JP4244777B2 - Curing accelerator for curable resin, curable resin composition, electronic component device, and method for producing phosphine derivative - Google Patents

Description

  The present invention is sealed with a curing accelerator for a curable resin, a molding material using the curing accelerator, a curable resin composition suitable for a laminate or an adhesive, and the curable resin composition. The present invention relates to an electronic component device provided with an element, and a production method for obtaining a phosphine derivative used for the curing accelerator.

  Conventionally, curable resins such as epoxy resins have been widely used for molding materials, laminates, adhesive materials, and the like. Since these curable resins are required to have fast curability from the viewpoint of improving productivity, compounds that accelerate the curing reaction, that is, curing accelerators are widely used. In the field of device sealing of electronic parts such as transistors and ICs, epoxy resin compositions are particularly widely used among curable resins. This is because epoxy resins are balanced in various properties such as moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts. In particular, the combination of an ortho-cresol novolac type epoxy resin and a phenol novolac curing agent has an excellent balance between these, and has become the mainstream as a base resin for molding materials for IC sealing. In such epoxy resin compositions, amine compounds such as tertiary amines and imidazoles, and phosphorus compounds such as phosphines and phosphonium are generally used as curing accelerators.

  In recent years, high-density mounting of electronic components on printed wiring boards has progressed, and along with this, electronic components are becoming mainstream from conventional pin insertion type packages to surface mount type packages. In surface mount ICs such as ICs and LSIs, the volume occupied by the element package gradually increases in order to increase the mounting density, and the thickness of the package has become very thin. Furthermore, since the pin insertion type package is soldered from the back side of the wiring board after the pins are inserted into the wiring board, the package was not directly exposed to high temperature, whereas the surface mount type IC is not attached to the surface of the wiring board. After being temporarily fixed, it is exposed to the soldering temperature directly because it is processed by a solder bath or a reflow device. As a result, when the IC package absorbs moisture, the moisture absorption moisture rapidly expands at the time of soldering and leads to a package crack, which is a big problem.

In order to improve the resistance against package cracks during soldering, so-called reflow crack resistance, a curable resin composition containing a large amount of an inorganic filler has been proposed. However, an increase in the amount of inorganic fillers leads to a decrease in fluidity during molding, and molding performance such as defective filling and voiding, and IC chip bonding wires are broken, resulting in poor continuity. Since the decrease causes an increase in the amount of the inorganic filler, there is a limit, and as a result, there is a problem that a remarkable improvement in reflow crack resistance cannot be expected.
In particular, when a phosphorus curing accelerator such as triphenylphosphine or an amine curing accelerator such as 1,8-diazabicyclo [5.4.0] undecene-7 is used, the fluidity is low and the reflow crack resistance is remarkable. The fact is that improvement cannot be expected.

In order to improve such a problem, a method of using an addition reaction product of triphenylphosphine and 1,4-benzoquinone as a curing accelerator has been proposed (see JP-A-9-157497). However, when this is used as a curing accelerator, there is a problem in the curability when the resin composition is exposed to the outside air and absorbs moisture, that is, the curability when absorbing moisture. When molding materials with poor curability during moisture absorption absorb moisture from the outside air during manufacture, transportation and use, molding failures such as gate breaks, chip cracks, and releasability are likely to occur. There was also a problem that the performance of the molded product was not stabilized due to the difference in outside air humidity, especially the difference in season. In addition, when an organic phosphorane compound proposed as a curing accelerator having stable curability (see Japanese Patent Application Laid-Open No. 11-60906) is used, there are problems such as poor fast curability and failure to cure in a short time. It was.
In order to improve such problems, a method has been proposed in which an addition reaction product of a phosphine compound and a quinone compound in which at least one alkyl group is bonded to a phosphorus atom is used as a curing accelerator (Patent Document 1, Patent). Reference 2).
Japanese Patent Laid-Open No. 2002-3574 JP 2002-80563 A

However, a package sealed with a curable resin composition using this as a curing accelerator has problems such as poor conduction when exposed to high temperatures, that is, poor high-temperature storage characteristics.
The present invention has been made in view of such a situation, and a curing accelerator for a curable resin capable of exhibiting excellent curability at the time of moisture absorption, fluidity, reflow crack resistance, and high-temperature storage characteristics, and this A production method for obtaining a phosphine derivative used for a curing accelerator, a curable resin composition using the curing accelerator for the curable resin, and an electronic component device including an element sealed with the curable resin composition It is something to be offered.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a specific phosphorus compound as a curing accelerator, so that it has excellent curability at the time of moisture absorption, fluidity and reflow crack resistance. The present invention has been completed by finding that a functional resin composition is obtained and the above-mentioned object can be achieved.

（ここで、式（Ｉ）中のＲ¹〜Ｒ³は、水素原子又は炭素数１〜１８の置換又は非置換の炭化水素基を示し、それぞれ全てが同一でも異なっていてもよい。Ｒ¹〜Ｒ³の中の２つ以上が結合して環状構造となっていてもよい。）
（３）（ｂ）芳香環に置換したハロゲン原子１つ以上と放出可能なプロトン原子１つ以上を持つ化合物が下記一般式（II）で示される化合物である上記（１）又は（２）に記載の硬化性樹脂の硬化促進剤。

（ここで、式（II）中のＲ^４〜Ｒ^７は、水素原子又は炭素数１〜１８の一価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ＹＨは、炭素数０〜１８の１つ以上の放出可能なプロトンを有する１価の基を示す。Ｘは、ハロゲン原子を示す。また、Ｒ^４〜Ｒ^７及びＹＨの中の２つ以上が結合して環状構造となっていてもよい。）
（４）（ｂ）芳香環に置換したハロゲン原子１つ以上と放出可能なプロトン原子１つ以上を持つ化合物がフェノール性水酸基を有する化合物である上記（１）〜（３）に記載の硬化性樹脂の硬化促進剤。
（５）上記一般式（I）のＲ^１〜Ｒ^３がアルキル基及びフェノール性水酸基又はメルカプト基を持たないアリール基から選ばれる一価の置換基である上記（２）〜（４）のいずれかに記載の硬化性樹脂の硬化促進剤。
（６）（Ｂ）硬化性樹脂及び（Ａ）上記（１）〜（５）のいずれかの硬化性樹脂の硬化促進剤を１種類以上含有する硬化性樹脂組成物。
（７）（Ｂ）硬化性樹脂が（Ｃ）エポキシ樹脂を必須成分として含有する上記（６）記載の硬化性樹脂組成物。
（８）（Ｄ）硬化剤を必須成分として含有する上記（６）又は（７）に記載の硬化性樹脂組成物。
（９）（Ｅ）無機充填剤を必須成分として含有する上記（６）〜（８）のいずれかに記載の硬化性樹脂組成物。
（１０）（Ｃ）エポキシ樹脂がビフェニル型エポキシ樹脂、スチルベン型エポキシ樹脂、ジフェニルメタン型エポキシ樹脂、硫黄原子含有型エポキシ樹脂、ノボラック型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、サリチルアルデヒド型エポキシ樹脂、ナフトールとクレゾールの共重合型エポキシ樹脂、アラルキル型フェノール樹脂のエポキシ化物のいずれかのエポキシ樹脂を少なくとも１種を含有してなる上記（７）〜（９）のいずれかに記載の硬化性樹脂組成物。
（１１）（Ｄ）硬化剤がアラルキル型フェノール樹脂、ジシクロペンタジエン型フェノール樹脂、サリチルアルデヒド型フェノール樹脂、ベンズアルデヒド型フェノール樹脂とアラルキル型フェノール樹脂の共重合型樹脂、ノボラック型フェノール樹脂のいずれかの少なくとも１種を含有してなる上記（８）〜（１０）のいずれかに記載の硬化性樹脂組成物。
（１２）上記（６）〜（１１）のいずれかに記載の硬化性樹脂組成物により封止された素子を備えた電子部品装置。
（１３）（ａ）ホスフィン化合物と（ｂ）芳香環に置換したハロゲン原子１つ以上及び放出可能なプロトン原子１つ以上を持つ化合物とを反応させてホスホニウムハライドを得る工程、該ホスホニウムハライドを脱ハロゲン化水素させる工程を含むホスフィン誘導体の製造方法。 That is, the present invention relates to the following.
(1) (a) a phosphine compound and (b) a compound having one or more halogen atoms substituted on an aromatic ring and a compound having one or more releasable proton atoms, and then dehydrohalogenating them. Curing accelerator for curable resin.
(2) The curing accelerator for a curable resin according to the above (1), wherein the (a) phosphine compound is a compound represented by the following general formula (I).

(Here, R ^{1 to} R ³ in the formula (I) represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, and all may be the same or different. R ¹ Two or more of ˜R ³ may be bonded to form a cyclic structure.
(3) (b) In the above (1) or (2), the compound having one or more halogen atoms substituted on the aromatic ring and one or more releasable proton atoms is a compound represented by the following general formula (II) The hardening accelerator of description curable resin.

(Here, R ^{4 to} R ⁷ in the formula (II) each represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all may be the same or different. YH is the number of carbon atoms. Represents a monovalent group having one or more releasable protons of 0 to 18. X represents a halogen atom, and two or more of R ^{4 to} R ⁷ and YH are bonded to form a cyclic structure It may be.)
(4) (b) The curability according to (1) to (3) above, wherein the compound having one or more halogen atoms substituted on the aromatic ring and one or more releasable proton atoms is a compound having a phenolic hydroxyl group. Resin curing accelerator.
(5) Any of the above (2) to (4), wherein R ^{1 to} R ^{3 in} the general formula (I) are a monovalent substituent selected from an alkyl group and an aryl group having no phenolic hydroxyl group or mercapto group A curing accelerator for the curable resin according to claim 1.
(6) A curable resin composition containing (B) a curable resin and (A) one or more curing accelerators of the curable resin according to any one of (1) to (5) above.
(7) The curable resin composition according to the above (6), wherein the (B) curable resin contains (C) an epoxy resin as an essential component.
(8) The curable resin composition according to the above (6) or (7), which contains (D) a curing agent as an essential component.
(9) The curable resin composition according to any one of (6) to (8), which contains (E) an inorganic filler as an essential component.
(10) (C) Epoxy resin is biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom containing type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, salicylaldehyde type epoxy resin, naphthol The curable resin composition according to any one of the above (7) to (9), comprising at least one epoxy resin selected from the group consisting of a copolymer epoxy resin of cresol and an epoxidized aralkyl phenol resin .
(11) (D) The curing agent is any one of an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a salicylaldehyde type phenol resin, a copolymer type resin of a benzaldehyde type phenol resin and an aralkyl type phenol resin, or a novolac type phenol resin. Curable resin composition in any one of said (8)-(10) formed by containing at least 1 sort (s).
(12) An electronic component device including an element sealed with the curable resin composition according to any one of (6) to (11).
(13) A step of reacting (a) a phosphine compound with (b) a compound having at least one halogen atom substituted on an aromatic ring and at least one releasable proton atom to obtain a phosphonium halide, and removing the phosphonium halide. A method for producing a phosphine derivative, comprising a step of hydrogen halide.

  The curing accelerator of the curable resin according to the present invention can exhibit excellent moisture-curing property, fluidity, reflow crack resistance, and high temperature storage properties, and curing using the curing accelerator of the curable resin. The curable resin composition has excellent curability and fluidity at the time of moisture absorption, and if this curable resin composition is used to seal electronic components such as IC and LSI, the reflow crack resistance and high temperature storage characteristics are good. Since an electronic component device having excellent reliability can be obtained, its industrial value is great.

  As the curing accelerator (A) for the curable resin of the present invention, (a) a phosphine compound and (b) a compound having one or more halogen atoms substituted on an aromatic ring and one or more releasable proton atoms are reacted. There is no particular limitation as long as it is a compound that can be obtained by dehydrohalogenation after the formation.

（ここで、式（Ｉ）中のＲ¹〜Ｒ³は、水素原子又は炭素数１〜１８の置換又は非置換の炭化水素基を示し、それぞれ全てが同一でも異なっていてもよい。Ｒ¹〜Ｒ³の中の２つ以上が結合して環状構造となっていてもよい。） (A) Although it will not specifically limit if it is a phosphine compound which can be manufactured, For example, the compound shown by the following general formula (I) is mentioned.

(Here, R ^{1 to} R ³ in the formula (I) represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, and all may be the same or different. R ¹ Two or more of ˜R ³ may be bonded to form a cyclic structure.

R ^{1 to} R ^{3 in} the general formula (I) represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, but as a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms. Is not particularly limited, for example, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon group having 1 to 18 carbon atoms, or a substitution having 1 to 18 carbon atoms. Or an unsubstituted aromatic hydrocarbon group etc. are mentioned.
Examples of the substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and a pentyl group. , Alkyl groups such as hexyl group, octyl group, decyl group, dodecyl group, allyl group, vinyl group and the like, and those substituted with alkyl group, alkoxy group, aryl group, hydroxyl group, amino group, halogen, etc. .
Examples of the substituted or unsubstituted alicyclic hydrocarbon group having 1 to 18 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group, and the like, and an alkyl group, an alkoxy group, and an aryl group. And a group, aryloxy group, hydroxyl group, amino group, halogen and the like substituted.
Examples of the substituted or unsubstituted aromatic hydrocarbon group having 1 to 18 carbon atoms include aryl groups such as phenyl group and tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, and tert-butylphenyl group. Alkyl group-substituted aryl group, alkoxy group-substituted aryl group such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group and the like, and alkyl group, alkoxy group, aryl group, aryloxy group, amino group, etc. Examples include those substituted with halogen.
R ^{1 to} R ³ are preferably a monovalent substituent selected from an alkyl group and an aryl group having no phenolic hydroxyl group or mercapto group. Among them, from the viewpoint of availability of phosphine, unsubstituted phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, etc. Alternatively, an alkyl group or an alkoxy group-substituted phenyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, octyl group, cyclohexyl group, or other chain or cyclic alkyl group Is preferred.

  Among the phosphine compounds represented by the above general formula (I), from the viewpoint of reflow crack resistance, triphenylphosphine, diphenyl (alkylphenyl) phosphine such as diphenyl-p-tolylphosphine, diphenyl-p-anisylphosphine, etc. Of diphenyl (alkoxyphenyl) phosphine, phenylbis (alkylphenyl) phosphine such as phenyldi-p-tolylphosphine, and the like. From the viewpoint of curability during moisture absorption, tri-p-tolylphosphine, tri-o-tolyl Phosphine, tris (alkylphenyl) phosphine such as tri-m-tolylphosphine, tris (alkoxyphenyl) phosphine such as tri-p-anisylphosphine, phenylbis (alkoxyphenyl) phosphine such as phenyldi-p-anisylphosphine, n-butyldiphenylphosphine, Alkyldiarylphosphine such as cyclohexyl diphenylphosphine, dialkylarylphosphine such as di-n-butylphenylphosphine, dicyclohexylphenylphosphine, tri-n-butylphosphine, tricyclohexylphosphine, tri-n-octylphosphine, trimethylphosphine, triethylphosphine , Trialkylphosphine such as triisopropylphosphine and tricyclopentylphosphine, and the like are preferable.

（ここで、式（II）中のＲ^４〜Ｒ^７は、水素原子又は炭素数１〜１８の一価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ＹＨは、炭素数０〜１８の１つ以上の放出可能なプロトンを有する１価の基を示す。Ｘは、ハロゲン原子を示す。また、Ｒ^４〜Ｒ^７及びＹＨの中の２つ以上が結合して環状構造となっていてもよい。） (B) The compound having one or more halogen atoms substituted on the aromatic ring and one or more releasable proton atoms is not particularly limited as long as it is a manufacturable compound. For example, the following general formula (II) ).

(Here, R ^{4 to} R ⁷ in the formula (II) each represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all may be the same or different. YH is the number of carbon atoms. Represents a monovalent group having one or more releasable protons of 0 to 18. X represents a halogen atom, and two or more of R ^{4 to} R ⁷ and YH are bonded to form a cyclic structure It may be.)

R ^{4 to} R ⁷ in the general formula (II) represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, but the monovalent organic group having 1 to 18 carbon atoms is not particularly limited. For example, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon group having 1 to 18 carbon atoms, a substituted or unsubstituted aromatic group having 1 to 18 carbon atoms C1-C18 substituted or unsubstituted aliphatic, alicyclic compound or aromatic oxy group, C1-C18 substituted or unsubstituted aliphatic, alicyclic compound or aromatic Carbonyl group, substituted or unsubstituted aliphatic, alicyclic compound or aromatic oxycarbonyl group having 1 to 18 carbon atoms, substituted or unsubstituted aliphatic, alicyclic compound having 1 to 18 carbon atoms or An aromatic carbonyloxy group and the like can be mentioned.
The substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group and aromatic hydrocarbon group having 1 to 18 carbon atoms are as described above.
Examples of the substituted or unsubstituted aliphatic, alicyclic compound or aromatic oxy group having 1 to 18 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy Group, tert-butoxy group, cyclohexoxy group, allyloxy group, vinyloxy group and other aliphatic oxy groups, phenoxy group, methylphenoxy group, ethylphenoxy group, methoxyphenoxy group, butoxyphenoxy group, phenoxyphenoxy group, etc. Groups and the like, and those substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen, and the like.
The substituted or unsubstituted aliphatic, alicyclic compound or aromatic carbonyl group having 1 to 18 carbon atoms is aliphatic such as formyl group, acetyl group, ethylcarbonyl group, butyryl group, cyclohexylcarbonyl group, and allylcarbonyl. Aromatic carbonyl groups such as carbonyl group, phenylcarbonyl group, methylphenylcarbonyl group and the like, and those in which these are substituted with alkyl group, alkoxy group, aryl group, aryloxy group, amino group, halogen and the like can be mentioned.
Examples of the substituted or unsubstituted aliphatic, alicyclic compound or aromatic oxycarbonyl group having 1 to 18 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, allyloxycarbonyl group, cyclohexyloxycarbonyl group and the like. Aromatic oxycarbonyl groups such as aliphatic oxycarbonyl groups, phenoxycarbonyl groups, methylphenoxycarbonyl groups, etc., and those substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogens, etc. Can be mentioned.
Examples of the substituted or unsubstituted aliphatic, alicyclic compound or aromatic carbonyloxy group having 1 to 18 carbon atoms include methylcarbonyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, allylcarbonyloxy group, cyclohexylcarbonyl An aliphatic carbonyloxy group such as an oxy group, an aromatic carbonyloxy group such as a phenylcarbonyloxy group, a methylphenylcarbonyloxy group, etc., and an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen, etc. Substituted ones are listed.
When two or more of R ^{4 to} R ⁷ in formula (II) form a cyclic structure, for example, compounds such as 1-bromo-2-naphthol, 4-chloro-1-naphthol and the like can be mentioned. It is not limited to.

YH in the formula (II) represents a monovalent group having one or more releasable protons having 0 to 18 carbon atoms. The monovalent group having one or more releasable protons having 0 to 18 carbon atoms is not particularly limited. For example, a group in which a hydrogen atom is bonded to a group 16 atom such as a hydroxyl group, a mercapto group, or a hydroseleno group. A group having 1 to 18 carbon atoms having a carboxyl group such as a carboxyl group, a carboxymethyl group, a carboxyethyl group, a carboxyphenyl group, a carboxynaphthyl group, a hydroxyphenyl group, a hydroxyphenylmethyl group, a hydroxynaphthyl group, a hydroxyfuryl group, a hydroxy group C1-C18 groups etc. which have phenolic hydroxyl groups, such as a thienyl group and a hydroxy pyridyl group, are mentioned.
When YH in formula (II) forms a cyclic structure with any of R ^{4 to} R ⁷ , for example, compounds such as 6-bromo-2-naphthol can be mentioned, but the invention is not limited thereto.

The aromatic compound substituted with one or more halogen atoms represented by the general formula (II) and the compound having one or more releasable protons include 4-bromobenzoic acid, 3-bromobenzoic acid, 2- Bromobenzoic acid, 4-chlorobenzoic acid, 3-chlorobenzoic acid, 2-chlorobenzoic acid, 4-iodobenzoic acid, 3-iodobenzoic acid, 2-iodobenzoic acid, 4-bromophenylacetic acid, 3 Compounds having a carboxylic acid such as 2-bromophenylacetic acid, 2-bromophenylacetic acid, 4-chlorophenylacetic acid, 3-chlorophenylacetic acid, 2-chlorophenylacetic acid, 4-bromophenol, 3-bromophenol, 2-bromophenol, 4- Chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylpheno 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro- Compounds having a phenolic hydroxyl group such as 1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4′-hydroxybiphenyl, bromohydroxypyridine, bromohydroxyfuran, bromohydroxythiophene, Examples thereof include compounds having thiols such as 4-bromothiol, 3-bromothiol, 2-bromothiol, 4-chlorothiol, and bromothionaphthol.
Above all, from the viewpoint of moisture absorption curing, 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo -2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl, bromohydroxypyridine, bromo Compounds having a phenolic hydroxyl group such as hydroxyfuran and bromohydroxythiophene are preferred.

The manufacturing method of the phosphine derivative of this invention is a manufacturing method of the phosphine derivative which can be used as a hardening accelerator of (A) curable resin, (a) A phosphine compound (henceforth a compound (a)) and (b). A step of reacting a compound having one or more halogen atoms substituted on an aromatic ring and one or more releasable proton atoms (hereinafter referred to as compound (b)) to obtain a phosphonium halide, and dehalogenating the phosphonium halide It includes a step of hydrogenation.
The production method of the present invention is not particularly limited as long as it is a production method and reaction conditions in which compound (a) and compound (b) are reacted to form phosphonium halide and then dehydrohalogenated. The reaction of compound (a) with compound (b) and the reaction of dehydrohalogenation may proceed in one step or in two or more steps, and may be produced in one pot or in two or more pots. It doesn't matter.

  In the reaction between the compound (a) and the compound (b), if necessary, the reaction can be performed using a coupling catalyst or the like.

  Coupling catalysts that can be used include nickel halides such as nickel (II) chloride and nickel (II) bromide, cobalt halides such as cobalt (II) chloride and cobalt (II), and tris (triphenyl). Examples thereof include nickel compounds having phosphine as a ligand, such as phosphine) nickel, but the catalyst is not limited thereto as long as it is a catalyst capable of reacting compound (a) and compound (b).

  In addition, in the reaction between the compound (a) and the compound (b), the reaction can be performed using a technique such as ultraviolet irradiation, if necessary.

  Examples of the compound (b) that can be reacted using an ultraviolet irradiation method include 4-iodophenol, 3-iodophenol, 2-iodophenol, 4-iodobenzoic acid, and 3-iodine. Examples of the compound (b) include halogenated iodine such as benzoic acid and 2-iodobenzoic acid, but the compound is not limited thereto as long as it can be reacted by this method.

  In order to dehydrohalogenate the product resulting from the reaction between the compound (a) and the compound (b), a reagent that assists the dehydrohalogenation reaction can be used if necessary. For example, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, sodium carbonate, calcium carbonate, rubidium carbonate , Cesium carbonate, sodium bicarbonate, potassium bicarbonate, triethylamine, tributylamine, pyridine, pyrazine, 1,5-diazabicyclo [4.3.0] nonene-5, 1,8-diazabicyclo [5.4.0] undecene Examples thereof include basic compounds such as -7, but are not limited to these as long as they are reagents that assist the dehydrohalogenation reaction.

ここで、式（III）中のＲ¹〜Ｒ³、Ｒ⁴〜Ｒ⁷は、前述の式（I）及び式（II）中のＲ¹〜Ｒ³、Ｒ⁴〜Ｒ⁷の通りである。また、Ｙ⁻は、炭素数０〜１８の１つ以上の放出可能なプロトンを有する１価の基からプロトンを一つ放出した基を示す。Ｒ⁴〜Ｒ⁷及びＹ⁻の中の２つ以上が結合して環状構造となっていてもよい。 As the structure of the curing accelerator (A) of the curable resin that can be obtained by reacting the compound (a) with the compound (b) and then dehydrohalogenating it, for example, the following general formula (III) ), But is not limited thereto.

Wherein, ^{R 1 ~R 3, R 4 ~R} 7 in the formula (III) are as ^{R 1 ~R 3, R 4 ~R} 7 in the aforementioned formula (I) and formula (II) . Further, Y ^- is a monovalent one release was based on proton from groups having one or more releasable protons 0-18 carbon atoms. Two or more of R ^{4 to} R ⁷ and Y ⁻ may be bonded to form a cyclic structure.

  The compound represented by the general formula (III) includes a compound that can be represented by the following resonance formula (IV).

（ここで、式（IV）中のＲ¹〜Ｒ^７及びＹ⁻は、前述のＲ¹〜Ｒ⁷及びＹ⁻と共通である。Ｒ⁴〜Ｒ⁷及びＹ⁻又はＹの中の２つ以上が結合して環状構造となっていてもよい。）

(Wherein, R ¹ to R ⁷ and Y in formula (IV) ^- the aforementioned R ¹ to R ⁷ and Y ^- two of or Y ^- is common that .R ⁴ to R ⁷ and Y The above may be combined to form a ring structure.)

As a compound that can be represented by the resonance formula (IV), for example, Y ^{− in the} general formula (I) is in the ortho position or the para position with respect to P ⁺ as represented by the following resonance formula (V) or (VI). Examples include, but are not limited to, compounds in which the element located and bonded to the ortho or para position has a lone pair of electrons. Further, for example, as shown by the following resonance formula (VII) or (VIII), the lone electron pair may be conjugated.

（ここで、式（Ｖ）及び（VI）中のＲ¹〜Ｒ^７は、前述のＲ¹〜Ｒ⁷と共通である。また、Ｚ⁻は、炭素数０〜１８の１つ以上の放出可能なプロトンを有する１価の基からプロトンを一つ放出し、かつベンゼン環に結合している原子が共役又は非共役の孤立電子対を有する基を示す。Ｒ⁴〜Ｒ⁷及びＺ⁻又はＺの中の２つ以上が結合して環状構造となっていてもよい。）

(Here, R ^{1 to} R ⁷ in the formulas (V) and (VI) are the same as the above-mentioned R ^{1 to} R ^7. Also, Z ⁻ represents one or more emission having 0 to 18 carbon atoms. A group in which one proton is released from a monovalent group having a possible proton and the atom bonded to the benzene ring has a conjugated or non-conjugated lone pair, R ^{4 to} R ⁷ and Z ⁻ or Two or more of Z may be bonded to form a cyclic structure.)

（ここで、式（VII）及び（VIII）中のＲ¹〜Ｒ⁷、Ｚ⁻及びＺは、前式（Ｖ）及び（VI）中のＲ¹〜Ｒ⁷、Ｚ⁻及びＺと共通である。また、Ｒ⁵¹〜Ｒ⁵⁷は、水素原子又は炭素数１〜１８の置換又は非置換の一価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。Ｒ⁴〜Ｒ⁷、Ｒ⁵¹〜Ｒ⁵⁷及びＺ⁻又はＺの中の２つ以上が結合して環状構造となっていてもよい。）

(Wherein, R ¹ to R ⁷ in the formula (VII) and (VIII), Z ^- and Z is Equation (V) and (R ¹ to R ⁷ in VI), Z ^- in common with and Z there. Furthermore, R ⁵¹ to R ⁵⁷ represents a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 18 carbon atoms, which may all each be the same or different .R ⁴ to R ^7, Two or more of R ^{51 to} R ⁵⁷ and Z ⁻ or Z may be bonded to form a cyclic structure.)

As compounds that cannot be represented by the resonance formula (IV), compounds represented by the following resonance formula (IX) or (X), wherein Y ^{− in the} general formula (I) is located at the meta position with respect to P ⁺ , and P Examples thereof include, but are not limited to, compounds that are bonded to the ortho position or the para position with respect to ⁺ , and the bonded atoms do not have a lone electron pair.

（ここで、式（IX）及び（X）中のＲ¹〜Ｒ^７及び式（IX）中のＺ⁻は、前述のＲ¹〜Ｒ^７及びＺ⁻と共通である。Ｗ⁻は、炭素数０〜１８の１つ以上の放出可能なプロトンを有する１価の基からプロトンを一つ放出し、かつベンゼン環に結合している原子が孤立電子対を有しない基を示す。Ｒ⁴〜Ｒ⁷、Ｚ⁻及びＷ⁻の中の２つ以上が結合して環状構造となっていてもよい。）

(Here, R ^{1 to} R ⁷ in formulas (IX) and (X) and Z ⁻ in formula (IX) are the same as R ^{1 to} R ⁷ and Z ⁻ described above. W ⁻ represents carbon. a monovalent group protons one released from and a radical having no atom bonded to the benzene ring lone pair having one or more releasable protons having 0 to 18 .R ⁴ ~ Two or more of R ⁷ , Z ⁻ and W ⁻ may be bonded to form a cyclic structure.)

The curable resin composition of this invention contains (A) 1 or more types of hardening accelerators of the curable resin of this invention, and (B) curable resin.
The curable resin (B) used in the present invention is not particularly limited as long as the curing accelerator (A) is a resin that promotes curing. For example, an epoxy resin, a phenol resin, a silicon resin, an amino resin, Examples thereof include unsaturated polyester resins, diallyl phthalate resins, alkyd resins, and the like. One of these may be used alone, or two or more may be used in combination. Among these, from the viewpoint that the effect of the curing accelerator (A) is sufficiently exhibited, (C) an epoxy resin is preferable.

When (C) an epoxy resin is used as the component (B), an epoxy resin having two or more epoxy groups in one molecule can be used. Examples of such an epoxy resin include, but are not limited to, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol, including phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, and the like. F and other phenols and / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene and a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde are condensed or co-polymerized in an acidic catalyst. A novolak epoxy resin obtained by epoxidizing a novolak resin obtained by condensation;
Bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenol, diglycidyl ethers such as stilbene phenols (bisphenol-type epoxy resin, biphenyl-type epoxy resin, stilbene-type epoxy resin),
Glycidyl ethers of alcohols such as butanediol, polyethylene glycol, polypropylene glycol;
Glycidyl ester type epoxy resins of carboxylic acids such as phthalic acid, isophthalic acid, tetrahydrophthalic acid;
Glycidyl-type or methylglycidyl-type epoxy resins such as those in which active hydrogen bonded to a nitrogen atom such as aniline or isocyanuric acid is substituted with a glycidyl group;
Vinylcyclohexene diepoxide obtained by epoxidizing an olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro ( 3,4-epoxy) cycloaliphatic epoxy resins such as cyclohexane-m-dioxane;
Glycidyl ether of paraxylylene and / or metaxylylene modified phenolic resin;
Glycidyl ether of terpene-modified phenolic resin;
Glycidyl ether of dicyclopentadiene-modified phenolic resin;
Glycidyl ether of cyclopentadiene modified phenolic resin;
Glycidyl ether of polycyclic aromatic ring-modified phenolic resin;
Glycidyl ether of a naphthalene ring-containing phenolic resin;
Halogenated phenol novolac epoxy resin;
Hydroquinone type epoxy resin;
Trimethylolpropane type epoxy resin;
A linear aliphatic epoxy resin obtained by oxidizing an olefinic bond with a peracid such as peracetic acid;
Diphenylmethane type epoxy resin;
Epoxidized products of aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins;
A sulfur atom containing epoxy resin etc. are mentioned.

  These may be used alone or in combination of two or more. Among these epoxy resins, biphenyl type epoxy resins, stilbene type epoxy resins, diphenylmethane type epoxy resins, sulfur atom containing type epoxy resins, novolac type epoxy resins, dicyclopentadiene type epoxy resins, salicylaldehyde type epoxy resins, naphthols and the like A copolymerized epoxy resin of phenol and an epoxidized product of an aralkyl type phenol resin are preferable in terms of reflow crack resistance and fluidity, and 4,4′-bis (2,3-epoxy is particularly preferable from the viewpoint of reflow crack resistance. Propoxy) -3,3 ′, 5,5′-tetramethylbiphenyl is more preferred, and 4,4′-bis (2,3-epoxypropoxy) -biphenyl is preferred from the viewpoint of moldability and heat resistance. Biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom containing type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, salicylaldehyde type epoxy resin, copolymerized epoxy of naphthols and phenols The epoxidized resin or aralkyl-type phenol resin may be used alone or in combination of two or more, but in order to demonstrate its performance, the total amount of epoxy resin 30% by weight or more is preferably used, and 50% by weight or more is more preferably used.

The biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton, but an epoxy resin represented by the following general formula (XI) is preferable. Among the epoxy resins represented by the following general formula (XI), the positions where the oxygen atom is substituted in R ⁸ are 4 and 4 'positions, and the 3, 3', 5, 5 'positions are methyl groups. YX-4000H (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), which is a hydrogen atom, and 4,4′-bis (2,3-epoxypropoxy) biphenyl, in which all R ⁸ are hydrogen atoms, and all R ⁸ are In the case of a hydrogen atom, and when the positions where oxygen atoms are substituted in R ⁸ are the 4 and 4 'positions, the 3, 3', 5, 5 'positions are methyl groups, and the rest are hydrogen atoms YL-6121H (trade name of Japan Epoxy Resin Co., Ltd.), which is a mixed product, is available as a commercial product.

（ここで、一般式（XI）中のＲ^８は水素原子又は炭素数１〜１２のアルキル基又は炭素数４〜１８のアリール基を示し、それぞれ全てが同一でも異なっていてもよい。ｎは平均値であり、０〜１０の正数を示す。）

(Here, R ⁸ in the general formula (XI) represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 4 to 18 carbon atoms, and each may be the same or different. (It is an average value and indicates a positive number from 0 to 10.)

The stilbene type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton, but an epoxy resin represented by the following general formula (XII) is preferable. Among the epoxy resins represented by the following general formula (XII), 3, ⁹ ′, 5 ′ and 5 ′ positions when R ⁹ is substituted with oxygen atoms at positions 4 and 4 ′ are methyl groups. The other is a hydrogen atom and all of R ¹⁰ are hydrogen atoms, and three of the 3, 3 ′, 5, 5 ′ positions are methyl groups, one is a tert-butyl group, and the others are hydrogen atoms and R ESLV-210 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), which is a mixture when all ¹⁰ are hydrogen atoms, is available as a commercial product.

（ここで、一般式（XII）中のＲ^９及びＲ^１０は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｎは平均値であり、０〜１０の正数を示す。）

(Here, R ⁹ and R ¹⁰ in the general formula (XII) each represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and they may be the same or different. N is an average value. Yes, indicates a positive number from 0 to 10.)

The diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton, but an epoxy resin represented by the following general formula (XIII) is preferable. Among the epoxy resins represented by the following general formula (XIII), all of R ¹¹ are hydrogen atoms, and the positions where oxygen atoms are substituted in R ¹² are 3, 3 ′, YSLV-80XY (trade name, manufactured by Nippon Steel Chemical Co., Ltd.), in which the 5,5′-position is a methyl group and the others are hydrogen atoms, is commercially available.

（ここで、一般式（XIII）中のＲ^１１及びＲ^１２は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｎは平均値であり、０〜１０の正数を示す。）

(Here, R ¹¹ and R ¹² in the general formula (XIII) each represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. N is an average value. Yes, indicates a positive number from 0 to 10.)

Although it will not specifically limit if it is an epoxy resin containing a sulfur atom as a sulfur atom containing type epoxy resin, For example, the epoxy resin shown by the following general formula (XIV) is mentioned. Among the epoxy resins represented by the following general formula (XIV), the tert-butyl group is 6, 6 when the positions where the oxygen atoms are substituted in R ¹³ are the 4 and 4 'positions. YSLV-120TE (trade name, manufactured by Nippon Steel Chemical Co., Ltd.) in which the '-position is a methyl group and the other is a hydrogen atom is commercially available.

（ここで、一般式（XIV）中のＲ^１３は水素原子又は炭素数１〜１８の１価の有機基示し、それぞれ全てが同一でも異なっていてもよい。ｎは平均値であり、０〜１０の正数を示す。）

(Here, R ¹³ in the general formula (XIV) represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. N is an average value, 10 represents a positive number.)

The novolak type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolak type phenol resin, but a novolak type phenol resin such as phenol novolak, cresol novolak, naphthol novolak, etc. is glycidyl etherified, etc. An epoxy resin epoxidized using the above method is preferable, and for example, an epoxy resin represented by the following general formula (XV) is more preferable. Among the epoxy resins represented by the general formula (XV) below, ESCN-190 and ESCN-195 (trade names, manufactured by Sumitomo Chemical Co., Ltd.), in which all of R ¹⁴ are hydrogen atoms, R ¹⁵ is a methyl group and i = 1. Etc. are available as commercial products.

（ここで、一般式（XV）中のＲ^１４及びＲ^１５は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｉは０〜３の整数、ｎは平均値であり、０〜１０の正数を示す。）

(Here, R ¹⁴ and R ¹⁵ in the general formula (XV) each represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. , N is an average value and represents a positive number from 0 to 10.)

  The dicyclopentadiene type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a compound having a dicyclopentadiene skeleton as a raw material, but an epoxy resin represented by the following general formula (XVI) is preferable. Among the epoxy resins represented by the following general formula (XVI), HP-7200 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) where i = 0 is available as a commercial product.

（ここで、一般式（XVI）中のＲ^１６は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｉは０〜３の整数、ｎは平均値であり、０〜１０の正数を示す。）

(Here, R ¹⁶ in the general formula (XVI) represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. I is an integer of 0 to 3, n is an average value and represents a positive number from 0 to 10.)

  The salicylaldehyde type epoxy resin is not particularly limited as long as it is an epoxy resin made from a compound having a salicylaldehyde skeleton, but a salicyl such as a novolak type phenolic resin of a compound having a salicylaldehyde skeleton and a compound having a phenolic hydroxyl group. A salicylaldehyde type epoxy resin such as an epoxy resin obtained by glycidyl etherification of an aldehyde type phenol resin is preferable, and an epoxy resin represented by the following general formula (XVII) is more preferable. Among the epoxy resins represented by the following general formula (XVII), MEH-7500 (trade name, manufactured by Meiwa Kasei Co., Ltd.) in which i = 0 and k = 0 is available as a commercial product.

（ここで、一般式（XVII）中のＲ^１７及びＲ^１８は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｉは０〜３の整数、ｋは０〜４の整数、ｎは平均値であり、０〜１０の正数を示す。）

(Here, R ¹⁷ and R ¹⁸ in the general formula (XVII) each represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. And k is an integer of 0 to 4, n is an average value and represents a positive number of 0 to 10.)

  The copolymerized epoxy resin of naphthols and phenols is not particularly limited as long as it is an epoxy resin using a compound having a naphthol skeleton and a compound having a phenol skeleton as a raw material, and a compound having a naphthol skeleton and Those obtained by glycidyl etherification of a novolak type phenol resin using a compound having a phenol skeleton are preferred, and an epoxy resin represented by the following general formula (XVIII) is more preferred. Among the epoxy resins represented by the following general formula (XVIII), NC-7300 (trade name, manufactured by Nippon Kayaku Co., Ltd.) having i = 0, j = 0, and k = 0 is available as a commercial product.

（ここで、一般式（XVIII）中のＲ^１９〜Ｒ^２１は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｉは０〜３の整数、ｊは０〜２の整数、ｋは０〜４の整数を示す。ｐは平均値で０〜１の正数を示し、ｌ、ｍはそれぞれ平均値で０〜１１の正数であり（ｌ＋ｍ）は１〜１１の正数を示す。）

(Here, R ^{19 to} R ²¹ in the general formula (XVIII) each represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. I is 0 to 3). , J is an integer of 0 to 2, k is an integer of 0 to 4. p is an average value of 0 to 1 and l and m are average values of 0 to 11 respectively. Yes (l + m) represents a positive number from 1 to 11.)

Epoxidized products of aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins include phenols such as phenol and cresol and / or naphthols such as naphthol and dimethylnaphthol, dimethoxyparaxylene, bis (methoxymethyl) biphenyl, and the like. The epoxy resin is not particularly limited as long as it is made of a phenol resin synthesized from the above derivatives. Phenol resins such as phenol and cresol and / or naphthols such as naphthol and dimethylnaphthol, and phenol resins synthesized from dimethoxyparaxylene, bis (methoxymethyl) biphenyl, and derivatives thereof are preferably glycidyl etherified, Epoxy resins represented by the formulas (XIX) and (XX) are more preferable. Among epoxy resins represented by the following general formula (XIX), i = 0, R- ²³ is a hydrogen atom, NC-3000S (trade name, manufactured by Nippon Kayaku Co., Ltd.), i = 0, and R ²³ is a hydrogen atom. CER-3000 (trade name, manufactured by Nippon Kayaku Co., Ltd.), which is a mixture of epoxy resin and epoxy resin in which all R ⁸ of general formula (XI) are hydrogen atoms in a weight ratio of 80:20, is available as a commercial product. It is. Among the epoxy resins represented by the following general formula (XX), ESN-175 (trade name of Nippon Steel Chemical Co., Ltd.) where j = 0, R ²⁵ k = 0, R ²⁶ k = 0, etc. It is available as a commercial product.

（ここで、一般式（XIX）及び（XX）中のＲ^２２〜Ｒ^２６は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｎは平均値であり、０〜１０の正数を示す。ｉは０〜３の整数、ｊは０〜２の整数、ｋは０〜４の整数を示し、Ｒ^２５のｋと、Ｒ^２６のｋとは同一でも異なっていても良い。）

(Here, R ^{22 to} R ²⁶ in the general formulas (XIX) and (XX) each represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all may be the same or different. Is an average value and represents a positive number from 0 to 10. i is an integer from 0 to 3, j is an integer from 0 to 2, k is an integer from 0 to 4, and k in R ²⁵ and R ²⁶ k may be the same or different.)

The meanings that R ^{8 to} R ²⁶ in the general formulas (XI) to (XX) may be the same as or different from each other include, for example, all ^{8 to} 88 R ^{8 in} the formula (XI) It means that they may be the same or different. It means that all of R ^{9 to} R ²⁶ may be the same or different with respect to the respective numbers included in the formula. R ^{8 to} R ²⁶ may be the same as or different from each other. For example, all of R ⁹ and R ¹⁰ may be the same or different.
As the epoxy resin represented by the general formula (XVIII), a random copolymer containing 1 constituent unit and m constituent units randomly, an alternating copolymer containing alternating units, a copolymer containing regular units, The block copolymer contained in a block shape is mentioned, Any one of these may be used independently or may be used in combination of 2 or more type.
In the above general formulas (XI) to (XX), n is in the range of 0 to 10, and when it exceeds 10, the melt viscosity of the component (B) is increased, so that the curable resin composition is melt molded. Viscosity also increases, and unfilled defects and bonding wires (gold wires connecting elements and leads) are likely to be deformed. The average n per molecule is preferably set in the range of 0-4. The values of i, j, and k in the general formulas (XV) to (XX) are independent for each R number.

  In the curable resin composition, (D) a curing agent can be used as necessary. (B) When an epoxy resin is used as the curable resin, the curing agent that can be used is not particularly limited as long as it is a compound that can cure the epoxy resin. Examples include phenolic compounds, amine compounds such as diamine and polyamine, organic acid anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride, and carboxylic acid compounds such as dicarboxylic acid and polycarboxylic acid. One type may be used alone, or two or more types may be used in combination. Among these, from the viewpoint that the effect of the (A) curing accelerator is sufficiently exhibited, a phenol resin is preferable.

There are no particular restrictions on the phenolic resin used as the curing agent for epoxy resin (D). For example, a phenolic resin having two or more phenolic hydroxyl groups in one molecule, resorcinol, catechol, bisphenol. A compound having two phenolic hydroxyl groups in one molecule such as A, bisphenol F, substituted or unsubstituted biphenol;
Phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and other phenols and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde, acetaldehyde, propionaldehyde, A novolak-type phenolic resin obtained by condensation or cocondensation with aldehydes such as benzaldehyde and salicylaldehyde under an acidic catalyst;
Aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl;
Paraxylylene and / or metaxylylene-modified phenolic resin;
Melamine-modified phenolic resin;
Terpene-modified phenolic resin;
Dicyclopentadiene type phenol resin, dicyclopentadiene type naphthol resin synthesized by copolymerization from phenols and / or naphthols and dicyclopentadiene;
Cyclopentadiene modified phenolic resin;
Polycyclic aromatic ring-modified phenolic resin;
Biphenyl type phenolic resin;
Triphenylmethane phenol resin;
Examples thereof include phenol resins obtained by copolymerizing two or more of these, and these may be used alone or in combination of two or more.

  Among these phenol resins, aralkyl-type phenol resins, dicyclopentadiene-type phenol resins, salicylaldehyde-type phenol resins, benzaldehyde-type and aralkyl-type copolymer phenol resins, and novolak-type phenol resins are used from the viewpoint of reflow crack resistance. preferable. These aralkyl-type phenol resins, dicyclopentadiene-type phenol resins, salicylaldehyde-type phenol resins, benzaldehyde-type and aralkyl-type copolymer phenol resins, and novolak-type phenol resins can be used alone or in combination of two or more. May be used in combination, but in order to exert its performance, it is preferably used in an amount of 30% by weight or more, more preferably 50% by weight or more, based on the total amount of the phenol resin.

The aralkyl type phenolic resin is not particularly limited as long as it is a phenolic resin synthesized from phenols and / or naphthols and dimethoxyparaxylene, bis (methoxymethyl) biphenyl or a derivative thereof. Phenol resins represented by (XXI) to (XXIII) are preferred.
Among the phenol resins represented by the following general formula (XXI), XL-225, XLC (trade name, manufactured by Mitsui Chemicals, Inc.), MEH-7800 (trade name, Meiwa Kasei Co., Ltd.), etc., where i = 0 and k = 0. It is available as a commercial product.
Among the phenol resins represented by the following general formula (XXII), ME = 07851 (trade name of Meiwa Kasei Co., Ltd.) in which i = 0 and all R ³⁰ are hydrogen atoms is commercially available.
Among the phenol resins represented by the following general formula (XXIII), SN-170 (trade name of Nippon Steel Chemical Co., Ltd.) in which j = 0, R ³² k = 0, and R ³³ k = 0 is a commercially available product. It is available.

（ここで、一般式（XXI）〜（XXIII）中のＲ^２７〜Ｒ^３３は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｉは０〜３の整数、ｋは０〜４の整数、ｊは０〜２の整数、ｎは平均値であり、０〜１０の正数を示す。Ｒ^３２のｋと、Ｒ^３３のｋとは同一でも異なっていても良い。）

(Here, R ^{27 to} R ³³ in the general formulas (XXI) to (XXIII) represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and they may be all the same or different. Is an integer from 0 to 3, k is an integer from 0 to 4, j is an integer from 0 to 2, n is an average value, and represents a positive number from 0 to 10. k of R ³² and k of R ³³ May be the same or different.)

  The dicyclopentadiene type phenol resin is not particularly limited as long as it is a phenol resin using a compound having a dicyclopentadiene skeleton as a raw material, but a phenol resin represented by the following general formula (XXIV) is preferable. Among the phenol resins represented by the following general formula (XXIV), DPP (trade name, manufactured by Nippon Petrochemical Co., Ltd.) where i = 0 is available as a commercial product.

（ここで、一般式（XXIV）中のＲ^３４は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｉは０〜３の整数、ｎは平均値であり、０〜１０の正数を示す。）

(Here, R ³⁴ in the general formula (XXIV) represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. I is an integer of 0 to 3, n is an average value and represents a positive number from 0 to 10.)

The salicylaldehyde type phenol resin is not particularly limited as long as it is a phenol resin using a compound having a salicylaldehyde skeleton as a raw material, but a phenol resin represented by the following general formula (XXV) is preferable.
Among phenol resins represented by the following general formula (XXV), MEH-7500 (trade name, manufactured by Meiwa Kasei Co., Ltd.) where i = 0 and k = 0 is available as a commercial product.

（ここで、一般式（XXV）中のＲ^３５及びＲ^３６は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｉは０〜３の整数、ｋは０〜４の整数、ｎは平均値であり、０〜１０の正数を示す。）

(Here, R ³⁵ and R ³⁶ in the general formula (XXV) each represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. I is 0 to 3). And k is an integer of 0 to 4, n is an average value and represents a positive number of 0 to 10.)

The benzaldehyde type and aralkyl type copolymeric phenol resin is not particularly limited as long as it is a copolymeric phenol resin of a phenol resin and an aralkyl type phenol resin using a compound having a benzaldehyde skeleton as a raw material. A phenol resin represented by the general formula (XXVI) is preferred.
Among phenol resins represented by the following general formula (XXVI), HE-510 (trade name, manufactured by Sumikin Kako Co., Ltd.) having i = 0, k = 0, and q = 0 is available as a commercial product.

（ここで、一般式（XXVI）中のＲ^３７〜Ｒ^３９は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｉは０〜３の整数、ｋは０〜４の整数、ｑは０〜５の整数、ｌ、ｍはそれぞれ平均値で０〜１１の正数であり（ｌ＋ｍ）は１〜１１の正数を示す。）

(Here, R ^{37 to} R ³⁹ in the general formula (XXVI) each represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. I is 0 to 3). , K is an integer of 0 to 4, q is an integer of 0 to 5, l and m are average values of 0 to 11 and (l + m) is a positive number of 1 to 11, respectively.)

The novolak type phenol resin is not particularly limited as long as it is a phenol resin obtained by condensation or cocondensation of phenols and / or naphthols and aldehydes in the presence of an acidic catalyst, but the following general formula (XXVII ) Is preferred.
I = 0 Among phenolic resin represented by the following general formula ^{(XXVII), R 40} are all hydrogen atoms TAMANOL 758, 759 (Arakawa Chemical Industries, Ltd., trade name), HP-850N (manufactured by Hitachi Chemical Co., Ltd. Product Name) etc. are commercially available.

（ここで、一般式（XXVII）中のＲ^４０及びＲ^４１は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｉは０〜３の整数、ｋは０〜４の整数、ｎは平均値であり、０〜１０の正数を示す。）

(Here, R ⁴⁰ and R ⁴¹ in the general formula (XXVII) each represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. I is 0 to 3). And k is an integer of 0 to 4, n is an average value and represents a positive number of 0 to 10.)

The meaning that R ^{27 to} R ⁴¹ in the general formulas (XXI) to (XXVII) may be the same or different from each other means that, for example, all i R ^{27 in} the formula (XXI) are the same. It means that they may be different from each other. It means that all the other R ^{28 to} R ⁴¹ may be the same as or different from each other. R ^{27 to} R ⁴¹ may be the same as or different from each other. For example, all of R ²⁷ and R ²⁸ may be the same or different, and all of R ³⁵ and R ³⁶ may be the same or different.
In the above general formulas (XXI) to (XXVII), n is in the range of 0 to 10, and when it exceeds 10, the melt viscosity of the component (B) becomes high. Viscosity also increases, and unfilled defects and bonding wires (gold wires connecting elements and leads) are likely to be deformed. The average n per molecule is preferably set in the range of 0-4. The values of i, j, k, and q in the general formulas (XXI) to (XXVII) are independent for each R number.

  In the present invention, when (C) an epoxy resin is used as the (B) curable resin and a phenol resin is used as the (D) curing agent of the epoxy resin, the blending ratio of the (C) component and the (D) component is as follows. The ratio of the hydroxyl equivalents of all phenol resins to the epoxy equivalents (number of hydroxyl groups in the phenol resin / number of epoxy groups in the epoxy resin) is preferably set in the range of 0.5 to 2.0. 5 is more preferable, and 0.8 to 1.3 is more preferable. If this ratio is less than 0.5, the epoxy resin is not sufficiently cured, and the heat resistance, moisture resistance and electrical properties of the cured product tend to be inferior. If it exceeds 2.0, the phenol resin component is excessive and curing is insufficient. There is a tendency that electrical properties and moisture resistance are deteriorated because of a sufficient amount of phenolic hydroxyl groups remaining in the cured resin.

  In addition to the curing accelerator component (A), the curable resin composition of the present invention is used in combination with one or more kinds of those generally used as a curing accelerator that accelerates the curing reaction of the curable resin. Can do. Examples of the curing accelerator used in combination include cyclohexane such as diazabicycloalkene such as 1,5-diazabicyclo [4.3.0] nonene-5, 1,8-diazabicyclo [5.4.0] undecene-7. Amidine compounds, derivatives thereof, phenol novolac salts thereof and maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethyl Π bonds such as benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, quinone compounds such as phenyl-1,4-benzoquinone, and diazophenylmethane. A compound with intramolecular polarization formed by adding a compound having triethylenediamine, benzyldimethylamine, Tertiary amines such as ethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, etc. Imidazoles, tetrasubstituted phosphonium tetrasubstituted borates such as tetraphenylphosphonium tetraphenylborate, tetraphenylboron salts such as 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate, tri Phenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phos Fins, Tris (dialkylphenyl) phosphine, Tris (trialkylphenyl) phosphine, Tris (tetraalkylphenyl) phosphine, Tris (dialkoxyphenyl) phosphine, Tris (trialkoxyphenyl) phosphine, Tris (tetraalkoxyphenyl) phosphine, Tris Organic phosphines such as alkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, or complexes of these organic phosphines with organic borons, these organic phosphines and maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4- Nzokinon, quinone compounds such as phenyl-1,4-benzoquinone, and compounds having an addition-intramolecular polarization comprising a compound having a π bond, such as diazo methane may be mentioned.

When these curing accelerators are used in combination, the amount of component (A) is preferably 30% by weight or more, more preferably 50% by weight or more, based on the total curing accelerator. When the blending amount of the component (A) is less than 30% by weight, curability and / or fluidity at the time of moisture absorption is lowered, and the effect of the present invention tends to be reduced.
(A) Although the total compounding quantity of all the hardening accelerators containing a component will not have a restriction | limiting especially if a hardening acceleration effect is acquired, from the viewpoint of sclerosis | hardenability at moisture absorption and fluidity | liquidity, (B) 100 weight of curable resin total 0.1-10 weight part is preferable with respect to a part, and 1-7.0 weight part is more preferable. If it is less than 0.1 part by weight, it is difficult to cure in a short time, and if it exceeds 10 parts by weight, the curing rate is too high and a good molded product may not be obtained.

  The curable resin composition of the present invention may further contain (E) an inorganic filler as necessary. In particular, when the curable resin composition is used as a molding material for sealing, it is preferable to blend (E) an inorganic filler. The (E) inorganic filler used in the present invention is not particularly limited as it is generally used for a molding material for sealing. For example, fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, Calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, talc, clay, mica, etc. Can be mentioned. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as composite hydroxide of magnesium and zinc, and zinc borate. Among these, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. These inorganic fillers may be used alone or in combination of two or more.

(E) Although the compounding quantity of an inorganic filler will not have a restriction | limiting in particular if the effect of this invention is acquired, It is preferable that it is the range of 70 to 95 weight% with respect to curable resin composition. These inorganic fillers are blended for the purpose of improving the thermal expansion coefficient, thermal conductivity, elastic modulus, etc. of the cured product. If the blending amount is less than 70% by weight, these properties tend to be insufficiently improved. If it exceeds 95% by weight, the viscosity of the curable resin composition increases, the fluidity tends to decrease, and molding tends to be difficult.
Moreover, 1-50 micrometers is preferable and, as for the average particle diameter of (E) inorganic filler, 10-30 micrometers is more preferable. If it is less than 1 μm, the viscosity of the curable resin composition is likely to increase, and if it exceeds 50 μm, the resin component and the inorganic filler are easily separated, resulting in unevenness of the cured product and variations in the properties of the cured product. There is a tendency for the fillability of the to decrease.
From the viewpoint of fluidity, the particle shape of (E) inorganic filler is preferably spherical rather than square, and (E) the particle size distribution of inorganic filler is preferably distributed over a wide range. For example, when the inorganic filler is blended in an amount of 60% by weight or more, it is preferable that 70% by weight or more of them be spherical particles and distributed in a wide range of 0.1 to 80 μm. Since such an inorganic filler tends to have a close-packed structure, a curable resin composition excellent in fluidity can be obtained with little increase in the viscosity of the material even when the blending amount is increased.

  An anion exchanger can be mix | blended with the curable resin composition of this invention as needed. In particular, when a curable resin composition is used as a molding material for sealing, an anion exchanger may be blended from the viewpoint of improving moisture resistance and high-temperature storage characteristics of an electronic component device including an element to be sealed. preferable. The anion exchanger used in the present invention is not particularly limited, and conventionally known anion exchangers can be used. For example, hydrotalcite, water content of an element selected from magnesium, aluminum, titanium, zirconium and bismuth can be used. An oxide etc. are mentioned, These can be used individually or in combination of 2 or more types. Among these, hydrotalcite represented by the following general formula (XXVIII) is preferable.

(Chemical formula 24)
Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (XXVIII)
(0 <X ≦ 0.5, m is a positive integer)
The compounding amount of these anion exchangers is not particularly limited as long as it is a sufficient amount capable of capturing anions such as halogen ions, but is in the range of 0.1 to 30% by weight with respect to (B) curable resin. Preferably, 1 to 5% by weight is more preferable.

  You may mix | blend well-known colorants, such as carbon black, an organic dye, an organic pigment, a titanium oxide, a red lead, a bengara, with the curable resin composition of this invention as needed.

  In the curable resin composition of the present invention, a mold release agent may be blended in order to give good mold releasability from the mold during molding. The release agent used in the present invention is not particularly limited and conventionally known release agents can be used. For example, higher fatty acids such as carnauba wax, montanic acid, stearic acid, higher fatty acid metal salts, montanic acid esters, etc. Examples thereof include polyolefin waxes such as ester wax, oxidized polyethylene and non-oxidized polyethylene, and these may be used alone or in combination of two or more. Among them, an oxidized or non-oxidized polyolefin wax is preferable, and the blending amount thereof is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight with respect to (B) the curable resin. If the blending amount of the polyolefin wax is less than 0.01% by weight, the releasability tends to be insufficient, and if it exceeds 10% by weight, the adhesion may be hindered. Examples of the polyolefin-based wax include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000 such as H4, PE, and PED series manufactured by Hoechst. Moreover, when using another mold release agent together with a polyolefin-type wax, 0.1 to 10 weight% is preferable with respect to (B) curable resin, and 0.5 to 3 weight% is more preferable.

  In the curable resin composition of the present invention, a flame retardant can be blended as necessary to impart flame retardancy. The flame retardant used in the present invention is not particularly limited, and examples thereof include known organic or inorganic compounds containing a halogen atom, antimony atom, nitrogen atom or phosphorus atom, metal hydroxide, acenaphthylene, and the like. One kind may be used alone, or two or more kinds may be used in combination. Although there will be no restriction | limiting in particular if the flame-retardant effect is achieved, the compounding quantity of a flame retardant is 1-30 weight% with respect to (C) epoxy resin, and 2-15 weight% is more preferable.

In addition, in the curable resin composition for sealing of the present invention, epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, as needed, in order to increase the adhesion between the resin component and the inorganic filler, Known coupling agents such as various silane compounds such as vinyl silane, titanium compounds, aluminum chelates, and aluminum / zirconium compounds can be added.
The blending amount of the coupling agent is preferably 0.05 to 5% by weight, more preferably 0.1 to 2.5% by weight, based on the inorganic filler (E). If it is less than 0.05% by weight, the adhesion to the frame tends to be lowered, and if it exceeds 5% by weight, the moldability of the package tends to be lowered.

Examples of the coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, and γ-acryloxypropyl. Trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxy Silane, γ-aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ-anilinopropylmethyl Rudiethoxysilane, γ-anilinopropylethyldiethoxysilane, γ-anilinopropylethyldimethoxysilane, γ-anilinomethyltrimethoxysilane, γ-anilinomethyltriethoxysilane, γ-anilinomethylmethyldimethoxysilane, γ-anilinomethylmethyldiethoxysilane, γ-anilinomethylethyldiethoxysilane, γ-anilinomethylethyldimethoxysilane, N- (p-methoxyphenyl) -γ-aminopropyltrimethoxysilane, N- (p -Methoxyphenyl) -γ-aminopropyltriethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylmethyldimethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylmethyldiethoxysilane, N- (P-methoxyphenyl) -γ-aminop Pyrethyldiethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylethyldimethoxysilane, γ- (N-methyl) aminopropyltrimethoxysilane, γ- (N-ethyl) aminopropyltrimethoxysilane, γ -(N-butyl) aminopropyltrimethoxysilane, γ- (N-benzyl) aminopropyltrimethoxysilane, γ- (N-methyl) aminopropyltriethoxysilane, γ- (N-ethyl) aminopropyltriethoxysilane , Γ- (N-butyl) aminopropyltriethoxysilane, γ- (N-benzyl) aminopropyltriethoxysilane, γ- (N-methyl) aminopropylmethyldimethoxysilane, γ- (N-ethyl) aminopropylmethyl Dimethoxysilane, γ- (N-butyl) aminopropylmethyldimethyl Toxisilane, γ- (N-benzyl) aminopropylmethyldimethoxysilane, γ- (β-aminoethyl) aminopropyltrimethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (Aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxy Silane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxy Silane, .gamma.-mercaptopropyl silane coupling agent such as methyldimethoxysilane,
Isopropyltriisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-aminoethyl-aminoethyl) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1 -Butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, Isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctylfo Feto) titanate, isopropyl tricumylphenyl titanate, although tetraisopropyl bis (dioctyl phosphite) titanate coupling agents such as titanates and the like, not limited thereto. Moreover, you may use these individually or in combination of 2 or more types. Among these, a coupling agent having a secondary amino group is preferable from the viewpoints of fluidity and wire flow.

  The curable resin composition of the present invention may contain a stress relaxation agent such as silicone oil or silicone rubber powder as required. By blending a stress relaxation agent, the amount of warp deformation and package cracking of the package can be reduced. The stress relaxation agent that can be used is not particularly limited as long as it is a known flexible agent (stress relaxation agent) that is generally used. Commonly used flexible agents include, for example, silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, polybutadiene-based thermoplastic elastomers, NR (natural rubber), NBR, and the like. (Acrylonitrile-butadiene rubber), rubber particles such as acrylic rubber, urethane rubber, silicone powder, methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate Examples thereof include rubber particles having a core-shell structure such as a copolymer, and these may be used alone or in combination of two or more. Among these, silicone-based flexible agents are preferable, and examples of the silicone-based flexible agents include those having an epoxy group, those having an amino group, and those obtained by modifying these with a polyether.

  The curable resin composition of the present invention can be prepared by any method as long as various components can be uniformly dispersed and mixed. However, as a general method, components of a predetermined blending amount are sufficiently mixed by a mixer or the like. Then, after melt-kneading with a mixing roll, an extruder or the like, cooling and pulverization can be mentioned. For example, a predetermined amount of the above-described components can be uniformly stirred and mixed, and can be obtained by a method such as kneading, cooling, and pulverizing with a kneader, roll, extruder, or the like that has been heated to 70 to 140 ° C. in advance. It is easy to use if it is tableted with dimensions and weight that match the molding conditions.

  As an electronic component device obtained by sealing an element with the curable resin composition obtained in the present invention, a lead frame, a wired tape carrier, a wiring board, glass, a support member such as a silicon wafer, a semiconductor chip, Examples include electronic component devices in which active elements such as transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, and coils are mounted, and necessary portions are sealed with the curable resin composition of the present invention. It is done. As such an electronic component device, for example, a semiconductor element is fixed on a lead frame, and a terminal portion and a lead portion of an element such as a bonding pad are connected by wire bonding or bump, and then the curable resin composition of the present invention. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead package) ), TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package) and other general resin-encapsulated ICs, and semiconductor chips connected to tape carriers by bumps are encapsulated with the curable resin composition of the present invention. TCP (Tape Carrier Package), connected to wiring formed on a wiring board or glass by wire bonding, flip chip bonding, solder, etc. COB (Chip On Board) module, hybrid IC, in which active elements such as conductor chips, transistors, diodes, thyristors and / or passive elements such as capacitors, resistors and coils are sealed with the curable resin composition of the present invention. A multi-chip module, an element is mounted on the surface of an organic substrate on which a terminal for connecting a wiring board is formed on the back surface, the element and the wiring formed on the organic substrate are connected by bump or wire bonding, and then the curable resin of the present invention Examples thereof include BGA (Ball Grid Array) and CSP (Chip Size Package) in which the element is sealed with a composition. Moreover, the curable resin composition of this invention can be used effectively also for a printed circuit board.

  As a method for sealing an electronic component device using the curable resin composition of the present invention, a low-pressure transfer molding method is the most common, but an injection molding method, a compression molding method, or the like may be used.

  EXAMPLES Next, although an Example demonstrates this invention, the scope of the present invention is not limited to these Examples.

[Synthesis example of curing accelerator of curable resin]
Synthesis example 1
A flask was charged with 20.4 g of triphenylphosphine, 26.9 g of 4-bromophenol, 3.5 g of nickel (II) chloride hexahydrate and 20 g of DMF, and stirred at 145 ° C. for 6 hours. The reaction solution was concentrated under reduced pressure, 60 ml of methanol and then 9.3 g of sodium hydroxide were added, and the mixture was stirred until the sodium hydroxide was completely dissolved.
The resulting solution was filtered through Celite, and the filtrate was concentrated under reduced pressure until the total amount reached about 50 ml, poured into 1 L of water, the precipitated crystals were filtered, washed with water, dried under reduced pressure, and compound 25 0.6 g was obtained. The results of elemental analysis were calculated value C: 81.34%, H: 5.40%, measured value C: 81.21%, and H: 5.34%.

Synthesis example 2
24.5g of compounds were obtained in the same manner as in Synthesis Example 1 except that 20g of 4-chlorophenol was used instead of 4-bromophenol. The results of elemental analysis were the calculated value C: 81.34%, H: 5.40%, measured value C: 81.23%, and H: 5.33%.

Synthesis example 3
A flask was charged with 20.4 g of triphenylphosphine, 26.9 g of 3-bromophenol, 3.5 g of nickel (II) chloride hexahydrate and 20 g of DMF, and stirred at 145 ° C. for 6 hours. The reaction solution was concentrated under reduced pressure, 60 ml of methanol and then 9.3 g of sodium hydroxide were added, and the mixture was stirred until sodium hydroxide was completely dissolved. The resulting solution was filtered through Celite, concentrated until the total amount was about 50 ml, and poured into 1 L of water. After concentrating this to about 200 ml, the precipitated crystals were filtered and dried to obtain 10.2 g of the compound. The results of elemental analysis were calculated C: 81.34%, H: 5.40%, measured C: 81.15%, H: 5.29%.

Synthesis example 4
24.3 g of compounds were obtained in the same manner as in Synthesis Example 1 except that 26.9 g of 2-bromophenol was used instead of 4-bromophenol. The results of elemental analysis were calculated C: 81.34%, H: 5.40%, measured C: 81.22%, H: 5.32%.

Synthesis example 5
25.2 g of compound was obtained in the same manner as in Synthesis Example 1 except that 20 g of 2-chlorophenol was used instead of 4-bromophenol. The results of elemental analysis were calculated C: 81.34%, H: 5.40%, measured C: 81.20%, H: 5.34%.

Synthesis Example 6
25.9 g of compound was obtained in the same manner as in Synthesis Example 1 except that 31.3 g of 4-bromo-2,6-dimethylphenol was used instead of 4-bromophenol. The results of elemental analysis were the calculated value C: 81.66%, H: 6.06%, measured value C: 81.47%, H: 5.9%.

Synthesis example 7
27.2 g of the compound was obtained in the same manner as in Synthesis Example 2 except that 23.7 g of tri-p-tolylphosphine was used instead of triphenylphosphine. The results of elemental analysis were calculated C: 81.80%, H: 6.36%, measured C: 81.67%, H: 6.29%.

Synthesis Example 8
25.9 g of compound was obtained in the same manner as in Synthesis Example 1 except that 36.2 g of 6-bromo-2-naphthol was used instead of 4-bromophenol. The results of elemental analysis were calculated C: 83.15%, H: 5.23%, measured C: 83.01%, H: 5.18%.

Synthesis Example 9
16.5 g of compound was obtained in the same manner as in Synthesis Example 2 except that 20.9 g of cyclohexyldiphenylphosphine was used instead of triphenylphosphine. The results of elemental analysis were as follows: calculated value C: 79.98%, H: 6.99%, measured value C: 79.86%, H: 6.90%.

Each analysis was performed by the following method about the compound obtained by the synthesis examples 1-9.
(1) ¹ H-NMR
About 10 mg of the compound was dissolved in about 0.5 ml of deuterated methanol, placed in a φ5 mm sample tube, and measured with AC-250 manufactured by Nippon Bruker. The shift value was based on CHD ₂ OH (3.3 ppm) contained in a trace amount in the solvent.
(2) ¹³ C-NMR
About 100 mg of the compound was dissolved in about 0.5 ml of deuterated methanol, placed in a φ5 mm sample tube, and measured with AC-250 manufactured by Nippon Bruker. The shift value was based on heavy methanol (49 ppm).
(3) ³¹ P-NMR
About 100 mg of the compound was dissolved in about 0.5 ml of deuterated methanol, placed in a φ5 mm sample tube, and measured with AC-250 manufactured by Nippon Bruker. The shift value was based on triphenyl phosphate (0 ppm).
(4) IR
Measurement was performed by KBr method using FTS 3000MX manufactured by Bio-Rad.

As a result of each analysis, it was confirmed that the compounds synthesized in Synthesis Examples 1 and 2 were the same compound (Compound 1) and had a structure represented by the following formula (XXIX). Yields were 93% and 89%, respectively. ¹ H-NMR (CD ₃ OD), ¹³ C-NMR (CD ₃ OD), ³¹ P-NMR (CD ₃ OD) and IR (KBr method) spectra of Compound 1 are shown in FIGS. Shown in

As a result of each analysis, it was confirmed that the compound (Compound 2) synthesized in Synthesis Example 3 had a structure represented by the following formula (XXX). The yield was 37%. ¹ H-NMR (CD ₃ OD), ¹³ C-NMR (CD ₃ OD), ³¹ P-NMR (CD ₃ OD) and IR (KBr) spectra of Compound 2 are shown in FIGS. 5, 6, 7 and 8, respectively. Show.

As a result of each analysis, it was confirmed that the compounds synthesized in Synthesis Examples 4 and 5 were the same compound (Compound 3) and had a structure represented by the following formula (XXXI). Yields were 88% and 91%, respectively. The spectra of ¹ H-NMR (CD ₃ OD), ¹³ C-NMR (CD ₃ OD), ³¹ P-NMR (CD ₃ OD) and IR (KBr) are shown in FIGS. 9, 10, 11 and 12, respectively.

As a result of each analysis, it was confirmed that the compound (Compound 4) synthesized in Synthesis Example 6 had a structure represented by the following formula (XXXII). The yield was 87%. The spectra of ¹ H-NMR (CD ₃ OD), ¹³ C-NMR (CD ₃ OD), ³¹ P-NMR (CD ₃ OD) and IR (KBr) are shown in FIGS. 13, 14, 15 and 16, respectively.

As a result of each analysis, it was confirmed that the compound (Compound 5) synthesized in Synthesis Example 7 had a structure represented by the following formula (XXXIII). The yield was 88%. The spectra of ¹ H-NMR (CD ₃ OD), ¹³ C-NMR (CD ₃ OD), ³¹ P-NMR (CD ₃ OD) and IR (KBr) are shown in FIGS. 17, 18, 19 and 20, respectively.

As a result of each analysis, it was confirmed that the compound (Compound 6) synthesized in Synthesis Example 8 had a structure represented by the following formula (XXXIV). The yield was 82%. The spectra of ¹ H-NMR (CD ₃ OD), ¹³ C-NMR (CD ₃ OD), ³¹ P-NMR (CD ₃ OD) and IR (KBr) are shown in FIGS. 21, 22, 23 and 24, respectively.

As a result of each analysis, it was confirmed that the compound (Compound 7) synthesized in Synthesis Example 9 had a structure represented by the following formula (XXXV). The yield was 59%. The spectra of ¹ H-NMR (CD ₃ OD), ¹³ C-NMR (CD ₃ OD), ³¹ P-NMR (CD ₃ OD) and IR (KBr) are shown in FIGS. 25, 26, 27 and 28, respectively.

上記の式（XXIX）〜（XXXV）で示す化合物のうち、（XXX）以外の化合物は、式（IV）の共鳴で示すことができる化合物であり、（XXX）は式（IV）の共鳴で示すことができない化合物である。

Of the compounds represented by the above formulas (XXIX) to (XXXV), compounds other than (XXX) are compounds that can be represented by the resonance of formula (IV), and (XXX) represents the resonance of formula (IV). It is a compound that cannot be shown.

[Preparation and characteristic evaluation of curable resin composition]
(Examples 1-61, Comparative Examples 1-81)
As an epoxy resin, an epoxy equivalent of 196, a biphenyl type epoxy resin having an melting point of 106 ° C. (epoxy resin 1: trade name YX-4000H manufactured by Japan Epoxy Resin Co., Ltd.), an epoxy equivalent of 245, and a sulfur atom-containing epoxy resin having an melting point of 110 ° C. Resin 2: Nippon Steel Chemical Co., Ltd. trade name YSLV-120TE), epoxy equivalent 192, melting point 79 ° C. diphenylmethane skeleton type epoxy resin (Epoxy resin 3: Nippon Steel Chemical Co., Ltd. trade name YSLV-80XY), epoxy An stilbene type epoxy resin having an equivalent weight of 210 and a melting point of 120 ° C. (epoxy resin 4: trade name ESLV-210 manufactured by Sumitomo Chemical Co., Ltd.), an ortho cresol novolac type epoxy resin having an epoxy equivalent of 195 and a softening point of 62 ° C. (epoxy resin 5: Sumitomo Product name ESCN manufactured by Chemical Industry Co., Ltd. 190-2), dicyclopentadiene-modified phenol novolac type epoxy resin having an epoxy equivalent of 264 and a softening point of 64 ° C. (epoxy resin 6: trade name HP-7200 manufactured by Dainippon Ink & Chemicals, Inc.), salicylaldehyde type having an epoxy equivalent of 167 Epoxy resin (Epoxy resin 7: Nippon Kayaku Co., Ltd., trade name EPPN-502H), epoxy equivalent 242 and epoxidized aralkyl-type phenol resin having a softening point of 95 ° C. and biphenyl-type epoxy resin in a weight ratio mixture of 80/20 (Epoxy resin 8: Nippon Kayaku Co., Ltd. trade name CER-3000), Epoxy equivalent 265, Epoxy product of aralkyl type phenol resin having a softening point of 66 ° C. (Epoxy resin 9: Nippon Steel Chemical Co., Ltd. trade name ESN-175 ), Epoxy equivalent 3 as an epoxy resin with flame retardant effect 3, a softening point of 80 ° C., was prepared bromine content 48% by weight of a brominated bisphenol A type epoxy resin (brominated epoxy resin).

  As a curing agent, a phenol aralkyl resin having a hydroxyl group equivalent of 176 and a softening point of 70 ° C. (curing agent 1: trade name Milex XL-225 manufactured by Mitsui Chemicals), a biphenyl skeleton type phenol resin having a hydroxyl group equivalent of 199 and a softening point of 89 ° C. (curing) Agent 2: Meiwa Kasei Co., Ltd. trade name MEH-7785), hydroxyl group equivalent 183, naphthol aralkyl resin having a softening point of 79 ° C. (curing agent 3: Nippon Steel Chemical Co., Ltd. trade name SN-170), hydroxyl group equivalent 170, Dicyclopentadiene-modified phenol novolak resin having a softening point of 93 ° C. (curing agent 4: product name DPP manufactured by Nippon Petrochemical Co., Ltd.), phenol novolac resin having a hydroxyl equivalent of 106 (curing agent 5: product name HP- manufactured by Hitachi Chemical Co., Ltd.) 850N), a copolymerized phenol resin of benzaldehyde type and aralkyl type having a hydroxyl group equivalent of 156 Curing agent 6: Sumikin Chemical Co., Ltd. trade name HE-510), hydroxyl equivalent 106 salicylaldehyde type phenol resin (hardening agent 7: Meiwa Kasei Co., Ltd. trade name MEH-7500), a flame retardant phenol resin A resin (curing agent 8: trade name SN-170AR10 manufactured by Nippon Steel Chemical Co., Ltd.) prepared by adding 10% by weight of acenaphthylene to a naphthol aralkyl resin having a hydroxyl group equivalent of 209 and a softening point of 73 ° C. was prepared.

  As the curing accelerator of the examples, the above-mentioned compound 1 (curing accelerator 1), compound 2 (curing accelerator 2), compound 3 (curing accelerator 3), compound 4 (curing accelerator 4), compound 5 ( Curing accelerator 5), compound 6 (curing accelerator 6), compound 7 (curing accelerator 7), and as a curing accelerator of Comparative Example, triphenylphosphine (curing accelerator A), triphenylphosphine and 1,4- Addition reaction product of benzoquinone (curing accelerator B), addition reaction product of tri-n-butylphosphine and 1,4-benzoquinone (curing accelerator C), addition reaction of tricyclohexylphosphine and 1,4-benzoquinone Product (curing accelerator D), (cyclopentadienylidene) triphenylphosphorane (curing accelerator E) represented by the following formula (XXXVI), 2- (triphenylphosphaaniani represented by the following formula (XXXVII) Den) succinate anhydrase hydride (curing accelerator F), phenol novolac salt (curing accelerator DBU G: San-Apro Ltd., trade name SA-841) was prepared.

Spherical fused silica having an average particle size of 17.5 μm and a specific surface area of 3.8 m ² / g is used as the inorganic filler, and epoxy silane (γ-glycidoxypropyltrimethoxysilane) is used as a coupling agent as the other additive component. Carbon black (trade name MA-100, manufactured by Mitsubishi Chemical Corporation) as a colorant, carnauba wax (manufactured by Celerica NODA) as a release agent, and antimony trioxide as a flame retardant were prepared.
These are blended in parts by weight shown in Tables 1 to 13 and roll kneaded under conditions of a kneading temperature of 80 ° C. and a kneading time of 15 minutes, and the curable resin compositions of Examples 1 to 61 and Comparative Examples 1 to 81 I got a thing.

The curable resin compositions of Examples and Comparative Examples were evaluated by the following tests. The evaluation results are shown in Tables 14 to 26.
The curable resin composition was molded by a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Further, post-curing was performed at 175 ° C. for 6 hours.
(1) Spiral flow (fluidity index)
Using a spiral flow measurement mold in accordance with EMMI-1-66, the curable resin composition was molded under the above conditions, and the flow distance (cm) was measured.
(2) Hardness upon heating The curable resin composition was molded into a disk having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and was measured using a Shore D type hardness meter immediately after molding.
(3) Hardness at the time of moisture absorption When the curable resin composition was allowed to stand for 72 hours under the condition of 25 ° C./50% RH, it was measured using a Shore D type hardness tester under the condition (2).
(4) Reflow crack resistance 1
A QFP80 pin package having an outer dimension of 14 × 20 × 2.0 mm, in which a test silicon chip having a size of 8 × 10 × 0.4 mm is mounted on a 42 alloy frame using a silver paste, is formed using a curable resin composition. Molding and post-curing under the above conditions, absorbing moisture for 168 hours at 30 ° C. and 85% RH, and then performing reflow treatment at 215 ° C. for 90 seconds with a vapor phase reflow device, The presence or absence of occurrence was confirmed, and the number of crack generation packages was evaluated against the number of test packages (5).
(5) Reflow crack resistance 2
Evaluation was performed under the same conditions as in the above (4) except that moisture was absorbed for 168 hours at 85 ° C. and 60% RH.
(6) Reflow crack resistance 3
Evaluation was performed under the same conditions as in the above (4) except that moisture was absorbed for 168 hours under the conditions of 85 ° C. and 85% RH.
(7) High-temperature storage characteristics 16-pin type with partial silver plating using a test element in which an aluminum wiring with a line / space of 10 μm is formed on a silicon substrate with an outer size of 5 × 9 mm and an oxide film of 5 μm A DIP (Dual Inline Package) 42 alloy lead frame is mounted using silver paste, and a package in which the bonding pads of the element and the inner leads are connected by Au wires at 200 ° C with a thermonic wire is used with a curable resin composition. Molded and post-cured under the above conditions, stored at 200 ° C. for 500 hours and 1000 hours, then taken out, conducted a continuity test, examined the number of defective packages, and a defective package for the number of test packages (10) Evaluated by number.

Examples 1 to 61 containing a curing accelerator for a curable resin of the present invention are all excellent in fluidity, storage stability, hardness during heat, hardness during heat absorption, resistance to reflow cracking, and high temperature storage characteristics.
On the other hand, in Comparative Examples 1 to 81 that do not include the curing accelerator of the curable resin of the present invention, compared to the examples of the same resin composition, storage stability, hot hardness, hot hardness during moisture absorption, It is inferior to at least one of reflow crack resistance and high temperature storage characteristics.

1 is a ¹ H-NMR spectrum of Compound 1 obtained in an example of the present invention. It is a ¹³ C-NMR spectrum of compound 1 obtained in the example of the present invention. It is a ³¹ P-NMR spectrum of the compound 1 obtained in the Example of this invention. It is IR spectrum of the compound 1 obtained in the Example of this invention. ¹ is a ¹ H-NMR spectrum of Compound 2 obtained in an example of the present invention. It is a ¹³ C-NMR spectrum of compound 2 obtained in the example of the present invention. It is a ³¹ P-NMR spectrum of compound 2 obtained in the example of the present invention. It is IR spectrum of the compound 2 obtained in the Example of this invention. ¹ is a ¹ H-NMR spectrum of Compound 3 obtained in an example of the present invention. It is a ¹³ C-NMR spectrum of compound 3 obtained in the example of the present invention. It is a ³¹ P-NMR spectrum of compound 3 obtained in the example of the present invention. It is IR spectrum of the compound 3 obtained in the Example of this invention. It is a ^{1 H-NMR} spectrum of Compound 4 obtained in Example of the present invention. It is a ¹³ C-NMR spectrum of compound 4 obtained in the example of the present invention. It is a ³¹ P-NMR spectrum of compound 4 obtained in the example of the present invention. It is IR spectrum of the compound 4 obtained in the Example of this invention. ¹ is a ¹ H-NMR spectrum of Compound 5 obtained in an example of the present invention. It is a ¹³ C-NMR spectrum of compound 5 obtained in the example of the present invention. It is a ³¹ P-NMR spectrum of compound 5 obtained in the example of the present invention. It is IR spectrum of the compound 5 obtained in the Example of this invention. ¹ is a ¹ H-NMR spectrum of compound 6 obtained in an example of the present invention. It is a ¹³ C-NMR spectrum of compound 6 obtained in the example of the present invention. It is a ³¹ P-NMR spectrum of compound 6 obtained in the example of the present invention. It is IR spectrum of the compound 6 obtained in the Example of this invention. It is a ^{1 H-NMR} spectrum of Compound 7 obtained in Example of the present invention. It is a ¹³ C-NMR spectrum of compound 7 obtained in the example of the present invention. It is a ³¹ P-NMR spectrum of compound 7 obtained in the example of the present invention. It is IR spectrum of the compound 7 obtained in the Example of this invention.

Claims (7)

(A) a step of reacting a phosphine compound with (b) one or more halogen atoms substituted on the aromatic ring and a compound having one or more releasable proton atoms to obtain a phosphonium halide, and dehydrohalogenating the phosphonium halide. A method for producing an epoxy resin composition, comprising a step of obtaining a phosphine derivative and mixing at least the phosphine derivative, an epoxy resin, a curing agent, and an inorganic filler. (A) The method according to claim 1 epoxy resin composition according phosphine compound is a compound represented by the following general formula (I).

(Here, R ^{1 to} R ³ in the formula (I) represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, and all may be the same or different. R ¹ Two or more of ˜R ³ may be bonded to form a cyclic structure. The method for producing an epoxy resin composition according to claim 2 , wherein R ^{1 to} R ^{3 in} the general formula (I) are monovalent substituents selected from an alkyl group and an aryl group having no phenolic hydroxyl group or mercapto group. (B) The epoxy according to any one of claims 1 to 3 , wherein the compound having one or more halogen atoms substituted on the aromatic ring and one or more releasable proton atoms is a compound represented by the following general formula (II): A method for producing a resin composition.

(Here, R ^{4 to} R ⁷ in the formula (II) each represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all may be the same or different. YH is the number of carbon atoms. Represents a monovalent group having one or more releasable protons of 0 to 18. X represents a halogen atom, and two or more of R ^{4 to} R ⁷ and YH are bonded to form a cyclic structure It may be.) (B) The method for producing an epoxy resin composition according to claim 4 , wherein the compound having one or more halogen atoms substituted on the aromatic ring and one or more releasable proton atoms is a compound having a phenolic hydroxyl group. Epoxy resin is biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom containing type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, salicylaldehyde type epoxy resin, copolymerization type of naphthol and cresol The method for producing an epoxy resin composition according to any one of claims 1 to 5 , comprising at least one epoxy resin selected from an epoxy resin and an epoxidized product of an aralkyl type phenol resin. The curing agent contains at least one of aralkyl type phenol resin, dicyclopentadiene type phenol resin, salicylaldehyde type phenol resin, copolymer type resin of benzaldehyde type phenol resin and aralkyl type phenol resin, and novolac type phenol resin. The manufacturing method of the epoxy resin composition in any one of Claims 1-6 .

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