JP4367046B2 - Curing accelerator, epoxy resin composition, and semiconductor device - Google Patents

Description

  The present invention relates to a curing accelerator, an epoxy resin composition, and a semiconductor device. More specifically, a curing accelerator useful for a thermosetting resin composition, an epoxy resin composition containing such a curing accelerator, having good curability, storage stability and fluidity, and suitably used in the field of electrical and electronic materials. And a semiconductor device having excellent solder crack resistance and moisture resistance reliability.

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

  However, in recent electronic equipment market trends, as devices become smaller, lighter, and have higher performance, higher integration of semiconductors has been progressing year by year, and in the manufacturing process, surface mounting of semiconductor devices has also been promoted. Has been. 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 devices are required to improve fast curing for the purpose of improving production efficiency and to improve storability for the purpose of improving handling during distribution and storage. It is becoming.

  Epoxy resin compositions for the electrical and electronic materials field contain tertiary phosphines and addition reaction products of tertiary phosphines and quinones as curing accelerators for the purpose of accelerating the curing reaction of the resin during curing. (For example, refer to Patent Document 1).

  However, since the above-mentioned curing accelerator exhibits a curing acceleration effect from a relatively low temperature region, for example, when mixing the epoxy resin composition before curing and other components, heat generated in the system and external The curing reaction of the epoxy resin composition partially proceeds by the heat applied from. In addition, the reaction further proceeds when the epoxy resin composition is stored at room temperature after mixing.

  The progress of the partial curing reaction causes an increase in viscosity or a decrease in fluidity when the epoxy resin composition is a liquid, and develops a viscosity when the epoxy resin composition is a solid. Such a change in state does not occur uniformly in the strict sense within the epoxy resin composition. For this reason, dispersion | variation arises in the sclerosis | hardenability of each part of an epoxy resin composition.

  Due to this, further, the curing reaction proceeds at a high temperature, and when molding the epoxy resin composition (including the concept of other shaping, hereinafter referred to as “molding”), the molding troubles due to lower fluidity and , Resulting in deterioration of the mechanical, electrical or chemical properties of the molded product.

  Therefore, when using a curing accelerator that causes a decrease in the storage stability of the epoxy resin composition in this way, strict quality control during mixing of various components, storage and transportation at low temperatures, and strict molding conditions are required. Management is essential and handling is very complicated.

  In order to solve this problem, research on so-called latent curing accelerators has been actively conducted that suppresses the change in viscosity and fluidity at low temperatures with time and causes a curing reaction only by heating during shaping or molding. Yes. As a means for this, studies have been made to develop the latent property by protecting the active sites of the curing accelerator with ion pairs, and latent curing accelerators having salt structures of various organic acids and phosphonium ions have been presented. (For example, refer to Patent Document 2).

  However, in a system using this phosphonium salt as a curing accelerator, there is a possibility that problems such as deterioration of solder crack resistance and moisture resistance reliability may occur due to the use of surface mounting of a semiconductor device for the following reasons. That is, in the material system using these phosphonium salts, the adhesiveness of the interface between the cured product of the resin composition in the semiconductor device and the substrate such as the semiconductor element or the lead frame is not sufficient, and in the solder dipping or solder reflow process, When exposed to a high temperature of 200 ° C. or higher, peeling easily occurs at the interface with the substrate. This peeling of the interface induces cracks in the semiconductor device and tends to cause a decrease in moisture resistance reliability.

On the other hand, latent curing accelerators having various phosphonium betaine salt structures have also been proposed (see, for example, Patent Document 3). However, in the system using the salt of phosphonium betaine as a curing accelerator, the problem of storage stability is insufficient in a semiconductor sealing material using a curing agent such as a low molecular weight epoxy resin or a phenol aralkyl resin in recent years. Has occurred.
Japanese Patent Laid-Open No. 10-25335 (second term) JP 2001-98053 A (pages 3 to 4) U.S. Pat. No. 4,171,420 (pages 2 to 3)

  An object of the present invention is to provide a curing accelerator useful for various curable resin compositions, an epoxy resin composition having good storage stability, curability and fluidity, and a semiconductor device having excellent solder crack resistance and moisture resistance reliability. There is.

  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): It has been found that a phosphonium silicate having a specific structure is extremely useful as a curing accelerator for accelerating the curing reaction of various curable resin compositions.

  (B): By mixing such a phosphonium silicate as a curing accelerator in a curable resin composition, particularly an epoxy resin composition, the epoxy resin composition has excellent curability, storage stability and fluidity. I found.

  (C): Even when a semiconductor device in which an electronic component such as a semiconductor element is sealed with a cured product of such an epoxy resin composition is exposed to high temperatures, defects such as cracks and peeling are unlikely to occur. I found out.

That is, the present invention is achieved by the following (1) to ( 7 ).

［式中、Ｒ⁴、Ｒ⁵およびＲ⁶は、それぞれ、水素原子、メチル基、メトキシ基および水酸基から選択される１種を表し、互いに同一であっても異なっていてもよい。式中Ｘ⁴は、置換基Ｙ⁷およびＹ⁸と結合する有機基である。Ｙ⁷およびＹ⁸は１価のプロトン供与性置換基がプロトンを放出してなる基であり、それらは互いに同一であっても異なっていてもよく、同一分子内の置換基Ｙ⁷およびＹ⁸が珪素原子と結合してキレート構造を形成するものである。式中の−Ｙ _７ −Ｘ _４ −Ｙ _８ −で表される基は、カテコール、ピロガロール、２，３−ジヒドロキシナフタレン、サリチル酸、１−ヒドロキシ−２−ナフトエ酸および３−ヒドロキシ−２−ナフトエ酸から選ばれるプロトン供与体が有する水酸基、カルボキシル基のプロトンを２個放出してなる基を表す。］ ( 1 ) A curing accelerator that is mixed in the curable resin composition and can accelerate the curing reaction of the curable resin composition,
A curing accelerator represented by the following general formula (2):

[Wherein R ⁴ , R ⁵ and R ⁶ 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 ⁴ is an organic group bonded to the substituents Y ⁷ and Y ⁸ . Y ⁷ and Y ⁸ are groups formed by releasing a proton from a monovalent proton-donating substituent, which may be the same or different from each other, and the substituents Y ⁷ and Y ⁸ in the same molecule Is bonded to a silicon atom to form a chelate structure. In the formula, a group represented by —Y ₇ —X ₄ —Y ₈ — represents catechol, pyrogallol, 2,3-dihydroxynaphthalene, salicylic acid, 1-hydroxy-2-naphthoic acid and 3-hydroxy-2-naphthoic acid. Represents a group formed by releasing two protons of a hydroxyl group and a carboxyl group of a proton donor selected from: ]

( 2 ) It contains a compound having two or more epoxy groups in one molecule, a compound having two or more phenolic hydroxyl groups in one molecule, and the curing accelerator described in (1 ) above. Epoxy resin composition.

［式中、Ｒ⁷、Ｒ⁸、Ｒ⁹およびＲ¹⁰は、それぞれ、水素原子、炭素数１〜６の鎖状もしくは環状アルキル基、フェニル基およびハロゲン原子から選択される１種を表し、互いに同一であっても異なっていてもよい。］

［式中、Ｒ¹¹〜Ｒ¹⁸は、それぞれ、水素原子、炭素数１〜４のアルキル基およびハロゲン原子から選択される１種を表し、互いに同一であっても異なっていてもよい。ただし、ａは、１〜１０の整数である。］ ( 3 ) The compound having two or more epoxy groups in one molecule has at least one of an epoxy resin represented by the following general formula (3) and an epoxy resin represented by the following general formula (4) as a main component. The epoxy resin composition according to ( 2 ) above.

[Wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each represent one selected from a hydrogen atom, a linear or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group and a halogen atom, They may be the same or different. ]

[Wherein, R ^{11 to} R ¹⁸ each represent one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom, and may be the same or different from each other. However, a is an integer of 1-10. ]

［式中、Ｒ¹⁹〜Ｒ²²は、それぞれ、水素原子、炭素数１〜４のアルキル基およびハロゲン原子から選択される１種を表し、互いに同一であっても異なっていてもよい。ただし、ｂは、１〜１０の整数である。］

［式中、Ｒ²³〜Ｒ³⁰は、それぞれ、水素原子、炭素数１〜４のアルキル基およびハロゲン原子から選択される１種を表し、互いに同一であっても異なっていてもよい。ただし、ｃは、１〜１０の整数である。］ ( 4 ) The compound having two or more phenolic hydroxyl groups in one molecule is mainly composed of at least one of a phenol resin represented by the following general formula (5) and a phenol resin represented by the following general formula (6). The epoxy resin composition according to ( 2 ) or ( 3 ) above.

[Wherein, R ^{19 to} R ²² each represent one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom, and may be the same or different from each other. However, b is an integer of 1-10. ]

[Wherein, R ^{23 to} R ³⁰ each represent one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom, and may be the same or different from each other. However, c is an integer of 1-10. ]

( 5 ) The epoxy resin composition according to any one of ( 2 ) to ( 4 ), including an inorganic filler.

( 6 ) 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 the above ( 5 ), which is 200 to 2400 parts by weight.

( 7 ) A semiconductor device comprising an electronic component sealed with a cured product of the epoxy resin composition according to ( 6 ) above.

  According to the curing accelerator of the present invention, the curable resin composition can be rapidly cured, and even when the cured product of the curable resin composition is exposed to high temperature, the cured product is defective. Can be suitably prevented.

Moreover, the epoxy resin composition of this invention is excellent in sclerosis | hardenability, preservability, and fluidity | liquidity.
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 curing accelerator, the epoxy resin composition, and the semiconductor device of the present invention will be described.

  The curing accelerator of the present invention can be applied as a curing accelerator for various curable resin compositions, but in the following, it represents a case where it is applied to an epoxy resin composition which is a kind of thermosetting resin composition. I will explain.

  The epoxy resin composition of the present embodiment includes 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 the curing acceleration of the present invention. It contains a phosphonium silicate (C) as an agent and an inorganic filler (D). Such an epoxy resin composition is excellent in curability, storage stability and fluidity.

Hereinafter, each component will be sequentially described.
[Compound (A)]
The compound (A) having two or more epoxy groups in one molecule used in the present invention is not limited as long as it has two or more epoxy groups in one molecule.

  Examples of the compound (A) include bisphenol A type epoxy resins, bisphenol F type epoxy resins, brominated bisphenol type epoxy resins and the like, biphenyl type epoxy resins, biphenyl aralkyl type epoxy resins, and stilbene type epoxy resins. , Phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, dihydroxybenzene type epoxy resin, etc., reacting epichlorohydrin with hydroxyl groups such as phenols, phenol resins and naphthols Epoxy compounds produced by oxidization, epoxy resins obtained by oxidizing olefins with peracid, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, etc. The recited may be used singly or in combination of two or more of them.

  Among these, the compound (A) particularly includes one or both of the biphenyl type epoxy resin represented by the general formula (4) and the biphenyl aralkyl type epoxy resin represented by the general formula (5). It is preferable to use the main component. Thereby, the fluidity at the time of molding of the epoxy resin composition (for example, at the time of manufacturing a semiconductor device) is improved, and the solder crack resistance of the obtained semiconductor device is further improved.

  Here, “improvement of solder crack resistance” means that the obtained semiconductor device is exposed to high temperatures in, for example, a solder dipping or solder reflow process, even if the cured product is cracked or peeled off. This means that the occurrence of defects is less likely to occur.

Here, the substituents R ^{7 to} R ¹⁰ in the biphenyl type epoxy resin represented by the general formula (3) are each a hydrogen atom, a chain or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group, and a halogen atom. Represents one selected from the above, and these may be the same or different.

As specific examples of these substituents R ^{7 to} R ¹⁰ , in addition to a hydrogen atom and a phenyl group, for example, as a chain or cyclic alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, Examples thereof include a butyl group and a cyclohexyl group, and examples of the halogen atom include a chlorine atom and a bromine atom. Among these, a methyl group is particularly preferable. Thereby, the melt viscosity of the epoxy resin composition is lowered, and the handling thereof becomes easy, for example, at the time of manufacturing a semiconductor device. In addition, since the water absorption of the cured product is reduced, the obtained semiconductor device is preferably prevented from deterioration over time (for example, occurrence of disconnection) of the internal members, and the moisture resistance reliability is further improved. .

Moreover, the substituents R ^{11 to} R ¹⁸ in the biphenyl aralkyl type epoxy resin represented by the general formula (4) represent one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom, These may be the same as or different from each other.

Specific examples of these substituents R ^{11 to} R ¹⁸ include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a chlorine atom and a bromine atom. Among these, in particular, a hydrogen atom Or it is preferably a methyl group. As a result, the melt viscosity of the epoxy resin composition is lowered, and for example, when the semiconductor device is manufactured, the handling becomes easy, and the moisture resistance reliability of the semiconductor device is further improved.

  In the general formula (4), a represents the average number of repeating epoxy resin units. That is, a is preferably in the range of 1 to 10, more preferably about 1 to 5. By setting a in the above range, the fluidity of the epoxy resin composition is further improved.

[Compound (B)]
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 resin, cresol novolak resin, bisphenol resin, phenol aralkyl resin, biphenyl aralkyl resin, trisphenol resin, xylylene modified novolak resin, terpene modified novolak resin and dicyclopentadiene modified phenol resin. 1 type or 2 types or more of these can be used in combination.

  Among these, the compound (B) is mainly composed of one or both of the phenol aralkyl resin represented by the general formula (5) and the biphenyl aralkyl resin represented by the general formula (6). It is preferable to use those that do. Thereby, the fluidity at the time of molding of the epoxy resin composition (for example, during the production of a semiconductor device) is improved, and the solder crack resistance and moisture resistance reliability of the obtained semiconductor device are further improved.

Here, the substituents R ^{19 to} R ²² in the phenol aralkyl resin represented by the general formula (5) and the substituents R ^{23 to} R ³⁰ in the biphenyl aralkyl resin represented by the general formula (6) are: Each represents one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms and a halogen atom, and these may be the same or different from each other.

Specific examples of these substituents R ^{19 to} R ²² and R ^{23 to} R ³⁰ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a chlorine atom and a bromine atom, respectively. Among these, a hydrogen atom or a methyl group is particularly preferable. Since such a phenol resin has a low melt viscosity per se, even when contained in the epoxy resin composition, the melt viscosity of the epoxy resin composition can be kept low. Moreover, the handling becomes easy. Moreover, the water absorption (hygroscopicity) of the cured product of the epoxy resin composition (obtained semiconductor device) is reduced, and the moisture resistance reliability is further improved, and the solder crack resistance is also improved.

  Moreover, b in the said General formula (5) and c in the said General formula (6) represent the average repeating number of a phenol resin unit, respectively. That is, b and c each preferably have a range of 1 to 10, more preferably about 1 to 5. By setting each of b and c within the above ranges, a decrease in fluidity of the epoxy resin composition is preferably prevented or suppressed.

[Phosphonium silicate (C): curing accelerator of the present invention]
Phosphonium silicate as a curing accelerator for use in the present invention (C) has an action capable of promoting the curing reaction of the epoxy resin composition (function), Ru der those represented in the previous following general formula (2) .

R ^4, R ⁵ and R ⁶ in one general formula (2) are each a hydrogen atom, it represents one species selected from a methyl group, a methoxy group and a hydroxyl group, may be the same or different from each other.

Further, in the general formula (2), wherein X ⁴ is an organic group bonding to the substituent Y ⁷ and Y ^8. Y ⁷ and Y ⁸ are groups formed by releasing a proton from a monovalent proton-donating substituent, which may be the same as or different from each other. The substituents Y ⁷ and Y in the same molecule ⁸ binds to a silicon atom to form a chelate structure .

Y ⁷ X ⁴ Y ⁸ in the general formula ( 2 ) is a group in which a divalent or higher proton donor releases two protons. As a specific example of a divalent or higher proton donor, is Ca Tekoru, pyrogallol, 2,3-dihydroxynaphthalene, salicylic acid, 1-hydroxy-2-naphthoic acid and 3-hydroxy-2-but-naphthoic acid. of these, catechol, 2,3 dihydroxy naphthalate emissions Contact and 3-hydroxy-2-naphthoic acid, from the viewpoint of storage stability and moisture resistance reliability, and more preferred.

  Such a phosphonium silicate (C), that is, the curing accelerator of the present invention, is extremely excellent in properties as a curing accelerator, in particular, curability, fluidity and storage stability, compared to conventional curing accelerators. .

  Since the curing accelerator of the present invention has a proton-donating hydroxyl group in the phosphonium cation part, the hydroxy etherification reaction by the epoxy group ring-opening reaction of the epoxy resin is further promoted, and the phosphonium cation part has a proton-donating hydroxyl group. Compared to conventional phosphonium silicate, it has high curing acceleration ability and imparts excellent curability.

  In addition, the anion that acts as the starting species for the curing reaction has a silicate anion structure with extremely low nucleophilicity, and does not easily initiate or accelerate the curing reaction at low temperatures, thus simultaneously providing excellent fluidity and storage stability. To do. Like the conventional adduct of tertiary phosphine and p-benzoquinone and the usual phosphonium phenoxide salt, the inner or outer salt of phosphonium cation and phenoxide anion has higher nucleophilicity of phenoxide anion. The curing acceleration reaction during storage (at room temperature) is more likely to occur, and the storage stability is lower.

Here, the method of synthesizing phosphonium silicate (C), i.e., a process for the synthesis of a curing accelerator before Symbol represented in one general formula (2) he will be described.

  As a method for synthesizing the curing accelerator of the present invention, for example, a tertiary phosphine (for example, triphenylphosphine, tris (4-tolyl) phosphine, tris (4-hydroxyphenyl) phosphine, tris (4-methylphenyl) phosphine, Tris (4-methoxyphenyl) phosphine) and a halogenated aromatic monohydroxy compound (for example, 2-iodophenol, 3-iodophenol, 2-bromophenol, 3-bromophenol, 6-bromo-2-naphthol). A phosphonium halide compound obtained by reacting in the presence of a transition metal catalyst, a bivalent or higher proton donor capable of forming a chelate bond with a tetraalkoxysilane and a silicon atom, and an alkaline water such as sodium hydroxide. Of silicate complex obtained by neutralization with oxide Synthetic route of contacting the alkali metal salt method can be mentioned by, its synthesis process is represented by the following reaction formula. By such a synthesis method, it is possible to synthesize easily and with high yield.

［式中、Ｒは、置換もしくは無置換の芳香環または複素環を有する１価の有機基または１価の脂肪族基を表し、Ａｒは置換もしくは無置換の２価の芳香族基を表す。Ｘは１価の陰イオンを表す。Ｒ'は１価の脂肪族基を表し、ＹおよびＺはプロトン供与性置換基がプロトンを１個放出してなる基を表す。Ｒ"は一価のプロトン供与性置換基であるＹＨおよびＺＨと結合する２価の有機基を表す。］

[Wherein, R represents a monovalent organic group or monovalent aliphatic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, and Ar represents a substituted or unsubstituted divalent aromatic group. X represents a monovalent anion. R ′ represents a monovalent aliphatic group, and Y and Z represent a group formed by releasing a proton from a proton-donating substituent. R ″ represents a divalent organic group bonded to YH and ZH which are monovalent proton-donating substituents.

  In the above synthesis step, in the first stage reaction, preferably, a transition metal halogen salt such as nickel, copper, cobalt, zinc and manganese is used as a reaction catalyst in an alcohol solvent having a high boiling point of 150 to 180 ° C. A phosphonium halide is obtained by heating and reaction. Thereby, substitution reaction can be advanced more efficiently. Examples of the transition metal catalyst include nickel chloride, nickel bromide, cobalt chloride, cobalt bromide and cupric chloride. Examples of the high boiling alcohol solvent include ethylene glycol and ethylene glycol monobutyl ether. , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and the like, and one or more of them can be used in combination.

  In the second-stage reaction, the phosphonium halide solution obtained in the first-stage reaction is mixed with tetraalkoxysilane and the divalent or higher proton donor solution with an alkali such as sodium hydroxide. A phosphonium silicate can be easily obtained by adding dropwise at room temperature to a solution of a silicate complex formed by neutralization. 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.

Incidentally, a process for the synthesis of a curing accelerator before Symbol represented in one general formula (2) is synthetic reaction route described above is generally not intended to be limited thereto.

[Inorganic filler (D)]
The inorganic filler (D) is blended (mixed) in the epoxy resin composition for the purpose of reinforcing the obtained semiconductor device, and there is no particular limitation on the type thereof, which is generally used as a sealing material. Can be used.

  Specific examples of the inorganic filler (D) include, for example, fused crushed silica, fused silica, crystalline silica, secondary agglomerated silica, alumina, titanium white, aluminum hydroxide, talc, clay and glass fiber. One or more of these can be used in combination. Among these, fused silica is particularly preferable. Since fused silica is poor in reactivity with the curing accelerator of the present invention, it is possible to prevent the curing reaction of the epoxy resin composition from being inhibited even when a large amount is blended (mixed) in the epoxy resin composition. Can do. Moreover, the reinforcement effect of the semiconductor device obtained improves by using a fused silica as an inorganic filler (D).

  Moreover, as a shape of an inorganic filler (D), what kind of thing, such as a granular form, a lump shape, and a scale shape, for example may be sufficient, but it is preferable that it is granular (especially spherical shape).

  In this case, the average particle diameter of the inorganic filler (D) is preferably about 1 to 100 μm, and more preferably about 5 to 35 μm. In this case, the particle size distribution is preferably wide. Thereby, the filling amount (use amount) of the inorganic filler (D) can be increased, and the reinforcing effect of the obtained semiconductor device is further improved.

  In the epoxy resin composition of the present invention, the content (blending amount) of phosphonium silicate (C) is not particularly limited, but is preferably about 0.01 to 10% by weight, preferably about 0.1 to 1% by weight. Is more preferable. Thereby, the sclerosis | hardenability, preservability, fluidity | liquidity, and hardened | cured material characteristic of an epoxy resin composition are expressed with sufficient balance.

  Further, 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 not particularly limited. It is preferable that the phenolic hydroxyl group of the compound (B) is used in an amount of about 0.5 to 2 mol, and about 0.7 to 1.5 mol with respect to 1 mol of the epoxy group of (A). More preferably it is used. 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 inorganic filler (D) 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 content of an inorganic filler (D) is less than the said lower limit, there exists a possibility that the reinforcement effect by an inorganic filler (D) may not fully express, On the other hand, content of an inorganic filler (D) is the said 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 (D) 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 (D) is based on the specific gravity of the compound (A), the compound (B) and the inorganic filler (D) 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) of (A) to (D), 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).

  Further, in the epoxy resin composition, for example, triphenylphosphine, 1,8-diazabicyclo (5,4,0), as long as the properties of the phosphonium silicate (C) functioning as a curing accelerator in the present invention 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 is prepared by mixing the above-mentioned compounds (components) (A) to (D) and, if necessary, other additives and the like at room temperature using a mixer, a heat roll, a heating kneader. It can be obtained by heating and kneading using a method such as cooling, pulverizing.

  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. The reason is considered to be related to the stability of the phosphonium silicate (C), which is the curing accelerator of the present invention, in the soldering conditions (for example, solder reflow process).

  The phosphonium silicate (C) that is the curing accelerator of the present invention is thermally stable, and the phosphonium cation part has a hydroxyl group that is reactive with the epoxy resin, and the silicate anion part is bulky. Since the ion mobility of free ions derived from the dissociated curing accelerator is lowered, the solder crack resistance and the moisture resistance reliability are excellent.

In the present embodiment, the curing accelerator of the present invention (prior SL phosphonium silicate represented in one general formula (2) (C)), has been described as a representative case of using the epoxy resin composition, the The curing accelerator of the invention can be used for a thermosetting resin composition that can suitably use a phosphine or phosphonium salt as a curing accelerator. Examples of such thermosetting resin compositions include resin compositions containing thermosetting resins such as epoxy compounds, maleimide compounds, cyanate compounds, isocyanate compounds, acrylate compounds, alkenyl compounds, and alkynyl compounds.

  In addition to the thermosetting resin composition, the curing accelerator of the present invention is used for various curable resin compositions such as a reactive curable resin composition, a photocurable resin composition, and an anaerobic curable resin composition. Can be used.

  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.

  As mentioned above, although preferred embodiment of the hardening accelerator of this invention, an epoxy resin composition, and a semiconductor device was described, this invention is not limited to this.

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

  First, compounds C1 to C6 and triphenylphosphine used as a curing accelerator were prepared.

(Synthesis of Compound C1)
In a separable flask (volume: 200 mL) equipped with a condenser and a stirrer, 10.38 g (0.060 mol) of 2-bromophenol, 17.29 g (0.066 mol) of triphenylphosphine, 0.65 g (5 mmol) of nickel chloride Then, 40 mL of ethylene glycol was 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 triphenyl (2-hydroxyphenyl) phosphonium bromide. Next, to a separable flask (volume: 200 mL) equipped with a condenser and a stirrer, 4.17 g (0.020 mol) of tetraethoxysilane, 6.60 g (0.060 mol) of catechol, and 1.60 g of sodium hydroxide (in advance) 0.040 mol) in 50 mL of methanol and sodium hydroxide solution dissolved in 10 mL of methanol were charged and stirred to dissolve uniformly. When a solution prepared by previously dissolving 17.40 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 dried under vacuum to obtain 16.6 g of pale red white 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 phosphonium silicate represented by the following formula (8). The yield of the obtained compound C1 was 78%.

(Synthesis of Compound C2)
In a separable flask (volume: 200 mL) equipped with a condenser and a stirrer, 10.38 g (0.060 mol) of 3-bromophenol, 17.29 g (0.066 mol) of triphenylphosphine and 0.65 g (5 mmol) of nickel chloride Then, 40 mL of ethylene glycol was 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 triphenyl (3-hydroxyphenyl) phosphonium bromide. Next, to a separable flask (volume: 200 mL) equipped with a condenser and a stirrer, 4.17 g (0.020 mol) of tetraethoxysilane, 6.60 g (0.060 mol) of catechol, and 1.60 g of sodium hydroxide (in advance) 0.04 mol) was dissolved in 10 mL of methanol and sodium hydroxide solution and 50 mL of methanol were charged and stirred to dissolve uniformly. When a solution obtained by dissolving 17.40 g (0.040 mol) of triphenyl (3-hydroxyphenyl) phosphonium bromide obtained above in advance with 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 14.9 g of pale red white crystals.

This compound was designated C2. As a result of analyzing Compound C2 by ¹ H-NMR, mass spectrum, and elemental analysis, it was confirmed that it was the target phosphonium silicate represented by the following formula (9). The yield of the obtained compound C2 was 72%.

(Synthesis of Compound C3)
In a separable flask (volume: 200 mL) equipped with a condenser and a stirrer, 10.38 g (0.060 mol) of 3-bromophenol, 17.29 g (0.066 mol) of triphenylphosphine, 0.65 g (5 mmol) of nickel chloride Then, 40 mL of ethylene glycol was 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 triphenyl (3-hydroxyphenyl) phosphonium bromide. Next, 4.17 g (0.020 mol) of tetraethoxysilane, 9.60 g (0.060 mol) of 2,3-dihydroxynaphthalene, hydroxylated in advance into a separable flask (volume: 200 mL) equipped with a condenser and a stirrer. A sodium hydroxide solution in which 1.60 g (0.040 mol) of sodium 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 17.40 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 dried under vacuum to obtain 19.6 g of pale red white 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 borate represented by the following formula (10). The yield of the obtained compound C3 was 81%.

(Synthesis of Compound C4)
In a separable flask (volume: 200 mL) equipped with a condenser and a stirrer, 13.38 g (0.060 mol) of 6-bromo-2-naphthol, 17.2 of triphenylphosphine
9 g (0.066 mol), 0.65 g (5 mmol) of nickel chloride and 40 mL of ethylene glycol 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 triphenyl (6-hydroxy-2-naphthalene) phosphonium bromide. Next, 4.17 g (0.020 mol) of tetraethoxysilane, 9.60 g (0.060 mol) of 2,3-dihydroxynaphthalene, hydroxylated in advance into a separable flask (volume: 200 mL) equipped with a condenser and a stirrer. A sodium hydroxide solution in which 1.60 g (0.040 mol) of sodium was dissolved in 10 mL of methanol and 50 mL of methanol were charged and stirred to dissolve uniformly. When a solution obtained by previously dissolving 19.40 g (0.040 mol) of triphenyl (6-hydroxy-2-naphthalene) 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 dried under vacuum to obtain 18.4 g of pale red 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 that it was the target phosphonium silicate represented by the following formula (11). The yield of the obtained compound C4 was 70%.

(Synthesis of Compound C5)
In a separable flask (volume: 200 mL) equipped with a condenser and a stirrer, 10.38 g (0.060 mol) of 2-bromophenol, 20.06 g (0.066 mol) of tris (4-methylphenyl) 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-methylphenyl) (3-hydroxyphenyl) phosphonium bromide. Next, to a separable flask (volume: 200 mL) equipped with a condenser and a stirrer, 4.17 g (0.020 mol) of tetraethoxysilane, 6.60 g (0.060 mol) of catechol, and 1.60 g of sodium hydroxide (in advance) 0.04 mol) in 10 mL of methanol was charged with a sodium hydroxide solution and 50 mL of methanol, and the mixture was stirred and dissolved uniformly. When a solution obtained by previously dissolving 19.08 g (0.040 mol) of tris (4-methylphenyl) (3-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 dried under vacuum to obtain 16.9 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 (12). The yield of the obtained compound C5 was 73%.

(Synthesis of Compound C6)
In a separable flask (volume: 200 mL) equipped with a condenser and a stirrer, 10.38 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, in a separable flask (volume: 200 mL) equipped with a condenser and a stirrer, 4.17 g (0.020 mol) of tetraethoxysilane, 11.29 g (0.060 mol) of 3-hydroxy-2-naphthoic acid, water in advance 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 obtained by previously dissolving 19.08 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 dried under vacuum to obtain 19.0 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 that it was the target phosphonium silicate represented by the following formula (13). The yield of the obtained compound C6 was 67%.

[Preparation of epoxy resin composition and manufacture of semiconductor device]
As described below, an epoxy resin composition containing the compounds C1 to C6 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 (14) as the compound (A), and a phenol aralkyl resin represented by the following formula (15) as the compound (B). (However, the number of repeating units: 3 represents an average value. XLC-LL manufactured by Mitsui Chemicals, Inc.) Compound C1 as a curing accelerator (phosphonium silicate (C)), fused spherical silica as an inorganic filler (D) (Average particle diameter 15 μm) Carbon black, brominated bisphenol A type epoxy resin and carnauba wax were prepared as other additives.

＜式（１４）の化合物の物性＞
融点 ：１０５℃
エポキシ当量 ：１９３
１５０℃のＩＣＩ溶融粘度：０．１５ｐｏｉｓｅ

<Physical Properties of Compound of Formula (14)>
Melting point: 105 ° C
Epoxy equivalent: 193
ICI melt viscosity at 150 ° C .: 0.15 poise

＜式（１５）の化合物の物性＞
軟化点 ：７７℃
水酸基当量 ：１７２
１５０℃のＩＣＩ溶融粘度：３．６ｐｏｉｓｅ

<Physical Properties of Compound of Formula (15)>
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: 5.31 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, then cooled and crushed to obtain 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 a compound (A), a biphenylaralkyl type epoxy resin represented by the following formula (16) (however, the number of repeating units: 3 shows an average value. NC-3000P manufactured by Nippon Kayaku Co., Ltd.), a compound ( B) a biphenylaralkyl type phenol resin represented by the following formula (17) (however, the number of repeating units: 3 represents an average value. MEH-7851SS manufactured by Meiwa Kasei Co., Ltd.), a curing accelerator (phosphonium silicate ( Compound C1) was prepared as C)), fused spherical silica (average particle size 15 μm) was prepared as inorganic filler (D), and carbon black, brominated bisphenol A type epoxy resin and carnauba wax were prepared as other additives.

＜式（１６）の化合物の物性＞
軟化点 ：６０℃
エポキシ当量 ：２７２
１５０℃のＩＣＩ溶融粘度：１．３ｐｏｉｓｅ

<Physical Properties of Compound of Formula (16)>
Softening point: 60 ° C
Epoxy equivalent: 272
ICI melt viscosity at 150 ° C .: 1.3 poise

＜式（１７）の化合物の物性＞
軟化点 ：６８℃
水酸基当量 ：１９９
１５０℃のＩＣＩ溶融粘度：０．９ｐｏｉｓｅ

<Physical Properties of Compound of Formula (17)>
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: 5.31 parts by weight, fused spherical silica: 650 parts by weight, carbon black: 2 parts by weight, bromine Bisphenol A type epoxy resin: 2 parts by weight, carnauba wax: 2 parts by weight are first mixed at room temperature, then kneaded at 105 ° C. for 8 minutes using a hot roll, cooled and pulverized to obtain an epoxy resin composition ( A thermosetting resin composition) was obtained.

  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 5.31 parts by weight of compound C2 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 4)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2, except that 5.31 parts by weight of compound C2 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 5)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1, except that 6.06 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 6.06 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)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 6.56 parts by weight of compound C4 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 8)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 6.56 parts by weight of compound C4 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 9
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 5.79 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 5.79 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 composition) was obtained in the same manner as in Example 1 except that 6.90 parts by weight of compound C6 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 12
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 6.90 parts by weight of compound C6 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.

(Comparative Example 1)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 1.85 parts by weight of triphenylphosphine / p-benzoquinone adduct was used instead of compound C1. Using this epoxy resin composition, a package (semiconductor device) was manufactured 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 instead of compound C1, triphenylphosphine / p-benzoquinone adduct: 1.85 parts by weight was used. Using this epoxy resin composition, a package (semiconductor device) was manufactured in the same manner as in Example 2.

(Comparative Example 3)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 1.00 part by weight of triphenylphosphine was used instead of compound C1, and this epoxy resin composition was obtained. Then, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Comparative Example 4)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 1.00 part by weight of triphenylphosphine was used instead of compound C1, and this epoxy resin composition was obtained. Then, a package (semiconductor device) was manufactured 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 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.
Table 1 shows the results of the characteristic evaluations (1) to (5).

  As shown in Table 1, the epoxy resin compositions (epoxy resin compositions of the present invention) obtained in Examples 1 to 12 all have good curability, storage stability, 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 poor in storage stability, and the packages obtained in these Comparative Examples are both poor in solder crack resistance. The moisture resistance reliability was extremely low. In addition, the epoxy resin compositions obtained in Comparative Example 3 and Comparative Example 4 are extremely poor in curability, storage stability, and fluidity, and the packages obtained in these Comparative Examples are all solder resistant. It was inferior to cracking property.

(Examples 13 to 18, Comparative Examples 5 and 6)
As the compound (A), the biphenyl type epoxy resin represented by the formula (14): 26 parts by weight, the biphenyl aralkyl type epoxy resin represented by the formula (16): 28.5 parts by weight, and the compound (B ), Except for blending 45.5 parts by weight of the phenol aralkyl resin represented by the formula (15), respectively, Examples 1, 3, 5, 7, 9, 11, and Comparative Examples 1, 3 and Similarly, an epoxy resin composition (thermosetting resin composition) was obtained, and a package (semiconductor device) was manufactured using this epoxy resin composition.

  When the characteristics of the epoxy resin compositions and packages obtained in Examples 13 to 18 and Comparative Examples 5 and 6 were evaluated in the same manner as described above, the same results as in Table 1 were obtained.

(Examples 19 to 24, Comparative Examples 7 and 8)
As compound (A), biphenyl type epoxy resin represented by the formula (14): 54.5 parts by weight, as compound (B), phenol aralkyl resin represented by the formula (15): 24 parts by weight, and Biphenyl aralkyl type phenol resin represented by the formula (17): Except for blending 21.5 parts by weight, Examples 1, 3, 5, 7, 9 and 11 and Comparative Examples 1 and 3, respectively, Similarly, an epoxy resin composition (thermosetting resin composition) was obtained, and a package (semiconductor device) was manufactured using this epoxy resin composition.

  When the characteristics of the epoxy resin compositions and packages obtained in Examples 19 to 24 and Comparative Examples 7 and 8 were evaluated in the same manner as described above, almost the same results as in Table 1 were obtained.

(Examples 25 to 30, Comparative Example 9)
As the bismaleimide resin, 100 parts by weight of 4,4′-diphenylmethane bismaleimide (manufactured by Kay Kasei Co., Ltd .: BMI-H), compounds C1 to C6 and triphenylphosphine as curing accelerators, respectively, are shown in Table 2. The resin composition (thermosetting resin composition) which mix | blended by the compounding ratio shown to these and mixed these uniformly was obtained.

The gelation time at 190 ° C. was measured for the resin compositions obtained in Examples 25 to 30 and Comparative Example 9.
The results are shown in Table 2 together with the blending ratio of each curing accelerator.

  As shown in Table 2, all of the resin compositions obtained in Examples 25 to 30 were rapidly cured. On the other hand, the resin composition obtained in Comparative Example 9 did not reach curing and was microgelled.

Such a curing accelerator is useful for a thermosetting resin composition. Furthermore, by using an epoxy resin composition, an epoxy resin composition having good curability, storage stability and fluidity can be obtained. . This epoxy resin can be suitably used in the electric / electronic material field, and in particular, an electronic component device in which an electronic component such as a semiconductor element excellent in solder crack resistance and moisture resistance reliability is sealed can be obtained.

Claims (7)

A curing accelerator that is mixed in the curable resin composition and can accelerate the curing reaction of the curable resin composition,
A curing accelerator represented by the following general formula (2):

[Wherein R ⁴ , R ⁵ and R ⁶ 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 ⁴ is an organic group bonded to the substituents Y ⁷ and Y ⁸ . Y ⁷ and Y ⁸ are groups formed by releasing a proton from a monovalent proton-donating substituent, which may be the same or different from each other, and the substituents Y ⁷ and Y ⁸ in the same molecule Is bonded to a silicon atom to form a chelate structure. In the formula, a group represented by —Y ₇ —X ₄ —Y ₈ — represents catechol, pyrogallol, 2,3-dihydroxynaphthalene, salicylic acid, 1-hydroxy-2-naphthoic acid and 3-hydroxy-2-naphthoic acid. Represents a group formed by releasing two protons of a hydroxyl group and a carboxyl group of a proton donor selected from: ] An epoxy resin composition comprising a compound having two or more epoxy groups in one molecule, a compound having two or more phenolic hydroxyl groups in one molecule, and the curing accelerator according to claim 1 . . The compound having two or more epoxy groups in one molecule is mainly composed of at least one of an epoxy resin represented by the following general formula (3) and an epoxy resin represented by the following general formula (4). 2. The epoxy resin composition according to 2.

[Wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each represent one selected from a hydrogen atom, a linear or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group and a halogen atom, They may be the same or different. ]

[Wherein, R ^{11 to} R ¹⁸ each represent one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom, and may be the same or different from each other. However, a is an integer of 1-10. ] The compound having two or more phenolic hydroxyl groups in one molecule is mainly composed of at least one of a phenol resin represented by the following general formula (5) and a phenol resin represented by the following general formula (6). Item 4. The epoxy resin composition according to Item 2 or 3 .

[Wherein, R ^{19 to} R ²² each represent one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom, and may be the same or different from each other. However, b is an integer of 1-10. ]

[Wherein, R ^{23 to} R ³⁰ each represent one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom, and may be the same or different from each other. However, c is an integer of 1-10. ] The epoxy resin composition according to any one of claims 2 to 4 , comprising an inorganic filler. The content of the inorganic filler is 200 to 2400 per 100 parts by weight of the total amount 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 part by weight. An electronic component is sealed with a cured product of the epoxy resin composition according to claim 6 .