 100.3% of spiral flow after 96 h Gelation time 15.9 18.4 20.2
20.2 24.5 41.5 [s]
TABLE-US-00008 TABLE 8 Ex. 59 Ex. 60 Ex. 61 Ex. 62 Ex. 63 Ex. 64
Ex. 65 Clathrate S17 S18 S19 S20 S21 S22 S23 complex No. o-cresol
novolac 100 100 100 100 100 100 100 epoxy Novolac phenol 50 50 50
50 50 50 50 Mold lubricant 2 2 2 2 2 2 2 Coupling agent 5 5 5 5 5 5
5 Silica 900 900 900 900 900 900 900 Curing catalyst 3.945 3.261
3.999 3.494 3.89 3.899 4.286 Spiral flow level 156.7 156.2 157.3
160.5 157.2 168.7 193.8 (initial value) [cm] Spiral flow level 94.2
125.2 97.8 105.2 119.5 145 198.3 (30.degree. C. .times. after 96 h)
[cm] Retention rate of 60.1% 80.2% 62.2% 65.5% 76.0% 86.0% 102.3%
spiral flow after 96 h Gelation time [s] 33.2 33.6 34.1 38.1 40.3
42.3 58.5
TABLE-US-00009 TABLE 9 Ex. 66 Ex. 67 Ex. 68 Ex. 69 Clathrate
complex No. S27 S28 S29 S30 o-cresol novolac epoxy 100 100 100 100
Novolac phenol 50 50 50 50 Mold lubricant 2 2 2 2 Coupling agent 5
5 5 5 Silica 900 900 900 900 Curing catalyst 3.149 3.149 4.244
4.361 Spiral flow level 158.5 151.2 170.5 192.7 (initial value)
[cm] Spiral flow level 99.8 104.8 165 148.8 (30.degree. C. .times.
after 96 h) [cm] Retention rate of spiral 63.0% 69.3% 96.8% 77.2%
flow after 96 h Gelation time [s] 37.7 38 39.8 43.4
TABLE-US-00010 TABLE 10 Ex. 70 Ex. 71 Ex. 72 Ex. 73 Clathrate
complex No. S31 S32 S33 S34 o-cresol novolac epoxy 100 100 100 100
Novolac phenol 50 50 50 50 Mold lubricant 2 2 2 2 Coupling agent 5
5 5 5 Silica 900 900 900 900 Curing catalyst 2.884 7.752 3.765
4.233 Spiral flow level 172.7 185.0 196.0 184.7 (initial value)
[cm] Spiral flow level 137.2 104 169.5 188.3 (30.degree. C. .times.
after 96 h) [cm] Retention rate of spiral 79.4% 56.2% 86.5% 101.9%
flow after 96 h Gelation time [s] 44 47.6 52.1 60
TABLE-US-00011 TABLE 11 Ex. 74 Ex. 75 Ex. 76 Ex. 77 Ex. 78 Ex. 79
Ex. 80 Clathrate S37 S38 S41 S42 S43 S44 S46 complex No. o-cresol
novolac 100 100 100 100 100 100 100 epoxy Novolac 50 50 50 50 50 50
50 phenol Mold 2 2 2 2 2 2 2 lubricant Coupling 5 5 5 5 5 5 5 agent
Silica 900 900 900 900 900 900 900 Curing 3.092 3.935 7.267 4.798
5.815 4.307 5.925 catalyst Spiral flow 182.5 199.7 74.5 98.7 123.3
160.8 117 level (initial value) [cm] Spiral flow 122.8 188.5 40
59.5 135.5 169.7 77.2 level (30.degree. C. .times. after 96 h) [cm]
Retention rate 67.3% 94.4% 53.7% 60.3% 109.9% 105.5% 66.0% of
spiral flow after 96 h Gelation time 37.8 47.2 18.4 24.0 40.1 44.2
28.6 [s]
TABLE-US-00012 TABLE 12 Comparative Examples Comp. Comp. Comp.
Comp. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Imidazole compound 2E4MZ 2MZ CllIm
2P4MHZ o-cresol novolac epoxy 100 100 100 100 Novolac phenol 50 50
50 50 Mold lubricant 2 2 2 2 Coupling agent 5 5 5 5 Silica 900 900
900 900 Curing catalyst 2 2 2 2 Spiral flow level 50.3 19.2 121.5
153.7 (initial value) [cm] Spiral flow level 24.5 14.7 64 61.8
(30.degree. C. .times. after 96 h) [cm] Retention rate of spiral
48.7% 76.6% 52.7% 40.2% flow after 96 h Gelation time [s] 11.5 7.6
24.2 32.4
[0086] In the Table, "2E4MZ" denotes 2-ethyl-4-methylimidazole,
"2MZ" denotes 2-methylimidazole, "C11Im" denotes
2-undecylimidazole, and "2P4 MHZ" denotes
2-phenyl-4-methyl-5-hydroxymethylimidazole.
INDUSTRIAL APPLICABILITY
[0087] By using the epoxy resin composition for sealing a
semiconductor of the present invention, it is possible to ensure
storage stability of a sealant that is applicable to delicate
semiconductor pathway, retain the flowability of the sealant when
sealing, and to cure the sealant effectively.
* * * * *