JP2008189824A - Epoxy resin composition and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition satisfying both good curing property and excellent fluidity and further, capable of imparting excellent shelf life when formulated as the epoxy resin composition and a semiconductor device excellent in solder crack resistance and moistureproof reliability. <P>SOLUTION: The epoxy resin composition comprises an epoxy resin, a compound having two or more phenolic hydroxy groups in one molecule, a curing accelerator and a curing retarding ingredient obtained by reacting an aromatic dihydroxy compound represented by general formula (1) with an alkoxysilane compound represented by general formula (2) and an amine compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an epoxy resin composition and a semiconductor device.

  In recent years, materials used for sealing semiconductor elements include inorganic fillers to improve fast curability for the purpose of improving production efficiency and heat resistance and reliability when sealing semiconductors. Even if it is highly filled, high fluidity that is not impaired is being demanded.

  In such an epoxy resin composition for the electric / electronic material field, an addition reaction product of a tertiary phosphine and a quinone has an excellent fast curing property for the purpose of accelerating the curing reaction of the resin at the time of curing. Although added as a curing accelerator (see, for example, Patent Document 1), such a curing accelerator has a temperature range that exhibits a curing acceleration effect reaching a relatively low temperature. Is slightly promoted, and this reaction causes the resin component in the resin composition to have a high molecular weight. Such a high molecular weight causes an increase in the melt viscosity of the resin composition, and as a result, in a resin composition that is highly filled with a filler for improving the reliability, a lack of fluidity is caused, thereby causing a molding failure or the like. Cause problems.

  In order to improve the fluidity of the resin composition, various attempts have been made to protect reactive substrates using components that suppress curability in the curing accelerator. For example, studies have been made to develop latency by protecting the active sites of curing accelerators with ion pairs, and latent catalysts having salt structures of various organic acids and phosphonium ions are known ( For example, see Patent Documents 2 to 4.) However, in such a latent catalyst having a normal salt structure, from the initial stage to the final stage of the curing reaction, since the curability suppressing component is always present in the salt structure, fluidity can be obtained, Curability was not sufficiently obtained, and fluidity and curability were not compatible.

Japanese Patent Laid-Open No. 10-25335 (page 2) JP 2001-98053 A (page 5) U.S. Pat. No. 4,171,420 (pages 2-4) JP 11-5829 A (page 3-4)

  In the case of an epoxy resin composition, the present invention has both excellent curability and fluidity, and further can provide excellent preservability, epoxy resin composition and solder crack resistance and moisture resistance reliability. An excellent semiconductor device is provided.

  As a result of intensive studies to solve the above-described problems, the present inventors have found the following items (a) to (b) and completed the present invention.

(A) The epoxy resin composition contains a curing delay component obtained by reacting a specific alkoxysilane compound, a specific aromatic dihydroxy compound, and an amine compound in the epoxy resin composition. It has been found that both excellent storage stability, fluidity and curability can be achieved.

(B) Furthermore, the present inventors have found that the epoxy resin composition obtained by the above method can exhibit high fluidity and good curability even when highly filled with an inorganic filler. The present invention has been completed.

  That is, the present invention of the following items (1) to (6) is achieved.

(1) An epoxy resin composition comprising an epoxy resin (A), a compound (B) having two or more phenolic hydroxyl groups in one molecule, a curing accelerator (C), and a curing retarding component (G) The curing retarding component (G) includes an aromatic dihydroxy compound (D) represented by the following general formula (1), an alkoxysilane compound (E) represented by the following general formula (2), An epoxy resin composition obtained by reacting with an amine compound (F).

［式中、Ａｒ¹は、芳香環又は複素環を有する炭素数５〜３０の有機基を表す。有機基Ａｒ¹上の２つのＯＨ基は、前記芳香環又は複素環に直接結合するものである。また、有機基Ａｒ¹上の２つのＯＨ基がプロトンを放出して形成される２つの酸素アニオン基は、珪素原子と結合してキレート構造を形成し得るものである。］

[In formula, Ar < ¹ > represents a C5-C30 organic group which has an aromatic ring or a heterocyclic ring. Two OH groups on the organic group Ar ¹ are directly bonded to the aromatic ring or heterocyclic ring. In addition, two oxygen anion groups formed by releasing protons from the two OH groups on the organic group Ar ¹ can form a chelate structure by combining with a silicon atom. ]

［式中、Ｒ¹は、炭素数１〜４の脂肪族基を示し、互いに同一でも異なっていてもよい。Ｘ¹は、芳香環を有する炭素数６〜１５の有機基、又は炭素数１〜１５の脂肪族基を示す。ａは３または４を示す。］

[In formula, R < ¹ > shows a C1-C4 aliphatic group, and may mutually be same or different. X ¹ represents an organic group having from 6 to 15 carbon atoms having an aromatic ring, or an aliphatic group having 1 to 15 carbon atoms. a represents 3 or 4. ]

(2) The epoxy resin composition according to item (1), wherein the amine compound (F) is an aromatic amine compound represented by the following general formula (3).

［式中、Ｒ²及びＲ³は、それぞれ、水素原子及び炭素数１〜６の有機基を示し、互いに同一でも異なっていてもよく、Ｒ²とＲ³が互いに結合して環構造を形成してもよい。式中、Ａｒ²は、芳香環を有する有機基を示す。有機基Ａｒ²上の窒素原子は前記芳香環に直接結合するものである。ｂは１以上６以下の整数を示す。］

[Wherein R ² and R ³ each represent a hydrogen atom and an organic group having 1 to 6 carbon atoms, and may be the same or different from each other, and R ² and R ³ are bonded to each other to form a ring structure. May be. In the formula, Ar ² represents an organic group having an aromatic ring. The nitrogen atom on the organic group Ar ² is directly bonded to the aromatic ring. b represents an integer of 1 to 6. ]

(3) The epoxy according to item (1) or item (2), wherein the curing retardation component (G) is an ammonium silicate compound represented by the following general formula (4) or the following general formula (5): Resin composition.

[In formula, Q shows ammonium formed when an amine compound is protonated. In the formula, Ar ³ represents an organic group having 5 to 30 carbon atoms having an aromatic ring or a heterocyclic ring. Two oxygen atoms on the organic group Ar ³ are directly bonded to the aromatic ring or heterocyclic ring. In addition, two oxygen anion groups formed by releasing protons from two OH groups on the organic group Ar ³ can form a chelate structure by bonding with a silicon atom. Wherein, X ² represents an organic group having from 6 to 15 carbon atoms having an aromatic ring, or an aliphatic group having 1 to 15 carbon atoms. c represents an integer of 1 to 6. d represents 1 or 2. e and f each represent an integer of 1 to 6 that satisfies e × d = 2f. ]

  Item (1) to Item (3), wherein the curing delay component (G) is an ammonium silicate compound represented by the following general formula (6) or the following general formula (7). Epoxy resin composition.

[Wherein, R ⁴ and R ⁵ each represent a hydrogen atom and an organic group having 1 to 6 carbon atoms, and may be the same or different, and R ⁴ and R ⁵ are bonded to each other to form a ring structure. May be. In the formula, Ar ⁴ represents an organic group having an aromatic ring, and a nitrogen atom on the organic group Ar ⁴ is directly bonded to the aromatic ring. In the formula, Ar ⁵ represents an organic group having 5 to 30 carbon atoms having an aromatic ring or a heterocyclic ring, and two oxygen atoms on the organic group Ar ⁵ are directly bonded to the aromatic ring or the heterocyclic ring. . In addition, two oxygen anion groups formed by releasing protons from two OH groups on the organic group Ar ⁵ can form a chelate structure by combining with silicon atoms. Wherein, X ³ represents an organic group having from 6 to 15 carbon atoms having an aromatic ring, or an aliphatic group having 1 to 15 carbon atoms. m represents an integer of 1 to 6. n represents 1 or 2. p and q represent an integer of 1 to 6 that satisfies p × n = 2q. ]

(5) The epoxy resin composition according to any one of (1) to (4), wherein the epoxy resin composition further includes an inorganic filler.
(6) A semiconductor device formed by sealing an electronic component with a cured product of the epoxy resin composition according to any one of (1) to (5).

The epoxy resin composition of the present invention has both excellent curability, fluidity and storage stability, and can exhibit good fluidity even when an inorganic filler is used.
In addition, the semiconductor device of the present invention can be obtained with excellent reliability in characteristics such as solder crack resistance and moisture resistance reliability.

  Hereinafter, preferred embodiments of the epoxy resin composition of the present invention will be described.

  The epoxy resin composition of the present invention comprises an epoxy resin (A), a compound (B) having two or more phenolic hydroxyl groups in one molecule, a curing accelerator (C), a curing retardation component (G), The curing delay component (G) is an aromatic dihydroxy compound (D) represented by the general formula (1) and an alkoxysilane represented by the general formula (2). By using what is obtained by reacting the compound (E) with the amine compound (F), the epoxy resin (A) and two or more phenolic hydroxyl groups in one molecule in a specific temperature range. Reaction with a compound (B) can be delayed, and, thereby, an epoxy resin composition can express the outstanding fluidity | liquidity and preservability, without impairing sclerosis | hardenability.

  Hereinafter, each component in the epoxy resin composition of this invention is demonstrated one by one.

  The epoxy resin (A) used in the present invention is a monomer, oligomer or polymer in general having two or more epoxy groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, a phenol novolac type Epoxy resin, cresol novolac type epoxy resin, hydroquinone type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, triphenolmethane type epoxy resin, alkyl-modified triphenolmethane type epoxy Resin, triazine nucleus-containing epoxy resin, dicyclopentadiene modified phenol type epoxy resin, phenol aralkyl type epoxy resin having phenylene and / or biphenylene skeleton, naphthol type epoxy resin, naphtha Emission type epoxy resin, naphthol aralkyl type epoxy resins. Having a phenylene and / or biphenylene skeleton, it no problem is used singly or in admixture.

  The compound (B) having two or more phenolic hydroxyl groups in one molecule used in the present invention is a monomer, oligomer or polymer in general having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are particularly Without limitation, for example, phenol novolak resin, cresol novolak resin, triphenolmethane type phenol resin, terpene modified phenol resin, dicyclopentadiene modified phenol resin, phenol aralkyl resin having phenylene and / or biphenylene skeleton, phenylene and Examples thereof include a naphthol aralkyl resin having a biphenylene skeleton and a bisphenol compound, and these may be used alone or in combination.

As a hardening accelerator (C) used for this invention, what is necessary is just to accelerate | stimulate the hardening reaction of an epoxy group and a phenolic hydroxyl group, and what is generally used for a sealing material can be used.
Examples of such compounds include nitrogen-containing compounds, phosphorus-containing compounds, sulfur-containing compounds and the like, and these may be used alone or in combination.

  Examples of the nitrogen-containing compound include imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole; triethylamine, tributylamine, benzyldimethylamine, and 2- (dimethylaminomethyl) phenol. Amine compounds; bicyclic diaza compounds such as 1,8-diazabicyclo (5,4,0) undecene-7 and 1,5-diazabicyclo (4,3,0) nonene-5; tetramethylammonium bromide, tetraethyl Ammonium chloride, tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium chloride, tetraoctylammonium chloride, tetraoctylammonium bromide, tetrabutylammonium Ammonium salt compounds such um phenolate and tetraoctylammonium phenolate; 1-carboxylic -N, N, betaine compounds such as N- trimethyl meth Nami bromide; and the like. In addition, these include forms subjected to processing such as encapsulation, inclusion, pulverization, and nano-dispersion.

  Examples of the sulfur-containing compound include sulfonium salt compounds such as diphenylsulfonium bromide, triphenylsulfonium bromide, triphenylsulfonium chloride and triphenylsulfonium phenolate. These include encapsulation, inclusion, pulverization, Examples include nano-dispersed forms

Examples of the phosphorus-containing compound include phosphine compounds such as triphenylphosphine, methyldiphenylphosphine and tributylphosphine; tetraphosphonium chloride, tetraphosphonium bromide, tetraphenylphosphonium iodide, tetraphenylphosphonium and bisphenols such as bisphenol A. Molecular compounds, molecular compounds comprising tetrabutylphosphonium and dihydroxynaphthalene such as 2,3-dihydroxynaphthalene, and tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / tetrabenzoic acid borate, tetraphenylphosphonium / tetranaphthoic acid Borate, tetraphenylphosphonium tetranaphthoyloxyborate and tetrafer Phosphonium salt compounds such as tetra-substituted phosphonium and tetra-substituted borates such as ruphosphonium and tetranaphthyloxyborate; 2- (triphenylphosphonio) phenolate, adducts of triphenylphosphine and 1,4-benzoquinone, 2- (tri Phosphobetaine compounds such as phenylphosphonio) phenolate and 3- (triphenylphosphonio) phenolate; and the like. Moreover, the form etc. which performed processing, such as encapsulation, inclusion, pulverization, and nano dispersion, etc. are mentioned.
Among these, in particular, phosphonium salt compounds such as molecular compounds of tetraphenylphosphonium and bisphenols and molecular compounds of tetraphenylphosphonium and dihydroxynaphthalene, adducts of triphenylphosphine and 1,4-benzoquinone, and 2- When a phosphobetaine compound such as (triphenylphosphonio) phenolate is used, an epoxy resin composition is preferable because it can achieve both excellent curability and fluidity.

  The curing retardation component (G) used in the present invention comprises an aromatic dihydroxy compound (D) represented by general formula (1), an alkoxysilane compound (E) represented by general formula (2), and an amine compound (F). ).

In the aromatic dihydroxy compound (D) represented by the general formula (1) used in the present invention, Ar ¹ is an organic group having 5 to 30 carbon atoms having an aromatic ring or a heterocyclic ring, and on the organic group Ar ¹ . These two OH groups are directly bonded to the aromatic ring or heterocyclic ring. In addition, two oxygen anion groups formed by releasing protons from the two OH groups on the organic group Ar ¹ can form a chelate structure by combining with a silicon atom.

Examples of such an organic group Ar ¹ having 5 to 30 carbon atoms having an aromatic ring include arylene groups such as a phenylene group, a naphthylene group, a biphenylene group, and a binaphthylene group. In these groups, , Having an OH group at an adjacent position, and examples of the biarylene group such as the biphenylene group and the binaphthylene group include those having a 2,2 ′ position. Examples of the organic group Ar ¹ having 5 to 30 carbon atoms having a heterocyclic ring include organic groups having a heterocyclic ring such as a pyridinyl group and a quinoxalyl group. These groups usually have an OH group at the adjacent position. The C5-C30 organic group having an aromatic ring may have a substituent. Examples of the substituent include aliphatic alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group; , Aromatic groups such as phenyl groups; alkoxy groups such as methoxy groups and ethoxy groups; alkoxycarbonyl groups such as methoxycarbonyl groups, ethoxycarbonyl groups, propoxycarbonyl groups, butoxycarbonyl groups and octoxycarbonyl groups; nitro groups , A cyano group, a hydroxyl group, a halogen group, and the like. Among these, the C5-C30 organic group which has the said aromatic ring which has an alkoxycarbonyl group and a hydroxyl group in a substituent is preferable in the epoxy resin composition, since outstanding coexistence of curability and fluidity is seen. .

Examples of the aromatic dihydroxy compound (HO—Ar ¹ —OH) represented by the general formula (1) include, for example, catechol, 3-methylcatechol, 4-methylcatechol, 4-ethylcatechol, 4- Propylcatechol, 4-butylcatechol, 4-nitrocatechol, 3-methoxycatechol, 3-ethoxycatechol, 3-fluorocatechol, 3-chlorocatechol, 4-bromocatechol, 4-chlorocatechol, 3 ′, 4′-dihydroxy Acetophenone, 4-t-butylcatechol, 3,4-dihydroxybenzonitrile, 3,4-dihydroxybenzoic acid, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzyl alcohol, ethyl-3,4-dihydroxybenzoate, pyrogallol , 5-methyl pyrogallo 1,2,4-trihydroxybenzene, 2,3,4-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2 ', 3', 4 ',-trihydroxyacetophenone, gallic acid, gallic acid Methyl acid, ethyl gallate, propyl gallate, butyl gallate, isoamyl gallate, octyl gallate, dodecyl gallate, stearyl gallate, 2,2'-biphenol, 1,2-dihydroxynaphthalene, 2,3-dihydroxy Naphthalene, 1,8-dihydroxynaphthalene, 1,2-dihydroxyanthraquinone, 1,2,3-trihydroxyanthraquinone, 1,2,4-trihydroxyanthraquinone, 2,3,4-trihydroxybenzophenone, 2,3, 4,4′-tetrahydroxybenzophenone, 2,3 ′, 4 , 4′-tetrahydroxybenzophenone, 2,3,4-trihydroxydiphenylmethane, aromatic hydroxy compounds having an organic group having an aromatic ring such as 1,1′-bi-2-naphthol, 2,3-dihydroxypyridine, and Examples include dihydroxy compounds having an organic group having a heterocyclic ring such as 2,3-dihydroxyquinoxaline. Among these, catechol, pyrogallol, propyl gallate, 2,2′-biphenol, 1,2-dihydroxynaphthalene and 2 , 3-dihydroxynaphthalene is more preferable because in the epoxy resin composition, outstanding balance between curability and fluidity is observed.

The alkoxysilane compound (E) represented by the general formula (2) used in the present invention has an aliphatic group having 1 to 4 carbon atoms as R ¹ in the general formula (2). May be different.
Examples of the aliphatic group having 1 to 4 carbon atoms as R ¹ in the general formula (2) include a methyl group, an ethyl group, a propyl group, an allyl group, and a butyl group.

X ¹ in the general formula (2) represents an organic group having 6 to 15 carbon atoms or an aliphatic group having 1 to 15 carbon atoms having an aromatic ring.

Examples of the organic group having 6 to 15 carbon atoms having an aromatic ring as X ¹ in the general formula (2) include an aryl group and an arylalkyl group. Specific examples of the aryl group having 6 to 15 carbon atoms include phenyl group, bentafluorophenyl group, methoxyphenyl group, tolyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, nitrophenyl group, cyanophenyl group, amino group Examples thereof include a phenyl group, an indenyl group, a naphthyl group, and a biphenyl group. Specific examples of the arylalkyl group having 6 to 15 carbon atoms include benzyl group, phenylethyl group, phenylpropyl group, anilinomethyl group, anilinoethyl group, anilinopropyl group, N-phenylanilinopropyl group and aminophenoxypropyl group. Etc. The organic group having 6 to 15 carbon atoms having an aromatic ring may have a substituent. Examples of the substituent include aliphatic alkyl groups such as a methyl group, an ethyl group, and a propyl group; And an alkoxy group such as an ethoxy group; a halogen group such as a fluoro group, a chloro group and a bromo group: a hydroxyl group and an amino group. Among these organic groups having 6 to 15 carbon atoms having an aromatic ring, a phenyl group, a naphthyl group, and an anilinopropyl group are preferable because they have excellent curing retarding ability as the curing retarding component (G).

Examples of the aliphatic group having 1 to 15 carbon atoms as X ¹ in the general formula (2), an alkyl group having 1 to 15 carbon atoms, and alkenyl and alkynyl groups and the like. Specific examples of the alkyl group having 1 to 15 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and dodecyl group. , Cyclopentyl group, cyclohexyl group, bicycloheptyl group, glycidyloxypropyl group, mercaptopropyl group, aminopropyl group, chloromethyl group, bromomethyl group, chloropropyl group and cyanopropyl group. Specific examples of the alkenyl group having 1 to 15 carbon atoms include vinyl group, allyl group, methacryloxymethyl group, methacryloxypropyl group, pentadienyl group and bicycloheptenyl group. Specific examples of the alkynyl group having 1 to 15 carbon atoms include ethynyl group, propynyl group, butynyl group, and hexynyl group. The aliphatic group having 1 to 15 carbon atoms may have a substituent. Examples of the substituent include a glycidyl group, a mercapto group, an amino group, a halogen group, and a cyano group. May be. Among these aliphatic groups, a vinyl group, allyl, and glycidyloxypropyl group are preferable because they have excellent curing retarding ability as the curing retarding component (G).

In the general formula (2), a represents 3 or 4, and specific examples thereof will be described below.
Specific examples of the alkoxysilane compound (E) in which a in the general formula (2) is 4 include tetramethyl orthosilicate, tetraethyl orthosilicate, tetraallyl orthosilicate, tetraisopropyl orthosilicate, tetrapropyl orthosilicate, and tetrabutyl. Examples include orthosilicates. Among these, tetramethyl orthosilicate and tetraethyl orthosilicate are preferable because of excellent reactivity with the aromatic dihydroxy compound (D).

Next, the specific example of the alkoxysilane compound (E) whose a in the said General formula (2) is 3 is given. Examples of the alkoxysilane compound having an aromatic ring-containing organic group having 6 to 15 carbon atoms as X ¹ in the general formula (2) include phenyltrimethoxysilane, phenyltriethoxysilane, bromophenyltrimethoxysilane, p- Tolyltrimethoxysilane, pentafluorophenyltriethoxysilane, 3- (m-aminophenoxy) propyltrimethoxysilane, m, p-ethylphenylethyltrimethoxysilane, 1-naphthyltrimethoxysilane, N-phenyl-3-amino Propyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) -propyltrimethoxysilane, and the like, and X ¹ in the general formula (2) is the aliphatic group having 1 to 15 carbon atoms. Examples of alkoxysilane compounds having Rutrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hexyltrimethoxysilane, vinyltrimethoxysilane, hexyl Triethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptotri Ethoxysilane, 3-aminopropyltrimethoxysilane, 3-cyanotriethoxysilane, 4-aminobutyltriethoxysilane, N- (2-aminoethyl) -3-aminop Pills trimethoxysilane and 5- (bicycloheptyl) triethoxysilane, and the like. Among these, vinyltrimethoxysilane, phenyltrimethoxysilane, 1-naphthyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane are preferable because they have excellent curing retardation ability as the curing retardation component (G).

  The amine compound (F) used in the present invention is a primary amine, secondary amine or tertiary amine monomer, and polymers thereof in general, and its structure and molecular weight are not particularly limited. Examples thereof include aliphatic amine compounds, aromatic amine compounds, alicyclic amine compounds, and heterocyclic amine compounds. Here, the number of nitrogen atoms contained in one molecule of the amine compound is preferably 1 or more and 6 or less, and more preferably 1 or more and 3 or less. The amine compound preferably has 3 to 50 carbon atoms, and more preferably 3 to 25 carbon atoms. Within the above range, the curing retardation component (G) has excellent curing retardation ability.

Examples of such amine compounds (F) include, for example, n-propylamine, cyclopropylamine, allylamine, n-butylamine, isobutylamine, sec-butylamine, diethylamine, dimethylaminoethanol as the aliphatic amine compound. , Diethanolamine, n-amylamine, tert-amylamine, isoamylamine, 2-aminopentane, cyclopentylamine, 3-aminopentane, 1,2-dimethylpropylamine, N-ethylisopropylamine, N-ethyl-n-propylamine, N-methylisobutylamine, N-methyl-n-butylamine, N-tert-butylethylamine, N, N-dimethylisopropylamine, triethylamine, 3-dimethylaminopropionitrile, 1-dimethyl Amino-2-propanol, 3-dimethylamino-1-propanol, n-hexylamine, cyclohexaneamine, 1,3-dimethyl-n-butylamine, diisopropylamine, diallylamine, dipropylamine, Nn-butylethylamine, N -Tert-butylethylamine, Nn-butyldimethylamine, n-heptylamine, aminomethylcyclohexane, cycloheptylamine, 4-methylcyclohexylamine, 2-methylcyclohexylamine, N-methylcyclohexylamine, N, N-diethyl Allylamine, 3-diethylamino-1,2-propanediol, 1-diethylamino-2-propanol, n-octylamine, 2-aminooctane, 1,5-dimethylhexylamine, cyclooctylamine, -Ethylhexylamine, dibutylamine, N-ethylcyclohexylamine, N-cyclohexylethanolamine, N, N-diisopropylethylamine, N, N-dimethylcyclohexylamine, 3,3,5-trimethylcyclohexylamine, N-isopropylcyclohexylamine, Tripropylamine, triallylamine, benzyldimethylamine, 2-dimethylaminomethyl) phenol, N, N-diethylcyclohexylamine, N, N- (dimethyl-n-octylamine, 3-di-n-butylamino-1-propyne, Triisobutylamine, tributylamine, dicyclohexylamine, N, N-dicyclohexylmethylamine, diheptylamine, triamylamine, triisoamylamine, N-methyldi-n-octyl Aliphatic monoamine compounds such as ruamine, trihexylamine, N-methyldi-n-octylamine, N, N-dimethylhexadecylamine, tri-n-heptylamine and tri-n-octylamine;
1,3-diaminopropane, N-methylethylenediamine, 1,3-diamino-2-propanol, 2-methyl-1,3-propanediol, diethylenetriamine, 1,4-diaminobutane, N-methyl-1,3- Diaminopropane, 1,2-diamino-2-methylpropane, 1,3-diaminopentane, N-methyl-2,2′-diaminodiethylamine, N- (2-hydroxypropyl) ethylenediamine, N, N-dimethyl-1 , 3-propanediamine, N- (3-hydroxypropyl) ethylenediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,2-cyclohexanediamine, 3,3′-diaminodipropylamine, triethylenetetramine N, N-diethyl-1,3-diaminopropane, N, N N ′, N′-tetramethyl-1,3-diaminopropane, N, N, 2,2-tetramethyl-1,3-propanediamine, N, N-bis (3-aminopropyl) methylamine, N, N′-dimethyl-1,6-diaminohexane, 1,3-bis (aminoethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, N, N, N ′, N′-tetramethyl-1,4 -Diaminobutane, N, N, N ', N'-tetramethyl-1,3-diaminobutane, 1,8-diaminooctane, 4-amino-1-diethylaminopentane, N- (3-aminopropyl) cyclohexylamine N, N, N ′, N′-tetramethyl-1,6-diaminohexane, N, N′-diethyl-1,6-diaminohexane, 4,4′-methylenebis (cyclohexylamine) and 2, , 6- tris (dimethylaminomethyl) aliphatic polyamine compound such as phenol.

Examples of the aromatic amine compound include aniline, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiol, 3-aminobenzenethiol, 4-aminobenzenethiol, 2-chloroaniline, 3- Chloroaniline, 4-chloroaniline, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2-bromoaniline, 3-bromoaniline, 4-bromoaniline, 2-iodoaniline, 3-iodoaniline, 4- Iodoaniline, o-toluidine, p-toluidine, N-methylaniline, 3,4-methylenedioxyaniline, 2-amino-p-cresol, 2-aminobenzonitrile, 3-aminobenzonitrile, 4-aminobenzonitrile 2,6-dimethylaniline, 3,5-di Tyraniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 3,4-dimethylaniline, N, N-dimethylaniline, 2-ethylaniline, 3-ethylaniline, N-ethyl Aniline, N, N-dimethyl-3-aminophenol, 4-methoxy-2-methylaniline, 4-aminophthalonitrile, o-ethoxyaniline, p-ethoxyaniline, 2,4,6-trimethylaniline, N-isopropyl Aniline, 2- (N-methylanilino) ethanol, N-allylaniline, N-ethyl-o-toluidine, N-ethyl-p-toluidine, 4-dimethylaminobenzaldehyde, N, N-dimethyl-p-toluidine, 2- Propylaniline, 4-propylaniline, 2-isopropylaniline, 3- Sopropylaniline, 4-isopropylaniline, 1-naphthylamine, Nn-butylaniline, 2- (N-ethylanilino) ethanol, N- (2-cyanoethyl) -N-methylaniline, 1-phenyl-2-pyrrolidone, 4-butylaniline, 2-butylaniline, 4-sec-butylaniline, 4-tert-butylaniline, N, N-diethyl-m-toluidine, 4-diethylaminobenzaldehyde, N, N-diethyl-3-aminophenol, Nn-pentylaniline, N, N-diethyl-o-toluidine, N- (4-aminophenyl) piperidine, N, N-di-n-propylaniline, N, N-dimethyl-2-naphthylamine, N, N -Dimethyl-1-naphthylamine, diphenylamine, N-ethyl-1-naphthylami , 3-aminobiphenyl, 2-aminobiphenyl, 4-aminodiphenyl ether, 2-aminophenyl, 2-aminophenylphenyl sulfide, N-methyldiphenylamine, 3-methyldiphenylamine, 4-aminodiphenylmethane, 4-aminobenzophenone, N , N-diethyl-1-naphthylamine, m, m′-ditolylamine, N-benzyl-N-ethylaniline, N-phenyl-1-naphthylamine, triphenylamine, Nn-dodecylaniline, bis (4-tert- Butylphenyl) amine, 4,4′-dimethyltriphenylamine, 1,1′-dinaphthyleneamine, 1,2′-dinaphthyleneamine and N, N-dibenzylaniline, and the like,
1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 3,4-diaminotoluene, 2,6-diaminotoluene, 2-aminobenzylamine, 3- Aminobenzylamine, 4-aminobenzylamine, 2,5-dimethyl-1,4-phenylenediamine, 4,5-dimethyl-1,2-phenylenediamine, N, N-dimethyl-1,4-phenylenediamine, N -Phenylethylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3-diaminonaphthalene, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, N, N-diethyl-1,4- Phenylenediamine, tryptamine, N-1-naphthylethylenediamine, N- (3-aminopropyl)- -Methylaniline, N- (2-aminoethyl) -N-ethyl-m-toluidine, 3,3'-diaminobenzidine, 3,3'-dihydroxybenzidine, bis (4-aminophenyl) sulfide, bis (2- Aminophenyl) sulfide, bis (4-aminophenyl) sulfone, bis (3-aminophenyl) sulfone, 4,4′-diaminodiphenylmethane, 4,4′-diaminobenzophenone, 3,4′-diaminodiphenylmethane, 3,3 '-Diaminodiphenylmethane, 3,4-diaminobenzophenone, 2,7-diaminofluorene, 4,4'-methylenebis (2-chloroaniline), o-tolidine, 4,4'-ethylenedianiline, 2,2'- Ethylenedianiline, N, N-diphenylethylenediamine, 4,4'-diamino-3,3'-dimethyl Diphenylmethane, bis [4- (dimethylamino) phenyl] methane, 4,4′-diamino-3,3′-diethyldiphenylmethane, 4,4′-methylenebis (2-ethyl-6-methylaniline) and N, N ′ -Aromatic polyamine compounds such as di-2-naphthyl-1,4-phenylenediamine.

  Examples of the alicyclic amine compound include pyrrolidine, 3-pyrrolidinol, 2-pyrrolidone, piperazine, 1-methylpyrrolidine, piperidine, 4-aminopiperidine, 4-hydroxypiperidine, 2-piperidone, N-ethylpyrrolidone, 1-methyl. Piperidine, 3-pipecoline, 4-pipecoline, hexamethyleneimine, 2-pipecoline, N-ethylpyrrolidone, 4- (aminomethyl) piperidine, 1- (2-aminoethyl) pyrrolidine, 4-hydroxy-1-methylpiperidine, 3,5-dimethylpiperidine, 1-ethylpiperidine, 2,6-dimethylpiperidine, 2-ethylpiperidine, 1- (2-aminoethyl) piperidine, 2-piperidineethanol, 1-methyl-2-piperidinemethanol, decahydro Isoquinoxaline, Decahi Rokinorin, 2,2,6,6-tetramethylpiperidine, 1- (3-aminopropyl) -2-pipecoline and 1-cyclohexyl piperazine, and the like.

  Examples of the heterocyclic amine compound include N-methylimidazole, pyrrole, pyrazine, pyridazine, 2-methylimidazole, 4-methylimidazole, pyridine, 1-methylpyrrole, 4-aminopyridine, 4-hydroxypyridine, and 3-hydroxy. Pyridine, 2-hydroxypyridine, 2-mercaptopyridine, 2,6-diaminopyridine, 1,2-dimethylimidazole, 2-picoline, 2,5-dimethylpyrrole, 4-cyanopyridine, 4-pyridinecarboxaldehyde, 4- Methoxypyridine, 4-pyridinemethanol, 4-picolylamine, 3-amino-4-picoline, 2-n-propyl-2-imidazoline, 2-ethyl-4-methylimidazole, 4-ethylpyridine, 3,5-lutidine 2,6-lutidine, 2-vinyl pyridine Gin, 4-vinylpyridine, 3-ethylpyridine, 2-ethylpyridine, 4- (2-aminoethyl) pyridine, 2-acetylpyridine, 3-acetylpyridine, 3-ethylpyridine, 3-pyridineacetonitrile, 2-pyridine Acetonitrile, 2- (2-aminoethyl) pyridine, 2-pyridineethanol, 2-cyano-3-methylpyridine, 4-dimethylaminopyridine, quinoxaline, 4-n-propylpyridine, 2-propylpyridine, 5-ethyl-2 -Picoline, 2,4,6-trimethylpyridine, 2,3,5-trimethylpyridine, indole, N-ethyl-4-picolylamine, 1-cyanoethyl-2-methylimidazole, 2-methylindole, isoquinoline, Quinoline, N-methylindole, 4-tert-butyl Lysine, 3-butylpyridine, 5,6,7,8-tetrahydroisoquinoline, 2-phenylimidazole, 4- (3-pentyl) pyridine, 7-methylquinoline, 4-methylquinoline, 6-methylquinoline, 1-benzyl 2-methylimidazole, carbazole, iminostilbene, 2-undecylimidazole and 1,8-diazabicyclo (5,4,0) undecene-7, 1,5-diazabicyclo (4,3,0) nonene-5, etc. Is mentioned.

  Of these amine compounds, the aromatic amine compound represented by the general formula (3) is more preferable from the viewpoint of the curing retardation ability as the curing retardation component (G).

In the aromatic amine compound represented by the general formula (3), Ar ² represents an organic group having an aromatic ring, and a nitrogen atom on the organic group Ar ² is directly bonded to the aromatic ring.

Examples of such an organic group Ar ² include an aryl group and an arylene group. Specific examples of the aryl group include a phenyl group, a naphthyl group, a benzaldehyde group, a fluorene group, and a biphenyl group. Specific examples of the arylene group include a phenylene group, a naphthylene group, a biphenylene group, and a diphenylene ether group. , Diphenylene methane group, diphenylene ketone group, diphenylene ethane group, diphenylene sulfone group, diphenylene sulfide group and the like. The organic group having an aromatic ring may have a substituent, for example, an aliphatic group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. An alkyl group; an alkoxy group such as a methoxy group and an ethoxy group; a cyano group, a thiol group, a hydroxyl group, an amino group, and a halogen group.

  Further, b in the general formula (3) represents an integer of 1 to 6, and is preferably an integer of 1 to 3. When it is within the above range, the curing retardation component (G) has excellent curing retardation ability.

In the aromatic amine compound represented by the general formula (3), R ² and R ³ each represents a hydrogen atom and an organic group having 1 to 6 carbon atoms, may be the same or different from each other, R ² And R ³ may be bonded to each other to form a ring structure.

Examples of such R ² and R ³ include alkyl groups, alkenyl groups, and aryl groups as the organic group having 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, and the like. Group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group and the like. Examples of the alkenyl group include allyl group and butenyl group. Examples of the aryl group include phenyl group. In addition, when R ² and R ³ are bonded to each other to form a ring structure, the substituent for the nitrogen atom is a hydrocarbon group having a main chain of 4 to 6 carbon atoms, such as tetramethylene and pentamethylene. Groups and the like. The organic group having 1 to 6 carbon atoms may have a substituent, for example, a cyano group, a carbonyl group, a hydroxyl group, an amino group, and the like.

Examples of the aromatic amine compound represented by the general formula (3) include aniline, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiol, and 3-aminobenzene. Thiol, 4-aminobenzenethiol, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2-bromoaniline, 3-bromoaniline, 4- Bromoaniline, 2-iodoaniline, 3-iodoaniline, 4-iodoaniline, o-toluidine, p-toluidine, N-methylaniline, 3,4-methylenedioxyaniline, 2-amino-p-cresol, 2- Aminobenzonitrile, 3-aminobenzonitrile, 4-aminobenzonitrile 2,6-dimethylaniline, 3,5-dimethylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 3,4-dimethylaniline, N, N-dimethylaniline, 2-ethylaniline, 3-ethylaniline, N-ethylaniline, N, N-dimethyl-3-aminophenol, 4-methoxy-2-methylaniline, 4-aminophthalonitrile, o-ethoxyaniline, p-ethoxyaniline 2,4,6-trimethylaniline, N-isopropylaniline, 2- (N-methylanilino) ethanol, N-allylaniline, N- (2-butenyl) aniline, N-ethyl-o-toluidine, N-ethyl- p-toluidine, 4-dimethylaminobenzaldehyde, N, N-dimethyl-p-toluidine, 2- Lopylaniline, 4-propylaniline, 2-isopropylaniline, 3-isopropylaniline, 4-isopropylaniline, 1-naphthylamine, Nn-butylaniline, 2- (N-ethylanilino) ethanol, N- (2-cyanoethyl)- N-methylaniline, 1-phenyl-2-pyrrolidone, 4-butylaniline, 2-butylaniline, 4-sec-butylaniline, 4-tert-butylaniline, N, N-diethyl-m-toluidine, 4-diethylamino Benzaldehyde, N, N-diethyl-3-aminophenol, Nn-pentylaniline, N, N-diethyl-o-toluidine, N- (4-aminophenyl) piperidine, N, N-di-n-propylaniline, N, N-dimethyl-2-naphthylamine, N, N-dimethyl Ru-1-naphthylamine, diphenylamine, N-ethyl-1-naphthylamine, 3-aminobiphenyl, 2-aminobiphenyl, 4-aminodiphenyl ether, 2-aminophenyl, 2-aminophenylphenyl sulfide, N-methyldiphenylamine, 3- Aromatic monoamine compounds such as methyldiphenylamine, 4-aminodiphenylmethane, 4-aminobenzophenone, N, N-diethyl-1-naphthylamine, N-phenyl-1-naphthylamine and triphenylamine;
1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 3,4-diaminotoluene, 2,6-diaminotoluene, 2,5-dimethyl-1,4 -Phenylenediamine, N, N-dimethyl-1,4-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3-diaminonaphthalene, 1,8-diaminonaphthalene, 1,5- Diaminonaphthalene, N, N-diethyl-1,4-phenylenediamine, 3,3′-diaminobenzidine, 3,3′-dihydroxybenzidine, bis (4-aminophenyl) sulfide, bis (2-aminophenyl) sulfide, bis (4-aminophenyl) sulfone, bis (3-aminophenyl) sulfone, 4,4′-diaminodiph Nylmethane, 4,4′-diaminobenzophenone, 3,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,4-diaminobenzophenone, 2,7-diaminofluorene, 4,4′-methylenebis (2-chloro) Aniline), o-tolidine, 4,4′-ethylenedianiline, 2,2′-ethylenedianiline, 4,4′-diamino-3,3′-dimethyldiphenylmethane, bis [4- (dimethylamino) phenyl] methane Aromatic polyamine compounds such as 4,4′-diamino-3,3′-diethyldiphenylmethane and 4,4′-methylenebis (2-ethyl-6-methylaniline), among these, -Diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane and , 4'-diaminodiphenylmethane are preferred for excellent curing delay capability as a curing delay component (G).

Here, a method for synthesizing the curing retardation component (G) used in the present invention will be described.
As a synthesis method of the curing delay component (G), an aromatic dihydroxy compound (D) represented by the general formula (1), an alkoxysilane compound (E) represented by the general formula (2), It is obtained by reacting with the amine compound (F). For example, a method of performing the reaction in a solvent, a method of performing the reaction in a solvent-free manner, a method of performing the reaction in other components, etc. The aromatic dihydroxy compound (D) represented by the general formula (1), the alkoxysilane compound (E) represented by the general formula (2), and the amine compound (F). The method is not limited as long as it can be reacted to obtain the curing retardation component (G).

  As a method of performing the reaction in a solvent, for example, the aromatic dihydroxy compound (D) and the alkoxysilane compound (E) can be dissolved in alcohol, acetonitrile, N, N-dimethylformamide and the like. A method of reacting in a temperature range of 0 ° C. to 150 ° C., preferably 20 ° C. to 80 ° C. Can do. As the amine compound (F), a solution previously dissolved in an organic solvent may be used.

As a method for performing the reaction in the absence of a solvent, for example, the aromatic dihydroxy compound (D), the alkoxysilane compound (E), and the amine compound (F) are mixed as they are, and preferably 50 It can be obtained by heating and solvent-free reaction in a temperature range of not less than 200 ° C and more preferably in a temperature range of not less than 80 ° C and not more than 170 ° C.
In this way, by reacting the above three components in a solvent-free manner under heating conditions, formation of the curing retardation component (G) is promoted, and desorbing components such as alcohol generated in the reaction are vaporized, and the system is discharged outside the system. Can be removed.
In the above temperature range, a suitable heating temperature is adjusted depending on the types of the aromatic dihydroxy compound (D), the alkoxysilane compound (E), and the amine compound (F) to be used. It is necessary to exceed the boiling point at the pressure in the system. For example, when R ¹ in the alkoxysilane compound (E) represented by the general formula (2) is a butyl group, the alcohol to be eliminated is butanol. Therefore, the reaction is performed under a condition exceeding 117 ° C. which is the boiling point of butanol. Preferably it is done. On the other hand, when the heating temperature exceeds 200 ° C., the formed curing delay component may be denatured by a reaction such as oxidation or decomposition to adversely affect the curing delay effect.
Furthermore, when depressurizing the pressure atmosphere to such an extent that a desorbing component such as alcohol can be sucked and released out of the system during a solvent-free reaction, the desorbing component can be more efficiently removed. More preferred.

As a method of performing the reaction by mixing with other components, for example, the aromatic dihydroxy compound (D), the alkoxysilane compound (E), and the amine compound (F) are phenolic in one molecule. The temperature range from the softening point temperature of the compound (B) having two or more hydroxyl groups, preferably the compound (B) having two or more phenolic hydroxyl groups in one molecule to 200 ° C., more preferably in the one molecule. The compound (B) having two or more phenolic hydroxyl groups can be obtained by melt-mixing in a temperature range of not lower than the softening point temperature and not higher than 170 ° C.
At this time, the amount of the compound (B) having two or more phenolic hydroxyl groups in one molecule is at least the aromatic dihydroxy compound (D), the alkoxysilane compound (E), and the amine compound (F). As long as the amount can be easily reacted, a part or all of the amount used for the epoxy resin composition of the present invention can be used. As a result, the obtained curing retarding component (G) is uniformly dispersed in the compound (B) having two or more phenolic hydroxyl groups in one molecule as a curing agent, and exhibits better curing retarding ability. This is preferable.
More specifically, as a condition for melting and mixing each component, since the compound (B) having two or more phenolic hydroxyl groups in one molecule is melted, it may be above its softening point. In a high temperature range from 10 ° C. to 100 ° C. from the softening point, the compound (B) having two or more phenolic hydroxyl groups in one molecule is melted, and the aromatic dihydroxy compound (D) and the The curing retardation component (G) can be obtained by adding the alkoxysilane compound (E) and the amine compound (F) and reacting them.
Furthermore, when the desorption component such as alcohol produced in the reaction is sucked and reduced to a pressure atmosphere that can be released out of the system, the desorption component can be removed more efficiently. More preferred.

  In the above reaction, when the alkoxysilane compound (E) in which the molar ratio is adjusted by the number of a in the general formula (2) and a is 4, the aromatic dihydroxy compound (D) and the alkoxysilane compound ( The charged molar ratio with E) is preferably (D) / (E) = 1.5 to 6 and more preferably 2 to 4. The molar ratio charged between the aromatic dihydroxy compound (D) and the amine compound (F) depends on the number of moles of nitrogen atoms contained in 1 mol of the amine compound (F), but the aromatic dihydroxy compound ( D) and the molar ratio (M) of nitrogen atoms contained in the amine compound (F) are preferably reacted in the range of (D) / (M) = 0.5-4, preferably in the range of 1-2 It is more preferable to make it react with.

  When the alkoxysilane compound (E) in which a in the general formula (2) is 3 is used, the charged molar ratio between the aromatic dihydroxy compound (D) and the alkoxysilane compound (E) is (D) / ( E) It is preferable to make it react in the range of 0.5-5, and it is more preferable to make it react in the range of 1.5-2.5. The molar ratio of the aromatic dihydroxy compound (D) to the amine compound (F) depends on the number of moles of nitrogen atoms contained in 1 mole of the amine compound (F), but the aromatic dihydroxy compound (D ) And the nitrogen atom (M) contained in the amine compound (F) are preferably reacted in a molar ratio of (D) / (M) = 0.75-5, 1.5-2. It is more preferable to react in the range of 5.

By the above synthesis method, the aromatic dihydroxy compound (D), the alkoxysilane compound (E), and the amine compound (F) react to form a cation formed from the amine compound (F), and the aromatic An ammonium silicate compound composed of a silicon atom from which two protons in the group dihydroxy compound (D) are released and an alkoxy group in the alkoxysilane compound (E) is eliminated and an anion formed by forming a chelate; Obtainable. The ammonium silicate compound has at least one proton in the cation portion, and the proton has two phenolic hydroxyl groups in the epoxy resin (A) and the molecule in the curing accelerator (C). By protecting the active point that promotes curing with the compound (B) having the above, the curing reaction is suppressed and curing is delayed, so that it functions as a curing delay component.
The ammonium silicate compound obtained by such a reaction is preferably an ammonium silicate compound represented by the general formulas (4) and (5).

Here, in the cation part which comprises the ammonium silicate compound represented by the said General Formula (4) and (5), Q shows ammonium formed when an amine compound is protonated.
Such protonation of the amine compound occurs when a proton generated when the aromatic dihydroxy compound (D) and the alkoxysilane compound (E) react with each other is added to the amine compound.

  As these ammonium, the ammonium formed when the said amine compound (F) is protonated can be mentioned. The number of nitrogen atoms contained in such ammonium is preferably 1 or more and 6 or less, and more preferably 1 or more and 3 or less. In addition, the ammonium preferably has 3 to 50 carbon atoms, and more preferably 3 to 25 carbon atoms. Within the above range, the curing retardation component (G) has excellent curing retardation ability.

Further, the silicate anion portion constituting the general formula (4) and (5) an ammonium silicate compound represented by, Ar ³ each represent an organic group having 5 to 30 carbon atoms having an aromatic ring or a heterocyclic ring . Two oxygen atoms on the organic group Ar ³ are directly bonded to the aromatic ring or heterocyclic ring. In addition, two oxygen anion groups formed by releasing protons from two OH groups on the organic group Ar ³ can form a chelate structure by bonding with a silicon atom. As said Ar < ³ >, the thing similar to Ar < ¹ > in the aromatic dihydroxy compound (D) represented by the said General formula (1) can be mentioned.

The group represented by O—Ar ³ —O in the ammonium silicate compounds represented by the general formulas (4) and (5) is a group formed by releasing a proton from a compound having a proton-donating substituent. The aromatic dihydroxy compound represented by the general formula (1) (HO—Ar ¹ —OH) may be the same as the group formed by releasing a proton, and among these, catechol, pyrogallol, Groups in which propyl gallate, 2,2′-biphenol, 1,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene release protons are more preferable because of outstanding balance between curability and fluidity. .

X ² in the silicate anion moiety constituting the ammonium silicate compound represented by the general formula (4) represents an organic group having 6 to 15 carbon atoms or an aliphatic group having 1 to 15 carbon atoms having an aromatic ring. Specific examples thereof include the same as X ¹ in the alkoxysilane compound (E) represented by the general formula (2). Among these, a vinyl group, a phenyl group, a naphthyl group, and an anilinopropyl group are preferable because of their excellent curing retarding ability.

  In the ammonium silicate compounds represented by the general formulas (4) and (5), c represents an integer of 1 to 6, and preferably an integer of 1 to 3. e and f each represent an integer of 1 to 6 that satisfies e × d = 2f, and is preferably an integer of 1 to 3. Within the above range, the curing retarding ability as the curing retarding component (G) is excellent. d represents 1 or 2.

  The curing retardation component obtained by the synthesis method is more preferably an ammonium silicate compound represented by the general formulas (6) and (7).

Here, in the cation moiety constituting the ammonium silicate compound represented by the general formulas (6) and (7), R ⁴ and R ⁵ represent a hydrogen atom and an organic group having 1 to 6 carbon atoms, respectively. They may be the same or different from each other, and R ⁴ and R ⁵ may be bonded to each other to form a ring structure. Specific examples thereof include those similar to R ² and R ³ in the aromatic amine compound represented by the general formula (3).

In the cation moiety constituting the ammonium silicate compound represented by the general formulas (6) and (7), Ar ⁴ represents an organic group having an aromatic ring. Specific examples thereof include the general formula It may be mentioned the same as Ar ² in the aromatic amine compound represented by (3). The nitrogen atom on the organic group Ar ⁴ is directly bonded to the aromatic ring.

  Examples of the cation moiety constituting the ammonium silicate compound represented by the general formulas (6) and (7) include that the aromatic amine compound represented by the general formula (3) is protonated. Examples of the ammonium that can be formed include 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, An ammonium cation formed by protonating 4′-diaminodiphenylmethane is preferable because it has excellent curing retarding ability as the curing retarding component (G).

Further, the silicate anion portion constituting the general formula (6) and (7) ammonium silicate compound represented by, Ar ⁵ each represent an organic group having 5 to 30 carbon atoms having an aromatic ring or a heterocyclic ring . Two oxygen atoms on the organic group Ar ⁵ are directly bonded to the aromatic ring or the heterocyclic ring. In addition, two oxygen anion groups formed by releasing protons from two OH groups on the organic group Ar ⁵ can form a chelate structure by combining with silicon atoms. As the Ar ^5, it may be mentioned the same as Ar ¹ in the aromatic dihydroxy compound represented by the general formula (1).

In the ammonium silicate compounds represented by the general formulas (6) and (7), the group represented by O—Ar ⁵ —O is a group formed by releasing a proton from a compound having a proton-donating substituent. The aromatic dihydroxy compound represented by the general formula (1) (HO—Ar ¹ —OH) may be the same as the group formed by releasing a proton, and among these, catechol, pyrogallol, When propyl gallate, 2,2′-biphenol, 1,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene release a proton, the epoxy resin composition has excellent curability and fluidity. Since compatibility is seen, it is more preferable.

X ³ in the silicate anion moiety constituting the ammonium silicate compound represented by the general formula (6) represents an organic group having 6 to 15 carbon atoms or an aliphatic group having 1 to 15 carbon atoms having an aromatic ring. Specific examples thereof include the same as X ¹ in the alkoxysilane compound (E) represented by the general formula (2). Among these, a vinyl group, a phenyl group, a naphthyl group, and an anilinopropyl group are preferable because they have excellent curing retarding ability as the curing retarding component (G).

  Moreover, in the ammonium silicate compound represented by the general formulas (6) and (7), m represents an integer of 1 to 6, and is preferably an integer of 1 to 3. p and q each represent an integer of 1 to 6 that satisfies p × n = 2q, and is preferably an integer of 1 to 3. Within the above range, the curing retardation component (G) has excellent curing retardation ability. n represents 1 or 2.

In the present invention, the curing retarding component (G) has the function as the curing retarding component described above, the chelate ring in the anion component is disintegrated by heating, and the proton of the cation part of the ammonium silicate compound is lost. It is considered that the curing delaying action is gradually lost.
The temperature at which the chelate structure collapses can be adjusted according to the type of components constituting the curing retarding component, and when molding using the epoxy resin composition of the present invention, the molding temperature is preferably 100 to 230. It can adjust so that a chelate structure may be collapsed and hardening may be accelerated | stimulated in the temperature range of 140 degreeC, More preferably in the temperature range of 140-200 degreeC.
On the other hand, according to the present invention, when compared with conventional curing-inhibiting components that continue to inhibit the curing reaction from the beginning to the end of the reaction, and sufficient curability cannot be obtained, according to the present invention, In the curing reaction between (A) and the compound (B) having two or more phenolic hydroxyl groups in one molecule, at the initial stage of heating, it has a latent property, the curing reaction proceeds and the curing delay function is weak. In this stage, the epoxy resin composition can quickly obtain a sufficient degree of curing.

  In the epoxy resin composition of the present invention, the content (mixing ratio) of the epoxy resin (A) and the compound (B) having two or more phenolic hydroxyl groups in one molecule is not particularly limited. It is used such that the phenolic hydroxyl group of the compound (B) having two or more phenolic hydroxyl groups in one molecule is about 0.5 to 2 mol per 1 mol of the epoxy group of the epoxy resin (A). Preferably, it is more preferably used so as to be about 0.7 to 1.5 mol. Thereby, various characteristics improve more, maintaining the balance of the various characteristics of an epoxy resin composition to a suitable thing.

  The content (blending amount) of the curing accelerator (C) is not particularly limited, but is a resin component composed of an epoxy resin (A) and a compound (B) having two or more phenolic hydroxyl groups in one molecule. The amount is preferably about 0.01 to 20% by weight, and more preferably about 0.1 to 10% by weight. Thereby, the sclerosis | hardenability, preservability, fluidity | liquidity, and hardened | cured material characteristic of an epoxy resin composition are expressed with sufficient balance.

  In the epoxy resin composition of the present invention, the content (addition amount) of the curing delay component (G) can be adjusted according to the desired degree of curing delay. As a more specific example, at the temperature at which the epoxy resin composition of the present invention is stored, for example, from room temperature to 60 ° C., the effect of the curing retarding component (G) is exhibited, and storage stability is exhibited. When molding using the epoxy resin composition, the curing retarding component (G) is suppressed and cured at a molding temperature of preferably 100 to 230 ° C, more preferably 140 to 200 ° C. Can be adjusted to promote.

  The optimum amount varies depending on the types of the curing accelerator (C) and the curing retarding component (G) to be used, but in general, the curing retarding component (G ) Is preferably added so that the molar amount of silicon contained in the range of 0.1 to 5 mol, and more preferably in the range of 0.5 to 2 mol. When the content (addition amount) is in the range, an epoxy resin composition having both curability, fluidity, and storage stability can be obtained.

  In the present invention, as the inorganic filler that is optionally used, those that are generally used in epoxy resin compositions for semiconductor encapsulation can be used. For example, fused spherical silica, fused crushed silica, crystalline silica, talc, alumina, titanium white, silicon nitride and the like can be mentioned, and the most suitably used is spherical fused silica (and crushed fused silica). These inorganic fillers may be used alone or in combination. Moreover, these may be surface-treated with a coupling agent. The shape of the inorganic filler is preferably as spherical as possible and the particle size distribution is broad in order to improve fluidity.

  The content (blending amount) of the inorganic filler is not particularly limited, but the total amount of the epoxy resin (A) and the compound (B) having two or more phenolic hydroxyl groups in one molecule is 100 parts by weight. It is preferably about 200 to 2400 parts by weight, more preferably about 400 to 1400 parts by weight. The content of the inorganic filler can be used outside the above range, but if it is less than the lower limit, the reinforcing effect by the inorganic filler may not be sufficiently exhibited, while the content of the inorganic filler is the upper limit. In the case of exceeding the above, the fluidity of the epoxy resin composition is lowered, and there is a possibility that poor filling or the like may occur when the epoxy resin composition is molded (for example, during manufacturing of a semiconductor device).

  In addition, the content (blending amount) of the inorganic filler is 400 to 1400 per 100 parts by weight of the total amount of the epoxy resin (A) and the compound (B) having two or more phenolic hydroxyl groups in one molecule. If it is a weight part, since the moisture absorption rate of the hardened | cured material of an epoxy resin composition becomes lower and generation | occurrence | production of a solder crack can be prevented, it is more preferable. Since such an epoxy resin composition also has good fluidity when heated and melted, it is suitably prevented from causing deformation of the gold wire inside the semiconductor device.

  Further, in the epoxy resin composition of the present invention, the epoxy resin (A), a compound (B) having two or more phenolic hydroxyl groups in one molecule, a curing accelerator (C), a curing retarding component (G) Further, optionally, in addition to the inorganic filler, if necessary, for example, epoxy silane such as 3-glycidyloxypropyltrimethoxysilane, mercaptosilane such as 3-mercaptopropyltrimethoxysilane, N-phenyl-3- Aminosilanes such as aminopropyltrimethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane, silane coupling agents such as alkylsilane, vinylsilane and phenyltrimethoxysilane, titanate coupling agents, aluminum coupling agents, aluminum / Zirconium coupling agent and other cups Flame retardants such as coloring agents, colorants such as carbon black and bengara, brominated epoxy resins, antimony oxide, aluminum hydroxide, magnesium hydroxide, zinc oxide and phosphorus compounds, low stress components such as silicone oil and silicone rubber, Natural waxes such as carnauba wax, synthetic waxes such as polyethylene wax, higher fatty acids such as stearic acid and zinc stearate, metal salts of the higher fatty acids and mold release agents such as paraffin, ions such as magnesium, aluminum, titanium and bismuth You may make it mix | blend (mix) various additives, such as a catcher and a bismuth antioxidant.

  The epoxy resin composition of the present invention is obtained by uniformly mixing the above components and, if necessary, other additives using a mixer, and further mixed at room temperature. It can also be obtained by heating and kneading using a kneader such as a roll, a kneader, a kneader and a twin screw extruder, followed by cooling and pulverization. Moreover, when the epoxy resin composition obtained above is a powder, it can be used in a tablet form by pressurizing it with a press or the like in order to improve workability in use.

  The epoxy resin composition of the present invention can be used, for example, by using it as a mold resin to seal various electronic components such as semiconductor elements and manufacturing a semiconductor device. Further, it may be cured by a conventional molding method such as an injection mold to seal various electronic components such as semiconductor elements. Thereby, the semiconductor device of the present invention is obtained.

The form of the semiconductor device of the present invention is not particularly limited. For example, SIP (Single Inline Package), HSIP (SIP with Heatsink), ZIP (Zig-zag 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), and the like.
The semiconductor device of the present invention thus obtained is excellent in solder crack resistance and moisture resistance reliability.

  The preferred embodiments of the epoxy resin composition and the semiconductor device of the present invention have been described above, but the present invention is not limited thereto.

  Next, specific examples of the present invention will be described, but the present invention is not limited thereto.

  First, compounds C1 to C4 used as curing accelerators were prepared.

[Synthesis of curing accelerator]
Each of the compounds C1 to C4 was synthesized as follows.

(Synthesis of Compound C1)
A beaker equipped with a stirrer (capacity: 1000 mL) was charged with 25.2 g (0.060 mol) of tetraphenylphosphonium bromide, 27.4 g (0.120 mol) of bisphenol A, and 200 mL of methanol and dissolved well with stirring. 60 ml of 1 mol / L sodium hydroxide aqueous solution and 600 mL of pure water were sequentially added. The precipitated powder was washed with pure water, filtered and dried to obtain a white powder.

This compound was designated C1. As a result of analyzing the compound C1 by ¹ H-NMR, mass spectrum, and elemental analysis, it was confirmed that it was the target phosphonium molecular compound represented by the following formula (8). The yield of the obtained compound C1 was 83%.

(Synthesis of Compound C2)
A separable flask (volume: 200 mL) equipped with a condenser and a stirrer was charged with 6.49 g (0.060 mol) of benzoquinone, 17.3 g (0.066 mol) of triphenylphosphine and 40 mL of acetone, and reacted at room temperature with stirring. . The precipitated crystals were washed with acetone, filtered and dried to obtain 20.0 g of brown crystals.

This compound was designated C2. Compound C2 was analyzed by ¹ H-NMR, mass spectrum, and elemental analysis, and as a result, it was confirmed to be the target phosphobetaine represented by the following formula (9). The yield of the obtained compound C2 was 82%.

(Synthesis of Compound C3)
In a separable flask (volume: 200 mL) equipped with a condenser and a stirrer, 10.4 g (0.060 mol) of 2-bromophenol, 17.3 g (0.066 mol) of triphenylphosphine, 0.65 g (5 mmol) of nickel chloride In addition, 40 mL of ethylene glycol was charged, and the reaction was performed at 160 ° C. with stirring. After cooling the reaction solution, 40 mL of pure water was added dropwise, and the precipitated powder was washed with toluene, filtered and dried to obtain a white powder.

  Next, the obtained powder was dissolved in 100 ml of methanol, and 60 ml of 1 mol / L sodium hydroxide aqueous solution and 500 ml of pure water were sequentially added. The obtained crystals were filtered and washed to obtain 12.7 g of pale yellow crystals.

This compound was designated as C3. Compound C3 was analyzed by ¹ H-NMR, mass spectrum, and elemental analysis, and as a result, it was confirmed to be the target phosphobetaine represented by the following formula (10). The yield of the obtained compound C3 was 79%.

(Synthesis of Compound C4)
After charging 17.9 g (0.060 mol) of triphenylsulfonium chloride, 27.4 g (0.120 mol) of bisphenol A, and 200 mL of methanol in a beaker with a stirrer (capacity: 1000 mL), well dissolved with stirring. 60 ml of 1 mol / L sodium hydroxide aqueous solution and 400 mL of pure water were sequentially added. The precipitated powder was washed with pure water, filtered and dried to obtain a yellow powder.

This compound was designated as C4. Compound C4 was analyzed by ¹ H-NMR, mass spectrum, and elemental analysis, and as a result, it was confirmed to be the target sulfonium molecular compound represented by the following formula (11). The yield of the obtained compound C4 was 58%.

[Synthesis of curing retarding components]
A curing retardation component (G) obtained by reacting an aromatic dihydroxy compound (D), an alkoxysilane compound (E) and an amine compound (F) having one or more nitrogen atoms in the molecule is prepared as follows. did.

(Preparation Example 1)
[Curing retarding component 1]
Catechol 22.0 g (0.20 mol), phenyltrimethoxysilane 19.8 g (0.10 mol), and ethanol 150 mL were charged into a separable flask (capacity: 500 mL) equipped with a condenser and a stirrer. Dissolved. A solution obtained by dissolving 9.3 g (0.10 mol) of aniline in 20 mL of ethanol in advance was dropped into the stirred flask. After reacting at room temperature for 1 hour, the reaction solution was allowed to stand for a while to sufficiently precipitate crystals, and then the precipitated crystals were purified by filtration, washing and vacuum drying to obtain a curing delay component 1 . From the analysis result, it was confirmed that the obtained compound was ammonium silicate represented by the following formula (12).

(Preparation Example 2)
[Curing retarding component 2]
Synthesis was performed in the same manner as in Preparation Example 1 except that 25.5 g (0.1 mol) of N-phenyl-3-aminopropyltrimethoxysilane was used instead of phenyltrimethoxysilane, and a curing retardation component 2 was obtained as a purified crystal. It was. From the analysis result, it was confirmed that the obtained compound was ammonium silicate represented by the following formula (13).

(Preparation Example 3)
[Curing retarding component 3]
Synthesis was carried out in the same manner as in Preparation Example 1 except that 32.0 g (0.2 mol) of 2,3-dihydroxynaphthalene was used in place of catechol to obtain a curing retardation component 3 as a purified crystal. From the analysis results, it was confirmed that the obtained compound was ammonium silicate represented by the following formula (14).

(Preparation Example 4)
[Curing retarding component 4]
The preparation was performed except that 22.3-g of 2,3-dihydroxypyridine (0.2 mol) was used instead of 2,3-dihydroxynaphthalene, and 12.1 g (0.1 mol) of N, N-dimethylaniline was used instead of aniline. Synthesis was conducted in the same manner as in Example 1 to obtain a retarding component 4 as purified crystals. From the analysis results, it was confirmed that the obtained compound was ammonium silicate represented by the following formula (15).

(Preparation Example 5)
[Curing retarding component 5]
Instead of 32.0 g (0.2 mol) of 2,3-dihydroxynaphthalene, 64.1 g (0.4 mol) of 2,3-dihydroxynaphthalene was substituted with phenyltrimethoxysilane, and 29.6 g (0. 2 mol) was synthesized in the same manner as in Preparation Example 3 except that 7.4 g (0.1 mol) of 1,3-diaminopropane was used in place of aniline, to obtain a curing retardation component 5 as a purified crystal. From the analysis result, it was confirmed that the obtained compound was ammonium silicate represented by the following formula (16).

(Preparation Example 6)
[Curing retarding component 6]
In place of 2,3-dihydroxynaphthalene, 84.9 g (0.4 mol) of propyl gallate was used, and 11.4 g (0.1 mol) of 4- (aminomethyl) piperidine was used instead of 1,3-diaminopropane. Were synthesized in the same manner as in Preparation Example 5 to obtain a curing retardation component 6 as purified crystals. From the analysis result, it was confirmed that the obtained compound was ammonium silicate represented by the following formula (17).

(Preparation Example 7)
[Curing retarding component 7]
Use 42.4 g (0.2 mol) of propyl gallate instead of catechol, 14.8 g (0.1 mol) of vinyltrimethoxysilane instead of phenyltrimethoxysilane, and 7.9 g (0.1 mol) of pyridine instead of aniline. The other components were synthesized in the same manner as in Preparation Example 1 to obtain a curing retardation component 7 as purified crystals. From the analysis results, it was confirmed that the obtained compound was ammonium silicate represented by the following formula (18).

(Preparation Example 8)
[Curing retarding component 8]
Instead of catechol, 50.4 g (0.4 mol) of pyrogallol, 39.6 g (0.2 mol) of phenyltrimethoxysilane instead of 19.8 g (0.1 mol) of phenyltrimethoxysilane, 4,4′- The compound was synthesized in the same manner as in Preparation Example 1 except that 25.4 g (0.1 mol) of diamino-3,3′-diethyldiphenylmethane was used, and a curing retardation component 8 was obtained as a purified crystal. From the analysis results, it was confirmed that the obtained compound was ammonium silicate represented by the following formula (19).

(Preparation Example 9)
[Curing retarding component 9]
Synthesis was performed in the same manner as in Preparation Example 8 except that 64.1 g (0.4 mol) of 2,3-dihydroxynaphthalene was used in place of pyrogallol to obtain a curing retardation component 9 as purified crystals. From the analysis result, it was confirmed that the obtained compound was ammonium silicate represented by the following formula (20).

(Preparation Example 10)
[Curing retarding component 10]
Catechol 33.0 g (0.30 mol), tetraethylene orthosilicate 20.8 g (0.10 mol), and ethanol 150 mL were charged into a separable flask (capacity: 500 mL) equipped with a condenser and a stirrer. Dissolved. A solution prepared by previously dissolving 18.6 g (0.20 mol) of aniline in 20 mL of ethanol was dropped into the stirred flask. After reacting at room temperature for 1 hour, the reaction solution was allowed to stand for a while to sufficiently precipitate crystals, and then the precipitated crystals were purified by filtration, washing and vacuum drying to obtain a curing retarding component 10. . From the analysis results, it was confirmed that the obtained compound was ammonium silicate represented by the following formula (21).

(Preparation Example 11)
[Curing retarding component 11]
Synthesis was performed in the same manner as in Preparation Example 10 except that 24.2 g (0.20 mol) of N, N-dimethylaniline was used in place of aniline to obtain a curing retardation component 11 as purified crystals. From the analysis results, it was confirmed that the obtained compound was ammonium silicate represented by the following formula (22).

(Preparation Example 12)
[Curing retarding component 12]
The purified crystals were synthesized in the same manner as in Preparation Example 10 except that 63.7 g (0.30 mol) of propyl gallate was used instead of catechol and 7.4 g (0.10 mol) of 1,3-diaminopropane was used instead of aniline. As a result, a curing retardation component 12 was obtained. From the analysis result, it was confirmed that the obtained compound was ammonium silicate represented by the following formula (23).

(Preparation Example 13)
[Curing retarding component 13]
Pyrogallol 37.8 g (0.30 mol) was used instead of catechol, and 4- (aminomethyl) piperidine 11.4 g (0.10 mol) was used instead of aniline. As a result, a curing retardation component 13 was obtained. From the analysis results, it was confirmed that the obtained compound was ammonium silicate represented by the following formula (24).

(Preparation Example 14)
[Curing retarding component 14]
Synthesized in the same manner as in Preparation Example 10 except that 48.1 g (0.30 mol) of 2,3-dihydroxynaphthalene was used instead of catechol and 15.8 g (0.20 mol) of pyridine was used instead of aniline, and cured as purified crystals. A delay component 14 was obtained. From the analysis results, it was confirmed that the obtained compound was ammonium silicate represented by the following formula (25).

(Preparation Example 15)
[Curing retarding component 15]
Other than using 48.1 g (0.30 mol) of 2,3-dihydroxynaphthalene instead of catechol and using 25.4 g (0.10 mol) of 4,4′-diamino-3,3′-diethyldiphenylmethane instead of aniline, Synthesis was performed in the same manner as in Preparation Example 10 to obtain a curing retardation component 15 as purified crystals. From the analysis results, it was confirmed that the obtained compound was ammonium silicate represented by the following formula (26).

(Preparation Example 16)
[Curing retarding component 16]
Preparation Example 10 except that 63.7 g (0.30 mol) of propyl gallate was used in place of catechol and 25.4 g (0.10 mol) of 4,4′-diamino-3,3′-diethyldiphenylmethane was used in place of aniline. The curing retarding component 16 was obtained as a purified crystal. From the analysis results, it was confirmed that the obtained compound was ammonium silicate represented by the following formula (27).

(Preparation Example 17)
[Curing retarding component 17]
The same as Preparation Example 10 except that 37.8 g (0.30 mol) of pyrogallol was used in place of catechol and 25.4 g (0.10 mol) of 4,4′-diamino-3,3′-diethyldiphenylmethane was used in place of aniline. To obtain a curing retarding component 17 as purified crystals. From the analysis results, it was confirmed that the obtained compound was ammonium silicate represented by the following formula (28).

(Preparation Example 18)
[Curing retarding component 18]
To a separable flask (capacity: 500 mL) equipped with a condenser and a stirrer, 64.1 g (0.40 mol) of 2,3-dihydroxynaphthalene, 39.6 g (0.20 mol) of phenyltrimethoxysilane, 4,4′- 25.4 g (0.10 mol) of diamino-3,3′-diethyldiphenylmethane and 200 g of biphenylaralkyl-type phenol resin (MEH-7851SS manufactured by Meiwa Kasei Co., Ltd.), which is an epoxy resin curing agent, are added and stirred at 130 ° C. , Reacted in a molten state for 30 minutes. In the reaction, 17.8 (93% of the theoretical amount) of methanol was trapped as a gas phase product, confirming that the reaction was sufficiently advanced. This was cooled and then pulverized, and the resulting reaction product was designated as a retarding component 18 (softening point 47 ° C.).

(Preparation Example 19)
[Curing retarding component 19]
In a separable flask (capacity: 500 mL) equipped with a condenser and a stirrer, 48.1 g (0.30 mol) of 2,3-dihydroxynaphthalene, 20.8 g (0.10 mol) of tetraethylene orthosilicate, 4,4′- 25.4 g (0.10 mol) of diamino-3,3′-diethyldiphenylmethane and 200 g of biphenylaralkyl-type phenol resin (MEH-7851SS manufactured by Meiwa Kasei Co., Ltd.), which is an epoxy resin curing agent, are added and stirred at 130 ° C. , Reacted in a molten state for 30 minutes. In the reaction, 16.3 g (88% of the theoretical amount) of ethanol was trapped as a gas phase product, confirming that the reaction was sufficiently advanced. This was cooled and pulverized, and the resulting reaction product was designated as a retarding component 19 (softening point 47 ° C.).

[Preparation of epoxy resin composition]
In the following manner, an epoxy resin composition containing the curing retardation components 1 to 19 was prepared, and a semiconductor device was manufactured.

(Example 1)
First, as a compound (A), a biphenyl type epoxy resin (YX-4000K manufactured by Japan Epoxy Resin Co., Ltd., melting point: 105 ° C., epoxy equivalent: 193, ICI melt viscosity at 150 ° C .: 0.15 poise), and compound (B) XLC-LL manufactured by Mitsui Chemicals Co., Ltd., softening point: 77 ° C., hydroxyl equivalent: 172, ICI melt viscosity at 3.6 ° C .: 3.6 poise), triphenylphosphine, curing retarding component 1, fused spherical silica (inorganic filler) Carbon black, brominated bisphenol A type epoxy resin and carnauba wax were prepared as other additives.

  Next, the biphenyl type epoxy resin: 52 parts by weight, the phenol aralkyl resin: 48 parts by weight, triphenylphosphine: 1.31 parts by weight, the curing retarding component 1: 2.08 parts by weight, fused spherical silica: 730 parts by weight , Carbon black: 2 parts by weight, brominated bisphenol A type epoxy resin: 2 parts by weight, carnauba wax: 2 parts by weight are first mixed at room temperature, then kneaded at 95 ° C. for 8 minutes using a hot roll, and then cooled. By pulverizing, an epoxy resin composition was obtained.

  Next, using this epoxy resin composition as a mold resin, 8 100-pin TQFP packages (semiconductor devices) and 15 16-pin DIP packages (semiconductor devices) were produced, respectively.

  The 100-pin TQFP was manufactured by transfer molding at a mold temperature of 175 ° C., an injection pressure of 7.4 MPa and a curing time of 2 minutes, and post-cured at 175 ° C. for 8 hours.

  The package size of the 100-pin TQFP was 14 × 14 mm, the thickness was 1.4 mm, the silicon chip (semiconductor element) size was 8.0 × 8.0 mm, and the lead frame was 42 alloy.

  The 16-pin DIP was manufactured by transfer molding at a mold temperature of 175 ° C., an injection pressure of 6.8 MPa and a curing time of 2 minutes, and post-cured at 175 ° C. for 8 hours.

  The package size of the 16-pin DIP is 6.4 × 19.8 mm, the thickness is 3.5 mm, the silicon chip (semiconductor element) size is 3.5 × 3.5 mm, and the lead frame is made of 42 alloy. .

(Example 2)
First, as compound (A), biphenyl aralkyl type epoxy resin (NC-3000 manufactured by Nippon Kayaku Co., Ltd., softening point: 60 ° C., epoxy equivalent: 272, ICI melt viscosity at 150 ° C .: 1.3 poise), compound (B ) As a biphenyl aralkyl type phenol resin (MEH-7851SS manufactured by Meiwa Kasei Co., Ltd., softening point: 68 ° C., hydroxyl equivalent: 199, ICI melt viscosity at 150 ° C .: 0.9 poise), triphenylphosphine, curing retardation component 2, Fused spherical silica (average particle size 15 μm) was prepared as an inorganic filler (D), and carbon black, brominated bisphenol A type epoxy resin and carnauba wax were prepared as other additives.

  Next, the biphenyl aralkyl type epoxy resin: 57 parts by weight, the biphenyl aralkyl type phenol resin: 43 parts by weight, triphenylphosphine: 1.31 parts by weight, the curing retarding component 2: 2.36 parts by weight, fused spherical silica: 650 parts by weight, carbon black: 2 parts by weight, brominated bisphenol A type epoxy resin: 2 parts by weight, carnauba wax: 2 parts by weight are first mixed at room temperature and then kneaded at 105 ° C. for 8 minutes using a hot roll. Thereafter, the mixture was cooled and pulverized to obtain an epoxy resin composition.

  Next, using this epoxy resin composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 3)
An epoxy resin composition was obtained in the same manner as in Example 1, except that 2.58 parts by weight of the curing delay component 3: 2.58 parts by weight was used instead of the curing delay component 1, and this epoxy resin composition was used for the above-described implementation. A package (semiconductor device) was manufactured in the same manner as in Example 1.

Example 4
An epoxy resin composition was obtained in the same manner as in Example 2, except that 2.23 parts by weight of the curing delay component 4: 2.23 parts by weight was used instead of the curing delay component 2. A package (semiconductor device) was manufactured in the same manner as in Example 2.

(Example 5)
An epoxy resin composition was obtained in the same manner as in Example 1 except that 2.05 parts by weight of the curing delay component 5 was used instead of the curing delay component 1, and the above-described implementation was performed using this epoxy resin composition. A package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 6)
An epoxy resin composition was obtained in the same manner as in Example 2 except that 2.70 parts by weight of the curing delay component 6 was used instead of the curing delay component 2, and the above-described implementation was performed using this epoxy resin composition. A package (semiconductor device) was manufactured in the same manner as in Example 2.

(Example 7)
An epoxy resin composition was obtained in the same manner as in Example 1 except that 3.03 parts by weight of the curing delay component 7 was used instead of the curing delay component 1, and the above-described implementation was performed using this epoxy resin composition. A package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 8)
An epoxy resin composition was obtained in the same manner as in Example 2 except that the curing delay component 8: 2.41 parts by weight was used in place of the curing delay component 2, and the epoxy resin composition was used to perform the above-described implementation. A package (semiconductor device) was manufactured in the same manner as in Example 2.

Example 9
An epoxy resin composition was obtained in the same manner as in Example 1 except that 2.75 parts by weight of the curing delay component 9 was used in place of the curing delay component 1, and this epoxy resin composition was used to perform the above-described implementation. A package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 10)
An epoxy resin composition was obtained in the same manner as in Example 2, except that 1.35 parts by weight of the curing delay component 10 was used in place of the curing delay component 2, and the epoxy resin composition was used for the above-described implementation. A package (semiconductor device) was manufactured in the same manner as in Example 2.

(Example 11)
An epoxy resin composition was obtained in the same manner as in Example 1 except that 1.49 parts by weight of the curing delay component 11 was used in place of the curing delay component 1, and the epoxy resin composition was used to perform the above-described implementation. A package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 12)
An epoxy resin composition was obtained in the same manner as in Example 2 except that 1.07 parts by weight of the curing delay component 12 was used instead of the curing delay component 2, and the above-described implementation was performed using this epoxy resin composition. A package (semiconductor device) was manufactured in the same manner as in Example 2.

(Example 13)
An epoxy resin composition was obtained in the same manner as in Example 1 except that 1.29 parts by weight of the curing delay component 13 was used in place of the curing delay component 1, and the epoxy resin composition was used for the above-described implementation. A package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 14)
An epoxy resin composition was obtained in the same manner as in Example 2 except that the curing delay component 14: 2.05 parts by weight was used in place of the curing delay component 2, and this epoxy resin composition was used for the above-described implementation. A package (semiconductor device) was manufactured in the same manner as in Example 2.

(Example 15)
An epoxy resin composition was obtained in the same manner as in Example 1 except that the curing retardation component 15: 1.90 parts by weight was used in place of the curing retardation component 1, and this epoxy resin composition was used to perform the above-described implementation. A package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 16)
An epoxy resin composition was obtained in the same manner as in Example 2 except that the curing delay component 16: 2.29 parts by weight was used in place of the curing delay component 2, and this epoxy resin composition was used to perform the above-described implementation. A package (semiconductor device) was manufactured in the same manner as in Example 2.

(Example 17)
An epoxy resin composition was obtained in the same manner as in Example 1 except that the curing delay component 17: 1.64 parts by weight was used in place of the curing delay component 1, and this epoxy resin composition was used to perform the above-described implementation. A package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 18)
An epoxy resin composition was obtained in the same manner as in Example 2, except that 7.75 parts by weight of the curing delay component 18 was used in place of the curing delay component 2, and this epoxy resin composition was used to perform the above-described implementation. A package (semiconductor device) was manufactured in the same manner as in Example 2.

(Example 19)
An epoxy resin composition was obtained in the same manner as in Example 2 except that 6.90 parts by weight of the curing delay component 19 was used in place of the curing delay component 2, and the epoxy resin composition was used for the above-described implementation. A package (semiconductor device) was manufactured in the same manner as in Example 2.

(Example 20)
An epoxy resin composition was obtained in the same manner as in Example 1 except that compound C1: 3.97 parts by weight and curing retarding component 15: 0.95 parts by weight were used instead of triphenylphosphine, and this epoxy resin composition was obtained. Using the product, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 21)
An epoxy resin composition was obtained in the same manner as in Example 1 except that compound C1: 3.97 parts by weight and curing retarding component 15: 1.90 parts by weight were used instead of triphenylphosphine, and this epoxy resin composition was obtained. Using the product, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 22)
An epoxy resin composition was obtained in the same manner as in Example 1 except that compound C1: 3.97 parts by weight and curing retarding component 15: 2.85 parts by weight were used instead of triphenylphosphine, and this epoxy resin composition was obtained. Using the product, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 23)
An epoxy resin composition was obtained in the same manner as in Example 1 except that compound C1: 3.97 parts by weight and curing retarding component 15: 3.80 parts by weight were used instead of triphenylphosphine, and this epoxy resin composition was obtained. Using the product, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 24)
Epoxy resin composition in the same manner as in Example 1 except that 2-methylimidazole: 0.41 parts by weight instead of triphenylphosphine, and curing retardation component 15: 1.90 parts by weight instead of curing retardation component 1 were used. A product (semiconductor device) was manufactured in the same manner as in Example 1 using this epoxy resin composition.

(Example 25)
Except for using 1,8-diazabicyclo (5,4,0) undecene-7: 0.76 parts by weight in place of triphenylphosphine, and using 15: 1.90 parts by weight of cure retarding component in place of cure retarding component 1. An epoxy resin composition was obtained in the same manner as in Example 1, and a package (semiconductor device) was produced in the same manner as in Example 1 by using this epoxy resin composition.

(Example 26)
An epoxy resin composition was prepared in the same manner as in Example 1 except that Compound C2: 1.77 parts by weight instead of triphenylphosphine and Curing Delay Component 15: 1.90 parts by weight instead of Curing Delay Component 1 were used. Using this epoxy resin composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 27)
An epoxy resin composition was prepared in the same manner as in Example 1 except that 1.85 parts by weight of compound C3 instead of triphenylphosphine and 15: 1.90 parts by weight of hardening delay component instead of curing delay component 1 were used. Using this epoxy resin composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 28)
An epoxy resin composition was prepared in the same manner as in Example 1 except that compound C4: 2.45 parts by weight was used instead of triphenylphosphine, and cure retarder component 15: 1.90 parts by weight was used instead of cure retarder component 1. Using this epoxy resin composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Comparative Example 1)
An epoxy resin composition was obtained in the same manner as in Example 1 except that the curing delay component 1 was not added, and a package (semiconductor device) was obtained in the same manner as in Example 1 using this epoxy resin composition. Manufactured.

(Comparative Example 2)
An epoxy resin composition was obtained in the same manner as in Example 2 except that the curing delay component 2 was not added, and a package (semiconductor device) was obtained in the same manner as in Example 2 using this epoxy resin composition. Manufactured.

(Comparative Example 3)
An epoxy resin composition was obtained in the same manner as in Example 1 except that the compound C1: 3.97 parts by weight instead of triphenylphosphine and the curing retardation component 1 were not added, and using this epoxy resin composition, A package (semiconductor device) was manufactured in the same manner as in Example 1.

(Comparative Example 4)
An epoxy resin composition was obtained in the same manner as in Example 1 except that 2-methylimidazole: 0.41 part by weight and curing retardation component 1 was not used instead of triphenylphosphine, and this epoxy resin composition was used. In the same manner as in Example 1, a package (semiconductor device) was manufactured.

(Comparative Example 5)
Epoxy resin composition in the same manner as in Example 1 except that 1,8-diazabicyclo (5,4,0) undecene-7: 0.76 parts by weight and curing retardation component 1 were not added instead of triphenylphosphine. A product (semiconductor device) was manufactured in the same manner as in Example 1 using this epoxy resin composition.

(Comparative Example 6)
An epoxy resin composition was obtained in the same manner as in Example 1 except that compound C2: 1.77 parts by weight and curing delay component 1 were not added instead of triphenylphosphine, and using this epoxy resin composition, A package (semiconductor device) was manufactured in the same manner as in Example 1.

(Comparative Example 7)
Except that the compound C3: 1.85 parts by weight instead of triphenylphosphine and the curing retardation component 1 were not added, an epoxy resin composition was obtained in the same manner as in Example 1, and this epoxy resin composition was used. A package (semiconductor device) was manufactured in the same manner as in Example 1.

(Comparative Example 8)
An epoxy resin composition was obtained in the same manner as in Example 1 except that 2.45 parts by weight of compound C4 instead of triphenylphosphine and curing retardation component 1 were not added, and using this epoxy resin composition, A package (semiconductor device) was manufactured in the same manner as in Example 1.

[Characteristic evaluation]
Characteristic evaluations (1) to (3) of the epoxy resin compositions obtained in Examples 1 to 28 and Comparative Examples 1 to 8 and the semiconductor devices obtained in Examples 1 to 28 and Comparative Examples 1 to 8 Characteristic evaluations (4) and (5) were performed as follows.
(1) Spiral flow Using a mold for spiral flow measurement according to EMMI-I-66, measurement was performed at a mold temperature of 175 ° C, an injection pressure of 6.8 MPa, and a curing time of 2 minutes.
This spiral flow is a parameter of fluidity, and the larger the value, the better the fluidity.
(2) Curing torque Using a curast meter (Orientec Co., Ltd., JSR curast meter IV PS type), the torque after 175 ° C. and 45 seconds was measured.
This hardening torque shows that curability is so favorable that a numerical value is large.
(3) Flow residual ratio After the obtained epoxy resin composition was stored in the atmosphere at 40 ° C. for 1 week, the spiral flow was measured in the same manner as in the above characteristic evaluation (1), and the percentage of the spiral flow immediately after preparation ( %).
This flow residual ratio indicates that the larger the numerical value, the better the storage stability.
(4) Solder crack resistance 100 pin TQFP was left in an environment of 85 ° C. and relative humidity 85% for 168 hours, and then immersed in a solder bath at 260 ° C. for 10 seconds.
Then, the presence or absence of the occurrence of external cracks was observed under a microscope, and displayed as a percentage (%) as crack generation rate = (number of packages in which cracks occurred) / (total number of packages) × 100.
Further, the ratio of the peeled area between the silicon chip and the cured epoxy resin composition was measured using an ultrasonic flaw detector, and the peel rate = (peeled area) / (silicon chip area) × 100. The average value of the package was obtained and expressed as a percentage (%).
These crack generation rate and peel rate indicate that the smaller the numerical value, the better the solder crack resistance.
(5) Moisture resistance reliability A voltage of 20 V was applied to a 16-pin DIP in water vapor at 125 ° C. and a relative humidity of 100%, and the disconnection failure was examined. The time until a defect appears in 8 or more of the 15 packages was defined as a defect time.
Note that the measurement time is 500 hours at the longest, and when the number of defective packages is less than 8 at that time, the defective time is indicated as over 500 hours (> 500).
This failure time indicates that the larger the numerical value, the better the moisture resistance reliability.
Tables 1 and 2 show the results of the characteristic evaluations (1) to (5).

As shown in Tables 1 and 2, the epoxy resin composition obtained in the examples (the epoxy resin composition of the present invention) is shown in the comparative example and the resin composition using only the curing accelerator, In both cases, the fluidity and storage stability are greatly improved without impairing the curability. Further, each of the packages (semiconductor devices of the present invention) sealed with this cured product had good solder crack resistance and moisture resistance reliability. Moreover, by adjusting the amount of the curing retarding component, it has succeeded in adjusting fluidity and storage stability while maintaining the curability sufficient for practical use.
On the other hand, since the epoxy resin compositions obtained in Comparative Examples 1 and 2 do not contain a curing retarding component, both are inferior in fluidity and storage stability, and the resulting package is resistant to solder cracking. It was inferior. Moreover, the epoxy resin composition obtained by Comparative Examples 3-8 was inferior to fluidity | liquidity and a preservability. Furthermore, the epoxy resin compositions obtained in Comparative Examples 4, 5, 7, and 8 had extremely low moisture resistance reliability.

Claims (6)

An epoxy resin composition comprising an epoxy resin (A), a compound (B) having two or more phenolic hydroxyl groups in one molecule, a curing accelerator (C), and a curing retardation component (G). The curing retardation component (G) comprises an aromatic dihydroxy compound (D) represented by the following general formula (1), an alkoxysilane compound (E) represented by the following general formula (2), and an amine compound ( An epoxy resin composition obtained by reacting with F).

[In formula, Ar < ¹ > represents a C5-C30 organic group which has an aromatic ring or a heterocyclic ring. Two OH groups on the organic group Ar ¹ are directly bonded to the aromatic ring or heterocyclic ring. In addition, two oxygen anion groups formed by releasing protons from the two OH groups on the organic group Ar ¹ can form a chelate structure by combining with a silicon atom. ]

[In formula, R < ¹ > shows a C1-C4 aliphatic group, and may mutually be same or different. X ¹ represents an organic group having from 6 to 15 carbon atoms having an aromatic ring, or an aliphatic group having 1 to 15 carbon atoms. a represents 3 or 4. ] The epoxy resin composition according to claim 1, wherein the amine compound (F) is an aromatic amine compound represented by the following general formula (3).

[Wherein R ² and R ³ each represent a hydrogen atom and an organic group having 1 to 6 carbon atoms, and may be the same or different from each other, and R ² and R ³ are bonded to each other to form a ring structure. May be. In the formula, Ar ² represents an organic group having an aromatic ring. The nitrogen atom on the organic group Ar ² is directly bonded to the aromatic ring. b represents an integer of 1 to 6. ] The epoxy resin composition according to claim 1 or 2, wherein the curing delay component (G) is an ammonium silicate compound represented by the following general formula (4) or the following general formula (5).

[In formula, Q shows ammonium formed when an amine compound is protonated. In the formula, Ar ³ represents an organic group having 5 to 30 carbon atoms having an aromatic ring or a heterocyclic ring. Two oxygen atoms on the organic group Ar ³ are directly bonded to the aromatic ring or heterocyclic ring. In addition, two oxygen anion groups formed by releasing protons from two OH groups on the organic group Ar ³ can form a chelate structure by bonding with a silicon atom. Wherein, X ² represents an organic group having from 6 to 15 carbon atoms having an aromatic ring, or an aliphatic group having 1 to 15 carbon atoms. c represents an integer of 1 to 6. d represents 1 or 2. e and f each represent an integer of 1 to 6 that satisfies e × d = 2f. ] The epoxy resin composition according to any one of claims 1 to 3, wherein the curing delay component (G) is an ammonium silicate compound represented by the following general formula (6) or the following general formula (7).

[Wherein, R ⁴ and R ⁵ each represent a hydrogen atom and an organic group having 1 to 6 carbon atoms, and may be the same or different, and R ⁴ and R ⁵ are bonded to each other to form a ring structure. May be. In the formula, Ar ⁴ represents an organic group having an aromatic ring, and a nitrogen atom on the organic group Ar ⁴ is directly bonded to the aromatic ring. In the formula, Ar ⁵ represents an organic group having 5 to 30 carbon atoms having an aromatic ring or a heterocyclic ring, and two oxygen atoms on the organic group Ar ⁵ are directly bonded to the aromatic ring or the heterocyclic ring. . In addition, two oxygen anion groups formed by releasing protons from two OH groups on the organic group Ar ⁵ can form a chelate structure by combining with silicon atoms. Wherein, X ³ represents an organic group having from 6 to 15 carbon atoms having an aromatic ring, or an aliphatic group having 1 to 15 carbon atoms. m represents an integer of 1 to 6. n represents 1 or 2. p and q represent an integer of 1 to 6 that satisfies p × n = 2q. ]   The epoxy resin composition according to any one of claims 1 to 4, wherein the epoxy resin composition further includes an inorganic filler.   A semiconductor device formed by sealing an electronic component with a cured product of the epoxy resin composition according to claim 1.