JP4894383B2 - Epoxy resin composition and semiconductor device - Google Patents

Description

  The present invention relates to an epoxy resin composition, a curing delay method thereof, 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. It is added as a curing accelerator (see, for example, Patent Document 1)

  Since such a curing accelerator has a temperature range that exhibits a curing acceleration effect extending to a relatively low temperature, at the initial stage of the curing reaction, the reaction is promoted little by little. The resin component in the resin composition has 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 highly filled with a filler for improving 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)

  The present invention provides an epoxy resin composition capable of achieving both good curability and fluidity, and further providing storability, and a semiconductor excellent in solder crack resistance and moisture resistance reliability when used as an epoxy resin composition. A 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 (c) and have completed the present invention.

(A) The epoxy resin composition is excellently preserved by mixing a curing retarding component obtained by reacting a specific trialkoxysilane compound with a compound having a specific hydroxyl group into the epoxy resin composition. It has been found that compatibility, fluidity and curability are compatible.

(B) In addition, the present inventors have found that the degree of curing delay can be adjusted by adjusting the amount of the above-mentioned curing retardation component.

(C) 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 is achieved by the following (1) to (10).
(1) An epoxy resin composition comprising an epoxy resin (A), a compound (B) having two or more phenolic hydroxyl groups in one molecule, and a curing accelerator (C), wherein the following general formula ( It includes a curing retardation component (F) obtained by reacting a proton donor (D) represented by 1) with a trialkoxysilane compound (E) represented by the following general formula (2): An epoxy resin composition.

[Wherein Y ¹ and Y ² each represent a group in which a proton-donating substituent releases one proton, and may be the same or different from each other. Z ¹ represents a substituted or unsubstituted organic group that binds to proton-donating substituents Y ¹ H and Y ² H. ]

[Wherein R ¹ , R ² , and R ³ are aliphatic groups having 1 to 3 carbon atoms, and may be the same as or different from each other. X ¹ represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group. ]

(2) The epoxy resin composition according to item (1), wherein the curing accelerator (C) is a nitrogen, phosphorus or sulfur-containing compound.
(3) Item (1) to Item (2), wherein the epoxy resin composition further includes any one or two of the proton donor (D) and the trialkoxysilane compound (E). The epoxy resin composition according to item.
(4) The proton donor (D) represented by the general formula (1) is an aromatic dihydroxy compound represented by the following general formula (3), the items (1) to (3) The epoxy resin composition according to any one of the above.

[Wherein Ar ¹ represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring. ]

(5) The curing retarding component (F) comprises the proton donor (D) and the trialkoxysilane compound (E) in a temperature range of 0 ° C. to 250 ° C., preferably 50 ° C. to 200 ° C. The epoxy resin composition according to any one of items (1) to (4), which is obtained by reacting in a temperature range of ° C or lower.
(6) The curing retardation component (F) comprises the proton donor (D) and the trialkoxysilane compound (E) in a solvent-free temperature range of 50 ° C. or more and 250 ° C. or less, preferably 80 ° C. or more. The epoxy resin composition according to any one of items (1) to (4), which is obtained by heating and reaction in a temperature range of 200 ° C. or lower.
(7) The curing retarding component (F) is a compound (B) having the proton donor (D) and the trialkoxysilane compound (E), the compound (B) having two or more phenolic hydroxyl groups in one molecule. Part or all, and the temperature range of the softening point temperature to 250 ° C. or less of (B) having two or more phenolic hydroxyl groups in one molecule, preferably having two or more phenolic hydroxyl groups in one molecule (B The epoxy resin composition according to any one of items (1) to (4), which is obtained by melting and mixing in a temperature range of the softening point temperature to 180 ° C. object.
(8) The curing retarding component (F) is preferably a molar ratio satisfying the following formula (1), more preferably the following formula, with respect to the proton donor (D) and the trialkoxysilane compound (E). The epoxy resin composition according to any one of items (1) to (7), which is obtained by reaction at a molar ratio satisfying (2).
Mc ≧ Md (1)
Mc ≧ 2Md (2)
[In the formula, Mc represents the number of moles of the proton donor (D), and Md represents the number of moles of the trialkoxysilane compound (E). ]
(9) The epoxy resin composition according to any one of (1) to (8), wherein the epoxy resin composition further includes an inorganic filler.
(10) A semiconductor device formed by sealing an electronic component with a cured product of the epoxy resin composition according to any one of items (1) to (9).

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 and the curing delay method of the present invention will be described.

  The epoxy resin composition of the present invention is an epoxy resin composition comprising an epoxy resin (A), a compound (B) having two or more phenolic hydroxyl groups in one molecule, and a curing accelerator (C). Then, a curing delay component (F) obtained by reacting the proton donor (D) represented by the general formula (1) with the trialkoxysilane compound (E) represented by the general formula (2). The reaction between the epoxy resin (A) and the compound (B) having two or more phenolic hydroxyl groups in one molecule in a specific temperature range by using the curing delay component (F) As a result, the epoxy resin composition can exhibit excellent fluidity and storability without impairing curability.

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

  The epoxy resin 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 Core-containing epoxy resin, dicyclopentadiene-modified phenol type epoxy resin, phenol aralkyl type epoxy resin having phenylene and / or biphenylene skeleton, naphthol type epoxy resin, naphthalene type Epoxy resin, naphthol aralkyl type epoxy resin having a phenylene and / or biphenylene skeleton and the like, which no problem be used singly or in admixture.

  The compounds having two or more phenolic hydroxyl groups in one molecule used in the present invention are all monomers, oligomers and polymers having two or more phenolic hydroxyl groups in one molecule, and the molecular weight and molecular structure thereof are particularly limited. Although not, 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 / or biphenylene Examples thereof include a naphthol aralkyl resin having a 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, and amines such as triethylamine, tributylamine, benzyldimethylamine and 2- (dimethylaminomethyl) phenol. 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, tetraethylammonium chloride, Tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium chloride, tetraoctylammonium chloride, tetraoctylammonium bromide, tetrabutylammonium Enorato and ammonium salt compounds such as tetra-octyl ammonium phenolate, 1-carboxyl -N, N, betaine compounds such as N- trimethyl meth Nami chloride, and the like. In addition, these include forms subjected to processing such as encapsulation, inclusion, pulverization, and nano-dispersion.

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

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 composed of tetrabutylphosphonium and dihydroxynaphthalenes such as 2,3-dihydroxynaphthalene, tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / tetrabenzoic acid borate, tetraphenylphosphonium / tetranaphthoic acid borate , Tetraphenylphosphonium tetranaphthoyloxyborate and tetraphenyl Phosphonium salt compounds such as tetrasubstituted phosphonium and tetrasubstituted borates such as suphonium and tetranaphthyloxyborate, 2- (triphenylphosphonio) phenolate, and an adduct of triphenylphosphine and 1,4-benzoquinone, 2- (triphenyl) And phosphobetaine compounds such as phosphonio) phenolate and 3- (triphenylphosphonio) phenolate. 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 phosphonium betaine compound such as (triphenylphosphonio) phenolate is used, an epoxy resin composition is preferable because extremely good curability and fluidity can be achieved.

  The curing retardation component (F) used in the present invention can be obtained by reacting the proton donor (D) represented by the general formula (1) with the trialkoxysilane compound (E).

The proton donor (D) represented by the general formula (1) used in the present invention is a compound having at least two proton donating substituents in the molecule, and represented by the general formula (1). In the compound having a proton-donating substituent (HY ¹ Z ¹ Y ² H), the substituent Z ¹ is a substituted or unsubstituted organic compound that binds to the proton-donating substituents Y ¹ H and Y ² H. Each of Y ¹ and Y ² is a group formed by releasing one proton from the proton-donating substituent, which may be the same or different from each other.

Examples of such substituent Z ¹ include aliphatic groups such as ethylene group, methylethylene group, propylene group, butylene group, pentylene group, hexylene group, cyclobutylene group, cyclopentylene group and cyclohexylene group, Examples thereof include aromatic groups such as phenylene group, naphthylene group, biphenylene group and binaphthylene group, and organic groups having a heterocyclic ring such as pyridinyl group and quinoxalinyl group. Among these groups, those having groups Y ¹ and Y ² in adjacent positions, and those having the 2,2 ′ positions in the biphenylene group and binaphthylene group can be exemplified. Examples of the substituent in the substituted organic group as the substituent Z ¹ include aliphatic alkyl groups such as methyl group, ethyl group, propyl group, butyl group and hexyl group, aromatic groups such as phenyl group, methoxy group and ethoxy group And alkoxy groups, nitro groups, cyano groups, hydroxyl groups, halogen groups, and the like.
Examples of the groups Y ¹ and Y ² include an oxygen atom, a sulfur atom, and a carboxylate group.

Examples of the compound having a proton donating substituent represented by the general formula (1) (HY ¹ Z ¹ Y ² H) include, for example, 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, 1,2,3-propanetriol, 2,3-dimethyl-2,3-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,5-hexanediene-3,4-diol, 3-mercapto-1,2-propanediol, 3-amino-1,2-propanediol, 3-chloro-1,2-propanediol, 1,2- Aliphatic hydroxy compounds such as cyclohexanediol, 3,4-dihydroxy-3-cyclobutene-1,2-dione and glycerin;
Glycolic acid, 2-hydroxy-n-butyric acid, 2-hydroxyisobutyric acid, 4-amino-2-hydroxybutyric acid, 2-hydroxy-2-methyl-n-butyric acid, 2-hydroxy-n-octanoic acid and thioacetic acid An aliphatic carboxylic acid compound of
Benzoin, catechol, 3-methylcatechol, 4-methylcatechol, 4-ethylcatechol, 3-fluorocatechol, 3-chlorocatechol, 4-bromocatechol, 4-chlorocatechol, 3 ′, 4′-dihydroxyacetophenone, 4- t-butylcatechol, 3,4-dihydroxybenzonitrile, 3,4-dihydroxybenzoic acid, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzyl alcohol, ethyl-3,4-dihydroxybenzoic acid, pyrogallol, 5- Methyl pyrogallol, 1,2,4-trihydroxybenzene, 2,3,4-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2 ′, 3 ′, 4 ′,-trihydroxyacetophenone, gallic acid, Methyl gallate, gallic acid Ethyl, propyl gallate, octyl gallate, stearyl gallate, tannic acid, 2-hydroxyaniline, 2-hydroxybenzyl alcohol, 2,2'-biphenol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1 , 8-dihydroxynaphthalene, 1,2-dihydroxyanthraquinone, 1,2,3-trihydroxyanthraquinone, 1,2,4-trihydroxyanthraquinone, 2,3,4-trihydroxybenzophenone, 2,3,4,4 Aromatic hydroxy compounds such as '-tetrahydroxybenzophenone, 2,3', 4,4'-tetrahydroxybenzophenone, 2,3,4-trihydroxydiphenylmethane and 1,1'-bi-2-naphthol,
Salicylic acid, 3-methylsalicylic acid, 4-methylsalicylic acid, 5-methylsalicylic acid, 4-methoxysalicylic acid, 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 5-formylsalicylic acid, 4-chlorosalicylic acid, 5-chloro Salicylic acid, 5-fluorosalicylic acid, 5-iodosalicylic acid, 5-bromosalicylic acid, 3-phenylsalicylic acid, 2,6-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,5- Dihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid, 2,6-dihydroxy-4-methylbenzoic acid, 4-hydroxyisophthalic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid 3,5-dihydroxy-2-naphthoic acid, 1,4-di Aromatic carboxylic acid compounds such as Dorokishi-2-naphthoic acid and 3-hydroxy-2-naphthoic acid,
And dihydroxy compounds having an organic group having a heterocyclic ring such as 2,3-dihydroxypyridine and 2,3-dihydroxyquinoxaline.

  Of these proton donors, the aromatic dihydroxy compound represented by the general formula (3) is more preferable from the viewpoint of curing retardation ability.

In the aromatic dihydroxy compound represented by the general formula (3), each of the substituents Ar ¹ represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring.

Examples of such substituent Ar ¹ include organic groups having an aromatic ring such as phenylene group, naphthylene group, biphenylene group and binaphthylene group, and organic groups having a heterocyclic ring such as pyridinyl group and quinoxalinyl group. These groups have an OH group at the adjacent position, and examples of the biphenylene group and binaphthylene group include those at the 2,2 ′ position. Examples of the substituent in the organic group having a substituted aromatic ring or substituted heterocyclic ring as the substituent Ar ¹ include an aliphatic alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, an aromatic group such as a phenyl group, and a methoxy group And alkoxy groups such as ethoxy group, nitro group, cyano group, hydroxyl group, halogen group and the like.

Examples of the aromatic dihydroxy compound (HO—Ar ¹ —OH) represented by the general formula (3) include benzoin, catechol, 3-methylcatechol, 4-methylcatechol, 4-ethylcatechol, 3-fluorocatechol, 3-chlorocatechol, 4-bromocatechol, 4-chlorocatechol, 3 ′, 4′-dihydroxyacetophenone, 4-t-butylcatechol, 3,4-dihydroxybenzonitrile, 3,4-dihydroxybenzoic acid, 3,4 -Dihydroxybenzaldehyde, 3,4-dihydroxybenzyl alcohol, ethyl-3,4-dihydroxybenzoate, pyrogallol, 5-methyl pyrogallol, 1,2,4-trihydroxybenzene, 2,3,4-trihydroxybenzaldehyde, 2, 4,5-trihydroxybenz Rudehydr, 2 ′, 3 ′, 4 ′,-trihydroxyacetophenone, gallic acid, methyl gallate, ethyl gallate, propyl gallate, octyl gallate, stearyl gallate, tannic acid, 2-hydroxyaniline, 2-hydroxy Benzyl alcohol, 2,2′-biphenol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 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 and 1,1'-bi-2- Examples include aromatic hydroxy compounds having an organic group having an aromatic ring such as phthal, dihydroxy compounds having an organic group having a heterocyclic ring such as 2,3-dihydroxypyridine and 2,3-dihydroxyquinoxaline. Among these, Catechol, pyrogallol, propyl gallate, 2,2′-biphenol, 1,2-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene are more preferable because of outstanding balance between curability and fluidity.

The trialkoxysilane compound represented by the general formula (2) used in the present invention has an aliphatic group having 1 to ³ carbon atoms as R ¹ , R ² and R ³ in the formula (2). May be the same as or different from each other.
Examples of the aliphatic group having 1 to 3 carbon atoms as R ¹ , R ² and R ³ in the general formula (2) include a methyl group, an ethyl group and a propyl group.
X ¹ in the general formula (2) represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group.
Examples of the organic group having an aromatic ring as X ¹ in the general formula (2) include a phenyl group, a pentafluorophenyl group, a benzyl group, a methoxyphenyl group, a tolyl group, a fluorophenyl group, a chlorophenyl group, and a bromophenyl group. Nitrophenyl group, cyanophenyl group, aminophenyl group, aminophenoxy group, N-phenylanilino group, N-phenylanilinopropyl group, N-phenylaminopropyl group, phenoxypropyl group, phenylethynyl group, indenyl group, Examples of the organic group having a heterocyclic ring include a pyridyl group, a pyrrolinyl group, an imidazolyl group, an imidazolylpropyl group, an indonyl group, a triazolyl group, a benzotriazolyl group, a carbazolyl group, and a triazinyl group. Piperidyl group Examples include an aryl group, a morpholinyl group, a furyl group, a furfuryl group, and a thienyl group, and examples of the aliphatic group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a glycidyloxypropyl group, a mercaptopropyl group, Aminopropyl, anilinopropyl, butyl, hexyl, octyl, chloromethyl, bromomethyl, chloropropyl, cyanopropyl, diethylamino, vinyl, allyl, methacryloxymethyl, methacryloxypropyl Group, pentadienyl group, bicycloheptyl group, bicycloheptenyl group and ethynyl group. Examples of the substituent in the aromatic ring and heterocyclic ring include a methyl group, an ethyl group, a hydroxyl group, and an amino group. Examples of the substituent in the aliphatic group include a glycidyl group, a mercapto group, and an amino group. It is done. Among these, a vinyl group, a phenyl group, a naphthyl group, and an N-phenylaminopropyl group are preferable because they are excellent in retarding ability to cure.

Specific examples of such trialkoxysilane compounds (E) include phenyltrimethoxysilane as a trialkoxysilane compound having a group having a substituted or unsubstituted aromatic ring as X ¹ in the general formula (2). , Phenyltriethoxysilane, pentafluorophenyltriethoxysilane, 1-naphthyltrimethoxysilane, (N-phenylaminopropyl) trimethoxysilane and the like, and a trialkoxysilane compound having the above-mentioned substituted or unsubstituted aliphatic group As methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, vinyltrimethoxysilane, hexyltriethoxysilane, 3-glycidoxypropyltrimeth Sisilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and the like. Examples of the trialkoxysilane compound having a group having a substituted or unsubstituted heterocyclic ring include 2- (trimethoxysilylethyl). Examples include pyridine and N- (3-trimethoxysilylpropyl) pyrrole, N- (3-trimethoxysilylpropyl) -4,5-dihydroxyimidazole.

Here, a synthesis method of the curing retardation component (F) used in the present invention will be described.
As a synthesis method of the curing retardation component (F), a proton donor (D) represented by the general formula (1) and a trialkoxysilane compound (E) represented by the general formula (2) are used. For example, a method of performing the reaction in a solvent, a method of performing the reaction in the absence of a solvent, a method of performing the reaction in another component, and the like. In a method in which the proton-donor (D) represented by (1) and the trialkoxysilane compound (E) represented by the general formula (2) are reacted to obtain the curing retardation component (F). There is no limitation as long as there is.

As a method of performing the reaction in a solvent, for example, the proton donor (D) and the trialkoxysilane compound (E) are preferably used in a solvent in a temperature range of 0 ° C. or higher and 250 ° C. or lower. More preferably, it can be obtained by reacting in a temperature range of 50 ° C. or higher and 200 ° C. or lower.
More specifically, an organic solvent such as alcohol, acetonitrile, N, N-dimethylformamide or the like in which the proton donor (D) and the trialkoxysilane compound (E) are soluble is used as the solvent. The proton donor (D) and trialkoxysilane compound (E) are uniformly dissolved therein, and this is heated and mixed at a temperature of 50 ° C. or higher and 200 ° C. or lower, for example, depending on the type of solvent used. Then, the curing retardation component (F) can be obtained by condensation reaction.

As a method for performing the reaction in the absence of a solvent, for example, the proton donor (D) and the trialkoxysilane compound (E) are mixed as they are, and preferably in a temperature range of 50 ° C. or more and 250 ° C. or less. More preferably, it can be obtained by heating without solvent reaction in a temperature range of 80 ° C. or higher and 200 ° C. or lower. If the proton donor (D) and the trialkoxysilane compound (E) are solid, they may be mixed as they are in a powder so as to be easily mixed.
In this way, by reacting the two components in a solvent-free manner under heating conditions, formation of the curing retardation component (F) 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 by the proton donor (D) and the trialkoxysilane compound (E) to be used, but at least exceeds the boiling point of the desorbed alcohol at the pressure in the reaction system. There is. For example, when R ¹ in the trialkoxysilane compound (E) represented by the general formula (2) is a butyl group, the alcohol to be eliminated is butanol, and thus the reaction is performed under conditions exceeding 117 ° C. which is the boiling point of butanol. It is preferable to carry out. On the other hand, when the heating temperature exceeds 250 ° C., the formed curing delay component may be transformed by a reaction such as oxidation or decomposition, which may 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, a compound having two or more phenolic hydroxyl groups in one molecule of the proton donor (D) and the trialkoxysilane compound (E). (B), preferably a temperature range of not less than the softening point temperature of the compound (B) having two or more phenolic hydroxyl groups in one molecule and not more than 250 ° C., more preferably two phenolic hydroxyl groups in one molecule. The compound (B) having the above can be obtained by melt-mixing in the temperature range of the softening point temperature or higher and 180 ° C. or lower.
At this time, the amount of the compound (B) having two or more phenolic hydroxyl groups in one molecule is such that at least the proton donor (D) and the trialkoxysilane compound (E) can be easily reacted. Any part or all of the amount used for the epoxy resin composition of the present invention may be used. As a result, the resulting curing retarding component (F) is uniformly dispersed in the compound (B) having two or more phenolic hydroxyl groups in one molecule as a curing agent, and exhibits a 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. The compound (B) having two or more phenolic hydroxyl groups in one molecule is melted at a high temperature in the range of 10 ° C. to 120 ° C. from the softening point, and the proton donor (D) and the A cure retarding component can be obtained by adding and reacting the trialkoxysilane compound (E).
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 curing retardation component (F) used in the present invention, the reaction molar ratio of the proton donor (D) and the trialkoxysilane compound (E) is set to a desired degree of curing delay in the epoxy resin composition of the present invention. However, it is preferable to react at a molar ratio represented by the following mathematical formula (1), and it is more preferred to react at a molar ratio represented by the following mathematical formula (2).
Mc ≧ Md (1)
Mc ≧ 2Md (2)
[Wherein, Mc is the number of moles of the proton donor (D), and Md is the number of moles of the trialkoxysilane compound (E). ]

  As a specific example, the proton donor (D) is preferably 2 to 10 mol or more, more preferably 2 to 5 mol, per 1 mol of the trialkoxysilane compound (E). When the reaction molar ratio is within the range, the balance between curability and fluidity is excellent. Although it can be used outside the range, when the amount of the proton donor (D) is 0.5 mol or less with respect to 1 mol of the trialkoxysilane compound (E), the unreacted content of the trialkoxysilane compound (E). May be mixed in the product in large amounts and cause voids during molding.

  By carrying out the reaction, the proton donor (D) and the trialkoxysilane compound (E) react to obtain a silicate compound that functions as a curing retarding component. A typical example of this is a compound represented by the following general formula (4).

[Wherein Y ³ , Y ⁴ , Y ⁵ and Y ⁶ each represent a group formed by releasing one proton from a proton-donating substituent. Z ² represents a substituted or unsubstituted organic group bonded to Y ³ and Y ⁴ , and ^two groups Y ³ and Y ⁴ in the same molecule can be bonded to a silicon atom to form a chelate structure. is there. Z ³ represents a substituted or unsubstituted organic group bonded to Y ⁵ and Y ^6, and the two groups Y ⁵ and Y ⁶ in the same molecule can bond to a silicon atom to form a chelate structure. is there. X ² represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group. ]

Examples of the group in which the proton-donating substituent releases one proton as the groups Y ³ , Y ⁴ , Y ⁵ and Y ^{6 are the same} as the groups Y ¹ and Y ² in the general formula (1). Preferably, an oxygen atom can be mentioned. Examples of the groups Z ² and Z ³ include a substituted or unsubstituted organic group bonded to Y ³ and Y ⁴ and a substituted or unsubstituted organic group bonded to Y ⁵ and Y ⁶ . The same group as Z ¹ can be exemplified, and preferably, the same group as substituent Ar ¹ in the aromatic dihydroxy compound represented by the general formula (3) can be exemplified.
Specific examples of the groups Y ³ Z ² Y ⁴ and Y ⁵ Z ³ Y ⁶ include compounds having a proton-donating substituent represented by the general formula (1) (HY ¹ Z ¹ Y ² H). In the examples, groups obtained by releasing two protons (H) can be mentioned, and preferred specific examples include aromatic dihydroxy compounds (HO—Ar ¹ —OH) represented by the general formula (3). In the example, a group obtained by releasing two protons (H) can be mentioned.
Further, examples of groups X ^2, may be mentioned the same as X ¹ in the general formula (2).

  In the present invention, the curing retarding component (F) functions as a curing inhibiting component for suppressing the curing promoting action of the curing accelerator (C) on the epoxy resin (A). For example, in the general formula (4), In the compound represented, since the component constituting the chelate ring with respect to the silicon atom in the anion component has reactivity with the epoxy resin, the chelate ring collapses as the curing reaction proceeds due to heating, thereby inhibiting the curing. It is thought that the action is gradually lost. 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 consistently and sufficient curability is not obtained, Since the inhibitory action becomes weak at the end, the reaction at the initial stage of curing is only latent, and the cured product can quickly obtain a sufficient degree of curing.

  In the present invention, any one or two of the proton donor (D) and the trialkoxysilane compound (E) are optionally added to the epoxy resin composition containing the curing retardation component (F). By further adding, it is possible to obtain a further curing delay effect.

  In the present invention, the optionally added proton donor (D) and trialkoxysilane compound (E) are such that the curing retarding component (F) is, for example, an anion component in the compound represented by the general formula (6). However, in the process of losing the curing inhibitory action as the curing reaction proceeds, the function of regenerating the broken chelate ring with the proton donor (D) and the trialkoxysilane compound (E) is expressed. It is something that can be done. That is, the proton that can form a chelate ring with the silicon atoms constituting the trialkoxysilane compound (E) and the trialkoxysilane compound (E) as compared with the case where the curing of the epoxy resin is suppressed only by the curing delay component (F). As long as the donor (D) is added in excess, the latent effect of the curing accelerator by the curing retarding component (F) is exhibited over a long period of time.

  As the addition amount of the proton donor (D) and trialkoxysilane compound (E) that are optionally added, the trialkoxysilane compound (E) is added in an amount of 0.1 to 1 mol of the curing retardation component (F). It is preferable to add in the range of 5 mol, and it is more preferable to add in the range of 0.5 to 2 mol. The proton donor (D) is preferably added in the range of 0.5 to 10 mol, and added in the range of 1 to 4 mol, with respect to 1 mol of the optionally added trialkoxysilane compound (E). It is more preferable to do. When the content (addition amount) is within the range, the balance between curability and fluidity is further improved. However, with respect to 1 mol of the optionally added trialkoxysilane compound (E), the arbitrary When the amount of the proton donor (D) to be added is less than 0.5 mol, a large amount of unreacted portion of the trialkoxysilane compound (E) is mixed, which may cause a void during molding.

  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 (F) can be adjusted depending on 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 (F) is exhibited, and storage stability is exhibited. When molding using the epoxy resin composition, the curing retarding component (F) is suppressed and cured at a molding temperature of preferably 120 to 250 ° C, more preferably 140 to 200 ° C. Can be adjusted to promote. The optimum amount varies depending on the type of the curing accelerator (C) and the curing retarding component (F) used. Generally, the curing retarding component (F) is used per 1 mole of the curing accelerator (C). As an anion component that constitutes, for example, in an anion conversion of the anion component represented by the general formula (4), it is preferably added in a range of 0.1 to 5 mol, and added in a range of 0.5 to 2 mol. More preferably. When the content (addition amount) is within 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. 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 (F) Optionally, the proton donor (D) and the trialkoxysilane compound (E), and optionally, in addition to the inorganic filler, if necessary, for example, an epoxy such as 3-glycidyloxypropyltrimethoxysilane Silane, mercaptosilane such as 3-mercaptopropyltrimethoxysilane, aminosilane such as N-phenyl-3-aminopropyltrimethoxysilane, ureidosilane such as 3-ureidopropyltriethoxysilane, alkylsilane, vinylsilane and phenyltrimethoxysilane Silane coupling agent such as titanate coupling agent, aluminum Um coupling agents, coupling agents such as aluminum / zirconium coupling agent,
Colorants such as carbon black and bengara, flame retardants such as brominated epoxy resins, antimony oxide, aluminum hydroxide, magnesium hydroxide, zinc oxide and phosphorus compounds, low stress components such as silicone oil and silicone rubber, carnauba wax, etc. Natural waxes, 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, ion catchers such as magnesium, aluminum, titanium and bismuth, bismuth You may make it mix | blend (mix) various additives, such as antioxidant.

  The epoxy resin composition of the present invention is obtained by uniformly mixing the above components and, if necessary, other additives and the like using a mixer. It can also be obtained by heating and kneading using a kneader such as a kneader, a kneader, or a twin screw extruder, followed by cooling and pulverization. Moreover, when the epoxy resin composition obtained above is a powder, it can be used as a pressure tablet by 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, when it is used as a mold resin to seal various electronic components such as semiconductor elements to manufacture a semiconductor device, such as a transfer mold or a compression mold. Further, it may be cured by a conventional molding method such as an injection mold, and various electronic components such as semiconductor elements may be sealed. 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.

  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 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 (5). The yield of the obtained compound C1 was 82%.

(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. As a result of analyzing the compound C2 by ¹ H-NMR, mass spectrum, and elemental analysis, it was confirmed that it was the target phosphobetaine represented by the following formula (6). The yield of the obtained compound C2 was 85%.

(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 Then, 40 mL of ethylene glycol was charged, and the reaction was performed with stirring at 160 ° C. 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 (7). The yield of the obtained compound C3 was 81%.

(Synthesis of Compound C4)
A beaker with a stirrer (capacity: 1000 mL) was charged with 17.9 g (0.060 mol) of triphenylsulfonium chloride, 30.0 g (0.120 mol) of 4,4′-sulfonyldiphenol, and 200 mL of methanol and stirred. After dissolving well, 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. As a result of analyzing the compound C4 by ¹ H-NMR, mass spectrum, and elemental analysis, it was confirmed that it was the target sulfonium molecular compound represented by the following formula (8). The yield of the obtained compound C4 was 58%.

[Synthesis of curing retarding components]
The curing retardation component (F) obtained by reacting the proton donor (D) with the trialkoxysilane compound (E) was prepared as follows.

(Adjustment example 1)
[Curing retarding component 1]
Pyrogallol 25.2 g (0.20 mol) as component (D), 19.8 g (0.10 mol) of phenyltrimethoxysilane as component (E), separable flask (capacity with condenser, fractionator, stirrer) : 500 mL) and allowed to react in a molten state at 170 ° C. for 30 minutes with stirring. In the reaction, 9.4 g (98% of the theoretical amount) of methanol was trapped as a gas phase product, so that it was confirmed that the reaction was sufficiently advanced. This was cooled and pulverized, and the resulting reaction product was designated as a retarding component 1 (softening point 92 ° C.).

(Preparation Example 2)
[Curing retarding component 2]
As component (D), 2,3-dihydroxynaphthalene (32.0 g, 0.20 mol) and as component (E), phenyltrimethoxysilane (19.8 g, 0.10 mol) were equipped with a condenser, a fractionating tube, and a stirrer. The mixture was put into a separable flask (capacity: 500 mL) and reacted in a molten state at 170 ° C. for 30 minutes with stirring. In the reaction, 9.2 g (96% 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 2 (softening point 48 ° C.). The infrared absorption spectrum of the compound obtained above is shown in FIG. The infrared absorption spectrum was measured by KBr tablet method using FT-IR8900 manufactured by Shimadzu Corporation.

(Preparation Example 3)
[Curing retarding component 3]
As a component (D), 22.0 g (0.20 mol) of catechol and 19.8 g (0.10 mol) of phenyltrimethoxysilane as a component (E) are separable flasks with a condenser, a fractionating tube and a stirrer (capacity) : 500 mL) and allowed to react in a molten state at 170 ° C. for 30 minutes with stirring. In the reaction, 9.2 g (96% of the theoretical amount) of methanol was trapped as a gas phase product, confirming that the reaction was sufficiently advanced. The obtained reaction product was in a molten state at room temperature, and this was designated as a curing retardation component 3.

(Preparation Example 4)
[Curing retarding component 4]
As component (D), 42.4 g (0.20 mol) of propyl gallate, and 19.8 g (0.10 mol) of phenyltrimethoxysilane as component (E) are separable flasks equipped with a condenser, a fractionating tube and a stirrer. (Volume: 500 mL) was added and reacted in a molten state at 170 ° C. for 30 minutes with stirring. In the reaction, 8.9 g (93% of the theoretical amount) of methanol was trapped as a gas phase product, so that it was confirmed that the reaction was sufficiently progressed. This was cooled and then pulverized, and the resulting reaction product was designated as a retarding component 4 (softening point 90 ° C.). The infrared absorption spectrum of the compound obtained above is shown in FIG.

(Preparation Example 5)
[Curing retarding component 5]
As component (D), 12.4 g (0.20 mol) of 1,2-ethanediol and 19.8 g (0.10 mol) of phenyltrimethoxysilane as component (E) are equipped with a condenser, a fractionating tube and a stirrer. The mixture was put into a separable flask (capacity: 500 mL) and reacted in a molten state at 170 ° C. for 30 minutes with stirring. In the reaction, 8.6 g (90% of the theoretical amount) of methanol was trapped as a gas phase product, confirming that the reaction was sufficiently advanced. The obtained reaction product was in a molten state at room temperature, and this was designated as a retarding component 5.

(Preparation Example 6)
[Curing retarding component 6]
As component (D), 2,3-dihydroxypyridine (22.2 g, 0.20 mol) and as component (E), phenyltrimethoxysilane (19.8 g, 0.10 mol) were equipped with a condenser, a fractionating tube, and a stirrer. The mixture was put into a separable flask (capacity: 500 mL) and reacted in a molten state at 170 ° C. for 30 minutes with stirring. In the reaction, 8.1 g (85% of the theoretical amount) of methanol was trapped as a gas phase product, so that it was confirmed that the reaction was sufficiently advanced.
This was cooled and then pulverized, and the resulting reaction product was designated as a retarding component 6 (softening point 54 ° C.).

(Preparation Example 7)
[Curing retarding component 7]
As the component (D), 32.0 g (0.20 mol) of 2,3-dihydroxynaphthalene, and 19.6 g (0.10 mol) of 3-mercaptopropyltrimethoxysilane as the component (E) were cooled, fractionated, and stirred. It was put into a separable flask (capacity: 500 mL) equipped with a device, and reacted in a molten state at 170 ° C. for 30 minutes with stirring. In the reaction, 8.6 g (90% of the theoretical amount) of methanol was trapped as a gas phase product, confirming that the reaction was sufficiently advanced. The obtained reaction product was in a molten state at room temperature, and this was designated as a curing retardation component 7.

(Preparation Example 8)
[Curing retarding component 8]
As component (D), 32.0 g (0.20 mol) of 2,3-dihydroxynaphthalene, as component (E), 22.0 g (0.10 mol) of N-phenyl-3-aminopropyltrimethoxysilane and 150 ml of methanol were cooled. The mixture was put into a separable flask (capacity: 500 mL) equipped with a tube and a stirrer, and reacted with heating at 50 ° C. for 30 minutes with stirring. Thereafter, when the reaction solution was cooled, white crystals were precipitated. The precipitated crystals were purified by filtration, washed with methanol, and vacuum dried to obtain crystals. The yield of the obtained product was 72%, and the melting point was 308 ° C. This reaction product was used as a curing retardation component 8.

(Preparation Example 9)
[Curing retarding component 9]
As component (D), 2,3-dihydroxynaphthalene (32.0 g, 0.20 mol) and as component (E), vinyltrimethoxysilane (14.8 g, 0.10 mol) were provided with a condenser, a fractionating tube, and a stirrer. The mixture was put into a separable flask (capacity: 500 mL) and reacted in a molten state at 100 ° C. for 60 minutes with stirring. In the reaction, 8.6 g (90% of the theoretical amount) of methanol 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 9 (softening point 55 ° C.).

(Preparation Example 10)
[Curing retarding component 10]
As component (D), 32.0 g (0.20 mol) of 2,3-dihydroxynaphthalene and as component (E) 13.6 g (0.10 mol) of methyltrimethoxysilane were equipped with a condenser, a fractionating tube and a stirrer. The mixture was put into a separable flask (capacity: 500 mL) and reacted in a molten state at 100 ° C. for 60 minutes with stirring. In the reaction, 8.9 g (93% of the theoretical amount) of methanol was trapped as a gas phase product, so that it was confirmed that the reaction was sufficiently progressed. The obtained reaction product was in a molten state at room temperature, and this was designated as a curing retarding component 10.

(Preparation Example 11)
[Curing retarding component 11]
As the component (D), 32.0 g (0.20 mol) of 2,3-dihydroxynaphthalene, and as the component (E), 27.4 g (0.10 mol) of N- (3-triexylsilylpropyl) -4,5-dihydroxyimidazole. ) And 150 ml of methanol were put into a separable flask (capacity: 500 mL) equipped with a condenser and a stirrer, and reacted with heating at 50 ° C. for 30 minutes with stirring. Thereafter, when the reaction solution was cooled, white crystals were precipitated. The precipitated crystals were purified by filtration, washed with methanol, and vacuum dried to obtain crystals. The yield of the obtained product was 96%, and the melting point was 321 ° C. This reaction product was used as a curing retardation component 11.

(Preparation Example 12)
[Curing retarding component 12]
As component (D), 42.4 g (0.20 mol) of propyl gallate, as component (E), 22.0 g (0.10 mol) of N-phenyl-3-aminopropyltrimethoxysilane and 150 ml of methanol were added to a cooling tube and stirred. The mixture was put into a separable flask equipped with a device (volume: 500 mL), and reacted with heating at 50 ° C. for 30 minutes with stirring. Thereafter, when the reaction solution was cooled, white crystals were precipitated. The precipitated crystals were purified by filtration, washed with methanol, and vacuum dried to obtain crystals. The yield of the obtained product was 53%, and the melting point was 246 ° C. This reaction product was used as a curing retarding component 12. The infrared absorption spectrum of the compound obtained above is shown in FIG.

(Preparation Example 13)
[Curing retarding component 13]
As component (D), 42.4 g (0.20 mol) of propyl gallate, 22.0 g (0.10 mol) of N-phenyl-3-aminopropyltrimethoxysilane as component (E), and an epoxy resin curing agent, 100 g of biphenyl aralkyl type phenol resin (MEH-7851SS manufactured by Meiwa Kasei Co., Ltd.) is put into a separable flask (capacity: 500 mL) equipped with a cooling tube, a fractionating tube and a stirrer, and melted at 130 ° C. for 30 minutes with stirring. It reacted with. In the reaction, 9.2 g (96% of the theoretical amount) of methanol 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 13 (softening point 60 ° C.).

(Preparation Example 14)
[Curing retarding component 14]
As component (D), 42.4 g (0.20 mol) of propyl gallate, 19.8 g (0.10 mol) of phenyltrimethoxysilane as component (E), and a biphenylaralkyl type phenol resin (Maywa) as an epoxy resin curing agent 100 g of MEH-7785SS manufactured by Kasei Co., Ltd. was charged into a separable flask (capacity: 500 mL) equipped with a cooling tube, a fractionating tube, and a stirring device, and reacted in a molten state at 130 ° C. for 30 minutes with stirring. In the reaction, 9.2 g (96% 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 used as a curing retardation component 14 (softening point 47 ° C.).

(Preparation Example 15)
[Curing retarding component 15]
As component (D), 2,3-dihydroxynaphthalene (16.0 g, 0.10 mol) and as component (E), phenyltrimethoxysilane (19.8 g, 0.10 mol) were equipped with a condenser, a fractionating tube, and a stirrer. The solution was put into a separable flask (volume: 500 mL) and reacted in a molten state at 170 ° C. for 30 minutes with stirring. In the reaction, 4.3 g (90% 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 15 (softening point 52 ° C.).

(Preparation Example 16)
[Curing retarding component 16]
As component (D), 64.0 g (0.40 mol) of 2,3-dihydroxynaphthalene and as component (E) 19.8 g (0.10 mol) of phenyltrimethoxysilane were equipped with a condenser, a fractionating tube and a stirrer. The solution was put into a separable flask (volume: 500 mL) and reacted in a molten state at 170 ° C. for 30 minutes with stirring. In the reaction, 8.9 g (93% of the theoretical amount) of methanol was trapped as a gas phase product, so that it was confirmed that the reaction was sufficiently progressed. This was cooled and then pulverized, and the resulting reaction product was designated as a retarding component 16 (softening point 48 ° C.).

[Preparation of epoxy resin composition]
In the following manner, an epoxy resin composition containing the curing retarding components 1 to 16 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: 1.77 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 (thermosetting 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-3000P 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 cure retarding component 2: 2.11 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 (thermosetting 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 (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 1.61 parts by weight of the curing delay component 3: 1.61 parts by weight was used instead of the curing delay component 1, and this epoxy resin was obtained. Using the composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.

Example 4
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 2.63 parts by weight of the curing delay component 4: 2.63 parts by weight was used instead of the curing delay component 2, and this epoxy resin was obtained. Using the composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 5)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 0.81 part by weight of the curing delay component 5 was used instead of the curing delay component 1, and this epoxy resin was obtained. Using the composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 6)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 1.62 parts by weight of the curing delay component 6 was used instead of the curing delay component 2, and this epoxy resin was obtained. Using the composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 7)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 2.10 parts by weight of the curing delay component 7 was used instead of the curing delay component 1, and this epoxy resin was obtained. Using the composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 8)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 2.40 parts by weight of the curing delay component 8 was used instead of the curing delay component 2, and this epoxy resin was obtained. Using the composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.

Example 9
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 1.86 parts by weight of the curing delay component 9 was used instead of the curing delay component 2, and this epoxy resin was obtained. Using the composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 10)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 1.80 parts by weight of the curing delay component 10 was used instead of the curing delay component 2, and this epoxy resin was obtained. Using the composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 11)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 2.28 parts by weight of the curing delay component 11 was used instead of the curing delay component 2, and this epoxy resin was obtained. Using the composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 12)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 2.92 parts by weight of the curing delay component 12 was used instead of the curing delay component 2, and this epoxy resin was obtained. Using the composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 13)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2, except that 4.52 parts by weight of the curing delay component 13 was used instead of the curing delay component 2, and this epoxy resin was obtained. Using the composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 14)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 4.11 parts by weight of the curing delay component 14 was used instead of the curing delay component 2, and this epoxy resin was obtained. Using the composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 15)
The epoxy resin composition (heat) was the same as Example 1 except that 2,3-dihydroxynaphthalene: 1.60 parts by weight and phenyltrimethoxysilane: 0.99 parts by weight were used as additional additives. A curable resin composition) was obtained, and a package (semiconductor device) was manufactured in the same manner as in Example 1 using this epoxy resin composition.

(Example 16)
As an additional additive, an epoxy resin composition (heat) was obtained in the same manner as in Example 2 except that 2,3-dihydroxynaphthalene: 1.60 parts by weight and phenyltrimethoxysilane: 0.99 parts by weight were used. A curable resin composition) was obtained, and a package (semiconductor device) was manufactured in the same manner as in Example 1 using this epoxy resin composition.

(Example 17)
An epoxy resin composition (thermosetting resin composition) was carried out in the same manner as in Example 1 except that compound C1: 3.97 parts by weight and curing retarding component 2: 1.06 parts by weight were used instead of triphenylphosphine. Using this epoxy resin composition, a package (semiconductor device) was produced in the same manner as in Example 1.

(Example 18)
An epoxy resin composition (thermosetting resin composition) was used in the same manner as in Example 1 except that compound C1: 3.97 parts by weight and curing retarding component 2: 2.11 parts by weight were used instead of triphenylphosphine. Using this epoxy resin composition, a package (semiconductor device) was produced in the same manner as in Example 1.

(Example 19)
An epoxy resin composition (thermosetting resin composition) was used in the same manner as in Example 1 except that compound C1: 3.97 parts by weight and curing retarding component 2: 3.17 parts by weight were used instead of triphenylphosphine. Using this epoxy resin composition, a package (semiconductor device) was produced in the same manner as in Example 1.

(Example 20)
An epoxy resin composition (thermosetting resin composition) was used in the same manner as in Example 1 except that compound C1: 3.97 parts by weight and curing retarding component 2: 4.22 parts by weight were used instead of triphenylphosphine. Using this epoxy resin composition, a package (semiconductor device) was produced in the same manner as in Example 1.

(Example 21)
Epoxy resin composition in the same manner as in Example 1 except that compound C1: 3.97 parts by weight instead of triphenylphosphine, and curing retarder component 15: 1.55 parts by weight were used instead of cure retarder component 1. (Thermosetting resin composition) was obtained, and using this epoxy resin composition, a package (semiconductor device) was produced in the same manner as in Example 1.

(Example 22)
Epoxy resin composition in the same manner as in Example 1 except that compound C1: 3.97 parts by weight instead of triphenylphosphine, and curing retarder component 16: 3.71 parts by weight were used instead of cure retarder component 1. (Thermosetting resin composition) was obtained, and using this epoxy resin composition, a package (semiconductor device) was produced in the same manner as in Example 1.

(Example 23)
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 2: 2.11 parts by weight instead of curing retardation component 1 were used. A product (thermosetting resin composition) was obtained, and a package (semiconductor device) was produced in the same manner as in Example 1 using this epoxy resin composition.

(Example 24)
Except for using 0.78 parts by weight of 1,8-diazabicyclo (5,4,0) undecene-7 instead of triphenylphosphine and using 2.11 parts by weight of curing retarding component 2 instead of curing retarding component 1. An epoxy resin composition (thermosetting 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 using this epoxy resin composition.

(Example 25)
In the same manner as in Example 1 except that Compound C2: 1.77 parts by weight instead of triphenylphosphine and Curing Delaying Component 2: 2.11 parts by weight instead of Curing Delaying Component 1 were used, an epoxy resin composition ( A thermosetting resin composition) was obtained, and a package (semiconductor device) was manufactured in the same manner as in Example 1 using this epoxy resin composition.

(Example 26)
In the same manner as in Example 1 except that 1.85 parts by weight of compound C3 instead of triphenylphosphine and 2.11 parts by weight of hardening delay component 2 instead of curing delay component 1 were used, an epoxy resin composition ( A thermosetting resin composition) was obtained, and a package (semiconductor device) was manufactured in the same manner as in Example 1 using this epoxy resin composition.

(Example 27)
In the same manner as in Example 1 except that 2.45 parts by weight of compound C4 instead of triphenylphosphine and 2.11 parts by weight of hardening delay component 2 instead of curing delay component 1 were used, an epoxy resin composition ( A thermosetting resin composition) was obtained, and a package (semiconductor device) was manufactured in the same manner as in Example 1 using this epoxy resin composition.

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

(Comparative Example 2)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that the curing delay component 2 was not added, and this epoxy resin composition was used in the same manner as in Example 1 above. Thus, a package (semiconductor device) was manufactured.

(Comparative Example 3)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 17 except that the curing delay component 2 was not added, and this epoxy resin composition was used as in Example 1 above. Thus, a package (semiconductor device) was manufactured.

(Comparative Example 4)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 23 except that the curing delay component 2 was not added, and this epoxy resin composition was used as in Example 1 above. Thus, a package (semiconductor device) was manufactured.

(Comparative Example 5)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 24 except that the curing delay component 2 was not added, and this epoxy resin composition was used as in Example 1 above. Thus, a package (semiconductor device) was manufactured.

(Comparative Example 6)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 25 except that the curing delay component 2 was not added, and this epoxy resin composition was used as in Example 1 above. Thus, a package (semiconductor device) was manufactured.

(Comparative Example 7)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 26 except that the curing delay component 2 was not added, and this epoxy resin composition was used as in Example 1 above. Thus, a package (semiconductor device) was manufactured.

(Comparative Example 8)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 27 except that the curing delay component 2 was not added, and this epoxy resin composition was used as in Example 1 above. Thus, a package (semiconductor device) was manufactured.

[Characteristic evaluation]
Characteristic evaluations (1) to (3) of the epoxy resin compositions obtained in Examples 1 to 27 and Comparative Examples 1 to 8, and the semiconductor devices obtained in Examples 1 to 27 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 compositions (the epoxy resin composition of the present invention) obtained in the examples are shown in the comparative examples, and the resin compositions using only the curing accelerator are: In either case, improved fluidity and storage stability are exhibited without impairing 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.

It is an infrared absorption spectrum of the curing retardation component 2 obtained in Preparation Example 2. It is an infrared absorption spectrum of the curing retardation component 4 obtained in Adjustment Example 4. It is an infrared absorption spectrum of the curing retardation component 12 obtained in Adjustment Example 12.

Claims (9)

An epoxy resin composition comprising an epoxy resin (A), a compound (B) having two or more phenolic hydroxyl groups in one molecule, and a curing accelerator (C), which is represented by the following general formula (1) A curing retarding component (F) obtained by reacting the proton donor (D) represented by the following general formula (2) with the trialkoxysilane compound (E) ; An epoxy resin composition comprising one or two of (D) and the trialkoxysilane compound (E) .
[Wherein Y ¹ and Y ² each represent a group in which a proton-donating substituent releases one proton, and may be the same or different from each other. Z ¹ represents a substituted or unsubstituted organic group that binds to proton-donating substituents Y ¹ H and Y ² H. ]
[In formula, R < ¹ >, R < ² > and R < ³ > show a C1-C3 aliphatic group, and may mutually be same or different. X ¹ represents an organic group or a substituted or unsubstituted aliphatic group, having a substituted or unsubstituted aromatic ring or heterocyclic ring. ] The epoxy resin composition according to claim 1, wherein the curing accelerator (C) is a nitrogen, phosphorus or sulfur-containing compound. The epoxy donor composition according to claim 1 or 2 , wherein the proton donor (D) represented by the general formula (1) is an aromatic dihydroxy compound represented by the following general formula (3).
[Wherein Ar ¹ represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring. ] The curing retardation component (F) is obtained by reacting the proton donor (D) and the trialkoxysilane compound (E) in a temperature range of 0 ° C. or more and 250 ° C. or less. The epoxy resin composition according to any one of claims 1 to 3 . The curing retardation component (F) is obtained by reacting the proton donor (D) and the trialkoxysilane compound (E) by heating them in a temperature range from 50 ° C. to 250 ° C. without solvent. The epoxy resin composition according to any one of claims 1 to 3 , wherein the epoxy resin composition is obtained. The curing retardation component (F) is a part or all of the proton donor (D) and the trialkoxysilane compound (E), and the compound (B) having two or more phenolic hydroxyl groups in the molecule. When the phenolic hydroxyl groups in the molecule in the temperature range of the softening point temperature above 250 ° C. or less of having two or more (B), and was obtained by reacting with the molten mixture, according to claim 1 to 3 The epoxy resin composition according to any one of the above. The curing retardation component (F) is obtained by reacting the proton donor (D) and the trialkoxysilane compound (E) at a molar ratio satisfying the following mathematical formula (1). Item 7. The epoxy resin composition according to any one of Items 1 to 6 .
Mc ≧ Md (1)
[In the formula, Mc represents the number of moles of the proton donor (D), and Md represents the number of moles of the trialkoxysilane compound (E). ] The epoxy resin composition according to any one of claims 1 to 7 , wherein the epoxy resin composition further includes an inorganic filler. The semiconductor devices obtained by encapsulating an electronic component with a cured product of the epoxy resin composition according to any one of claims 1 to 8.