JP2006083212A - Epoxy resin molding material for sealing and electronic component device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin molding material for sealing having excellent reliability and to provide an electronic component device sealed with the molding material. <P>SOLUTION: The epoxy resin molding material for sealing comprises (A) an epoxy resin, (B) a curing agent and (C) an acrylic compound represented by general formula (I) äwherein, R<SP>1</SP>s and R<SP>2</SP>s denote each a hydrogen atom and a methyl group; R<SP>3</SP>s denote each a 1-6C hydrocarbon group; R<SP>4</SP>s denote each a group represented by general formula (II) (wherein, R<SP>5</SP>s denote each a hydrogen atom and a 1-6C hydrocarbon group; R<SP>6</SP>s denote each a 1-6C hydrocarbon group; and p denotes an integer of 1-3); m denotes an integer of 1-20; n denotes an integer of 0-20; and the average value of n/m in the compound is 0.05 to 3}. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an epoxy resin molding material for sealing and an electronic component device including an element sealed with the molding material.

Conventionally, epoxy resin molding materials have been widely used in the field of sealing electronic components such as transistors and ICs. This is because the epoxy resin has a good balance of electrical properties, moisture resistance, heat resistance, mechanical properties, adhesiveness with inserts, and the like. In particular, the combination of an ortho-cresol novolac type epoxy resin and a novolac type phenol curing agent has an excellent balance between these, and has become the mainstream of the base resin of the molding material for 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 attaching a semiconductor device to a wiring board, the conventional pin insertion type package is soldered from the back of the wiring board after the pins are inserted into the wiring board, so that the package was 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 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, but this method has a problem of causing a significant decrease in fluidity, although the moisture absorption inside the semiconductor device is reduced. As a method for increasing the filler content without impairing the fluidity of the epoxy resin molding material, a method for optimizing the filler particle size distribution has been proposed (see, for example, Patent Document 1). This method does not provide a sufficient effect for improving the fluidity. In addition, if the fluidity of the epoxy resin molding material for sealing is low, new problems such as the occurrence of gold wire flow, voids, pinholes, etc. occur at the time of molding, and improvement in fluidity is required (for example, non-patent) Reference 2).

Hitachi, Ltd. Semiconductor Division, "Surface Mounted LSI Package Mounting Technology and its Reliability Improvement" Applied Technology Publishing, November 16, 1988, pages 254-256 Japanese Patent Laid-Open No. 06-224328 Technical Information Association, Inc. “High Reliability of Semiconductor Encapsulation Resin” Technical Information Association, January 31, 1990, pages 172-176

  The present invention has been made in view of such a situation, and includes an epoxy resin molding material for sealing excellent in fluidity and solder reflow resistance without reducing curability, and an electronic component device including an element sealed thereby. It is something to be offered.

（一般式（Ｉ）で、Ｒ^１、Ｒ^２は水素原子及びメチル基を示し、Ｒ^３は炭素数１〜６の炭化水素基を示し、Ｒ^４は下記一般式（ＩＩ）で示す基、ｍは１〜２０の整数、ｎは０〜２０の整数を示し、化合物中のｎ／ｍの平均値が０．０５以上３以下。）

（一般式（ＩＩ）で、Ｒ^５は水素原子及び炭素数１〜６の炭化水素基を示し、Ｒ^６は炭素数１〜６の炭化水素基を示し、ｐは１〜３の整数を示す。）
（２）封止用エポキシ樹脂成形材料に対して（Ｃ）上記一般式（Ｉ）で示されるアクリル化合物の割合が０．０５〜０．７重量％である上記１記載の封止用エポキシ樹脂成形材料、
（３）（Ａ）エポキシ樹脂がビフェニル型エポキシ樹脂、硫黄原子含有エポキシ樹脂、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、ナフタレン型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂及びビフェニレン骨格含有フェノール・アラルキル型エポキシ樹脂の少なくとも１種を含有する上記１又は２記載の封止用エポキシ樹脂成形材料、
（４）（Ｂ）硬化剤がビフェニレン骨格含有フェノール・アラルキル樹脂、フェノール・アラルキル樹脂、ナフトール・アラルキル樹脂、ジシクロペンタジエン型フェノール樹脂、トリフェニルメタン型フェノール樹脂、ノボラック型フェノール樹脂及び共重合型フェノール・アラルキル樹脂の少なくとも１種を含有する上記１〜３のいずれかに記載の封止用エポキシ樹脂成形材料、
（５）（Ｄ）シラン化合物をさらに含有する上記１〜４のいずれかに記載の封止用エポキシ樹脂成形材料、
（６）硬化促進剤をさらに含有する上記１〜５のいずれかに記載の封止用エポキシ樹脂成形材料、
（７）無機充てん剤をさらに含有する上記１〜６のいずれかに記載の封止用エポキシ樹脂成形材料、
（８）上記１〜７のいずれかに記載の封止用エポキシ樹脂成形材料により封止された素子を備える電子部品装置、
に関する。 The present invention
(1) (A) an epoxy resin, (B) a curing agent, (C) an epoxy resin molding material for sealing containing an acrylic compound represented by the following general formula (I),

(In the general formula (I), R ¹ and R ² represent a hydrogen atom and a methyl group, R ³ represents a hydrocarbon group having 1 to 6 carbon atoms, R ⁴ represents a group represented by the following general formula (II), m represents an integer of 1 to 20, n represents an integer of 0 to 20, and the average value of n / m in the compound is 0.05 or more and 3 or less.)

(In General Formula (II), R ⁵ represents a hydrogen atom and a hydrocarbon group having 1 to 6 carbon atoms, R ⁶ represents a hydrocarbon group having 1 to 6 carbon atoms, and p represents an integer of 1 to 3. .)
(2) The epoxy resin for sealing according to 1 above, wherein the proportion of the acrylic compound represented by the general formula (I) is 0.05 to 0.7% by weight with respect to the epoxy resin molding material for sealing. Molding material,
(3) (A) The epoxy resin is biphenyl type epoxy resin, sulfur atom-containing epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, triphenylmethane type epoxy resin, bisphenol F type epoxy resin, and The epoxy resin molding material for sealing according to 1 or 2 above, which contains at least one of a biphenylene skeleton-containing phenol / aralkyl type epoxy resin,
(4) (B) The curing agent is a biphenylene skeleton-containing phenol-aralkyl resin, phenol-aralkyl resin, naphthol-aralkyl resin, dicyclopentadiene-type phenol resin, triphenylmethane-type phenol resin, novolac-type phenol resin, and copolymer-type phenol -The epoxy resin molding material for sealing according to any one of the above 1 to 3, containing at least one kind of aralkyl resin,
(5) The epoxy resin molding material for sealing according to any one of the above 1 to 4, further comprising (D) a silane compound,
(6) The epoxy resin molding material for sealing according to any one of 1 to 5, further containing a curing accelerator,
(7) The epoxy resin molding material for sealing according to any one of the above 1 to 6, further containing an inorganic filler,
(8) An electronic component device including an element sealed with the sealing epoxy resin molding material according to any one of 1 to 7 above,
About.

  The epoxy resin molding material for sealing obtained according to the present invention can provide a highly reliable electronic component device with excellent fluidity and solder reflow resistance without deteriorating curability, and its industrial value is great. is there.

The (A) epoxy resin used in the present invention is generally used for an epoxy resin molding material for sealing and is not particularly limited. For example, a phenol novolac type epoxy resin, an orthocresol novolak type epoxy resin, Phenols such as epoxy resins having a phenylmethane skeleton, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and other phenols and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde, Epoxidized novolak resin obtained by condensation or cocondensation with a compound having an aldehyde group such as acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde in the presence of an acidic catalyst, Glycidyl obtained by reaction of polychlorobasic acid such as enol A, bisphenol F, bisphenol S, diglycidyl ether such as alkyl-substituted or unsubstituted biphenol, stilbene-type epoxy resin, hydroquinone-type epoxy resin, phthalic acid, dimer acid and epichlorohydrin Ester-type epoxy resin, diaminodiphenylmethane, isocyanuric acid and other polyamines obtained by reaction of epichlorohydrin with glycidylamine-type epoxy resin, epoxidized product of dicyclopentadiene and phenol co-condensation resin, epoxy resin having naphthalene ring, phenol and Aralkyl type phenolic resin, naphthol / aralkyl resin, etc. synthesized from naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl Epoxy compounds of sulfhydryl phenol resins, trimethylolpropane epoxy resins, terpene modified epoxy resins, linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracids such as peracetic acid, alicyclic epoxy resins, sulfur atoms Containing epoxy resins and the like, and these may be used alone or in combination of two or more.
Among them, biphenyl type epoxy resins, sulfur atom-containing epoxy resins, and bisphenol F type epoxy resins are preferable from the viewpoint of solder reflow resistance, and novolak type epoxy resins are preferable from the viewpoint of curability, and from the viewpoint of low hygroscopicity. Dicyclopentadiene type epoxy resin is preferable, naphthalene type epoxy resin and triphenylmethane type epoxy resin are preferable from the viewpoint of heat resistance and low warpage, and biphenylene skeleton-containing phenol / aralkyl type epoxy resin is preferable from the viewpoint of flame retardancy. Preferably, it contains at least one of these epoxy resins.

  Examples of the biphenyl type epoxy resin include an epoxy resin represented by the following general formula (III). Examples of the sulfur atom-containing epoxy resin include an epoxy resin represented by the following general formula (IV). As an epoxy resin, the epoxy resin shown by the following general formula (V) is mentioned, for example.

（一般式（ＩＩＩ）で、Ｒ^１〜Ｒ^８は水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、これらは全てが同一でも異なっていてもよい。ｎは０〜３の整数を示す。）

(In the general formula (III), R ^{1 to} R ⁸ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, which may all be the same or different. n represents an integer of 0 to 3.)

（一般式（ＩＶ）で、Ｒ^１〜Ｒ^８は水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、これらは全てが同一でも異なっていてもよい。ｎは０〜３の整数を示す。）

(In the general formula (IV), R ^{1 to} R ⁸ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and these may be all the same or different. n represents an integer of 0 to 3.)

（一般式（Ｖ）で、Ｒ^１〜Ｒ^８は水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、これらは全てが同一でも異なっていてもよい。ｎは０〜３の整数を示す。）
上記一般式（ＩＩＩ）で示されるビフェニル型エポキシ樹脂としては、たとえば、４，４’−ビス（２，３−エポキシプロポキシ）ビフェニル又は４，４’−ビス（２，３−エポキシプロポキシ）−３，３’，５，５’−テトラメチルビフェニルを主成分とするエポキシ樹脂、エピクロルヒドリンと４，４’−ビフェノール又は４，４’−（３，３’，５，５’−テトラメチル）ビフェノールとを反応させて得られるエポキシ樹脂等が挙げられる。なかでも４，４’−ビス（２，３−エポキシプロポキシ）−３，３’，５，５’−テトラメチルビフェニルを主成分とするエポキシ樹脂が好ましい。
上記一般式（ＩＶ）で示される硫黄原子含有エポキシ樹脂のなかでも、Ｒ^１〜Ｒ^８が水素原子、置換又は非置換の炭素数１〜１０のアルキル基及び置換又は非置換の炭素数１〜１０のアルコキシ基から選ばれるエポキシ樹脂が好ましく、Ｒ^１、Ｒ^４、Ｒ^５及びＲ^８が水素原子で、Ｒ^２、Ｒ^３、Ｒ^６及びＲ^７がアルキル基であるエポキシ樹脂がより好ましく、Ｒ^１、Ｒ^４、Ｒ^５及びＲ^８が水素原子で、Ｒ^２及びＲ^７がメチル基で、Ｒ^３及びＲ^６がｔ−ブチル基であるエポキシ樹脂がさらに好ましい。このような化合物としては、ＹＳＬＶ−１２０ＴＥ（新日鐵化学社製）等が市販品として入手可能である。
上記一般式（Ｖ）で示されるビスフェノールＦ型エポキシ樹脂としては、例えば、Ｒ^１、Ｒ^３、Ｒ^６及びＲ^８がメチル基で、Ｒ^２、Ｒ^４、Ｒ^５及びＲ^７が水素原子であり、ｎ＝０を主成分とするＹＳＬＶ−８０ＸＹ（新日鉄化学株式会社製商品名）が市販品として入手可能である。
これらビフェニル型エポキシ樹脂、硫黄原子含有エポキシ樹脂及びビスフェノールＦ型エポキシ樹脂はいずれか１種を単独で用いても２種以上を組合わせて用いてもよいが、その配合量は、その性能を発揮するためにエポキシ樹脂全量に対して合わせて２０重量％以上とすることが好ましく、３０重量％以上がより好ましく、５０重量％以上とすることがさらに好ましい。

(In the general formula (V), R ^{1 to} R ⁸ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, which may all be the same or different. n represents an integer of 0 to 3.)
Examples of the biphenyl type epoxy resin represented by the general formula (III) include 4,4′-bis (2,3-epoxypropoxy) biphenyl or 4,4′-bis (2,3-epoxypropoxy) -3. , 3 ′, 5,5′-tetramethylbiphenyl as the main component, epichlorohydrin and 4,4′-biphenol or 4,4 ′-(3,3 ′, 5,5′-tetramethyl) biphenol An epoxy resin obtained by reacting is used. Among these, an epoxy resin mainly composed of 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl is preferable.
Among the sulfur atom-containing epoxy resins represented by the general formula (IV), R ^{1 to} R ⁸ are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted carbon number 1 to 1. An epoxy resin selected from 10 alkoxy groups is preferred, an epoxy resin in which R ¹ , R ⁴ , R ⁵ and R ⁸ are hydrogen atoms and R ² , R ³ , R ⁶ and R ⁷ are alkyl groups is more preferred, More preferred is an epoxy resin in which R ¹ , R ⁴ , R ⁵ and R ⁸ are hydrogen atoms, R ² and R ⁷ are methyl groups, and R ³ and R ⁶ are t-butyl groups. As such a compound, YSLV-120TE (manufactured by Nippon Steel Chemical Co., Ltd.) and the like are commercially available.
As the bisphenol F type epoxy resin represented by the general formula (V), for example, R ¹ , R ³ , R ⁶ and R ⁸ are methyl groups, and R ² , R ⁴ , R ⁵ and R ⁷ are hydrogen atoms. Yes, YSLV-80XY (trade name, manufactured by Nippon Steel Chemical Co., Ltd.) having n = 0 as a main component is available as a commercial product.
These biphenyl type epoxy resins, sulfur atom-containing epoxy resins and bisphenol F type epoxy resins may be used alone or in combination of two or more, but the blending amount exhibits their performance. Therefore, the total amount is preferably 20% by weight or more, more preferably 30% by weight or more, and still more preferably 50% by weight or more based on the total amount of the epoxy resin.

  Examples of the novolac type epoxy resin include an epoxy resin represented by the following general formula (VI).

（一般式（ＶＩ）で、Ｒは水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、ｎは０〜１０の整数を示す。）
上記一般式（ＶＩ）で示されるノボラック型エポキシ樹脂は、ノボラック型フェノール樹脂にエピクロルヒドリンを反応させることによって容易に得られる。なかでも、上記一般式（ＶＩ）中のＲとしては、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、イソブチル基等の炭素数１〜１０のアルキル基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等の炭素数１〜１０のアルコキシル基が好ましく、水素原子又はメチル基がより好ましい。ｎは０〜３の整数が好ましい。上記一般式（ＶＩ）で示されるノボラック型エポキシ樹脂のなかでも、オルソクレゾールノボラック型エポキシ樹脂が好ましい。
ノボラック型エポキシ樹脂を使用する場合、その配合量は、その性能を発揮するためにエポキシ樹脂全量に対して２０重量％以上とすることが好ましく、３０重量％以上がより好ましい。

(In general formula (VI), R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10)
The novolak type epoxy resin represented by the general formula (VI) can be easily obtained by reacting a novolak type phenol resin with epichlorohydrin. Among them, R in the general formula (VI) may be an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, or an isobutyl group, a methoxy group, an ethoxy group, or a propoxy group. C1-C10 alkoxyl groups, such as a group and a butoxy group, are preferable, and a hydrogen atom or a methyl group is more preferable. n is preferably an integer of 0 to 3. Among the novolac type epoxy resins represented by the general formula (VI), orthocresol novolac type epoxy resins are preferable.
In the case of using a novolac type epoxy resin, its blending amount is preferably 20% by weight or more, more preferably 30% by weight or more, based on the total amount of the epoxy resin in order to exhibit its performance.

  Examples of the dicyclopentadiene type epoxy resin include an epoxy resin represented by the following general formula (VII).

（一般式（ＶＩＩ）で、Ｒ^１及びＲ^２は水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基からそれぞれ独立して選ばれ、ｎは０〜１０の整数を示し、ｍは０〜６の整数を示す。）
上記一般式（ＶＩＩ）中のＲ^１としては、たとえば、水素原子、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、ｔ−ブチル基等のアルキル基、ビニル基、アリル基、ブテニル基等のアルケニル基、ハロゲン化アルキル基、アミノ基置換アルキル基、メルカプト基置換アルキル基などの炭素数１〜１０の置換又は非置換の一価の炭化水素基が挙げられ、なかでもメチル基、エチル基等のアルキル基及び水素原子が好ましく、メチル基及び水素原子がより好ましい。Ｒ^２としては、たとえば、水素原子、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、ｔ−ブチル基等のアルキル基、ビニル基、アリル基、ブテニル基等のアルケニル基、ハロゲン化アルキル基、アミノ基置換アルキル基、メルカプト基置換アルキル基などの炭素数１〜１０の置換又は非置換の一価の炭化水素基が挙げられ、なかでも水素原子が好ましい。
ジシクロペンタジエン型エポキシ樹脂を使用する場合、その配合量は、その性能を発揮するためにエポキシ樹脂全量に対して２０重量％以上とすることが好ましく、３０重量％以上がより好ましい。

(In General Formula (VII), R ¹ and R ² are each independently selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 0 to 10. M represents an integer of 0 to 6.)
R ¹ in the general formula (VII) is, for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a t-butyl group or other alkyl group, a vinyl group, an allyl group, or a butenyl group. Examples thereof include substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms such as alkenyl groups, halogenated alkyl groups, amino group-substituted alkyl groups, mercapto group-substituted alkyl groups, etc., among which methyl group, ethyl An alkyl group such as a group and a hydrogen atom are preferable, and a methyl group and a hydrogen atom are more preferable. Examples of R ² include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and a t-butyl group, an alkenyl group such as a vinyl group, an allyl group, and a butenyl group, and an alkyl halide. Examples thereof include substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms such as a group, an amino group-substituted alkyl group, and a mercapto group-substituted alkyl group, and among them, a hydrogen atom is preferable.
When a dicyclopentadiene type epoxy resin is used, its blending amount is preferably 20% by weight or more, more preferably 30% by weight or more based on the total amount of the epoxy resin in order to exhibit its performance.

Examples of the naphthalene type epoxy resin include an epoxy resin represented by the following general formula (VIII), and examples of the triphenylmethane type epoxy resin include an epoxy resin represented by the following general formula (IX).
The naphthalene type epoxy resin represented by the following general formula (VIII) includes a random copolymer randomly containing m structural units and n structural units, an alternating copolymer alternately containing, and a copolymer containing regularly. Examples thereof include block copolymers including a block and a block, and any one of these may be used alone, or two or more may be used in combination. The triphenylmethane type epoxy resin represented by the following general formula (IX) is not particularly limited, but a salicylaldehyde type epoxy resin is preferable.

（一般式（ＶＩＩＩ）で、Ｒ^１〜Ｒ^３は水素原子及び炭素数１〜１２の置換又は非置換の一価の炭化水素基から選ばれ、これらは全てが同一でも異なっていてもよい。ｐは１又は０で、ｍ、ｎはそれぞれ０〜１１の整数であって、（ｍ＋ｎ）が１〜１１の整数でかつ（ｍ＋ｐ）が１〜１２の整数となるよう選ばれる。ｉは０〜３の整数、ｊは０〜２の整数、ｋは０〜４の整数を示す。）

(In General Formula (VIII), R ^{1 to} R ³ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, which may all be the same or different. p is 1 or 0, m and n are each an integer of 0 to 11, and (m + n) is an integer of 1 to 11 and (m + p) is an integer of 1 to 12. i is 0. An integer of -3, j is an integer of 0-2, and k is an integer of 0-4.)

（一般式（ＩＸ）で、Ｒは水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、ｎは１〜１０の整数を示す。）
これらナフタレン型エポキシ樹脂及びトリフェニルメタン型エポキシ樹脂はいずれか１種を単独で用いても両者を組合わせて用いてもよいが、その配合量は、その性能を発揮するためにエポキシ樹脂全量に対して合わせて２０重量％以上とすることが好ましく、３０重量％以上がより好ましく、５０重量％以上とすることがさらに好ましい。

(In General Formula (IX), R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 1 to 10.)
These naphthalene-type epoxy resins and triphenylmethane-type epoxy resins may be used alone or in combination with each other, but the blending amount thereof is the total amount of the epoxy resin in order to exhibit its performance. In total, it is preferably 20% by weight or more, more preferably 30% by weight or more, and further preferably 50% by weight or more.

Examples of the biphenylene skeleton-containing phenol / aralkyl epoxy resin include epoxy resins represented by the following general formula (X). From the viewpoint of flame retardancy and reflow resistance, R ^{1 to} R ⁸ of the following general formula (X) are: A hydrogen atom is preferable, and as such a compound, NC-3000 (manufactured by Nippon Kayaku Co., Ltd.) and the like are commercially available.

（一般式（Ｘ）で、Ｒ^１〜Ｒ^９は水素原子、炭素数１〜１０の置換又は非置換のアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜１０のアリール基及び炭素数６〜１０のアラルキル基から選ばれ、全てが同一でも異なっていてもよい。ｉは０〜３の整数を示し、ｎは０〜１０の整数を示す。）
ビフェニレン骨格含有フェノール・アラルキル型エポキシ樹脂を使用する場合、その配合量は、その性能を発揮するためにエポキシ樹脂全量に対して２０重量％以上とすることが好ましく、３０重量％以上がより好ましい。

(In General Formula (X), R ^{1 to} R ⁹ are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and carbon. (Choose from several 6 to 10 aralkyl groups, all of which may be the same or different. I represents an integer of 0 to 3, and n represents an integer of 0 to 10.)
When the biphenylene skeleton-containing phenol / aralkyl type epoxy resin is used, the blending amount thereof is preferably 20% by weight or more, more preferably 30% by weight or more, based on the total amount of the epoxy resin in order to exhibit its performance.

Moreover, it is preferable to contain the epoxy resin shown by the said general formula (III) from a viewpoint of coexistence of a flame retardance, reflow resistance, and fluidity, especially R < ¹ >-of the said general formula (X)- More preferably, R ⁸ is a hydrogen atom and R ^{1 to} R ^{8 in} the general formula (III) are hydrogen atoms and n = 0. In particular, the blending weight ratio is preferably (III) / (X) = 50/50 to 5/95, more preferably 40/60 to 10/90, and 30/70 to 15/85. Is more preferred. As a compound satisfying such a blending weight ratio, CER-3000L (manufactured by Nippon Kayaku Co., Ltd.) and the like are commercially available.

  Biphenyl type epoxy resin, sulfur atom-containing epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, triphenylmethane type epoxy resin and biphenylene skeleton containing phenol / aralkyl type The epoxy resin may be used alone or in combination of two or more, but the blending amount is preferably 50% by weight or more based on the total amount of the epoxy resin. More preferably, it is more than 80% by weight.

The (B) curing agent used in the present invention is generally used for an epoxy resin molding material for sealing and is not particularly limited. For example, phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenyl Phenols such as phenol and aminophenol and / or naphthols such as α-naphthol, β-naphthol, and dihydroxynaphthalene and compounds having an aldehyde group such as formaldehyde, benzaldehyde, and salicylaldehyde are condensed or co-condensed in an acidic catalyst. Aralkyls such as phenol / aralkyl resins and naphthol / aralkyl resins synthesized from novolak-type phenolic resins, phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl Kill-type phenol resin, copolymer-type phenol-aralkyl resin in which phenol / novolak structure and phenol-aralkyl structure are random, block or alternately repeated, paraxylylene and / or metaxylylene-modified phenol resin, melamine-modified phenol resin, terpene-modified phenol resin , Dicyclopentadiene-modified phenol resin, cyclopentadiene-modified phenol resin, polycyclic aromatic ring-modified phenol resin, and the like. These may be used alone or in combination of two or more.
Among them, biphenylene skeleton-containing phenol / aralkyl resins and copolymeric phenol / aralkyl resins are preferable from the viewpoint of flame retardancy, and phenol / aralkyl resins and naphthol / aralkyl resins are preferable from the viewpoint of solder reflow resistance and curability. From the viewpoint of low hygroscopicity, dicyclopentadiene type phenol resin is preferable, from the viewpoint of heat resistance, low expansion coefficient and low warpage, triphenylmethane type phenol resin is preferable, and from the viewpoint of curability, novolac type phenol resin It is preferable that it contains at least one of these phenol resins.

  Examples of the biphenylene skeleton-containing phenol-aralkyl resin include phenol resins represented by the following general formula (XI).

（一般式（ＸＩ）で、Ｒ^１〜Ｒ^９は水素原子、炭素数１〜１０の置換又は非置換のアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜１０のアリール基及び炭素数６〜１０のアラルキル基から選ばれ、全てが同一でも異なっていてもよい。ｎは０〜１０の整数を示す。）
上記一般式（ＸＩ）中のＲ^１〜Ｒ^９としては、水素原子、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、イソブチル基等の炭素数１〜１０のアルキル基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等の炭素数１〜１０のアルコキシ基、フェニル基、トリル基、キシリル基等の炭素数６〜１０のアリール基及びベンジル基、フェネチル基等の炭素数６〜１０のアラルキル基から選ばれ、なかでも水素原子とメチル基が好ましい。ｎは０〜１０の整数を示す。上記一般式（ＸＩ）で示されるビフェニレン骨格含有フェノール・アラルキル樹脂としては、たとえばＲ^１〜Ｒ^９が全て水素原子である化合物等が挙げられ、なかでも溶融粘度の観点から、ｎが１以上の縮合体を５０重量％以上含む縮合体の混合物が好ましい。
ビフェニレン骨格含有フェノール・アラルキル樹脂を使用する場合、その配合量はその性能を発揮するために硬化剤全量に対して３０重量％以上とすることが好ましく、５０重量％以上がより好ましく、６０重量％以上がさらに好ましい。

(In General Formula (XI), R ^{1 to} R ⁹ are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and carbon. (Selected from aralkyl groups of formulas 6 to 10, all may be the same or different. N represents an integer of 0 to 10.)
As R < ¹ > -R < ⁹ > in the said general formula (XI), C1-C10 alkyl groups, such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a methoxy group, C1-C10 alkoxy groups, such as an ethoxy group, a propoxy group, and a butoxy group, C6-C10 aryl groups, such as a phenyl group, a tolyl group, and a xylyl group, and C6-C10, such as a benzyl group and a phenethyl group Of these, a hydrogen atom and a methyl group are preferred. n represents an integer of 0 to 10. Examples of the biphenylene skeleton-containing phenol-aralkyl resin represented by the general formula (XI) include compounds in which R ^{1 to} R ⁹ are all hydrogen atoms, and in particular, from the viewpoint of melt viscosity, n is 1 or more. A mixture of condensates containing 50% by weight or more of condensates is preferred.
When the biphenylene skeleton-containing phenol / aralkyl resin is used, its blending amount is preferably 30% by weight or more, more preferably 50% by weight or more, more preferably 60% by weight in order to exhibit its performance. The above is more preferable.

  Examples of the phenol / aralkyl resin include a phenol / aralkyl resin represented by the following general formula (XII).

（一般式（ＸＩＩ）で、Ｒは水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、ｎは０〜１０の整数を示す。）
上記一般式（ＸＩＩ）中のＲとしては、たとえば、水素原子、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、ｔ−ブチル基等のアルキル基、ビニル基、アリル基、ブテニル基等のアルケニル基、ハロゲン化アルキル基、アミノ基置換アルキル基、メルカプト基置換アルキル基などの炭素数１〜１０の置換又は非置換の一価の炭化水素基が挙げられ、なかでも、Ｒが水素原子で、ｎの平均値が０〜８であるフェノール・アラルキル樹脂が好ましく、具体例としては、ｐ−キシリレン型ザイロック、ｍ−キシリレン型ザイロック等が挙げられる。このフェノール・アラルキル樹脂を用いる場合、その配合量はその性能を発揮するために硬化剤全量に対して３０重量％以上とすることが好ましく、５０重量％以上がより好ましく、６０重量％以上がさらに好ましい。

(In General Formula (XII), R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10)
Examples of R in the general formula (XII) include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and a t-butyl group, a vinyl group, an allyl group, and a butenyl group. A substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms such as an alkenyl group, a halogenated alkyl group, an amino group-substituted alkyl group, a mercapto group-substituted alkyl group, and the like. Among them, R is a hydrogen atom. In addition, a phenol / aralkyl resin having an average value of n of 0 to 8 is preferable, and specific examples thereof include p-xylylene type zylock and m-xylylene type zylock. When this phenol-aralkyl resin is used, its blending amount is preferably 30% by weight or more, more preferably 50% by weight or more, and more preferably 60% by weight or more based on the total amount of the curing agent in order to exhibit its performance. preferable.

  Examples of the naphthol / aralkyl resin include naphthol / aralkyl resins represented by the following general formula (XIII).

（一般式（ＸＩＩＩ）で、Ｒ^１〜Ｒ^３は全てが同一でも異なっていてもよく、水素原子及び炭素数１〜６のアルキル基を示す。ｎは０〜１０の整数、ｊは０〜２の整数、ｋは０〜４の整数、ｒは０〜４の整数を示す。）
上記一般式（ＸＩＩＩ）中のＲ^１〜Ｒ^３としてはたとえば水素原子、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、イソプロピル基、イソブチル基等の炭素数１〜６のアルキル基から選ばれ、なかでもＲ^１〜Ｒ^３水素原子で１分子中の平均ｎが０〜４の範囲に設定されることが好ましい。
ナフトール・アラルキル樹脂を用いる場合、その配合量はその性能を発揮するために硬化剤全量に対して３０重量％以上とすることが好ましく、５０重量％以上がより好ましい。

(In General Formula (XIII), R ^{1 to} R ³ may all be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. N is an integer of 0 to 10, j is 0 to 0. 2 is an integer, k is an integer of 0 to 4, and r is an integer of 0 to 4.)
R ^{1 to} R ³ in the general formula (XIII) include, for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, and an isobutyl group. It is preferably selected from alkyl groups, among which R ^{1 to} R ^{3 are} hydrogen atoms and the average n in one molecule is preferably set in the range of 0 to 4.
When a naphthol / aralkyl resin is used, its blending amount is preferably 30% by weight or more, more preferably 50% by weight or more based on the total amount of the curing agent in order to exhibit its performance.

  The phenol / aralkyl resin represented by the general formula (XII) and the naphthol / aralkyl resin represented by the general formula (XIII) may be partially or fully mixed with acenaphthylene from the viewpoint of flame retardancy. . Although acenaphthylene can be obtained by dehydrogenating acenaphthene, a commercially available product may be used. Further, it can be used as a polymer of acenaphthylene or a polymer of acenaphthylene and other aromatic olefins. (B) As a method of pre-mixing part or all of the curing agent with acenaphthylene, (B) a method of finely grinding the curing agent and acenaphthylene, respectively, and mixing them with a mixer or the like in a solid state, dissolving both components A method of removing the solvent after being uniformly dissolved in the solvent, (B) a method of melt-mixing both at a temperature equal to or higher than the softening point of the curing agent and / or acenaphthylene, etc. Therefore, a melt mixing method with less contamination of impurities is preferable. In that case, acenaphthylene may superpose | polymerize or react with (B) hardening | curing agent during mixing.

  Examples of the dicyclopentadiene type phenol resin include a phenol resin represented by the following general formula (XIV).

（一般式（ＸＩＶ）で、Ｒ^１及びＲ^２は水素原子、炭素数１〜１０の置換又は非置換の一価の炭化水素基からそれぞれ独立して選ばれ、ｎは０〜１０の整数を示し、ｍは０〜６の整数を示す。）
上記一般式（ＸＩＶ）中のＲ^１としては、たとえば、水素原子、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、ｔ−ブチル基等のアルキル基、ビニル基、アリル基、ブテニル基等のアルケニル基、ハロゲン化アルキル基、アミノ基置換アルキル基、メルカプト基置換アルキル基などの炭素数１〜１０の置換又は非置換の一価の炭化水素基が挙げられ、なかでもメチル基、エチル基等のアルキル基及び水素原子が好ましく、メチル基及び水素原子がより好ましい。Ｒ^２としては、たとえば、水素原子、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、ｔ−ブチル基等のアルキル基、ビニル基、アリル基、ブテニル基等のアルケニル基、ハロゲン化アルキル基、アミノ基置換アルキル基、メルカプト基置換アルキル基などの炭素数１〜１０の置換又は非置換の一価の炭化水素基が挙げられ、なかでも水素原子が好ましい。また１分子中の平均ｎが０〜４の範囲に設定されることが好ましい。
ジシクロペンタジエン型フェノール樹脂を用いる場合、その配合量はその性能を発揮するために硬化剤全量に対して３０重量％以上とすることが好ましく、５０重量％以上がより好ましい。

(In the general formula (XIV), R ¹ and R ² are each independently selected from a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 0 to 10. M represents an integer of 0 to 6.)
Examples of R ¹ in the general formula (XIV) include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and a t-butyl group, a vinyl group, an allyl group, and a butenyl group. Examples thereof include substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms such as alkenyl groups, halogenated alkyl groups, amino group-substituted alkyl groups, mercapto group-substituted alkyl groups, etc., among which methyl group, ethyl An alkyl group such as a group and a hydrogen atom are preferable, and a methyl group and a hydrogen atom are more preferable. Examples of R ² include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and a t-butyl group, an alkenyl group such as a vinyl group, an allyl group, and a butenyl group, and an alkyl halide. Examples thereof include substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms such as a group, an amino group-substituted alkyl group, and a mercapto group-substituted alkyl group, and among them, a hydrogen atom is preferable. Moreover, it is preferable that the average n in 1 molecule is set to the range of 0-4.
When a dicyclopentadiene type phenol resin is used, its blending amount is preferably 30% by weight or more, more preferably 50% by weight or more based on the total amount of the curing agent in order to exhibit its performance.

  Examples of the triphenylmethane type phenol resin include a phenol resin represented by the following general formula (XV).

（一般式（ＸＶ）で、Ｒは水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、ｎは０〜１０の整数を示す。）
上記一般式（ＸＶ）中のＲとしては、たとえば、水素原子、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、ｔ−ブチル基等のアルキル基、ビニル基、アリル基、ブテニル基等のアルケニル基、ハロゲン化アルキル基、アミノ基置換アルキル基、メルカプト基置換アルキル基などの炭素数１〜１０の置換又は非置換の一価の炭化水素基が挙げられ、なかでもメチル基、エチル基等のアルキル基及び水素原子が好ましく、メチル基及び水素原子がより好ましい。
トリフェニルメタン型フェノール樹脂を用いる場合、その配合量はその性能を発揮するために硬化剤全量に対して３０重量％以上とすることが好ましく、５０重量％以上がより好ましい。

(In general formula (XV), R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10)
R in the general formula (XV) is, for example, a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, or a t-butyl group, a vinyl group, an allyl group, or a butenyl group. C1-C10 substituted or unsubstituted monovalent hydrocarbon group such as alkenyl group, halogenated alkyl group, amino group-substituted alkyl group, mercapto group-substituted alkyl group, etc., among which methyl group, ethyl group Alkyl groups and hydrogen atoms such as methyl groups and hydrogen atoms are more preferable.
When a triphenylmethane type phenol resin is used, its blending amount is preferably 30% by weight or more, more preferably 50% by weight or more, based on the total amount of the curing agent in order to exhibit its performance.

  Examples of the novolak-type phenol resin include novolak-type phenol resins such as a phenol resin represented by the following general formula (XVI), cresol novolak resins, and the like. Among these, novolak-type phenol resins represented by the following general formula (XVI) are exemplified. preferable.

（一般式（ＸＶＩ）で、Ｒは水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、ｉは０〜３の整数を示し、ｎは０〜１０の整数を示す。）
上記一般式（ＸＶＩ）中のＲとしては、たとえば、水素原子、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、ｔ−ブチル基等のアルキル基、ビニル基、アリル基、ブテニル基等のアルケニル基、ハロゲン化アルキル基、アミノ基置換アルキル基、メルカプト基置換アルキル基などの炭素数１〜１０の置換又は非置換の一価の炭化水素基が挙げられ、なかでもメチル基、エチル基等のアルキル基及び水素原子が好ましく、水素原子がより好ましく、ｎの平均値が０〜８であることが好ましい。
ノボラック型フェノール樹脂を用いる場合、その配合量はその性能を発揮するために硬化剤全量に対して３０重量％以上とすることが好ましく、５０重量％以上がより好ましい。

(In General Formula (XVI), R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, i represents an integer of 0 to 3, and n represents 0 to 10 Indicates an integer.)
Examples of R in the general formula (XVI) include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and a t-butyl group, a vinyl group, an allyl group, and a butenyl group. C1-C10 substituted or unsubstituted monovalent hydrocarbon group such as alkenyl group, halogenated alkyl group, amino group-substituted alkyl group, mercapto group-substituted alkyl group, etc., among which methyl group, ethyl group Alkyl groups and hydrogen atoms such as hydrogen atoms, hydrogen atoms are more preferable, and the average value of n is preferably 0 to 8.
When a novolac type phenol resin is used, its blending amount is preferably 30% by weight or more, more preferably 50% by weight or more, based on the total amount of the curing agent in order to exhibit its performance.

  As a copolymerization type phenol aralkyl resin, the phenol resin shown, for example by the following general formula (XVII) is mentioned.

（一般式（ＸＶＩＩ）で、Ｒは水素原子、炭素数１〜１２の置換又は非置換の一価の炭化水素基及び水酸基から選ばれ、すべてが同一でも異なっていてもよい。またＸは芳香環を含む基を示す。ｎ及びｍは０又は１〜１０の整数を示す。）
上記一般式（ＸＶＩＩ）中のＲとしては、たとえば、メチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基等の鎖状アルキル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロペンテニル基、シクロヘキセニル基等の環状アルキル基、ベンジル基、フェネチル基等のアリール基置換アルキル基、メトキシ基置換アルキル基、エトキシ基置換アルキル基、ブトキシ基置換アルキル基等のアルコキシ基置換アルキル基、ジメチルアミノ基、ジエチルアミノ基等のアミノ基置換アルキル基、水酸基置換アルキル基、フェニル基、ナフチル基、ビフェニル基等の無置換アリール基、トリル基、ジメチルフェニル基、エチルフェニル基、ブチルフェニル基、ｔ−ブチルフェニル基、ジメチルナフチル基等のアルキル基置換アリール基、メトキシフェニル基、エトキシフェニル基、ブトキシフェニル基、ｔ−ブトキシフェニル基、メトキシナフチル基等のアルコキシ基置換アリール基、ジメチルアミノ基、ジエチルアミノ基等のアミノ基置換アリール基、水酸基置換アリール基などが挙げられ、なかでも水素原子又はメチル基が好ましく、またｎ及びｍは０又は１〜１０の整数を示し、平均で６以下がより好ましい。
上記一般式（ＸＶＩＩ）中のＸとしては、たとえばフェニレン基、ビフェニレン基、ナフチレン基等のアリーレン基、トリレン基、キシリレン基等のアルキル基置換アリーレン基、アルコキシル基置換アリーレン基、ベンジル基、フェネチル基等のアラルキル基、アラルキル基置換アリーレン基などが挙げられ、なかでも、置換又は非置換のフェニレン基及びビフェニレン基が好ましい。一般式（ＸＶＩＩ）で示される化合物としては、ＨＥ−５１０住金エア・ウォーター・ケミカル株式会社製）等が市販品として入手可能である。共重合型フェノール・アラルキル樹脂を用いる場合、その配合量はその性能を発揮するために硬化剤全量に対して３０重量％以上とすることが好ましく、５０重量％以上がより好ましい。

(In the general formula (XVII), R is selected from a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms and a hydroxyl group, all of which may be the same or different. A group containing a ring; n and m are 0 or an integer of 1 to 10)
As R in the general formula (XVII), for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, Decyl group, chain alkyl group such as dodecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, cyclohexenyl group and other cyclic alkyl groups, benzyl group, phenethyl group and other aryl group substituted alkyl groups, methoxy group Substituted alkyl group, ethoxy group substituted alkyl group, alkoxy group substituted alkyl group such as butoxy group substituted alkyl group, amino group substituted alkyl group such as dimethylamino group, diethylamino group, hydroxyl group substituted alkyl group, phenyl group, naphthyl group, biphenyl group Unsubstituted aryl group such as, tolyl group, dimethylphenyl group, Alkyl group-substituted aryl groups such as ruphenyl group, butylphenyl group, t-butylphenyl group and dimethylnaphthyl group, alkoxy group substitution such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, t-butoxyphenyl group and methoxynaphthyl group Examples include an aryl group, a dimethylamino group, an amino group-substituted aryl group such as a diethylamino group, and a hydroxyl group-substituted aryl group. Among them, a hydrogen atom or a methyl group is preferable, and n and m represent 0 or an integer of 1 to 10. On average, 6 or less is more preferable.
X in the general formula (XVII) is, for example, an arylene group such as a phenylene group, a biphenylene group, or a naphthylene group, an alkyl group-substituted arylene group such as a tolylene group or a xylylene group, an alkoxyl group-substituted arylene group, a benzyl group, or a phenethyl group. And an aralkyl group-substituted arylene group and the like. Among them, a substituted or unsubstituted phenylene group and a biphenylene group are preferable. As the compound represented by the general formula (XVII), HE-510 Sumikin Air Water Chemical Co., Ltd.) and the like are commercially available. In the case of using a copolymeric phenol / aralkyl resin, the blending amount is preferably 30% by weight or more, more preferably 50% by weight or more based on the total amount of the curing agent in order to exhibit its performance.

  Any of the above-mentioned biphenylene skeleton-containing phenol / aralkyl resins, phenol / aralkyl resins, naphthol / aralkyl resins, dicyclopentadiene type phenol resins, triphenylmethane type phenol resins, novolac type phenol resins and copolymeric type phenol / aralkyl resins One kind may be used alone or two or more kinds may be used in combination, but the blending amount is preferably 50% by weight or more, more preferably 60% by weight or more, based on the total amount of phenol resin. 80% by weight or more is more preferable.

  In the present invention, the equivalent ratio of (A) epoxy resin and (B) curing agent, that is, the ratio of the number of hydroxyl groups in the curing agent to the epoxy group (number of hydroxyl groups in the curing agent / number of epoxy groups in the epoxy resin) is particularly Although there is no restriction | limiting, in order to suppress each unreacted part few, it is preferable to set to the range of 0.5-2, and 0.6-1.3 are more preferable. In order to obtain a sealing epoxy resin molding material excellent in moldability and solder reflow resistance, it is more preferably set in the range of 0.8 to 1.2.

The (C) acrylic compound represented by the following general formula (I) used in the present invention is not particularly limited as long as it has a structure represented by the following general formula, and randomly includes m structural units and n structural units. Copolymers, alternating copolymers containing alternately, copolymers containing regularly, block copolymers containing in block form, and any one of these may be used alone or in combination of two or more. You may use together. The terminal structure of the acrylic compound may be modified with a conventionally known chain transfer agent or the like, such as a hydrogen atom and mercapto group-containing compound. Examples of R ¹ and R ² in the structure include a hydrogen atom and a methyl group, and a methyl group is preferable from the viewpoint of fluidity. R ³ includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a pentyl group, and a hexyl group, and among them, a methyl group and an n-butyl group are preferable. A methyl group is particularly preferred from the viewpoint of the balance between fluidity and moldability. Although m shows the integer of 1-20, 1-15 are preferable from a viewpoint of a moldability, and 3-10 are more preferable. Although n shows the integer of 0-20, 1-15 are preferable from a viewpoint of fluidity | liquidity and the balance of a moldability, and 3-10 are more preferable. The average value of n / m in the compound is 0.05 or more and 3 or less, but is preferably 0.1 or more and 2.5 or less, more preferably 0.2 or more and 2 or less from the viewpoint of the balance between fluidity and moldability. preferable. R ⁵ and R ^{6 in} R ^{4 represented} by the following general formula (II) are alkyl groups such as methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, t-butyl group, vinyl group, C1-C6 hydrocarbon groups, such as alkenyl groups, such as an allyl group, a propenyl group, and a butenyl group, are mentioned, Especially, a C1-C6 alkyl group is preferable, and it is a methyl group from a moldability or adhesive viewpoint. C1-C4 alkyl groups such as ethyl group, propyl group, and butyl group are more preferable. Moreover, although p shows the integer of 1-3, what is 2 or 3 is preferable from an adhesive viewpoint, and what is 3 is more preferable. As a preferable compound among the acrylic compounds represented by the general formula (I), AS-300 (manufactured by Soken Chemical Co., Ltd.) is available as a commercial product.

（一般式（Ｉ）で、Ｒ^１、Ｒ^２は水素原子及びメチル基を示し、Ｒ^３は炭素数１〜６の炭化水素基を示し、Ｒ^４は下記一般式（ＩＩ）で示す基、ｍは１〜２０の整数、ｎは０〜２０の整数を示し、化合物中のｎ／ｍの平均値が０．０５以上３以下。）

(In the general formula (I), R ¹ and R ² represent a hydrogen atom and a methyl group, R ³ represents a hydrocarbon group having 1 to 6 carbon atoms, R ⁴ represents a group represented by the following general formula (II), m represents an integer of 1 to 20, n represents an integer of 0 to 20, and the average value of n / m in the compound is 0.05 or more and 3 or less.)

（一般式（ＩＩ）で、Ｒ^５は水素原子及び炭素数１〜６の炭化水素基を示し、Ｒ^６は炭素数１〜６の炭化水素基を示し、ｐは１〜３の整数を示す。）

(In General Formula (II), R ⁵ represents a hydrogen atom and a hydrocarbon group having 1 to 6 carbon atoms, R ⁶ represents a hydrocarbon group having 1 to 6 carbon atoms, and p represents an integer of 1 to 3. .)

  (C) The total amount of the acrylic compound represented by the above general formula is preferably 0.03 to 0.8% by weight with respect to the sealing epoxy resin molding material from the viewpoint of fluidity, moldability and reflow resistance, 0.04 to 0.75% by weight is more preferable, and 0.05 to 0.7% by weight is more preferable. If the amount is less than 0.03% by weight, the effect of the invention tends to be small. If the amount exceeds 0.8% by weight, the fluidity is improved, but the reflow resistance tends to be greatly reduced.

  The method for producing the acrylic compound represented by the general formula (I) used in the present invention is not particularly limited as long as the obtained compound has a structure represented by the general formula (I). For example, an azo compound or peroxide is used as a polymerization initiator, and an acrylic monomer is polymerized in the presence of a mercaptan as a chain transfer agent, or a reactive silyl group such as a metallocene compound and γ-mercaptopropyltrimethoxysilane is present. Examples include a method of polymerizing the lower acrylic monomer.

  The (D) silane compound used in the present invention is various silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane, and examples thereof include vinyl trichlorosilane, vinyl trimethoxy silane, Vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane , Γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyldimethylethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxy Silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycine Sidoxypropylmethyldiethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyldimethylethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, bis (Triethoxysilylpropyl) tetrasulfide, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (a Noethyl) -γ-aminopropyltriethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, isocyanatepropyltrimethoxysilane, isocyanatepropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxy Silane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenylsilanediol, triphenylmethoxysilane, triphenylethoxysilane, triphenylsilanol, N-β- (N-vinylbenzylaminoethyl) ) -Γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, γ-anilinopropi Trimethoxysilane, γ-anilinopropyltriethoxysilane, 2-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) Propylamine, N- (3-triethoxysilylpropyl) phenylimine, 3- (3- (triethoxysilyl) propylamino) -N, N-dimethylpropionamide, N-triethoxysilylpropyl-β-alanine methyl ester Silane compounds such as 3- (triethoxysilylpropyl) dihydro-3,5-furandione, bis (trimethoxysilyl) benzene, 1H-imidazole, 2-alkylimidazole, 2,4-dialkylimidazole, 4-vinyl Imidazole compounds such as imidazole and γ-glycid Examples include imidazole-based silane compounds which are reaction products of γ-glycidoxypropylalkoxysilane such as cyclopropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane. A combination of the above may also be used.

  (D) 0.06 to 2 weight% is preferable with respect to the epoxy resin molding material for sealing from a viewpoint of moldability and adhesiveness, and, as for the total compounding quantity of a silane compound, 0.1 to 0.75 weight% is more preferable. 0.2 to 0.7% by weight is more preferable. If it is less than 0.06% by weight, the adhesion to various package members tends to be reduced, and if it exceeds 2% by weight, molding defects such as voids tend to occur.

  A conventionally well-known coupling agent may be mix | blended with the epoxy resin molding material for sealing of this invention. For example, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl) -1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropylisostearoyldiacrylic Titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumi Examples include titanate coupling agents such as phenyl titanate and tetraisopropyl bis (dioctyl phosphite) titanate, aluminum chelates, aluminum / zirconium compounds, etc. Even if one of these is used alone, two or more are combined. It may be used. Further, the total amount of these coupling agents is preferably 0.06 to 2% by weight, more preferably 0.1 to 0.75% by weight based on the epoxy resin molding material for sealing from the viewpoint of moldability and adhesiveness. 0.2 to 0.7% by weight is more preferable. If it is less than 0.06% by weight, the adhesion to various package members tends to be reduced, and if it exceeds 2% by weight, molding defects such as voids tend to occur.

The (E) curing accelerator used in the present invention is generally used in an epoxy resin molding material for sealing and is not particularly limited. For example, 1,8-diazabicyclo [5.4.0] undecene is used. Cycloamidine compounds such as -7,1,5-diazabicyclo [4.3.0] nonene-5,5,6-dibutylamino-1,8-diazabicyclo [5.4.0] undecene-7, and these compounds Maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4 Quinone compounds such as benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, diazophenylmethane, phenol resin, etc. Compound having intramolecular polarization formed by adding a compound having a bond, tertiary amines such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives, 2-methylimidazole Imidazoles such as 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole and their derivatives, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenyl Organic phosphines such as phosphine and phenylphosphine, and compounds obtained by adding compounds having a π bond such as maleic anhydride, the above quinone compound, diazophenylmethane, and phenol resin to these phosphines. Phosphorus compounds with internal polarization, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, tetrabutylphosphonium tetrabutylborate, etc. tetrasubstituted phosphonium tetrasubstituted borate, 2-ethyl-4-methylimidazole tetraphenylborate And tetraphenylboron salts such as N-methylmorpholine and tetraphenylborate, and derivatives thereof. These may be used alone or in combination of two or more.
Among these, an adduct of a tertiary phosphine and a quinone compound is preferable from the viewpoint of curability and fluidity, and an adduct of a cycloamidine compound and a phenol resin is preferable from the viewpoint of storage stability, and diazabicycloundecene. The novolac type phenol resin salt is more preferable. The blending amount of these curing accelerators is preferably 60% by weight or more, more preferably 80% by weight or more, based on the total amount of the curing accelerator.

The tertiary phosphine used in the adduct of the tertiary phosphine and the quinone compound is not particularly limited, but examples thereof include dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, and tris (4-methylphenyl) phosphine. , Tris (4-ethylphenyl) phosphine, tris (4-propylphenyl) phosphine, tris (4-butylphenyl) phosphine, tris (isopropylphenyl) phosphine, tris (t-butylphenyl) phosphine, tris (2,4- Dimethylphenyl) phosphine, tris (2,6-dimethylphenyl) phosphine, tris (2,4,6-trimethylphenyl) phosphine, tris (2,6-dimethyl-4-ethoxyphenyl) phosphine, tris (4 Methoxyphenyl) phosphine, tertiary phosphines are exemplified with an aryl group such as tris (4-ethoxyphenyl) phosphine, triphenylphosphine is preferable in view of moldability.
Further, the quinone compound used for the adduct of the tertiary phosphine and the quinone compound is not particularly limited, and examples thereof include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, anthraquinone, and the like. P-benzoquinone is preferable from the viewpoint of stability or storage stability.

  The blending amount of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved. However, the blending amount of the curing accelerator is 0.00 with respect to 100 parts by weight of the total amount of (A) epoxy resin and (B) curing agent. 1-10 weight part is preferable and 0.3-5 weight part is more preferable. If it is less than 0.1 parts by weight, it is difficult to cure in a short time, and if it exceeds 10 parts by weight, the curing rate tends to be too fast and a good molded product tends not to be obtained.

  The (F) inorganic filler used in the present invention is blended in a molding material for hygroscopicity, linear expansion coefficient reduction, thermal conductivity improvement and strength improvement, and is generally used as an epoxy resin molding material for sealing. There is no particular limitation as long as it is used, for example, fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride. , Beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, etc., or spherical beads, glass fibers, etc. May be used. Among these, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity, and the filler shape is preferably spherical from the viewpoint of fluidity during molding and mold wear. In particular, spherical fused silica is preferable from the viewpoint of a balance between cost and performance.

  The blending amount of the inorganic filler is preferably 70 to 95% by weight based on the epoxy resin molding material for sealing, from the viewpoint of flame retardancy, moldability, hygroscopicity, reduction of linear expansion coefficient and improvement of strength. From the viewpoint of reducing the linear expansion coefficient, 85 to 95% by weight is more preferable. If it is less than 70% by weight, the flame retardancy and reflow resistance tend to decrease, and if it exceeds 95% by weight, the fluidity tends to be insufficient.

  Moreover, an anion exchanger can be blended with the epoxy resin molding material for sealing of the present invention, if necessary, for the purpose of improving the moisture resistance and high temperature storage characteristics of the IC. The anion exchanger is not particularly limited, and conventionally known anion exchangers can be used. Examples thereof include hydrotalcites and hydrated oxides of elements selected from magnesium, aluminum, titanium, zirconium, and bismuth. These may be used alone or in combination of two or more. Of these, hydrotalcite represented by the following composition formula (XVIII) is preferable.

（０＜ｘ≦０．５、ｍは正の数）
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限定されるものではないが、（Ａ）エポキシ樹脂１００重量部に対して、０．１〜３０重量部が好ましく、１〜５重量部がより好ましい。

(0 <x ≦ 0.5, m is a positive number)
The amount of the anion exchanger is not particularly limited as long as it is a sufficient amount capable of capturing anions such as halogen ions, but it is 0.1 to 30 weights with respect to 100 parts by weight of (A) epoxy resin. Part is preferable, and 1 to 5 parts by weight is more preferable.

  In the sealing epoxy resin molding material of the present invention, an adhesion promoter can be used as necessary in order to further improve the adhesion. Examples of the adhesion promoter include derivatives such as imidazole, triazole, tetrazole and triazine, anthranilic acid, gallic acid, malonic acid, malic acid, maleic acid, aminophenol, quinoline and the like, and derivatives thereof, aliphatic acid amide compounds, Examples thereof include dithiocarbamate and thiadiazole derivatives. One of these may be used alone, or two or more may be used in combination.

  A release agent may be used in the sealing epoxy resin molding material of the present invention as necessary. As the release agent, it is preferable to use 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the epoxy resin (A), using an oxidized or non-oxidized polyolefin. . If it is less than 0.01 part by weight, the releasability tends to be insufficient, and if it exceeds 10 parts by weight, the adhesiveness tends to decrease. Examples of the oxidized or non-oxidized polyolefin 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 Corporation. Other examples of the release agent include carnauba wax, montanic acid ester, montanic acid, stearic acid, and the like. These may be used alone or in combination of two or more. When these other release agents are used in combination with the oxidized or non-oxidized polyolefin, the combined amount thereof is 0. 1 to 10 parts by weight is preferable, and 0.5 to 3 parts by weight is more preferable.

  A conventionally known flame retardant can be blended in the sealing epoxy resin molding material of the present invention as required. For example, red phosphorus coated with inorganic substances such as brominated epoxy resin, antimony trioxide, red phosphorus, aluminum hydroxide, magnesium hydroxide, zinc oxide and / or thermosetting resins such as phenol resin, phosphoric acid ester, etc. Phosphorus compounds, melamine, melamine derivatives, melamine-modified phenol resins, compounds having a triazine ring, nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives, phosphorus and nitrogen-containing compounds such as cyclophosphazene, aluminum hydroxide, magnesium hydroxide And a composite metal hydroxide represented by the following composition formula (XIX).

（一般式（ＸＩＸ）で、Ｍ^１、Ｍ^２及びＭ^３は互いに異なる金属元素を示し、ａ、ｂ、ｃ、ｄ、ｐ、ｑ及びｍは正の数、ｒは０又は正の数を示す。）
上記組成式（ＸＩＸ）中のＭ^１、Ｍ^２及びＭ^３は互いに異なる金属元素であれば特に制限はないが、難燃性の観点からは、Ｍ^１が第３周期の金属元素、ＩＩＡ族のアルカリ土類金属元素、ＩＶＢ族、ＩＩＢ族、ＶＩＩＩ族、ＩＢ族、ＩＩＩＡ族及びＩＶＡ族に属する金属元素から選ばれ、Ｍ^２がＩＩＩＢ〜ＩＩＢ族の遷移金属元素から選ばれることが好ましく、Ｍ^１がマグネシウム、カルシウム、アルミニウム、スズ、チタン、鉄、コバルト、ニッケル、銅及び亜鉛から選ばれ、Ｍ^２が鉄、コバルト、ニッケル、銅及び亜鉛から選ばれることがより好ましい。流動性の観点からは、Ｍ^１がマグネシウム、Ｍ^２が亜鉛又はニッケルで、ｒ＝０のものが好ましい。ｐ、ｑ及びｒのモル比は特に制限はないが、ｒ＝０で、ｐ／ｑが１／９９〜１／１であることが好ましい。なお、金属元素の分類は、典型元素をＡ亜族、遷移元素をＢ亜族とする長周期型の周期率表（出典：共立出版株式会社発行「化学大辞典４」１９８７年２月１５日縮刷版第３０刷）に基づいて行った。また、酸化亜鉛、錫酸亜鉛、硼酸亜鉛、酸化鉄、酸化モリブデン、モリブデン酸亜鉛、ジシクロペンタジエニル鉄等の金属元素を含む化合物などが挙げられ、これらの１種を単独で用いても２種以上を組合わせて用いてもよい。難燃剤の配合量は特に制限はないが、（Ａ）エポキシ樹脂１００重量部に対して１〜３０重量部が好ましく、２〜１５重量部がより好ましい。
また、本発明の封止用エポキシ樹脂成形材料には、カーボンブラック、有機染料、有機顔料、酸化チタン、鉛丹、ベンガラ等の着色剤を用いても良い。
さらに、その他の添加剤として、シリコーンオイルやシリコーンゴム粉末等の応力緩和剤等を必要に応じて配合することができる。

(In the general formula (XIX), M ¹ , M ² and M ³ represent different metal elements, a, b, c, d, p, q and m are positive numbers, and r is 0 or a positive number. Show.)
M ¹ , M ² and M ^{3 in the} composition formula (XIX) are not particularly limited as long as they are different metal elements, but from the viewpoint of flame retardancy, M ¹ is a metal element of the third period, group IIA Preferably selected from metal elements belonging to the alkaline earth metal elements, group IVB, group IIB, group VIII, group IB, group IIIA and group IVA, and M ² is selected from transition metal elements of groups IIIB to IIB, More preferably, M ¹ is selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and M ² is selected from iron, cobalt, nickel, copper and zinc. From the viewpoint of fluidity, it is preferable that M ¹ is magnesium, M ² is zinc or nickel, and r = 0. The molar ratio of p, q and r is not particularly limited, but preferably r = 0 and p / q is 1/99 to 1/1. In addition, the classification of metal elements is a long-period type periodic rate table in which the typical element is the A subgroup and the transition element is the B subgroup (Source: Kyoritsu Shuppan Co., Ltd., “Chemical Dictionary 4”, February 15, 1987) (Reduced plate 30th printing). Further, compounds containing metal elements such as zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate, dicyclopentadienyl iron, etc. may be mentioned, and one of these may be used alone. Two or more kinds may be used in combination. Although the compounding quantity of a flame retardant does not have a restriction | limiting in particular, 1-30 weight part is preferable with respect to 100 weight part of (A) epoxy resins, and 2-15 weight part is more preferable.
Moreover, you may use coloring agents, such as carbon black, an organic dye, an organic pigment, a titanium oxide, a red lead, a bengara, for the epoxy resin molding material for sealing of this invention.
Furthermore, as other additives, stress relaxation agents such as silicone oil and silicone rubber powder can be blended as required.

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

  As an electronic component device provided with an element sealed with an epoxy resin molding material for sealing obtained in the present invention, a semiconductor chip is mounted on a support member such as a lead frame, a wired tape carrier, a wiring board, glass, or a silicon wafer. An electronic component device equipped with active elements such as transistors, diodes and thyristors, and passive elements such as capacitors, resistors and coils, and encapsulated with the epoxy resin molding material for sealing of the present invention Etc. As such an electronic component device, for example, a semiconductor element is fixed on a lead frame, a terminal portion of a device such as a bonding pad and a lead portion are connected by wire bonding or a bump, and then the sealing epoxy resin of the present invention is used. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Out Package), which is sealed by molding using a molding material. General resin-sealed type I such as lead package, TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package), etc. A semiconductor chip connected to a tape carrier with a bump is sealed with a tape carrier package (TCP) sealed with an epoxy resin molding material of the present invention, wiring formed on a wiring board or glass, wire bonding, flip chip bonding COB (Chip) in which active elements such as semiconductor chips, transistors, diodes, thyristors and / or passive elements such as capacitors, resistors, coils, etc., which are connected by solder, etc., are sealed with the sealing epoxy resin molding material of the present invention On Board) Modules, hybrid ICs, multi-chip modules, devices mounted on the surface of the organic substrate with the wiring board connection terminals formed on the back, and the devices and the wiring formed on the organic substrate were connected by bump or wire bonding After, the epoxy resin molding material for sealing of the present invention Examples thereof include BGA (Ball Grid Array) and CSP (Chip Size Package) in which the element is sealed with a material. Moreover, the epoxy resin molding material for sealing of the present invention can also be used effectively for printed circuit boards.

  As a method for sealing an element using the epoxy resin molding material for sealing of the present invention, a low-pressure transfer molding method is the most common, but an injection molding method, a compression molding method, or the like may be used.

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

  The following components are blended in parts by weight shown in Tables 1 to 8 and roll kneaded under conditions of a kneading temperature of 80 ° C. and a kneading time of 10 minutes, for sealing Examples 1 to 40 and Comparative Examples 1 to 40 An epoxy resin molding material was produced.

  As an epoxy resin, an ortho-cresol novolak type epoxy resin having an epoxy equivalent of 200 and a softening point of 67 ° C. (Epoxy resin 1, trade name ESCN-190 manufactured by Sumitomo Chemical Co., Ltd.), an epoxy equivalent of 196 and a biphenyl type epoxy resin having a melting point of 106 ° C. Epoxy resin 2, Japan Epoxy Resin Co., Ltd. trade name YX-4000H), epoxy equivalent 176, melting point 111 ° C. biphenyl type epoxy resin (Epoxy Resin 3, Japan Epoxy Resin Co., Ltd. trade name YL-6121H), epoxy equivalent 242 , A sulfur atom-containing epoxy resin having an melting point of 118 ° C. (epoxy resin 4, trade name YSLV-120TE manufactured by Shin Nippon Steel Chemical Co., Ltd.), an epoxy equivalent of 264, and a dicyclopentadiene type epoxy resin having a softening point of 64 ° C. (epoxy resin 5, Dai Nippon Ink Chemical Co., Ltd. Company brand name HP-7200), epoxy equivalent 217, softening point 72 ° C naphthalene type epoxy resin (epoxy resin 6, Nippon Kayaku Co., Ltd. product name NC-7300), epoxy equivalent 170, softening point 65 ° C tri Phenylmethane type epoxy resin (Epoxy resin 7, Nippon Kayaku Co., Ltd. trade name EPPN-502H), epoxy equivalent 192, melting point 79 ° C. bisphenol F type epoxy resin (Epoxy resin 8, Shin Nippon Steel Chemical Co., Ltd. product) Name YSLV-80XY), epoxy equivalent 241 and softening point 96 ° C. biphenylene skeleton-containing phenol-aralkyl epoxy resin (epoxy resin 9, Nippon Kayaku Co., Ltd., trade name CER-3000L), epoxy equivalent 375, softening point 80 ° C. Bisphenol A brominated epoxy resin with 48% by weight bromine (epoxy Shi resin 10) was used.

  As the curing agent, a biphenylene skeleton type phenol resin having a hydroxyl group equivalent of 199 and a softening point of 89 ° C. (curing agent 1, trade name MEH-7851 manufactured by Meiwa Kasei Co., Ltd.), a phenol aralkyl resin having a hydroxyl equivalent of 176 and a softening point of 70 ° C. Agent 2, Mitsui Chemicals Co., Ltd. trade name Millex XLC), hydroxyl group equivalent 183, naphthol aralkyl resin having a softening point of 79 ° C. (curing agent 3, Shin Nippon Steel Chemical Co., Ltd. trade name SN-170), hydroxyl group equivalent 170 , Dicyclopentadiene type phenol resin having a softening point of 93 ° C. (curing agent 4, product name DPP manufactured by Nippon Petrochemical Co., Ltd.), hydroxyl group equivalent of 104, triphenylmethane type phenol resin having a softening point of 83 ° C. (curing agent 5, Meiwa Kasei) Product name MEH-7500 manufactured by Co., Ltd., novolak type phenolic resin (hard) having a hydroxyl equivalent weight of 106 and a softening point of 64 ° C. Agent 6, Meiwa Kasei Co., Ltd. trade name H-4), hydroxyl equivalent 156, softening point 83 ° C. of the phenolic resin (curing agent 7 was used Sumitomo Metal Air Water Chemical Co. trade name HE-510).

The silane compound is γ-glycidoxypropyltrimethoxysilane (silane compound 1), γ-aminopropyltriethoxysilane (silane compound 2), and the curing accelerator is a betaine adduct of triphenylphosphine and p-benzoquinone. (Curing Accelerator 1), Betaine-type adduct of tributylphosphine and p-benzoquinone (Curing Accelerator 2), Inorganic filler as spherical fused silica having an average particle size of 17.5 μm and a specific surface area of 3.8 m ² / g As other additive components, carnauba wax, antimony trioxide, and carbon black were used.

  As an acrylic compound, among the compounds represented by the following general formula (XX), n / m is 1.1, number average molecular weight (Mn) 691, molecular weight distribution (Mw / Mn) 1.44, viscosity (25 ° C.) 1 A 6 Pa · S acrylic compound (trade name AS-300, manufactured by Soken Chemical Co., Ltd.) was used. Mn and Mw / Mn were measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve. GPC uses a pump (L-6200 manufactured by Hitachi, Ltd.), a column (TSKgel-G2000H8 + TSKgel-G1000H8, both of which are trade names manufactured by Tosoh Corporation), and a detector (L-3300RI manufactured by Hitachi, Ltd.) Tetrahydrofuran was used as an eluent, and measurement was performed under conditions of a temperature of 30 ° C. and a flow rate of 1.0 ml / min.

（一般式（ＸＸ）で、ｍは１〜２０の整数、ｎは０〜２０の整数を示し、化合物中のｎ／ｍの平均値が０．０５以上３以下。）

(In general formula (XX), m represents an integer of 1 to 20, n represents an integer of 0 to 20, and the average value of n / m in the compound is 0.05 or more and 3 or less.)

The epoxy resin molding materials for sealing of Examples and Comparative Examples were evaluated by the following various characteristic tests (1) to (8). The evaluation results are shown in Tables 14 to 26. The epoxy resin molding material for sealing was molded by a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Further, post-curing was performed at 180 ° C. for 5 hours.
(1) Spiral flow Using a spiral flow measurement mold in accordance with EMMI-1-66, the sealing epoxy molding material was molded under the above conditions, and the flow distance (cm) was determined.
(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, 5 g of the sealing epoxy resin molding material weighed with an upper pan balance is placed on the center of the lower mold heated to 180 ° C., and after 5 seconds, the upper mold heated to 180 ° C. is closed and a load of 78 N Then, compression molding was performed under the condition of a curing time of 90 seconds, and the major axis (mm) and minor axis (mm) of the molded product were measured with calipers, and the average value (mm) was defined as a disc flow.
(3) Hardness during heating The sealing epoxy resin molding material was molded into a disk having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and was measured immediately after molding using a Shore D type hardness meter.
(4) Adhesion retention rate Under the above conditions, an epoxy resin molding material for sealing is molded on a 30 μm aluminum foil, post-cured to prepare a test piece, and before and after PCT treatment (121 ° C., 0.2 MPa, 100 hours). The peel strength (N / m) in the 90-degree direction of the test piece was measured and evaluated by the adhesive retention (%) = PCA treated aluminum peel strength / PCT treated aluminum peel strength × 100.
(5) Resistance to solder reflow Molding of an 80-pin flat package with an external dimension of 20 x 14 x 2 mm with an 8 x 10 mm silicone chip mounted on a 42 alloy lead frame using the sealing epoxy resin molding material under the above conditions , Post-cured, humidified under conditions of 85 ° C. and 85% RH, reflowed at a predetermined time of 240 ° C. for 10 seconds, observed for cracks, and the number of test packages ( Evaluation was made based on the number of crack generation packages for 10).
(6) Water absorption rate The disk molded in the above (3) is post-cured under the above conditions, left under conditions of 85 ° C. and 85% RH for 72 hours, and the weight change before and after being left is measured. (Weight%) = (disc weight after being left−disc weight before being left) / disc weight before being left × 100.
(7) Glass transition temperature (Tg)
Under the above conditions, an epoxy resin molding material for sealing was molded into a shape of 19 mm × 3 mm × 3 mm, post-cured to prepare a test piece, and a thermomechanical analyzer (TMA-8140, TAS-100) manufactured by Rigaku Corporation. The glass transition temperature (Tg, unit: ° C) was determined from the inflection point of the linear expansion curve.
(8) Flame retardance Using a mold for molding a 1/16 inch thick test piece, the epoxy resin molding material for sealing is molded under the above conditions and post-cured, and difficult in accordance with the UL-94 test method. Flammability was evaluated.

As can be seen in Tables 9 to 12, Examples 1 to 40 show better characteristics in spiral flow and disc flow than in Comparative Examples having the same resin composition. Further, there is almost no defect in the reflow treatment after 72 hours of moisture absorption, and there is no package crack in the reflow treatment after 48 hours of moisture absorption, and the solder reflow resistance is excellent.
In particular, as shown in Examples 8, 10, 13, 39, or 40, epoxy resin 2 (biphenyl type epoxy resin) is used as an epoxy resin, curing agent 2 (phenol aralkyl resin) is used as a curing agent, and curing agent 4 is When cyclopentadiene type phenol resin) or curing agent 7 is used in combination, and as shown in Example 15 or 17, epoxy resin 4 (sulfur atom-containing epoxy resin) is used as curing agent, curing agent 2 (phenol aralkyl resin), When the curing agent 4 (dicyclopentadiene type phenolic resin) is used in combination, the fluidity is excellent. In particular, as shown in Example 10 or 17, when the curing agent 4 (dicyclopentadiene type phenolic resin) is used in combination. Excellent hygroscopicity.
Further, as shown in Example 5, when epoxy resin 1 (orthocresol novolac type epoxy resin) is used as an epoxy resin and curing agent 6 (novolac type phenol resin) is used as a curing agent, and in Examples 27 and 30 Thus, when the epoxy resin 7 (triphenylmethane type epoxy resin) is used as an epoxy resin and the curing agent 5 (triphenylmethane type phenol resin) is used in combination as a curing agent, it exhibits a particularly high Tg and is excellent in heat resistance.
On the other hand, a comparative example having a composition different from that of the present invention does not satisfy the object of the present invention. That is, in Comparative Examples 1 to 40 shown in Tables 13 to 16, the fluidity is low, 50% or more of the package cracks are generated in the reflow treatment after 72 hours of moisture absorption, and the package cracks are also generated in the reflow treatment after 48 hours of moisture absorption. Has occurred and the solder reflow resistance is poor.

Claims (8)

(A) Epoxy resin, (B) curing agent, (C) An epoxy resin molding material for sealing containing an acrylic compound represented by the following general formula (I).

(In the general formula (I), R ¹ and R ² represent a hydrogen atom and a methyl group, R ³ represents a hydrocarbon group having 1 to 6 carbon atoms, R ⁴ represents a group represented by the following general formula (II), m represents an integer of 1 to 20, n represents an integer of 0 to 20, and the average value of n / m in the compound is 0.05 or more and 3 or less.)

(In General Formula (II), R ⁵ represents a hydrogen atom and a hydrocarbon group having 1 to 6 carbon atoms, R ⁶ represents a hydrocarbon group having 1 to 6 carbon atoms, and p represents an integer of 1 to 3. .)   2. The epoxy resin molding material for sealing according to claim 1, wherein the proportion of the acrylic compound represented by the general formula (I) is 0.05 to 0.7% by weight with respect to the epoxy resin molding material for sealing. .   (A) Epoxy resin contains biphenyl type epoxy resin, sulfur atom-containing epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, triphenylmethane type epoxy resin, bisphenol F type epoxy resin and biphenylene skeleton The epoxy resin molding material for sealing according to claim 1 or 2, comprising at least one phenol-aralkyl type epoxy resin.   (B) The curing agent is a biphenylene skeleton-containing phenol-aralkyl resin, phenol-aralkyl resin, naphthol-aralkyl resin, dicyclopentadiene-type phenol resin, triphenylmethane-type phenol resin, novolac-type phenol resin, and copolymer-type phenol-aralkyl resin. The epoxy resin molding material for sealing in any one of Claims 1-3 containing at least 1 sort (s) of these.   (D) The epoxy resin molding material for sealing according to any one of claims 1 to 4, further comprising a silane compound.   (E) The epoxy resin molding material for sealing according to any one of claims 1 to 4, further comprising a curing accelerator.   (F) The epoxy resin molding material for sealing according to any one of claims 1 to 6, further comprising an inorganic filler. An electronic component device comprising an element sealed with the sealing epoxy resin molding material according to claim 1.