JP4013118B2 - Epoxy resin composition, resin composition for electronic material, resin for electronic material, coating agent, and method for producing coating agent cured film - Google Patents

Description

【００１８】
本発明で用いるメトキシ基含有シラン変性エポキシ樹脂（Ａ）は、前記ビスフェノール型エポキシ樹脂（１）と、メトキシシラン部分縮合物（２）との脱アルコール反応により得られる。ビスフェノール型エポキシ樹脂（１）とメトキシシラン部分縮合物（２）の使用割合は、得られるメトキシ基含有シラン変性エポキシ樹脂（Ａ）中に、メトキシ基が残存するような割合であれば特に制限されないが、メトキシシラン部分縮合物（２）のシリカ換算重量／ビスフェノール型エポキシ樹脂（１）の重量（重量比）が０．２５〜１．２の範囲であるのが好ましい。ここでメトキシシラン部分縮合物（２）のシリカ換算重量とは、メトキシシラン部分縮合物（２）がゾル−ゲル反応し、シリカに硬化した時の重量である。
【００１９】
かかるメトキシ基含有シラン変性エポキシ樹脂（Ａ）の製造は、例えば、ビスフェノール型エポキシ樹脂（１）とメトキシシラン部分縮合物（２）を仕込み、加熱して副生するアルコールを留去または冷却管で還流させて系内に戻すことにより行なわれる。反応温度は５０〜１３０℃程度、好ましくは７０〜１１０℃であり、全反応時間は１〜１５時間程度である。この反応は、メトキシシラン部分縮合物（２）自体の重縮合反応を防止するため、実質的に無水条件下で行うのが好ましい。
【００２０】
また、上記の脱アルコール反応に際しては、反応促進のために従来公知の触媒の内、エポキシ環を開環しないものを使用することができる。該触媒としては、たとえば、リチウム、ナトリウム、カリウム、ルビジウム、セシウム、マグネシウム、カルシウム、バリウム、ストロンチウム、亜鉛、アルミニウム、チタン、コバルト、ゲルマニウム、錫、鉛、アンチモン、砒素、セリウム、硼素、カドミウム、マンガンのような金属；これら金属の酸化物、有機酸塩、ハロゲン化物、メトキシド等があげられる。これらの中でも、特に有機錫、有機酸錫が好ましく、具体的には、ジブチル錫ジラウレート、オクチル酸錫等が有効である。
【００２１】
また、上記反応は溶剤中でも、無溶剤でも行うこともできる。溶剤としては、ビスフェノール型エポキシ樹脂（１）およびメトキシシラン部分縮合物（２）を溶解し、且つこれらに対し非活性である有機溶剤であれば特に制限はない。このような有機溶剤としては、例えば、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、イソホロン等のケトン系、酢酸エチル、酢酸ブチル等のエステル系、トルエン、キシレン等の芳香族系、セロソルブアセテート、メチルセロソルブアセテート等のセロソルブ系、テトラヒドロフラン、ジエチレングリコールジメチルエーテル等のエーテル系、イソプロピルアルコール、ｎ−ブチルアルコール等のアルコール類、ジメチルホルムアミドなどの非プロトン性極性溶媒があげられる。これらの中でも、メチルエチルケトンなどの常圧での沸点が７０〜１１０℃のものが以下の理由により特に好ましい。沸点が１１０℃を超える溶剤を使用した場合には、溶剤残存率を低下させるために半硬化状態（Ｂステージ）とする温度を過度に上昇させる必要が生じる。また使用溶剤の沸点が７０℃未満である場合は、ビスフェノール型エポキシ樹脂（１）とメトキシシラン部分縮合物（２）との脱アルコール反応に長時間を要するため好ましくない。
【００２２】
こうして得られたメトキシ基含有シラン変性エポキシ樹脂（Ａ）は、ビスフェノール型エポキシ樹脂（１）中の水酸基がシラン変性されてなるエポキシ樹脂を主成分とするが、当該メトキシ基含有シラン変性エポキシ樹脂（Ａ）中には未反応のビスフェノール型エポキシ樹脂（１）や未反応のメトキシシラン部分縮合物（２）が含有されていてもよい。
【００２３】
メトキシ基含有シラン変性エポキシ樹脂（Ａ）は、その分子中にメトキシシラン部分縮合物（２）に由来するメトキシシリル部位とビスフェノール型エポキシ樹脂に由来するエポキシ基を有している。このメトキシシリル部位は、溶剤の蒸発や加熱処理により、又は水分（湿気）との反応により、相互に結合した硬化物を形成する。かかる硬化物は、ゲル化した微細なシリカ部位（シロキサン結合の高次網目構造）を有するものである。従って、メトキシ基含有シラン変性エポキシ樹脂（Ａ）中に含まれるメトキシ基は、用いたメトキシシラン部分縮合物（２）のメトキシル基の６０モル％以上を保持しているのが好ましい。またエポキシ基はエポキシ樹脂硬化剤（Ｃ）と反応するものである。
【００２４】
本発明のエポキシ樹脂組成物では分子末端をエポキシ変性して得られるブタジエンニトリルゴム（Ｂ）（以下、単にエポキシ基含有ゴム（Ｂ）ということがある。）を必須成分とする。これを用いることにより、メトキシ基含有シラン変性エポキシ樹脂由来のエポキシ樹脂―シリカハイブリッド相とゴム相を硬化物中で、微細に相分離させる事ができ、室温で液状のエポキシ基含有ゴム（Ｂ）由来の相は、硬化物を柔軟にするため、ゾル−ゲル硬化過程において生成するメタノールが速やかに揮発し、そのため、ゾル−ゲル硬化がさらに進み、後の硬化過程において揮発分の発生源となりうるメトキシ基の大部分が硬化反応に関与し消失するため、硬化時（Ｃステージ）の揮発分の発生を減少させることができるためである。また、ミクロ相分離したゴム相は、氷点下にガラス転移点を持つため、硬化物の室温以上の弾性率変化はエポキシ樹脂−シリカハイブリッド相によって支配され、高耐熱性を保持でき、さらに、ミクロ相分離したゴム相の存在により硬化物の弾性率が下がり、硬化物が強靭となる。
【００２５】
本発明に用いるエポキシ基含有合成ゴム（Ｂ）とは、末端にカルボキシル基を有する合成ゴムと、ジエポキシ化合物を反応させることにより得られるものである。なお、カルボキシル基が分子鎖内にある場合には、上記相分離構造が得られず、エポキシ樹脂−シリカハイブリッド相はゴム相の影響を受け、ガラス転移点が低下し、耐熱性が大きく失われる場合があるため分子末端にカルボキシル基を有するものの方が好ましい。末端にカルボキシル基を有する合成ゴムとしては、特に制限されず、公知のもの、例えば、末端にカルボキシル基を有するブタジエンゴム、末端にカルボキシル基を有するブタジエンニトリルゴムなどがあげられるが、エポキシ樹脂との反応性の点から末端にカルボキシル基を有するブタジエンニトリルゴムが好ましい。末端にカルボキシル基を有するブタジエンニトリルゴムとしては、市販のものを用いることができ、例えば、ＨＹＣＡＲ ＣＴＢＮ１３００×８、ＨＹＣＡＲ ＣＴＢＮ１３００×１３、ＨＹＣＡＲ ＣＴＢＮ１３００×３１（いずれも商品名 宇部興産（株）製）といったものがあげられる。末端にカルボキシル基を有する合成ゴムの数平均分子量は、２０００〜５０００程度のものを用いるのが好ましい。数平均分子量を２０００以上とすることにより上記のミクロ相分離構造が生じるため、エポキシ樹脂−シリカハイブリッド相の耐熱性を維持でき、また、数平均分子量を５０００以下とすることにより、メトキシ基含有シラン変性エポキシ樹脂と混和が容易になり、安定な樹脂組成物が調整できる。
【００２６】
なお、末端にカルボキシル基を有するブタジエンニトリルゴムの場合、結合アクリロニトリル含量は、通常、３〜３０％であり、好ましくは５〜２０％である。結合アクリロニトリル含量を３％以上とすることにより、エポキシ基含有合成ゴム（Ｂ）とメトキシ基含有シラン変性エポキシ樹脂（Ａ）が溶解し、エポキシ樹脂組成物が均一になり、硬化物の透明性が良好となるため好ましい。一方、結合アクリロニトリル含量を３０％以下とすることにより、エポキシ基含有合成ゴム（Ｂ）はミクロ相分離構造を形成し、エポキシ樹脂−シリカハイブリッド相のガラス転移点がゴム相の影響を受けず、高耐熱性が維持される。
【００２７】
ジエポキシ化合物は、ビスフェノール類とエピクロルヒドリンまたはβ−メチルエピクロルヒドリン等のハロエポキシドとを反応させることにより得られる。当該ジエポキシ化合物は、ビスフェノール繰り返し単位を通常１〜５程度含有するものであり、好ましくは１〜３である。繰り返し単位を５以下とすることで、カルボキシ基を有する合成ゴムとの相溶性が向上するため、反応が進行しやすくなるため好ましい。
【００２８】
末端にカルボキシル基を有する合成ゴムとジエポキシ化合物の反応は、通常公知の方法を採用することができ、通常、１００〜２００℃程度で１〜５時間反応することで得られる。また当該反応は、例えば、アミン触媒存在下に６０〜１５０℃程度で反応させる方法を採用することもできる。アミン触媒としては、特に制限されず公知のものを使用でき、例えば、トリエチルアミン、トリメチルアミン等の３級アミンやジエチルアミンやピペリジン等の２級アミン、アンモニアやエチルアミン等の１級アミン等をあげることができる。このようにして得られた当該エポキシ基含有合成ゴム（Ｂ）は、通常、数平均分子量が２０００〜１００００程度であり、ガラス転移点が好ましくは−３０℃以下である。何故ならば、硬化物中のゴム相のガラス転移点が−３０℃を超えると、室温付近（１０〜３０℃）にまで弾性率の変化が続く場合があり、物性に悪影響を及ぼす場合がある。当該エポキシ基含有合成ゴム（Ｂ）は、分子末端にビスフェノール構造を有するため、メトキシ基含有シラン変性エポキシ樹脂（Ａ）と親和性を有するため、混合して樹脂組成物を調製できる。エポキシ基含有合成ゴム（Ｂ）の配合割合は、メトキシ基含有シラン変性エポキシ樹脂（Ａ）の硬化残分１００重量部に対して３０〜１５０重量部である。当該配合割合が３０重量部未満であれば、発明の効果が不充分となり、また１５０重量部を超えると硬化物が柔らかくなりすぎ、逆に強靭性が失われる場合がある。なお、メトキシ基含有シラン変性エポキシ樹脂（Ａ）の硬化残分は次のようにして求められる。すなわち、メトキシ基含有シラン変性エポキシ樹脂（Ａ）と当量のトリエチレンテトラミンを混合し、当該混合液をアルミカップ（５０ｍｍ径）に約１ｇを秤り取り（計量）、これを１００℃で１時間、続いて２００℃で２時間乾燥、硬化させて再計量（計量）し、下式から算出する。
【００２９】
硬化残分（％）＝（計量▲２▼−トリエチレンテトラミン重量）×１００／計量▲１▼
【００３０】
本発明に用いるエポキシ樹脂用硬化剤（Ｃ）は、フェノール樹脂系硬化剤、ポリアミン系硬化剤およびポリカルボン酸系硬化剤から選ばれる。具体的には、フェノール樹脂系硬化剤としては、フェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノールノボラック樹脂、ポリｐ−ビニルフェノール等があげられ、ポリアミン系硬化剤としてはジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ジシアンジアミド、ポリアミドアミン（ポリアミド樹脂）、ケチミン化合物、イソホロンジアミン、ｍ−キシレンジアミン、ｍ−フェニレンジアミン、１，３−ビス（アミノメチル）シクロヘキサン、Ｎ-アミノエチルピペラジン、４，４′−ジアミノジフェニルメタン、４,４′−ジアミノ−３，３′−ジエチルジフェニルメタン、ジアミノジフェニルスルフォン等があげられ、ポリカルボン酸系硬化剤としては、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、３，６−エンドメチレンテトラヒドロ無水フタル酸、ヘキサクロルエンドメチレンテトラヒドロ無水フタル酸、メチル−３，６−エンドメチレンテトラヒドロ無水フタル酸があげられる。
【００３１】
本発明のエポキシ樹脂組成物は、通常、Ｂステージを経て、完全硬化物状態（Ｃステージ）とする。そのため、Ｃステージでの揮発分発生を防ぐためには、Ｂステージにおいて、エポキシ樹脂組成物に含まれる揮発分（メトキシ基含有シラン変性エポキシ樹脂（Ａ）中の製造用溶剤、当該樹脂（Ａ）のメトキシシリル部位のゾル−ゲル硬化反応により副生するメタノール、溶剤）の残存率を低減させる必要がある。しかしながら、当該Ｂステージでは、引き続いて得られるＣステージ層の導体に対する層間密着性も考慮する必要がある。すなわち、Ｂステージの半硬化物層が導体と密着させる温度で十分な表面タックを発現しうるよう、エポキシ基を残存させておく必要があり、そのためＢステージにおいては当該樹脂（Ａ）のエポキシ基との硬化が進行しない潜在性硬化剤を用いるのが好ましい。このような潜在性硬化剤としては、フェノール樹脂系硬化剤が最適である。
【００３２】
上記のＢステージやＣステージでの設計観点から、エポキシ樹脂用硬化剤（Ｃ）の配合割合は、メトキシ基含有シラン変性エポキシ樹脂（Ａ）及びエポキシ基含有合成ゴム（Ｂ）に由来するエポキシ基１当量に対してエポキシ樹脂用硬化剤（Ｃ）中の活性水素を有する官能基が０．５〜１．２当量の範囲である。
【００３３】
前記のように、Ｃステージにおける気泡発生を避けるため、Ｂステージでの揮発分残存率の調整が重要となり、本発明の組成物においてゾル−ゲル硬化促進剤（Ｄ）を使用することが好ましい。ゾル−ゲル硬化促進剤（Ｄ）としては、例えばリチウム、ナトリウム、カリウム、ルビジウム、セシウム、マグネシウム、カルシウム、バリウム、ストロンチウム、亜鉛、アルミニウム、チタン、コバルト、ゲルマニウム、錫、鉛、アンチモン、砒素、セリウム、硼素、カドミウム、マンガンのような金属；これら金属の酸化物、有機酸塩、ハロゲン化物、メトキシド等があげられる。これらの中でも、特に有機錫、有機酸錫が好ましく、具体的には、ジブチル錫ジラウレート、オクチル酸錫等が有効である。当該ゾル−ゲル硬化促進剤（Ｄ）の使用量は、エポキシ樹脂組成物の硬化残分に対して０．１〜５．０重量％であるのが好ましい。０．１％未満であれば、Ｂステージでのゾル−ゲル硬化反応が完了せず、５％を超えるとエポキシ樹脂組成物に増粘が見られ、安定性が低下する傾向がある。
【００３４】
本発明のエポキシ樹脂組成物には必要に応じて溶剤を用いることができる。本発明のエポキシ樹脂組成物に用いる溶剤としては、例えばメチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、イソホロン等のケトン系、酢酸エチル、酢酸ブチル等のエステル系、トルエン、キシレン等の芳香族系、セロソルブアセテート、メチルセロソルブアセテート等のセロソルブ系、テトラヒドロフラン、ジエチレングリコールジメチルエーテル等のエーテル系、イソプロピルアルコール、ｎ−ブチルアルコール等のアルコール類、ジメチルホルムアミドなどの非プロトン性極性溶媒があげられる。メトキシ基含有シラン変性エポキシ樹脂（Ａ）の製造用溶剤を選定するのと同じ理由で、メチルエチルケトンが最も好ましい。溶剤の配合割合は特に限定されず、用途に応じて適宜決定すればよい。
【００３５】
本発明のエポキシ樹脂組成物は、上記の各種必須構成成分、すなわちメトキシ基含有シラン変性エポキシ樹脂（Ａ）、エポキシ基含有合成ゴム（Ｂ）およびエポキシ樹脂用硬化剤（Ｃ）を必須成分とし、必要に応じてゾル−ゲル硬化促進剤（Ｄ）ならびに溶剤を配合して調製される。
【００３６】
エポキシ樹脂組成物の組成は、その用途に応じて適宜に調整できるが、通常は、当該エポキシ樹脂組成物を硬化して得られる硬化物中のシリカ換算重量が３〜４０重量％になるよう配合するのが好ましい。ここでシリカ換算重量とは、エポキシ樹脂組成物中に含まれるメトキシ基含有シラン変性エポキシ樹脂（Ａ）に用いたメトキシシラン部分縮合物（２）をゾル−ゲル硬化反応せしめて得られるシリカの重量をいう。
【００３７】
また、前記エポキシ樹脂組成物には、エポキシ樹脂と硬化剤との硬化反応を促進するための硬化促進剤（前記ゾル−ゲル硬化促進剤（Ｄ）とは異なる）を含有させることができる。例えば、１，８−ジアザ−ビシクロ［５．４．０］ウンデセン−７、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス（ジメチルアミノメチル）フェノールなどの三級アミン類；２−メチルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール、２−ヘプタデシルイミダゾールなどのイミダゾール類；トリブチルホスフィン、メチルジフェニルホスフィン、トリフェニルホスフィン、ジフェニルホスフィン、フェニルホスフィンなどの有機ホスフィン類；テトラフェニルホスホニウム・テトラフェニルボレート、２−エチル−４−メチルイミダゾール・テトラフェニルボレート、Ｎ−メチルモルホリン・テトラフェニルボレートなどのテトラフェニルボロン塩などをあげることができる。当該硬化促進剤はエポキシ樹脂の１００重量部に対し、０．１〜５重量部の割合で使用するのが好ましい。
【００３８】
本発明のエポキシ樹脂組成物には、本発明の効果を損なわない範囲で、必要に応じて、充填剤、離型剤、表面処理剤、難燃剤、粘度調節剤、可塑剤、抗菌剤、防黴剤、レベリング剤、消泡剤、着色剤、安定剤、カップリング剤等を配合してもよい。
【００３９】
本発明のエポキシ樹脂組成物から直接、硬化物を得るには、上記エポキシ樹脂組成物を室温〜２５０℃で硬化させる。硬化温度は、エポキシ樹脂用硬化剤（Ｃ）によって適宜決定される。当該硬化剤（Ｃ）として、フェノール樹脂系硬化剤やポリカルボン酸系硬化剤を用いる場合には、当該硬化剤（Ｃ）以外にゾル−ゲル硬化触媒を０．１％以上併用して、１５０〜２５０℃で硬化させるのが好ましい。ポリアミン系硬化剤を用いると室温〜１００℃の低温硬化が可能であるが、オクチル酸錫など活性の高いゾル−ゲル硬化触媒を０．３％以上併用して硬化させるのが好ましい。なぜなら、メトキシシリル部位のゾル−ゲル硬化反応ではアルコールが発生するため、メトキシ基含有シラン変性エポキシ樹脂（Ａ）中のエポキシ基とエポキシ樹脂用硬化剤（Ｃ）とのエポキシ基の開環・架橋反応による硬化が進行した後に、当該アルコールが発生した場合には、発泡やクラックを生じる。そのため、触媒を適宜に選択することによってゾル−ゲル硬化反応速度を調整する必要がある。
【００４０】
本発明のエポキシ樹脂組成物からＢステージ、即ち半硬化物を経て硬化物を得るには、上記エポキシ樹脂組成物のエポキシ硬化剤（Ｃ）として、フェノール樹脂系硬化剤、ポリカルボン酸系硬化剤、イミダゾール類等の潜在性硬化剤を用い、錫系のゾル−ゲル硬化触媒を配合することが好ましい。エポキシ樹脂組成物を用いて半硬化物を作製するには、好ましくは４０〜１５０℃程度で加熱することにより、溶剤を蒸発させ、エポキシ樹脂組成物中にゾル−ゲル硬化によるシロキサン結合を７０％以上、好ましくは９０％以上、生成させるようゾル−ゲル硬化反応を進行させる。
【００４１】
更にこのような半硬化物は、熱成形や熱圧着の後、通常１６０℃以上２５０℃以下の温度で完全硬化させて、硬化物が得られる。
【００４２】
当該エポキシ樹脂組成物は、電子材料用樹脂組成物、電子材料用樹脂組成物を硬化して得られる電子材料用樹脂、コーティング剤組成物等として使用することができる。
【００４３】
本発明の電子材料用樹脂組成物からプリント基板用プリプレグを得るには、例えば、特開平９−１４３２８６号公報に記載されているように、エポキシ樹脂組成物を補強基材に含浸し、加熱してプリプレグシートを得ることができる。上記エポキシ樹脂組成物の組成や作製条件については、上記の半硬化物を経る硬化方法に従い硬化させればよい。なお、ワニスの溶剤としては、例えばメチルエチルケトン、アセトン、エチルセロソルブ、ジメチルホルムアミド、メタノール、エタノール、イソプロピルアルコールなどの沸点が１６０℃以下の極性溶剤があげられ、これらはプレプリグ中に残存しないため好ましい。加熱温度は、用いる溶剤の種類を考慮して決定され、好ましくは４０〜１５０℃とされる。尚、補強基材の種類は特に限定はされず、例えば紙、ガラス布、ガラス不織布、アラミド紙、アラミド布、ガラスマット、ガラスロービング布、液晶ポリマーなどの各種を例示できる。また、樹脂分と補強基材の割合も特に限定されないが、通常、プリプレグ中の樹脂分が２０〜８０重量％となるように調整するのが好ましい。
【００４４】
本発明の電子材料用樹脂組成物から銅張り積層板を得るには、例えば特開平５−８６２１５号公報や特開平６−１００７６３号公報に記載されているように、上記のプリプレグを３〜８枚程度重ね、さらに上下に銅箔を重ねて、１〜３０ＭＰａの加圧下に、１７０〜２５０℃で１０分〜３時間、加熱圧着させる。
【００４５】
上記プリプレグと銅張り積層板からプリント配線基板やインターポーザーを得るには、銅張り積層板をレジストエッチングして回路を形成させた後、プリプレグおよび銅箔を重ねて上記の銅張り積層板作製時と同じ条件で加熱圧着し、多層化すればよい。
【００４６】
本発明の電子材料用樹脂組成物からビルドアップ基板用層間絶縁材料を得る方法としては特に限定されないが、例えば特公平４−６１１６号、特開平７−３０４９３１号、特開平８−６４９６０号、特開平９−７１７６２号、特開平９−２９８３６９号公報などに記載の各種方法を採用できる。より具体的には、フィラーなどを適宜含有した当該電子材料用樹脂組成物を、回路を形成した配線基板にスプレーコーティング法、カーテンコーティング法、スクリーン印刷法等の公知の方法で塗布した後、上記のような直接ハイブリッド体を得る方法に従って硬化させる。その後、必要に応じて所定のスルーホール部等の穴あけを行った後、粗化剤により処理し、その表面を湯洗することによって、凹凸を形成させ、銅などの金属をめっき処理する。当該めっき方法としては、無電解めっき、電解めっき処理が好ましく、また上記の粗化剤としては酸化剤、アルカリ及び有機溶剤の中から選ばれた少なくとも１種が用いられる。このような操作を所望に応じて順次繰り返し、樹脂絶縁層及び所定の回路パターンの導体層を交互にビルドアップして形成することができる。但し、スルーホール部の穴あけは、最外層の樹脂絶縁層の形成後に行なう。また、本発明の電子材料用樹脂組成物から得られたＢステージフィルム（半硬化物）を用いてビルドアップ基板用層間絶縁材料を作製することもできる。たとえば、回路を形成した配線基板上で、前記と同様の条件下に当該電子材料用樹脂組成物を半硬化させ、その後、必要に応じて所定のスルーホール部等の穴あけを行った後、粗化剤により粗面化処理を行ない、樹脂絶縁層の表面及びスルーホール部に凹凸状の良好な粗化面を形成させる。次いで、このように粗面化された樹脂絶縁層表面に前記と同様に金属めっきを施した後、再度、当該電子材料用樹脂組成物をコーティングし、１７０〜２５０℃で加熱処理を行う。このような操作を所望に応じて順次繰り返し、樹脂絶縁層及び所定の回路パターンの導体層を交互にビルドアップして形成することもできる。また、銅箔上で当該エポキシ樹脂組成物を半硬化させた樹脂付き銅箔を、回路を形成した配線基板上に、１７０〜２５０℃で加熱圧着することで、粗化面を形成、メッキ処理の工程を省き、ビルドアップ基板を作製することも可能である。
【００４７】
本発明の電子材料用樹脂組成物は電子部品用封止剤として使用することができ、電子部品用封止剤としては、モールド型封止剤、テープ状封止剤、ポッティング型液状封止剤など各種のものが知られている。本発明の電子材料用樹脂組成物から、例えばモールド型封止剤を調製する場合、その方法について特に限定されないが、当該樹脂組成物をゾル−ゲル硬化させた硬化物の粉末を用いる方法が好ましい。例えば、メトキシ基含有シラン変性エポキシ樹脂に錫系のゾル−ゲル硬化触媒を樹脂分当り０．０５〜５％と、必要に応じてシリカなど無機充填剤を配合して本発明のエポキシ樹脂組成物（エポキシ樹脂硬化剤を配合せず）とした後、テフロン（登録商標）シート上で１００〜２００℃にて硬化させ、更に当該ゾル−ゲル硬化物を粉砕機にかけて、粉末化する方法がある。また、当該樹脂組成物を溶剤で希釈し、２５℃で５００ｍＰａ・ｓ以下の粘度になるよう調整した後、スプレーして空気中の湿気と反応させることにより、ゾル−ゲル硬化物の粉末を得ることもできる。当該溶剤としては、前記と同様のものであり、特に沸点が１００℃以下の溶剤が好ましい。この様にして得られたゾル−ゲル硬化物の粉末に、エポキシ樹脂硬化剤としてのノボラックフェノール樹脂、エポキシ樹脂硬化触媒、および無機充填剤を通常８０〜１７０℃の温度で３０〜３００秒間、混練りして、封止剤用組成物を得る。当該封止剤用組成物を金型に封入し、通常１７０〜２５０℃、５〜２０ＭＰａでトランスファー成形する事により、半導体や電子部品を封止する。封止剤の使用は電子部品や半導体を長寿命化する事が目的であるため、低吸水性は最も大切な性能である。本特許のメトキシ基含有シラン変性エポキシ樹脂の製造において、メトキシシラン部分縮合物（２）にメチルトリメトキシシランの部分縮合物を用いると、硬化物が低い吸水率を示し、好適である。
【００４８】
またテープ状封止剤として使用する場合には、必要に応じてシリカなど無機充填剤を配合した本発明のエポキシ樹脂組成物を用いて、前記手順に従って半硬化シートを作製し、封止剤テープとする。この封止剤テープを半導体チップ上に置き、１００〜１５０℃に加熱して軟化させ成形した後、１７０〜２５０℃で完全に硬化させる。
【００４９】
更にポッティング型液状封止剤として使用する場合には、必要に応じてシリカなど無機充填剤を配合した本発明のエポキシ樹脂組成物を半導体チップや電子部品上に塗布し、直接、硬化させればよい。
【００５０】
本発明の電子材料用樹脂組成物をアンダーフィル樹脂として使用する方法についても特に限定されないが、例えば特開平９−２６６２２１号公報や「エレクトロニクス分野のプラスチック」（工業調査会発行、１９９９年、２７〜３４頁）に記載されるような方法を採用できる。より具体的には、フリップチップ実装時に電極のついた半導体素子と半田のついたプリント配線基板との空隙に、本発明のエポキシ樹脂組成物を、毛細管現象を利用してキャピラリーフロー法によって注入し、上記直接ハイブリッド体を得る方法で硬化させる方法と、予め基板無いし半導体素子上に前記手順に従って、半硬化樹脂を形成させてから、加熱して半導体素子と基板を半硬化樹脂で密着させ、完全硬化させるコンプレッションフロー法などによりアンダーフィル樹脂層を形成する。この場合、本発明のエポキシ樹脂組成物を、溶剤を含有しない液状の樹脂組成物の形態で使用するのが好ましい。特にキャピラリーフロー法を用いる場合には、低粘度である必要があり、５０００ｍＰａ・ｓ以下の粘度であることが好ましい。電子材料用樹脂組成物がこれを超える粘度であれば、室温〜１００℃以下に加温して注入することもできる。また、アンダーフィル樹脂の目的は、半導体素子と基板の線膨張性の違いから生じる半田周辺の応力を緩和する事であり、界面ジョイントである半田の線膨張係数に近い、低い線膨張係数を持つ絶縁材料が好ましいとされている。そのため、エポキシ樹脂組成物が低粘度であれば、シリカなどフィラーを添加することによって、線膨張率係数を更に下げることもできる。
【００５１】
本発明の電子材料用樹脂組成物をソルダーレジストなどの熱硬化型レジストインキとして使用する場合には、例えば特開平５−１８６５６７号公報や特開平８−３０７０４１号公報に記載の方法に準じて、レジストインキ用組成物とした後、スクリーン印刷方式で、プリント基板上に塗布した後、直接ハイブリッド硬化物を得る方法によって、レジストインキ硬化物とする。好適には、レジストインキ用組成物として、当該電子材料用樹脂組成物に、必要に応じてアクリル酸エステルやメタクリル酸エステルなどのエチレン性不飽和二重結合を有するビニル系モノマー、フタロシアニンブルーをはじめとする各種の顔料、シリカ、アルミナ等の充填剤、レベリング剤などを添加する。
【００５２】
本発明の電子材料用樹脂組成物を半導体の層間絶縁材料として使用する場合は、例えば特開平６−８５０９１公報の記載の方法が採用できる。具体的には、半導体上に当該樹脂組成物をスピンコートし、直接ハイブリッド硬化物を得る方法によって得られる。層間絶縁膜に用いる場合は、特に硬化物の線膨張率が低いことが要求されるため、本発明のエポキシ樹脂組成物においては、メトキシ基含有シラン変性エポキシ樹脂（Ａ）の硬化残分中のシリカ重量換算Ｓｉ含有量が３０％以上であることが好ましい。
【００５３】
本発明の電子材料用樹脂組成物を導電ペーストとして使用する場合には、例えば特開平９−３５５３０号公報に記載されるように、真球状やリン片状の銀やニッケルなどの導電粉を絶縁材料に配合しなければならない。導電粉の含有量は、導電ペーストに対して導電性と経済性の観点から、５０〜８０重量％であることが好ましい。この含有率が５０重量％未満であると抵抗値が高くなる傾向にあり、８０重量％を超えると接着性が低下したり製品の価格が上昇するなどの不利がある。導電ペーストは高温や高湿等の過酷な条件にさらされた後に比抵抗変化が小さいことが求められる。吸水率を低減させる観点から、本発明のエポキシ樹脂組成物におけるメトキシ基含有シラン変性エポキシ樹脂（Ａ）の成分であるメトキシシラン部分縮合物（２）として、メチルトリメトキシシランの部分縮合物を用いること、更にはエポキシ樹脂硬化剤としてノボラックフェノール樹脂を用いることが特に好ましい。
【００５４】
本発明の電子材料用樹脂組成物からＩＣトレイなどの電子部品を収納するための容器（成形物）を製造する場合には、前記方法で得られた半硬化シートや成形用中間材料を得た後、これらを６０〜１５０℃で再溶融させて金型に入れ、１５０〜２５０℃、１〜３０ＭＰａの条件下で成形することにより得られる。
【００５５】
本発明の電子材料用樹脂組成物をプリント基板用接着剤として使用する場合には、例えば特開平５−５１５７１号、特開平６−１４５６２８号公報に記載された方法を適用できる。なお、作業性の面から、有機溶剤、好ましくは沸点が１５０℃未満のものを適宜に配合してもよい。当該プリント基板用接着剤は、半硬化膜を経て銅箔と接着させる必要があるため、これに用いるエポキシ樹脂用硬化剤としては、フェノール樹脂系硬化剤、ポリカルボン酸系硬化剤、イミダゾール系硬化剤等の潜在性硬化剤が好ましい。当該プリント基板用接着剤の具体的な使用方法としては、コーティング剤組成物をポリイミドなど絶縁フィルム上に塗布し、上記方法に従って５〜５０μｍ程度の半硬化膜を形成させた後、当該半硬化膜上に銅箔を重ねて、６０〜１５０℃でラミネートし、当該ラミネートを１５０〜２５０℃で加熱硬化させることにより、積層板を得ることができる。
【００５６】
なお、特にフレキシブルプリント配線基板やテープオートメーテッドボンディング（ＴＡＢ）テープ用接着剤として使用する場合には、例えば、特開平６−３３８６８１号公報に記載された方法を好ましく適用できる。前記フレキシブルプリント配線基板の作成方法と同様にして、膜厚が１０〜１５μｍ程度になるようにＢステージ層を作製し、必要に応じて離型性保護フィルムを張り合わせることにより、ＴＡＢ用接着剤付きテープが得られる。当該保護フィルムとしては、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレートなどが好ましく使用される。また、上記保護フィルム上にＢステージ層を形成させ、ついでここに耐熱性有機絶縁フィルムを張り合わせることによってもＴＡＢ用接着剤付きテープを作製できる。こうして得られるＴＡＢ用接着剤付きテープは、使用時に保護フィルムを取り去り、銅箔にラミネートして使用される。
【００５７】
本発明のコーティング剤組成物は、目的用途に応じて、溶剤により適宜に濃度や粘度を調整できる。溶剤としては、メトキシ基含有シラン変性エポキシ樹脂（Ａ）の製造に用いたものと同様のものを使用できる。その他、当該コーティング剤組成物には、本発明の効果を損なわない範囲で、必要に応じて、充填剤、離型剤、表面処理剤、難燃剤、粘度調節剤、可塑剤、抗菌剤、防黴剤、レベリング剤、消泡剤、着色剤、安定剤、カップリング剤等を配合してもよい。
【００５８】
なお、本発明のコーティング剤組成物から硬化膜を直接的に得るには、前記したエポキシ樹脂−シリカハイブリッド硬化物の製造方法をそのまま採用することができる。
【００５９】
本発明のコーティング剤組成物は、シーラー、プライマー、床剤の表面コート剤、プラスチック用ハードコート剤などの塗料；メッキ用アンカーコート、金属蒸着アンカーコートなどのアンカーコート剤；電子材料用、液晶板用、建材用などのシーリング剤；プリント基板用、建材用などの接着剤などに好適であり、上記硬化方法の何れかを適用して容易に硬化膜を形成させることができる。
【００６０】
次に、本発明のコーティング剤組成物の各種用途への適用例を後述する。本発明のコーティング剤組成物は、無機基材の１層目に塗工される塗料（シーラー）として特に有用である。ここで無機基材とはコンクリート、モルタル、ガラス等のセラミック基材の他、鉄、ステンレス、マグネシウム合金、亜鉛合金などの金属基材をも包含する。当該シーラーを屋外で施行する場合には、加熱硬化が困難なため室温硬化が可能なポリアミン系硬化剤を用いて、上記の直接硬化膜を得る方法で硬化させるのがよい。一方、焼き付け塗装が可能な場合には、上記の各種エポキシ樹脂用硬化剤の他、フェノール樹脂系やポリカルボン酸系硬化剤、イミダゾール系硬化剤を使用し、所定の加熱条件下で硬化膜を得ることができる。特に硬化膜の色調を重視する場合には、ポリカルボン酸系硬化剤が好ましい。当該塗料を基材に塗工する方法としては、刷毛塗り、スプレーコート、ロールコート、ディップコートなど何れの手法も適用でき、必要に応じて有機溶剤で粘度調整することにより通常５〜１００μｍ程度の硬化膜となるよう塗工される。なお当該塗料には、防錆性などを向上するために、各種フィラーを配合してもよい。当該フィラーの種類も特に限定されないが、チタン白、黄色酸化鉄、カーボンブラック等の着色顔料；シリカ、タルク、沈降性バリウム等の体質顔料；亜鉛華、リン酸アルミニウム系等の防錆顔料等を例示できる。
【００６１】
本発明のコーティング剤組成物をプライマーとして使用する場合には、例えば特開平６−１２８３５３号公報に記載されるような床材用プライマーの使用方法を適用できる。コンクリートなど基材の上に沸点が１５０℃未満の溶剤を含むコーティング剤組成物を硬化膜の膜厚が３〜５０μｍ程度になるよう塗布し、室温で１時間〜２日間放置して硬化させる。室温硬化であるため、エポキシ樹脂用硬化剤にはポリアミン系硬化剤を用いるのが好ましい。硬化時間は硬化剤であるポリアミン系硬化剤の可使時間などを考慮して決定できる。当該プライマーを硬化させた後は、常法に従って、例えば床材用エポキシ樹脂が塗工される。本発明のコーティング剤組成物は、コンクリートなどの無機基材に対する密着性が特に良好なことから、ブリスターなどの生じない高耐久性コーティング硬化物となる。
【００６２】
本発明のコーティング剤組成物を床材の表面コーティングに適用する場合には、例えば特開平４−２２４８５８号、特開平６−１２８３５３号公報に記載された方法を採用できる。すなわち、本発明のコーティング剤組成物をプライマー処理したコンクリートに、硬化膜の膜厚が１００〜５０００μｍ程度になるように、ローラーを用いて塗布し、１〜７日間、室温硬化させる。当該コーティング剤組成物には、エポキシ樹脂用硬化剤（Ｃ）としてポリアミン系硬化剤が必須成分とされるが、その他の成分として、上記シーラーの調製に用いた充填剤や可塑剤を適宜に配合できる。
【００６３】
本発明のコーティング剤組成物をプラスチック用ハードコート剤として使用する場合には、プラスチック基材上に当該コーティング剤組成物を硬化膜の膜厚が５〜５０μｍ程度になるよう公知の方法によって塗布し、直接硬化膜を得る方法によって硬化させればよい。当該硬化温度は基材プラスチックの熱変形温度以下に設定する必要があるため、硬化剤としてポリアミン系エポキシ樹脂用硬化剤を用い低温硬化させるのが好ましい。
【００６４】
本発明のコーティング剤組成物をアンカーコート剤として使用する場合には、基材上に硬化膜の膜厚が２〜１００μｍ程度になるよう、上記塗料の塗工方法と同様に塗布し、直接硬化膜を得る方法で硬化させればよい。硬化膜上にメッキを施す場合には、粗化剤により処理し、その表面を湯洗することによって、凹凸を形成させ、金属をめっき処理する。当該めっき方法としては、無電解めっき、電解めっき処理が好ましく、また上記の粗化剤としては、硫酸、重クロム酸、酸化剤、アルカリの中から選ばれた少なくとも１種が用いられる。本発明のコーティング剤組成物から得られる硬化膜は、これらの粗化剤によって適度に表面が荒れているため、メッキ層との密着性に優れている。また金属蒸着を施す場合には、硬化膜を上にして、従来公知のシリカ、アルミニウム、アルミナなどの金属又は金属酸化物を蒸着させればよい。
【００６５】
本発明のコーティング剤組成物を建材用シーリングや建材用接着剤として使用する場合には、例えば、特開平１０−２０４１５２号公報に記載の方法を例示できる。すなわち、建材用シーリングや接着剤を調製するには、メトキシ基含有シラン変性エポキシ樹脂（Ａ）に充填剤や可塑剤を加え、公知の混練機を用いて強力混練すればよい。当該充填剤としては、各種形状の有機または無機充填材を使用できるが、酸性または中性のものを選定するのが好ましい。当該充填剤としては、ヒュームドシリカ、焼成シリカ、沈降シリカ、粉砕シリカ、溶融シリカ；けいそう土；酸化鉄、酸化亜鉛、酸化チタン；ろう石クレー、カオリンクレー、焼成クレー；あるいはカーボンブラック；炭酸カルシウム等が挙げられる。なお、塩基性を示す充填剤は、当該シーリング剤のゾル−ゲル硬化を過度に促進し、十分なポットライフが得られないため好ましくない。充填剤の配合量は、硬化物の物性面から、メトキシ基含有シラン変性エポキシ樹脂（Ａ）の固形残分１００重量部に対して、５０〜１５０重量部であることが好ましい。使用するエポキシ樹脂用硬化剤としては室温硬化が可能なポリアミン系硬化剤が好ましい。作業性の点からジオクチルフタレート、ジブチルフタレートなどの可塑剤を用い、建材用シーリングや接着剤の粘度が２５℃で１０００〜１０００００ｍＰａ・ｓ程度となるよう調整するのがよい。
【００６６】
【発明の効果】
本発明のエポキシ樹脂組成物は、耐熱性、加工性等に優れるものであり、ゾル−ゲル硬化反応が速やかに進むため、Ｃステージでの揮発分の発生を抑制することができ、また、本発明のエポキシ樹脂組成物は硬化物とした場合であっても適度の柔軟性を有するため、クラッキング等を防止することができるものである。また、本発明の電子材料用樹脂組成物を用いることにより、耐熱性、絶縁性、密着性に優れ、しかもボイド、クラック等を生じない電子材料を収得しうる。さらに、本発明のコーティング剤組成物は、耐熱性、強靭性、密着性、耐酸性、耐傷つき性に優れ、しかも透明な硬化膜を収得しうる。
【００６７】
【実施例】
次に本発明の実施例を挙げるが、本発明はこれら実施例に限定されるものではない。
【００６８】
合成例１（エポキシ基含有合成ゴム（Ｂ）の製造）
攪拌機、冷却管、温度計、窒素吹き込み口を備えた反応装置に、末端カルボキシル基含有ブタジエンニトリルゴム（宇部興産（株）製、商品名、「ＨＹＣＡＲＣＴＢＮ１３００×３１」数平均分子量３５００、結合アクリロニトリル含量１０％）を１４２ｇ、ジエポキシ化合物としてビスフェノールＡ型液状エポキシ樹脂（商品名「エピコート８２８」、油化シェルエポキシ（株）製、エポキシ当量１９０ｇ／ｅｑ）を２９ｇ仕込み、１５０℃で３時間反応した。反応後、８０℃以下まで冷却してからＭＥＫを５７ｇ加えてエポキシ基含有合成ゴム（Ｂ―１）溶液とした。
【００６９】
合成例２（エポキシ基含有合成ゴム（Ｂ）の製造）
末端カルボキシル基含有ブタジエンニトリルゴム（宇部興産（株）製 商品名、「ＨＹＣＡＲ ＣＴＢＮ１３００×８」、数平均分子量３５００、結合アクリロニトリル含量１７％）を使用した以外は合成１と同じ仕込量で同じ操作を行い、エポキシ基含有合成ゴム（Ｂ―２）溶液を得た。
【００７０】
実施例１（エポキシ樹脂組成物の調製）
合成例１で得られたエポキシ基含有合成ゴム（Ｂ―１）溶液４．２ｇと合成例２で得られたエポキシ基含有合成ゴム（Ｂ―２）溶液１．１ｇの混合物に、メトキシ基含有シラン変性エポキシ樹脂（Ａ―１）メチルエチルケトン溶液（荒川化学工業（株）製、商品名「コンポセランＥ１０３」 ビスフェノール型エポキシ樹脂（１）の平均エポキシ当量４８０ｇ／ｅｑ、メトキシシラン部分縮合物（２）がメチルトリメトキシシラン（ＣＨ₃Ｓｉ（ＯＣＨ₃）₃）の部分縮合物でＳｉの平均個数が３．５、シリカ換算重量／ビスフェノール型エポキシ樹脂（１）の重量（重量比）が０．５４、エポキシ当量１４００ｇ／ｅｑ、硬化残分５０％）を１０ｇ、エポキシ樹脂用硬化剤としてオルソクレゾールノボラック樹脂（旭有機材工業（株）製、商品名「ＯＣＮ５」、水酸基当量１２０ｇ／ｅｑ）の５０％ＭＥＫ溶液を１．７ｇ、ゾル−ゲル硬化促進剤としてオクチル酸第１錫（吉富ファインケミカル（株）製、商品名「スタノクト」）を０．２ｇ、エポキシ樹脂用硬化促進剤として、２−エチル−４−メチルイミダゾール（四国化成（株）製、商品名「キュアゾール２Ｅ４ＭＺ」）を０．０２ｇ、溶剤としてメチルエチルケトンを３ｇ加え均一に溶解してエポキシ樹脂組成物を調製した。エポキシ基含有合成ゴム（Ｂ）の使用量は、メトキシ基含有シラン変性エポキシ樹脂（Ａ）の硬化残分１００重量部に対して７９重量部であった。エポキシ樹脂用硬化剤（Ｃ）中の活性水素を有する官能基が、メトキシ基含有シラン変性エポキシ樹脂（Ａ）及びエポキシ基含有合成ゴム（Ｂ）に由来するエポキシ基１当量に対して０．８当量であった。
【００７１】
実施例２（エポキシ樹脂組成物の調製）
合成例１で得られたエポキシ基含有合成ゴム（Ｂ―１）溶液の仕込量を４．９ｇ、合成例２で得られたエポキシ基含有合成ゴム（Ｂ―２）溶液の仕込量を０．３ｇに変更した以外は実施例１と同じ仕込量で同じ操作を行い、エポキシ樹脂組成物を調製した。エポキシ基含有合成ゴム（Ｂ）の使用量は、メトキシ基含有シラン変性エポキシ樹脂（Ａ）の硬化残分１００重量部に対して７９重量部であった。エポキシ樹脂用硬化剤（Ｃ）中の活性水素を有する官能基が、メトキシ基含有シラン変性エポキシ樹脂（Ａ）及びエポキシ基含有合成ゴム（Ｂ）に由来するエポキシ基１当量に対して０．８当量であった。
【００７２】
実施例３（エポキシ樹脂組成物の調製）
合成例１で得られたエポキシ基含有合成ゴム（Ｂ―１）溶液８．６ｇに、コンポセランＥ１０３を１０ｇ、エポキシ樹脂用硬化剤としてフェノールノボラック樹脂（荒川化学工業（株）製、商品名「タマノル７５９」、水酸基当量１０６ｇ／ｅｑ）の５０％ＭＥＫ溶液を２．５ｇ、スタノクトを０．２ｇ、キュアゾール２Ｅ４ＭＺを０．０２ｇ、ＭＥＫを５ｇ加え均一に溶解してエポキシ樹脂組成物を調製した。エポキシ基含有合成ゴム（Ｂ）の使用量は、メトキシ基含有シラン変性エポキシ樹脂（Ａ）の硬化残分１００重量部に対して１２８重量部であった。エポキシ樹脂用硬化剤（Ｃ）中の活性水素を有する官能基が、メトキシ基含有シラン変性エポキシ樹脂（Ａ）及びエポキシ基含有合成ゴム（Ｂ）に由来するエポキシ基１当量に対して１．２当量であった。
【００７３】
比較例１（エポキシ樹脂組成物の調製）
ビスフェノール型エポキシ樹脂（油化シェルエポキシ（株）製、商品名「エピコート１００１」、エポキシ当量４８０ｇ／ｅｑ）の５０％ＭＥＫ溶液１０ｇに、タマノル７５９の５０％ＭＥＫ溶液を１．８ｇ、スタノクトを０．２ｇ、キュアゾール２Ｅ４ＭＺを０．０２ｇ加え均一に溶解してエポキシ樹脂組成物を調製した。
【００７４】
比較例２（エポキシ樹脂組成物の調製）
コンポセランＥ１０３を１０ｇに、タマノル７５９の５０％ＭＥＫ溶液を１．２ｇ、スタノクトを０．２ｇ、キュアゾール２Ｅ４ＭＺを０．０２ｇ加え均一に溶解してエポキシ樹脂組成物を調製した。
【００７５】
比較例３（エポキシ樹脂組成物の調製）
合成例１で得られたエポキシ基含有合成ゴム（Ｂ―１）溶液５．４ｇに、エピコート１００１の５０％ＭＥＫ溶液を１０ｇ、タマノル７５９の５０％ＭＥＫ溶液を２．１ｇ、スタノクトを０．２ｇ、キュアゾール２Ｅ４ＭＺを０．０２ｇ加え均一に溶解してエポキシ樹脂組成物を調製した。
【００７６】
＜硬化物の評価＞
（粘弾性測定による耐熱性の評価）
実施例１〜３及び比較例１〜３で得られた各樹脂組成物を、アルミカップに注ぎ込み、１００℃で３０分硬化して半硬化物にし、その後２００℃で２時間硬化することによって厚さ３００μｍの完全硬化物フィルムを作製した。得られた硬化フィルムを６ｍｍ×２０ｍｍにカットし、粘弾性測定器（レオロジ社製、商品名「ＤＶＥ−Ｖ４」、測定条件振幅５μｍ、振動数１０Ｈｚ、スロープ５℃／分）を用いて動的貯蔵弾性率Ｅ’、ｔａｎδを測定して、耐熱性を評価した。Ｅ’の測定結果を図１に、ｔａｎδの測定結果を図２に示す。
【００７７】
図1および図２から明らかなように、実施例１〜３では、硬化フィルム（エポキシ樹脂硬化物）は、比較例３と同様、−４０℃付近に合成ゴム（Ｂ）由来のガラス転移点（Ｔｇ）が存在し、その為、室温での貯蔵弾性率が低い上、室温以上に見られるＴｇは、比較例２硬化物と同様、比較例１および比較例３硬化物に比べて高く、高耐熱性を示している。また比較例２硬化物のＴｇ（１４０℃）付近のｔａｎδは何れの実施例においても減少しており、このことからも耐熱性の高さが伺える。
【００７８】
（熱重量損失による耐熱性評価）
粘弾性測定時に作製した各硬化フィルムを用いて、示差熱・熱重量同時測定装置（セイコーインスツルメンス（株）製、商品名「ＴＧ／ＤＴＡ２２０」、測定条件：スロープ１０℃／分）で熱重量損失を測定した。結果を表１に示す。
【００７９】
【表１】

【００８０】
表１から明らかなように、実施例１〜３の１０％重量損失時の温度は比較例２と同様に十分に高く、ゴム成分による耐熱分解性の低下は認められない。
【００８１】
（密着性）
実施例１〜３及び比較例１〜３で得られた各樹脂組成物を圧延銅板（日本テストパネル（株）製、商品名「銅板ＪＩＳＨ３１００（Ｃ１１００Ｐ）」）にバ−コーター＃６０を使って塗布し、１００℃で３０分硬化して半硬化物にし、その後２００℃で１時間硬化することによって硬化物フィルム４０μｍがコーティングされた銅板が得られた。得られた銅板を用いて、ＪＩＳ Ｋ−５４００一般試験法によるゴバン目セロハンテープ剥離試験を行った。結果を表２に示す。
【００８２】
【表２】

【００８３】
（絶縁性）
実施例１および比較例１で得られた硬化フィルムを使って、周波数１ＭＨｚで誘電率および誘電損失を測定した。結果を表３に示す。
【００８４】
【表３】

【００８５】
（線膨張率）
実施例１、３で得られた硬化フィルムを使って、熱応力歪測定装置（セイコー電子工業（株）製、商品名 ＴＭＡ１２０Ｃ）で、４０〜１００℃、１５０〜１８０℃の線膨張率を測定した。結果を表４に示す。
【００８６】
【表４】

【００８７】
＜半硬化物の評価＞
実施例１〜３及び比較例１〜３で得られた各樹脂組成物を、アルミカップに注ぎ、１００℃で３０分硬化し１００μｍの半硬化フィルム（Ｂステージ）を得た。
【００８８】
（揮発分測定）
１００℃で３０分硬化後の重量（加工前の半硬化物の重量）を測定し、その後更に２００℃で１時間硬化させた（Ｃステージ）を行い、この時の重量（加工後の完全硬化物の重量）を測定し、減量率を算出した。結果を表５に示す。
【００８９】
【数１】

【００９０】
（加工性の評価）
半硬化物（Ｂステージ）を１００℃のホットプレート上に乗せ、再流動可能かを評価した。この結果を表５に示す。
〇：再流動可能
×：再流動可能
【００９１】
【表５】

【００９２】
表５から、実施例のエポキシ樹脂組成物は、いずれも比較例２よりも減量率が低下しており、完全硬化物作製時の寸法安定性に優れることが分かる。
【００９３】
（力学強度）
半硬化物をダンベル１号で切り抜き、テンシロン試験機（オリエンテック社製，商品名ＵＣＴ−５００）を用いて、５ｃｍ／分の引っ張り速度で、フィルムを引き伸ばし、引張り弾性率、破断するまでのフィルム伸びおよび破断時の強度を測定した。２５℃で３回、同じ方法で引っ張り試験を行い、その平均値を表６に示す。
【００９４】
【表６】

【００９５】
表６から明らかなように、実施例の半硬化物は弾性率が低く、伸張率が大きいため、屈曲、引張りなどの変形に対する耐性が強い。また破断強度が高い事から、強靭なフィルムといえる。
【００９６】
＜プリプレグ、銅張り積層板の作製＞
実施例１、３、比較例１、２で得られたエポキシ樹脂組成物を厚さ ０．１０ｍｍのガラス織布に樹脂分約４０％になる様に含浸させた後、１００℃で１５分間、乾燥、硬化し、プリプレグを作製した。このプリプレグ３枚とその両面に１８μｍ厚の銅箔を重ね、２１０℃、１０ＭＰａで２時間加熱加圧して両面銅張り積層板を作製した。
【００９７】
比較例２のエポキシ樹脂組成物を使用した場合には、２１０℃加温時に発泡が見られ、銅張り積層板の銅箔が剥離していたが、その他のものは問題無く、銅張り積層板を作製する事が出来た。
【００９８】
（銅箔の剥離強度）
ＪＩＳ Ｃ−６４８１に準拠して測定した。その結果を表７に示す。
【００９９】
【表７】

【０１００】
表７から明らかなように、本発明の銅張り積層板は密着性に優れており、通常のプリント配線板はもちろん、多層プリント配線板の製造に最適であることが分かる。
【０１０１】
（銅張り積層板の粘弾性）
実施例１、３で得られたエポキシ樹脂組成物を用いて作製した両面銅張り積層板の銅箔を剥がしたものを、硬化物の粘弾性測定と同じ条件で粘弾性測定を行った。Ｅ’の測定結果を図３に示す。
【０１０２】
図３から明らかなように、実施例１、３で得られたエポキシ樹脂組成物は両面を銅箔で覆われたクローズドの状態でも、高温での貯蔵弾性率が高く、優れた耐熱性を示すことが分かる。
【０１０３】
＜ビルドアップ基板用層間絶縁膜、ビルドアップ基板の作製＞
剥離ＰＥＴ（ポリエチレンテレフタレート）フィルム（パナック（株）製ＳＧ―１）上に実施例１、３及び比較例１、２で使用したエポキシ樹脂組成物をロールコーターを用いて塗布し、１００℃で１５分、乾燥、硬化させ、剥離フィルム付き半硬化樹脂（ドライフィルム）膜厚１００μｍを作製した。これらのドライフィルムを先の銅張り積層板上に１２０℃で、１０分間、６ＭＰａで加熱圧着した後、室温に戻して剥離フィルムを除去し、２００℃で２時間硬化させた。この時、比較例２のエポキシ樹脂組成物を使用したドライフィルムは、硬化時に発泡が激しく、クラックが発生したが、実施例及び比較例１からは良好な積層体が得られた。更にこれらの積層体を過マンガン酸カリウム水溶液でデスミア処理をした後、パラジウム触媒溶液で処理して、無電解銅メッキを施した。更に厚さ０．５μｍ電解銅メッキを行い、ビルドアッププリント基板を得た。
【０１０４】
（吸湿半田耐熱試験）
吸湿条件：プレッシャークッカー処理、１２５℃、２３０ｋＰa、３０分間
試験条件：ｎ＝５で、全ての試験片が２８０℃、１２０秒間で膨れが無かった場合を○とし、膨れが生じたものを×とした。結果を表８に示す。
【０１０５】
（剥離強度）
ＪＩＳ Ｃ−６４８１に準じて、めっき銅と絶縁基板との剥離強度を測定した。結果を表８に示す。
【０１０６】
【表８】

【０１０７】
＜ビルドアップ基板用層間絶縁膜（樹脂付き銅箔を用いる方法による）、ビルドアップ基板の作製＞
１８μｍ厚の電解銅箔上（古河電気工業（株）製、商品名「Ｆ２−ＷＳ」）に、実施例１、３及び比較例２のエポキシ樹脂組成物を硬化後の厚みが４０μｍとなるようにロールコーターにて塗布、乾燥して１００℃で１５分、乾燥、硬化させ、半硬化樹脂付き銅箔を作製した。洗浄した両面プリント配線板の導体パターンを覆うように両面の全体に前記の樹脂付き銅箔を樹脂面が回路面と接触する様に重ね合わせ、２１０℃、６ＭＰａで１２０分間加熱加圧して、層間絶縁膜を有するビルドアップ基板を作製した。比較例２のエポキシ樹脂組成物を使用したものは２１０℃硬化時に発泡を生じ、層間剥離を生じたが、それ以外は問題無く高耐熱ビルドアップ基板用層間絶縁膜層を作製できた。
【０１０８】
＜封止剤の作製−コンプレッションフロー法＞
実施例１、３で得たエポキシ樹脂組成物に、フィリップチップ実装対応の片面プリント配線基板の上に、この封止剤用樹脂組成物を厚さ６０μｍになる様に１ｃｍ角に塗布し、１３０℃で１０分乾燥、硬化後、半硬化樹脂付きガラス基板を作製した。この半硬化樹脂付きプリント基板を１１０℃に加熱したオーブンに１０分入れた後、同じ温度で、３７０μｍ厚、１ｃｍ角のシリコンチップを半硬化樹脂上に乗せ、３００ｇの荷重を加えて基板のバンプとチップの電極を接触させた後、２１０℃で１時間完全硬化させ封止剤硬化物層を作製した。実施例１、３を使用し、高耐熱封止剤層を問題無く作製できた。
【０１０９】
＜導電ペーストの作製＞
実施例３で得られたエポキシ樹脂組成物１２０ｇに、平均粒子径が１２μｍ、アスペクト比が８のりん片状銀粉（徳力化学研究所（株）製）１６０ｇ及び平均粒子径が１０μｍ、アスペクト比が９のりん片状ニッケル粉（高純度化学（株）製、商品名「ＮＩ１１０１０４」）６０ｇを添加し、均一になるまで撹拌後、三本ロールで均一に分散して導電ペーストとした。得られた導電ペーストを、厚さ１．６ｍｍの紙フェノール基板上にスクリーン印刷した後、２００℃で１時間、加熱硬化させた。得られた配線板の比抵抗を測定した結果、比抵抗値は１００.５μΩ・ｍであった。
【０１１０】
＜成形物の作製＞
実施例１のエポキシ樹脂組成物を、フッ素樹脂コーティングされた容器（縦×横×深さ＝１０ｃｍ×１０ｃｍ×１．５ｃｍ）に注ぎ、８０℃で３０分および１３０℃で３０分放置することによりゾル−ゲル硬化させ、膜厚３００μｍのゴム状の半硬化シートを得た。得られた半硬化シートは、柔軟（最大伸張率が約４０％）であり、また７０℃以上で成形加工することができた。
この半硬化物を５枚重ね、２００℃、１０ＭＰａでプレス成形し、特に問題無く高耐熱性板状成形物を得た。
【０１１１】
＜接着剤の調整＞
実施例１、３、比較例２のエポキシ樹脂組成物を、乾燥後の膜厚が２０μｍとなるようにバーコーターでポリイミドフィルム（東レ・デュポン（株）製、「カプトンＨ」）上に塗布し、１１０℃で５分間乾燥し、接着剤層を半硬化した。この接着剤層に銅箔を重ね、１１０℃でラミネートし、その後２００℃で３時間加熱硬化（Ｃステージ化）させ、フレキシブルプリント基板を作製した。
【０１１２】
（耐熱性、接着性）
上記で得られた試験板を用い、以下の方法で接着剤性能を評価した。評価結果を表９に示す。
（１）剥離強度
得られた試験板を固定して９０°方向に５０ｍｍ／分の速度で銅箔を引き剥がし、その強度を測定した（ＪＩＳ Ｃ ６４８１に準拠）。
（２）半田耐熱性
得られた試験板をフロー半田浴に３０秒間浮かべた後、膨れ、剥がれが生じない最高温度を測定した（ＪＩＳ Ｃ ６４８１に準拠）。
【０１１３】
【表９】

【０１１４】
表９から明らかなように、本発明のプリント配線板用接着剤を用いてなるプリント配線板は、従来のエポキシ系接着剤を用いたプリント配線板に比べ、耐熱性や、銅箔に対する接着性に優れることが分かる。
【０１１５】
実施例４（エポキシ樹脂組成物の作製）
合成例２で得られたエポキシ基含有合成ゴム（Ｂ―２）溶液５．５ｇに、コンポセランＥ１０４を１０ｇ、エポキシ樹脂用硬化剤として酸無水物である４−メチルヘキサヒドロ無水フタル酸（新日本理化（株）製、商品名「リカシッドＭＨ７００」、酸無水物当量１６４ｇ／ｅｑ）を１．４ｇ、スタノクトを０．２ｇ、キュアゾール２Ｅ４ＭＺを０．０２ｇ、ＭＥＫを４．５ｇ加え均一に溶解してエポキシ樹脂組成物を調製した。エポキシ基含有合成ゴム（Ｂ）の使用量は、メトキシ基含有シラン変性エポキシ樹脂（Ａ）の硬化残分１００重量部に対して８３重量部であった。エポキシ樹脂用硬化剤（Ｃ）中の活性水素を有する官能基が、メトキシ基含有シラン変性エポキシ樹脂（Ａ）及びエポキシ基含有合成ゴム（Ｂ）に由来するエポキシ基１当量に対して１当量であった。
【０１１６】
比較例４（エポキシ樹脂組成物の調製）
エピコート１００１の５０％ＭＥＫ溶液１０ｇに、リカシッドＭＨ７００を１．７ｇ、スタノクトを０．１ｇ、キュアゾール２Ｅ４ＭＺを０．０１ｇ、ＭＥＫを２ｇ加え均一に溶解してエポキシ樹脂組成物を調製した。
【０１１７】
＜コーティング膜の作製＞
実施例４、比較例４のガラス板、モルタルに膜厚２０μｍとなるように塗布、１５０℃、３時間硬化した。
【０１１８】
＜耐熱密着性＞
上記で作成した各塗板を１５０℃で８時間放置した後の密着性を評価した。
ＪＩＳ Ｋ−５４００一般試験法によるゴバン目セロハンテープ剥離試験を行った。結果を表１０に示す
【０１１９】
【表１０】

▲１▼ガラス板（JIS R3202-85）
▲２▼モルタル（JIS R5201-92）
【図面の簡単な説明】
【図１】 実施例１〜３及び比較例１〜３で得られた硬化フィルムの動的貯蔵弾性率Ｅ´の測定結果である。
【図２】 実施例１〜３及び比較例１〜３で得られた硬化フィルムのｔａｎδの測定結果である。
【図３】 実施例１及び３で得られたエポキシ樹脂組成物を用いて作製した両面銅張り積層板の銅箔を剥がしたものの動的貯蔵弾性率Ｅ´の測定結果である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an epoxy resin composition. This epoxy resin composition can be used for each use, such as a resin composition for electronic materials and a coating agent. The resin composition for electronic materials includes a resin composition for prepreg for printed circuit boards, a resin composition for copper-clad laminates for printed circuit boards, a coating agent for interlayer insulation materials for build-up printed circuit boards, and a resin composition for semiconductor interlayer insulation films. Resin composition for electronic component encapsulant, resin composition for semiconductor chip encapsulant, cured resin for underfill, resist ink, conductive paste, resin composition for electronic component storage molding and anisotropic Used for various applications such as conductive film compositions, etc., by curing the resin composition for electronic materials, printed circuit board prepregs, printed circuit board copper-clad laminates, printed wiring boards, interposers, build-up printed circuit boards Interlayer insulation material, semiconductor interlayer insulation film, electronic component sealant, semiconductor chip sealant, cured underfill resin Resist ink cured product, conductive paste cured product, the electronic material resin such as an electronic component storing moldings and anisotropic conductive film is obtained. Moreover, the coating agent composition of the present invention is used for various applications such as sealers, primers, hard coats for plastics, anchor coat agents, sealing, adhesives and the like.
[0002]
[Prior art]
Epoxy resin is generally used as a composition combined with a curing agent and has been awarded in the field of electrical and electronic materials, but with the recent development of electrical and electronic materials, epoxy resin composition Higher performance has been demanded for cured products, and in particular, improvement in heat resistance has been desired. For this reason, the present inventors have intensively studied to meet such demands, and in JP-A-2001-59013, an epoxy resin composition that can provide a cured product that has good heat resistance and does not cause voids or the like. I made a proposal about.
[0003]
The epoxy resin composition proposed by the present inventors is suitable as an insulating material for printed wiring boards because of its excellent heat resistance, electrical properties, chemical properties, and good compatibility with paper and glass substrates. However, the processability was not sufficient.
[0004]
In general, an insulating material is produced by coating or impregnating a resin composition with a resin composition, and then removing the volatile components such as solvent by heating to obtain a semi-cured state (B stage) in which a curing reaction is advanced. Then, this semi-cured sheet is laminated or sandwiched between conductors and further completely cured at a high temperature to form a completely cured body (C stage) to produce an insulating layer. This semi-cured sheet has a low volatile content and needs to be heat-softened to obtain adhesion.
[0005]
By the way, the epoxy resin composition proposed by the present inventors can be made into a cured product by two kinds of curing reactions of sol-gel curing of an alkoxysilyl site and curing by an epoxy group. When the resin composition is used as an electrically insulating material, control of these curing reactions is important. In other words, sol-gel curing is a curing reaction in which silica is generated while alcohol is by-produced, and since generation of volatile components is inevitable, sol-gel curing is performed together with solvent evaporation during semi-cured product preparation. It is desirable to proceed and suppress the generation of volatile components at the C stage. However, since the resin composition has a high elastic modulus of the semi-cured product and is brittle, the sol-gel curing is difficult to proceed at a low temperature. When the thickness is large, volatile matter tends to be generated between the layers at the C stage. In addition, when the B stage production temperature is raised, the generation of volatile matter at the C stage can be suppressed, but in addition to the sol-gel curing during the B stage production, the epoxy group curing reaction proceeds, and the adhesion when heating the semi-cured product is improved. There was a problem of a drop.
[0006]
In addition, the epoxy resin composition is extremely excellent in heat resistance and hardness even in the fields of coating agents and adhesives, but sol-gel curing is difficult when a thick film is formed using a low boiling point solvent. It has been pointed out that the problem of foaming due to alcohol is delayed after solvent evaporation and epoxy group curing, and the cured film obtained from the epoxy resin composition is brittle, although it has a higher elastic modulus than a general epoxy resin, There was also a problem that the cured film was easily broken.
[0007]
[Problems to be solved by the invention]
The present invention has a heat resistance equivalent to that of an epoxy resin composition having a conventional alkoxy group-containing silane-modified epoxy resin, has excellent processability, etc., and has a good volatile content release property. It aims at providing the epoxy resin composition which produces a film | membrane.
[0008]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventor required a methoxy group-containing silane-modified epoxy resin and an epoxy group-containing synthetic rubber obtained by modifying a specific epoxy resin with a specific methoxysilane compound. The present inventors have found that the object can be solved by using the resin composition as described above, and have completed the present invention.
[0009]
That is, bisphenol type epoxy resin (1) andOf methyltrimethoxysilane represented by a specific formulaPartial condensate (2)(Hereinafter simply referred to as methoxysilane partial condensate (2))Methoxy group-containing silane-modified epoxy resin (A) obtained by dealcoholizingButadiene nitrile rubber obtained by epoxy modification of molecular ends(B) and, Selected from phenol resin curing agents, polyamine curing agents and polycarboxylic acid curing agentsFrom epoxy resin curing agent (C)And the blending ratio of the butadiene nitrile rubber (B) obtained by epoxy-modifying the molecular terminals is 30 to 150 parts by weight with respect to 100 parts by weight of the cured residue of the methoxy group-containing silane-modified epoxy resin (A). Yes, and the mixing ratio of the curing agent for epoxy resin (C) is 1 equivalent of epoxy group derived from methoxy group-containing silane-modified epoxy resin (A) and butadiene nitrile rubber (B) obtained by epoxy-modifying molecular ends. On the other hand, the functional group having active hydrogen in the curing agent for epoxy resin (C) is 0.5 to 1.2 equivalents,An epoxy resin composition; a resin composition for electronic materials containing the epoxy resin composition; a resin for electronic materials obtained by curing the resin composition for electronic materials; a coating agent composition containing the epoxy resin composition Related to things.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The methoxy group-containing silane-modified epoxy resin (A) used in the present invention is composed of a bisphenol type epoxy resin (1) and a methoxysilane partial condensate (2) as described above. The bisphenol-type epoxy resin (1) is obtained by a reaction between bisphenols and a haloepoxide such as epichlorohydrin or β-methylepichlorohydrin. Examples of bisphenols include reaction products of phenol or 2,6-dihalophenol with aldehydes or ketones such as formaldehyde, acetaldehyde, acetone, acetophenone, cyclohexanone, and benzophenone, as well as oxidation of dihydroxyphenyl sulfide with peracid, Examples thereof include those obtained by etherification reaction between hydroquinones.
[0011]
The bisphenol-type epoxy resin (1) has a hydroxyl group that can be dealcoholized with the methoxysilane partial condensate (2). The hydroxyl group need not be contained in all molecules constituting the bisphenol-type epoxy resin (1), and it is sufficient that the bisphenol-type epoxy resin (1) has a hydroxyl group. Since the epoxy equivalent of the bisphenol type epoxy resin (1) varies depending on the structure of the bisphenol type epoxy resin (1), an epoxy equivalent having an appropriate epoxy equivalent can be appropriately selected and used depending on the use, but 350 to 1000 g / eq. The following are preferred. If it is less than 350 g / eq, the adhesiveness of the resulting cured product tends to decrease, and if it exceeds 1000 g / eq, the storage stability of the methoxy group-containing silane-modified epoxy resin tends to decrease. Among these bisphenol-type epoxy resins (1), bisphenol A-type epoxy resins are particularly preferred because they are most widely used and inexpensive.
[0012]
As the methoxysilane partial condensate (2) constituting the methoxy-containing silane-modified epoxy resin (A), an oligomer obtained by partially hydrolyzing and condensing methoxysilane generally used in a sol-gel methodThe partial condensate of methyltrimethoxysilane represented by the following general formula (wherein the average number of repeating units n is 3 to 12) is that of the methoxy group-containing silane-modified epoxy resin (A). The sol-gel curing rate is fast, and the cured film is highly flexible, so it is preferably used. In addition, it is preferable that the average number of Si is less than 3 because the amount of toxic methoxysilanes flowing out of the system together with by-product alcohol increases in the dealcoholization reaction with the bisphenol type epoxy resin (1). Absent. On the other hand, if it exceeds 12, the reactivity with the bisphenol type epoxy resin (1) falls, and it takes a long time to obtain the target methoxy group-containing silane-modified epoxy resin (A), which is not preferable.
[0015]
General formula:
[0016]
[Chemical 1]

[0018]
The methoxy group-containing silane-modified epoxy resin (A) used in the present invention is obtained by a dealcoholization reaction between the bisphenol type epoxy resin (1) and the methoxysilane partial condensate (2). The use ratio of the bisphenol type epoxy resin (1) and the methoxysilane partial condensate (2) is not particularly limited as long as the methoxy group remains in the resulting methoxy group-containing silane-modified epoxy resin (A). However, it is preferable that the silica conversion weight of the methoxysilane partial condensate (2) / the weight (weight ratio) of the bisphenol type epoxy resin (1) is in the range of 0.25 to 1.2. Here, the weight in terms of silica of the methoxysilane partial condensate (2) is the weight when the methoxysilane partial condensate (2) is sol-gel reacted and cured to silica.
[0019]
The methoxy group-containing silane-modified epoxy resin (A) can be produced, for example, by charging the bisphenol-type epoxy resin (1) and the methoxysilane partial condensate (2) and heating to distill off alcohol produced as a by-product or using a cooling tube. It is carried out by returning to the system by refluxing. The reaction temperature is about 50 to 130 ° C., preferably 70 to 110 ° C., and the total reaction time is about 1 to 15 hours. In order to prevent the polycondensation reaction of the methoxysilane partial condensate (2) itself, this reaction is preferably carried out under substantially anhydrous conditions.
[0020]
In the above dealcoholization reaction, a catalyst that does not open an epoxy ring among conventionally known catalysts can be used to promote the reaction. Examples of the catalyst include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, and manganese. And metals such as oxides, organic acid salts, halides, and methoxides of these metals. Among these, organic tin and organic acid tin are particularly preferable, and specifically, dibutyltin dilaurate, tin octylate and the like are effective.
[0021]
The above reaction can be performed in a solvent or without a solvent. The solvent is not particularly limited as long as it is an organic solvent that dissolves the bisphenol-type epoxy resin (1) and the methoxysilane partial condensate (2) and is inactive to these. Examples of such an organic solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone, esters such as ethyl acetate and butyl acetate, aromatics such as toluene and xylene, cellosolve acetate, methyl cellosolve acetate, and the like. And an aprotic polar solvent such as dimethylformamide, ethers such as cellosolve, tetrahydrofuran and diethylene glycol dimethyl ether, alcohols such as isopropyl alcohol and n-butyl alcohol, and the like. Among these, those having a boiling point of 70 to 110 ° C. at normal pressure such as methyl ethyl ketone are particularly preferable for the following reasons. When a solvent having a boiling point exceeding 110 ° C. is used, it is necessary to excessively increase the temperature at which the solvent is in a semi-cured state (B stage) in order to reduce the residual ratio of the solvent. Moreover, when the boiling point of the solvent used is less than 70 ° C., a long time is required for the dealcoholization reaction between the bisphenol type epoxy resin (1) and the methoxysilane partial condensate (2), which is not preferable.
[0022]
The methoxy group-containing silane-modified epoxy resin (A) thus obtained is mainly composed of an epoxy resin in which the hydroxyl group in the bisphenol-type epoxy resin (1) is silane-modified. A) may contain unreacted bisphenol-type epoxy resin (1) and unreacted methoxysilane partial condensate (2).
[0023]
The methoxy group-containing silane-modified epoxy resin (A) has a methoxysilyl moiety derived from the methoxysilane partial condensate (2) and an epoxy group derived from a bisphenol type epoxy resin in the molecule. The methoxysilyl moiety forms a cured product bonded to each other by evaporation of the solvent, heat treatment, or reaction with moisture (humidity). Such a cured product has fine gelled silica sites (high-order network structure of siloxane bonds). Therefore, the methoxy group contained in the methoxy group-containing silane-modified epoxy resin (A) preferably retains 60 mol% or more of the methoxyl group of the used methoxysilane partial condensate (2). The epoxy group reacts with the epoxy resin curing agent (C).
[0024]
In the epoxy resin composition of the present invention,Butadiene nitrile rubber obtained by epoxy modification of molecular ends(B)(Hereinafter, it may be simply referred to as an epoxy group-containing rubber (B).)Is an essential component. thisTheBy using it, the epoxy resin-silica hybrid phase derived from the methoxy group-containing silane-modified epoxy resin and the rubber phase can be finely phase-separated in the cured product and derived from the epoxy group-containing rubber (B) that is liquid at room temperature. In order to make the cured product flexible, the methanol generated in the sol-gel curing process is volatilized quickly, so that the sol-gel curing further proceeds and the methoxy group that can be a source of volatiles in the later curing process. This is because most of the water is involved in the curing reaction and disappears, so that the generation of volatile components at the time of curing (C stage) can be reduced. In addition, since the rubber phase separated by the micro phase has a glass transition point below the freezing point, the change in elastic modulus at room temperature or higher of the cured product is governed by the epoxy resin-silica hybrid phase, and can maintain high heat resistance. Due to the presence of the separated rubber phase, the elastic modulus of the cured product decreases and the cured product becomes tough.
[0025]
The epoxy group-containing synthetic rubber (B) used in the present invention is obtained by reacting a synthetic rubber having a carboxyl group at the terminal with a diepoxy compound. When the carboxyl group is in the molecular chain, the phase separation structure cannot be obtained, and the epoxy resin-silica hybrid phase is affected by the rubber phase, the glass transition point is lowered, and the heat resistance is greatly lost. In some cases, those having a carboxyl group at the molecular end are preferred. The synthetic rubber having a carboxyl group at the terminal is not particularly limited, and examples thereof include known rubbers such as a butadiene rubber having a carboxyl group at the terminal and a butadiene nitrile rubber having a carboxyl group at the terminal. From the viewpoint of reactivity, a butadiene nitrile rubber having a carboxyl group at the terminal is preferred. As the butadiene nitrile rubber having a carboxyl group at the terminal, commercially available ones can be used. Things can be raised. The number average molecular weight of the synthetic rubber having a carboxyl group at the terminal is preferably about 2000 to 5000. When the number average molecular weight is 2000 or more, the above microphase separation structure is produced, so that the heat resistance of the epoxy resin-silica hybrid phase can be maintained, and when the number average molecular weight is 5000 or less, a methoxy group-containing silane Mixing with the modified epoxy resin is facilitated, and a stable resin composition can be prepared.
[0026]
In the case of a butadiene nitrile rubber having a carboxyl group at the terminal, the bound acrylonitrile content is usually 3 to 30%, preferably 5 to 20%. By setting the bound acrylonitrile content to 3% or more, the epoxy group-containing synthetic rubber (B) and the methoxy group-containing silane-modified epoxy resin (A) are dissolved, the epoxy resin composition becomes uniform, and the cured product has transparency. Since it becomes favorable, it is preferable. On the other hand, by making the bound acrylonitrile content 30% or less, the epoxy group-containing synthetic rubber (B) forms a microphase separation structure, and the glass transition point of the epoxy resin-silica hybrid phase is not affected by the rubber phase, High heat resistance is maintained.
[0027]
The diepoxy compound is obtained by reacting a bisphenol with a haloepoxide such as epichlorohydrin or β-methylepichlorohydrin. The diepoxy compound usually contains about 1 to 5 bisphenol repeating units, preferably 1 to 3. By setting the repeating unit to 5 or less, compatibility with a synthetic rubber having a carboxy group is improved, and thus the reaction is likely to proceed, which is preferable.
[0028]
For the reaction between the synthetic rubber having a carboxyl group at the terminal and the diepoxy compound, a generally known method can be adopted, and it is usually obtained by reacting at about 100 to 200 ° C. for 1 to 5 hours. Moreover, the said reaction can also employ | adopt the method made to react at about 60-150 degreeC in the presence of an amine catalyst, for example. The amine catalyst is not particularly limited and known ones can be used. Examples thereof include tertiary amines such as triethylamine and trimethylamine, secondary amines such as diethylamine and piperidine, and primary amines such as ammonia and ethylamine. . The epoxy group-containing synthetic rubber (B) thus obtained usually has a number average molecular weight of about 2000 to 10,000 and a glass transition point of preferably −30 ° C. or lower. This is because when the glass transition point of the rubber phase in the cured product exceeds −30 ° C., the elastic modulus may continue to change to near room temperature (10 to 30 ° C.), which may adversely affect physical properties. . Since the epoxy group-containing synthetic rubber (B) has a bisphenol structure at the molecular end and has an affinity for the methoxy group-containing silane-modified epoxy resin (A), it can be mixed to prepare a resin composition. Compounding ratio of epoxy group-containing synthetic rubber (B)Is, 30 to 150 parts by weight with respect to 100 parts by weight of the cured residue of the methoxy group-containing silane-modified epoxy resin (A)Is. If the blending ratio is less than 30 parts by weight, the effect of the invention is insufficient, and if it exceeds 150 parts by weight, the cured product becomes too soft and the toughness may be lost. The cured residue of the methoxy group-containing silane-modified epoxy resin (A) is obtained as follows. That is, methoxy group-containing silane-modified epoxy resin (A) and an equivalent amount of triethylenetetramine were mixed, and about 1 g of the mixed solution was weighed (measured) into an aluminum cup (50 mm diameter), and this was measured at 100 ° C. for 1 hour. Subsequently, it is dried and cured at 200 ° C. for 2 hours, re-measured (measured), and calculated from the following equation.
[0029]
Curing residue (%) = (Weighing (2) -Triethylenetetramine weight) × 100 / Weighing (1)
[0030]
Curing agent for epoxy resin used in the present invention (C)Is selected from phenol resin curing agents, polyamine curing agents and polycarboxylic acid curing agents. Specifically, examples of the phenol resin-based curing agent include phenol novolak resin, cresol novolac resin, bisphenol novolak resin, poly p-vinylphenol, and the like. Examples of the polyamine curing agent include diethylenetriamine, triethylenetetramine, and tetraethylenepenta. Min, dicyandiamide, polyamidoamine (polyamide resin), ketimine compound, isophoronediamine, m-xylenediamine, m-phenylenediamine, 1,3-bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 4,4'-diamino Examples include diphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, diaminodiphenylsulfone, and the like. Polycarboxylic acid curing agents include phthalic anhydride, tetrahydroanhydrofuran. Le, methyl tetrahydrophthalic anhydride, 3,6-tetrahydrophthalic anhydride, hexa-chloro endomethylene tetrahydrophthalic anhydride, methyl-3,6-methylene tetrahydrophthalic anhydride and the like.
[0031]
The epoxy resin composition of the present invention is usually in a completely cured product state (C stage) through a B stage. Therefore, in order to prevent volatile matter generation at the C stage, the volatile matter contained in the epoxy resin composition (the solvent for production in the methoxy group-containing silane-modified epoxy resin (A), the resin (A) It is necessary to reduce the residual ratio of methanol and solvent by-produced by the sol-gel curing reaction at the methoxysilyl site. However, in the B stage, it is necessary to consider interlayer adhesion to the conductor of the C stage layer obtained subsequently. That is, it is necessary to leave an epoxy group so that the semi-cured product layer of the B stage can exhibit a sufficient surface tack at a temperature at which the B stage semi-cured layer is brought into close contact with the conductor, and therefore the epoxy group of the resin (A) in the B stage. It is preferable to use a latent curing agent that does not proceed with curing. As such a latent curing agent, a phenol resin curing agent is optimal.
[0032]
From the design viewpoint in the B stage and C stage, the blending ratio of the curing agent for epoxy resin (C) is an epoxy group derived from a methoxy group-containing silane-modified epoxy resin (A) and an epoxy group-containing synthetic rubber (B). The functional group having active hydrogen in the epoxy resin curing agent (C) is in the range of 0.5 to 1.2 equivalents per equivalent.Ru.
[0033]
As described above, in order to avoid the generation of bubbles in the C stage, it is important to adjust the residual ratio of volatile matter in the B stage, and it is preferable to use the sol-gel curing accelerator (D) in the composition of the present invention. Examples of the sol-gel curing accelerator (D) include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, and cerium. And metals such as boron, cadmium and manganese; oxides, organic acid salts, halides and methoxides of these metals. Among these, organic tin and organic acid tin are particularly preferable, and specifically, dibutyltin dilaurate, tin octylate and the like are effective. The amount of the sol-gel curing accelerator (D) used is preferably 0.1 to 5.0% by weight based on the curing residue of the epoxy resin composition. If it is less than 0.1%, the sol-gel curing reaction at the B stage is not completed, and if it exceeds 5%, the epoxy resin composition is thickened and the stability tends to be lowered.
[0034]
If necessary, a solvent can be used in the epoxy resin composition of the present invention. Examples of the solvent used in the epoxy resin composition of the present invention include ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone, esters such as ethyl acetate and butyl acetate, aromatics such as toluene and xylene, cellosolve acetate, Examples thereof include cellosolves such as methyl cellosolve acetate, ethers such as tetrahydrofuran and diethylene glycol dimethyl ether, alcohols such as isopropyl alcohol and n-butyl alcohol, and aprotic polar solvents such as dimethylformamide. Methyl ethyl ketone is most preferred for the same reason as selecting a solvent for producing the methoxy group-containing silane-modified epoxy resin (A). The blending ratio of the solvent is not particularly limited, and may be appropriately determined according to the use.
[0035]
The epoxy resin composition of the present invention has the above-mentioned various essential components, that is, methoxy group-containing silane-modified epoxy resin (A), epoxy group-containing synthetic rubber (B), and epoxy resin curing agent (C) as essential components, If necessary, it is prepared by blending a sol-gel curing accelerator (D) and a solvent.
[0036]
The composition of the epoxy resin composition can be appropriately adjusted according to its use, but is usually blended so that the weight in terms of silica in the cured product obtained by curing the epoxy resin composition is 3 to 40% by weight. It is preferable to do this. Here, the weight in terms of silica means the weight of silica obtained by subjecting the methoxysilane partial condensate (2) used in the methoxy group-containing silane-modified epoxy resin (A) contained in the epoxy resin composition to a sol-gel curing reaction. Say.
[0037]
The epoxy resin composition may contain a curing accelerator (different from the sol-gel curing accelerator (D)) for promoting the curing reaction between the epoxy resin and the curing agent. For example, tertiary amines such as 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2 -Imidazoles such as methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; Organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine; Tetraphenylphosphonium / tetraphenylborate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, etc. Such as boron salt can be mentioned. The curing accelerator is preferably used at a ratio of 0.1 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin.
[0038]
In the epoxy resin composition of the present invention, a filler, a release agent, a surface treatment agent, a flame retardant, a viscosity modifier, a plasticizer, an antibacterial agent, an antibacterial agent are included in the epoxy resin composition of the present invention, as long as the effects of the present invention are not impaired. A glaze, a leveling agent, an antifoaming agent, a coloring agent, a stabilizer, a coupling agent and the like may be blended.
[0039]
In order to obtain a cured product directly from the epoxy resin composition of the present invention, the epoxy resin composition is cured at room temperature to 250 ° C. The curing temperature is appropriately determined depending on the epoxy resin curing agent (C). When a phenol resin curing agent or a polycarboxylic acid curing agent is used as the curing agent (C), a sol-gel curing catalyst is used in combination with 0.1% or more in addition to the curing agent (C). Curing at ~ 250 ° C is preferred. When a polyamine curing agent is used, low temperature curing at room temperature to 100 ° C. is possible, but it is preferable to cure by using 0.3% or more of a highly active sol-gel curing catalyst such as tin octylate. This is because alcohol is generated in the sol-gel curing reaction of the methoxysilyl moiety, and thus the epoxy group ring-opening / crosslinking of the epoxy group in the methoxy group-containing silane-modified epoxy resin (A) and the epoxy resin curing agent (C) When the alcohol is generated after curing by reaction proceeds, foaming and cracks are generated. Therefore, it is necessary to adjust the sol-gel curing reaction rate by appropriately selecting a catalyst.
[0040]
In order to obtain a cured product from the epoxy resin composition of the present invention through a B stage, that is, a semi-cured product, as the epoxy curing agent (C) of the epoxy resin composition, a phenol resin curing agent and a polycarboxylic acid curing agent It is preferable to blend a tin-based sol-gel curing catalyst using a latent curing agent such as imidazole. In order to produce a semi-cured product using the epoxy resin composition, the solvent is preferably evaporated by heating at about 40 to 150 ° C., and the siloxane bond by sol-gel curing is 70% in the epoxy resin composition. Above, preferably 90% or more, the sol-gel curing reaction is allowed to proceed.
[0041]
Further, such a semi-cured product is completely cured at a temperature of usually 160 ° C. or higher and 250 ° C. or lower after thermoforming or thermocompression bonding to obtain a cured product.
[0042]
The epoxy resin composition can be used as a resin composition for electronic materials, a resin for electronic materials obtained by curing a resin composition for electronic materials, a coating agent composition, and the like.
[0043]
In order to obtain a prepreg for a printed circuit board from the resin composition for electronic materials of the present invention, for example, as described in JP-A-9-143286, an epoxy resin composition is impregnated into a reinforcing substrate and heated. Thus, a prepreg sheet can be obtained. What is necessary is just to harden | cure according to the hardening method which passes through said semi-hardened | cured material about the composition and preparation conditions of the said epoxy resin composition. Examples of the varnish solvent include polar solvents having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, ethyl cellosolve, dimethylformamide, methanol, ethanol, isopropyl alcohol, and these are preferable because they do not remain in the prepreg. The heating temperature is determined in consideration of the type of solvent used, and is preferably 40 to 150 ° C. In addition, the kind of reinforcement base material is not specifically limited, For example, various types, such as paper, a glass cloth, a glass nonwoven fabric, an aramid paper, an aramid cloth, a glass mat, a glass roving cloth, a liquid crystal polymer, can be illustrated. Further, the ratio of the resin component and the reinforcing substrate is not particularly limited, but it is usually preferable that the resin component in the prepreg is adjusted to 20 to 80% by weight.
[0044]
In order to obtain a copper-clad laminate from the resin composition for electronic materials of the present invention, as described in, for example, JP-A-5-86215 and JP-A-6-1000076, the above prepreg is added to 3-8. About 1 sheet is stacked, and copper foil is further stacked on the top and bottom, and thermocompression bonding is performed at 170 to 250 ° C. for 10 minutes to 3 hours under a pressure of 1 to 30 MPa.
[0045]
To obtain a printed wiring board or interposer from the prepreg and copper-clad laminate, the copper-clad laminate is resist-etched to form a circuit, and then the prepreg and copper foil are stacked to produce the copper-clad laminate. The film may be multilayered by thermocompression bonding under the same conditions.
[0046]
A method for obtaining an interlayer insulating material for a build-up substrate from the resin composition for electronic materials of the present invention is not particularly limited. For example, JP-B-4-6116, JP-A-7-304931, JP-A-8-64960, Various methods described in, for example, Kaihei 9-71762 and JP-A-9-298369 can be employed. More specifically, after applying the resin composition for electronic materials appropriately containing a filler or the like to a wiring board on which a circuit is formed by a known method such as a spray coating method, a curtain coating method, or a screen printing method, Curing is performed according to a method for obtaining a direct hybrid as follows. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable. As the roughening agent, at least one selected from an oxidizing agent, an alkali, and an organic solvent is used. Such operations can be sequentially repeated as desired, and the resin insulating layer and the conductor layer having a predetermined circuit pattern can be alternately built up and formed. However, the through hole portion is formed after the outermost resin insulating layer is formed. Moreover, the interlayer insulation material for buildup boards can also be produced using the B stage film (semi-cured material) obtained from the resin composition for electronic materials of the present invention. For example, on the wiring board on which the circuit is formed, the resin composition for electronic materials is semi-cured under the same conditions as described above, and then after drilling a predetermined through-hole portion or the like as necessary, A roughening treatment is performed with an agent to form a rough rough surface on the surface of the resin insulating layer and the through-hole portion. Next, the surface of the resin insulating layer thus roughened is subjected to metal plating in the same manner as described above, and then the resin composition for electronic material is coated again, and heat treatment is performed at 170 to 250 ° C. Such an operation can be sequentially repeated as desired, and a resin insulating layer and a conductor layer having a predetermined circuit pattern can be alternately built up and formed. Moreover, a roughened surface is formed by heat-pressing a copper foil with resin obtained by semi-curing the epoxy resin composition on a copper foil onto a wiring board on which a circuit is formed at 170 to 250 ° C. It is also possible to produce a build-up substrate by omitting this process.
[0047]
The resin composition for electronic materials of the present invention can be used as an electronic component sealant, and as an electronic component sealant, a mold-type sealant, a tape-type sealant, and a potting-type liquid sealant Various things are known. For example, when preparing a mold-type sealant from the resin composition for electronic materials of the present invention, the method is not particularly limited, but a method using a cured product powder obtained by sol-gel curing the resin composition is preferable. . For example, the epoxy resin composition of the present invention is prepared by adding a tin-based sol-gel curing catalyst to a methoxy group-containing silane-modified epoxy resin at 0.05 to 5% per resin component and, if necessary, an inorganic filler such as silica. There is a method in which the composition is cured at 100 to 200 ° C. on a Teflon (registered trademark) sheet, and the sol-gel cured product is pulverized by a pulverizer. Further, the resin composition is diluted with a solvent, adjusted to have a viscosity of 500 mPa · s or less at 25 ° C., and then sprayed to react with moisture in the air to obtain a powder of a sol-gel cured product. You can also. The solvent is the same as described above, and a solvent having a boiling point of 100 ° C. or less is particularly preferable. The novolak phenol resin, epoxy resin curing catalyst, and inorganic filler as an epoxy resin curing agent are usually mixed at a temperature of 80 to 170 ° C. for 30 to 300 seconds with the sol-gel cured product powder thus obtained. A kneading composition is obtained by kneading. The said composition for sealing agents is enclosed with a metal mold | die, and a semiconductor and an electronic component are sealed by carrying out transfer molding normally at 170-250 degreeC and 5-20 MPa. Since the use of the sealant is intended to extend the life of electronic components and semiconductors, low water absorption is the most important performance. In the production of the methoxy group-containing silane-modified epoxy resin of this patent, when a methyltrimethoxysilane partial condensate is used for the methoxysilane partial condensate (2), the cured product exhibits a low water absorption rate, which is preferable.
[0048]
When used as a tape-shaped sealant, a semi-cured sheet is prepared according to the above procedure using the epoxy resin composition of the present invention, which is blended with an inorganic filler such as silica as necessary, and a sealant tape. And This sealant tape is placed on a semiconductor chip, heated to 100 to 150 ° C., softened and molded, and then completely cured at 170 to 250 ° C.
[0049]
Furthermore, when used as a potting type liquid sealant, if necessary, the epoxy resin composition of the present invention containing an inorganic filler such as silica is applied onto a semiconductor chip or electronic component and directly cured. Good.
[0050]
The method of using the resin composition for electronic materials of the present invention as an underfill resin is not particularly limited. For example, Japanese Patent Application Laid-Open No. 9-266221 and “Plastics in the Electronics Field” (Industry Research Council, 1999, 27- 34)). More specifically, the epoxy resin composition of the present invention is injected into the gap between the semiconductor element with electrodes and the printed wiring board with solder during flip-chip mounting by a capillary flow method using a capillary phenomenon. The method of curing by the method of directly obtaining the hybrid body, and the semi-cured resin is formed on the semiconductor element in advance according to the procedure described above, and then the semiconductor element and the substrate are adhered with the semi-cured resin by heating, An underfill resin layer is formed by a compression flow method for complete curing. In this case, it is preferable to use the epoxy resin composition of the present invention in the form of a liquid resin composition containing no solvent. In particular, when the capillary flow method is used, the viscosity needs to be low, and the viscosity is preferably 5000 mPa · s or less. If the resin composition for electronic materials has a viscosity higher than this, it can be injected by heating to room temperature to 100 ° C. or less. The purpose of the underfill resin is to relieve stress around the solder caused by the difference in linear expansion between the semiconductor element and the substrate, and has a low linear expansion coefficient that is close to the linear expansion coefficient of the solder that is the interface joint. Insulating materials are preferred. Therefore, if the epoxy resin composition has a low viscosity, the coefficient of linear expansion can be further reduced by adding a filler such as silica.
[0051]
When the resin composition for electronic materials of the present invention is used as a thermosetting resist ink such as a solder resist, according to the methods described in, for example, JP-A-5-186567 and JP-A-8-307041 After the resist ink composition is obtained, the resist ink is cured by a method of obtaining a hybrid cured product directly after being applied on a printed board by a screen printing method. Preferably, as the resist ink composition, the resin composition for electronic materials includes, as necessary, vinyl monomers having an ethylenically unsaturated double bond, such as acrylic acid ester and methacrylic acid ester, and phthalocyanine blue. Add various pigments, fillers such as silica and alumina, leveling agents and the like.
[0052]
When the resin composition for electronic materials of the present invention is used as a semiconductor interlayer insulating material, for example, the method described in JP-A-6-85091 can be employed. Specifically, the resin composition is spin-coated on a semiconductor to obtain a hybrid cured product directly. When used for an interlayer insulating film, since it is required that the linear expansion coefficient of the cured product is particularly low, in the epoxy resin composition of the present invention, in the cured residue of the methoxy group-containing silane-modified epoxy resin (A) The Si content in terms of silica weight is preferably 30% or more.
[0053]
When the resin composition for electronic materials of the present invention is used as a conductive paste, for example, as described in JP-A-9-35530, conductive powder such as true spherical or flake shaped silver or nickel is insulated. Must be blended into the material. The content of the conductive powder is preferably 50 to 80% by weight from the viewpoint of conductivity and economy with respect to the conductive paste. When the content is less than 50% by weight, the resistance value tends to increase. When the content exceeds 80% by weight, there are disadvantages such as a decrease in adhesiveness and an increase in product price. The conductive paste is required to have a small specific resistance change after being exposed to severe conditions such as high temperature and high humidity. From the viewpoint of reducing the water absorption rate, a methyltrimethoxysilane partial condensate is used as the methoxysilane partial condensate (2) which is a component of the methoxy group-containing silane-modified epoxy resin (A) in the epoxy resin composition of the present invention. In particular, it is particularly preferable to use a novolak phenol resin as the epoxy resin curing agent.
[0054]
When producing a container (molded product) for storing electronic components such as an IC tray from the resin composition for electronic materials of the present invention, the semi-cured sheet and the molding intermediate material obtained by the above method were obtained. Thereafter, these are remelted at 60 to 150 ° C., placed in a mold, and molded under conditions of 150 to 250 ° C. and 1 to 30 MPa.
[0055]
When the resin composition for electronic materials of the present invention is used as an adhesive for printed circuit boards, for example, methods described in JP-A-5-51571 and JP-A-6-145628 can be applied. From the viewpoint of workability, an organic solvent, preferably one having a boiling point of less than 150 ° C. may be appropriately blended. Since the printed circuit board adhesive needs to be bonded to the copper foil through a semi-cured film, the epoxy resin curing agent used for this is a phenol resin curing agent, polycarboxylic acid curing agent, imidazole curing Latent curing agents such as agents are preferred. As a specific method of using the adhesive for printed circuit boards, a coating composition is applied on an insulating film such as polyimide, and a semi-cured film of about 5 to 50 μm is formed according to the above method. A laminated sheet can be obtained by stacking a copper foil on top of the laminate and laminating at 60 to 150 ° C., and heating and curing the laminate at 150 to 250 ° C.
[0056]
In particular, when used as an adhesive for a flexible printed wiring board or a tape automated bonding (TAB) tape, for example, the method described in JP-A-6-338681 can be preferably applied. In the same manner as the method for producing the flexible printed wiring board, a B-stage layer is produced so that the film thickness is about 10 to 15 μm, and a release protective film is laminated as necessary, whereby an adhesive for TAB A sticky tape is obtained. As the protective film, polyethylene, polypropylene, polyethylene terephthalate and the like are preferably used. A tape with an adhesive for TAB can also be produced by forming a B stage layer on the protective film and then laminating a heat resistant organic insulating film thereon. The tape with adhesive for TAB obtained in this way is used after removing the protective film and laminating it on a copper foil.
[0057]
The concentration and viscosity of the coating agent composition of the present invention can be appropriately adjusted with a solvent according to the intended use. As a solvent, the thing similar to what was used for manufacture of a methoxy group containing silane modified epoxy resin (A) can be used. In addition, the coating agent composition includes a filler, a release agent, a surface treatment agent, a flame retardant, a viscosity modifier, a plasticizer, an antibacterial agent, an antibacterial agent, as necessary, as long as the effects of the present invention are not impaired. A glaze, a leveling agent, an antifoaming agent, a coloring agent, a stabilizer, a coupling agent and the like may be blended.
[0058]
In addition, in order to obtain a cured film directly from the coating agent composition of the present invention, the above-described method for producing an epoxy resin-silica hybrid cured product can be employed as it is.
[0059]
The coating composition of the present invention comprises a sealer, a primer, a surface coating agent for a flooring agent, a coating material such as a hard coating agent for plastics, an anchor coating agent such as an anchor coating for plating and a metal deposition anchor coating, an electronic material, a liquid crystal plate It is suitable for a sealing agent for use in building materials and the like; an adhesive for printed circuit boards and building materials, etc., and a cured film can be easily formed by applying any of the above curing methods.
[0060]
Next, application examples of the coating agent composition of the present invention to various uses will be described later. The coating agent composition of the present invention is particularly useful as a paint (sealer) applied to the first layer of an inorganic substrate. Here, the inorganic substrate includes not only a ceramic substrate such as concrete, mortar, and glass but also a metal substrate such as iron, stainless steel, magnesium alloy, and zinc alloy. When the sealer is used outdoors, it is preferably cured by a method of obtaining the above-mentioned directly cured film using a polyamine curing agent that can be cured at room temperature because heat curing is difficult. On the other hand, when baking coating is possible, in addition to the above-mentioned curing agents for epoxy resins, phenolic resin-based, polycarboxylic acid-based curing agents, and imidazole-based curing agents are used. Obtainable. In particular, when importance is attached to the color tone of the cured film, a polycarboxylic acid-based curing agent is preferable. As a method of applying the paint to the substrate, any method such as brush coating, spray coating, roll coating, dip coating, etc. can be applied, and the viscosity is usually adjusted to about 5 to 100 μm by adjusting the viscosity with an organic solvent as necessary. It is applied to form a cured film. In addition, in order to improve rust prevention property etc., you may mix | blend various fillers with the said coating material. The type of the filler is not particularly limited, but coloring pigments such as titanium white, yellow iron oxide, and carbon black; extender pigments such as silica, talc, and precipitated barium; rust preventive pigments such as zinc white and aluminum phosphate It can be illustrated.
[0061]
When using the coating agent composition of the present invention as a primer, for example, a method for using a primer for flooring as described in JP-A-6-128353 can be applied. A coating composition containing a solvent having a boiling point of less than 150 ° C. is applied onto a base material such as concrete so that the cured film has a thickness of about 3 to 50 μm, and is allowed to stand at room temperature for 1 to 2 days to be cured. Since it is room temperature curing, it is preferable to use a polyamine curing agent as the curing agent for epoxy resin. The curing time can be determined in consideration of the pot life of the polyamine curing agent that is the curing agent. After the primer is cured, for example, an epoxy resin for flooring is applied according to a conventional method. Since the coating agent composition of the present invention has particularly good adhesion to an inorganic substrate such as concrete, it becomes a highly durable coating cured product that does not cause blistering.
[0062]
When applying the coating agent composition of the present invention to the surface coating of flooring, for example, methods described in JP-A-4-224858 and JP-A-6-128353 can be employed. That is, it applies to the concrete which primed the coating agent composition of this invention with the roller so that the film thickness of a cured film may be set to about 100-5000 micrometers, and it hardens at room temperature for 1 to 7 days. In the coating agent composition, a polyamine-based curing agent is an essential component as the curing agent for epoxy resin (C), but as other components, the filler and plasticizer used in the preparation of the sealer are appropriately blended. it can.
[0063]
When the coating agent composition of the present invention is used as a hard coating agent for plastics, the coating agent composition is applied onto a plastic substrate by a known method so that the thickness of the cured film is about 5 to 50 μm. What is necessary is just to harden | cure by the method of obtaining a cured film directly. Since the curing temperature needs to be set to be equal to or lower than the heat distortion temperature of the base plastic, it is preferable to cure at low temperature using a polyamine-based epoxy resin curing agent as the curing agent.
[0064]
When the coating agent composition of the present invention is used as an anchor coating agent, it is applied in the same manner as the above coating method so that the cured film has a thickness of about 2 to 100 μm on the substrate, and is directly cured. What is necessary is just to harden by the method of obtaining a film | membrane. When plating on the cured film, the surface is treated with a roughening agent, and the surface is washed with hot water to form irregularities and the metal is plated. As the plating method, electroless plating or electrolytic plating treatment is preferable, and as the roughening agent, at least one selected from sulfuric acid, dichromic acid, oxidizing agent, and alkali is used. Since the surface of the cured film obtained from the coating agent composition of the present invention is appropriately roughened by these roughening agents, it has excellent adhesion to the plating layer. When metal deposition is performed, a conventionally known metal or metal oxide such as silica, aluminum, or alumina may be deposited with the cured film facing upward.
[0065]
When the coating agent composition of the present invention is used as a building material sealing or a building material adhesive, for example, a method described in JP-A-10-204152 can be exemplified. That is, in order to prepare a sealing material for a building material or an adhesive, a filler or a plasticizer may be added to the methoxy group-containing silane-modified epoxy resin (A) and kneaded strongly using a known kneader. As the filler, organic or inorganic fillers of various shapes can be used, but it is preferable to select an acidic or neutral filler. Examples of the filler include fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide; wax stone clay, kaolin clay, calcined clay; or carbon black; Examples include calcium. In addition, the filler which shows basicity is not preferable because the sol-gel curing of the sealing agent is excessively accelerated and a sufficient pot life cannot be obtained. It is preferable that the compounding quantity of a filler is 50-150 weight part with respect to 100 weight part of solid residues of a methoxy group containing silane modified epoxy resin (A) from the physical property side of hardened | cured material. The epoxy resin curing agent to be used is preferably a polyamine curing agent capable of curing at room temperature. From the viewpoint of workability, it is preferable to use a plasticizer such as dioctyl phthalate or dibutyl phthalate so that the viscosity of the sealing or adhesive for building materials is about 1000 to 100,000 mPa · s at 25 ° C.
[0066]
【The invention's effect】
The epoxy resin composition of the present invention is excellent in heat resistance, processability, etc., and since the sol-gel curing reaction proceeds rapidly, the generation of volatile matter at the C stage can be suppressed. Even when the epoxy resin composition of the present invention is a cured product, it has moderate flexibility and thus can prevent cracking and the like. Moreover, by using the resin composition for electronic materials of the present invention, it is possible to obtain an electronic material that is excellent in heat resistance, insulation, and adhesion, and that does not cause voids, cracks, or the like. Furthermore, the coating agent composition of the present invention is excellent in heat resistance, toughness, adhesion, acid resistance, and scratch resistance, and can obtain a transparent cured film.
[0067]
【Example】
Next, examples of the present invention will be given, but the present invention is not limited to these examples.
[0068]
Synthesis Example 1 (Production of epoxy group-containing synthetic rubber (B))
A terminal carboxyl group-containing butadiene nitrile rubber (manufactured by Ube Industries, Ltd., trade name, “HYCARCTBN 1300 × 31”) number average molecular weight 3500, bound acrylonitrile content 10 in a reactor equipped with a stirrer, condenser, thermometer, nitrogen inlet %) Was added as a diepoxy compound and 29 g of a bisphenol A type liquid epoxy resin (trade name “Epicoat 828”, Yuka Shell Epoxy Co., Ltd., epoxy equivalent 190 g / eq) was charged and reacted at 150 ° C. for 3 hours. After the reaction, the reaction mixture was cooled to 80 ° C. or lower, and 57 g of MEK was added to obtain an epoxy group-containing synthetic rubber (B-1) solution.
[0069]
Synthesis Example 2 (Production of epoxy group-containing synthetic rubber (B))
The same operation was performed with the same charge as in Synthesis 1 except that terminal carboxyl group-containing butadiene nitrile rubber (trade name, “HYCAR CTBN 1300 × 8”, number average molecular weight 3500, bound acrylonitrile content 17%, manufactured by Ube Industries, Ltd.) was used. And an epoxy group-containing synthetic rubber (B-2) solution was obtained.
[0070]
Example 1 (Preparation of epoxy resin composition)
To a mixture of 4.2 g of the epoxy group-containing synthetic rubber (B-1) solution obtained in Synthesis Example 1 and 1.1 g of the epoxy group-containing synthetic rubber (B-2) solution obtained in Synthesis Example 2, Silane-modified epoxy resin (A-1) methyl ethyl ketone solution (Arakawa Chemical Industries, Ltd., trade name “COMPOCERAN E103”) Average epoxy equivalent of 480 g / eq of bisphenol type epoxy resin (1), methoxysilane partial condensate (2) Methyltrimethoxysilane (CH_ThreeSi (OCH_Three)_Three), The average number of Si is 3.5, the weight in terms of silica / the weight (weight ratio) of the bisphenol type epoxy resin (1) is 0.54, the epoxy equivalent is 1400 g / eq, and the curing residue is 50%). 10 g, 1.7 g of a 50% MEK solution of orthocresol novolak resin (trade name “OCN5”, hydroxyl group equivalent 120 g / eq, manufactured by Asahi Organic Materials Co., Ltd.) as a curing agent for epoxy resin, sol-gel curing accelerator 0.2 g of stannous octylate (trade name “STANOCTO”, manufactured by Yoshitomi Fine Chemical Co., Ltd.), 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., product) as a curing accelerator for epoxy resin The epoxy resin composition was prepared by adding 0.02 g of the name “CURESOL 2E4MZ”) and 3 g of methyl ethyl ketone as a solvent and uniformly dissolving the mixture. The amount of the epoxy group-containing synthetic rubber (B) used was 79 parts by weight with respect to 100 parts by weight of the cured residue of the methoxy group-containing silane-modified epoxy resin (A). The functional group having active hydrogen in the curing agent for epoxy resin (C) is 0.8 relative to 1 equivalent of epoxy group derived from the methoxy group-containing silane-modified epoxy resin (A) and the epoxy group-containing synthetic rubber (B). Equivalent.
[0071]
Example 2 (Preparation of epoxy resin composition)
The amount of the epoxy group-containing synthetic rubber (B-1) solution obtained in Synthesis Example 1 was 4.9 g, and the amount of the epoxy group-containing synthetic rubber (B-2) solution obtained in Synthesis Example 2 was 0.00. Except having changed to 3g, the same operation was performed by the same preparation amount as Example 1, and the epoxy resin composition was prepared. The amount of the epoxy group-containing synthetic rubber (B) used was 79 parts by weight with respect to 100 parts by weight of the cured residue of the methoxy group-containing silane-modified epoxy resin (A). The functional group having active hydrogen in the curing agent for epoxy resin (C) is 0.8 relative to 1 equivalent of epoxy group derived from the methoxy group-containing silane-modified epoxy resin (A) and the epoxy group-containing synthetic rubber (B). Equivalent.
[0072]
Example 3 (Preparation of epoxy resin composition)
8.6 g of the epoxy group-containing synthetic rubber (B-1) solution obtained in Synthesis Example 1, 10 g of Composelan E103, and a phenol novolac resin (Arakawa Chemical Industries, Ltd., trade name “TAMANOR” as a curing agent for epoxy resin) 759 ", hydroxyl group equivalent 106 g / eq) of 50% MEK solution 2.5 g, stanocto 0.2 g, cure sol 2E4MZ 0.02 g, and MEK 5 g were dissolved uniformly to prepare an epoxy resin composition. The amount of the epoxy group-containing synthetic rubber (B) used was 128 parts by weight with respect to 100 parts by weight of the cured residue of the methoxy group-containing silane-modified epoxy resin (A). The functional group having active hydrogen in the curing agent for epoxy resin (C) is 1.2 with respect to 1 equivalent of epoxy group derived from the methoxy group-containing silane-modified epoxy resin (A) and the epoxy group-containing synthetic rubber (B). Equivalent.
[0073]
Comparative Example 1 (Preparation of epoxy resin composition)
10 g of 50% MEK solution of bisphenol type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., trade name “Epicoat 1001”, epoxy equivalent 480 g / eq), 1.8 g of 50% MEK solution of Tamanol 759, 0 stanoct .2 g and 0.02 g of Curazole 2E4MZ were added and dissolved uniformly to prepare an epoxy resin composition.
[0074]
Comparative Example 2 (Preparation of epoxy resin composition)
An epoxy resin composition was prepared by uniformly dissolving 10 g of Composelan E103, 1.2 g of a 50% MEK solution of Tamorol 759, 0.2 g of stanocto, and 0.02 g of Curazole 2E4MZ.
[0075]
Comparative Example 3 (Preparation of epoxy resin composition)
To 5.4 g of the epoxy group-containing synthetic rubber (B-1) solution obtained in Synthesis Example 1, 10 g of 50% MEK solution of Epicoat 1001, 2.1 g of 50% MEK solution of Tamorol 759, and 0.2 g of stanoct Then, 0.02 g of Curazole 2E4MZ was added and dissolved uniformly to prepare an epoxy resin composition.
[0076]
<Evaluation of cured product>
(Evaluation of heat resistance by measuring viscoelasticity)
Each resin composition obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was poured into an aluminum cup, cured at 100 ° C. for 30 minutes to form a semi-cured product, and then cured at 200 ° C. for 2 hours to thicken the resin composition. A fully cured product film having a thickness of 300 μm was prepared. The obtained cured film was cut into 6 mm × 20 mm, and dynamically using a viscoelasticity measuring device (manufactured by Rheology, trade name “DVE-V4”, measurement condition amplitude 5 μm, vibration frequency 10 Hz, slope 5 ° C./min). The storage elastic modulus E ′ and tan δ were measured to evaluate the heat resistance. FIG. 1 shows the measurement result of E ′, and FIG. 2 shows the measurement result of tan δ.
[0077]
As is clear from FIG. 1 and FIG. 2, in Examples 1 to 3, the cured film (cured epoxy resin) had a glass transition point derived from the synthetic rubber (B) around −40 ° C. as in Comparative Example 3. Therefore, the storage modulus at room temperature is low, and the Tg observed at room temperature or higher is higher than that of the cured products of Comparative Example 1 and Comparative Example 3 as in the cured product of Comparative Example 2. It shows heat resistance. Further, tan δ around Tg (140 ° C.) of the cured product of Comparative Example 2 is decreased in any of the Examples, and this also indicates high heat resistance.
[0078]
(Evaluation of heat resistance by thermal weight loss)
Using each cured film prepared at the time of measuring viscoelasticity, heat was measured with a differential heat / thermogravimetric simultaneous measurement device (manufactured by Seiko Instruments Inc., trade name “TG / DTA220”, measurement condition: slope 10 ° C./min). The weight loss was measured. The results are shown in Table 1.
[0079]
[Table 1]

[0080]
As is clear from Table 1, the temperature at the time of 10% weight loss in Examples 1 to 3 is sufficiently high as in Comparative Example 2, and no deterioration in the thermal decomposition resistance due to the rubber component is observed.
[0081]
(Adhesion)
Using the bar coater # 60 for each resin composition obtained in Examples 1 to 3 and Comparative Examples 1 to 3 on a rolled copper plate (trade name “Copper plate JISH3100 (C1100P)” manufactured by Nippon Test Panel Co., Ltd.). The coated copper plate was cured at 100 ° C. for 30 minutes to form a semi-cured product, and then cured at 200 ° C. for 1 hour to obtain a copper plate coated with 40 μm of the cured product film. Using the obtained copper plate, a Goban eyes cellophane tape peeling test was conducted according to a JIS K-5400 general test method. The results are shown in Table 2.
[0082]
[Table 2]

[0083]
(Insulation)
Using the cured films obtained in Example 1 and Comparative Example 1, the dielectric constant and dielectric loss were measured at a frequency of 1 MHz. The results are shown in Table 3.
[0084]
[Table 3]

[0085]
(Linear expansion coefficient)
Using the cured films obtained in Examples 1 and 3, the linear expansion coefficients of 40 to 100 ° C. and 150 to 180 ° C. were measured with a thermal stress strain measuring device (trade name TMA120C, manufactured by Seiko Denshi Kogyo Co., Ltd.). did. The results are shown in Table 4.
[0086]
[Table 4]

[0087]
<Evaluation of semi-cured product>
Each resin composition obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was poured into an aluminum cup and cured at 100 ° C. for 30 minutes to obtain a 100 μm semi-cured film (B stage).
[0088]
(Measurement of volatile content)
The weight after curing for 30 minutes at 100 ° C. (weight of semi-cured material before processing) was measured, and further cured at 200 ° C. for 1 hour (C stage), and the weight at this time (complete curing after processing) The weight of the product was measured, and the weight loss rate was calculated. The results are shown in Table 5.
[0089]
[Expression 1]

[0090]
(Processability evaluation)
The semi-cured product (B stage) was placed on a hot plate at 100 ° C. and evaluated whether it could be reflowed. The results are shown in Table 5.
○: Reflowable
×: Reflowable
[0091]
[Table 5]

[0092]
From Table 5, it can be seen that the epoxy resin compositions of the examples all have a lower weight loss rate than that of Comparative Example 2, and are excellent in dimensional stability during the production of a completely cured product.
[0093]
(Mechanical strength)
A semi-cured product is cut out with dumbbell No. 1 and stretched at a pulling speed of 5 cm / min using a Tensilon tester (Orientec Co., Ltd., product name UCT-500). Elongation and strength at break were measured. A tensile test was performed three times at 25 ° C. in the same manner, and the average value is shown in Table 6.
[0094]
[Table 6]

[0095]
As is clear from Table 6, the semi-cured product of the example has a low elastic modulus and a high elongation rate, and therefore has high resistance to deformation such as bending and tension. Moreover, since the breaking strength is high, it can be said that it is a tough film.
[0096]
<Preparation of prepreg and copper-clad laminate>
After impregnating the epoxy resin composition obtained in Examples 1 and 3 and Comparative Examples 1 and 2 into a glass woven fabric having a thickness of 0.10 mm so that the resin content is about 40%, the resin composition was 100 ° C. for 15 minutes. It dried and hardened and produced the prepreg. Three prepregs and 18 μm thick copper foil were stacked on both sides thereof, and heated and pressed at 210 ° C. and 10 MPa for 2 hours to prepare a double-sided copper-clad laminate.
[0097]
When the epoxy resin composition of Comparative Example 2 was used, foaming was observed when heated at 210 ° C., and the copper foil of the copper-clad laminate was peeled off, but there was no problem with the other, and the copper-clad laminate Was able to be made.
[0098]
(Peeling strength of copper foil)
It measured based on JIS C-6481. The results are shown in Table 7.
[0099]
[Table 7]

[0100]
As is clear from Table 7, the copper-clad laminate of the present invention is excellent in adhesion, and is found to be optimal for the production of multilayer printed wiring boards as well as ordinary printed wiring boards.
[0101]
(Viscoelasticity of copper-clad laminate)
The viscoelasticity measurement was performed under the same conditions as the viscoelasticity measurement of the cured product after peeling off the copper foil of the double-sided copper-clad laminate produced using the epoxy resin composition obtained in Examples 1 and 3. The measurement result of E ′ is shown in FIG.
[0102]
As is apparent from FIG. 3, the epoxy resin compositions obtained in Examples 1 and 3 have a high storage elastic modulus at high temperatures and excellent heat resistance even in a closed state in which both surfaces are covered with copper foil. I understand that.
[0103]
<Production of interlayer insulation film for build-up substrate and build-up substrate>
The epoxy resin compositions used in Examples 1 and 3 and Comparative Examples 1 and 2 were applied on a peeled PET (polyethylene terephthalate) film (SG-1 manufactured by Panac Co., Ltd.) using a roll coater, and the coating was applied at 15 ° C. at 15 ° C. Minutes, dried and cured to produce a semi-cured resin (dry film) film thickness of 100 μm with a release film. These dry films were thermocompression-bonded on the above copper-clad laminate at 120 ° C. for 10 minutes at 6 MPa, then returned to room temperature, the release film was removed, and cured at 200 ° C. for 2 hours. At this time, the dry film using the epoxy resin composition of Comparative Example 2 was severely foamed at the time of curing and cracks were generated, but good laminates were obtained from Examples and Comparative Example 1. Further, these laminates were desmeared with a potassium permanganate aqueous solution, then treated with a palladium catalyst solution, and electroless copper plating was performed. Furthermore, 0.5 μm thick electrolytic copper plating was performed to obtain a build-up printed circuit board.
[0104]
(Hygroscopic solder heat resistance test)
Moisture absorption conditions: pressure cooker treatment, 125 ° C., 230 kPa, 30 minutes
Test conditions: A case where n = 5 and all the test pieces did not bulge at 280 ° C. for 120 seconds was evaluated as “◯”, and a case where the bulge occurred was evaluated as “X”. The results are shown in Table 8.
[0105]
(Peel strength)
The peel strength between the plated copper and the insulating substrate was measured according to JIS C-6481. The results are shown in Table 8.
[0106]
[Table 8]

[0107]
<Build-up board interlayer insulation film (by a method using a resin-coated copper foil), build-up board production>
The thickness after curing the epoxy resin compositions of Examples 1 and 3 and Comparative Example 2 on an electrolytic copper foil with a thickness of 18 μm (trade name “F2-WS” manufactured by Furukawa Electric Co., Ltd.) is 40 μm. And then dried and cured at 100 ° C. for 15 minutes to produce a semi-cured resin-coated copper foil. The resin-coated copper foil is overlaid on both surfaces so that the conductor pattern of the cleaned double-sided printed wiring board is covered so that the resin surface is in contact with the circuit surface, and heated and pressed at 210 ° C. and 6 MPa for 120 minutes to A build-up substrate having an insulating film was produced. In the case of using the epoxy resin composition of Comparative Example 2, foaming occurred at 210 ° C. and delamination occurred, but other than that, a high heat resistant build-up substrate interlayer insulating film layer could be produced without any problem.
[0108]
<Preparation of sealant-compression flow method>
The epoxy resin composition obtained in Examples 1 and 3 was applied to a 1 cm square so as to have a thickness of 60 μm on a single-sided printed wiring board compatible with Philip chip mounting. After drying and curing at 10 ° C. for 10 minutes, a glass substrate with a semi-cured resin was produced. This printed circuit board with semi-cured resin is placed in an oven heated to 110 ° C. for 10 minutes, and at the same temperature, a 370 μm thick, 1 cm square silicon chip is placed on the semi-cured resin, and a load of 300 g is applied to the bumps of the circuit board. And the electrode of the chip were brought into contact with each other, and then completely cured at 210 ° C. for 1 hour to prepare a cured sealant layer. Using Examples 1 and 3, a high heat-resistant sealant layer could be produced without any problem.
[0109]
<Preparation of conductive paste>
To 120 g of the epoxy resin composition obtained in Example 3, 160 g of flaky silver powder having an average particle diameter of 12 μm and an aspect ratio of 8 (manufactured by Tokuru Chemical Laboratory Co., Ltd.), an average particle diameter of 10 μm, and an aspect ratio of 60 g of flake nickel powder of No. 9 (trade name “NI110104”, manufactured by High-Purity Chemical Co., Ltd.) was added, stirred until uniform, and then uniformly dispersed with three rolls to obtain a conductive paste. The obtained conductive paste was screen-printed on a paper phenol substrate having a thickness of 1.6 mm, and then heat-cured at 200 ° C. for 1 hour. As a result of measuring the specific resistance of the obtained wiring board, the specific resistance value was 100.5 μΩ · m.
[0110]
<Production of molded product>
The epoxy resin composition of Example 1 was poured into a fluororesin-coated container (length × width × depth = 10 cm × 10 cm × 1.5 cm) and left at 80 ° C. for 30 minutes and 130 ° C. for 30 minutes. Sol-gel curing was performed to obtain a rubber-like semi-cured sheet having a film thickness of 300 μm. The obtained semi-cured sheet was flexible (the maximum elongation was about 40%) and could be molded at 70 ° C. or higher.
Five sheets of this semi-cured product were stacked and press-molded at 200 ° C. and 10 MPa to obtain a highly heat-resistant plate-shaped product with no particular problems.
[0111]
<Adhesive adjustment>
The epoxy resin compositions of Examples 1 and 3 and Comparative Example 2 were applied onto a polyimide film (manufactured by Toray DuPont, “Kapton H”) with a bar coater so that the film thickness after drying was 20 μm. The adhesive layer was semi-cured by drying at 110 ° C. for 5 minutes. A copper foil was layered on this adhesive layer, laminated at 110 ° C., and then heat-cured (C-staged) at 200 ° C. for 3 hours to produce a flexible printed board.
[0112]
(Heat resistance, adhesiveness)
Using the test plate obtained above, the adhesive performance was evaluated by the following method. Table 9 shows the evaluation results.
(1) Peel strength
The obtained test plate was fixed, the copper foil was peeled off at a speed of 50 mm / min in the 90 ° direction, and the strength was measured (based on JIS C 6481).
(2) Solder heat resistance
The obtained test plate was floated in a flow solder bath for 30 seconds, and then the maximum temperature at which swelling and peeling did not occur was measured (according to JIS C 6481).
[0113]
[Table 9]

[0114]
As is apparent from Table 9, the printed wiring board using the adhesive for printed wiring boards of the present invention has higher heat resistance and adhesion to copper foil than conventional printed wiring boards using epoxy adhesives. It is understood that it is excellent.
[0115]
Example 4 (Preparation of epoxy resin composition)
To 5.5 g of the epoxy group-containing synthetic rubber (B-2) solution obtained in Synthesis Example 2, 10 g of Composelan E104 and 4-methylhexahydrophthalic anhydride (Shin Nippon) as an acid anhydride as a curing agent for epoxy resin 1.4 g of Rika Co., Ltd., trade name “Licacid MH700”, acid anhydride equivalent 164 g / eq), 0.2 g of stanoct, 0.02 g of Curazole 2E4MZ, 4.5 g of MEK, and uniformly dissolved. An epoxy resin composition was prepared. The amount of the epoxy group-containing synthetic rubber (B) used was 83 parts by weight with respect to 100 parts by weight of the cured residue of the methoxy group-containing silane-modified epoxy resin (A). The functional group having active hydrogen in the curing agent for epoxy resin (C) is 1 equivalent to 1 equivalent of epoxy group derived from the methoxy group-containing silane-modified epoxy resin (A) and the epoxy group-containing synthetic rubber (B). there were.
[0116]
Comparative Example 4 (Preparation of epoxy resin composition)
An epoxy resin composition was prepared by uniformly dissolving 10 g of 50% MEK solution of Epicoat 1001 by adding 1.7 g of Ricacid MH700, 0.1 g of stanoct, 0.01 g of Curazole 2E4MZ, and 2 g of MEK.
[0117]
<Preparation of coating film>
The glass plate and mortar of Example 4 and Comparative Example 4 were applied to a film thickness of 20 μm and cured at 150 ° C. for 3 hours.
[0118]
<Heat resistant adhesion>
The adhesion after each of the coated plates prepared above was left at 150 ° C. for 8 hours was evaluated.
A gobang eyes cellophane tape peeling test was conducted according to the JIS K-5400 general test method. The results are shown in Table 10.
[0119]
[Table 10]

(1) Glass plate (JIS R3202-85)
(2) Mortar (JIS R5201-92)
[Brief description of the drawings]
1 is a measurement result of dynamic storage elastic modulus E ′ of cured films obtained in Examples 1 to 3 and Comparative Examples 1 to 3. FIG.
FIG. 2 is a measurement result of tan δ of cured films obtained in Examples 1 to 3 and Comparative Examples 1 to 3.
FIG. 3 is a measurement result of a dynamic storage elastic modulus E ′ of a double-sided copper-clad laminate produced by using the epoxy resin composition obtained in Examples 1 and 3 after peeling off the copper foil.

Claims (15)

Obtained by dealcoholizing a bisphenol-type epoxy resin (1) and a partial condensate (2) of methyltrimethoxysilane represented by the following general formula (wherein the average number of repeating units n is 3 to 12). Methoxy group-containing silane-modified epoxy resin (A), butadiene nitrile rubber (B) obtained by epoxy-modifying molecular ends, and epoxy selected from phenol resin-based curing agents, polyamine-based curing agents, and polycarboxylic acid-based curing agents resin curing agent (C) Tona is, and the blending ratio of the butadiene nitrile rubber obtained a molecular terminal and an epoxy-modified (B) is cured residue 100 parts by weight of a methoxy group-containing silane-modified epoxy resin (a) 30 to 150 parts by weight with respect to the epoxy resin curing agent (C), The functional group having active hydrogen in the curing agent for epoxy resin (C) is equal to 0.1 equivalent to 1 equivalent of the epoxy group derived from the butadiene nitrile rubber (B) obtained by epoxy-modifying the xy resin (A) and the molecular terminal. The epoxy resin composition which is 5-1.2 equivalent .

The epoxy resin composition according to claim 1, wherein the epoxy resin curing agent (C) is a phenol resin curing agent. The epoxy resin composition according to claim 1, wherein the epoxy resin curing agent (C) is a polycarboxylic acid curing agent. Furthermore, the epoxy resin composition in any one of Claims 1-3 formed by mix | blending a sol-gel hardening accelerator (D). The epoxy resin composition according to any one of claims 1 to 4, wherein the bisphenol-type epoxy resin (1) is a bisphenol-type epoxy resin having an average epoxy equivalent of 350 to 1000 g / eq. The methoxy group-containing silane-modified epoxy resin (A) is 0.25 to 1.2 in terms of silica weight of methoxysilane partial condensate (2) / weight of bisphenol type epoxy resin (1) (weight ratio). The epoxy resin composition in any one of 1-5 . The epoxy resin composition according to any one of claims 1 to 6 carbon average molecular weight of the epoxy group-containing synthetic rubber (B) is 2,000 to 10,000. Claim 1-7 sol 40 to 150 ° C. The epoxy resin composition according to any one of the - cured product obtained by cured gel. A cured product obtained by completely curing the epoxy resin composition according to any one of claims 1 to 7 at room temperature to 250 ° C. Electronic material resin composition containing an epoxy resin composition according to any one of claims 1-7. Resin composition for prepreg for printed circuit board, resin composition for copper-clad laminate for printed circuit board, coating agent for interlayer insulation material for build-up printed circuit board, resin composition for semiconductor interlayer insulation film, sealing agent for electronic parts A group consisting of a resin composition, a resin composition for an encapsulant for semiconductor chips, a cured resin for underfill, a resist ink, a conductive paste, a resin composition for molded electronic component storage, and a composition for anisotropic conductive film The resin composition for electronic materials according to claim 10 , which is used for at least one application selected from the group consisting of: A prepreg for a printed circuit board, a copper-clad laminate for a printed circuit board, a printed wiring board, an interposer, an interlayer insulating material for a build-up printed circuit board, and a semiconductor obtained by curing the resin composition for an electronic material according to claim 10 Interlayer insulation film, electronic component sealant, semiconductor chip sealant, cured underfill resin, cured resist ink, cured conductive paste, molded electronic component storage, anisotropic conductive film and printed circuit board A resin for electronic materials used for at least one application selected from the group consisting of adhesives for use. The coating composition containing the epoxy resin composition according to any one of claims 1-7. The coating composition according to claim 13 , which is used for at least one application selected from the group consisting of a sealer, a primer, a hard coat for plastic, an anchor coat agent, a sealant and an adhesive. The coating agent composition according to claim 13 or 14 is applied on an adherend (A) and sol-gel cured at 40 to 150 ° C to obtain a semi-cured film, and then deposited on the semi-cured film. A method for producing a cured coating agent film in which the body (B) is stacked and then completely cured at 150 to 250 ° C.

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