JP2008081591A - Epoxy resin composition and electronic part device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin molding material for sealing having excellent fluidity and produced by using a compound effective for suppressing the agglomeration of an inorganic filler independent of the production method of the epoxy resin composition and the pretreatment method of the inorganic filler and provide an electronic part device having an element sealed by the epoxy resin composition. <P>SOLUTION: The epoxy resin composition contains (A) an epoxy resin, (B) an inorganic filler, (C) a coupling agent and (D) a compound having nitrogen atom bonded to an aryl group in the molecule. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an epoxy resin composition suitable as a molding material, a laminate or an adhesive material, and an electronic component device including an element sealed using the epoxy resin composition.

Conventionally, epoxy resins have been widely used in the fields of molding materials, laminates and adhesives. In addition, compositions based on epoxy resins are also widely used in the field of sealing technology relating to elements of electronic components such as transistors and ICs. The reason for this is that epoxy resins are balanced in various properties such as moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts. In particular, a combination of an ortho-cresol novolac type epoxy resin and a phenol novolac curing agent has an excellent balance in the above-mentioned characteristics, and therefore has become the mainstream as a base resin for molding materials for IC sealing.
As electronic devices have become smaller, lighter, and higher performance in recent years, mounting density has been increasing, and electronic component devices have come to be made surface mount packages from conventional pin insertion types. . When a semiconductor device is attached to a wiring board, the conventional pin insertion type package is soldered from the back side of the wiring board after the pins are inserted into the wiring board, so that the package is not directly exposed to high temperatures. However, in the surface mount type package, the entire semiconductor device is processed by a solder bath, a reflow device or the like, so that it is directly exposed to the soldering temperature. As a result, when the package absorbs moisture, the moisture absorption moisture rapidly expands during soldering, causing peeling of the adhesive interface and package cracks, resulting in a decrease in package reliability during mounting.
As measures to solve the above problems, in order to reduce moisture absorption inside the semiconductor device, IC moisture-proof packaging, or a method of sufficiently drying the IC in advance before mounting on a wiring board is used. However, these methods are time-consuming and costly (see, for example, Non-Patent Document 1). As another countermeasure, there is a method of increasing the content of the filler. However, this method has a problem that although the moisture absorption inside the semiconductor device is reduced, the fluidity is drastically lowered. So far, as a method for increasing the content of the filler without impairing the fluidity of the epoxy resin molding material, a method in which a coupling agent treatment is performed on the filler in advance has been proposed (see, for example, Patent Documents 1 to 5). .)

Hitachi, Ltd. Semiconductor Division, "Surface Mounted LSI Package Mounting Technology and its Reliability Improvement" Applied Technology Publishing, November 16, 1988, pages 254-256 JP-A-8-20673 JP 2003-138099 A JP 2003-213095 A JP-A-8-81543 Japanese Patent Laid-Open No. 7-304851

However, in the method in which the coupling agent treatment is performed on the filler in advance, the filler may agglomerate and fluidity may be reduced depending on the treatment method. . Further, even in a method in which the coupling agent treatment is not performed in advance, the aggregation of the filler may be confirmed by the production method. From this point of view, there is a coupling agent that does not cause aggregation without depending on the production method and the treatment method. It has been demanded.
The present invention has been made in view of such circumstances, and by using a compound that does not easily cause aggregation of the inorganic filler without depending on the method for producing the epoxy resin composition and the pretreatment method for the inorganic filler, the fluidity can be improved. An object of the present invention is to provide an excellent epoxy resin molding material for sealing, and an electronic component device including an element sealed thereby.

  As a result of intensive studies to solve the above problems, the present inventors have obtained an epoxy resin composition having excellent fluidity by using a combination of a coupling agent and a compound having a specific nitrogen atom. After confirming that the intended purpose can be achieved, the present invention has been completed.

The present invention relates to the following.
(1) An epoxy resin composition comprising (A) an epoxy resin, (B) an inorganic filler, (C) a coupling agent, and (D) a compound having a nitrogen atom bonded to an aryl group in the molecule.
(2) (D) The epoxy resin composition according to (1), wherein the compound having a nitrogen atom bonded to an aryl group in the molecule contains at least one compound represented by the following general formula (Ia): .

（式中、Ｒ^１は、それぞれ独立して、水素原子及び炭素数１〜１８の置換又は非置換の有機基からなる群より選ばれ、全てが同一でも異なっていてもよく、Ａｒは、炭素数６〜２４の置換又は非置換のアリール基からなる群より選ばれる。また、Ｒ^１及びＡｒの中から２以上が互いに結合して環状構造を形成してもよい。）
（３） （Ｃ）カップリング剤が、シランカップリング剤である（１）又は（２）に記載のエポキシ樹脂組成物。
（４） （Ｃ）カップリング剤が、下記一般式（Ｉ−ｂ）で示される少なくとも一種類の化合物及び（Ｉ−ｂ）で示される少なくとも一種類の化合物を含有する（１）〜（３）のいずれかに記載のエポキシ樹脂組成物。

Wherein R ¹ is independently selected from the group consisting of a hydrogen atom and a substituted or unsubstituted organic group having 1 to 18 carbon atoms, all of which may be the same or different, and Ar is carbon (It is selected from the group consisting of substituted or unsubstituted aryl groups of formula 6 to 24. Also, two or more of R ¹ and Ar may be bonded to each other to form a cyclic structure.)
(3) The epoxy resin composition according to (1) or (2), wherein (C) the coupling agent is a silane coupling agent.
(4) (C) The coupling agent contains at least one compound represented by the following general formula (Ib) and at least one compound represented by (Ib) (1) to (3 The epoxy resin composition according to any one of the above.

（式中、Ｒ^２は、それぞれ独立して、水素原子及び炭素数１〜１８の置換又は非置換の有機基からなる群より選ばれ、全てが同一でも異なっていてもよく、Ｒ^３は、それぞれ独立して、水素原子及び炭素数１〜１８の置換又は非置換の有機基からなる群より選ばれ、全てが同一でも異なっていてもよく、Ｒ^４は、それぞれ独立して、水素原子及び炭素数１〜１８の置換又は非置換の有機基からなる群より選ばれ、全てが同一でも異なっていてもよく、Ｒ^２、Ｒ^３及びＲ^４から選ばれる２以上が互いに結合して環状構造を形成してもよい。）
（５） （Ｅ）硬化剤を含有する（１）〜（４）のいずれかに記載のエポキシ樹脂組成物。
（６） （Ｆ）硬化促進剤を含有する（１）〜（５）のいずれかに記載のエポキシ樹脂組成物。
（７） 上記（Ｅ）硬化剤が分子内にフェノール性水酸基を２つ以上有する化合物を含有する（１）〜（６）のいずれかに記載の樹脂組成物。
（８） （Ｂ）無機充填剤の含有量が５５〜９５重量％であることを特徴とする（１）〜（７）のいずれかに記載のエポキシ樹脂組成物。
（９） （Ｃ）カップリング剤及び（Ｄ）分子内にアリール基に結合した窒素原子を有する化合物の混合物を予め（Ｂ）無機充填剤に表面処理を施したことを特徴とする（１）〜（８）のいずれかに記載のエポキシ樹脂組成物。
（１０） （Ｄ）分子内にアリール基に結合した窒素原子を有する化合物が（Ｃ）カップリング剤の０．１〜１００ｍｏｌ％である（１）〜（９）のいずれかに記載のエポキシ樹脂組成物。
（１１） （Ａ）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、ナフトール類とフェノール類と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、からなる群より選ばれる１以上のエポキシ樹脂を含有することを特徴とする（１）〜（１０）のいずれかに記載のエポキシ樹脂組成物。
（１２） （Ｅ）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との共重合型樹脂、ノボラック型フェノール樹脂、からなる群より選ばれる１以上の樹脂を含有することを特徴する（５）〜（１１）のいずれかに記載のエポキシ樹脂組成物。
（１３） （Ｂ）無機充填剤の平均粒径が１〜５０μｍである（１）〜（１２）のいずれかに記載のエポキシ樹脂組成物。
（１４） （１）〜（１３）のいずれかに記載のエポキシ樹脂組成物を用いて封止された素子を備えることを特徴とする電子部品装置。

(Wherein, R ² are each independently selected from hydrogen atom and the group consisting of substituted or unsubstituted organic group having 1 to 18 carbon atoms, all may be the same or different, R ³ is Each independently selected from the group consisting of a hydrogen atom and a substituted or unsubstituted organic group having 1 to 18 carbon atoms, all of which may be the same or different, and each R ⁴ independently represents a hydrogen atom and It is selected from the group consisting of substituted or unsubstituted organic groups having 1 to 18 carbon atoms, all of which may be the same or different, and two or more selected from R ² , R ³ and R ⁴ are bonded to each other to form a cyclic structure May be formed.)
(5) The epoxy resin composition according to any one of (1) to (4), which contains (E) a curing agent.
(6) The epoxy resin composition according to any one of (1) to (5), which contains (F) a curing accelerator.
(7) The resin composition according to any one of (1) to (6), wherein the (E) curing agent contains a compound having two or more phenolic hydroxyl groups in the molecule.
(8) The epoxy resin composition according to any one of (1) to (7), wherein the content of the (B) inorganic filler is 55 to 95% by weight.
(9) A (B) inorganic filler is surface-treated in advance with a mixture of (C) a coupling agent and (D) a compound having a nitrogen atom bonded to an aryl group in the molecule (1) The epoxy resin composition in any one of-(8).
(10) (D) The epoxy resin according to any one of (1) to (9), wherein the compound having a nitrogen atom bonded to an aryl group in the molecule is 0.1 to 100 mol% of the (C) coupling agent. Composition.
(11) (A) The epoxy resin is a biphenyl type epoxy resin, a stilbene type epoxy resin, a diphenylmethane type epoxy resin, a sulfur atom-containing type epoxy resin, a novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a salicylaldehyde type epoxy resin, Any one of (1) to (10), comprising one or more epoxy resins selected from the group consisting of copolymerized epoxy resins of naphthols and phenols, and epoxidized products of aralkyl type phenol resins The epoxy resin composition described in 1.
(12) (E) The curing agent is 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. The epoxy resin composition according to any one of (5) to (11), which contains one or more resins selected from the group consisting of:
(13) The epoxy resin composition according to any one of (1) to (12), wherein the average particle diameter of the inorganic filler (B) is 1 to 50 μm.
(14) An electronic component device comprising an element sealed using the epoxy resin composition according to any one of (1) to (13).

  The epoxy resin composition according to the present invention is excellent in moldability such as fluidity and can be highly filled with an inorganic filler. In particular, it is possible to provide an epoxy resin composition suitable for a thin electronic component device that is required to have excellent fluidity, and its industrial value is high.

  Hereinafter, the present invention will be described in detail.

(A) Epoxy Resin In the present invention, an epoxy resin having two or more epoxy groups in one molecule can be used as the (A) epoxy resin. Such an epoxy resin is not particularly limited. For example, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F including phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, and the like. And / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene and compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde in an acidic catalyst. A novolac-type epoxy resin obtained by epoxidizing a novolac resin obtained by heating;
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 and 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 the 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 independently or may be used in combination of 2 or more type.

  Among the above epoxy resins, 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 in terms of reflow crack resistance and fluidity, Epoxy compounds of aralkyl type phenol resins such as salicylaldehyde type epoxy resins, naphthols and phenol copolymer type epoxy resins, phenol aralkyl resins, naphthol aralkyl resins, biphenyl type epoxy resins, stilbene type epoxy resins, diphenylmethane type Epoxy resin, sulfur atom-containing epoxy resin, dicyclopentadiene type epoxy resin, salicylaldehyde type epoxy resin, copolymerized epoxy resin of naphthols and phenols, Ruararukiru resins, epoxidized aralkyl phenolic resins such as a naphthol aralkyl resin is more preferable. These epoxy resins may be used alone or in combination of two or more. However, in order to exhibit these performances, it is preferable to use them in total of 30% by weight or more, more preferably 50% by weight or more, based on the total amount of epoxy resin. Specific examples of preferable epoxy resins are shown below.

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 (II) is preferable. Among the epoxy resins represented by the following general formula (II), the positions where the oxygen atoms are substituted in R ⁸ are the 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.) in which all are hydrogen atoms, 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, manufactured by Japan Epoxy Resin Co., Ltd.), which is a mixed product, is available as a commercial product.

（式（ＩＩ）中、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く、ｎは平均値であり、０〜１０の数を示す。）
スチルベン型エポキシ樹脂としては、スチルベン骨格を有するエポキシ樹脂であれば特に限定されるものではないが、下記一般式（ＩＩＩ）で示されるエポキシ樹脂が好ましい。下記一般式（ＩＩＩ）で示されるエポキシ樹脂の中でも、Ｒ^９のうち酸素原子が置換している位置を４及び４´位とした時の３，３´，５，５´位がメチル基でそれ以外が水素原子でありＲ^１０の全てが水素原子の場合と３，３´，５，５´位のうちの３つがメチル基、１つがｔｅｒｔ−ブチル基でそれ以外が水素原子でありＲ^１０の全てが水素原子の場合の混合品であるＥＳＬＶ−２１０（住友化学工業株式会社製商品名）等が市販品として入手可能である。

(In Formula (II), R ⁸ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 4 to 18 carbon atoms, all of which may be the same or different, and n is an average value. , Represents a 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 (III) is preferable. Among the epoxy resins represented by the following general formula (III), 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 other is a hydrogen atom and R ESLV-210 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), which is a mixture when all ¹⁰ are hydrogen atoms, is available as a commercial product.

（式（ＩＩＩ）中、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く、ｎは平均値であり、０〜１０の数を示す。）
ジフェニルメタン型エポキシ樹脂としては、ジフェニルメタン骨格を有するエポキシ樹脂であれば特に限定されるものではないが、下記一般式（ＩＶ）で示されるエポキシ樹脂が好ましい。下記一般式（ＩＶ）で示されるエポキシ樹脂の中でも、Ｒ^１１の全てが水素原子でありＲ^１２のうち酸素原子が置換している位置を４及び４´位とした時の３，３´，５，５´位がメチル基でそれ以外が水素原子であるＹＳＬＶ−８０ＸＹ（新日鐵化学株式会社製商品名）等が市販品として入手可能である。

(In the formula (III), R ⁹ and R ^{10 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, and n is an average value. Indicates a number of 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 (IV) is preferable. Among the epoxy resins represented by the following general formula (IV), 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.

（式（ＩＶ）中、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く、ｎは平均値であり、０〜１０の数を示す。）
硫黄原子含有型エポキシ樹脂としては、硫黄原子を含有するエポキシ樹脂であれば特に限定されるものではないが、例えば下記一般式（Ｖ）で示されるエポキシ樹脂が挙げられる。下記一般式（Ｖ）で示されるエポキシ樹脂の中でも、Ｒ^１３のうち酸素原子が置換している位置を４及び４´位とした時の３，３´位がｔｅｒｔ−ブチル基で６，６´位がメチル基でそれ以外が水素原子であるＹＳＬＶ−１２０ＴＥ（新日鐵化学株式会社製商品名）等が市販品として入手可能である。

(In the formula (IV), R ¹¹ and R ¹² represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, and n is an average value. Indicates a number of 10.)
Although it will not specifically limit as a sulfur atom containing type epoxy resin if it is an epoxy resin containing a sulfur atom, For example, the epoxy resin shown by the following general formula (V) is mentioned. Among the epoxy resins represented by the following general formula (V), the tert-butyl group is the tert-butyl group when the positions where the oxygen atom substitution positions in R ¹³ are the 4 and 4 'positions, and 6, 6 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.

（式（Ｖ）中、Ｒ^１３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く、ｎは平均値であり、０〜１０の数を示す。）
ノボラック型エポキシ樹脂としては、ノボラック型フェノール樹脂をエポキシ化したエポキシ樹脂であれば、特に限定されるものではないが、フェノールノボラック、クレゾールノボラック、ナフトールノボラック等のノボラック型フェノール樹脂をグリリシジルエーテル化等の手法を用いてエポキシ化したエポキシ樹脂が好ましく、例えば下記一般式（ＶＩ）で示されるエポキシ樹脂がより好ましい。下記一般式（ＶＩ）で示されるエポキシ樹脂の中でも、Ｒ^１４の全てが水素原子でありＲ^１５がメチル基でｉ＝１であるＥＳＣＮ−１９０、ＥＳＣＮ−１９５（住友化学株式会社製商品名）等が市販品として入手可能である。

(In the formula (V), R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, n is an average value, and a number of 0 to 10 Is shown.)
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 or the like is glycidyl etherified. Epoxy resins epoxidized using the above method are preferred, and for example, epoxy resins represented by the following general formula (VI) are more preferred. Among the epoxy resins represented by the following general formula (VI), 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.

（式（ＶＩ）中、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く、ｉは０〜３の整数、ｎは平均値であり、０〜１０の数を示す。）
ジシクロペンタジエン型エポキシ樹脂としては、ジシクロペンタジエン骨格を有する化合物を原料としてエポキシ化したエポキシ樹脂であれば特に限定されるものではないが、下記一般式（ＶＩＩ）で示されるエポキシ樹脂が好ましい。下記一般式（ＶＩＩ）で示されるエポキシ樹脂の中でも、ｉ＝０であるＨＰ−７２００（大日本インキ化学株式会社製商品名）等が市販品として入手可能である。

(In the formula (VI), R ¹⁴ and R ¹⁵ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, and i is an integer of 0 to 3, n Is an average value and represents a 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 (VII) is preferable. Among epoxy resins represented by the following general formula (VII), HP-7200 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) where i = 0 is available as a commercial product.

（式（ＶＩＩ）中、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く、ｉは０〜３の整数、ｎは平均値であり、０〜１０の数を示す。）
サリチルアルデヒド型エポキシ樹脂としては、サリチルアルデヒド骨格を持つ化合物を原料とするエポキシ樹脂であれば特に制限はないが、サリチルアルデヒド骨格を持つ化合物とフェノール性水酸基を有する化合物とのノボラック型フェノール樹脂等のサリチルアルデヒド型フェノール樹脂をグリシジルエーテル化したエポキシ樹脂等のサリチルアルデヒド型エポキシ樹脂が好ましく、下記一般式（ＶＩＩＩ）で示されるエポキシ樹脂がより好ましい。下記一般式（ＶＩＩＩ）で示されるエポキシ樹脂の中でも、ｉ＝０、ｋ＝０である１０３２Ｈ６０（ジャパンエポキシレジン株式会社製商品名）、ＥＰＰＮ−５０２Ｈ（日本化薬株式会社製商品名）等が市販品として入手可能である。

(In the formula (VII), R ¹⁶ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, and n is an average value. And represents a 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 novolak type phenol resin of a compound having a salicylaldehyde skeleton and a compound having a phenolic hydroxyl group, etc. A salicylaldehyde type epoxy resin such as an epoxy resin obtained by glycidyl etherification of a salicylaldehyde type phenol resin is preferable, and an epoxy resin represented by the following general formula (VIII) is more preferable. Among epoxy resins represented by the following general formula (VIII), 1032H60 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-502H (trade name, manufactured by Nippon Kayaku Co., Ltd.), etc., where i = 0 and k = 0. It is available as a commercial product.

（式（ＶＩＩＩ）中、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く、ｉは０〜３の整数、ｋは０〜４の整数、ｎは平均値であり、０〜１０の数を示す。）
ナフトール類とフェノール類との共重合型エポキシ樹脂としては、ナフトール骨格を有する化合物及びフェノール骨格を有する化合物を原料とするエポキシ樹脂であれば、特に限定されるものではないが、ナフトール骨格を有する化合物及びフェノール骨格を有する化合物を用いたノボラック型フェノール樹脂をグリシジルエーテル化したものが好ましく、下記一般式（ＩＸ）で示されるエポキシ樹脂がより好ましい。下記一般式（ＩＸ）で示されるエポキシ樹脂の中でも、Ｒ^２１がメチル基でｉ＝１であり、ｊ＝０、ｋ＝０であるＮＣ−７３００（日本化薬株式会社製商品名）等が市販品として入手可能である。

(In the formula (VIII), R ¹⁷ and R ¹⁸ 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 an integer of 0 to 3, k Is an integer from 0 to 4, n is an average value, and represents a number from 0 to 10.)
The copolymer type epoxy resin of naphthols and phenols is not particularly limited as long as it is an epoxy resin made from a compound having a naphthol skeleton and a compound having a phenol skeleton, but a compound having a naphthol skeleton And a novolak-type phenol resin using a compound having a phenol skeleton, which is glycidyl etherified, and more preferably an epoxy resin represented by the following general formula (IX). Among the epoxy resins represented by the following general formula (IX), NC-7300 (trade name, manufactured by Nippon Kayaku Co., Ltd.) in which R ²¹ is a methyl group, i = 1, j = 0, and k = 0, etc. It is available as a commercial product.

（式（ＩＸ）中、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く、ｉは０〜３の整数、ｊは０〜２の整数、ｋは０〜４の整数を示し、ｐは平均値で０〜１の数を示し、ｌ、ｍはそれぞれ平均値で０〜１１の数であり（ｌ＋ｍ）は１〜１１の数を示す。）
上記一般式（ＩＸ）で示されるエポキシ樹脂としては、ｌ個の構成単位及びｍ個の構成単位をランダムに含むランダム共重合体、交互に含む交互共重合体、規則的に含む共重合体、ブロック状に含むブロック共重合体が挙げられ、これらのいずれか１種を単独で用いても、２種以上を組み合わせて用いてもよい。

(In the formula (IX), R ^{19 to} R ²¹ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 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, l and m are average values of 0 to 11 and (l + m) is 1 Indicates the number of ~ 11.)
As the epoxy resin represented by the general formula (IX), a random copolymer containing 1 structural unit and m structural units randomly, an alternating copolymer containing alternately, a copolymer containing regularly, 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.

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. For example, a phenol resin synthesized from phenols such as phenol and cresol and / or naphthols such as naphthol and dimethylnaphthol and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, and derivatives thereof is preferably glycidyl ether, Epoxy resins represented by the following general formulas (X) and (XI) are more preferable. Among epoxy resins represented by the following general formula (X), i = 0, R ⁴⁰ is a hydrogen atom, NC-3000S (trade name, manufactured by Nippon Kayaku Co., Ltd.), i = 0, R ⁴⁰ is a hydrogen atom. CER-3000 (trade name, manufactured by Nippon Kayaku Co., Ltd.), in which an epoxy resin and an epoxy resin in which all R ^{8 in} the general formula (II) are hydrogen atoms are mixed at a weight ratio of 80:20, is represented by the following general formula (XI). Among these epoxy resins, ESN-175 (trade name of Nippon Steel Chemical Co., Ltd.) having i = 0, j = 0, and k = 0 is available as a commercial product.

（式（Ｘ）及び（ＸＩ）において、Ｒ^３７〜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く、ｉは０〜３の整数、ｊは０〜２の整数、ｋは０〜４の整数を示す。）
上記一般式（ＩＩ）〜（ＸＩ）中のＲ^８〜Ｒ^２１及びＲ^３７〜Ｒ^４１について、「それぞれ全てが同一でも異なっていてもよい」とは、例えば、式（ＩＩ）中の８〜８８個のＲ^８の全てが同一でも異なっていてもよいことを意味している。他のＲ^９〜Ｒ^２１及びＲ^３７〜Ｒ^４１についても、式中に含まれるそれぞれの個数について全てが同一でも異なっていてもよいことを意味している。また、Ｒ^８〜Ｒ^２１及びＲ^３７〜Ｒ^４１はそれぞれが同一でも異なっていてもよい。例えば、Ｒ^９とＲ^１０の全てについて同一でも異なっていてもよい。

(In the formulas (X) and (XI), R ^{37 to} R ^{41 each} represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different, and i is 0 to 3). And j represents an integer of 0 to 2, and k represents an integer of 0 to 4.)
Regarding R ^{8 to} R ²¹ and R ^{37 to} R ^{41 in the} general formulas (II) to (XI), “all may be the same or different” means, for example, 8 to 8 in the formula (II) It means that all 88 R ⁸ may be the same or different. It means that all of R ^{9 to} R ²¹ and R ^{37 to} R ⁴¹ may be the same or different with respect to the respective numbers included in the formula. R ^{8 to} R ²¹ and R ^{37 to} R ⁴¹ 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.

  N in the above general formulas (II) to (XI) needs to be in the range of 0 to 10, and if it exceeds 10, the melt viscosity of the component (A) becomes high, so the melting of the epoxy resin composition Viscosity at the time of molding is also increased, 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.

  As mentioned above, although the specific example of the preferable epoxy resin which can be used for the epoxy resin composition by this invention was demonstrated along the said general formula (II)-(XI), as a more specific preferable epoxy resin, reflow crack resistance From the viewpoint of the above, 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl is mentioned, and from the viewpoint of moldability and heat resistance, 4,4 And '-bis (2,3-epoxypropoxy) -biphenyl.

(B) Inorganic filler The (B) inorganic filler used in the present invention may be one generally used in a resin composition and is not particularly limited. 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, Examples include talc, clay, mica and other fine powders, or beads obtained by spheroidizing these. 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 them, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and crystalline silica, alumina, silicon nitride, aluminum nitride, and boron nitride are preferable from the viewpoint of high thermal conductivity. Among inorganic fillers having a flame-retardant effect, composite metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and composite hydroxide of magnesium and zinc are preferable from the viewpoint of reliability. These inorganic fillers may be used alone or in combination of two or more.

  (B) Although there will be no restriction | limiting in particular if the compounding quantity of an inorganic filler will acquire the effect of this invention, It is preferable that it is the range of 55-90 volume% with respect to an epoxy 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 55% by volume, these properties tend to be insufficiently improved. If it exceeds 90% by volume, the viscosity of the epoxy resin composition is increased, the fluidity is lowered, and molding tends to be difficult.

  Moreover, 1-50 micrometers is preferable and, as for the average particle diameter of (B) inorganic filler, 10-30 micrometers is more preferable. If it is less than 1 μm, the viscosity of the epoxy resin composition tends 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 the (B) inorganic filler is preferably spherical rather than square, and the particle size distribution of the (B) inorganic filler is preferably distributed over a wide range. For example, when blending 75% by volume or more of the inorganic filler, it is preferable that 70% by weight or more of the filler be spherical particles and distributed over a wide range of 0.1 to 80 μm. Since such an inorganic filler can easily have a close-packed structure, even if the amount is increased, an increase in the viscosity of the material is small, and an epoxy resin composition excellent in fluidity can be obtained.

  The epoxy resin composition according to the present invention must contain (C) a coupling agent.

  As the coupling agent (C), vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-anilinopropyltrimethoxy Silane, γ-anilinopropylmethyldimethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (β- Amino Eth ) Aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzyl) Aminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, triphenylsilanol, trimethylsilanol, triethylsilanol, tert-butyl Dimethylsilanol, (3-glycidoxypropyl) dimethylethoxysilane, triphenylethoxysilane, phenyldimethylethoxysilane, diphenyl Rumethylethoxysilane, (3-acryloxypropyl) dimethylmethoxysilane, 3-aminoethylaminomethylbenzyloxydimethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldiisopropylethoxysilane, tert-butyldiphenylmethoxysilane, Chloromethyldimethylethoxysilane, chloromethyldimethylisopropoxysilane, chloropropyldimethylmethoxysilane, dimethylethoxysilane, diphenylphosphinoethyldimethylethoxysilane, methacryloxymethyldimethylethoxysilane, dimethylethoxyethynylsilane, methoxydimethylvinylsilane, n-octadecyl Dimethylmethoxysilane, triethylethoxysilane, trimethylethoxysilane, trimethylmeth Silane coupling agents such as silane, vinyldiphenylethoxysilane, vinylphenylmethylmethoxysilane, benzyldimethylethoxysilane, isopropyltriisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-aminoethyl-aminoethyl) ) Titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyro) Phosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate , Titanate coupling agents such as isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate, etc. These may be used alone or in combination of two or more. From the viewpoint of easily exhibiting the effects of the present invention, it is preferable to use a silane coupling agent, and among these, a compound represented by the following general formula (Ib) is more preferable.

（式中、Ｒ^２は、それぞれ独立して、水素原子及び炭素数１〜１８の置換又は非置換の有機基からなる群より選ばれ、全てが同一でも異なっていてもよく、Ｒ^３は、それぞれ独立して、水素原子及び炭素数１〜１８の置換又は非置換の有機基からなる群より選ばれ、全てが同一でも異なっていてもよく、Ｒ^４は、それぞれ独立して、水素原子及び炭素数１〜１８の置換又は非置換の有機基からなる群より選ばれ、全てが同一でも異なっていてもよく、Ｒ^２、Ｒ^３及びＲ^４から選ばれる２以上が互いに結合して環状構造を形成してもよい。）

(Wherein, R ² are each independently selected from hydrogen atom and the group consisting of substituted or unsubstituted organic group having 1 to 18 carbon atoms, all may be the same or different, R ³ is Each independently selected from the group consisting of a hydrogen atom and a substituted or unsubstituted organic group having 1 to 18 carbon atoms, all of which may be the same or different, and each R ⁴ independently represents a hydrogen atom and It is selected from the group consisting of substituted or unsubstituted organic groups having 1 to 18 carbon atoms, all of which may be the same or different, and two or more selected from R ² , R ³ and R ⁴ are bonded to each other to form a cyclic structure May be formed.)

The term “substituted or unsubstituted organic group having 1 to 18 carbon atoms” described as R ^{2 to} R ^{4 in the} general formula (Ib) has 1 to 18 carbon atoms and may be substituted. It means an aliphatic hydrocarbon group and an aromatic hydrocarbon group which may be unsubstituted.

  More specifically, examples of the substituted or unsubstituted aliphatic hydrocarbon group 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 pentyl. Group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, vinyl group and other aliphatic hydrocarbon groups, and substituted with alkyl group, alkoxy group, aryl group, hydroxyl group, amino group, halogen, etc. Things.

  The substituted or unsubstituted aliphatic hydrocarbon group also includes a substituted or unsubstituted alicyclic hydrocarbon group. Examples of the substituted or unsubstituted alicyclic hydrocarbon group 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, an aryl group, and an aryloxy group. And those substituted with a group, a hydroxyl group, an amino group, a glycidyl group, a halogen and the like.

  Examples of the substituted or unsubstituted aromatic hydrocarbon group include aryl groups such as a phenyl group and a tolyl group, and alkyl group-substituted aryl groups such as a dimethylphenyl group, an ethylphenyl group, a butylphenyl group, and a tert-butylphenyl group. Alkoxy group-substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group, aminophenyl group, N-methylaminophenyl group, N-butylaminophenyl group, N, N-dibutylamino Examples thereof include amino group-substituted aryl groups such as phenyl group, N, N-dimethylaminophenyl group, etc., which are further substituted with alkyl group, alkoxy group, aryl group, aryloxy group, amino group, glycidyl group, halogen, etc. The thing etc. which were done may be sufficient.

R ^{2 in the} general formula (Ib) is not particularly limited, but is a hydrogen atom, an alkyl group, an aryl group, a glycidoxy group-substituted alkyl group or aryl group, an amino group-substituted alkyl group or aryl. Group, a hydroxyl-substituted alkyl group or an aryl group is preferred. Among these, from the viewpoint of easy availability of raw materials, a methyl group, an ethyl group, a phenyl group, a tolyl group, and the like are more preferable.

R ^{3 in the} general formula (Ib) is not particularly limited, but is a hydrogen atom, alkyl group, aryl group, glycidoxy group-substituted alkyl group or aryl group, amino group-substituted alkyl group or aryl. Group, a hydroxyl-substituted alkyl group or an aryl group is preferred. Among these, from the viewpoint of easy availability of raw materials, a methyl group, an ethyl group, an isopropyl group, a 2-methoxyethoxy group, a tert-butyl group, a phenoxy group, and the like are more preferable.

R ^{4 in the} general formula (Ib) is not particularly limited, but is a hydrogen atom, alkyl group, aryl group, glycidoxy group-substituted alkyl group or aryl group, amino group-substituted alkyl group or aryl. Group, a hydroxyl-substituted alkyl group or an aryl group is preferred. Above all, from the viewpoint of easy availability of raw materials, methyl group, ethyl group, propyl group, butyl group, octyl group, decyl group, cyclohexyl group, phenyl group, glycididoxypropyl group, aminopropyl group, N-phenylamino A propyl group, a mercaptopropyl group, an aminoethylaminopropyl group, a vinyl group, an epoxycyclohexylethyl group and the like are more preferable.

  The compounds represented by the general formula (Ib) are not limited to these, but vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- Anilinopropyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) amino Propyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) ) -Γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, triphenylsilanol, trimethylsilanol, triethylsilanol, tert-butyldimethylsilanol, (3- Glycidoxypropyl) dimethylethoxysilane, triphenylethoxysilane, phenyldimethylethoxysilane, diphenylmethylethoxysilane, (3- (Acryloxypropyl) dimethylmethoxysilane, 3-aminoethylaminomethylbenzyloxydimethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldiisopropylethoxysilane, tert-butyldiphenylmethoxysilane, chloromethyldimethylethoxysilane, chloromethyl Dimethylisopropoxysilane, chloropropyldimethylmethoxysilane, dimethylethoxysilane, diphenylphosphinoethyldimethylethoxysilane, methacryloxymethyldimethylethoxysilane, dimethylethoxyethynylsilane, methoxydimethylvinylsilane, n-octadecyldimethylmethoxysilane, triethylethoxysilane, Trimethylethoxysilane, trimethylmethoxysilane, vinyl diphenyl ether Kishishiran, vinyl phenylmethyl silane, benzyl dimethyl silane and the like, may be used in combination of two or more be used in combination of them alone. Among them, it is more preferable to use a compound having an epoxy group from the viewpoint of easily exhibiting the effect of the present invention.

  (C) It is preferable that the whole compounding quantity of a coupling agent is 0.05 to 5 weight% with respect to (B) inorganic filler, and 0.1 to 2.5 weight% is more preferable. If it is less than 0.05% by weight, the effect of improving 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.

  (C) There is no restriction | limiting in particular as a compounding method of a coupling agent, For example, the integral blend method added to other structural materials as it is, The dry processing method mixed with other structural materials previously mixed with a filler. , A wet processing method, and a master batch method in which it is mixed with an epoxy resin or / and a curing agent before mixing with other constituent materials (hereinafter, dry-type mixing with a filler and then mixing with other constituent materials) Treatment methods and wet treatment methods are referred to as “pretreatment methods”.) If the effect of the present invention is exhibited, the blending method is not limited, but from the viewpoint that the effect of the present invention is efficiently exhibited, the pretreatment method is preferable, and the effect of the present invention is exhibited with a simple manufacturing method. From the viewpoint of being integrated, the integral blend method is preferable. Moreover, you may combine multiple said compounding methods. In that case, it is preferable from the viewpoint of balance of properties to use a part in the pretreatment method and a part in the integral blend method.

  The epoxy resin composition according to the present invention must include (D) a compound having a nitrogen atom bonded to an aryl group in the molecule.

  (D) It is preferable that the compound which has the nitrogen atom couple | bonded with the aryl group in a molecule | numerator is a compound shown by the following general formula (Ia).

（式中、Ｒ^１は、それぞれ独立して、水素原子及び炭素数１〜１８の置換又は非置換の有機基からなる群より選ばれ、全てが同一でも異なっていてもよく、
Ａｒは、炭素数６〜２４の置換又は非置換のアリール基からなる群より選ばれる。
また、Ｒ^１及びＡｒの中から２以上が互いに結合して環状構造を形成してもよい。）

Wherein R ¹ is independently selected from the group consisting of a hydrogen atom and a substituted or unsubstituted organic group having 1 to 18 carbon atoms, all of which may be the same or different,
Ar is selected from the group consisting of substituted or unsubstituted aryl groups having 6 to 24 carbon atoms.
Two or more of R ¹ and Ar may be bonded to each other to form a cyclic structure. )

The term “substituted or unsubstituted organic group having 1 to 18 carbon atoms” described as R ^{1 in the} general formula (Ia) has 1 to 18 carbon atoms and is substituted or unsubstituted. It means an aliphatic hydrocarbon group and an aromatic hydrocarbon group which may be present.

  More specifically, examples of the substituted or unsubstituted aliphatic hydrocarbon group 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 pentyl. Group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, vinyl group and other aliphatic hydrocarbon groups, and substituted with alkyl group, alkoxy group, aryl group, hydroxyl group, amino group, halogen, etc. Things.

  The substituted or unsubstituted aliphatic hydrocarbon group also includes a substituted or unsubstituted alicyclic hydrocarbon group. Examples of the substituted or unsubstituted alicyclic hydrocarbon group 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, an aryl group, and an aryloxy group. And those substituted with a group, a hydroxyl group, an amino group, a glycidyl group, a halogen and the like.

  Examples of the substituted or unsubstituted aromatic hydrocarbon group include aryl groups such as a phenyl group and a tolyl group, and alkyl group-substituted aryl groups such as a dimethylphenyl group, an ethylphenyl group, a butylphenyl group, and a tert-butylphenyl group. Alkoxy group-substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group, aminophenyl group, N-methylaminophenyl group, N-butylaminophenyl group, N, N-dibutylamino Examples thereof include amino group-substituted aryl groups such as phenyl group, N, N-dimethylaminophenyl group, etc., which are further substituted with alkyl group, alkoxy group, aryl group, aryloxy group, amino group, glycidyl group, halogen, etc. The thing etc. which were done may be sufficient.

  The term “substituted or unsubstituted aryl group having 6 to 24 carbon atoms” described as Ar in the above general formula (Ia) has 6 to 24 carbon atoms and may be substituted or unsubstituted. Means an aromatic hydrocarbon group which may be Examples of the aromatic hydrocarbon group include the groups described above.

  Examples of the substituted or unsubstituted aromatic hydrocarbon group include aryl groups such as a phenyl group and a tolyl group, and alkyl group-substituted aryl groups such as a dimethylphenyl group, an ethylphenyl group, a butylphenyl group, and a tert-butylphenyl group. Alkoxy group-substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group, aminophenyl group, N-methylaminophenyl group, N-butylaminophenyl group, N, N-dibutylamino Examples thereof include amino group-substituted aryl groups such as phenyl group, N, N-dimethylaminophenyl group, etc., which are further substituted with alkyl group, alkoxy group, aryl group, aryloxy group, amino group, glycidyl group, halogen, etc. The thing etc. which were done may be sufficient.

Further, the term “two or more of R ¹ and Ar may be bonded to each other to form a cyclic structure” described as R ¹ and Ar in the general formula (Ia) means that R ¹ and Ar It means a case where 2 or 3 groups selected from the inside are bonded to form a divalent or trivalent organic group as a whole. For example, alkylene groups such as ethylene, propylene, butylene, pentylene and hexylene, which can be bonded to Si atoms to form a cyclic structure, alkenyl groups such as ethylenyl, propylenyl and butyrenyl groups, aralkylene groups such as methylenephenylene groups, phenylene and naphthylene , Arylene groups such as anthracenylene, these alkylene groups, alkenyl groups, aralkylene groups, oxy groups or dioxy groups of arylene groups, which are further alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, It may be substituted with halogen or the like.

R ^{1 in the} general formula (Ia) is not particularly limited, but is hydrogen atom, alkyl group, aryl group, alkyl group or aryl group substituted with glycidoxy group, amino group substituted alkyl group or aryl Group, a hydroxyl-substituted alkyl group or an aryl group is preferred. Among these, from the viewpoint of easy availability of raw materials, a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a tolyl group, a glycidyl group and the like are more preferable.

  Ar in the general formula (Ia) is not particularly limited, and examples thereof include aryl groups such as phenyl group and tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, and tert-butylphenyl. Alkyl group-substituted aryl group such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group, glycidoxyphenyl group and other alkoxy group-substituted aryl groups, aminophenyl group, N-alkylaminophenyl group N, N-dialkylaminophenyl group, N-diglycidylaminophenyl group, N, N-diglycidylaminophenyl group, and 4- (N, N-diglycidylamino) -3-ethylphenylmethyl group are preferable. Among these, from the viewpoint of easy availability of raw materials, a phenyl group, an ethylphenyl group, a glycidoxyphenyl group, and a 4- (N, N-diglycidylamino) -3-ethylphenylmethyl group are more preferable.

Examples of the compound represented by the general formula (Ia) include, but are not limited to, aniline, N-methylaniline, N-butylaniline, N, N-dimethylaniline, N, N-dibutylaniline. 2-isopropylaniline, 2,6-dimethylaniline, N-allylaniline, N-allyl-N-methylaniline, benzylaniline, N-benzyl-N-ethylaniline, N-benzyl-p-methoxyaniline, m- (Benzyloxy) aniline, 4,4 ′-(p-biphenylenedioxy) dianiline, N, N-bis (2-chloroethyl) aniline, bromoaniline, chloroaniline, 2-bromo-N, N-dimethylaniline, 4 -Bromo-2,6-dimethylaniline, 4-bromo-N, N-dimethylaniline, p-butoxyaniline P-butylaniline, 4-butyl-2-methylaniline, 3-chloro-4-methylaniline, 3-chloro-N-methylaniline, 4-chloro-N-methylaniline, N-cyclohexylaniline, N, N -Dibenzylaniline, N, N-diethylaniline, 2,6-diethylaniline, dimethoxyaniline, 2,3-dimethylaniline, 2,5-dimethylaniline, N, N-di-n-propylaniline, N-ethyl Aniline, 2-ethylaniline, 4-fluoro-N-methylaniline, N-isopropylaniline, 4,4 ′-[isopropylidenebis (p-phenyleneoxy)] dianiline, 2-methoxy-5-methylaniline, 2- Methyl-N-methylaniline, 4- (methylthio) aniline, 4-phenoxyaniline, 4,4 ′-(m- Enedioxy) dianiline, o- (phenylsulfonyl) aniline, o- (phenylthio) aniline, N-propylaniline, 3,3 ′-[sulfonylbis (p-phenyleneoxy)] dianiline, 4,4 ′-[sulfonylbis ( p-phenyleneoxy)] dianiline, 2,2′-thiodianiline, 4,4′-thiodianiline, 2,4,6-tri-tert-butylaniline, 3,4,5-trimethoxyaniline, 2,4,6 -Trimethylaniline, N-benzylaniline, 3-benzylaniline, 4-tert-butylaniline, 4,4'-methylenebis (2-chloroaniline), 4,4'-methylenebis (N, N-dimethylaniline), 4 , 4'-methylenebis (2-ethyl-6-methylaniline), 3,4- (methylenedioxy) aniline p-aminodiphenylamine, 2,4-diaminodiphenylamine, 2,6-dichlorodiphenylamine, 3,3′-dimethyldiphenylamine, p, p′-dioctyldiphenylamine, diphenylamine, 3-methoxydiphenylamine, N-methyldiphenylamine, 3-methyl Diphenylamine, triphenylamine, 4,4′-dimethoxydiphenylamine, 3-hydroxydiphenylamine, 4-hydroxydiphenylamine, 4,4′-diaminodiphenylmethane, phenylenediamine, 4,4′-diaminodiphenylsulfone, diethyltoluenediamine, diaminodiethyl Diphenylmethane, N, N-diglycidylaniline, N, N-diglycidyltoluidine, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphe Lumethane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylsulfone, N, N-diglycidyl-4-glycidoxyaniline, N, N-diglycidyl-3-glycidoxyaniline , N, N-diglycidyl-2-glycidoxyaniline, N, N-diglycidyl-2-ethyl-4-glycidoxyaniline, and the like, but are not limited thereto, and are known by the formula (Ia) These compounds can be used.
Among them, aniline, N-methylaniline, N-butylaniline, N, N-dimethylaniline, N, N-dibutylaniline, 2-isopropylaniline, 2,6-dimethylaniline, N-allylaniline, N-allyl-N -Methylaniline, benzylaniline, N-benzyl-N-ethylaniline, N-benzyl-p-methoxyaniline, m- (benzyloxy) aniline, 4,4 '-(p-biphenylenedioxy) dianiline, N, N -Bis (2-chloroethyl) aniline, bromoaniline, chloroaniline, 2-bromo-N, N-dimethylaniline, 4-bromo-2,6-dimethylaniline, 4-bromo-N, N-dimethylaniline, p- Butoxyaniline, p-butylaniline, 4-butyl-2-methylaniline, 3-chloro-4-methyl Aniline, 3-chloro-N-methylaniline, 4-chloro-N-methylaniline, N-cyclohexylaniline, N, N-dibenzylaniline, N, N-diethylaniline, 2,6-diethylaniline, dimethoxyaniline, 2,3-dimethylaniline, 2,5-dimethylaniline, N, N-di-n-propylaniline, N-ethylaniline, 2-ethylaniline, 4-fluoro-N-methylaniline, N-isopropylaniline, 4 , 4 ′-[isopropylidenebis (p-phenyleneoxy)] dianiline, 2-methoxy-5-methylaniline, 2-methyl-N-methylaniline, 4- (methylthio) aniline, 4-phenoxyaniline, 4,4 '-(M-phenylenedioxy) dianiline, o- (phenylsulfonyl) aniline, o- (fluoro Nylthio) aniline, N-propylaniline, 3,3 ′-[sulfonylbis (p-phenyleneoxy)] dianiline, 4,4 ′-[sulfonylbis (p-phenyleneoxy)] dianiline, 2,2′-thiodianiline, 4,4′-thiodianiline, 2,4,6-tri-tert-butylaniline, 3,4,5-trimethoxyaniline, 2,4,6-trimethylaniline, N-benzylaniline, 3-benzylaniline, 4 -Tert-butylaniline, 4,4'-methylenebis (2-chloroaniline), 4,4'-methylenebis (N, N-dimethylaniline), 4,4'-methylenebis (2-ethyl-6-methylaniline) 3,4- (methylenedioxy) aniline, p-aminodiphenylamine, 2,4-diaminodiphenylamine, 4,4′-dia Nodiphenylmethane, phenylenediamine, 4,4'-diaminodiphenylsulfone, diethyltoluenediamine, diaminodiethyldiphenylmethane, N, N-diglycidylaniline, N, N-diglycidyltoluidine, N, N, N ', N'-tetra Glycidyl-4,4′-diaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylsulfone, N, N-diglycidyl-4-glycidoxyaniline, N, N -Diglycidyl-3-glycidoxyaniline, N, N-diglycidyl-2-glycidoxyaniline, N, N-diglycidyl-2-ethyl-4-glycidoxyaniline and the like in the above general formula (Ia) Of the compounds shown, compounds in which two R ^{1 s} are not both aromatic hydrocarbon groups are preferred.

  In the present invention, (D) the compounding amount of the compound having a nitrogen atom bonded to an aryl group in the molecule is not limited as long as the effect of the present invention is exhibited, but (C) coupling It is preferable that it is 0.1-100 mol% with respect to an agent, It is more preferable that it is 0.5-50 mol%, It is further more preferable that it is 1.0-30 mol%. When the amount is 0.1 mol% or less, the effect of the present invention tends not to be sufficiently exhibited, and when the amount is 100 mol% or more, the reliability tends to decrease.

(D) Although there is no restriction | limiting in particular as a compounding method of the compound which has the nitrogen atom couple | bonded with the aryl group in a molecule | numerator, From a viewpoint that the effect of this invention is easy to be exhibited, it mixes with (C) coupling agent beforehand. And preferably used. (C) When mixed with a coupling agent in advance, the mixed components (C) and (D) can be blended with the component (B) by an integral blend method, a pretreatment method, or a master batch method. If the effect of the present invention is exhibited, the blending method is not limited, but from the viewpoint that the effect of the present invention is efficiently exhibited, the pretreatment method is preferable, and the effect of the present invention is exhibited with a simple manufacturing method. From the viewpoint of being integrated, the integral blend method is preferable. Moreover, you may combine multiple said compounding methods. In that case, the balance of characteristics is to use the component (C) mixed with the component (D) in the pretreatment method and the component (C) mixed or not mixed with the component (D) in the integral blend method. From the viewpoint of
When the pretreatment method is used, the mixing method is not particularly limited, but it is preferable that the mixing method is more uniform. The mixing method is not limited to these, but after mixing the coupling agent, remove the lumps with a sieve etc. so as to be uniform, and then mix, after mixing the coupling agent, super mixer, Henschel mixer For example, a method of mechanically mixing to make uniform.

(E) Hardener (E) A hardener can be used for the epoxy resin composition by this invention. The usable curing agent is not particularly limited as long as it is a compound capable of curing (A) an epoxy resin. For example, phenol compounds such as phenol resin, amine compounds such as diamine and polyamine, phthalic anhydride, trimellitic anhydride, organic anhydrides such as pyromellitic anhydride, carboxylic acid compounds such as dicarboxylic acid, polycarboxylic acid, etc. These compounds may be used alone or in combination of two or more. Among these, a phenol compound is preferable from the viewpoint that the effects of the present invention are sufficiently exhibited.

(E) There is no restriction | limiting in particular as a phenolic compound which can be used as a hardening | curing agent. For example, it may be a phenol compound having two or more phenolic hydroxyl groups in one molecule generally used as a curing agent, and in one molecule such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol. A compound having two phenolic hydroxyl groups;
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 the above-mentioned phenol compounds, 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. Aralkyl type phenol resins, dicyclopentadiene type phenol resins, salicylaldehyde type phenol resins, and benzaldehyde type and aralkyl type copolymer type phenol resins are more preferable. These phenolic resins may be used alone or in combination of two or more, but in order to exert their performance, they are 30 in total with respect to the total amount of phenolic resin. It is preferable to use at least 50% by weight, and more preferably at least 50% by weight.

  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 (XII) to (XIV) are preferred.

（式（ＸＩＩ）〜（ＸＩＶ）において、Ｒ^２２〜Ｒ^２８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く、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の数を示す。）
上記一般式（ＸＩＩ）で示されるフェノール樹脂の中でも、ｉ＝０、Ｒ^２３が全て水素原子であるＭＥＨ−７８５１（明和化成株式会社商品名）等が市販品として入手可能である。

(In the formulas (XII) to (XIV), R ^{22 to} R ^{28 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 i is 0 to 3 , K is an integer of 0 to 4, j is an integer of 0 to 2, n is an average value, and represents a number of 0 to 10.)
Among the phenol resins represented by the general formula (XII), MEH-7851 (trade name of Meiwa Kasei Co., Ltd.) in which i = 0 and R ²³ are all hydrogen atoms is commercially available.

  Among the phenol resins represented by the above general formula (XIII), XL = 0, i = 0, k = 0, XLC (trade name, manufactured by Mitsui Chemicals), MEH-7800 (trade name, Meiwa Kasei Co., Ltd.), etc. Is commercially available.

Among the phenol resins represented by the above general formula (XIV), SN-170 (trade name of Nippon Steel Chemical Co., Ltd.) in which j = 0, R ²⁷ k = 0, and R ²⁸ k = 0 is a commercial product. Is available as

  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 (XV) is preferable. Among the phenol resins represented by the following general formula (XV), DPP (trade name, manufactured by Nippon Petrochemical Co., Ltd.) where i = 0 is available as a commercial product.

（式（ＸＶ）中、Ｒ^２９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く、ｉは０〜３の整数、ｎは平均値であり、０〜１０の数を示す。）
サリチルアルデヒド型フェノール樹脂としては、サリチルアルデヒド骨格を有する化合物を原料として用いたフェノール樹脂であれば特に限定されるものではないが、下記一般式（ＸＶＩ）で示されるフェノール樹脂が好ましい。

(In the formula (XV), R ²⁹ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, and n is an average value. And represents a 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 (XVI) is preferable.

  Among phenol resins represented by the following general formula (XVI), MEH-7500 (trade name, manufactured by Meiwa Kasei Co., Ltd.) where i = 0 and k = 0 is available as a commercial product.

（式（ＸＶＩ）中、Ｒ^３０及びＲ^３１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く、ｉは０〜３の整数、ｋは０〜４の整数、ｎは平均値であり、０〜１０の数を示す。）
ベンズアルデヒド型とアラルキル型との共重合型フェノール樹脂としては、ベンズアルデヒド骨格を有する化合物を原料として用いたフェノール樹脂とアラルキル型フェノール樹脂との共重合型フェノール樹脂であれば特に限定されるものではないが、下記一般式（ＸＶＩＩ）で示されるフェノール樹脂が好ましい。

(In the formula (XVI), R ³⁰ and R ³¹ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, and i is an integer of 0 to 3, k Is an integer from 0 to 4, n is an average value, and represents a number from 0 to 10.)
The copolymer type phenol resin of benzaldehyde type and aralkyl type is not particularly limited as long as it is a copolymer type 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 following general formula (XVII) is preferable.

  Among phenol resins represented by the following general formula (XVII), HE-510 (trade name, manufactured by Air Water Chemical Co., Ltd.) having i = 0, k = 0, and q = 0 is available as a commercial product. .

（式（ＸＶＩＩ）中、Ｒ^３２〜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く、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の数であり（ｌ＋ｍ）は１〜１１の数を示す。）
ノボラック型フェノール樹脂としては、フェノール類及び／又はナフトール類とアルデヒド類とを酸性触媒下で縮合又は共縮合させて得られるフェノール樹脂であれば特に限定されるものではないが、下記一般式（ＸＶＩＩＩ）で示されるフェノール樹脂が好ましい。

(In the formula (XVII), R ^{32 to} R ^{34 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, and i is an integer of 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 number of 1 to 11.)
The novolak-type phenol resin is not particularly limited as long as it is a phenol resin obtained by condensation or co-condensation of phenols and / or naphthols and aldehydes under an acidic catalyst, but the following general formula (XVIII ) Is preferred.

I = 0 Among phenolic resin represented by the following general formula ^{(XVIII), R 35} 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.

（式（ＸＶＩＩＩ）中、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く、ｉは０〜３の整数、ｋは０〜４の整数、ｎは平均値であり、０〜１０の数を示す。）
上記一般式（ＸＩＩ）〜（ＸＶＩＩＩ）におけるＲ^２２〜Ｒ^３６について記載した「それぞれ全てが同一でも異なっていてもよい」は、例えば、式（ＸＩＶ）中のｉ個のＲ^２２の全てが同一でも相互に異なっていてもよいことを意味している。他のＲ^２３〜Ｒ^３６についても、式中に含まれるそれぞれの個数について全てが同一でも相互に異なっていてもよいことを意味している。また、Ｒ^２２〜Ｒ^３６は、それぞれが同一でも異なっていてもよい。例えば、Ｒ^２２およびＲ^２３の全てについて同一でも異なっていてもよく、Ｒ^３０およびＲ^３１の全てについて同一でも異なっていてもよい。

(In the formula (XVIII), R ³⁵ and R ^{36 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, k Is an integer from 0 to 4, n is an average value, and represents a number from 0 to 10.)
“All may be the same or different” described for R ^{22 to} R ³⁶ in the general formulas (XII) to (XVIII) means that, for example, all i R ^{22s in} the formula (XIV) are the same. But it means they can be different from each other. For the other R ^{23 to} R ³⁶ , it is meant that all the numbers contained in the formula may be the same or different from each other. R ^{22 to} R ³⁶ may be the same as or different from each other. For example, all of R ²² and R ²³ may be the same or different, and all of R ³⁰ and R ³¹ may be the same or different.

  In the above general formulas (XII) to (XVIII), n needs to be in the range of 0 to 10, and when it exceeds 10, the melt viscosity of the (E) curing agent component becomes high. Viscosity at the time of melt molding also increases, which tends to cause unfilling failure and deformation of the bonding wire (gold wire connecting the element and the lead). The average n per molecule is preferably set in the range of 0-4.

  In the epoxy resin composition according to the present invention, when (A) an epoxy resin is used as the epoxy resin and a phenol compound is used as the (E) curing agent of the epoxy resin, the mixing ratio of the above components (A) and (E) Is preferably set in the range of 0.5 to 2.0 by the ratio of the hydroxyl equivalents of all phenolic compounds to the epoxy equivalents of all epoxy resins (number of hydroxyl groups in phenolic compound / number of epoxy groups in epoxy resin), The ratio is more preferably 0.7 to 1.5, and further preferably 0.8 to 1.3. When the ratio is less than 0.5, the epoxy resin is not sufficiently cured, and the effects of heat resistance, moisture resistance, and electrical characteristics of the cured product tend to be reduced. On the other hand, if the ratio exceeds 2.0, the phenol compound component becomes excessive and not only the curing efficiency is lowered, but also a large amount of phenolic hydroxyl group remains in the cured resin, so that the electrical characteristics and moisture resistance effect of the package are improved. There is a tendency to decrease.

  In the epoxy resin composition by this invention, it is preferable to use a (F) hardening accelerator as needed. The curing accelerator that can be used in the present invention is not limited as long as it is a compound that accelerates the reaction between (A) the epoxy resin and (E) the curing agent. For example, 1,5-diazabicyclo [4.3 0.0] nonene-5, 1,8-diazabicyclo [5.4.0] undecene-7, and other cycloamidine compounds such as diazabicycloalkenes, derivatives thereof, phenol novolac salts thereof, and maleic anhydride to these compounds 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2 Quinone compounds such as 1,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and π bonds such as diazophenylmethane A compound having an intramolecular polarization formed by adding a compound having a cation, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and derivatives thereof, 2- Imidazoles such as methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, tetra-substituted phosphonium / tetrasubstituted borates such as tetraphenylphosphonium / tetraphenylborate, 2-ethyl-4- Tetraphenylboron salts such as methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenol) Enyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine , Tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, and the like, or complexes of these organic phosphines with organic borons, and these organic phosphines And maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-di Quinone compounds such as tilbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and π bonds such as diazophenylmethane A compound having an intramolecular polarization formed by adding a compound having the following: these organic phosphines and 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 And compounds having intramolecular polarization (described in JP-A No. 2004-156036), and the like. When these curing accelerators are used in combination, from the viewpoint of fluidity, a compound having an intramolecular polarization formed by adding a compound having an organic phosphines and a π bond, an organic phosphine and a halogenated phenol compound are reacted. Later, a compound having intramolecular polarization obtained by dehydrohalogenation; from the viewpoint of curability, it has intramolecular polarization obtained by reacting an organic phosphine with a halogenated phenol compound and then dehydrohalogenating. Compounds are preferred.

  Among the curing accelerators exemplified above, from the viewpoint of fluidity, it is more preferable to contain at least one compound selected from a compound represented by the following general formula (XIX) and an intermolecular salt thereof.

（（ＸＩＸ）式中、Ｒ^３は、それぞれ独立して、水素原子及び炭素数１〜１８の置換又は非置換の炭化水素基からなる群より選ばれ、全てが同一でも異なっていてもよく、２以上のＲ^３が互いに結合して環状構造を形成してもよく、Ｒ^４は、それぞれ独立して、水素原子、水酸基、及び炭素数１〜１８の置換又は非置換の有機基からなる群より選ばれ、全てが同一でも異なっていてもよく、２以上のＲ^４が互いに結合して環状構造を形成してもよく、Ｙ⁻は、１以上の放出可能なプロトンを有する炭素数０〜１８の有機基から１つのプロトンが脱離した有機基であり、１以上のＲ^４と互いに結合して環状構造を形成してもよい。）
なお、上記一般式（ＸＩＸ）のＲ^３として記載した用語「炭素数１〜１８の置換又は非置換の炭化水素基」は、炭素数１〜１８を有し、置換されても又は非置換であってもよい脂肪族炭化水素基及び芳香族炭化水素基を含むことを意味する。

(In the formula (XIX), each R ³ is independently selected from the group consisting of a hydrogen atom and a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, and all may be the same or different, Two or more R ³ may be bonded to each other to form a cyclic structure, and each R ⁴ is independently a group consisting of a hydrogen atom, a hydroxyl group, and a substituted or unsubstituted organic group having 1 to 18 carbon atoms. All may be the same or different, and two or more R ⁴ may be bonded to each other to form a cyclic structure, and Y ⁻ represents 0 to 1 carbon atoms having one or more releasable protons. An organic group in which one proton is eliminated from 18 organic groups, and may be bonded to one or more R ⁴ groups to form a cyclic structure.)
Note that the term “substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms” described as R ^{3 in the} general formula (XIX) has 1 to 18 carbon atoms and may be substituted or unsubstituted. It is meant to include an aliphatic hydrocarbon group and an aromatic hydrocarbon group which may be present.

  More specifically, the substituted or unsubstituted aliphatic hydrocarbon group and aromatic hydrocarbon group are as described above.

The term “two or more R ^3s may be bonded to each other to form a cyclic structure” described as R ^{3 in the} general formulas (I) and (XIX) means that two or three R ³ are bonded together As a bivalent or trivalent hydrocarbon group. For example, an alkylene group such as ethylene, propylene, butylene, pentylene and hexylene, which can be bonded to a P atom to form a cyclic structure, an alkenyl group such as ethylenyl, propylenyl and butyrenyl groups, an aralkylene group such as a methylenephenylene group, phenylene and naphthylene And arylene groups such as anthracenylene, which may be substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogens, and the like.

Note that R ^{3 in the} general formula (XIX) is not particularly limited, but is preferably a monovalent substituent selected from the group consisting of an alkyl group and an aryl group. Among these, from the viewpoint of easy availability of raw materials, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, p- Hydroxyphenyl group, m-hydroxyphenyl group, o-hydroxyphenyl group, 2,5-dihydroxyphenyl group, 4- (4-hydroxyphenyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 1- (2- Hydroxynaphthyl) group, 1- (4-hydroxynaphthyl) group, unsubstituted or alkyl group or / and alkoxy group or / and hydroxyl group-substituted aromatic group, methyl group, ethyl group, propyl group, isopropyl group, butyl Substituents selected from a chain or cyclic alkyl group such as a group, sec-butyl group, tert-butyl group, octyl group, cyclohexyl group, etc. More preferable. Phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, p-hydroxyphenyl group, m-hydroxyphenyl group, o- Hydroxyphenyl group, 2,5-dihydroxyphenyl group, 4- (4-hydroxyphenyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 1- (2-hydroxynaphthyl) group, 1- (4-hydroxynaphthyl) And a non-substituted alkyl group or / and an alkoxy group or / and a hydroxyl group-substituted aryl group.

The term “substituted or unsubstituted organic group having 1 to 18 carbon atoms” described as R ^{4 in the} general formula (XIX) has 1 to 18 carbon atoms and is substituted or unsubstituted. Means including aliphatic hydrocarbon group, aromatic hydrocarbon group, and aliphatic hydrocarbon oxy group, aromatic hydrocarbon oxy group, carbonyl group, oxycarbonyl group, and carbonyloxy group bonded .

  More specifically, the substituted or unsubstituted aliphatic hydrocarbon group and aromatic hydrocarbon group are as described above.

  Examples of the aliphatic hydrocarbon oxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, cyclopropyloxy group, cyclohexyloxy group, and cyclopentyl. An oxy group having a structure in which an oxygen atom is bonded to the above-mentioned aliphatic hydrocarbon group such as an oxy group, an allyloxy group, a vinyloxy group, and the like. Substituted ones are mentioned. Examples of the aromatic hydrocarbon oxy group include an oxy having a structure in which an oxygen atom is bonded to the above aromatic hydrocarbon group such as a phenoxy group, a methylphenoxy group, an ethylphenoxy group, a methoxyphenoxy group, a butoxyphenoxy group, and a phenoxyphenoxy group. 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.

  Examples of the carbonyl group include a formyl group, an acetyl group, an ethylcarbonyl group, a butyryl group, a cyclohexylcarbonyl group, an aliphatic hydrocarbon carbonyl group such as allylcarbonyl, an aromatic hydrocarbon carbonyl group such as a phenylcarbonyl group, and a methylphenylcarbonyl group. And those substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen, or the like.

  Examples of the oxycarbonyl group include aliphatic hydrocarbon oxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, allyloxycarbonyl group, cyclohexyloxycarbonyl group, and aromatic groups such as phenoxycarbonyl group and methylphenoxycarbonyl group. Examples thereof include hydrocarbon oxycarbonyl groups and the like, and those substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogens and the like.

  Examples of the carbonyloxy group include methylcarbonyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, allylcarbonyloxy group, cyclohexylcarbonyloxy group and other aliphatic hydrocarbon carbonyloxy groups, phenylcarbonyloxy group, methylphenylcarbonyloxy And aromatic hydrocarbon carbonyloxy groups such as groups, and those substituted with an alkyl group, alkoxy group, aryl group, aryloxy group, amino group, halogen, and the like.

The "also may form two or more bonds of R ⁴ with each other to a cyclic structure" the term described as R ⁴ in the general formula (XIX), bonded to two to four R ^4, respectively as a whole 2 It means a case where it becomes a tetravalent organic group. For example, an alkylene group such as ethylene, propylene, butylene, pentylene and hexylene, which can form a cyclic structure, an alkenyl group such as ethylenyl, propylenyl and butyrenyl groups, an aralkylene group such as a methylenephenylene group, and an arylene group such as phenylene, naphthylene and anthracenylene , An alkylene group, an alkenyl group, an aralkylene group, an arylene group, an oxy group or a dioxy group, which are substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen, or the like. Also good.

R ^{4 in the} general formula (XIX) is not particularly limited, but is preferably a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group. Among these, from the viewpoint of easy availability of raw materials, alkoxy groups such as hydrogen atom, hydroxyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, tert-butoxy group, phenoxy group, unsubstituted or alkyl such as aryloxy group such as p-crezoxy group, m-crezoxy group, o-crezoxy group, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, etc. Groups or / and alkoxy groups or / and hydroxyl-substituted aromatic groups, methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, sec-butyl groups, tert-butyl groups, octyl groups, cyclohexyl groups, etc. Alternatively, a substituent selected from cyclic alkyl groups is more preferable. Hydrogen atom, hydroxyl group, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, etc. unsubstituted or alkyl group or / and alkoxy group or / and hydroxyl group-substituted aromatic group Substituents selected from chain or cyclic alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, octyl group and cyclohexyl group are more preferable. In the case where two or more R ⁴ are bonded to each other to form a cyclic structure, the ring structure is not particularly limited, but in combination with the benzene ring to which R ⁴ is bonded, a 1- (2-hydroxynaphthyl) group, 1- (4 An organic group that forms a polycyclic aromatic group such as a -hydroxynaphthyl) group is preferred.

Y ⁻ in the general formula (XIX) is an organic group in which one proton is eliminated from an organic group having 0 to 18 carbon atoms and having one or more releasable protons (H ⁺ ), and one or more R ⁴ May be combined with each other to form a ring structure. For example, Y ^- represents a hydroxyl group, a mercapto group, a group proton from groups having a hydrogen atom bonded to the Group 16 atoms such as hydro seleno group is eliminated, a carboxyl group, a carboxymethyl group, a carboxyethyl group, carboxyphenyl group carboxymethyl naphthyl group A group in which a carboxylic acid proton is eliminated from a group having 1 to 18 carbon atoms having a carboxyl group, such as a hydroxyphenyl group, a hydroxyphenylmethyl group, a hydroxynaphthyl group, a hydroxyfuryl group, a hydroxythienyl group, a hydroxypyridyl group, etc. And a monovalent organic group in which a phenolic proton is eliminated from a group having 1 to 18 carbon atoms having a phenolic hydroxyl group.

Moreover, when Y < ^- > in Formula (XIX) couple | bonds with one or more R < ⁴ > and forms a cyclic structure, for example, Y < ^- > combines with the benzene ring to which it has couple | bonded, 2- (6- And a divalent organic group that forms a group in which a proton is eliminated from a hydroxyl group of a hydroxy polycyclic aromatic group such as a hydroxy naphthyl group.

Previously illustrated Y ^- among, but are not limited to, oxygen anion proton from the hydroxyl group is eliminated, or hydroxyphenyl group, hydroxyphenyl methyl group, hydroxynaphthyl group, hydroxy furyl group, hydroxy thienyl group And a monovalent organic group having an oxygen anion formed by removing a proton from a phenolic hydroxyl group such as a hydroxypyridyl group.

  Examples of the compound represented by the general formula (XIX) include addition reaction product of tri- (4-methoxyphenyl) phosphine and 1,4-benzoquinone, addition reaction product of tri-p-tolylphosphine and 1,4-benzoquinone. , Addition reaction product of tri-o-tolylphosphine and 1,4-benzoquinone, addition reaction product of tri-m-tolylphosphine and 1,4-benzoquinone, di- (4-methoxyphenyl) phenylphosphine and 1, Addition reaction product of 4-benzoquinone, addition reaction product of di-p-tolylphenylphosphine and 1,4-benzoquinone, addition reaction product of di-o-tolylphenylphosphine and 1,4-benzoquinone, diphenyl- ( 4-methoxyphenyl) phosphine and 1,4-benzoquinone addition reaction, diphenyl-p-tolylphosphine and 1,4-ben Addition reaction product of quinone, addition reaction product of diphenyl-o-tolylphosphine and 1,4-benzoquinone, addition reaction product of diphenyl-m-tolylphosphine and 1,4-benzoquinone, triphenylphosphine and 1,4 -Addition reaction product of benzoquinone, addition reaction product of triphenylphosphine and methyl-1,4-benzoquinone, addition reaction product of triphenylphosphine and 2,3-dimethyl-1,4-benzoquinone, triphenylphosphine and An addition reaction product of 2,5-dimethyl-1,4-benzoquinone, an addition reaction product of triphenylphosphine and methoxy-1,4-benzoquinone, triphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone Addition reaction product of triphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone Addition reaction product, addition reaction product of triphenylphosphine and t-butyl-1,4-benzoquinone, addition reaction product of triphenylphosphine and phenyl-1,4-benzoquinone, tricyclohexylphosphine and 1,4-benzoquinone Addition reaction product of tri-n-butylphosphine and 1,4-benzoquinone, addition reaction product of tri-n-butylphosphine and methyl-1,4-benzoquinone, tri-n-butylphosphine and Addition reaction product of 2,3-dimethyl-1,4-benzoquinone, addition reaction product of tri-n-butylphosphine and 2,5-dimethyl-1,4-benzoquinone, tri-n-butylphosphine and methoxy- Addition reaction product with 1,4-benzoquinone, addition of tri-n-butylphosphine and 2,3-dimethoxy-1,4-benzoquinone Addition reaction product, addition reaction product of tri-n-butylphosphine and 2,5-dimethoxy-1,4-benzoquinone, addition reaction product of tri-n-butylphosphine and t-butyl-1,4-benzoquinone, Addition reaction product of tri-n-butylphosphine and phenyl-1,4-benzoquinone, addition reaction product of tri-n-octylphosphine and 1,4-benzoquinone, addition of cyclohexyldiphenylphosphine and 1,4-benzoquinone Reaction product, addition reaction product of n-butyldiphenylphosphine and 1,4-benzoquinone, addition reaction product of n-octyldiphenylphosphine and 1,4-benzoquinone, addition reaction of dicyclohexylphenylphosphine and 1,4-benzoquinone Products, addition reaction products of di-n-butylphenylphosphine and 1,4-benzoquinone, etc. Addition reaction product of a fin compound and a quinone compound, a phosphine compound and 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-dimethyl Phenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl, etc. Intramolecular polarization obtained by reacting a halogenated phenolic compound and then dehydrohalogenating And the like (described in JP-A No. 2004-156036) and the like. Among these, from the viewpoint of availability, an addition reaction product of tri- (4-methoxyphenyl) phosphine and 1,4-benzoquinone, an addition reaction product of tri-p-tolylphosphine and 1,4-benzoquinone, -Addition reaction product of o-tolylphosphine and 1,4-benzoquinone, addition reaction product of tri-m-tolylphosphine and 1,4-benzoquinone, addition of diphenyl-p-tolylphosphine and 1,4-benzoquinone Reaction product, addition reaction product of triphenylphosphine and 1,4-benzoquinone, addition reaction product of triphenylphosphine and methyl-1,4-benzoquinone, addition reaction product of tricyclohexylphosphine and 1,4-benzoquinone, An addition reaction product of n-butylphosphine and 1,4-benzoquinone cyclohexyldiphenylphosphine and 1, - addition reaction product of an benzoquinone, the compounds of structure according to Formula prepared in Synthesis Example 1-9 of JP 2004-156035 (XXIX) ~ (XXXVII) is preferred.

  The intermolecular salt of the compound represented by the general formula (XIX) is not limited, but the compound represented by the formula (XIX) and phenol, naphthol, and two or more phenolic hydroxyl groups in the molecule. Compounds having phenolic hydroxyl groups such as phenol compounds having, compounds having silanol groups such as triphenylsilanol, diphenylsilanediol, trimethylsilanol, organic acids such as oxalic acid, acetic acid, benzoic acid, hydrochloric acid, hydrogen bromide, sulfuric acid, Examples include intermolecular salt compounds with inorganic acids such as nitric acid.

  (F) The compounding quantity of a hardening accelerator will not have a restriction | limiting in particular if the hardening acceleration effect can be achieved. However, from the viewpoint of improving the curability and fluidity at the time of moisture absorption of the resin composition, the total amount of (F) curing accelerator is preferably 0.1 to 10 with respect to 100 parts by weight of the total of (A) epoxy resin. It is desirable to add 1 part by weight, more preferably 1 to 7.0 parts by weight. When the blending amount is less than 0.1 parts by weight, it is difficult to cure in a short time, and when it exceeds 10 parts by weight, the curing rate is too fast and a good molded product may not be obtained.

  In the epoxy resin composition according to the present invention, if necessary, in addition to the component (A) epoxy resin, (B) inorganic filler, (C) coupling agent, (E) curing agent, and (F) curing accelerator. Various additives such as ion exchangers, release agents, stress relaxation agents, flame retardants, and colorants exemplified below may be added. However, the epoxy resin composition according to the present invention is not limited to the following additives, and various additives may be added as necessary.

  An anion exchanger can be mix | blended with the epoxy resin composition of this invention as needed. In particular, when an epoxy resin composition is used as a molding material for sealing, it is preferable to blend an anion exchanger from the viewpoint of improving the moisture resistance and high-temperature standing characteristics of an electronic component device including an element to be sealed. . 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. Especially, the hydrotalcite shown by the following general formula (XIX) is preferable.

（０＜Ｘ≦０．５、ｍは正の数）
これらの陰イオン交換体の配合量は、ハロゲンイオンなどの陰イオンを捕捉できる十分量であれば特に制限はないが、（Ａ）エポキシ樹脂に対して０．１〜３０重量％の範囲が好ましく、１〜５重量％がより好ましい。

(0 <X ≦ 0.5, m is a positive number)
The 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 preferably in the range of 0.1 to 30% by weight with respect to (A) the epoxy resin. 1 to 5% by weight is more preferable.

  In the epoxy 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. There is no restriction | limiting in particular as a mold release agent used in this invention, A conventionally well-known thing can be used. Examples include higher fatty acids such as carnauba wax, montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, polyolefin waxes such as polyethylene oxide and non-oxidized polyethylene, and the like. It may be used alone or in combination of two or more. Of these, oxidized or non-oxidized polyolefin-based waxes are preferable, and the blending amount thereof is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on (A) the epoxy resin. If the blending amount of the polyolefin wax is less than 0.01% by weight, the effect of releasability tends to be insufficient, and if it exceeds 10% by weight, the adhesiveness may be inhibited. 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 polyolefin-type wax, 0.1 to 10 weight% is preferable with respect to (A) epoxy resin, and 0.5 to 3 weight% is more preferable.

  The epoxy 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.

  In the epoxy resin composition of the present invention, a flame retardant can be blended as necessary to impart flame retardancy. There is no restriction | limiting in particular as a flame retardant used in this invention, For example, the well-known organic or inorganic compound containing a halogen atom, an antimony atom, a nitrogen atom, or a phosphorus atom, a metal hydroxide, etc. are mentioned, These 1 type May be used alone or in combination of two or more. The blending amount of the flame retardant is not particularly limited as long as the flame retardant effect is achieved, but is preferably 1 to 30% by weight, and more preferably 2 to 15% by weight with respect to the (A) epoxy resin such as an epoxy resin.

  Moreover, 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.

  The epoxy resin composition of the present invention described above can be prepared by any method as long as various components can be uniformly dispersed and mixed. As a general technique, there can be mentioned a method in which components of a predetermined blending amount are sufficiently mixed by a mixer or the like, then melt kneaded by a mixing roll, an extruder or the like, and then cooled and pulverized. More specifically, for example, a method of uniformly stirring and mixing predetermined amounts of the above-described components, kneading with a kneader, roll, extruder, or the like that has been heated to 70 to 140 ° C., cooling, pulverizing, etc. Can be obtained at The resin composition is easy to handle when it is tableted with a size and weight suitable for the molding conditions of the package.

  An electronic component device according to the present invention includes an element sealed with the above-described epoxy resin composition. Electronic component devices include, for example, lead frames, wired tape carriers, wiring boards, glass, silicon wafers, and other supporting members, active elements such as semiconductor chips, transistors, diodes, thyristors, capacitors, resistors, coils, etc. And those in which the element portion is sealed with the epoxy resin composition of the present invention. More specifically, for example, a semiconductor element is fixed on a lead frame, the terminal part of the element such as a bonding pad and the lead part are connected by wire bonding or bump, and then transferred using the epoxy resin composition of the present invention. Sealed by molding or the like, DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-Tap) General resin-sealed ICs such as Outline Package (Tline) and TQFP (Thin Quad Flat Package), bumps on tape carriers TCP (Tape Carrier Package) encapsulated with the epoxy resin composition of the present invention, a semiconductor chip connected to a wiring formed on a wiring board or glass by wire bonding, flip chip bonding, solder, etc. COB (Chip On Board) module, hybrid IC, multichip module, in which active elements such as transistors, diodes, thyristors and / or passive elements such as capacitors, resistors, coils, etc. are sealed with the epoxy resin composition of the present invention 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, and after connecting the element and the wiring formed on the organic substrate by bump or wire bonding, the element is bonded with the epoxy resin composition of the present invention. Sealed BGA (Ball Grid A ray), CSP (Chip Size Package) and the like. The epoxy resin composition of the present invention can also be used effectively for printed circuit boards.

  As a method for sealing an electronic component device using the epoxy 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 Hereinafter, although an Example demonstrates this invention more concretely, the scope of the present invention is not limited by the Example shown below.
[Production of surface-treated fused silica]
Spherical fused silica having an average particle size of 17.5 μm and a specific surface area of 3.8 m ² / g as an inorganic filler, and 3-glycidoxypropyltrimethoxysilane (coupling agent 1: Toray Dow Corning Co., Ltd.) as a coupling agent Product name A-187) was prepared. As a compound having a nitrogen atom bonded to an aryl group in the molecule of the present invention, aniline (nitrogen-containing compound 1), N-methylaniline (nitrogen-containing compound 2), N-butylaniline (nitrogen-containing compound 3), comparative example As the nitrogen-containing compound, tributylamine (nitrogen-containing compound A), butylamine (nitrogen-containing compound B), 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) (nitrogen-containing compound C), diethylamine ( A nitrogen-containing compound D) was prepared. After mixing the coupling agent and the nitrogen-containing compound at the ratio shown in Table 1, this mixture was mixed with spherical fused silica, and all of the molten silica was crushed with fingers so as to be uniform. Through a 100 μm sieve until no fused silica was left. Then, it put into the plastic bottle and mixed for 14 days using the mix rotor, and obtained the surface treatment fused silica of Examples 1-4 and Comparative Examples 1-5.

[Preparation of epoxy resin composition and evaluation of its properties]
As an epoxy resin,
Biphenyl type epoxy resin having an epoxy equivalent of 196 and a melting point of 106 ° C. (epoxy resin 1: trade name YX-4000H manufactured by Japan Epoxy Resin Co., Ltd.),
Diphenylmethane skeleton epoxy resin having an epoxy equivalent of 192 and a melting point of 79 ° C. (epoxy resin 2: trade name YSLV-80XY manufactured by Nippon Steel Chemical Co., Ltd.)
Orthocresol novolak type epoxy resin having an epoxy equivalent of 195 and a softening point of 62 ° C. (epoxy resin 3: trade name ESCN-190-2 manufactured by Sumitomo Chemical Co., Ltd.),
A salicylaldehyde type epoxy resin having an epoxy equivalent of 167 (epoxy resin 4: Nippon Kayaku Co., Ltd., trade name EPPN-502H),
Epoxy product of aralkyl type phenol resin having an epoxy equivalent of 282 and a softening point of 59 ° C. (epoxy resin 6: trade name NC-3000 manufactured by Nippon Kayaku Co., Ltd.),
Brominated bisphenol A type epoxy resin (brominated epoxy resin) having an epoxy equivalent of 393, a softening point of 80 ° C. and a bromine content of 48% by weight as an epoxy resin having a flame-retardant effect
Prepared.

As a curing agent,
Phenol aralkyl resin having a hydroxyl group equivalent of 176 and a softening point of 70 ° C. (curing agent 1: trade name “Mirex XL-225” manufactured by Mitsui Chemicals, Inc.)
Biphenyl skeleton type phenol resin having a hydroxyl group equivalent of 199 and a softening point of 89 ° C. (curing agent 2: trade name MEH-7851 manufactured by Meiwa Kasei Co., Ltd.),
Phenol novolak resin having a hydroxyl group equivalent of 106 (curing agent 3: trade name HP-850N, manufactured by Hitachi Chemical Co., Ltd.),
A copolymerized phenol resin of benzaldehyde type and aralkyl type having a hydroxyl equivalent weight of 156 (curing agent 4: trade name HE-510, manufactured by Air Water Co., Ltd.),
Naphthol aralkyl resin having a hydroxyl group equivalent of 183 and a softening point of 79 ° C. (curing agent 5: trade name SN-170 manufactured by Nippon Steel Chemical Co., Ltd.)
Salicylaldehyde type phenol resin having a hydroxyl equivalent weight of 106 (curing agent 6: trade name MEH-7500 manufactured by Meiwa Kasei Co., Ltd.)
Prepared.

As a coupling agent
3-glycidoxypropyltrimethoxysilane (coupling agent 1: trade name A-187 manufactured by Toray Dow Corning Co., Ltd.)
Prepared.

As a compound having a nitrogen atom bonded to an aryl group in the molecule of the present invention,
Aniline (nitrogen-containing compound 1),
N-methylaniline (nitrogen-containing compound 2),
N-butylaniline (nitrogen-containing compound 3),
As a nitrogen-containing compound of the comparative example,
Tributylamine (nitrogen-containing compound A),
Butylamine (nitrogen-containing compound B),
1,8-diazabicyclo [5.4.0] undecene-7 (DBU) (nitrogen-containing compound C), diethylamine (nitrogen-containing compound D)
Prepared.
These nitrogen-containing compounds were mixed with a coupling agent in advance and then blended with other raw materials.

As a curing accelerator,
Addition reaction product of triphenylphosphine and 1,4-benzoquinone (curing accelerator 1),
Addition reaction product of tri-n-butylphosphine and 1,4-benzoquinone (curing accelerator 2),
4-triphenylphosphoniophenolate (curing accelerator 3),
Triphenylphosphine (curing accelerator 4),
1,8-diazabicyclo [5.4.0] undecene-7 (DBU) (curing accelerator 5)
Prepared.

As an inorganic filler,
Spherical fused silica having an average particle diameter of 17.5 μm and a specific surface area of 3.8 m ² / g was prepared. Also, prepared surface treated fused silica 1 to 4 (corresponding to Examples 1 to 4) and A to E (corresponding to Comparative Examples 1 to 5) were prepared.
In addition, carbon black (trade name: MA-100, manufactured by Mitsubishi Chemical Corporation) as a colorant, carnauba wax (manufactured by Celalica NODA), and antimony trioxide, a flame retardant, are prepared as various additives. did.

  The above-mentioned components are blended in parts by weight shown in Tables 2 to 5, and roll kneading is carried out under the conditions of a kneading temperature of 80 ° C. and a kneading time of 15 minutes. A resin composition was obtained.

次に、実施例５〜２６、及び比較例６〜２４によって得られたエポキシ樹脂組成物を、以下に示す各種試験によって評価した。評価結果を表６〜９に示す。なお、エポキシ樹脂組成物の成形は、トランスファー成形機を用い、金型温度１８０℃、成形圧力６．９ＭＰａ、硬化時間９０秒の条件下で行った。また、後硬化は１７５℃で６時間行った。
（１）スパイラルフロー（流動性の指標）
ＥＭＭＩ−１−６６に準じたスパイラルフロー測定用金型を用いて、上記条件でエポキシ樹脂組成物を成形して流動距離（ｃｍ）を測定した。
（２）円板フロー
２００ｍｍ（Ｗ）×２００ｍｍ（Ｄ）×２５ｍｍ（Ｈ）の上型と２００ｍｍ（Ｗ）×２００ｍｍ（Ｄ）×１５ｍｍ（Ｈ）の下型を有する円板フロー測定用平板金型を用いて、上皿天秤にて秤量したエポキシ樹脂組成物５ｇを１８０℃に加熱した下型の中心部にのせ、５秒後に１８０℃に加熱した上型を閉じて、荷重７８Ｎ、硬化時間９０秒の条件で圧縮成形し、ノギスで成形品の長径（ｍｍ）及び短径（ｍｍ）を測定して、その平均値（ｍｍ）を円板フローとした。
（３）熱時硬度
エポキシ樹脂組成物を上記条件で直径５０ｍｍ×厚さ３ｍｍの円板に成形し、成形後直ちにショアＤ型硬度計を用いて測定した。

Next, the epoxy resin composition obtained by Examples 5-26 and Comparative Examples 6-24 was evaluated by the various tests shown below. The evaluation results are shown in Tables 6-9. The epoxy resin composition was molded using 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)
An epoxy resin composition was molded under the above conditions using a spiral flow measurement mold according to EMMI-1-66, and the flow distance (cm) was measured.
(2) Disc flow Flat plate for disc flow measurement having an upper mold of 200 mm (W) x 200 mm (D) x 25 mm (H) and a lower mold of 200 mm (W) x 200 mm (D) x 15 mm (H) Using a mold, put 5 g of the epoxy resin composition weighed on an upper pan balance on the center of the lower mold heated to 180 ° C., and after 5 seconds, close the upper mold heated to 180 ° C. and load 78 N, curing time Compression molding was performed under the condition of 90 seconds, the major axis (mm) and minor axis (mm) of the molded product were measured with a caliper, and the average value (mm) was defined as a disc flow.
(3) Hardness upon heating The epoxy resin composition was molded into a disc having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and measured immediately using a Shore D type hardness meter after molding.

As can be seen from Tables 6 to 9, Examples 5 to 26 containing a compound having a nitrogen atom bonded to an aryl group in the molecule according to the present invention are the same resin composition except for the compound according to the present invention. Compared to the example, the fluidity was excellent. In particular, Examples containing fused silica surface-treated with a coupling agent containing a compound having a nitrogen atom bonded to an aryl group in the molecule according to the present invention resulted in excellent fluidity.
On the other hand, in Comparative Examples 6 to 24 that do not contain a compound having a nitrogen atom bonded to an aryl group in the molecule according to the present invention, the results are inferior in fluidity as compared with Examples having the same resin composition except for the silane compound. It became. In particular, Examples containing fused silica surface-treated with a coupling agent not containing a compound having a nitrogen atom bonded to an aryl group in the molecule according to the present invention resulted in poor fluidity.

Claims (14)

  An epoxy resin composition comprising (A) an epoxy resin, (B) an inorganic filler, (C) a coupling agent, and (D) a compound having a nitrogen atom bonded to an aryl group in the molecule. The epoxy resin composition according to claim 1, wherein the compound (D) having a nitrogen atom bonded to an aryl group in the molecule contains at least one compound represented by the following general formula (Ia).

Wherein R ¹ is independently selected from the group consisting of a hydrogen atom and a substituted or unsubstituted organic group having 1 to 18 carbon atoms, all of which may be the same or different, and Ar is carbon (It is selected from the group consisting of substituted or unsubstituted aryl groups of formula 6 to 24. Also, two or more of R ¹ and Ar may be bonded to each other to form a cyclic structure.)   (C) The epoxy resin composition according to claim 1 or 2, wherein the coupling agent is a silane coupling agent. (C) The coupling agent contains at least one compound represented by the following general formula (Ib) and at least one compound represented by (Ib): The epoxy resin composition as described.

(Wherein, R ² are each independently selected from hydrogen atom and the group consisting of substituted or unsubstituted organic group having 1 to 18 carbon atoms, all may be the same or different, R ³ is Each independently selected from the group consisting of a hydrogen atom and a substituted or unsubstituted organic group having 1 to 18 carbon atoms, all of which may be the same or different, and each R ⁴ independently represents a hydrogen atom and It is selected from the group consisting of substituted or unsubstituted organic groups having 1 to 18 carbon atoms, all of which may be the same or different, and two or more selected from R ² , R ³ and R ⁴ are bonded to each other to form a cyclic structure May be formed.)   (E) The epoxy resin composition in any one of Claims 1-4 containing a hardening | curing agent.   (F) The epoxy resin composition in any one of Claims 1-5 containing a hardening accelerator.   The resin composition according to any one of claims 1 to 6, wherein the (E) curing agent contains a compound having two or more phenolic hydroxyl groups in the molecule.   (B) Content of an inorganic filler is 55 to 95 weight%, The epoxy resin composition in any one of Claims 1-7 characterized by the above-mentioned.   The mixture of (C) a coupling agent and (D) a compound having a nitrogen atom bonded to an aryl group in the molecule is subjected to surface treatment on (B) the inorganic filler in advance. The epoxy resin composition in any one.   (D) The compound which has a nitrogen atom couple | bonded with the aryl group in the molecule | numerator is 0.1-100 mol% of (C) coupling agent, The epoxy resin composition in any one of Claims 1-9.   (A) 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, naphthols The epoxy resin according to any one of claims 1 to 10, comprising one or more epoxy resins selected from the group consisting of a copolymerization type epoxy resin with phenols and an epoxidized product of an aralkyl type phenol resin. Composition.   (E) The curing agent is selected from the group consisting of aralkyl type phenol resins, dicyclopentadiene type phenol resins, salicylaldehyde type phenol resins, benzaldehyde type phenol resins and aralkyl type phenol resins, and novolac type phenol resins. The epoxy resin composition according to claim 5, comprising one or more resins selected.   (B) The average particle diameter of an inorganic filler is 1-50 micrometers, The epoxy resin composition in any one of Claims 1-12.   An electronic component device comprising an element sealed using the epoxy resin composition according to claim 1.