JP4665616B2 - Epoxy resin composition and semiconductor device - Google Patents

Description

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

  As a method for obtaining a semiconductor device by sealing semiconductor elements such as IC and LSI, transfer molding of an epoxy resin composition is widely used in that it is suitable for mass production at low cost. In addition, improvement of the characteristics and reliability of the semiconductor device has been achieved by improving the epoxy resin and the phenol resin which is a curing agent.

  However, in recent market trends of downsizing, weight reduction, and high performance of electronic devices, higher integration of semiconductors has been progressing year by year, and surface mounting of semiconductor devices has been promoted. Along with this, the demand for epoxy resin compositions used for sealing semiconductor elements has become increasingly severe. For this reason, the conventional epoxy resin composition also has a problem that cannot be solved (cannot be handled).

  In recent years, materials used for sealing semiconductor elements have been filled with inorganic materials to improve fast curing for the purpose of improving production efficiency and to improve heat resistance and reliability when sealing semiconductors. High fluidity that is not impaired even when the material is highly filled has been demanded.

  Epoxy resin compositions for the electrical and electronic materials field contain an addition reaction product of tertiary phosphine and quinones, which are excellent in rapid curing, for the purpose of promoting the curing reaction of the resin during curing. (For example, see Patent Document 1).

  By the way, in such a curing accelerator, a temperature range showing a curing acceleration effect extends to a relatively low temperature. For this reason, in the initial stage of the curing reaction, the reaction is promoted little by little, and this reaction causes the resin composition to have a high molecular weight. Such high molecular weight causes an increase in resin viscosity. As a result, in a resin composition that is highly filled with a filler for improving reliability, problems such as poor molding due to insufficient fluidity are caused.

In order to improve fluidity, various attempts have been made to protect reactive substrates using components that suppress curability. 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 3.) However, in such normal salts, since there are always inhibiting components from the initial stage to the final stage of the curing reaction, fluidity can be obtained, but sufficient curability cannot be obtained, and both cannot be achieved. there were.
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)

  An object of the present invention is to provide an epoxy resin composition having good curability, fluidity and storage stability, and a semiconductor device excellent in solder crack resistance and moisture resistance reliability.

Such an object is achieved by the present inventions (1) to (10) below.
(1) a compound (A) having two or more epoxy groups in one molecule, a compound (B) having two or more phenolic hydroxyl groups in one molecule, and a cation moiety capable of promoting the curing reaction of the epoxy resin; , A latent catalyst (C) having a silicate anion part that suppresses the activity of promoting the curing reaction, and two or more adjacent carbon atoms constituting an alicyclic structure, aromatic ring structure or heterocyclic structure each have a hydroxyl group An epoxy resin composition comprising a bonded compound (D).
(2) The epoxy resin composition according to the above (1), wherein the cation part of the latent catalyst (C) contains a nitrogen cation or a phosphorus cation.
(3) The epoxy resin composition according to (2), wherein the latent catalyst (C) is represented by the following general formula (1).

[Wherein, A ¹ represents a nitrogen atom or a phosphorus atom. In the formula, each of R ¹ , R ² , R ³ and R ⁴ represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group, and is the same as each other May be different. In the formula, X ¹ is an organic group bonded to the substituents Y ¹ and Y ² . In the formula, X ² is an organic group bonded to the substituents Y ³ and Y ⁴ . Y ¹ and Y ² are groups formed by proton-donating substituents releasing protons, and the substituents Y ¹ and Y ² in the same molecule are combined with a silicon atom to form a chelate structure. Y ³ and Y ⁴ are groups formed by proton-donating substituents releasing protons, and the substituents Y ³ and Y ⁴ in the same molecule are combined with a silicon atom to form a chelate structure. X ¹ and X ² may be the same or different from each other, and Y ¹ , Y ² , Y ³ , and Y ⁴ may be the same or different from each other. Z ¹ represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group. ]

(4) The latent catalyst (C) is the above (3), wherein at least one of R ¹ , R ² , R ³ and R ^{4 in} the general formula (1) is an organic group having a substituted or unsubstituted aromatic ring. The epoxy resin composition described in 1.
(5) The epoxy resin composition according to (4), wherein the latent catalyst (C) is represented by the following general formula (2).

[Wherein R ⁵ , R ⁶ and R ⁷ each represents a substituted or unsubstituted aromatic group or heterocyclic organic group, or a substituted or unsubstituted aliphatic group, and may be the same or different from each other. It may be. Ar represents a substituted or unsubstituted aromatic group. In the formula, X ³ is an organic group bonded to the substituents Y ⁵ and Y ⁶ . In the formula, X ⁴ is an organic group bonded to the substituents Y ⁷ and Y ⁸ . Y ⁵ and Y ⁶ are groups formed by proton-donating substituents releasing protons, and substituents Y ⁵ and Y ⁶ in the same molecule are combined with a silicon atom to form a chelate structure. Y ⁷ and Y ⁸ are groups formed by proton-donating substituents releasing protons, and the substituents Y ⁷ and Y ⁸ in the same molecule are combined with a silicon atom to form a chelate structure. X ³ and X ⁴ may be the same or different, and Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ may be the same or different from each other. Z ² represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group. ]

(6) The epoxy resin composition according to (5), wherein the latent catalyst (C) is represented by the following general formula (3).

[Wherein R ⁸ , R ⁹ and R ¹⁰ each represent one selected from a hydrogen atom, a methyl group, a methoxy group and a hydroxyl group, and may be the same or different from each other. In the formula, X ⁵ is an organic group bonded to the substituents Y ⁹ and Y ¹⁰ . Y ⁹ and Y ¹⁰ are groups formed by proton-donating substituents releasing protons, which may be the same or different from each other, and the substituents Y ⁹ and Y ¹⁰ in the same molecule are silicon It combines with atoms to form a chelate structure. Z ³ represents an organic group or a substituted or unsubstituted aliphatic group, having a substituted or unsubstituted aromatic ring or heterocyclic ring. ]

(7) The epoxy resin composition according to the above (6), which contains an inorganic filler.
(8) The content of the inorganic filler is about 100 parts by weight in total of the compound having two or more epoxy groups in one molecule and the compound having two or more phenolic hydroxyl groups in one molecule. The epoxy resin composition according to (7), which is 200 to 2400 parts by weight.
(9) A semiconductor device comprising an electronic component sealed with a cured product of the epoxy resin composition according to (8).

The epoxy resin composition of the present invention is excellent in curability, storage stability, fluidity, and adhesion.
In addition, even when the semiconductor device of the present invention is exposed to a high temperature, defects such as cracks and peeling hardly occur, and deterioration with time due to moisture absorption hardly occurs.

Hereinafter, preferred embodiments of the epoxy resin composition and the semiconductor device of the present invention will be described.
[Epoxy resin composition of the present invention]
The epoxy resin composition of the present invention comprises a compound (A) having two or more epoxy groups in one molecule, a compound (B) having two or more phenolic hydroxyl groups in one molecule, and a curing reaction of the epoxy resin. A latent catalyst (C) having a cation moiety that can be promoted, a silicate anion moiety that suppresses the activity of promoting the curing reaction, and two or more adjacent ones constituting an alicyclic structure, aromatic ring structure, or heterocyclic structure It includes a compound (D) in which a hydroxyl group is bonded to each carbon atom, and optionally an inorganic filler (E). Such an epoxy resin composition is excellent in curability, fluidity and storage stability.

Hereinafter, each component used for the epoxy resin composition of this invention is demonstrated one by one.
[Compound (A) having two or more epoxy groups in one molecule]
The compound (A) having two or more epoxy groups in one molecule used in the present invention is not particularly limited as long as it has two or more epoxy groups in one molecule.
Examples of the compound (A) include bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins and brominated bisphenol type epoxy resins; biphenyl type epoxy resins, biphenyl aralkyl type epoxy resins, and stilbene type epoxies. Resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, dihydroxybenzene type epoxy resin, etc .; and further, epithelial hydroxyl groups such as phenols, phenol resins and naphthols. Epoxy compounds produced by reacting chlorohydrin, epoxy resins obtained by oxidizing olefins with peracids and epoxidized, glycidyl ester type epoxy resins and glycidyl amides Type epoxy resins and the like may be used singly or in combination of two or more of them.

[Compound (B) having two or more phenolic hydroxyl groups in one molecule]
The compound (B) having two or more phenolic hydroxyl groups in one molecule used in the present invention has two or more phenolic hydroxyl groups in one molecule and acts as a curing agent for the compound (A) (function). )
Examples of the compound (B) include phenol novolak resins, cresol novolak resins, bisphenol resins, phenol aralkyl resins, biphenyl aralkyl resins, trisphenol resins, xylylene-modified novolak resins, terpene-modified novolak resins and dicyclopentadiene-modified phenol resins. 1 type or 2 types or more of these can be used in combination.

[Latent catalyst (C)]
The latent catalyst used in the present invention has a cation part that can promote the curing reaction of the epoxy resin, and a silicate anion part that has an effect of suppressing the activity of promoting the curing reaction in the cation part, and is desired. The silicate anion does not dissociate at a temperature lower than the reaction temperature, for example, the molding temperature of the epoxy resin composition, and the promotion of the curing reaction in the cation portion can be suppressed.

  In the latent catalyst used in the present invention, the silicate anion structure having extremely low nucleophilicity does not easily initiate and accelerate the curing reaction in the low temperature region, and thus simultaneously imparts excellent properties in fluidity and storage stability. Can do. Like the conventional adduct of tertiary phosphine and p-benzoquinone and the usual onium phenoxide salt, the inner or outer salt of onium cation and phenoxide anion has higher nucleophilicity of phenoxide anion. The curing acceleration reaction is more likely to occur and the fluidity is lower.

  In addition, a silicate anion structure having extremely low nucleophilicity is dissociated by cleaving the chelate bond in the structure during the curing reaction, for example, by heating, and the silicate site is incorporated into the resin, and the cation moiety Since it loses the function of suppressing the curing accelerating activity and the liberated cation moiety promotes the curing reaction, it imparts excellent fluidity and curability at the same time. Like conventional onium borate salts, which are conventional technologies, borate anions with extremely low nucleophilicity continue to exist in the curing process in the inner or outer salt of an onium cation and borate anion, and curability is suppressed. Is done.

  As a structure (form) of the latent catalyst used in the present invention, an anion portion and a cation portion are coordinated with an excess anion portion or cation portion in addition to a simple salt in which an ionic bond is formed at a ratio of 1: 1. Complexes, complex salts, and known compounds formed by noncovalent bonds such as molecular compounds also suppress the cation moiety that can accelerate the curing reaction of the epoxy resin and the activity that accelerates the curing reaction. There is no problem as long as it is composed of an anion moiety.

  In the latent catalyst used in the present invention, examples of the cation moiety include those containing a nitrogen atom, phosphorus atom, sulfur atom or iodine atom, and those containing a nitrogen atom or phosphorus atom from the viewpoint of reaction activity. Is preferred. As these cation parts, phosphine, tertiary amines, onium salts and the like used as curing accelerators for epoxy resins can be used, and among these, onium salts are preferable.

  In the latent catalyst of the present invention, examples of the onium silicate comprising an onium salt containing a nitrogen atom or a phosphorus atom as a preferred cation moiety and a silicate anion include those represented by the general formula (1). Examples thereof include sulfonium silicate, ammonium silicate, pyridinium silicate, phosphonium silicate, iodonium silicate and selenium silicate, and one or more of these can be used in combination.

Here, in the general formula (1), the atom A ¹ is a phosphorus atom or a nitrogen atom, and the substituents R ¹ , R ² , R ³ and R ⁴ bonded to the atom A ¹ are substituted or unsubstituted, respectively. Or an organic group having an aromatic ring or a heterocyclic ring, or a substituted or unsubstituted aliphatic group, which may be the same as or different from each other.
Examples of these substituents R ^{1 to} R ⁴ include phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, naphthyl group, hydroxynaphthyl group, benzyl group, methyl group, ethyl group, n-butyl group, n-octyl group, cyclohexyl group, and the like. From the viewpoint of reaction activity and stability, substituted or unsubstituted aromatic groups such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, and hydroxynaphthyl group may be used. More preferred.

Further, in the general formula (1), the substituent ^{X 1} is an organic group bonding to the substituent ^{Y 1} and ^{Y 2.} Similarly, the substituent X ² is an organic group bonded to the substituents Y ³ and Y ⁴ . Substituents Y ¹ and Y ² are groups formed by proton-donating substituents releasing protons, and they may be the same or different from each other. Substituents Y ¹ and Y ² in the same molecule Is bonded to a silicon atom to form a chelate structure. Similarly, the substituents Y ³ and Y ⁴ are groups formed by proton-donating substituents releasing protons, and the substituents Y ³ and Y ⁴ in the same molecule bind to a silicon atom to form a chelate structure. Is. The substituents X ¹ and X ² may be the same or different from each other, and the substituents Y ¹ , Y ² , Y ³ , and Y ⁴ may be the same or different from each other.
Such a group represented by Y ¹ X ¹ Y ² and Y ³ X ² Y ⁴ in the general formula (1) is composed of a group formed by releasing two protons from a bivalent or higher proton donor. Examples of divalent or higher proton donors include catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 2,2′-binaphthol, Examples include salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, and glycerin. Among these, catechol, 1,2-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene are storage stable. From the viewpoint of reliability and moisture resistance reliability.

Z ¹ in the general formula (1) represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group. Specific examples thereof include a methyl group Aliphatic hydrocarbon groups such as ethyl group, propyl group, butyl group, hexyl group and octyl group, aromatic hydrocarbon groups such as phenyl group, benzyl group, naphthyl group and biphenyl group, glycidyloxypropyl group, mercaptopropyl Examples thereof include reactive substituents such as a group, aminopropyl group and vinyl group, and among these, a methyl group, a phenyl group, a naphthyl group and a biphenyl group are more preferable from the viewpoint of thermal stability.

  Such an onium silicate, that is, a preferred latent catalyst used in the present invention, is extremely excellent in properties as a curing accelerator, particularly curability, fluidity and storage stability, as compared with conventional curing accelerators.

  Among these onium silicates, more preferable latent catalysts include those having a phosphonium cation represented by the general formula (2).

Here, in the general formula (2), the substituents R ⁵ , R ⁶ , and R ⁷ bonded to the phosphorus atom are each an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted group. And these may be the same as or different from each other.
Examples of these substituents R ^{5 to} R ⁷ include phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, naphthyl group, hydroxynaphthyl group, benzyl group, methyl group, ethyl group, n-butyl group, n-octyl group, cyclohexyl group and the like. From the viewpoint of reaction activity and stability, substituted or unsubstituted aromatic groups such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group and hydroxynaphthyl group are present. More preferred.

  In the general formula (2), the substituent Ar represents a substituted or unsubstituted aromatic group. Examples of the substituent Ar include a phenyl group, a methylphenyl group, a methoxyphenyl group, a hydroxyphenyl group, a naphthyl group, and a hydroxynaphthyl group. From the viewpoint of reaction activity and stability, a phenyl group, a methylphenyl group, A substituted or unsubstituted aromatic group such as a methoxyphenyl group, a hydroxyphenyl group and a hydroxynaphthyl group is more preferable.

In the general formula (2), the substituent X ³ is an organic group bonded to the substituents Y ⁵ and Y ⁶ . Similarly, the substituent X ⁴ is an organic group bonded to the substituents Y ⁷ and Y ⁸ . Substituent Y ⁵ and Y ⁶ is a group proton donating substituent group releases a proton, those substituents Y ⁵ in the same ^molecule, and the Y ⁶ are linked with the silicon atom to form a chelate structure is there. Similarly, the substituents Y ⁷ and Y ⁸ are groups formed by proton-donating substituents releasing protons, and the substituents Y ⁷ and Y ⁸ in the same molecule bind to a silicon atom to form a chelate structure. Is. The substituents X ³ and X ⁴ may be the same or different from each other, and the substituents Y ⁵ , Y ⁶ , Y ⁷ , and Y ⁸ may be the same or different from each other.
Such a group represented by Y ⁵ X ³ Y ⁶ and Y ⁷ X ⁴ Y ⁸ in the general formula (2) is composed of a group formed by releasing two protons from a bivalent or higher proton donor. Examples of divalent or higher proton donors include catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 2,2′-binaphthol, Examples include salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, and glycerin. Among these, catechol, 1,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene are preserved. It is more preferable from the viewpoint of stability and moisture resistance reliability.

Z ² in the general formula (2) represents an organic group having a substituted or unsubstituted aromatic ring or a heterocyclic ring or a substituted or unsubstituted aliphatic group. Specific examples thereof include a methyl group Aliphatic hydrocarbon groups such as ethyl group, propyl group, butyl group, hexyl group and octyl group, aromatic hydrocarbon groups such as phenyl group, benzyl group, naphthyl group and biphenyl group, glycidyloxypropyl group, mercaptopropyl Examples thereof include reactive substituents such as a group, aminopropyl group and vinyl group, and among these, a methyl group, a phenyl group, a naphthyl group and a biphenyl group are more preferable from the viewpoint of thermal stability.

  Among these onium silicates, an even more preferred latent catalyst is a phosphonium cation represented by the general formula (3), wherein the organic group bonded to the phosphorus atom is a substituted or unsubstituted phenyl group. The thing which has can be mentioned.

Here, in the general formula (3), the substituents R ⁸ , R ⁹ , and R ¹⁰ on the phenyl group each represent one selected from a hydrogen atom, a methyl group, a methoxy group, and a hydroxyl group, These may be the same as or different from each other.

Further, in the general formula (3), the substituent ^{X 5} is an organic group bonding to the substituent ^{Y 9} and ^{Y 10.} Substituents Y ⁹ and Y ¹⁰ are groups formed by proton-donating substituents releasing protons, and they may be the same as or different from each other, and substituents Y ⁹ and Y ¹⁰ in the same molecule may be the same. Is bonded to a silicon atom to form a chelate structure.
The group represented by Y ⁹ X ⁵ Y ¹⁰ in the general formula (3) is composed of a group in which a divalent or higher proton donor releases two protons. Examples of the proton donor include catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 2,2′-binaphthol, salicylic acid, 1-hydroxy-2- Examples include naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, and glycerin. Among these, catechol 1,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene are excellent in storage stability and moisture resistance reliability. To more preferable.

Z ³ in the general formula (3) represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group. Specific examples thereof include a methyl group Aliphatic hydrocarbon groups such as ethyl group, propyl group, butyl group, hexyl group and octyl group, aromatic hydrocarbon groups such as phenyl group, benzyl group, naphthyl group and biphenyl group, glycidyloxypropyl group, mercaptopropyl Examples thereof include reactive substituents such as a group, aminopropyl group and vinyl group, and among these, a methyl group, a phenyl group, a naphthyl group and a biphenyl group are more preferable from the viewpoint of thermal stability.

  Such a phosphonium silicate represented by the general formula (3) is preferable because the two proton-donating substituents constituting the chelate are the same, and thus the synthesis is particularly easy to synthesize.

  Here, the method for synthesizing the latent catalyst represented by the general formula (1) as the onium silicate among the latent catalysts used in the present invention will be described, but the present invention is not limited thereto.

  Examples of the method for synthesizing the latent catalyst used in the present invention include a method using a synthetic route in which an onium halide compound and an alkali metal salt of silicate are brought into contact with each other. The alkali metal salt of the silicate can be obtained by neutralizing the trialkoxysilanes and the proton donor capable of forming a chelate bond with a silicon atom with an alkali hydroxide such as sodium hydroxide. These synthesis steps are represented by the following reaction formula. By such a synthesis method, it is possible to synthesize easily and with high yield.

  Here, the trialkoxysilanes include, for example, phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, and hexyltrimethoxysilane. An ethoxysilane etc. are mentioned.

  Examples of the onium halide compound include an onium halide compound having an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring which may have a substituent. For example, triphenyl which may have a substituent Sulfonium bromide, methyltrioctylammonium bromide, tetraphenylammonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, triphenyl (2-hydroxyphenyl) phosphonium bromide, triphenyl (3-hydroxyphenyl) phosphonium bromide, triphenyl (6 -Hydroxy-2-naphthalene) phosphonium bromide, tris (4-methylphenyl) (2-hydroxyphenyl) phosphonium bromide and tris (4-methoxyphenyl) (2- Rokishifeniru) such as bromide, and the like.

[Wherein, A represents a phosphorus atom or a nitrogen atom. R represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group. X represents a monovalent anion. R ′ represents an aliphatic group, and Y and Z represent a group formed by releasing one proton from a proton-donating substituent. R ″ represents an organic group bonded to proton-donating substituents YH and ZH. R ′ ″ represents an organic group or aliphatic group having a substituted or unsubstituted aromatic ring or heterocyclic ring. ]

In the above reaction, a solution of an onium halide compound is dropped at room temperature into a silicate solution produced by neutralizing a trialkoxysilane and a proton donor solution with an alkali such as sodium hydroxide at room temperature. Onium silicate can be easily obtained.
As the solvent used here, for example, alcohol solvents such as methanol, ethanol and propanol are preferable, and for the purpose of improving the yield, it can be appropriately mixed with a reprecipitation solvent such as water.

[Compound (D)]
The compound (D) (hereinafter referred to as compound D) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting the alicyclic structure, aromatic ring structure or heterocyclic structure used in the present invention is based on such a latent catalyst. The acceleration of the curing reaction can be suppressed. Therefore, the reaction in a lower temperature region than the desired reaction temperature can be suppressed, and more excellent fluidity and storage stability can be imparted.

  Further, the compound (D) (hereinafter referred to as Compound D) in which a hydroxyl group is bonded to two or more adjacent carbon atoms constituting the alicyclic structure, aromatic ring structure or heterocyclic structure used in the present invention is a compound other than a hydroxyl group. It may have a substituent. Specific examples of monocyclic compounds include 1,2-cyclohexanediol, catechol, pyrogallol, gallic acid, gallic acid esters or derivatives thereof. Specific examples of polycyclic compounds include, for example, 1,2- Dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 2,2′-binaphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid and These derivatives are mentioned. Of these, from the viewpoint of easy control of fluidity and curability, a compound in which a hydroxyl group is bonded to each of two adjacent carbon atoms constituting an aromatic ring is preferred. In view of thermal stability, the mother nucleus is more preferably a compound having a low volatility and a highly stable naphthalene ring. In this case, specifically, the compound (D) can be a compound having a naphthalene ring such as 2,3-dihydroxynaphthalene and a derivative thereof. One or more of these can be used in combination.

[Inorganic filler (E)]
The inorganic filler (E) is blended (mixed) in the epoxy resin composition for the purpose of improving the solder resistance of the resulting semiconductor device. The type of the inorganic filler (E) is not particularly limited and is generally sealed. What is used for a stop material can be used.

  Examples of the inorganic filler (E) include fused crushed silica, fused silica, crystalline silica, secondary agglomerated silica, alumina, titanium white, aluminum hydroxide, talc, clay, and glass fiber. These can be used alone or in combination of two or more.

  In the epoxy resin composition of the present invention, the compounding ratio of the compound (A) having two or more epoxy groups in one molecule and the compound (B) having two or more phenolic hydroxyl groups in one molecule is also as follows. Although not particularly limited, it is preferably used such that the phenolic hydroxyl group of the compound (B) is about 0.5 to 2 moles relative to 1 mole of the epoxy group of the compound (A). It is more preferable to use so that it may become about 5 mol. Thereby, various characteristics improve more, maintaining the balance of the various characteristics of an epoxy resin composition to a suitable thing.

  Further, the content (blending amount) of the latent catalyst (C) is not particularly limited, but is preferably about 0.01 to 10% by weight, preferably about 0.1 to 5% by weight with respect to the resin component. More preferably. Thereby, the sclerosis | hardenability, fluidity | liquidity, preservability, and hardened | cured material characteristic of an epoxy resin composition are expressed with sufficient balance.

  Further, the content (blending amount) of the compound (D) is not particularly limited, but is preferably about 0.01% by weight or more and 10% by weight, or more preferably 0.1% by weight or more and 5% by weight with respect to the resin component. More preferred is the degree. Viscosity and flow characteristics that are expected to be less than the lower limit cannot be obtained. When the upper limit is exceeded, the curing of the epoxy resin composition is inhibited, the physical properties of the cured product are inferior, and the performance as a semiconductor encapsulating resin is lowered.

  The content (blending amount) of the inorganic filler (E) is not particularly limited, but is about 200 to 2400 parts by weight per 100 parts by weight of the total amount of the compound (A) and the compound (B). It is preferable that the amount is about 400 to 1400 parts by weight. When the content of the inorganic filler (E) is less than the lower limit, the reinforcing effect by the inorganic filler (E) may not be sufficiently exhibited, while the content of the inorganic filler (E) 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, if content (blending amount) of an inorganic filler (E) is 400-1400 weight part per 100 weight part of total amounts of the said compound (A) and the said compound (B), an epoxy resin composition The moisture absorption rate of the cured product becomes low, and the occurrence of solder cracks can be prevented. 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.

  In addition, the content (blending amount) of the inorganic filler (E) is based on the specific gravity of the compound (A), the compound (B), and the inorganic filler (E) itself, and the parts by weight are volume%. You may make it handle by converting.

  Further, in the epoxy resin composition of the present invention, in addition to the compounds (components) (A) to (E), if necessary, for example, coupling of γ-glycidoxypropyltrimethoxysilane or the like Agents, colorants such as carbon black, flame retardants such as brominated epoxy resins, antimony oxide and phosphorus compounds, low stress components such as silicone oil and silicone rubber, natural wax, synthetic wax, higher fatty acids or their metal salts, paraffin, etc. Various additives such as mold release agents and antioxidants may be blended (mixed).

  In the present invention, the epoxy resin composition contains, for example, triphenylphosphine, 1,8-diazabicyclo (5,4,0) as long as the properties of the latent catalyst (C) that functions as a curing accelerator are not impaired. ) There is no problem even if other known catalysts such as -7-undecene and 2-methylimidazole are blended (mixed).

  The epoxy resin composition of the present invention comprises the above-mentioned compounds (A) to (D) (component), optionally (E) component, and optionally other additives, etc. at room temperature using a mixer. It is obtained by mixing, heating and kneading using a hot roll, a heating kneader, etc., cooling and pulverizing.

  Moreover, there is no problem even if the latent catalyst (C) and the compound (D) are previously melt-mixed and then mixed with the (A), (B), (E), and other additives.

  The obtained epoxy resin composition is used as a mold resin, and is cured and molded by a molding method such as transfer molding, compression molding, injection molding, and the like, thereby sealing 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.

  In the present embodiment, the case where the epoxy resin composition of the present invention is used as a sealing material for a semiconductor device has been described. However, the use of the epoxy resin composition of the present invention is not limited thereto. . Further, in the epoxy resin composition of the present invention, mixing (compounding) of the inorganic filler can be omitted depending on the use of the epoxy resin composition.

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

  Next, specific examples of the present invention will be described.

  First, compounds C1 to C7 and triphenylphosphine used as a latent catalyst were prepared.

(Synthesis of Compound C1)
In a separable flask (volume: 200 mL) equipped with a condenser and a stirrer, 7.92 g (0.040 mol) of phenyltrimethoxysilane, 8.81 g (0.080 mol) of catechol, and 1.60 g of sodium hydroxide (0. (04 mol) was dissolved in 10 mL of methanol and a sodium hydroxide solution and 50 mL of methanol were stirred and dissolved uniformly. When a solution in which 13.7 g (0.040 mol) of triphenylsulfonium bromide was previously dissolved in 50 mL of methanol was gradually dropped into the flask, crystals were deposited. The precipitated crystals were filtered, washed with water, and vacuum-dried to obtain 19.2 g of pale white brown crystals.
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 sulfonium silicate represented by the following formula (5). The yield of the obtained compound C1 was 82%.

(Synthesis of Compound C2)
In a separable flask (volume: 200 mL) equipped with a condenser and a stirrer, 7.92 g (0.040 mol) of phenyltrimethoxysilane, 8.81 g (0.080 mol) of catechol, and 1.60 g of sodium hydroxide (0. (040 mol) was dissolved in 10 mL of methanol, and 50 mL of methanol was charged and stirred to dissolve uniformly. When a solution prepared by previously dissolving 8.65 g (0.040 mol) of trimethylphenylammonium bromide in 25 mL of methanol was gradually dropped into the flask, crystals were deposited. The precipitated crystals were filtered, washed with water, and dried under vacuum to obtain 13.7 g of white 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 ammonium silicate represented by the following formula (6). The yield of the obtained compound C2 was 75%.

(Synthesis of Compound C3)
In a separable flask (capacity: 200 mL) with a condenser and a stirrer, 5.45 g (0.040 mol) of methyltrimethoxysilane, 12.82 g (0.080 mol) of 2,3-dihydroxynaphthalene, sodium hydroxide 1 A sodium hydroxide solution in which 60 g (0.040 mol) was dissolved in 10 mL of methanol and 50 mL of methanol were charged and stirred to dissolve uniformly. When a solution prepared by previously dissolving 16.8 g (0.040 mol) of tetraphenylphosphonium bromide in 25 mL of methanol was gradually dropped into the flask, crystals were deposited. The precipitated crystals were filtered, washed with water, and vacuum-dried to obtain 21.8 g of pale white red 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 phosphonium silicate represented by the following formula (7). The yield of the obtained compound C3 was 78%.

(Synthesis of Compound C4)
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 , And 40 mL of ethylene glycol were charged and reacted with heating at 160 ° C. with stirring. After cooling the reaction solution, 40 mL of pure water was added dropwise, and the precipitated crystals were washed with toluene, filtered and dried to obtain triphenyl (2-hydroxyphenyl) phosphonium bromide.
Next, 3.96 g (0.020 mol) of phenyltrimethoxysilane, 6.40 g (0.040 mol) of 2,3-dihydroxynaphthalene, water in advance in a separable flask (volume: 200 mL) equipped with a condenser and a stirrer. A sodium hydroxide solution in which 0.80 g (0.02 mol) of sodium oxide was dissolved in 10 mL of methanol and 50 mL of methanol were charged and stirred to dissolve uniformly. When a solution prepared by previously dissolving 17.4 g (0.040 mol) of triphenyl (2-hydroxyphenyl) phosphonium bromide in 25 mL of methanol was gradually dropped into the flask, crystals were deposited. The precipitated crystals were filtered, washed with water, and vacuum dried to obtain 16.7 g of pale yellowish white crystals.
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 phosphonium silicate molecular compound represented by the following formula (8). The yield of the obtained compound C4 was 81%.

(Synthesis of Compound C5)
In a separable flask (volume: 200 mL) equipped with a condenser and a stirrer, 10.4 g (0.060 mol) of 3-bromophenol, 17.3 g (0.066 mol) of triphenylphosphine, 0.65 g (5 mmol) of nickel chloride , And 40 mL of ethylene glycol were added, and the mixture was heated and reacted at 160 ° C. with stirring. After cooling the reaction solution, 40 mL of pure water was added dropwise, and the precipitated crystals were washed with toluene, filtered and dried to obtain triphenyl (3-hydroxyphenyl) phosphonium bromide.
Next, 7.92 g (0.040 mol) of phenyltrimethoxysilane, 6.40 g (0.040 mol) of 2,3-dihydroxynaphthalene, water in advance in a separable flask (volume: 200 mL) equipped with a condenser and a stirrer. A sodium hydroxide solution in which 1.60 g (0.04 mol) of sodium oxide was dissolved in 10 mL of methanol and 50 mL of methanol were charged and stirred to dissolve uniformly. When a solution prepared by previously dissolving 17.4 g (0.040 mol) of triphenyl (3-hydroxyphenyl) phosphonium bromide in 25 mL of methanol was dripped slowly into the flask, crystals were deposited. The precipitated crystals were filtered, washed with water, and vacuum-dried to obtain 20.3 g of pale red white crystals.
This compound was designated as C5. Compound C5 was analyzed by ¹ H-NMR, mass spectrum, and elemental analysis, and as a result, it was confirmed to be the target phosphonium silicate represented by the following formula (9). The yield of the obtained compound C5 was 75%.

(Synthesis of Compound C6)
In a separable flask (volume: 200 mL) equipped with a condenser and a stirrer, 10.4 g (0.060 mol) of 2-bromophenol, 23.20 g (0.066 mol) of tris (4-methoxyphenyl) phosphine, nickel chloride 0 .65 g (5 mmol) and ethylene glycol 40 mL were charged, and the mixture was heated and reacted at 160 ° C. with stirring. After cooling the reaction solution, 40 mL of pure water was added dropwise, and the precipitated crystals were washed with toluene, filtered and dried to obtain tris (4-methoxyphenyl) (2-hydroxyphenyl) phosphonium bromide.
Next, 7.93 g (0.040 mol) of phenyltrimethoxysilane, 15.1 g (0.080 mol) of 3-hydroxy-2-naphthoic acid, preliminarily placed in a separable flask (volume: 200 mL) equipped with a condenser and a stirring device. A sodium hydroxide solution in which 1.60 g (0.04 mol) of sodium hydroxide was dissolved in 10 mL of methanol and 50 mL of methanol were charged and stirred to dissolve uniformly. When a solution prepared by previously dissolving 19.1 g (0.040 mol) of tris (4-methoxyphenyl) (2-hydroxyphenyl) phosphonium bromide in 25 mL of methanol was gradually dropped into the flask, crystals were deposited. The precipitated crystals were filtered, washed with water, and vacuum-dried to obtain 24.1 g of pale yellowish white crystals.
This compound was designated as C6. Compound C6 was analyzed by ¹ H-NMR, mass spectrum, and elemental analysis, and as a result, it was confirmed to be the target phosphonium silicate represented by the following formula (10). The yield of the obtained compound C6 was 70%.

(Synthesis of Compound C7)
In a separable flask (volume: 200 mL) equipped with a condenser and a stirrer, 7.92 g (0.040 mol) of phenyltrimethoxysilane, 12.82 g (0.080 mol) of 2,3-dihydroxynaphthalene, sodium hydroxide 1 A sodium hydroxide solution in which 60 g (0.040 mol) was dissolved in 10 mL of methanol and 50 mL of methanol were charged and stirred to dissolve uniformly. When a solution prepared by previously dissolving 16.8 g (0.040 mol) of tetraphenylphosphonium bromide in 25 mL of methanol was gradually dropped into the flask, crystals were deposited. The precipitated crystals were filtered, washed with water, and vacuum-dried to obtain 28.9 g of pale white crystals.
This compound was designated as C7. Compound C3 was analyzed by ¹ H-NMR, mass spectrum, and elemental analysis, and as a result, it was confirmed that it was the target phosphonium silicate represented by the following formula (11). The yield of the obtained compound C7 was 95%.

[Preparation of epoxy resin composition and manufacture of semiconductor device]
In the following manner, an epoxy resin composition containing each of the compounds C1 to C7 and triphenylphosphine was prepared to manufacture a semiconductor device.

Example 1
First, a biphenyl type epoxy resin (YX-4000HK manufactured by Japan Epoxy Resin Co., Ltd.) represented by the following formula (12) as the compound (A), and a phenol aralkyl resin represented by the following formula (13) as the compound (B). (However, the number of repeating units: 3 indicates an average value. XLC-LL manufactured by Mitsui Chemicals, Inc.) Compound C1 as the latent catalyst (C), 2,3-dihydroxynaphthalene as the compound D, inorganic filler ( E) fused spherical silica (average particle size 15 μm) was prepared, and carbon black, brominated bisphenol A type epoxy resin and carnauba wax were prepared as other additives.

<Physical Properties of Compound Represented by Formula (12)>
Melting point: 105 ° C
Epoxy equivalent: 193
ICI melt viscosity at 150 ° C .: 0.15 poise

<Physical Properties of Compound Represented by Formula (13)>
Softening point: 77 ° C
Hydroxyl equivalent: 172
ICI melt viscosity at 150 ° C .: 3.6 poise

  Next, the biphenyl type epoxy resin: 52 parts by weight, the phenol aralkyl resin: 48 parts by weight, compound C1: 2.82 parts by weight, 2,3-dihydroxynaphthalene: 1.50 parts by weight, fused spherical silica: 730 parts by weight Part, carbon black: 2 parts by weight, brominated bisphenol A type epoxy resin: 2 parts by weight, carnauba wax: 2 parts by weight, first kneaded at room temperature and then kneaded at 95 ° C. for 8 minutes using a hot roll, The mixture was cooled and pulverized to obtain an epoxy resin composition (thermosetting resin composition).

  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 a compound (A), a biphenyl aralkyl type epoxy resin represented by the following formula (14) (however, the number of repeating units: 3 shows an average value. NC-3000P manufactured by Nippon Kayaku Co., Ltd.), a compound ( B) as a biphenyl aralkyl type phenol resin represented by the following formula (15) (however, the number of repeating units: 3 represents an average value. MEH-7851SS manufactured by Meiwa Kasei Co., Ltd.) and the latent catalyst (C) Compound C1, 2,3-dihydroxynaphthalene as compound D, fused spherical silica (average particle size 15 μm) as inorganic filler (E), carbon black, brominated bisphenol A type epoxy resin and carnauba wax as other additives, Each prepared.

<Physical Properties of Compound Represented by Formula (14)>
Softening point: 60 ° C
Epoxy equivalent: 272
ICI melt viscosity at 150 ° C .: 1.3 poise

<Physical properties of the compound represented by the formula (15)>
Softening point: 68 ° C
Hydroxyl equivalent: 199
ICI melt viscosity at 150 ° C .: 0.9 poise

  Next, said biphenyl aralkyl type epoxy resin: 57 parts by weight, said biphenyl aralkyl type phenol resin: 43 parts by weight, compound C1: 2.82 parts by weight, 2,3-dihydroxynaphthalene: 1.50 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. Then, it 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)
In the same manner as in Example 1 except that compound C2: 2.05 parts by weight instead of compound C1 and catechol: 1.00 parts by weight instead of 2,3-dihydroxynaphthalene 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 4
In the same manner as in Example 2 except that compound C2: 2.05 parts by weight instead of compound C1, and catechol: 1.00 parts by weight was used instead of 2,3-dihydroxynaphthalene, an epoxy resin composition ( A thermosetting resin composition) was obtained, and a package (semiconductor device) was manufactured in the same manner as in Example 2 using this epoxy resin composition.

(Example 5)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 3.13 parts by weight of compound C3 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 1, a package (semiconductor device) was manufactured.

(Example 6)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 3.13 parts by weight of compound C3 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 2, a package (semiconductor device) was manufactured.

(Example 7)
In the same manner as in Example 1 except that compound C4: 2.31 parts by weight instead of compound C1, and catechol: 1.00 parts by weight was used instead of 2,3-dihydroxynaphthalene, 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 8)
In the same manner as in Example 2 except that compound C4: 2.31 parts by weight instead of compound C1 and catechol: 1.00 parts by weight instead of 2,3-dihydroxynaphthalene 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 2 using this epoxy resin composition.

Example 9
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1, except that 3.27 parts by weight of compound C5 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 1, a package (semiconductor device) was manufactured.

(Example 10)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2, except that 3.27 parts by weight of compound C5 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 2, a package (semiconductor device) was manufactured.

(Example 11)
An epoxy resin composition (thermosetting resin) was prepared in the same manner as in Example 1 except that compound C6: 3.83 parts by weight and 2,3-dihydroxynaphthalene: 1.00 parts by weight were used instead of compound C1. And a package (semiconductor device) was produced in the same manner as in Example 1 using this epoxy resin composition.

(Example 12)
An epoxy resin composition (thermosetting resin) was prepared in the same manner as in Example 2 except that compound C6: 3.83 parts by weight and 2,3-dihydroxynaphthalene: 1.00 parts by weight were used instead of compound C1. Composition) was obtained, and a package (semiconductor device) was produced in the same manner as in Example 2 using this epoxy resin composition.

(Example 13)
An epoxy resin composition (thermosetting resin) was prepared in the same manner as in Example 1 except that compound C7: 3.80 parts by weight and 2,3-dihydroxynaphthalene: 1.00 parts by weight were used instead of compound C1. And a package (semiconductor device) was produced in the same manner as in Example 1 using this epoxy resin composition.

(Example 14)
An epoxy resin composition (thermosetting resin) was prepared in the same manner as in Example 2 except that compound C7: 3.80 parts by weight and 2,3-dihydroxynaphthalene: 1.00 parts by weight were used instead of compound C1. Composition) was obtained, and a package (semiconductor device) was produced in the same manner as in Example 2 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 1.67 parts by weight of triphenylphosphine-benzoquinone adduct was used instead of compound C1, and this epoxy was obtained. A package (semiconductor device) was manufactured using the resin composition in the same manner as in Example 1.

(Comparative Example 2)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 1.67 parts by weight of triphenylphosphine-benzoquinone adduct was used instead of compound C1, and this epoxy was obtained. A package (semiconductor device) was manufactured using the resin composition in the same manner as in Example 2.

(Comparative Example 3)
An epoxy resin composition was prepared in the same manner as in Example 1 except that triphenylphosphine: 0.90 parts by weight and catechol: 1.00 parts by weight instead of compound C1 were used instead of 2,3-dihydroxynaphthalene. (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.

(Comparative Example 4)
Epoxy resin composition in the same manner as in Example 2 except that triphenylphosphine: 0.90 parts by weight and catechol: 1.00 parts by weight instead of compound C1 was used instead of 2,3-dihydroxynaphthalene. (Thermosetting resin composition) was obtained, and using this epoxy resin composition, a package (semiconductor device) was produced in the same manner as in Example 2.

(Comparative Example 7)
As in Example 1 except that C9: 2.96 parts by weight represented by the following formula (17) was used instead of compound C1, and catechol: 1.00 parts by weight was used instead of 2,3-dihydroxynaphthalene. Thus, an epoxy resin composition (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 8)
In the same manner as in Example 2 except that C9: 2.96 parts by weight instead of compound C1 and catechol: 1.00 parts by weight instead of 2,3-dihydroxynaphthalene were used, the epoxy resin composition (heat A curable resin composition) was obtained, and a package (semiconductor device) was produced using this epoxy resin composition in the same manner as in Example 2.

[Characteristic evaluation]
Characteristic evaluation (1) to (3) of the epoxy resin composition obtained in each example and each comparative example, and characteristic evaluation (4) and (5) of the semiconductor device obtained in each example and each comparative example ) Was 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 30 ° C for 1 week, the spiral flow was measured in the same manner as in (1) above, and the percentage (% )
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 occurrence rate and peeling 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 disconnection defects were 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 Table 1 and Table 2, the epoxy resin compositions (epoxy resin compositions of the present invention) obtained in Examples 1 to 14 have good curability and fluidity. Each package (semiconductor device of the present invention) sealed with a cured product had good solder crack resistance and moisture resistance reliability.

On the other hand, the epoxy resin compositions obtained in Comparative Example 1 and Comparative Example 2 are both inferior in fluidity, and the packages obtained in these comparative examples are both inferior in solder crack resistance. The moisture resistance reliability was extremely low. Moreover, the epoxy resin compositions obtained in Comparative Example 3 and Comparative Example 4 are both inferior in fluidity. The epoxy resin composition obtained by the ratio Comparative Examples 7 and Comparative Example 8 are all inferior in curing property and cracking resistance and also not obtained sufficiently reliable.

(Examples 15-22, Comparative Examples 9-12)
As the compound (A), the biphenyl type epoxy resin represented by the formula (12): 26 parts by weight, the biphenyl aralkyl type epoxy resin represented by the formula (14): 28.5 parts by weight,
And as a compound (B), the phenol aralkyl resin represented by the said Formula (13): 4
Except for blending 5.5 parts by weight, Examples 1, 3, 5, 7, 9, 11, and 13 were used respectively.
, Comparative Examples 1 and 3, in the same manner as 及 beauty 7, to obtain an epoxy resin composition (thermosetting resin composition), by using the epoxy resin composition was prepared a package (semiconductor device).

  When the characteristics of the epoxy resin compositions and packages obtained in Examples 15 to 22 and Comparative Examples 9 to 12 were evaluated in the same manner as described above, the results were almost the same as the results corresponding to each of Table 1 above. was gotten.

(Examples 23-30, Comparative Examples 13-16)
As compound (A), biphenyl type epoxy resin represented by the above formula (12): 54.5 parts by weight, as compound (B), phenol aralkyl resin represented by the above formula (13): 24 parts by weight, And the biphenyl aralkyl type phenol resin represented by said Formula (14): Except having mix | blended 21.5 weight part, the said Example 1, 3, 5, 7, 9, 11, 13, and the comparative example 1, respectively. , 3, in the same manner as 及 beauty 7, to obtain an epoxy resin composition (thermosetting resin composition), by using the epoxy resin composition was prepared a package (semiconductor device).

  When the properties of the epoxy resin compositions and packages obtained in Examples 23 to 30 and Comparative Examples 13 to 16 were evaluated in the same manner as described above, the results were almost the same as the results corresponding to Table 1 above. was gotten.

  According to the present invention, since an epoxy resin composition having good curability, fluidity and storage stability can be obtained, a thermosetting resin composition using a phosphine or a phosphonium salt as a curing accelerator in the same manner as the epoxy resin. Also suitable. Moreover, these resin compositions can be suitably used in the electric / electronic material field.

Claims (7)

A compound (A) having two or more epoxy groups in one molecule, a compound (B) having two or more phenolic hydroxyl groups in one molecule, a cation moiety capable of promoting the curing reaction of the epoxy resin, and the curing A latent catalyst (C) having a silicate anion moiety that suppresses the activity of promoting the reaction, and a compound in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an alicyclic structure, aromatic ring structure or heterocyclic structure (D) , wherein the latent catalyst (C) is represented by the following general formula (1), and the compound (A): 0.5 to 2 moles of the phenolic hydroxyl group of the compound (B) with respect to 1 mole of the epoxy group, the content of the latent catalyst (C) is 0.01 to 10% by weight based on the resin component, the compound The content of (D) is Epoxy resin composition, which is a 10 wt% 0.01 wt% or more of the fat component.
[Wherein, A ¹ represents a nitrogen atom or a phosphorus atom. In the formula, each of R ¹ , R ² , R ³ and R ⁴ represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group, and is the same as each other May be different. In the formula, groups represented by Y ¹ X ¹ Y ² and Y ³ X ² Y ⁴ are groups formed by releasing two protons from a bivalent or higher proton donor . Y ¹ and Y ² are groups formed by proton-donating substituents releasing protons, and the substituents Y ¹ and Y ² in the same molecule are combined with a silicon atom to form a chelate structure. Y ³ and Y ⁴ are groups formed by proton-donating substituents releasing protons, and the substituents Y ³ and Y ⁴ in the same molecule are combined with a silicon atom to form a chelate structure. X ¹ and X ² may be the same or different from each other, and Y ¹ , Y ² , Y ³ , and Y ⁴ may be the same or different from each other. Z 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 according to claim 1 , wherein the latent catalyst (C) is an organic group in which at least one of R ¹ , R ² , R ³ and R ^{4 in} the general formula (1) has a substituted or unsubstituted aromatic ring. Resin composition. The epoxy resin composition according to claim 2 , wherein the latent catalyst (C) is represented by the following general formula (2).
[Wherein R ⁵ , R ⁶ and R ⁷ each represents a substituted or unsubstituted aromatic group or heterocyclic organic group, or a substituted or unsubstituted aliphatic group, and may be the same or different from each other. It may be. Ar represents a substituted or unsubstituted aromatic group. In the formula, groups represented by Y ⁵ X ³ Y ⁶ and Y ⁷ X ⁴ Y ⁸ are groups formed by releasing two protons from a divalent or higher proton donor . Y ⁵ and Y ⁶ are groups formed by proton-donating substituents releasing protons, and substituents Y ⁵ and Y ⁶ in the same molecule are combined with a silicon atom to form a chelate structure. Y ⁷ and Y ⁸ are groups formed by proton-donating substituents releasing protons, and the substituents Y ⁷ and Y ⁸ in the same molecule are combined with a silicon atom to form a chelate structure. X ³ and X ⁴ may be the same or different, and Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ may be the same or different from each other. Z ² represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group. ] The epoxy resin composition according to claim 3 , wherein the latent catalyst (C) is represented by the following general formula (3).
[Wherein R ⁸ , R ⁹ and R ¹⁰ each represent one selected from a hydrogen atom, a methyl group, a methoxy group and a hydroxyl group, and may be the same or different from each other. In the formula, a group represented by Y ⁹ X ⁵ Y ¹⁰ is a group formed by releasing two protons from a divalent or higher proton donor . Y ⁹ and Y ¹⁰ are groups formed by proton-donating substituents releasing protons, which may be the same or different from each other, and the substituents Y ⁹ and Y ¹⁰ in the same molecule are silicon It combines with atoms to form a chelate structure. Z ³ 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 4 , comprising an inorganic filler. The content of the inorganic filler is about 100 parts by weight in total of the compound having two or more epoxy groups in one molecule and the compound having two or more phenolic hydroxyl groups in one molecule.
The epoxy resin composition according to claim 5 , which is 200 to 2400 parts by weight. An electronic component is sealed with a cured product of the epoxy resin composition according to claim 6 .