JP4268835B2 - Epoxy resin composition and cured product thereof - Google Patents

Description

（但し、Ａはベンゼン環またはナフタレン環を示し、Ｒはハロゲン原子、または炭素数１から９の炭化水素基を示し、ｎは１〜１５の整数、ｍは１または２の整数、ｐは０〜２の整数を示す。）で表されるジスルフィド化合物がある。
【０００９】
上記一般式（１）で、Ａはベンゼン環またはナフタレン環を表すが、同一分子中にベンゼン環とナフタレン環が同時に含まれていてもよい。低粘度性の観点からは、ベンゼン環が好ましく、耐熱性、耐湿性および難燃性の観点からは、ナフタレン環が好ましい。また、Ｒはハロゲン原子または炭素数１から９の炭化水素基を表す。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子が例示され、炭化水素基としては、メチル基、エチル基、イソプロピル基、ｔｅｒｔ−ブチル基、アミル基、フェニル基、ベンジル基、スチリル基、α−メチルスチリル基、インデニル基等が挙げられる。また、ｐは０、１または２であり、ｍは１または２であるが、好ましくはｐは０であり、ｍは1である。さらに、ｎは１から１５の整数であるが、エポキシ樹脂組成物としての流動性の観点からは、ｎが小さいものほど好ましく、平均のｎ（数平均）としては、その範囲は１から６の範囲である。また、耐熱性の観点からは、ｎが大きいものほど好ましく、その範囲は４から１５の範囲である。
【００１０】
本発明に改質剤として用いるジスルフィド化合物は、常温で結晶状態をとるものであっても良いし、常温で液状または固体である樹脂状物であっても良い。ジスルフィド化合物の分子量は、特に制限されることはないが、通常、１５０から２０００の範囲であり、好ましくは、２００から１０００の範囲である。
【００１１】
ジスルフィド化合物の改質剤としての使用量は、エポキシ樹脂１００重量部に対して２〜８０重量部の範囲であるが、好ましくは５〜４０重量部の範囲である。これより少ないと密着性向上効果が小さく、これより多いとエポキシ樹脂組成物としての硬化反応性が低下するとともに、得られた硬化物の耐熱性が低下する。
【００１２】
ジスルフィド化合物がフェノール性水酸基、メルカプト基、カルボン酸、アミノ基等の活性プロトンを有している場合は、改質剤成分として作用するだけでなく、硬化剤として作用することがある。硬化剤として作用する場合は、ジスルフィド化合物を改質剤とするだけでなく、硬化剤でもあるとして計算する。この場合は、ジスルフィド化合物を硬化剤の使用一部又は全部として用いることができる。他の硬化剤と併用する場合は、通常、エポキシ樹脂中のエポキシ基１モルに対して、ジスルフィド化合物中の活性プロトンと他の硬化剤中の活性プロトンの合計量が０．５から２．０モルの範囲になるように配合するが、好ましくは、０．８から１．２モルの範囲である。これより多くても少なくても、得られた硬化物の耐熱性、耐湿性が低下する。
【００１３】
本発明に使用されるエポキシ樹脂としては、１分子中にエポキシ基を２個以上有するもの中から選択される。たとえば、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、フルオレンビスフェノール、４，４’−ビフェノール、２，２’−ビフェノール、テトラブロモビスフェノールＡ、ハイドロキノン、レゾルシン等の２価のフェノール類、あるいは、トリス−（４−ヒドロキシフェニル）メタン、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン等の３価以上のフェノール類、フェノール、クレゾール、ナフトール等のノボラック樹脂、フェノール、クレゾール、ナフトール等のアラルキル樹脂等のフェノール樹脂類のグルシジルエーテル化物等がある。これらのエポキシ樹脂は１種または２種以上を混合して用いることができる。
【００１４】
本発明の樹脂組成物に使用する硬化剤としては、一般にエポキシ樹脂の硬化剤として知られているものはすべて使用でき、ジシアンジアミド、酸無水物類、多価フェノール類、芳香族および脂肪族アミン類等がある。以下に硬化剤の具体例を示す。
【００１５】
酸無水物硬化剤としては、例えば、無水フタル酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、メチル無水ハイミック酸、無水ドデシニルコハク酸、無水ナジック酸、無水トリメリット酸等がある。
【００１６】
多価フェノール類としては、例えば、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、フルオレンビスフェノール、４，４’−ビフェノール、２，２’−ビフェノール、ハイドロキノン、レゾルシン、ナフタレンジオール等の２価のフェノール類、あるいは、トリス−（４−ヒドロキシフェニル）メタン、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン等の３価以上のフェノール類、フェノールノボラック、ｏ−クレゾールノボラック、ナフトールノボラック、ポリビニルフェノール等に代表されるフェノール樹脂類、さらにはフェノール類、ナフトール類等の１価のフェノール類またはビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、フルオレンビスフェノール、４，４’−ビフェノール、２，２’−ビフェノール、ハイドロキノン、レゾルシン、ナフタレンジオール等の２価のフェノール類と、ホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、ｐ−ヒドロキシベンズアルデヒド、１，４−ジメトキシメチルベンゼン、４，４’−ジメトキシメチルビフェニル、ジメトキシメチルナフタレン等の縮合剤との反応により合成される多価フェノール性化合物又は樹脂等がある。
【００１７】
アミン類としては、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルプロパン、４，４’−ジアミノジフェニルスルホン、ｍ−フェニレンジアミン、ｐ−キシリレンジアミン等の芳香族アミン類、エチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン等の脂肪族アミン類がある。
【００１８】
本発明のエポキシ樹脂組成物には、これら硬化剤の１種または２種以上を混合して用いることができる。これら硬化剤の配合量は前記のとおりエポキシ樹脂中のエポキシ基１モルに対して、硬化剤中の活性プロトンの合計量が０．５〜２．０モル、好ましくは０．８〜１．２モルの範囲である。
【００１９】
これらの中でも、半導体封止材等の高い電気絶縁性が要求される分野においては、多価フェノール類を硬化剤として用いることが好ましい。なかでも、半田リフロー性、難燃性等の観点から、フェノール、ナフトール等のフェノール性化合物を１，４−ジメトキシメチルベンゼン、４，４’−ジメトキシメチルビフェニル、ジメトキシメチルナフタレン、等の架橋剤で縮合させて得られるアラルキル構造を有する多価フェノール樹脂が好適に使用される。
【００２０】
さらに、本発明の樹脂組成物中には、ポリエステル、ポリアミド、ポリイミド、ポリエーテル、ポリウレタン、石油樹脂、フェノキシ樹脂、等のオリゴマーまたは高分子化合物を適宜配合してもよい。本発明のエポキシ樹脂組成物は、エポキシ樹脂、硬化剤及び改質剤を必須成分として含有し、これらが樹脂成分（充填剤や溶媒を除き、エポキシ樹脂の他、硬化剤、硬化促進剤や本発明のジスルフィド化合物からなる改質剤、樹脂系改質剤を含むとして計算する）の過半以上、好ましくは８０wt％以上含むことがよい。また、本発明のジスルフィド化合物からなる改質剤の他に、他の樹脂系改質剤を含む場合は、両者の合計の過半以上、好ましくは８０wt％以上が、本発明のジスルフィド化合物からなる改質剤であることがよい。
【００２１】
また、本発明の樹脂組成物には、無機充填剤、顔料、難然剤、揺変性付与剤、カップリング剤、流動性向上剤等の添加剤を配合できる。無機充填剤としては、例えば、球状あるいは破砕状の溶融シリカ、結晶シリカ等のシリカ粉末、アルミナ粉末、ガラス粉末、マイカ、タルク、炭酸カルシウム、アルミナまたは水和アルミナ等が挙げられ、顔料としては、有機系または無機系の体質顔料、鱗片状顔料等がある。揺変性付与剤としては、シリコン系、ヒマシ油系、脂肪族アマイドワックス、酸化ポリエチレンワックス、有機ベントナイト系等を挙げることができる。
【００２２】
さらに、本発明の樹脂組成物には必要に応じて、従来より公知の硬化促進剤を用いることができる。例を挙げれば、アミン類、イミダゾール類、有機ホスフィン類、ルイス酸等がある。添加量としては、通常、エポキシ樹脂１００重量部に対して、０．２〜５重量部の範囲である。また、必要に応じて、本発明の樹脂組成物には、カルナバワックス、ＯＰワックス等の離型剤、γ−グリシドキシプロピルトリメトキシシラン等のカップリング剤、カーボンブラック等の着色剤、三酸化アンチモン等の難燃剤、シリコンオイル等の低応力化剤、ステアリン酸カルシウム等の滑剤等を使用できる。
【００２３】
【実施例】
以下実施例により本発明をさらに具体的に説明する。
【００２４】
合成例１
３Lの４口セパラブルフラスコに、４-ヒドロキシチオフェノール２０２g、エタノール１６００gおよび純水４００gを量り採り、攪拌しながら溶解した後、２０℃にて３１％過酸化水素２０３．６gを１時間かけて滴下した。滴下終了後、さらに２時間反応を継続した。その後、純水８Lにより再沈殿させ、さらに水洗を行った後、減圧乾燥を行い、薄淡黄色の４，４’−ジヒドロキシジフェニルジスルフィド（以下、DHDPDSという）１８７gを得た。得られたDHDPDSの融点は１４５から１４９℃であった。
【００２５】
実施例１〜６および比較例１〜３
改質剤として合成例１で得られたDHDPDSを改質剤として用い、エポキシ樹脂成分としてｏ−クレゾールノボラック型エポキシ樹脂（エポキシ樹脂Ａ：日本化薬製、EOCN-1020-70；エポキシ当量 200、加水分解性塩素 400ppm、軟化点 70℃）、ビフェニル系エポキシ樹脂（エポキシ樹脂Ｂ：油化シェルエポキシ製、YX4000HK；エポキシ当量195、加水分解性塩素450ppm、融点105℃）、硬化剤としてフェノールノボラック（硬化剤Ａ：群栄化学製、PSM-4261；OH当量103、軟化点 82℃）、１−ナフトールアラルキル型樹脂（硬化剤Ｂ：新日鐵化学製、SN-475L；OH当量210、軟化点 73℃）、ビフェニルアラルキル型樹脂（硬化剤Ｃ：明和化成製、MEH-7851；OH当量212、軟化点 69℃）を用い、充填剤としてシリカ（平均粒径、２２μm）、硬化促進剤としてトリフェニルホスフィンを用い、表１に示す配合で混練してエポキシ樹脂組成物を得た。このエポキシ樹脂組成物を用いて１７５℃にて成形し、１７５℃にて１２時間ポストキュアを行い、硬化物試験片を得た後、各種物性測定に供した。なお、表１に示す配合量は重量部である。
【００２６】
ガラス転移点（Ｔｇ）は、熱機械測定装置により、昇温速度１０℃／分の条件で求めた。吸水率は、本エポキシ樹脂組成物を用いて、直径５０ｍｍ、厚さ３ｍｍの円盤を成形し、ポストキュア後、８５℃、相対湿度８５％の条件で１００時間吸湿させたときの値である。接着性の評価は、エポキシ樹脂組成物を用いて、銅箔上に１７５℃にて圧縮成形後、１７５℃にて１２時間ポストキュアを行い、ピール強度を測定した。難燃性は、厚さ１／１６インチの試験片を成形し、ＵＬ９４Ｖ-０規格によって評価し、５本の試験片での合計の燃焼時間で表した。結果をまとめて表２に示す。
【００２７】
【表１】

【００２８】
【表２】

【００２９】
【発明の効果】
本発明のエポキシ樹脂組成物は低吸湿性、高耐熱性および異種材料との高密着性等に優れるとともに、電気絶縁性に優れた硬化物を与え、半導体封止材等の電気・電子用途に好適に使用することができる。[0001]
[Industrial application fields]
The present invention is an epoxy useful for sealing electrical and electronic parts, circuit board materials, etc. that give a cured product excellent in low hygroscopicity, high heat resistance, and high adhesion to dissimilar materials and excellent in electrical insulation. The present invention relates to a resin composition.
[0002]
[Prior art]
Conventionally, epoxy resins have been used in a wide range of industrial applications, but their required performance has become increasingly sophisticated in recent years. For example, there is a semiconductor sealing material in a typical field of a resin composition mainly composed of an epoxy resin, but as the integration degree of semiconductor elements is improved, the package size is becoming larger and thinner, and the mounting method is also increased. The transition to surface mounting is progressing, and the development of materials with excellent solder heat resistance is desired. Therefore, as a sealing material, in addition to reducing moisture absorption, improvement in adhesion and adhesion at the interface between different materials such as lead frames and chips is strongly demanded.
[0003]
In order to overcome these problems, epoxy resins having various new structures have been studied from the side of the epoxy resin that is the main agent. However, it has been difficult to achieve a balance of physical properties, such as a decrease in heat resistance due to low moisture absorption and a decrease in curability associated with improved adhesion, only by improving the main agent.
[0004]
Therefore, various epoxy resin modifiers have been studied from the above background. Among these, from the viewpoint of improving adhesion to the metal surface, compounds having sulfur atoms have attracted attention. For example, Patent Document 1 below shows that a compound having a mercapto group is applied to an epoxy resin composition. However, it was not sufficient in terms of adhesion to metal.
[Patent Document 1]
Japanese Patent Laid-Open No. 2000-198823
[Problems to be solved by the invention]
An object of the present invention is to provide an epoxy resin composition that provides a cured product that is excellent in moldability and has excellent low moisture absorption, high heat resistance, high adhesion to different materials, and the like, and a cured product thereof.
[0006]
[Means for Solving the Problems]
That is, the present invention relates to an epoxy resin composition comprising an epoxy resin, a curing agent and a modifier, wherein the curing agent is a polyhydric phenol, and the disulfide compound represented by the following general formula (1) as the modifier component Is an epoxy resin composition characterized in that it is used in an amount of 2 to 80 parts by weight based on 100 parts by weight of the epoxy resin. Moreover, this invention is an epoxy resin hardened | cured material formed by hardening | curing this epoxy resin composition. Here, in the general formula (1), A represents a benzene ring or a naphthalene ring, R represents a halogen atom or a hydrocarbon group having 1 to 9 carbon atoms, n represents an integer of 1 to 15, and m represents 1 Or the integer of 2, p shows 0.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the disulfide compound having a disulfide structure used as a modifier component in the present invention include R ₁ —S—S—R ₂ (R ₁ and R ₂ are monovalent organic groups, and R ₁ or R ₂ includes And may have a disulfide structure). This disulfide structure may link an aliphatic hydrocarbon group, link an aromatic group, or link both, but it is resistant to heat and moisture. Therefore, a disulfide compound having an aromatic structure is preferable.
[0008]
Preferred disulfide compounds include the following general formula (1),
[Chemical formula 2]

(However, A represents a benzene ring or a naphthalene ring, R represents a halogen atom or a hydrocarbon group having 1 to 9 carbon atoms, n is an integer of 1 to 15, m is an integer of 1 or 2, and p is 0. A disulfide compound represented by the following formula:
[0009]
In the above general formula (1), A represents a benzene ring or a naphthalene ring, and the same molecule may contain a benzene ring and a naphthalene ring at the same time. A benzene ring is preferable from the viewpoint of low viscosity, and a naphthalene ring is preferable from the viewpoint of heat resistance, moisture resistance, and flame retardancy. R represents a halogen atom or a hydrocarbon group having 1 to 9 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom, and examples of the hydrocarbon group include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an amyl group, a phenyl group, a benzyl group, a styryl group, α -A methyl styryl group, an indenyl group, etc. are mentioned. P is 0, 1 or 2, and m is 1 or 2. Preferably, p is 0 and m is 1. Furthermore, although n is an integer of 1 to 15, from the viewpoint of fluidity as an epoxy resin composition, n is preferably as small as possible, and the average n (number average) ranges from 1 to 6. It is a range. Further, from the viewpoint of heat resistance, the larger n is preferable, and the range is from 4 to 15.
[0010]
The disulfide compound used as a modifier in the present invention may be in a crystalline state at room temperature, or may be a resinous material that is liquid or solid at room temperature. The molecular weight of the disulfide compound is not particularly limited, but is usually in the range of 150 to 2000, and preferably in the range of 200 to 1000.
[0011]
The amount of the disulfide compound used as a modifier is in the range of 2 to 80 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the epoxy resin. If the amount is less than this, the effect of improving the adhesion is small, and if it is more than this, the curing reactivity as the epoxy resin composition is lowered and the heat resistance of the obtained cured product is lowered.
[0012]
When the disulfide compound has an active proton such as a phenolic hydroxyl group, a mercapto group, a carboxylic acid, or an amino group, it may act not only as a modifier component but also as a curing agent. When acting as a curing agent, it is calculated that not only the disulfide compound is a modifier but also a curing agent. In this case, the disulfide compound can be used as part or all of the curing agent. When used in combination with another curing agent, the total amount of active protons in the disulfide compound and active protons in the other curing agent is usually 0.5 to 2.0 with respect to 1 mol of the epoxy group in the epoxy resin. Although it mix | blends so that it may become the range of mol, Preferably it is the range of 0.8 to 1.2 mol. Even if it is more or less than this, the heat resistance and moisture resistance of the obtained cured product are lowered.
[0013]
The epoxy resin used in the present invention is selected from those having two or more epoxy groups in one molecule. For example, divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, tetrabromobisphenol A, hydroquinone, resorcin, or tris- (4 -Hydroxyphenyl) methane, trivalent or higher phenols such as 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, novolak resins such as phenol, cresol and naphthol, and aralkyl resins such as phenol, cresol and naphthol And glycidyl etherified products of phenol resins. These epoxy resins can be used alone or in combination of two or more.
[0014]
As the curing agent used in the resin composition of the present invention, any of those generally known as epoxy resin curing agents can be used, such as dicyandiamide, acid anhydrides, polyhydric phenols, aromatic and aliphatic amines. Etc. Specific examples of the curing agent are shown below.
[0015]
Examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl hymic anhydride, dodecynyl succinic anhydride, nadic anhydride, There are trimellitic anhydride and the like.
[0016]
Examples of the polyhydric phenols include divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, and naphthalenediol, or , Tris- (4-hydroxyphenyl) methane, trivalent or higher phenols such as 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, naphthol novolak, polyvinylphenol, etc. Phenol resins represented by the above, monohydric phenols such as phenols and naphthols, or bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-bif Dihydric phenols such as enol, hydroquinone, resorcin, naphthalenediol, formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, 1,4-dimethoxymethylbenzene, 4,4′-dimethoxymethylbiphenyl, dimethoxymethylnaphthalene, etc. There are polyhydric phenolic compounds or resins synthesized by reaction with a condensing agent.
[0017]
Examples of amines include aromatic amines such as 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylsulfone, m-phenylenediamine, and p-xylylenediamine, ethylenediamine, There are aliphatic amines such as hexamethylenediamine, diethylenetriamine, and triethylenetetramine.
[0018]
In the epoxy resin composition of the present invention, one or more of these curing agents can be mixed and used. As described above, the amount of these curing agents is 0.5 to 2.0 mol, preferably 0.8 to 1.2, based on 1 mol of the epoxy group in the epoxy resin, the total amount of active protons in the curing agent. The range of moles.
[0019]
Among these, polyhydric phenols are preferably used as a curing agent in a field where high electrical insulation properties such as a semiconductor sealing material are required. Among them, from the viewpoint of solder reflow and flame retardancy, phenolic compounds such as phenol and naphthol are used as crosslinking agents such as 1,4-dimethoxymethylbenzene, 4,4'-dimethoxymethylbiphenyl, and dimethoxymethylnaphthalene. A polyhydric phenol resin having an aralkyl structure obtained by condensation is preferably used.
[0020]
Furthermore, you may mix | blend oligomers or high molecular compounds, such as polyester, polyamide, a polyimide, a polyether, a polyurethane, a petroleum resin, and a phenoxy resin, in the resin composition of this invention suitably. The epoxy resin composition of the present invention contains an epoxy resin, a curing agent, and a modifier as essential components, and these include resin components (except for the epoxy resin, the curing agent, the curing accelerator, the main component other than the epoxy resin). More than half, preferably 80 wt% or more of the modifier of the inventive disulfide compound (calculated as including a resin modifier). In addition to the modifying agent comprising the disulfide compound of the present invention, when other resin-based modifying agents are included, a majority of both, preferably 80 wt% or more, is modified by the disulfide compound of the present invention. It may be a quality agent.
[0021]
Moreover, additives, such as an inorganic filler, a pigment, a difficult agent, a thixotropic agent, a coupling agent, a fluidity improver, can be mix | blended with the resin composition of this invention. Examples of the inorganic filler include silica powder such as spherical or crushed fused silica and crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, and hydrated alumina. There are organic or inorganic extender pigments, scaly pigments, and the like. Examples of the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, polyethylene oxide wax, and organic bentonite-based.
[0022]
Furthermore, conventionally well-known hardening accelerators can be used for the resin composition of this invention as needed. Examples include amines, imidazoles, organic phosphines, Lewis acids and the like. As addition amount, it is the range of 0.2-5 weight part normally with respect to 100 weight part of epoxy resins. If necessary, the resin composition of the present invention may include a release agent such as carnauba wax and OP wax, a coupling agent such as γ-glycidoxypropyltrimethoxysilane, a colorant such as carbon black, and the like. A flame retardant such as antimony oxide, a low stress agent such as silicon oil, a lubricant such as calcium stearate, and the like can be used.
[0023]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples.
[0024]
Synthesis example 1
In a 3 L 4-neck separable flask, weigh 202 g of 4-hydroxythiophenol, 1600 g of ethanol and 400 g of pure water, dissolve with stirring, and then add 203.6 g of 31% hydrogen peroxide at 20 ° C. over 1 hour. It was dripped. After completion of dropping, the reaction was continued for another 2 hours. Thereafter, the precipitate was reprecipitated with 8 L of pure water, further washed with water, and then dried under reduced pressure to obtain 187 g of pale light yellow 4,4′-dihydroxydiphenyl disulfide (hereinafter referred to as DHDPDS). The melting point of the obtained DHDPDS was 145 to 149 ° C.
[0025]
Examples 1-6 and Comparative Examples 1-3
The DHDPDS obtained in Synthesis Example 1 was used as a modifier, and an o-cresol novolac type epoxy resin (epoxy resin A: Nippon Kayaku, EOCN-1020-70; epoxy equivalent 200) was used as an epoxy resin component. Hydrolyzable chlorine 400ppm, softening point 70 ° C), biphenyl epoxy resin (epoxy resin B: made by Yuka Shell Epoxy, YX4000HK; epoxy equivalent 195, hydrolyzable chlorine 450ppm, melting point 105 ° C), phenol novolac (curing agent) Curing agent A: manufactured by Gunei Chemical Co., PSM-4261; OH equivalent 103, softening point 82 ° C., 1-naphthol aralkyl type resin (hardening agent B: manufactured by Nippon Steel Chemical Co., Ltd. SN-475L; OH equivalent 210, softening point 73 ° C.), biphenyl aralkyl type resin (curing agent C: Meiwa Kasei Co., Ltd., MEH-7851; OH equivalent 212, softening point 69 ° C.), silica (average particle size, 22 μm) as filler, tri as curing accelerator Use phenylphosphine To obtain an epoxy resin composition was kneaded with the formulations shown in Table 1. This epoxy resin composition was molded at 175 ° C. and post-cured at 175 ° C. for 12 hours to obtain a cured product test piece, which was then subjected to various physical property measurements. In addition, the compounding quantity shown in Table 1 is a weight part.
[0026]
The glass transition point (Tg) was determined by a thermomechanical measuring device under conditions of a heating rate of 10 ° C./min. The water absorption is a value when a disk having a diameter of 50 mm and a thickness of 3 mm is formed using the epoxy resin composition, and after post-curing, the moisture is absorbed for 100 hours at 85 ° C. and a relative humidity of 85%. The evaluation of adhesiveness was performed by compression-molding on a copper foil at 175 ° C. using an epoxy resin composition, post-curing at 175 ° C. for 12 hours, and measuring the peel strength. Flame retardance was measured by molding a 1/16 inch thick test piece, evaluated according to the UL94V-0 standard, and expressed as the total burning time of 5 test pieces. The results are summarized in Table 2.
[0027]
[Table 1]

[0028]
[Table 2]

[0029]
【The invention's effect】
The epoxy resin composition of the present invention is excellent in low hygroscopicity, high heat resistance, high adhesion to dissimilar materials, etc., and gives a cured product excellent in electrical insulation, for electrical / electronic applications such as semiconductor encapsulants. It can be preferably used.

Claims (3)

In the epoxy resin composition containing an epoxy resin, a curing agent, and a modifier, the curing agent is a polyhydric phenol, and the following general formula (1),

(However, A represents a benzene ring or a naphthalene ring, R represents a halogen atom or a hydrocarbon group having 1 to 9 carbon atoms, n is an integer of 1 to 15, m is an integer of 1 or 2, and p is 0. An epoxy resin composition comprising 2 to 80 parts by weight of the disulfide compound represented by formula (1 ) based on 100 parts by weight of the epoxy resin. 2. The epoxy resin according to claim 1, wherein the disulfide compound of the modifier is 4,4′-dihydroxydiphenyl disulfide, and 5 to 40 parts by weight of 4,4′-dihydroxydiphenyl disulfide is blended with respect to 100 parts by weight of the epoxy resin. Composition.   An epoxy resin cured product obtained by curing the epoxy resin composition according to claim 1.