JP2004339417A - Casting epoxy resin composition for electric insulation and cured product - Google Patents
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Abstract
Description
【０００１】
【発明の属する技術分野】
この発明は、特殊な脂環式ジエポキシ化合物を含むエポキシ樹脂組成物と無機質充填材等を必須成分とする低粘度で作業性のよい電気絶縁用注型エポキシ樹脂組成物及びその硬化物に関するものである。
【０００２】
【従来の技術】
電気機器の絶縁部や電力ケーブルの接続部等においては、金属電極を埋め込んだエポキシ樹脂組成物注型品を設置して、上記金属電極部で導体を支持することが行われている。このようなエポキシ樹脂組成物注型品は、一般に、エポキシ樹脂と、酸無水物と、充填材等からなるエポキシ樹脂組成物を用いて製造されている。この内、エポキシ樹脂としてはビスフェノール型エポキシ樹脂が、酸無水物としては無水フタル酸が、無機質充填材としてはアルミナ、シリカ等の無機質粉末が用いられ、これらを用いることにより耐クラック性や機械的強度あるいは電気的特性をバランス良く向上させてきた。
【０００３】
【発明が解決しようとする課題】
近年、高電圧用機器の小形縮小化、超高電圧化の傾向はますます強く、エポキシ樹脂組成物注型品に要求される性能もますます高度化し、従来のエポキシ樹脂組成物注型品では、電気的特性、機械的特性において限界があり破壊に至る可能性も潜在している。すなわち、超高電圧化に伴い、絶縁体（電気絶縁用注型エポキシ樹脂組成物を使用した）には高電界がかかるため一層の耐電圧強度の向上が要求される。さらに、誘電損（ε・ｔａｎδ・Ｅ２）も超高電圧化に伴い増大し、その発生熱による絶縁体の熱的損傷も懸念される。特に、ε・ｔａｎδが温度上昇に伴い上昇すれば、熱暴走破壊も否定し難い。また、絶縁体に埋め込まれた金属電極との接着性や耐クラック性においても一層の向上が要求される。
例えば、特開平９−７７８４７号公報のように、エポキシ樹脂としてビスフェノールＡ型エポキシとノボラックエポキシを使用し、２種類以上の酸無水物を混合して絶縁用樹脂を作ることが、また特開平１１−６０９０８号公報には、エポキシ樹脂としてビスフェノールＡ型エポキシと結晶性エポキシに２種類以上の酸無水物を混合して絶縁用樹脂を作ることが例示されている。
これらの場合、組成物が固体であるため注型や含浸の用途には不向きである。
【０００４】
【特許文献１】
特開平９−７７８４７号公報
【特許文献２】
特開平１１−６０９０８号公報
【特許文献３】
特願２００２−２６０４９０号明細書
【非特許文献１】
ロシア文献（Ｎｅｆｔｅｋｈｉｍｉｙａ，１９７２，１２，３５３）
【０００５】
そこで、本出願人は分子内にエステル基を持たない別の脂環骨格を有するエポキシ化合物として、特願２００２−２６０４９０号明細書において、ロシア文献（Ｎｅｆｔｅｋｈｉｍｉｙａ，１９７２，１２，３５３）に記載されている技術を改善する目的で、実質的に水分を含まない有機過カルボン酸を用いて上記式（１）で表される脂環式ジエポキシ化合物（ａ−１）を効率的に合成する方法を提案した。本発明者は、この脂環式ジエポキシ化合物（ａ−１）を含むエポキシ樹脂組成物、酸無水物、硬化促進剤および無機充填材の配合割合を特定の範囲に設定することにより、電気絶縁用注型エポキシ樹脂組成物が注型作業性を損なうことなく、優れた耐熱性、電気的特性および機械的特性を有する硬化物を与えることを見出し、本発明を完成させた。本発明により、特に、上記無機質充填材として、溶融アルミナを用いることにより、電気的特性および機械的特性の双方に優れた電気絶縁用注型エポキシ樹脂組成物が得られ、特に、耐電圧特性においては電融アルミナを用いた場合に比べて３０〜５０％も向上させることができることが判明した。
【０００６】
【課題を解決するための手段】
本発明は、熱硬化性樹脂と無機質充填材を含有する電気絶縁用注型エポキシ樹脂組成物であって、上記熱硬化性樹脂が、下記の（Ａ）〜（Ｃ）成分
（Ａ）エポキシ樹脂組成物
下記の一般式（１）で表される脂環式ジエポキシ化合物（ａ−１）を５〜８０重量％
【化２】
一般式（１）で表される脂環式ジエポキシ化合物（ａ−１）以外のエポキシ化合物（ａ−２）９５〜２０重量％［脂環式ジエポキシ化合物（ａ−１）とエポキシ化合物（ａ−２）の合計は１００重量％］
（Ｂ）酸無水物
（Ｃ）硬化促進剤
からなり、さらに
（Ｄ）無機質充填材
を含み、上記（Ｂ）成分の配合割合が、（Ａ）成分１当量に対して０．６〜１．０当量の範囲に、（Ｃ）成分が（Ａ）及び（Ｂ）の合計量１００重量部に対して０．５〜１０重量部、（Ｄ）成分が（Ａ）〜（Ｄ）成分の合計量中３０〜８０重量％からなることを特徴とする電気絶縁用注型エポキシ樹脂組成物を提供する。
また、本発明は、式（１）で表される脂環式ジエポキシ化合物（ａ−１）がビシクロヘキシル−３，３’−ジエポキシドである上記の電気絶縁用注型エポキシ樹脂組成物を提供する。
また、本発明は、酸無水物がメチルヘキサヒドロ無水フタル酸またはメチルノルボルネンジカルボン酸無水物である上記の電気絶縁用注型エポキシ樹脂組成物を提供する。
また、本発明は、硬化促進剤がエチレングリコールまたはジアザビシクロウンデセンである上記の電気絶縁用注型エポキシ樹脂組成物を提供する。
また、本発明は、無機質充填材が球状の溶融シリカまたは溶融アルミナである上記の電気絶縁用注型エポキシ樹脂組成物を提供する。
また、本発明は、エポキシ化合物（ａ−２）が３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレート、ビスフェノール型エポキシ樹脂またはノボラックフェノール型エポキシ樹脂のいずれか少なくとも一つである上記の電気絶縁用注型エポキシ樹脂組成物を提供する。
また、本発明は、上記のいずれかに記載の電気絶縁用注型エポキシ樹脂組成物を硬化してなる硬化物を提供する。
【０００７】
【発明の実施の形態】
つぎに、本発明の実施の形態について詳しく説明する。
本発明の電気絶縁用注型エポキシ樹脂組成物（以下「注型エポキシ樹脂組成物」という）は、特定のエポキシ化合物を含有するエポキシ樹脂組成物（Ａ成分）と、酸無水物（Ｂ成分）と、硬化促進剤（Ｃ成分）とを用いて構成される熱硬化性樹脂と、無機質充填材（Ｄ成分）とを用いて得られるものである。
上記特定のエポキシ化合物を含有するエポキシ樹脂組成物（Ａ成分）は、一般式（１）で表されるエポキシ化合物（ａ−１）とこれ以外のエポキシ化合物（ａ−２）からなる。
上記特定のエポキシ化合物（ａ−１）は、下記の一般式（１）で表されるものであり、なかでも、Ｒ１〜Ｒ１８が水素原子のもの、すなわち、ビシクロヘキシル−３，３’−ジエポキシドが好適に用いられる。
【化３】
【０００８】
上記脂環式ジエポキシ化合物（ａ−１）は、例えば、前記特願２００２−２６０４９０号明細書に記載されているように、ビシクロヘキシル−３，３’−ジエン骨格を持つ不飽和化合物と酸化剤、特に、有機過カルボン酸 （過ギ酸、過酢酸、過安息香酸、過イソ酪酸、トリフルオロ過酢酸等）とを反応させることによって製造することができる。
有機過カルボンの中でも特に過酢酸は、本発明における脂環式ジエポキシ化合物（ａ−１）の製造の際に必要な反応性を有すると同時に、安定度が高いことから好ましいエポキシ化剤である。
中でも、実質的に水分を含まない、具体的には、水分含有量０．８重量％以下、好ましくは０．６重量％以下の有機過カルボン酸を使用することが高いエポキシ化率を有する脂環式ジエポキシ化合物（ａ−１）が得られるという点で好ましい。実質的に水分を含まない有機過カルボン酸は、アルデヒド類、例えば、アセトアルデヒドの空気酸化により製造されるものであり、例えば、過酢酸については特開昭５４−３００６に記載された方法により製造される。この方法によれば、過酸化水素から有機過カルボン酸を合成し、溶媒により抽出して有機過カルボン酸を製造する場合に比べて、連続して大量に高濃度の有機過カルボン酸を合成できるために、実質的に安価に得ることができる。
【０００９】
エポキシ化合物（ａ−１）およびこれ以外のエポキシ化合物（ａ−２）の配合割合は、（ａ−１）がエポキシ樹脂組成物（Ａ成分）全体の５〜８０重量％（以下「％」と略す）になるように、好ましくは、８〜７５重量％、そして、（ａ−２）が９５〜２０％、好ましくは、９２〜２５重量％、になるようにそれぞれ設定する必要がある。
【００１０】
（ａ−２）の具体例としては、ビスフェノール型エポキシ樹脂（ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＡＦ、ビスフェノールＳ型のエポキシ化合物、水添ビスフェノール型エポキシ化合物など。）、ノボラックフェノール型エポキシ樹脂、ノボラックフェノール型のＤＣＰＤ共重合体エポキシ樹脂、ノボラックフェノール型のキシレン共重合型エポキシ樹脂などが挙げられる。脂環式エポキシ樹脂として、ビス（３，４−エポキシシクロヘキシルメチル）アジペート［例えば、ユニオンカーバイド社製のＥＲＬ４２９９等］、３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレート［例えば、ダイセル化学工業株式会社製のＣＥＬ−２０２１Ｐ、ユニオンカーバイド社製のＥＲＬ４２２１］、３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレートへのラクトン付加物［ダイセル化学工業株式会社製のＣＥＬ−２０８０シリーズ］、エポキシ化３−シクロヘキセン−１，２−ジカルボン酸ビス３−シクロヘキセニルメチルエステルおよびそのε−カプロラクトン付加物［例えば、ダイセル化学工業株式会社製のエポリードＧＴ−３００シリーズ］、エポキシ化ブタンテトラカルボン酸テトラキス−３−シクロヘキセニルメチルエステルおよびそのラクトン付加物［例えば、ダイセル化学工業株式会社製のエポリードＧＴ−４００シリーズ］、トリメチロールプロパン構造を有するエポキシ化シクロヘキサンポリエーテル［例えば、ダイセル化学工業株式会社製のＥＨＰＥ−３１５０］、１，２，８，９−ジエポキシリモネン［例えば、ダイセル化学工業株式会社製のＣＥＬ−３０００］などが挙げられる。これらは、単独又は２種類以上混合して使用することができる。
【００１１】
本発明においては、２種類のエポキシ化合物を用いてエポキシ樹脂組成物（Ａ成分）を構成し、これとともに後述の酸無水物、硬化促進剤、無機質充填材を用いることにより、目的とする注型作業性を損なうことなく、優れた電気的特性および機械的特性を有する特性を備えた硬化物を与える電気絶縁用注型エポキシ樹脂組成物が得られる。
【００１２】
上記エポキシ樹脂組成物（Ａ成分）とともに用いられる酸無水物（Ｂ成分）は、上記エポキシ樹脂組成物（Ａ成分）の硬化剤として作用するものであり、特に限定されるものではなく従来公知のものが用いられる。例えば、無水フタル酸、無水マレイン酸、無水トリメリット酸、無水メチルハイミック酸、無水ピロメリット酸、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、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、ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、ビス（３，４−ジカルボキシフェニル）エーテル二無水物、ビス（３，４−ジカルボキシフェニル）メタン二無水物、２，２−ビス（３，４−ジカルボキシフェニル）プロパン二無水物、メチルノルボルネンカルボン酸無水物等の、好ましくは分子中に脂肪族環又は芳香族環を１個又は２個有すると共に、酸無水物基を１個又は２個有する、炭素原子数４〜２５個、好ましくは８〜２０個程度の酸無水物が等が挙げられる。
これら酸無水物は単独でもしくは２種以上併せて用いられる。なかでも、耐熱性に優れ、電気的特性および機械的強度が一層向上するという点から、メチルヘキサヒドロ無水フタル酸、テトラヒドロ無水フタル酸などを使用することが好ましい。
上記酸無水物（Ｂ成分）の配合割合は、上記特定のエポキシ化合物（ａ−１）および（ａ−１）以外のエポキシ化合物（ａ−２）を含有するエポキシ樹脂組成物（Ａ成分）１当量に対して０．６〜１．０当量の範囲に設定する必要がある。特に好ましくは、０．７〜０．９当量である。すなわち、酸無水物の配合割合が１．０当量を超えると電気的特性が低下し、逆に０．６当量未満では耐熱性が低下するからである。なお、上記酸無水物（Ｂ成分）の当量（酸無水物当量）は、つぎのように設定される。すなわち、Ａ成分中のエポキシ基１個に対して、酸無水物中の酸無水物基が１個の場合を１当量とする。そして、上記配合割合が０．６〜１．０当量とは、前記（ａ−１）および（ａ−２）の２種類のエポキシ化合物を含有するエポキシ樹脂組成物（Ａ成分）中のエポキシ基１個に対して、酸無水物中の酸無水物基の数が０．６〜１．０個であるという趣旨である。
【００１３】
上記Ａ成分およびＢ成分とともに用いられる硬化促進剤（Ｃ成分）としては、ベンジルジメチルアミン、トリスジメチルアミノメチルフェノール、トリエチレンジアミン等の第三級アミン類，テトラブチルアンモニウムブロミドなどの４級アミンの臭素塩、ジアザビシクロウンデセン（ＤＢＵ）やＤＢＵの有機酸塩、トリフェニルホスフィン、リン酸エステル、ホウ酸エステル，ルイス酸，チタンやアルミのアルコキシドやアセチルアセトン、アセト酢酸エステル類などの有機金属化合物，イミダゾール類等が挙げられる。これらは単独でもしくは２種以上併せて用いられる。特に、得られる硬化物の耐熱性が優れるという点から、上記第三級アミン類及び４級アミンの臭素塩を用いることが好ましい。
これらの商品名としては、ＳＡ−１０２（ジアザビシクロウンデセン系硬化促進剤），ＳＡ−５０６（ジアザビシクロウンデセン系硬化促進剤），Ｕ−ＣＡＴ５００３（ホスホニウム塩系硬化促進剤）［以上サンアプロ社製］が挙げられる。
上記硬化促進剤（Ｃ成分）の配合量は、前記２種類のエポキシ化合物からなるエポキシ樹脂組成物（Ａ成分）の合計１００重量部に対し０．５〜１０重量部の範囲に設定することが好ましい。すなわち、Ｃ成分の配合量が０．５％重量部未満では、硬化反応が遅くなり作業性に問題が生じ、１０重量部を超えると、反応時間が著しく速くなり、流動性の低下を招き、また、電気的にも体積抵抗率の低下を招く恐れがあるからである。
【００１４】
上記Ａ〜Ｃ成分とともに必須成分として用いられる（Ｄ）成分である無機質充填材としては、シリカ，アルミナ，タルク，ケイ砂，炭酸カルシウム，硫酸バリウム等が挙げられる。これらは単独でもしくは２種以上併せて用いられる。なかでも、ｔａｎδや耐電圧特性に優れるという点から、シリカのなかでも球状の溶融シリカ粉末、またアルミナのなかでも溶融アルミナを用いることが好ましい。すなわち、シリカのなかでも、球状の溶融シリカ粉末を用いることにより、界面分極を抑制し、かつ電気的ストレスの集中を排除するという作用から、誘電正接（ｔａｎδ）および耐電圧特性の一層の向上効果が得られる。特に、上記球状の溶融シリカを用いる場合は、粒径５０μｍ以下の粒子が全体の９９重量％以上〔要件（Ｘ）〕で、かつ平均粒径が３５μｍ以下〔要件（Ｙ）〕のものを用いることが、粘度上昇による注型作業性の低下が効果的に防止され、電気的特性および機械的強度の双方に優れた注型エポキシ樹脂組成物が得られるという点から好ましい。また、溶融アルミナは、一般に、バイヤー法アルミナまたはボーキサイトを主原料として電気炉で溶解し、析出、焼成、粉砕、脱鉄、水洗、乾燥といった一連の工程を経て得られるものであり、この溶融アルミナを用いることにより、上記溶融シリカを用いた場合と同様に、電気的特性および機械的特性の双方に優れ、特に、耐電圧特性は電融アルミナを用いた場合に比べて大幅な向上効果が得られる。
上記無機質充填材（Ｄ）の配合量は、本発明の電気絶縁用注型エポキシ樹脂組成物（Ａ）〜（Ｄ）成分の合計中３０〜８０重量％の範囲になるように設定することが必須である。すなわち、無機質充填材（Ｄ）の配合量が組成物全体の３０％未満では、本発明の電気絶縁用注型エポキシ樹脂組成物の溶融粘度が著しく低下し、無機質充填材（Ｄ）の沈降が発生する。また、機械的強度も低下する。逆に、８０％を超えると、高粘度になり過ぎて混合性および流動性が低下することから作業性の低下を招く恐れがあるからである。
【００１５】
なお、本発明の電気絶縁用注型エポキシ樹脂組成物には、上記Ａ〜Ｃ成分および（Ｄ）成分である無機質充填材以外に、必要に応じて、希釈剤、可塑剤、顔料、離型剤、難燃剤等の他の添加剤を適宜に配合することができる。
そして、本発明の電気絶縁用注型エポキシ樹脂組成物を調製するために、上記各原料が所定の割合で配合される。配合にはドライブレンダー、リボンブレンダー、ヘンシェルミキサー等公知のものを使用することができ、配合は通常、常温で行われる。
上記各成分の配合物は真空加熱下で気泡を排除しつつ攪拌・混合することにより電気絶縁用注型樹脂組成物として調製される。攪拌・混合する際の温度は、通常、４０〜１００℃に設定される。
調製時の設定温度が４０℃未満では、粘度が高すぎて均一な撹拌・混合作業が困難になり、逆に、調製時の温度が１００℃を超えると、硬化反応が起き、正常な電気絶縁用注型樹脂組成物が得られないので、好ましくない。攪拌・混合する際には、減圧装置を備えた１軸または多軸エクストルーダー、ニーダー汎用の機器を使用することができる。
【００１６】
そして、この調製された電気絶縁用注型エポキシ樹脂組成物は、所定の成形型内に注入され、所定の条件で加熱硬化されて所望の形状を有する本発明の硬化物に成形される。
本発明の電気絶縁用注型エポキシ樹脂組成物は、温度１００〜２００℃、好ましくは、１００〜１９０℃、さらに好ましくは、１００〜１８０℃で、硬化時間３０〜６００分、好ましくは、４５〜５４０分、さらに好ましくは、６０〜４８０分で硬化させることができる。
硬化温度と硬化時間が上記範囲下限値より低い場合は、硬化が不十分となり、逆に上記範囲上限値より高い場合、樹脂成分の分解が起きる場合があるので、何れも好ましくない。硬化条件は種々の条件に依存するが、硬化温度が高い場合は硬化時間は短く、硬化温度が低い場合は硬化時間は長く、適宜調整することができる。
【００１７】
【実施例】
つぎに、実施例を比較例と併せて説明する。
＜合成例１＞
脂環式ジオレフィン化合物であるビシクロヘキシル−３，３’−ジエン４０６ｇ、酢酸エチル１２１７ｇを仕込み、窒素を気相部に吹き込みながら、かつ、反応系内の温度を３７．５℃になるようにコントロールしながら約３時間かけて３０重量％過酢酸の酢酸エチル溶液（水分率０．４１重量％）４５７ｇを滴下した。過酢酸溶液滴下終了後、４０℃で１時間熟成し反応を終了した。さらに３０℃で反応終了時の粗液を水洗し、７０℃／２０ｍｍＨｇで低沸点化合物の除去を行い、エポキシ化合物４１５ｇを得た。このときの収率は８５％であった。
得られたエポキシ化合物のオキシラン酸素濃度は１４．７重量％（理論値：１６．５重量％）であった。
また１ＨＮＭＲの測定では、δ４．５〜５ｐｐｍ付近の内部二重結合に由来するピークが消失し、δ２．９〜３．１ｐｐｍ付近にエポキシ基に由来するプロトンのピークの生成が確認され、原料である脂環式ジオレフィン化合物に対応する前記一般式（１）で表される脂環式エポキシ化合物（ａ−１）であることが確認された。
【００１８】
まず、下記に示すエポキシ化合物またはエポキシ樹脂（ａ−１）および（ａ−２）、酸無水物１〜２、硬化促進剤１〜２、無機質充填材１〜２を準備した。
エポキシ化合物（ａ−１）として、合成例１のエポキシ化合物が用いられ、エポキシ化合物（ａ−２）として、下記のエポキシ樹脂２〜４が用いられた。
エポキシ樹脂２：ＣＥＬ−２０２１Ｐ（３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレート、ダイセル化学工業製）
エポキシ樹脂３：ＹＤ−１２８（東都化成製、ビスフェノールＡ型エポキシ樹脂、エポキシ当量１９０、粘度１３６００ｍＰａ・ｓ／２５℃）
エポキシ樹脂４：ＨＢＥ−１００（新日本理化製、水添ビスフェノールＡジグリシジルエーテル型エポキシ樹脂、エポキシ当量２１０、粘度２２１０ｍＰａ・ｓ／２５℃）
〔酸無水物１〕下記の構造式で表されるメチルヘキサヒドロ無水フタル酸（商品名 リカシッドＭＨ−７００：新日本理化社製）
〔酸無水物２〕下記の構造式で表される酸無水物（商品名 ＨＮＡ：新日本理化社製）
［硬化促進剤１］エチレングリコール
〔硬化促進剤２〕ＤＢＵ （ジアザビシクロウンデセン）
〔無機質充填材１〕球状の溶融シリカ（平均粒径５０μｍ以下の粒子が全体の９９重量％以上）
〔無機質充填材２〕溶融アルミナ（平均粒径５０μｍ以下の粒子が全体の９９重量％以上）
【００１９】
（実施例１〜８、比較例１〜４）
下記の表１〜表２に示す各成分を、同表に示す割合で配合し、約２５℃の温度にて減圧下（３〜５Ｔｏｒｒ）で「ＴＨＩＮＫＹ製、あわとり練太郎 ＡＲ−１００」を用いて攪拌混合することにより絶縁性注型エポキシ樹脂組成物を得た。そして、上記絶縁性注型エポキシ樹脂組成物を用い注型法により成形硬化して所定形状の成形品を作製した。なお、表１〜表２において、各成分の配合量はいずれも重量部を表す。
【００２０】
【表１】
【表２】
このようにして得られた実施例の電気絶縁用注型エポキシ樹脂組成物および比較例のエポキシ樹脂組成物を所定の条件下（１４０℃×２時間＋１７０℃×１０時間）で硬化させた硬化物の電気的特性（誘電正接、誘電率）、機械的特性（曲げ強度）、およびガラス転移温度（Ｔｇ）を下記に示す各試験条件下で測定した。結果を表３〜表４に示す。なお、下記いずれの試験においても、試料数５個の平均値を求めた。
【００２３】
【表３】
【表４】
〔誘電正接および誘電率〕
片面に主電極とその周囲のガード電極を、他面に対向電極を、それぞれ導電塗料により形成した、厚み１ｍｍ×直径６０ｍｍの試料を作製した。そして、この試料を恒温槽内で１００℃にして変成器ブリッジ法にてキャパシタンスおよびコンダクタンス（測定周波数：５０Ｈｚ）をそれぞれ測定し、これらの結果から誘電正接（ｔａｎδ）および誘電率（ε）を下記の式により算出した。
誘電正接（ｔａｎδ）＝Ｇｘ／２π・ｆ・Ｃｘ
誘電率（ε）＝Ｃｘ／Ｃｏ
Ｃｘ：ブリッジが平衡になったときのキャパシタンス値（ｐＦ）
Ｃｏ：主電極の面積および試料の厚みから算出したε＝１の静電容量（ｐＦ）
Ｇｘ：試料のコンダクタンス値（Ｓ）
ｆ：測定周波数（Ｈｚ）
〔曲げ強度〕
幅１０ｍｍ×長さ１００ｍｍ×厚み４ｍｍの試料を作製し、間隔６４ｍｍの両端支持で中央に加圧くさびにより荷重をかけ、曲げ破断したときの最大荷重を求めた。
〔Ｔｇ（ガラス転移温度：℃）〕
大きさ５ｘ５ｘ１０ｍｍの試料を作製し、熱膨張測定法（セイコーインスツルメント社製、熱機械分析装置ＴＭＡ／ＳＳ６１００による）により５℃／分で昇温したときの寸法変化を測定しプロットする。そして、熱膨張率の変位点によりガラス転移温度（Ｔｇ）を求めた。
【００２６】
【発明の効果】
表３および表４の結果から、本発明の電気絶縁用注型エポキシ樹脂組成物を硬化して得られる硬化物は曲げ強度およびＴｇが高く、かつ、誘電率が低いという優れた特性を有していることが明らかである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an epoxy resin composition containing a special alicyclic diepoxy compound, a castable epoxy resin composition for electric insulation having a low viscosity and good workability, which comprises an inorganic filler and the like as essential components, and a cured product thereof. is there.
[0002]
[Prior art]
2. Description of the Related Art In an insulating portion of an electric device, a connection portion of a power cable, and the like, an epoxy resin composition cast product having a metal electrode embedded therein is installed, and a conductor is supported by the metal electrode portion. Such an epoxy resin composition casting is generally manufactured using an epoxy resin composition comprising an epoxy resin, an acid anhydride, a filler and the like. Among them, bisphenol-type epoxy resin is used as the epoxy resin, phthalic anhydride is used as the acid anhydride, and inorganic powder such as alumina and silica is used as the inorganic filler. Strength or electrical characteristics have been improved in a well-balanced manner.
[0003]
[Problems to be solved by the invention]
In recent years, the trend toward miniaturization and ultra-high voltage of high-voltage equipment has become more and more strong, and the performance required for epoxy resin composition cast products has also become increasingly sophisticated. In addition, there is a limit in electric characteristics and mechanical characteristics, and there is a possibility of destruction. That is, with the increase in the voltage, a high electric field is applied to the insulator (using the cast epoxy resin composition for electrical insulation), so that a further improvement in withstand voltage strength is required. Furthermore, the dielectric loss (ε · tanδ · E2) also increases with the increase in the voltage, and there is a concern that the insulator may be thermally damaged by the heat generated. In particular, if ε · tan δ increases with a rise in temperature, it is difficult to deny thermal runaway destruction. Further, further improvement is required in the adhesiveness to the metal electrode embedded in the insulator and the crack resistance.
For example, as disclosed in JP-A-9-77847, it is possible to use a bisphenol A type epoxy and a novolak epoxy as an epoxy resin and mix two or more acid anhydrides to produce an insulating resin. Japanese Patent Application Laid-Open No. 60908 discloses that an insulating resin is prepared by mixing two or more acid anhydrides with a bisphenol A type epoxy and a crystalline epoxy as epoxy resins.
In these cases, since the composition is solid, it is not suitable for casting or impregnation.
[0004]
[Patent Document 1]
Japanese Patent Application Laid-Open No. 9-77847 [Patent Document 2]
Japanese Patent Application Laid-Open No. 11-60908 [Patent Document 3]
Japanese Patent Application No. 2002-260490 [Non-Patent Document 1]
Russian literature (Neftekhimiya, 1972, 12, 353)
[0005]
Accordingly, the present applicant has described, as an epoxy compound having another alicyclic skeleton having no ester group in the molecule, in Russian Patent (Neftekhimiya, 1972, 12, 353) in Japanese Patent Application No. 2002-260490. Proposed a method for efficiently synthesizing the alicyclic diepoxy compound (a-1) represented by the above formula (1) using an organic percarboxylic acid substantially free of water for the purpose of improving the existing technology. did. The present inventor sets the compounding ratio of the epoxy resin composition containing the alicyclic diepoxy compound (a-1), the acid anhydride, the curing accelerator and the inorganic filler in a specific range, thereby providing electric insulating material. The present inventors have found that the cast epoxy resin composition gives a cured product having excellent heat resistance, electrical properties, and mechanical properties without impairing the workability of casting, and completed the present invention. According to the present invention, in particular, by using fused alumina as the inorganic filler, a cast epoxy resin composition for electrical insulation excellent in both electrical properties and mechanical properties is obtained, and in particular, in withstand voltage characteristics It has been found that can be improved by 30 to 50% as compared with the case where fused alumina is used.
[0006]
[Means for Solving the Problems]
The present invention is a cast epoxy resin composition for electrical insulation containing a thermosetting resin and an inorganic filler, wherein the thermosetting resin comprises the following component (A) to (C) epoxy resin Composition 5 to 80% by weight of alicyclic diepoxy compound (a-1) represented by the following general formula (1)
Embedded image
95 to 20% by weight of an epoxy compound (a-2) other than the alicyclic diepoxy compound (a-1) represented by the general formula (1) [the alicyclic diepoxy compound (a-1) and the epoxy compound (a- The sum of 2) is 100% by weight]
It comprises (B) an acid anhydride, (C) a curing accelerator, and further contains (D) an inorganic filler, and the compounding ratio of the component (B) is 0.6 to 1. In the range of 0 equivalents, the component (C) is 0.5 to 10 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B), and the component (D) is the total of the components (A) to (D). The present invention provides a cast epoxy resin composition for electrical insulation, comprising 30 to 80% by weight of the composition.
The present invention also provides the above-mentioned cast epoxy resin composition for electrical insulation, wherein the alicyclic diepoxy compound (a-1) represented by the formula (1) is bicyclohexyl-3,3′-diepoxide. .
The present invention also provides the above-mentioned cast epoxy resin composition for electrical insulation, wherein the acid anhydride is methyl hexahydrophthalic anhydride or methyl norbornene dicarboxylic anhydride.
The present invention also provides the above-mentioned castable epoxy resin composition for electrical insulation, wherein the curing accelerator is ethylene glycol or diazabicycloundecene.
Further, the present invention provides the above-mentioned castable epoxy resin composition for electric insulation, wherein the inorganic filler is spherical fused silica or fused alumina.
Further, in the present invention, the epoxy compound (a-2) is at least one of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, a bisphenol type epoxy resin and a novolak phenol type epoxy resin. The present invention provides a cast epoxy resin composition for electrical insulation.
The present invention also provides a cured product obtained by curing the epoxy resin composition for electrical insulation described in any of the above.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
Next, embodiments of the present invention will be described in detail.
The cast epoxy resin composition for electrical insulation of the present invention (hereinafter referred to as “cast epoxy resin composition”) comprises an epoxy resin composition (A component) containing a specific epoxy compound and an acid anhydride (B component). And a thermosetting resin composed of a curing accelerator (component C) and an inorganic filler (component D).
The epoxy resin composition (component A) containing the above-mentioned specific epoxy compound comprises an epoxy compound (a-1) represented by the general formula (1) and another epoxy compound (a-2).
The specific epoxy compound (a-1) is a compound represented by the following general formula (1), in which R 1 to R 18 are each a hydrogen atom, that is, bicyclohexyl-3,3 ′. -Diepoxides are preferably used.
Embedded image
[0008]
The alicyclic diepoxy compound (a-1) is, for example, an unsaturated compound having a bicyclohexyl-3,3′-diene skeleton and an oxidizing agent as described in Japanese Patent Application No. 2002-260490. Particularly, it can be produced by reacting with an organic percarboxylic acid (performic acid, peracetic acid, perbenzoic acid, perisobutyric acid, trifluoroperacetic acid, etc.).
Among organic percarboxylic acids, peracetic acid is a preferred epoxidizing agent because it has the reactivity necessary for producing the alicyclic diepoxy compound (a-1) in the present invention and has high stability.
Above all, the use of an organic percarboxylic acid having substantially no water content, specifically, a water content of 0.8% by weight or less, preferably 0.6% by weight or less has a high epoxidation ratio. It is preferable in that the cyclic diepoxy compound (a-1) can be obtained. Organic percarboxylic acids containing substantially no water are produced by air oxidation of aldehydes, for example, acetaldehyde. For example, peracetic acid is produced by the method described in JP-A-54-3006. You. According to this method, an organic percarboxylic acid is synthesized from hydrogen peroxide, and a large amount of the organic percarboxylic acid can be continuously synthesized in a large amount as compared with a case where an organic percarboxylic acid is produced by extracting with a solvent. Therefore, it can be obtained substantially inexpensively.
[0009]
The mixing ratio of the epoxy compound (a-1) and the other epoxy compound (a-2) is such that (a-1) is 5 to 80% by weight of the entire epoxy resin composition (A component) (hereinafter referred to as “%”). (Abbreviated)), and it is necessary to set each so that 8 to 75% by weight, and (a-2) is 95 to 20%, preferably 92 to 25% by weight.
[0010]
Specific examples of (a-2) include bisphenol type epoxy resins (bisphenol A, bisphenol F, bisphenol AF, bisphenol S type epoxy compound, hydrogenated bisphenol type epoxy compound, etc.), novolak phenol type epoxy resin, novolak phenol Type DCPD copolymer epoxy resin and novolak phenol type xylene copolymer type epoxy resin. Examples of the alicyclic epoxy resin include bis (3,4-epoxycyclohexylmethyl) adipate [for example, ERL4299 manufactured by Union Carbide] and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate [for example, Daicel CEL-2021P manufactured by Chemical Industry Co., Ltd., ERL4221 manufactured by Union Carbide Co., Ltd., a lactone adduct to 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate [CEL-2080 manufactured by Daicel Chemical Industries, Ltd.] Series], epoxidized 3-cyclohexene-1,2-dicarboxylic acid bis-3-cyclohexenylmethyl ester and its ε-caprolactone adduct [for example, Eporide GT-300 series manufactured by Daicel Chemical Industries, Ltd.] ], Epoxidized butanetetracarboxylic acid tetrakis-3-cyclohexenylmethyl ester and its lactone adduct [e.g., EPOLIDE GT-400 series manufactured by Daicel Chemical Industries, Ltd.], epoxidized cyclohexane polyether having a trimethylolpropane structure [ Examples thereof include EHPE-3150 manufactured by Daicel Chemical Industries, Ltd. and 1,2,8,9-diepoxylimonene [for example, CEL-3000 manufactured by Daicel Chemical Industries, Ltd.]. These can be used alone or in combination of two or more.
[0011]
In the present invention, an epoxy resin composition (component A) is formed using two types of epoxy compounds, and an acid anhydride, a curing accelerator, and an inorganic filler described later are used together with the epoxy resin composition to achieve a desired casting. A cast epoxy resin composition for electrical insulation that gives a cured product having excellent electrical and mechanical properties without impairing workability can be obtained.
[0012]
The acid anhydride (component B) used together with the epoxy resin composition (component A) acts as a curing agent for the epoxy resin composition (component A), and is not particularly limited and is conventionally known. Things are used. For example, phthalic anhydride, maleic anhydride, trimellitic anhydride, methylhymic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, benzophenone Tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) Preferably, one or two aliphatic rings or aromatic rings are present in the molecule, such as methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, methyl norbornene carboxylic anhydride. And having one or two acid anhydride groups, and having 4 to 25 carbon atoms, preferably about 8 to 20 carbon atoms. Anhydrides and the like.
These acid anhydrides are used alone or in combination of two or more. Among them, it is preferable to use methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, or the like from the viewpoint of excellent heat resistance and further improvement in electrical properties and mechanical strength.
The mixing ratio of the above-mentioned acid anhydride (component B) is as follows: the epoxy resin composition (component A) containing the specific epoxy compound (a-1) and the epoxy compound (a-2) other than (a-1). It is necessary to set the range of 0.6 to 1.0 equivalent to the equivalent. Particularly preferably, it is 0.7 to 0.9 equivalent. That is, when the compounding ratio of the acid anhydride exceeds 1.0 equivalent, the electrical properties decrease, and when it is less than 0.6 equivalent, the heat resistance decreases. In addition, the equivalent (acid anhydride equivalent) of the said acid anhydride (B component) is set as follows. That is, one equivalent of one acid anhydride group in the acid anhydride per one epoxy group in the component A is defined as one equivalent. And, the mixing ratio of 0.6 to 1.0 equivalent means that the epoxy group in the epoxy resin composition (component A) containing the two types of epoxy compounds (a-1) and (a-2). The meaning is that the number of acid anhydride groups in the acid anhydride is 0.6 to 1.0 with respect to one.
[0013]
Examples of the curing accelerator (component C) used together with the above components A and B include tertiary amines such as benzyldimethylamine, trisdimethylaminomethylphenol and triethylenediamine, and bromine of quaternary amines such as tetrabutylammonium bromide. Salts, diazabicycloundecene (DBU) and organic acid salts of DBU, triphenylphosphine, phosphates, borates, Lewis acids, alkoxides of titanium and aluminum, acetylacetone, acetoacetates, and the like, And imidazoles. These may be used alone or in combination of two or more. In particular, it is preferable to use the above tertiary amines and bromine salts of quaternary amines from the viewpoint that the heat resistance of the obtained cured product is excellent.
These trade names include SA-102 (diazabicycloundecene-based curing accelerator), SA-506 (diazabicycloundecene-based curing accelerator), and U-CAT5003 (phosphonium salt-based curing accelerator). San Apro Co.].
The compounding amount of the curing accelerator (component C) may be set in the range of 0.5 to 10 parts by weight based on 100 parts by weight of the total of the epoxy resin composition (component A) composed of the two types of epoxy compounds. preferable. That is, when the amount of the component C is less than 0.5% by weight, the curing reaction is slowed down, causing a problem in workability. When the amount is more than 10 parts by weight, the reaction time becomes remarkably fast, and the fluidity is reduced. Also, it is possible that the volume resistivity may be reduced electrically.
[0014]
Examples of the inorganic filler which is the component (D) used as an essential component together with the components A to C include silica, alumina, talc, silica sand, calcium carbonate, barium sulfate, and the like. These may be used alone or in combination of two or more. Among them, from the viewpoint of excellent tan δ and withstand voltage characteristics, it is preferable to use spherical fused silica powder among silica and fused alumina among alumina. That is, among the silicas, the use of spherical fused silica powder suppresses interfacial polarization and eliminates the concentration of electrical stress, thereby further improving the dielectric loss tangent (tan δ) and withstand voltage characteristics. Is obtained. In particular, when the above-mentioned spherical fused silica is used, particles having a particle size of 50 μm or less are used in an amount of 99% by weight or more [Requirement (X)] and an average particle size of 35 μm or less [Requirement (Y)]. This is preferable because a decrease in casting workability due to an increase in viscosity is effectively prevented, and a cast epoxy resin composition excellent in both electrical properties and mechanical strength is obtained. Fused alumina is generally obtained by a series of steps such as Bayer method alumina or bauxite dissolved in an electric furnace as a main raw material, and is subjected to precipitation, firing, pulverization, deironing, washing, and drying. By using, as in the case of using the above-mentioned fused silica, both electrical and mechanical properties are excellent, and in particular, the withstand voltage characteristic is significantly improved compared to the case of using fused alumina. Can be
The compounding amount of the inorganic filler (D) may be set so as to be in the range of 30 to 80% by weight in the total of the components (A) to (D) of the cast epoxy resin composition for electric insulation of the present invention. Required. That is, when the blending amount of the inorganic filler (D) is less than 30% of the whole composition, the melt viscosity of the castable epoxy resin composition for electric insulation of the present invention is significantly reduced, and the sedimentation of the inorganic filler (D) is reduced. appear. Also, the mechanical strength decreases. Conversely, if it exceeds 80%, the viscosity becomes too high and the mixability and the fluidity are reduced, so that the workability may be reduced.
[0015]
The cast epoxy resin composition for electrical insulation according to the present invention may further comprise a diluent, a plasticizer, a pigment, a mold release, if necessary, in addition to the inorganic fillers as the components A to C and the component (D). Other additives such as an agent and a flame retardant can be appropriately compounded.
Then, in order to prepare the cast epoxy resin composition for electrical insulation of the present invention, the above-mentioned respective raw materials are blended at a predetermined ratio. Known ingredients such as a drive blender, a ribbon blender, and a Henschel mixer can be used for the compounding, and the compounding is usually performed at room temperature.
The compound of each of the above components is prepared as a cast resin composition for electrical insulation by stirring and mixing while eliminating bubbles under vacuum heating. The temperature at the time of stirring and mixing is usually set to 40 to 100 ° C.
If the temperature set at the time of preparation is less than 40 ° C, the viscosity is too high to make uniform stirring and mixing work difficult. On the other hand, if the temperature at the time of preparation exceeds 100 ° C, a curing reaction occurs and normal electrical insulation It is not preferable because a cast resin composition cannot be obtained. At the time of stirring and mixing, a single-shaft or multi-shaft extruder equipped with a decompression device or a general-purpose kneader can be used.
[0016]
Then, the prepared epoxy resin composition for electric insulation prepared is poured into a predetermined mold, and is heat-cured under predetermined conditions to be molded into a cured product of the present invention having a desired shape.
The cast epoxy resin composition for electrical insulation of the present invention has a temperature of 100 to 200 ° C, preferably 100 to 190 ° C, more preferably 100 to 180 ° C, and a curing time of 30 to 600 minutes, preferably 45 to 600 ° C. The curing can be performed in 540 minutes, more preferably 60 to 480 minutes.
When the curing temperature and the curing time are lower than the lower limit of the above range, the curing becomes insufficient. On the contrary, when the curing temperature and the curing time are higher than the upper limit of the above range, the decomposition of the resin component may occur. The curing conditions depend on various conditions, but when the curing temperature is high, the curing time is short, and when the curing temperature is low, the curing time is long, and can be appropriately adjusted.
[0017]
【Example】
Next, examples will be described together with comparative examples.
<Synthesis example 1>
A cycloaliphatic diolefin compound, bicyclohexyl-3,3'-diene (406 g) and ethyl acetate (1217 g) were charged, and nitrogen was blown into the gas phase so that the temperature in the reaction system became 37.5 ° C. While controlling, 457 g of a 30% by weight peracetic acid ethyl acetate solution (water content: 0.41% by weight) was added dropwise over about 3 hours. After completion of the dropwise addition of the peracetic acid solution, the mixture was aged at 40 ° C. for 1 hour to complete the reaction. The crude liquid at the end of the reaction was further washed with water at 30 ° C., and low-boiling compounds were removed at 70 ° C./20 mmHg to obtain 415 g of an epoxy compound. At this time, the yield was 85%.
The oxirane oxygen concentration of the obtained epoxy compound was 14.7% by weight (theoretical value: 16.5% by weight).
In 1 HNMR measurement, a peak derived from an internal double bond in the vicinity of δ 4.5 to 5 ppm disappeared, and a peak of a proton derived from an epoxy group was observed in the vicinity of δ 2.9 to 3.1 ppm. It was confirmed that it was the alicyclic epoxy compound (a-1) represented by the said General formula (1) corresponding to the alicyclic diolefin compound which is.
[0018]
First, the following epoxy compounds or epoxy resins (a-1) and (a-2), acid anhydrides 1-2, curing accelerators 1-2, and inorganic fillers 1-2 were prepared.
The epoxy compound of Synthesis Example 1 was used as the epoxy compound (a-1), and the following epoxy resins 2 to 4 were used as the epoxy compound (a-2).
Epoxy resin 2: CEL-2021P (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, manufactured by Daicel Chemical Industries)
Epoxy resin 3: YD-128 (manufactured by Toto Kasei, bisphenol A type epoxy resin, epoxy equivalent 190, viscosity 13600 mPa · s / 25 ° C.)
Epoxy resin 4: HBE-100 (manufactured by Shin Nippon Rika, hydrogenated bisphenol A diglycidyl ether type epoxy resin, epoxy equivalent 210, viscosity 2210 mPa · s / 25 ° C.)
[Acid Anhydride 1] Methylhexahydrophthalic anhydride represented by the following structural formula (trade name: RICIDID MH-700: manufactured by Shin Nippon Rika Co., Ltd.)
[Acid Anhydride 2] An acid anhydride represented by the following structural formula (trade name: HNA: manufactured by Shin Nippon Rika Co., Ltd.)
[Curing accelerator 1] Ethylene glycol [Curing accelerator 2] DBU (diazabicycloundecene)
[Inorganic filler 1] Spherical fused silica (99% by weight or more of particles having an average particle size of 50 μm or less)
[Inorganic filler 2] Fused alumina (particles having an average particle size of 50 μm or less are 99% by weight or more of the whole)
[0019]
(Examples 1 to 8, Comparative Examples 1 to 4)
The components shown in Tables 1 and 2 below were blended in the proportions shown in the same table, and at a temperature of about 25 ° C. under reduced pressure (3 to 5 Torr), “THINKY, Awatori Neritaro AR-100” was obtained. The resulting mixture was stirred and mixed to obtain an insulating cast epoxy resin composition. Then, the above-mentioned insulating cast epoxy resin composition was molded and cured by a casting method to produce a molded article having a predetermined shape. In addition, in Table 1 and Table 2, the compounding amount of each component represents all parts by weight.
[0020]
[Table 1]
[Table 2]
A cured product obtained by curing the thus obtained castable epoxy resin composition for electrical insulation of the example and the epoxy resin composition of the comparative example under predetermined conditions (140 ° C. × 2 hours + 170 ° C. × 10 hours) The electrical properties (dielectric loss tangent, dielectric constant), mechanical properties (flexural strength), and glass transition temperature (Tg) of were measured under the following test conditions. The results are shown in Tables 3 and 4. In each of the tests described below, an average value of five samples was obtained.
[0023]
[Table 3]
[Table 4]
[Dielectric loss tangent and permittivity]
A sample having a thickness of 1 mm and a diameter of 60 mm was prepared in which a main electrode and a guard electrode around the main electrode were formed on one side and a counter electrode was formed on the other side using a conductive paint. Then, the sample was heated to 100 ° C. in a constant temperature bath, and the capacitance and conductance (measuring frequency: 50 Hz) were measured by the transformer bridge method. From these results, the dielectric loss tangent (tan δ) and the dielectric constant (ε) were determined as It calculated by the formula of.
Dielectric tangent (tan δ) = Gx / 2π · f · Cx
Dielectric constant (ε) = Cx / Co
Cx: capacitance value (pF) when the bridge is balanced
Co: Capacitance (pF) of ε = 1 calculated from the area of the main electrode and the thickness of the sample
Gx: Conductance value of sample (S)
f: Measurement frequency (Hz)
(Bending strength)
A sample having a width of 10 mm, a length of 100 mm, and a thickness of 4 mm was prepared, a load was applied to the center by a pressure wedge with both ends supported at a distance of 64 mm, and the maximum load when bending and breaking was determined.
[Tg (glass transition temperature: ° C)]
A sample having a size of 5 × 5 × 10 mm is prepared, and a dimensional change when the temperature is increased at 5 ° C./min by a thermal expansion measurement method (by a thermomechanical analyzer TMA / SS6100 manufactured by Seiko Instruments Inc.) is measured and plotted. Then, the glass transition temperature (Tg) was determined from the displacement point of the coefficient of thermal expansion.
[0026]
【The invention's effect】
From the results in Tables 3 and 4, the cured product obtained by curing the cast epoxy resin composition for electrical insulation of the present invention has excellent properties such as high flexural strength and Tg and low dielectric constant. It is clear that.
Claims (7)
（Ａ）エポキシ樹脂組成物
下記の一般式（１）で表される脂環式ジエポキシ化合物（ａ−１）を５〜８０重量％
一般式（１）で表される脂環式ジエポキシ化合物（ａ−１）以外のエポキシ化合物（ａ−２）９５〜２０重量％［脂環式ジエポキシ化合物（ａ−１）とエポキシ化合物（ａ−２）の合計は１００重量％］
（Ｂ）酸無水物
（Ｃ）硬化促進剤
からなり、さらに
（Ｄ）無機質充填材
を含み、上記（Ｂ）成分の配合割合が、（Ａ）成分１当量に対して０．６〜１．０当量の範囲に、（Ｃ）成分が（Ａ）及び（Ｂ）の合計量１００重量部に対して０．５〜１０重量部、（Ｄ）成分が（Ａ）〜（Ｄ）成分の合計量中３０〜８０重量％からなることを特徴とする電気絶縁用注型エポキシ樹脂組成物。A cast epoxy resin composition for electrical insulation, comprising a thermosetting resin and an inorganic filler, wherein the thermosetting resin comprises the following components (A) to (C) (A): 5 to 80% by weight of the alicyclic diepoxy compound (a-1) represented by the general formula (1)
95 to 20% by weight of an epoxy compound (a-2) other than the alicyclic diepoxy compound (a-1) represented by the general formula (1) [the alicyclic diepoxy compound (a-1) and the epoxy compound (a- The sum of 2) is 100% by weight]
It comprises (B) an acid anhydride, (C) a curing accelerator, and further contains (D) an inorganic filler, and the compounding ratio of the component (B) is 0.6 to 1. In the range of 0 equivalents, the component (C) is 0.5 to 10 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B), and the component (D) is the total of the components (A) to (D). A cast epoxy resin composition for electrical insulation, comprising 30 to 80% by weight of the composition.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003139484A JP4322047B2 (en) | 2003-05-16 | 2003-05-16 | Cast epoxy resin composition for electrical insulation and cured product |
| EP03808875A EP1541567A4 (en) | 2002-09-05 | 2003-09-04 | Process for preparation of alicyclic diepoxy compounds, curable epoxy resin compositions, epoxy resin compositions for the encapsulation of electronic components, stabilizers for electrical insulating oils, and casting epoxy resin compositions for electrical insulation |
| US10/526,672 US20060009547A1 (en) | 2002-09-05 | 2003-09-04 | Process for preparation of alicyclic diepoxy compound, curable epoxy resin compositions, epoxy resin compositions for the encapsulation of electronic components, stabilizers for electrical insulating oils, and casting epoxy resin compositions for electrical insulation |
| EP12007091.7A EP2546275B1 (en) | 2002-09-05 | 2003-09-04 | Curable epoxy resin compositions, epoxy resin compositions for the encapsulation of electronic parts, stabilizers for electrical insulating oils, and casting epoxy resin compositions for electrical insulation. |
| KR1020057003792A KR101005948B1 (en) | 2002-09-05 | 2003-09-04 | Process for preparation of alicyclic diepoxy compounds, curable epoxy resin compositions, epoxy resin compositions for the encapsulation of electronic components, stabilizers for electrical insulating oils, and casting epoxy resin compositions for electrical insulation |
| PCT/JP2003/011287 WO2004035558A1 (en) | 2002-09-05 | 2003-09-04 | Process for preparation of alicyclic diepoxy compounds, curable epoxy resin compositions, epoxy resin compositions for the encapsulation of electronic components, stabilizers for electrical insulating oils, and casting epoxy resin compositions for electrical insulation |
| TW092124412A TWI312800B (en) | 2002-09-05 | 2003-09-04 | Process for the preparation of an alicyclic diepoxy compound, a curable epoxy resin composition, an epoxy resin composition for encapsulating electronics parts, a stabilizer for electrically insulating oils, and an epoxy resin composition for casting |
| CN 200710006254 CN101070373B (en) | 2002-09-05 | 2003-09-04 | Epoxy resin compositions, epoxy resin compositions for the encapsulation of electronic components, stabilizers for electrical insulating |
| US12/314,222 US7781543B2 (en) | 2002-09-05 | 2008-12-05 | Curable alicyclic diepoxy resin composition |
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| JP2003139484A JP4322047B2 (en) | 2003-05-16 | 2003-05-16 | Cast epoxy resin composition for electrical insulation and cured product |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012136577A (en) * | 2010-12-24 | 2012-07-19 | Nippon Zeon Co Ltd | Semiconductor-sealing material and semiconductor device |
| WO2014083844A1 (en) * | 2012-11-28 | 2014-06-05 | 日本化薬株式会社 | Resin composition, and cured product (2) thereof |
| JP2016130312A (en) * | 2015-01-14 | 2016-07-21 | ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツングＲｏｂｅｒｔ Ｂｏｓｃｈ Ｇｍｂｈ | Reactive resin having high thermal conductivity |
| JP2021174797A (en) * | 2020-04-20 | 2021-11-01 | 株式会社村田製作所 | Coil component and manufacturing method thereof |
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| US8482213B1 (en) | 2009-06-29 | 2013-07-09 | Panasonic Corporation | Electronic ballast with pulse detection circuit for lamp end of life and output short protection |
| US8947020B1 (en) | 2011-11-17 | 2015-02-03 | Universal Lighting Technologies, Inc. | End of life control for parallel lamp ballast |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012136577A (en) * | 2010-12-24 | 2012-07-19 | Nippon Zeon Co Ltd | Semiconductor-sealing material and semiconductor device |
| WO2014083844A1 (en) * | 2012-11-28 | 2014-06-05 | 日本化薬株式会社 | Resin composition, and cured product (2) thereof |
| JP2016130312A (en) * | 2015-01-14 | 2016-07-21 | ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツングＲｏｂｅｒｔ Ｂｏｓｃｈ Ｇｍｂｈ | Reactive resin having high thermal conductivity |
| JP2021174797A (en) * | 2020-04-20 | 2021-11-01 | 株式会社村田製作所 | Coil component and manufacturing method thereof |
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