WO2011114935A1 - Epoxy resin composition and cured substance - Google Patents

Epoxy resin composition and cured substance Download PDF

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Publication number
WO2011114935A1
WO2011114935A1 PCT/JP2011/055302 JP2011055302W WO2011114935A1 WO 2011114935 A1 WO2011114935 A1 WO 2011114935A1 JP 2011055302 W JP2011055302 W JP 2011055302W WO 2011114935 A1 WO2011114935 A1 WO 2011114935A1
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epoxy resin
resin composition
curing
epoxy
anhydride
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PCT/JP2011/055302
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French (fr)
Japanese (ja)
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篤彦 片山
スレスタ・二ランジャン・クマール
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新日鐵化学株式会社
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Priority to JP2012505621A priority Critical patent/JP5676563B2/en
Publication of WO2011114935A1 publication Critical patent/WO2011114935A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3218—Carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Abstract

The disclosed epoxy resin composition has a low viscosity before curing, exhibits good fluidity during molding, and has other good properties including high resistance to heat and moisture and a low degree of thermal expansion. Said epoxy resin composition is useful, for example, as a sealing material for electric/electronic components (e.g. a semiconductor sealing material), a molding material, a layering material, or an adhesive material. The disclosed epoxy resin composition contains an epoxy resin and an epoxy resin hardener, said epoxy resin being a triepoxyethylmicrohexane epoxy resin represented by formula (1).

Description

エポキシ樹脂組成物及び硬化物Epoxy resin composition and cured product
  本発明は低粘度性に優れるとともに、耐熱性、低熱膨張性等に優れた硬化物を与える電気・電子部品等の封止、コーティング材料、積層材料、複合材料等の用途として有用なエポキシ樹脂組成物並びにその硬化物に関するものであり、プリント配線板、半導体封止等の電気電子分野の絶縁材料、炭素繊維強化複合材料等に好適に使用される。 The present invention is an epoxy resin composition useful for applications such as sealing of electrical and electronic parts, coating materials, laminated materials, composite materials, etc. that give excellent cured products with excellent heat resistance, low thermal expansion, etc. The present invention relates to a cured product and a cured product thereof, and is suitably used for printed wiring boards, insulating materials in the electric and electronic fields such as semiconductor sealing, carbon fiber reinforced composite materials, and the like.
  エポキシ樹脂は工業的に幅広い用途で使用されてきているが、その要求性能は近年ますます高度化している。例えば、エポキシ樹脂を主剤とする樹脂組成物の代表的分野に半導体封止材料があるが、近年、半導体素子の集積度の向上に伴い、パッケージサイズが大面積化、薄型化に向かうとともに、実装方式も表面実装化への移行が進展しており、より半田耐熱性に優れた材料の開発が望まれている。 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 in recent years, as the integration degree of semiconductor elements has improved, the package size has become larger and thinner, and mounting The system is also shifting to surface mounting, and the development of materials with higher solder heat resistance is desired.
  また最近では、高集積化、高密度実装化の技術動向により、従来の金型を利用したトランスファー成形によるパッケージに代わり、ハイブリッドＩＣ、チップオンボード、テープキャリアパッケージ、プラスチックピングリッドアレイ、プラスチックボールグリッドアレイ等の金型を使用しないで液状材料を用いて封止し、実装する方式が増えてきている。しかし、一般に液状材料はトランスファー成形に用いる固形材料に比べて信頼性が低い欠点がある。これは、液状材料に粘度上の限界があり、用いる樹脂、硬化剤、充填剤等に制約があるからである。 Recently, due to technological trends of high integration and high-density mounting, hybrid ICs, chip-on-board, tape carrier packages, plastic pin grid arrays, plastic ball grids have been used instead of conventional molds using transfer molding. An increasing number of methods of sealing and mounting using a liquid material without using a mold such as an array. However, in general, liquid materials have a drawback that they are less reliable than solid materials used for transfer molding. This is because the liquid material has a limit in viscosity, and there are restrictions on the resin, curing agent, filler, and the like to be used.
  また、炭素繊維強化複合材料のマトリックス樹脂としては、成形性、耐熱性、機械特性等に優れるエポキシ樹脂が望まれている。特に、近年では、自動車部品、鉄道車両、航空機等の用途において低粘度化及び高耐熱化の両立といった要求が高まってきている。 Moreover, as a matrix resin for a carbon fiber reinforced composite material, an epoxy resin excellent in moldability, heat resistance, mechanical properties and the like is desired. In particular, in recent years, there has been an increasing demand for both low viscosity and high heat resistance in applications such as automobile parts, railway vehicles, and aircraft.
  これまでに、低粘度エポキシ樹脂としてはビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等が一般に広く知られているが、低粘度性及び耐熱性の点で充分ではない。また、低粘度性に優れたエポキシ樹脂として、特許３３３９０８３号公報には、シクロヘキサン骨格にオキシメチレン鎖を有するエポキシ樹脂が提案されている。シクロヘキサン骨格にオキシメチレン鎖を有するエポキシ樹脂は、芳香族環を有するエポキシ樹脂に比べ、透明性、耐候性に優れるが、耐熱性の点で充分ではなかった。 ビ ス So far, bisphenol A type epoxy resins, bisphenol F type epoxy resins and the like are generally widely known as low viscosity epoxy resins, but they are not sufficient in terms of low viscosity and heat resistance. As an epoxy resin excellent in low viscosity, Japanese Patent No. 3339083 proposes an epoxy resin having an oxymethylene chain in a cyclohexane skeleton. The epoxy resin having an oxymethylene chain in the cyclohexane skeleton is excellent in transparency and weather resistance as compared with an epoxy resin having an aromatic ring, but is not sufficient in terms of heat resistance.
  一方、ＵＳＰ３２５１８６１号明細書には、1,2,4-トリエポキシエチルシクロヘキサンが記載されている。しかし、エポキシ樹脂用硬化剤を含有するエポキシ樹脂組成物の例は示されておらず、その反応性や、エポキシ樹脂硬化物とした場合の詳細な物性検討はなされておらず、実用物性上の性能は知られていなかった。 On the other hand, US Pat. No. 3,251,861 describes 1,2,4-triepoxyethylcyclohexane. However, an example of an epoxy resin composition containing a curing agent for epoxy resin is not shown, and no detailed physical property examination has been made for its reactivity and epoxy resin cured product. The performance was unknown.
特許３３３９０８３号公報Japanese Patent No. 3339083 ＵＳＰ３２５１８６１号明細書USP3251861 Specification
  従って、本発明の目的は低粘度性に優れ、かつ耐熱性、低熱膨張性等に優れた硬化物を与えるエポキシ樹脂組成物ならびにその硬化物を提供することにある。 Therefore, an object of the present invention is to provide an epoxy resin composition that provides a cured product that is excellent in low viscosity, heat resistance, low thermal expansion, and the like, and a cured product thereof.
　すなわち、本発明は、エポキシ樹脂及びエポキシ樹脂用硬化剤を含有するエポキシ樹脂組成物において、下式（１）で表されるエポキシ樹脂を含むことを特徴とするエポキシ樹脂組成物に関する。
Figure JPOXMLDOC01-appb-I000003
　　　　　　　　　　　　　　　　　  That is, this invention relates to the epoxy resin composition containing the epoxy resin represented by the following Formula (1) in the epoxy resin composition containing the epoxy resin and the hardening | curing agent for epoxy resins.
Figure JPOXMLDOC01-appb-I000003
　上記エポキシ樹脂としては、1,2,4-トリエポキシエチルシクロヘキサンであることが好ましい。1,2,4-トリエポキシエチルシクロヘキサンは、下式（２）で表される。
Figure JPOXMLDOC01-appb-I000004
  The epoxy resin is preferably 1,2,4-triepoxyethylcyclohexane. 1,2,4-Triepoxyethylcyclohexane is represented by the following formula (2).
Figure JPOXMLDOC01-appb-I000004
　本発明において、上記エポキシ樹脂用硬化剤が、アミン類、酸無水物類、多価フェノール類、イミダゾール類、ブレンステッド酸塩類、ジシアンジアミド類、有機酸ヒドラジッド類、ポリカルボン酸類及び有機ホスフィン類から選ばれる少なくとも１種の化合物であることが好ましい。また、エポキシ樹脂用硬化剤に加えて、更に硬化促進剤を含むことが好ましい。そして、三級アミン類、イミダゾール類、ジシアンジアミド類、及び有機ホスフィン類から選ばれる少なくとも１種の化合物を硬化促進剤として含有することが好ましい。 In the present invention, the curing agent for epoxy resin is selected from amines, acid anhydrides, polyhydric phenols, imidazoles, Bronsted acid salts, dicyandiamides, organic acid hydrazides, polycarboxylic acids and organic phosphines. It is preferable that it is at least one compound. In addition to the curing agent for epoxy resin, it is preferable to further include a curing accelerator. And it is preferable to contain at least one compound selected from tertiary amines, imidazoles, dicyandiamides, and organic phosphines as a curing accelerator.
  更に、本発明は、無機充填材の含有率が８３重量％以上含有する上記のエポキシ樹脂組成物に関する。 Further, the present invention relates to the above epoxy resin composition containing 83 wt% or more of the inorganic filler.
  また、本発明は、電気・電子部品封止用である上記のエポキシ樹脂組成物、及び上記のエポキシ樹脂組成物を硬化してなるエポキシ樹脂硬化物に関する。 本 Further, the present invention relates to the above-mentioned epoxy resin composition for encapsulating electric / electronic parts and the cured epoxy resin obtained by curing the above epoxy resin composition.
発明を実施するため形態Mode for carrying out the invention
  以下、本発明について詳細に説明する。
  本発明のエポキシ樹脂組成物は、エポキシ樹脂、及びエポキシ樹脂用硬化剤を必須成分とし、且つこれら必須成分を樹脂成分の主成分とする。本発明のエポキシ樹脂組成物は無機充填材を含むことができ、この場合は、上記必須成分と無機充填材を主成分とする。
　本発明のエポキシ樹脂組成物は、式（１）で表されるエポキシ樹脂の構造に特徴があり、エポキシ基とシクロヘキサンとがエーテル結合を介さないで結合することで、低粘度性に優れ、かつ耐熱性、低熱膨張性等に優れた硬化物を与える。従って、エポキシ樹脂用硬化剤等の添加物の種類及び添加量は、適宜の条件が使用できる。 Hereinafter, the present invention will be described in detail.
The epoxy resin composition of the present invention includes an epoxy resin and a curing agent for epoxy resin as essential components, and these essential components as main components of the resin component. The epoxy resin composition of the present invention can contain an inorganic filler. In this case, the essential component and the inorganic filler are the main components.
The epoxy resin composition of the present invention is characterized by the structure of the epoxy resin represented by the formula (1), and is excellent in low viscosity by bonding an epoxy group and cyclohexane via an ether bond, and Gives a cured product with excellent heat resistance and low thermal expansion. Therefore, appropriate conditions can be used for the type and amount of additives such as epoxy resin curing agents.
  本発明のエポキシ樹脂組成物に使用されるエポキシ樹脂は式（１）で表される。 エ ポ キ シ The epoxy resin used in the epoxy resin composition of the present invention is represented by the formula (1).
　式（１）のエポキシ樹脂における、エポキシエチル基の置換位置は特に限定しないが、好ましくは、シクロヘキサン骨格の１位、２位及び４位に置換した、式（２）で表される1,2,4-トリエポキシエチルシクロヘキサンである。 The substitution position of the epoxyethyl group in the epoxy resin of the formula (1) is not particularly limited, but is preferably 1,2 represented by the formula (2) substituted at the 1-position, 2-position and 4-position of the cyclohexane skeleton. 4-Triepoxyethylcyclohexane.
  本発明で用いるエポキシ樹脂成分は、式（１）のエポキシ樹脂の他に、本発明の効果を損なわない範囲で他のエポキシ樹脂を併用することができる。他のエポキシ樹脂としては、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、２，２' －ビフェノール、３，３'，５，５'－テトラメチル－４，４'－ジヒドロキシビフェノール、レゾルシン、ナフタレンジオール類等の２価のフェノール類のエポキシ化物、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、フェノールノボラック、ｏ－クレゾールノボラック等の３価以上のフェノール類のエポキシ化物、ジシクロペンタジエンとフェノール類の共縮合樹脂のエポキシ化物、フェノール類とパラキシリレンジクロライド等から合成されるフェノールアラルキル樹脂類のエポキシ化物、フェノール類とビスクロロメチルビフェニル等から合成されるビフェニルアラルキル型フェノール樹脂のエポキシ化物、ナフトール類とパラキシリレンジクロライド等から合成されるナフトールアラルキル樹脂類のエポキシ化物等が好ましく挙げられる。これら他のエポキシ樹脂は、２種以上を併用してもよい。これら他のエポキシ樹脂を併用する場合、その使用量は全エポキシ樹脂の５０ｗｔ％以下、有利には２０ｗｔ％以下にとどめることがよい。 エ ポ キ シ In addition to the epoxy resin of formula (1), the epoxy resin component used in the present invention can be used in combination with other epoxy resins as long as the effects of the present invention are not impaired. Examples of other epoxy resins include bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 2,2′２-biphenol, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenol, resorcin, Epoxidized products of divalent phenols such as naphthalenediols, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac, o-cresol novolac, etc. Epoxides of trivalent or higher phenols, epoxidized products of co-condensation resins of dicyclopentadiene and phenols, epoxidized products of phenol aralkyl resins synthesized from phenols and paraxylylene dichloride, phenols and bischloromethyl Biphenyl etc. Epoxidized biphenyl aralkyl type phenolic resin synthesized, epoxidized naphthol aralkyl resin and the like which are synthesized from naphthols and para-xylylene dichloride, and the like preferably. Two or more of these other epoxy resins may be used in combination. When these other epoxy resins are used in combination, the amount used is preferably 50 wt% or less, more preferably 20 wt% or less of the total epoxy resin.
  本発明のエポキシ樹脂組成物に用いるエポキシ樹脂用硬化剤としては、次のものが挙げられる。 硬化 Examples of the curing agent for epoxy resin used in the epoxy resin composition of the present invention include the following.
　アミン類；ビス（４－アミノシクロヘキシル）メタン、ビス（アミノメチル）シクロヘキサン、ｍ－キシリレンジアミン、３，９－ビス（３－アミノプロピル）－２，４，８，１０－テトラスピロ［５，５］ウンデカン等の脂肪族及び脂環族アミン類、メタフェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン、ジエチルトルエンジアミン、１－メチル－３，５－ジエチル－２，４－ジアミノベンゼン、１－メチル－３，５－ジエチル－２，６－ジアミノベンゼン、１，３，５－トリエチル－２，６－ジアミノベンゼン、３，３’－ジエチル－４，４’－ジアミノジフェニルメタン、３，５，３’，５’－テトラメチル－４，４’－ジアミノジフェニルメタン等の芳香族アミン類、ベンジルジメチルアミン、２，４，６－トリス（ジメチルアミノメチル）フェノ－ル、１，８－ジアザビシクロ－（５，４，０）－ウンデセン－７、１，５－ジアザビシクロ－（４，３，０）－ノネン－７等の３級アミン類及びその塩類。  Amines; bis (4-aminocyclohexyl) methane, bis (aminomethyl) cyclohexane, m-xylylenediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5,5 ] Aliphatic and alicyclic amines such as undecane, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diethyltoluenediamine, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3 , 5-diethyl-2,6-diaminobenzene, 1,3,5-triethyl-2,6-diaminobenzene, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,5,3 ′, 5 Aromatic amines such as' -tetramethyl-4,4'-diaminodiphenylmethane, benzyldimethylamine, 2, , 6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo- (5,4,0) -undecene-7, 1,5-diazabicyclo- (4,3,0) -nonene-7, etc. Tertiary amines and salts thereof.
　酸無水物類；無水フタル酸、無水トリメリット酸、無水ピロメリット酸等の芳香族酸無水物類、無水テトラヒドロフタル酸、無水メチルテトラヒドロフタル酸、無水ヘキサヒドロフタル酸、無水メチルヘキサヒドロフタル酸、無水メチルエンドメチレンテトラヒドロフタル酸、無水シクロドデセニルコハク酸、無水トリアルキルテトラヒドロフタル酸等の環状脂肪族酸無水物類。  Acid anhydrides: aromatic anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride Cyclic aliphatic acid anhydrides such as methylendomethylenetetrahydrophthalic anhydride, cyclododecenyl succinic anhydride, and trialkyltetrahydrophthalic anhydride.
　多価フェノ－ル類；カテコ－ル、レゾルシン、ハイドロキノン、ビスフェノ－ルＦ、ビスフェノ－ルＡ、ビスフェノ－ルＳ、ビフェノ－ル、フェノ－ルノボラック類、クレゾ－ルノボラック類、ビスフェノ－ルＡ等の２価フェノ－ルのノボラック化物類、トリスヒドロキシフェニルメタン類、アラルキルポリフェノ－ル類、ジシクロペンタジエンポリフェノ－ル類等。  Multivalent phenols such as catechol, resorcin, hydroquinone, bisphenol F, bisphenol A, bisphenol S, biphenol, phenol novolacs, cresol novolacs, bisphenol A, etc. Novolak compounds of divalent phenols, trishydroxyphenylmethanes, aralkylpolyphenols, dicyclopentadiene polyphenols and the like.
　その他；２－メチルイミダゾール、２－エチル－４－メチルイミダゾール及び２－フェニルイミダゾール等のイミダゾ－ル類及びその塩類、ジシアンジアミド類、有機酸ヒドラジッド類である。これらのエポキシ樹脂用硬化剤は、単独で使用しても良いが、２種以上を併用して使用することも可能である。 Others: imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole and their salts, dicyandiamides and organic acid hydrazides. These epoxy resin curing agents may be used singly or in combination of two or more.
  これらの中でも、耐熱性、耐湿性、電気特性等の点で、半導体封止材料に好適なポリアミン、多価ヒドロキシ化合物が好ましく使用される。また、耐熱性、耐湿性、電気特性、透明性を要求される樹脂用途には、ポリアミン、酸無水物が特に好ましく使用される。 Among these, polyamines and polyvalent hydroxy compounds suitable for semiconductor encapsulating materials are preferably used in terms of heat resistance, moisture resistance, electrical characteristics, and the like. In addition, polyamines and acid anhydrides are particularly preferably used for resin applications that require heat resistance, moisture resistance, electrical characteristics, and transparency.
　ポリアミンとしては、ポリエチレンジアミン、メタキシレンジアミン、トリメチルヘキサメチレンジアミン、2－メチルペンタンメチレンジアミン等の脂肪族アミン、イソフォロンジアミン、1,3-ビスアミノメチルシクロヘキサン、ビス（4-アミノシクロヘキシル）メタン、ノルボルネンアミン、1,2-ジアミノシクロヘキサン、ビス（4-アミノ－３－メチルシクロヘキシル）メタン等の脂環式ポリアミン、ジアミノジフェニルメタン、メタフェニレンジアミン、ジアミノジフェニルスルホン、ジエチルトルエンジアミン等の芳香族ポリアミンが好ましく挙げられる。 Polyamines include aliphatic amines such as polyethylenediamine, metaxylenediamine, trimethylhexamethylenediamine and 2-methylpentanemethylenediamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, Preferred are alicyclic polyamines such as norborneneamine, 1,2-diaminocyclohexane and bis (4-amino-3-methylcyclohexyl) methane, and aromatic polyamines such as diaminodiphenylmethane, metaphenylenediamine, diaminodiphenylsulfone and diethyltoluenediamine. Can be mentioned.
　多価ヒドロキシ化合物としては、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、カテコール、ナフタレンジオール類等の２価のフェノール類、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、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３価以上のフェノール類、更にはフェノール類、ナフトール類又は、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、カテコール、ナフタレンジオール類等の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、ｐ－キシリレングリコール、ｐ－キシリレングリコールジメチルエーテル、ジビニルベンゼン、ジイソプロペニルベンゼン、ジメトキシメチルビフェニル類、ジビニルビフェニル、ジイソプロペニルビフェニル類等の架橋剤との反応により合成される多価ヒドロキシ化合物等が好ましい。これらの中で、耐熱性、耐湿性、電気特性等の点で優れる、ノボラック樹脂が特に好ましい。 Examples of the polyvalent hydroxy compound include divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4 ′ -biphenol, 2,2 ′ -biphenol, hydroquinone, resorcin, catechol, naphthalenediols, Trivalent or higher phenols typified by tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, naphthol novolak, polyvinylphenol, etc. , Further phenols, naphthols, or bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4 ′ -biphenol, 2,2 ′ -biphenol, hydroquinone, resorcin Divalent phenols such as catechol and naphthalenediol and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene glycol, p-xylylene glycol dimethyl ether, divinylbenzene, diisopropenylbenzene, dimethoxymethylbiphenyls, Polyhydric hydroxy compounds synthesized by reaction with a crosslinking agent such as divinylbiphenyl and diisopropenylbiphenyl are preferred. Among these, novolac resins are particularly preferable because they are excellent in terms of heat resistance, moisture resistance, electrical characteristics, and the like.
  多価ヒドロキシ化合物の軟化点範囲は、好ましくは４０～１５０℃、より好ましくは５０～１２０℃である。４０℃より低いと例えば無機材が充填されたエポキシ樹脂組成物としたときに粘度が低くなりすぎ無機材が沈降するといった問題があり、１５０℃より高いとエポキシ樹脂組成物調製時の混練性と成形性に問題がある。また、１５０℃における好ましい溶融粘度は１Ｐａ・ｓ以下であり、より好ましくは０.５Ｐａ・ｓ以下である。１Ｐａ・ｓより高いとエポキシ樹脂組成物の調製時の混練性、及び成形性に問題があるが、エポキシ樹脂組成物（無機充填材を含まない）としたときの２５℃での粘度が０．０１～１００Ｐａ・ｓとなるように適宜選定される。好適な例として荒川工業株式会社製　タマノールPA、タマノール531、タマノール758、タマノール759、DIC株式会社製　TD-2131、TD-2106,TD-2091、TD-2090として入手できるノボラック樹脂が挙げられる。 The softening point range of the polyvalent hydroxy compound is preferably 40 to 150 ° C, more preferably 50 to 120 ° C. When the temperature is lower than 40 ° C., for example, when the epoxy resin composition is filled with an inorganic material, there is a problem that the viscosity becomes too low and the inorganic material settles. When the temperature is higher than 150 ° C., kneadability at the time of preparing the epoxy resin composition There is a problem in formability. Moreover, the preferable melt viscosity in 150 degreeC is 1 Pa * s or less, More preferably, it is 0.5 Pa * s or less. If it is higher than 1 Pa · s, there are problems in kneadability and moldability during preparation of the epoxy resin composition, but the viscosity at 25 ° C. when the epoxy resin composition (not including inorganic filler) is 0.00. It is appropriately selected so as to be 01 to 100 Pa · s. Preferable examples include novolak resins available as Amanukawa Kogyo Co., Ltd. Tamanol PA, Tamanol 531, Tamanol 758, Tamanol 759, DIC Corporation TD-2131, TD-2106, TD-2091, TD-2090.
　酸無水物としては、ヘキサヒドロ無水フタル酸、テトラヒドロ無水フタル酸、無水フタル酸、３－メチルヘキサヒドロ無水フタル酸、４－メチルヘキサヒドロ無水フタル酸、３－メチルテトラヒドロ無水フタル酸、４－メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ドデセニル無水コハク酸、α－テルピネンやアロオシメン等のデカトリエンと無水マレイン酸とのディールス・アルダー反応物及びそれらの水素添加物、構造異性体若しくは幾何異性体をはじめ、それらの混合変性物が好ましく挙げられる。より好ましくは、これらの水素添加物である。 Acid anhydrides include hexahydrophthalic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydro Including phthalic anhydride, methyl nadic anhydride, dodecenyl succinic anhydride, Diels-Alder reaction product of decatriene and maleic anhydride such as α-terpinene and alloocimene and their hydrogenated products, structural isomers or geometric isomers, Those mixed modified products are preferred. More preferred are these hydrogenated products.
　本発明のエポキシ樹脂組成物は、硬化剤の官能基とエポキシ樹脂のエポキシ基の当量比を、０．５～２．０の範囲とすることがよい。好ましくは、０．８～１．２の範囲である。 In the epoxy resin composition of the present invention, the equivalent ratio of the functional group of the curing agent and the epoxy group of the epoxy resin is preferably in the range of 0.5 to 2.0. Preferably, it is in the range of 0.8 to 1.2.
　本発明のエポキシ樹脂組成物には、エポキシ樹脂用硬化剤とは別に硬化促進剤を配合することが好ましい。硬化促進剤としては、エポキシ樹脂の硬化促進剤として知られているものが使用できるが、トリス（ジメチルアミノメチル）フェノール、ベンジルジメチルアミン、１，８－ジアザビシクロ（５，４，０）ウンデセン－７（DBU）等の三級アミン類、２－メチルイミダゾール、２－エチル－４－メチルイミダゾール、２－フェニルイミダゾール等のイミダゾ－ル類及びその塩類、ジシアンジアミド類、トリフェニルホスフィン等の有機ホスフィン類等が好ましく挙げられる。これらの硬化促進剤は、単独で使用しても良いが、２種以上を併用して使用することも可能である。 In the epoxy resin composition of the present invention, a curing accelerator is preferably blended separately from the epoxy resin curing agent. As the curing accelerator, those known as curing accelerators for epoxy resins can be used. Tris (dimethylaminomethyl) phenol, benzyldimethylamine, 1,8-diazabicyclo (5,4,0) undecene-7 Tertiary amines such as (DBU), imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and their salts, organic phosphines such as dicyandiamide, triphenylphosphine, etc. Is preferred. These curing accelerators may be used alone or in combination of two or more.
  本発明のエポキシ樹脂組成物は、無機充填材を高含有率で配合するためには、低粘度であることが好ましい。そのため、エポキシ樹脂組成物から無機充填材を除いた状態でのエポキシ樹脂組成物の粘度は２５℃で、０．０１～１００Ｐａ・ｓ、好ましくは０．１～１００Ｐａ・ｓとなるようにする。 エ ポ キ シ The epoxy resin composition of the present invention preferably has a low viscosity in order to blend the inorganic filler with a high content. Therefore, the viscosity of the epoxy resin composition with the inorganic filler removed from the epoxy resin composition is set to 0.01 to 100 Pa · s, preferably 0.1 to 100 Pa · s at 25 ° C.
  本発明のエポキシ樹脂組成物には無機充填材を配合することができる。無機充填材を配合したエポキシ樹脂組成物は、封止用として適する。無機充填材としては、例えばシリカ、アルミナ、ジルコン、珪酸カルシウム、炭酸カルシウム、炭化ケイ素、窒化ケイ素、窒化ホウ素、ジルコニア、フォステライト、ステアタイト、スピネル、ムライト、チタニアなどがあり、これらの１種又は２種以上ものを組み合わせてもよいが、溶融シリカを主成分とすることが好ましく、その形態としては破砕状、又は球形状のものが挙げられる。通常、シリカは、数種類の粒径分布を持ったものを組み合わせて使用される。組み合わせるシリカの平均粒径の範囲は、０．５～１００μｍがよい。無機充填材を配合する場合の含有率は８３重量％以上が好ましく、より好ましくは８３～９０重量％である。８３重量％より少ないと有機成分の含有率が高くなり耐湿性、低線膨張性が十分に発揮されない。 無機 An inorganic filler can be blended in the epoxy resin composition of the present invention. An epoxy resin composition containing an inorganic filler is suitable for sealing. Examples of the inorganic filler include silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, mullite, titania, and one of these or Two or more kinds may be combined, but it is preferable to use fused silica as a main component, and examples of the form include crushed or spherical forms. Usually, silica is used in combination with those having several kinds of particle size distributions. The average particle diameter of the silica to be combined is preferably 0.5 to 100 μm. When the inorganic filler is blended, the content is preferably 83% by weight or more, more preferably 83 to 90% by weight. If it is less than 83% by weight, the organic component content will be high, and the moisture resistance and low linear expansion will not be sufficiently exhibited.
  また、本発明のエポキシ樹脂組成物中には、必要に応じて、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、インデンクマロン樹脂、フェノキシ樹脂等のオリゴマーや高分子化合物を適宜配合することができ、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することができる。顔料としては、有機系又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。また必要に応じて、アミン類、イミダゾール類、有機ホスフィン類、ルイス酸等の硬化促進剤を配合することができる。硬化促進剤の配合量としては、通常、エポキシ樹脂１００重量部に対し、０.２～５重量部が好ましい。更に必要に応じて、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配合できる。 Further, in the epoxy resin composition of the present invention, an oligomer or a polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene coumarone resin, or phenoxy resin is appropriately blended as necessary. And additives such as pigments, refractory agents, thixotropic agents, coupling agents, fluidity improvers and the like can be blended. Examples of the pigment include organic or inorganic extender pigments and scaly pigments. Examples of the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, oxidized polyethylene wax, and organic bentonite-based. If necessary, curing accelerators such as amines, imidazoles, organic phosphines, and Lewis acids can be blended. In general, the blending amount of the curing accelerator is preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin. Further, if necessary, the resin composition of the present invention includes a release agent such as carnauba wax and OP wax, a coupling agent such as γ-glycidoxypropyltrimethoxysilane, a colorant such as carbon black, and trioxide. A flame retardant such as antimony, a low stress agent such as silicone oil, a lubricant such as calcium stearate, and the like can be blended.
  本発明の硬化物は、上記エポキシ樹脂組成物を、注型、圧縮成形、トランスファー成形等の成形方法で硬化させることにより得ることができる。硬化物が生成する際の温度は、通常、１２０～２２０℃である。 The cured product of the present invention can be obtained by curing the above epoxy resin composition by a molding method such as casting, compression molding, transfer molding or the like. The temperature at which the cured product is produced is usually 120 to 220 ° C.
  上記式（１）で表されるエポキシ樹脂は、トリビニルシクロヘキサンを原料とし、ビニル基を過酸化物により酸化させエポキシ化反応を行うことことにより得られる。なお、上記式（２）で表されるエポキシ樹脂は、1,2,4-トリビニルシクロヘキサンを原料として得られる。 The epoxy resin represented by the above formula (1) can be obtained by using trivinylcyclohexane as a raw material and oxidizing the vinyl group with a peroxide to carry out an epoxidation reaction. The epoxy resin represented by the above formula (2) is obtained using 1,2,4-trivinylcyclohexane as a raw material.
  上記エポキシ化反応において使用される過酸化物としては、公知の製法を採用することができ、具体的には通常の過酸又は有機過酸化物が用いられる。過ギ酸、過酢酸、過プロピオン酸、ｍ－クロロ安息香酸等が例示される。 過 As the peroxide used in the epoxidation reaction, a known production method can be adopted, and specifically, a normal peracid or an organic peroxide is used. Examples include performic acid, peracetic acid, perpropionic acid, m-chlorobenzoic acid and the like.
　次に本発明の特徴を更に明確にするため実施例を挙げて具体的に説明する。なお、文中の「部」、「％」は全て重量基準を示すものである。　 Next, in order to further clarify the characteristics of the present invention, an example will be given and described in detail. In the text, “part” and “%” all indicate weight standards. *
実施例１～３、比較例１～４
  下記に示すエポキシ樹脂、硬化剤及び硬化促進剤を用い、表１及び表２に示す配合割合で混練してエポキシ樹脂組成物を調製した。表１～２中のカッコは重量部を表す。 Examples 1 to 3 and Comparative Examples 1 to 4
An epoxy resin composition was prepared by kneading using the following epoxy resin, curing agent, and curing accelerator at the blending ratios shown in Tables 1 and 2. The brackets in Tables 1 and 2 represent parts by weight.
  エポキシ樹脂成分として、上記式（２）で表されるエポキシ樹脂EP-ａ（エポキシ当量　９３／ｅｑ．２５℃での粘度は１１５ｍＰａ・ｓ）、比較として、シクロヘキサン骨格にオキシメチレン鎖を有するエポキシ樹脂である１，４－シクロヘキサンジメタノールジグリシジルエーテル　エポキシ樹脂EP-ｂ（新日本理化株式会社製、ＤＭＥ－１００；エポキシ当量１５８ｇ／ｅｑ．２５℃での粘度は１００ｍＰａ・ｓ）、水素化ビスフェノールＡジグリジジルエーテル　エポキシ樹脂EP-ｃ　（ジャパンエポキシレジン製　ＹＸ-８０００；エポキシ当量２１０ｇ／ｅｑ．２５℃での粘度は２５４８ｍＰａ・ｓ）を用いた。
  硬化剤成分として、ＰＮ（フェノールノボラック樹脂、荒川化学製、タマノール７５８；ＯＨ当量１０３、軟化点 ８２℃）、ＭＨ－７００（4-メチルヘキサヒドロ無水フタル酸/ヘキサヒドロ無水フタル酸混合物（70/30）、新日本理化株式会社製　リカシッド　ＭＨ-700）及びＥＣ-１００（1－メチル－3，5－ジエチル－2，4－ジアミノベンゼンと1－メチル－3，5－ジエチル－2，6－ジアミノベンゼンの混合物、アルベマール日本株式会社製　エタキュアー１００）を用いた。
　硬化促進剤成分として、２Ｅ４ＭＺ（２－エチル－４－メチルイミダゾール）を用いた。
　フィラーとして、電気化学工業（株）製の球状溶融シリカＦＢ－６０（平均粒径２１μｍ）及びＦＢ－３５（平均粒径１２μｍ）、（株）アドマテックス製の球状溶融シリカＳＯ－Ｃ３（平均粒径０．９μｍ）及びＳＯ－Ｃ２（平均粒径０．５μｍ）の４種類を混合して使用した。混合比は、重量比で、20：50：10：20とした。 As an epoxy resin component, an epoxy resin EP-a represented by the above formula (2) (epoxy equivalent 93 / eq. Viscosity at 25 ° C. is 115 mPa · s), for comparison, an epoxy resin having an oxymethylene chain in a cyclohexane skeleton 1,4-cyclohexanedimethanol diglycidyl ether epoxy resin EP-b (manufactured by Shin Nippon Rika Co., Ltd., DME-100; epoxy equivalent 158 g / eq, viscosity at 25 ° C. is 100 mPa · s), hydrogenated bisphenol A Diglycidyl ether epoxy resin EP-c (Japan Epoxy Resin YX-8000; epoxy equivalent 210 g / eq. Viscosity at 25 ° C. is 2548 mPa · s) was used.
As a curing agent component, PN (phenol novolak resin, manufactured by Arakawa Chemical, Tamanol 758; OH equivalent 103, softening point 82 ° C.), MH-700 (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride mixture (70/30 ), Shin Nippon Rika Co., Ltd., Ricacid MH-700) and EC-100 (1-methyl-3,5-diethyl-2,4-diaminobenzene and 1-methyl-3,5-diethyl-2,6-diamino A mixture of benzene, Ecure 100 manufactured by Albemarle Japan Ltd. was used.
2E4MZ (2-ethyl-4-methylimidazole) was used as a curing accelerator component.
As fillers, spherical fused silica FB-60 (average particle size 21 μm) and FB-35 (average particle size 12 μm) manufactured by Denki Kagaku Kogyo Co., Ltd., spherical fused silica SO-C3 (average particle size) manufactured by Admatechs Co., Ltd. A mixture of four types, 0.9 μm diameter) and SO—C2 (average particle diameter 0.5 μm) was used. The mixing ratio was 20: 50: 10: 20 by weight.
  エポキシ樹脂と硬化剤とを混合して得られた組成物（無機充填材と硬化促進剤を含まない）については、Ｅ型粘度計を用いて２５℃における組成物の粘度測定を行い、その結果を表１及び表２に示した。 About the composition obtained by mixing an epoxy resin and a hardening | curing agent (an inorganic filler and a hardening accelerator are not included), the viscosity measurement of the composition in 25 degreeC was performed using the E-type viscosity meter, and the result Are shown in Tables 1 and 2.
　更に、上記エポキシ樹脂組成物にフィラーを混合して得られたエポキシ樹脂組成物について、スパイラルフロー及びゲルタイムを測定した。スパイラルフローについては、規格（ＥＭＭＩ－１－６６）に準拠したスパイラルフロー測定用金型でエポキシ樹脂組成物をスパイラルフローの注入圧力（１５０ｋｇｆ／ｃｍ2）、硬化時間３分の条件で成形して流動長を調べた。ゲルタイムについては、予め１７５℃に加熱しておいたゲル化試験機（日新科学（株）製）の凹部にエポキシ樹脂組成物を流し込み、フッ素樹脂製棒を用いて一秒間に２回転の速度で攪拌し、エポキシ樹脂組成物が硬化するまでに要したゲル化時間を調べた。 Furthermore, the spiral flow and gel time were measured about the epoxy resin composition obtained by mixing a filler with the said epoxy resin composition. For spiral flow, an epoxy resin composition is molded using a spiral flow measurement mold in accordance with the standard (EMMI-1-66) under conditions of spiral flow injection pressure (150 kgf / cm 2 ) and curing time of 3 minutes. The flow length was examined. Regarding the gel time, the epoxy resin composition was poured into the concave portion of a gelation tester (Nisshin Kagaku Co., Ltd.) that had been heated to 175 ° C. in advance, and a speed of two revolutions per second using a fluororesin rod. And the gelation time required for the epoxy resin composition to cure was examined.
  次に、エポキシ樹脂組成物を１７５℃で成形し、１７５℃で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。ガラス転移点は、熱機械測定装置により、昇温速度７℃／分の条件で求めた。曲げ試験は、曲げ強度、曲げ弾性率を３点曲げ法により行った。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℃、８５％ＲＨの条件で１００時間吸湿させた時のものである。結果をまとめて表１及び表２に示す。 Next, the 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. The glass transition point was calculated | required on the conditions of the temperature increase rate of 7 degree-C / min with the thermomechanical measuring apparatus. The bending test was performed by a three-point bending method for bending strength and bending elastic modulus. The water absorption is the value obtained when a disk having a diameter of 50 mm and a thickness of 3 mm is molded using the epoxy resin composition and moisture-absorbed for 100 hours under conditions of 85 ° C. and 85% RH after post-curing. The results are summarized in Tables 1 and 2.
Figure JPOXMLDOC01-appb-T000005
  
Figure JPOXMLDOC01-appb-T000005
  
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　上記から、本発明のエポキシ樹脂組成物は、硬化前の粘度が低く、成形性時の流動性が良好であり、かつ耐熱性、耐湿性、低熱膨張性等に優れた硬化物を与えることがわかる。これらの硬化物は、半導体封止材等の電気・電子部品封止用材料、成形材料、積層材料、接着材料等に有用である。 From the above, the epoxy resin composition of the present invention has a low viscosity before curing, good fluidity at the time of moldability, and can give a cured product excellent in heat resistance, moisture resistance, low thermal expansion and the like. Recognize. These cured products are useful for electrical / electronic component sealing materials such as semiconductor sealing materials, molding materials, laminated materials, adhesive materials, and the like.
産業上の利用の可能性Industrial applicability
  本発明のエポキシ樹脂組成物は、低粘度性に優れ、耐熱性及び低熱膨張性等に優れた硬化物を与えることができる。本発明のエポキシ樹脂組成物は、低粘度性に優れたエポキシ樹脂を用いることにより成形時の優れた流動性が発揮される。また、低粘度性に起因してフィラー高充填率化が可能である。更には、エポキシ樹脂成分が一般的なエポキシ樹脂が有するグリシジルエーテル基と比較して、柔軟なオキシメチレン部位を持たないため、硬化物の分子運動が抑制されることにより優れた耐熱性、低熱膨張性が発揮される。以上の優れた流動性、耐熱性、低熱膨張性により、半導体封止材、各種成形材料、積層材料、粉体塗料及び接着材料等に好適に用いることができる。特に、電子部品封止用として優れる。 エ ポ キ シ The epoxy resin composition of the present invention is excellent in low viscosity, and can give a cured product excellent in heat resistance and low thermal expansion. The epoxy resin composition of the present invention exhibits excellent fluidity during molding by using an epoxy resin excellent in low viscosity. Moreover, the filler filling rate can be increased due to the low viscosity. Furthermore, since the epoxy resin component does not have a flexible oxymethylene moiety compared to the glycidyl ether group that general epoxy resins have, excellent heat resistance and low thermal expansion are achieved by suppressing the molecular motion of the cured product. Sex is demonstrated. Due to the above excellent fluidity, heat resistance, and low thermal expansibility, it can be suitably used for semiconductor encapsulating materials, various molding materials, laminated materials, powder coating materials, adhesive materials and the like. In particular, it is excellent for electronic component sealing.

Claims (7)

  1.   エポキシ樹脂及びエポキシ樹脂用硬化剤を含有するエポキシ樹脂組成物において、下式（１）で表されるエポキシ樹脂を含むことを特徴とするエポキシ樹脂組成物。
    Figure JPOXMLDOC01-appb-I000001
    　　　　　　　　　　　　　　　　　      An epoxy resin composition comprising an epoxy resin and an epoxy resin curing agent, comprising an epoxy resin represented by the following formula (1):
    Figure JPOXMLDOC01-appb-I000001
  2. 　エポキシ樹脂が下式（２）で表される1,2,4-トリエポキシエチルシクロヘキサンであることを特徴とする請求項１に記載のエポキシ樹脂組成物。
    Figure JPOXMLDOC01-appb-I000002
          The epoxy resin composition according to claim 1, wherein the epoxy resin is 1,2,4-triepoxyethylcyclohexane represented by the following formula (2).
    Figure JPOXMLDOC01-appb-I000002
  3.   エポキシ樹脂用硬化剤が、アミン類、酸無水物類、多価フェノール類、イミダゾール類、ジシアンジアミド類、及び有機酸ヒドラジッド類から選ばれる少なくとも１種の化合物であることを特徴とする請求項１に記載のエポキシ樹脂組成物。 The curing agent for epoxy resin is at least one compound selected from amines, acid anhydrides, polyhydric phenols, imidazoles, dicyandiamides, and organic acid hydrazides. The epoxy resin composition as described.
  4. 　硬化促進剤として、三級アミン類、イミダゾール類、ジシアンジアミド類、及び有機ホスフィン類から選ばれる少なくとも１種の化合物を含有することを特徴とする請求項１に記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 1, comprising at least one compound selected from tertiary amines, imidazoles, dicyandiamides, and organic phosphines as a curing accelerator.
  5.   無機充填材を８３重量％以上含有することを特徴とする請求項１に記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 1, comprising 83 wt% or more of an inorganic filler.
  6.   電気・電子部品封止用であることを特徴とする請求項１に記載のエポキシ樹脂組成物。 2. The epoxy resin composition according to claim 1, which is used for sealing electrical and electronic parts.
  7.   請求項１～５のいずれかに記載のエポキシ樹脂組成物を硬化してなることを特徴とするエポキシ樹脂硬化物。 A cured epoxy resin obtained by curing the epoxy resin composition according to any one of claims 1 to 5.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012020661A1 (en) * 2010-08-09 2012-02-16 新日鐵化学株式会社 Epoxy resin composition and hardener
WO2012108305A1 (en) * 2011-02-10 2012-08-16 新日鐵化学株式会社 Epoxy acrylate, acrylic curable composition, cured product and manufacturing processes therefor
WO2014066718A1 (en) * 2012-10-26 2014-05-01 Dow Global Technologies Llc Curable compositions comprising 1,3-dioxiranylcyclopentane epoxide compounds and thermosets prepared therefrom
WO2014066717A1 (en) * 2012-10-26 2014-05-01 Dow Global Technologies Llc Novel epoxide compounds: 1,3-dioxiranylcyclopentane derivatives
KR20220104959A (en) * 2021-01-19 2022-07-26 한국화학연구원 The composition containing trifunctional cycloaliphatic epoxy compounds and the cured product using the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB930431A (en) * 1960-10-03 1963-07-03 Rhone Poulenc Sa Epoxide derivatives of trivinylcyclohexane
US3251861A (en) * 1966-05-17 Di- and triepoxtoe derivatives of trivinylcyclohexane
JPH103084A (en) * 1996-06-18 1998-01-06 Sumitomo Bakelite Co Ltd Sealing material composition for liquid crystal display element, and liquid crystal display element formed by using the same
JP2007197647A (en) * 2005-12-27 2007-08-09 Sumitomo Electric Ind Ltd Liquid thermosetting resin composition and jointing material

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1694769A4 (en) * 2003-11-21 2007-08-29 Lord Corp Dual-stage wafer applied underfills

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3251861A (en) * 1966-05-17 Di- and triepoxtoe derivatives of trivinylcyclohexane
GB930431A (en) * 1960-10-03 1963-07-03 Rhone Poulenc Sa Epoxide derivatives of trivinylcyclohexane
JPH103084A (en) * 1996-06-18 1998-01-06 Sumitomo Bakelite Co Ltd Sealing material composition for liquid crystal display element, and liquid crystal display element formed by using the same
JP2007197647A (en) * 2005-12-27 2007-08-09 Sumitomo Electric Ind Ltd Liquid thermosetting resin composition and jointing material

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012020661A1 (en) * 2010-08-09 2012-02-16 新日鐵化学株式会社 Epoxy resin composition and hardener
JP5826751B2 (en) * 2010-08-09 2015-12-02 新日鉄住金化学株式会社 Epoxy resin composition and cured product
WO2012108305A1 (en) * 2011-02-10 2012-08-16 新日鐵化学株式会社 Epoxy acrylate, acrylic curable composition, cured product and manufacturing processes therefor
WO2014066718A1 (en) * 2012-10-26 2014-05-01 Dow Global Technologies Llc Curable compositions comprising 1,3-dioxiranylcyclopentane epoxide compounds and thermosets prepared therefrom
WO2014066717A1 (en) * 2012-10-26 2014-05-01 Dow Global Technologies Llc Novel epoxide compounds: 1,3-dioxiranylcyclopentane derivatives
JP2016500699A (en) * 2012-10-26 2016-01-14 ダウ グローバル テクノロジーズ エルエルシー Novel epoxide compound: 1,3-dioxiranylcyclopentane derivative
US9382373B2 (en) 2012-10-26 2016-07-05 Blue Cube Ip Llc Curable compositions and thermosets prepared therefrom
US9505731B2 (en) 2012-10-26 2016-11-29 Blue Cube Ip Llc Epoxide compound
KR20220104959A (en) * 2021-01-19 2022-07-26 한국화학연구원 The composition containing trifunctional cycloaliphatic epoxy compounds and the cured product using the same
KR102475977B1 (en) * 2021-01-19 2022-12-09 한국화학연구원 The composition containing trifunctional cycloaliphatic epoxy compounds and the cured product using the same

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