JP3807139B2 - Manufacturing method of electrical and electronic parts - Google Patents

Description

（Ｍはルテニウム又はオスミウムを示し、Ｘ及びＸ１はそれぞれ独立にアニオン性配位子を示し、Ｌ及びＬ１はそれぞれ独立に中性の電子供与基を示し、Ｑ及びＱ１はそれぞれ独立に水素、アルキル基、アルケニル基又は芳香族基を示し、アルキル基、アルケニル基又は芳香族基は置換基を有していてもよい。）
【００１３】
【化５】

（Ｍはルテニウム又はオスミウムを示し、Ｘ及びＸ１はそれぞれ独立にアニオン性配位子を示し、Ｌ及びＬ１はそれぞれ独立に中性の電子供与基を示し、Ｑ及びＱ１はそれぞれ独立に水素、アルキル基、アルケニル基又は芳香族基を示し、アルキル基、アルケニル基又は芳香族基は置換基を有していてもよい。）
【００１４】
【化６】

（Ｍはルテニウム又はオスミウムを示し、Ｘ及びＸ１はそれぞれ独立にアニオン性配位子を示し、Ｌ及びＬ１はそれぞれ独立に中性の電子供与基を示し、Ｒ１及びＲ２はそれぞれ独立に炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、炭素数２〜１８のアルキニル基、アリール基、炭素数１〜１８のカルボキシレート基、炭素数１〜１８のアルコキシ基、炭素数２〜１８のアルケニルオキシ基、炭素数２〜１８のアルキニルオキシ基、炭素数２〜１８のアリルオキシ基、炭素数２〜１８のアルコキシカルボニル、炭素数１〜１８のアルキルチオ基、炭素数１〜１８のアルキルスルホニル基又は炭素数１〜１８のアルキルスルフィニル基を示し、Ｒ３は水素、アリール基又は炭素数１〜１８のアルキル基を示す。）
電気・電子部品は、実質的に酸素の存在下に成形されることができる。
電気・電子部品として、磁性体の中心コア、その外側に巻かれた一次コイル、二次コイル、その外側に配設された磁性体の外部コアを備えたイグニッションコイルを封止することができる。
【００１５】
【発明の実施の形態】
本発明の電気・電子部品は、２３℃における粘度が３ポアズ未満の重合性液状物で、かつＪＩＳ−Ｋ−７２０３に規定される２３℃における曲げ弾性率が５００ＭＰａ以下の低弾性率樹脂が封止用樹脂として用いられる。
上記重合性液状物の粘度は３ポアズ未満であるが、好ましくは０．０５ポアズ〜２．０ポアズである。フライバックトランスやイグニッションコイルなどの電気・電子部品の場合、重合性液状物の粘度が３ポアズを越えると巻線コイル内部への含浸性が悪くなり、未充填部分が発生して絶縁性が低下することが見い出された。また、同様に粘度が３ポアズを超える重合性液状物をＤＩＰに代表される半導体素子封止材として用いた場合、チップとリードフレーム、ポリイミドフィルムやセラミックなどの基板との接続配線を切断してしまうことが見い出された。封止用樹脂の曲げ弾性率は５００ＭＰａ以下であるが、好ましくは３００ＭＰａ以下さらに好ましくは１００ＭＰａ以下である。５００ＭＰａを超えると剥離やクラックが発生しやすくなる。
【００１６】
上記の特性をもつ封止用樹脂の種類は特に制約されない。例えばエポキシ樹脂、ウレタン樹脂、シリコーン樹脂、アクリル樹脂およびメタクリル樹脂、ポリエステル樹脂、フェノール樹脂、オレフィン系樹脂など、２３℃で液状であり、３ポアズ未満の重合性液状物であればよい。好ましくは、アクリル樹脂およびメタクリル樹脂、ポリエステル樹脂、オレフィン系樹脂である。特に好ましくは電気特性が優れる点からオレフィン系樹脂である。
【００１７】
本発明の電気・電子部品に用いられる樹脂のガラス転移温度は８０℃以下が好ましく、更に好ましくは５０℃以下、より好ましくは２５℃以下とされる。ガラス転移温度が８０℃を超えると、封止用樹脂の内部にクラックが発生しやすくなる。また同様の理由から、樹脂の線膨張係数は１００ｐｐｍ以上が好ましい。さらに、封止用樹脂の吸水率は２３℃で２４時間水浸漬時に０．１％未満が好ましい。吸水率が０．１％以上では、絶縁性や耐はんだリフロー性が低下する傾向にある。また電気・電子部品の高密度化、高集積化に伴い、電磁波の相互干渉がないよう、樹脂の誘電率は２．０〜３．０が好ましく、より好ましくは２．０〜２．９である。
【００１８】
本発明の電気・電子部品に用いられる封止用樹脂には、物性、外観、成形性を考慮し、必要に応じて充填材、改質剤、重合速度調節剤、発泡剤、消泡剤、着色剤、安定化剤、接着性付与剤、難燃剤、カップリング剤および有機過酸化物などを任意に添加することができる。
【００１９】
本発明で用いられる充填材とは、例えば溶融シリカ、結晶シリカ、珪砂、炭酸カルシウム、水酸化アルミニウム、酸化マグネシウム、クレーなどの無機系充填材と木粉、ポリエステル、シリコーン、ポリスチレンアクリロニトリル−ブタジエン−スチレン（ＡＢＳ）などのビーズ状の有機系充填材が挙げられる。この中で、電気特性および熱伝導性の点からシリカおよび水酸化アルミニウムが好ましい。この市販品としてはＣＲＴ−ＡＡ、ＣＲＴ−Ｄ、ＲＤ−８（（株）龍森製 商品名）、ＣＯＸ−３１（（株）マイクロ製商品名）、Ｃ−３０３Ｈ、Ｃ−３１５Ｈ、Ｃ−３０８（住友化学工業（株）製商品名）、ＳＬ−７００（竹原化学工業（株）製商品名）などが挙げられる。これら無機充填材の配合量は樹脂中０〜９５重量％が好ましく、より好ましくは１０〜９５重量％、さらにより好ましくは３０〜９５重量％である。配合量が９５重量％を超えると樹脂の誘電率が３．０を越えてしまうため、電気的特性が低下し易い。さらに好ましくは３０〜７５重量％とされる。粒径、形状、品位などは電気・電子部品の用途により、適宜決めることができるが、平均粒径は０．１〜１００μｍの間のものが好ましく、特に好ましくは１〜５０μｍのものである。これらの平均粒径の異なるものを組み合た方が細密充填性および流動性を向上できる。さらに、無機充填材の形状は球状であることが好ましい。
【００２０】
また、ミルドガラス、カットファイバー、マイクロファイバー、マイクロバルーン、鱗片状ガラス粉、炭素繊維、アラミド繊維などの無機・有機繊維状充填材も挙げられ、これらを併用することもできる。目的に応じ、適宜、アスペクト比や形状を選ぶ。これら繊維状充填材の配合量は低弾性率樹脂１００重量部に対し０〜２０重量部が好ましく、より好ましくは０〜１０重量部である。
【００２１】
本発明で用いられる改質剤としては、例えばエラストマー、天然ゴム、ブタジエン系ゴムおよびスチレンーブタジエン共重合体（ＳＢＲ）、スチレンーブタジエンースチレンブロック共重合体（ＳＢＳ）、スチレン−マレイン酸共重合体、エチレン−酢酸ビニル共重合体などの共重合体、ポリメタクリル酸メチル、ポリ酢酸ビニル、ポリスチレンなどの熱可塑性樹脂などが挙げられる。また、これらの共重合体および熱可塑性樹脂はエステル化されていても良く、極性基がグラフトされていてもよい。また、エポキシ樹脂、ウレタン樹脂、ポリエステル樹脂、シリコーン樹脂、フェノール樹脂、ポリイミド樹脂、ポリアミド樹脂、ポリアミドイミド樹脂およびこれらの誘導体を配合し物性を改良することもできる。さらに、例えばエポキシとノルボルネンモノカルボキシリックアシッドを反応させて得られる化合物、イソシアネート化合物とノルボルネン−オールを反応させて得られる化合物、ハイミック酸変性ポリエステル、石油樹脂なども挙げられる。
【００２２】
石油樹脂には、エチレンプラントから精製される公知のＣ５またはＣ９留分を原料に製造されるものが挙げられ、例えば、クイントン（日本ゼオン製商品名）や熱可塑性ポリノルボルネン樹脂ノルソレックス（日本ゼオン製商品名）などが挙げられる。これら石油樹脂は、数平均分子量が１０００以上であることが好ましく、より好ましくは樹脂骨格中に水酸基やエステル基などの官能基を有しているものである。
【００２３】
これら改質剤の配合量は、目的とする樹脂の物性にもよるが、一般に重合性液状物１００重量部に対し０．２〜５０重量部の範囲で用いることができる。さらに好ましくは０．５〜４０重量部の範囲である。０．２重量部未満では改質剤の効果が発現し難く、５０重量部以上では重合性が低下してしまう傾向にある。
【００２４】
本発明で用いられる重合速度調節剤として、アクリル樹脂やポリエステル樹脂などのラジカル重合性樹脂ではメチルスチレンダイマーなどの連鎖移動剤が挙げられる。オレフィン系樹脂では、トリイソプロピルフォスフィン、トリフェニルフォスフィン、トリシクロヘキシルフォスフィンなどのリン酸塩が挙げられ、これらは重合性液状物１００重量部に対し０．００５〜２０重量部用いることができる。これら重合速度調節剤の配合量は、成形のための可使時間を制御する目的であり、可使時間が短くても良い時にはその使用量を少なくし、長くしたいときは多くする。
【００２５】
消泡剤としては例えば、シリコン系オイル、フッ素オイル、ポリカルボン酸系ポリマーなど公知の消泡剤が挙げられ、通常重合性液状物１００重量部に対し０．００１〜５重量部添加することができる。
【００２６】
発泡剤としては例えばペンタン、プロパン、ヘキサンなどの低沸点炭化水素系化合物、炭酸ガス、水蒸気などの一般公知の物理発泡剤、アゾビスイソブチロニトリルやＮ’Ｎ−ジニトロソペンタメチレンテトラミンなどのアゾ系化合物やニトロソ化合物などの分解により窒素ガスを発生する化合物など一般公知の化学発泡剤が挙げられる。
【００２７】
着色剤としては、二酸化チタン、コバルトブルー、カドミウムエローなどの無機顔料、カーボンブラック、アニリンブラック、β−ナフトール、フタロシアニン、キナクリドン、アゾ系、キノフタロン、インダンスレンブルーなどの有機系顔料が挙げられ、所望する色調に応じてそれぞれを配合する。これらは、２種以上組み合わせて使用しても良い。通常、これら顔料の添加量は重合性液状物１００重量部に対し、０．１〜５０重量部添加することができる。
【００２８】
本発明に用いられる安定化剤としては、紫外線吸収剤、光安定化剤および酸化防止剤が挙げられる。紫外線吸収剤としては、例えばフェニルサリシレート、パラ−ｔ−ブチルフェニルサリシレートなどのサリチル酸系紫外線吸収剤、２，４−ジヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン、２，２’−ジヒドロキシ−４，４’ジメトキシベンゾフェノンなどのベンゾフェノン系紫外線吸収剤、２−（２’−ヒドロキシ−５’−メチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔ−ブチルフェニル）ベンゾトリアゾール２−（２’−ヒドロキシ−３’，５’−ジ−ｔ−アミルフェニル）ベンゾトリアゾールなどのベンゾトリアゾール系紫外線吸収剤、２−エチルヘキシル−２−シアノ−３，３’−ジフェニルアクリレート、エチル−２−シアノ−３，３’−ジフェニルアクリレートなどのシアノアクリレート系紫外線吸収剤が挙げられる。これらは単独または２種類以上併用しても良い。これら紫外線吸収剤の添加量は電気・電子部品の使用環境、ハウジングの有無、要求特性により適宜決められるが、通常重合性液状物１００重量部に対し、０．０５〜２０重量部使用することができる。
【００２９】
また光安定化剤としてはビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジニル）セバケート、コハク酸ジメチル・１−（２−ヒドロキシエチル）−４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン重縮合物などのヒンダードアミン系光安定剤が挙げられる。この光安定剤は通常重合性液状物１００重量部に対し０．０５〜２０重量部添加できる。
【００３０】
さらに本発明に用いられる酸化防止剤としては、パラベンゾキノン、トルキノン、ナフトキノンなどのキノン類、ハイドロキノン、パラ−ｔ−ブチルカテコール、２，５−ジ−ｔ−ブチルハイドロキノンなどのハイドロキノン類、ジ−ｔ−ブチル・パラクレゾールハイドロキノンモノメチルエーテル、ピロガロールなどのフェノール類、ナフテン酸銅やオクテン酸銅などの銅塩、トリメチルベンジルアンモニウムクロライド、トリメチルベンジルアンモニウムマレエート、フェニルトリメチルアンモニウムクロライドなどの第４級アンモニウム塩類、キノンジオキシムやメチルエチルケトオキシムなどのオキシム類、トリエチルアミン塩酸塩やジブチルアミン塩酸塩などのアミン塩酸塩類、鉱油、精油、脂肪油などの油類などが挙げられる。これら酸化防止剤は充填材との相性や目的とする成形作業性および樹脂保存安定性などの条件により種類、量を変えて添加する。通常、添加量は重合性液状物１００重量部に対し１０〜１０，０００ｐｐｍ使用することができる。
【００３１】
本発明で用いられる接着性付与剤としてはシラン系カップリング剤が挙げられる。シランカップリング剤としては、通常式ＹＳｉＸ（Ｙは官能基を有し、Ｓｉに結合する１価の基、Ｘは加水分解性を有しＳｉに結合する１価の基）で表される。上記Ｙ中の官能基としては、例えばビニル、アミノ、エポキシ、クロロ、メルカプト、メタクリルオキシ、シアノ、カルバメート、ピリジン、スルホニルアジド、尿素、スチリル、クロロメチル、アンモニウム塩、アルコール等の基がある。Ｘとしては、例えばクロル、メトキシ、エトキシ、メトキシエトキシ等がある。具体例としては、ビニルトリメトキシシラン、ビニルトリス（２−メトキシエトキシ）シラン、γ−（２−アミノエチル）−アミノプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−メタクリルオキシプロピルトリメトキシシラン、Ｎ，Ｎ−ジメチルアミノフェニルトリエトキシシラン、メルカプトエチルトリエトキシシラン、メタクリルオキシエチルジメチル（３−トリメトキシシリルプロピル）アンモニウムクロライド、３−（Ｎ−スチリルメチル−２−アミノエチルアミノ）プロピルトリメトキシシラン塩酸塩等が挙げられ，これらを混合して使用することも可能である。シラン系カップリング剤は重合性液状物１００重量部に対し通常０．００１〜５重量部添加することができる。
【００３２】
難燃剤としては、ヘキサブロムベンゼン、テトラブロムビスフェノールＡ、デカブロムジフェニルオキサイド、トリブロムフェノール、ジブロモフェニルグリシジルエーテル、パークロロペンタシクロデカン、ヘット酸誘導体等のハロゲン系化合物が単独または２種以上併用される。また、リン酸トリス（ジクロロプロピル）、リン酸トリス（ジブロモプロピル）などのリン酸化合物、ホウ酸化合物なども併用できる。さらに、助難燃剤としては三酸化アンチモン、酸化鉄、水素化アルミなどが挙げられ、これらを難燃剤と併用するとより難燃効果が高められる。通常ハロゲン系難燃剤はシクロオレフィン系化合物１００重量部に対し１〜５０重量部で三酸化アンチモン等の助難燃剤は１〜１５重量部の範囲で用いられる。また、プラスチック用充填材として市販の水酸化アルミニウムや水酸化マグネシウムなどの水和物も難燃を目的とした充填材として用いることができる。これらの添加量は重合性液状物１００重量部に対し１０〜３００重量部の範囲で用いることが好ましい。
【００３３】
このほかにも、充填材の濡れ性を改良するため、例えばビックケミー社製ＢＹＫシリーズなどの市販の湿潤剤や分散剤に代表されるカップリング剤を添加することができる。また、作業性を改良するためにはシリコン系オイルやステアリン酸亜鉛などの離型剤なども添加することができる。
【００３４】
さらに有機過酸化物も添加することができる。有機過酸化物としては例えばクメンハイドロパーオキサイド、ターシャリブチルパーオキシ２−エチルヘキサネート、メチルエチルケトンパーオキサイド、ベンゾイルパーオキサイド、アセチルアセトンパーオキサイド、ビス−４−ターシャリブチルシクロヘキサンジカーボネート、２，５−ジメチル−２，５−ビス（ターシャリブチルパーオキシ）ヘキシン−３など公知のものが挙げられ、これらは２種以上併用しても良い。添加量は通常重合性液状物１００重量部に対して０．１〜１０重量部とされる。
【００３５】
本発明に用いられる重合性液状物には溶剤を含まない。この溶剤とは、ベンゼン、トルエン、キシレン、酢酸エチル、メチルエチルケトンなど一般公知の非反応性希釈溶剤のことである。但し、上記添加剤の中で、市販品に含まれる溶剤は、これを無視するものとする。しかし、この場合でも溶剤は重合性液状物に対し２重量部未満であることが、硬化時の膨れを防止する上で好ましい。
重合性液状物の粘度や低弾性率樹脂の機械的特性や電気的特性を調整するため、通常アクリル系モノマー、メタクリル系モノマー、ビニル系モノマー、ジアリルフタレートなどの低粘度の反応性希釈剤を用いても良く、これらは１種あるいは２種以上を併用してもよい。
【００３６】
本発明で用いられるオレフィン系樹脂の原料としてポリエチレン、ポリプロピレン、ポリブタジエンなど一般公知の汎用樹脂も挙げられるが、シクロオレフィン系化合物が好ましく、特に好ましくはメタセシス重合可能なシクロオレフィン化合物である。メタセシス重合可能なシクロオレフィン化合物としては、ノルボルネン系シクロオレフィン化合物と非ノルボルネン系シクロオレフィン化合物に大別される。ノルボルネン系シクロオレフィン化合物としては、例えば置換又は非置換のノルボルネン、メチルノルボルネン、ジメチルノルボルネン、エチルノルボルネン、エチリデンノルボルネン、ブチルノルボルネンなどの二環ノルボルネン、ジシクロペンタジエン（シクロペンタジエンの二量体）、ジヒドロジシクロペンタジエン、メチルジシクロペンタジエン、ジメチルジシクロペンタジエンなどの三環ノルボルネン、テトラシクロドデセン、メチルテトラシクロドデセン、ジメチルシクロテトラドデセンなどの四環ノルボルネン、トリシクロペンタジエン（シクロペンタジエンの三量体）、テトラシクロペンタジエン（シクロペンタジエンの四量体）などの五環以上のノルボルネンなどが挙げられる。非ノルボルネン系シクロオレフィン化合物としては、例えばシクロブテン、シクロペンテン、シクロオクテン、シクロドデセン、テトラヒドロインデン、メチルテトラヒドロインデンなどが挙げられる。また、２個以上のノルボルネン基を有する化合物、例えばテトラシクロドデカジエン、対称型トリシクロペンタジエン等を多官能架橋剤として用いることもできる。さらに、ハイミック酸、無水ハイミック酸、ノルボルナジエンなどのノルボルネン誘導体も用いることが可能である。これらのメタセシス重合性シクロオレフィン化合物を１種または２種以上組み合わせて用いることができる。
【００３７】
これらの中で、入手の容易さ、経済性などからジシクロペンタジエン、メチルテトラシクロドデセン、エチリデンノルボルネン、トリシクロペンタジエン、シクロオクテン、シクロオクタジエン、シクロドデカトリエンなどが好ましい。
【００３８】
ジシクロペンタジエンは、事前に加熱処理することで、ジシクロペンタジエンの一部をトリシクロペンタジエンやテトラシクロペンタジエン等のシクロペンタジエンオリゴマーにしたり、不純物であるビニルノルボルネンやメチルビニルノルボルネンをテトラヒドロインデンやメチルテトラヒドロインデンに異性化したりすることができる。加熱処理は通常１２０〜２５０℃で、０．５〜１０時間程度である。
【００３９】
なお、通常の市販されているこれらオレフィン樹脂の原料には不純物を含んでいることがある。例えばジシクロペンタジエンには、ビニルノルボルネン、テトラヒドロインデン、メチルビニルノルボルネン、メチルテトラヒドロインデン、メチルジシクロペンタジエン、ジメチルジシクロペンタジエン、トリシクロペンタジエン等を含んでおり、シクロオクタジエンには未反応ブタジエンやシクロオクタンなどを不純物として含んでいることがある。種々の純度のシクロオレフィン化合物が市販されているが、特に精製をしなくても良い。本発明の電気・電子部品に用いるこれら原料としては、通常９０％以上、好ましくは９５％以上、特に好ましくは９８％以上の純度ものである。
【００４０】
これらのシクロオレフィン化合物の中で、分子量３００未満のシクロオレフィン化合物を２種以上併用して、樹脂の弾性率を制御することができる。ジシクロペンタジエンやトリシクロペンタジエンなどの双環体あるいは多環体を重合して得られる樹脂は硬質なため、シクロペンテン、シクロオクテン、シクロオクタジエン、シクロドデカトリエン、シクロオクタテトラエンなどの単環体を併用させて、弾性率を低下させることができる。弾性率を低下するために用いられるこれら単環シクロオレフィン化合物は、多環体と単環体の配合総モル数に対して、４０モル％を越え９９モル％未満の範囲で配合することが好ましい。単環体が４０モル％未満では弾性率が５００ＭＰａ以上になってしまう。また、９９モル％以上使用すると架橋密度が低いため、樹脂の靭性が低くなってしまう。
【００４１】
本発明において用いることのできるメタセシス重合触媒は、従来知られているような触媒成分と活性化剤とを組み合わせた２液系の複分解触媒系とは異なり、空気中の酸素や水分によって容易にその触媒活性を失わずに、メタセシス重合性シクロオレフィン系化合物を複分解（メタセシス）反応で開環重合させることができる触媒である。このようなメタセシス重合触媒として好ましいものは、前記した一般式（１）
【００４２】
【化７】

一般式（Ａ）中、Ｍはルテニウムまたはオスミウムを示す。ＸおよびＸ１はそれぞれ独立にアニオン配位子を示す。アニオン配位子は、中心金属への配位を外したときに陰性電荷をもつ基のことである。このような基としては、例えば、水素、ハロゲン、ＣＦ₃ＣＯ₃、ＣＨ₃ＣＯ₂、ＣＦＨ₂ＣＯ₂、（ＣＨ₃）₃ＣＯ、
（ＣＦ₃）₂（ＣＨ₃）ＣＯ、（ＣＦ₃）（ＣＨ₃）₂ＣＯ、炭素数１〜５のアルキル基、端素数１〜５のアルコキシ基、フェニル基、フェノキシ基、トシル基、メシル基、トルフルオロメタンスルホネート基等があり、特に好ましいものは両方にハロゲン（特に、塩素）である。
【００４３】
ＬおよびＬ１はそれぞれ独立に中性の電子供与基を示す。中性の電子供与基は、中心金属への配位を外したときに中性電荷をもつ基のことである。このような基としては、例えば、ＰＲ２Ｒ３Ｒ４（ここで、Ｒ２は２級のアルキル基またはシクロアルキル基、Ｒ３およびＲ４はそれぞれ独立に、アリール基、炭素数１〜１０の１級アルキル基もしくは２級アルキル基、シクロアルキル基を示す。）で表されるホスフィン系電子供与基や、ピリジン、ｐ-フルオロピリジン、イミダゾリリデン化合物等がある。好ましいＬおよびＬ１は、両方共に−Ｐ（シクロヘキシル）３、−Ｐ（シクロペンチル）３、または−Ｐ（イソプロピル）３であるが
、ＬおよびＬ１互いに異なる電子供与基であっても良い。
【００４４】
Ｑ及びＱ１は、それぞれ独立に水素、アルキル基、アルケニル基または芳香族基を示す。アルキル基としては炭素数１〜２０のアルキル基、アルケニル基としては炭素数２〜２０のアルケニル基、芳香族基としてはアリール基等があり、前記アルキル基、アルケニル基または芳香族基は置換基を有していても良い。
【００４５】
このような触媒の具体的なものとして、好ましくは図１に示すＲｕカルベン触媒が挙げられる。
以下に図１に示すＲｕカルベン触媒の合成例を示す。
＜合成例＞
５００ｍｌのＦｉｓｈｅｒ−Ｐｏｒｔｅｒ ｂｏｔｔｌｅにシクロオクタジエンルテニウムジクロライド（２１ｍｍｏｌ）、トリシクロヘキシルホスフィン（４２ｍｍｏｌ）、水酸化ナトリウム（７．２ｇ）、酸素を除去したｓｅｃ−ブタノール２５０ｍｌを入れ、水素２気圧下、９０℃で加熱する。水素の吸収が終了するまで数回加圧を繰り返し、一晩撹拌を続ける。水素の圧力をかけたままで室温まで冷却し、淡黄色の沈殿物を得る。水３０ｍｌを加え沈殿物を濾過し、水素気流中で乾燥して、Ｒｕ（Ｈ）２（Ｈ２）２（Ｐｃｙ３）２を得る（収率約８０％）。次に、このＲｕ（Ｈ）２（Ｈ２）２（Ｐｃｙ３）２（１．５ｍｍｏｌ）をジクロロエタン溶液３０ｍｌに溶解し、−３０℃に冷却する。３−クロロ−３−メチル−１−ブチン（１．５ｍｍｏｌ）を加える。溶液は即座に赤紫に変わり、そのまま１５分反応させる。冷却浴をはずし、脱ガスしたメタノール（２０ｍｌ）を加えると紫色の結晶が沈殿する。メタノールで洗浄し、乾燥させて目的の触媒を得る（収率９５％）。（参考文献：Ｏｒｇａｎｏｍｅｔａｌｌｉｃｓ、 第１６巻、１８号、３８６７ページ（１９９７年））
【００４６】
このメタセシス重合触媒の添加量は、シクロオレフィン系重合性液状物に対し０．００１〜２０重量％であるが、経済性および硬化速度の理由から好ましくは０．０１〜５重量％の範囲が好ましい。
【００４７】
通常、重合はシクロオレフィン系重合性液状物にメタセシス重合触媒を加え溶かしたのち、加熱して行うことができる。重合性液状物にメタセシス重合触媒を加え溶かす際の温度は、通常は０〜８０℃、好ましくは室温〜５０℃である。重合体を得るための加熱の操作は１段階加熱でも２段階加熱あるいは多段加熱でもよい。１段階加熱とする場合は、その温度は、通常０〜２５０℃、好ましくは２０〜２００℃であり、２段階加熱とする場合は、１段階目の温度は、通常は０〜１５０℃、好ましくは１０〜１００℃であり、２段階目の温度は、通常は２０〜２００℃、好ましくは３０〜１８０℃である。また、重合時間は触媒の量および重合温度により適宜決めることができるが、通常１分〜５０時間である。
【００４８】
本発明の電気・電子部品の成形方法としては、例えば、真空注入成形法、加圧注入成形法、含浸成形法、ＲＴＭ成形法、ディッピング、ハンドレイアップやスプレイアップなどの積層成形法、プレス成形法、フィラメントワインディング法、遠心成形法、真空または加圧バック法、連続成形法、引抜き成形法、射出成形法、トランスファー成形などが挙げられる。本発明の一般式（１）〜（３）に示すメタセシス重合触媒を用いる場合は、これらの成形で不活性雰囲気にする必要はない。
【００４９】
本発明の電気・電子部品は、電気・電子部材とハウジングが一体成形されても良く、そのハウジングの材質はＳＵＳ、銅、鉄、アルミ、セラミックスなどの無機材料および熱硬化性樹脂、熱可塑性樹脂、生分解性樹脂、天然樹脂などの有機材料の中から目的、用途によって選ばれるもので制限はない。また、部品の形状や寸法も目的により任意に設計される。
【００５０】
【実施例】
以下本発明を実施例により説明する。なお実施例中、部とは特に限定しない限り重量部を意味する。
＜樹脂１：オレフィン系低弾性率樹脂＞
高純度ジシクロペンタジエン（丸善石油化学製、純度９９％以上）５０重量部、シクロオクタジエン（ＨＵＬＳ社製 純度９８．５％以上）５０重量部、およびシランカップリング剤（日本ユニカー製ＦＺ−３７７８）０．１重量部を混合した。次いで平均粒径１５μｍの溶融シリカ（（株）龍森製ヒューズレックスＲＤ−８）を所定量添加しコンパウンドを得た。このコンパウンドに図１で示されるメタセシス重合触媒０．２重量部を注型直前に添加し供試した。硬化条件は３８℃×２時間＋１００℃×１時間＋１２５℃×１時間とした。
【００５１】
＜樹脂２：アクリル系低弾性率樹脂＞
ラウリルメタクリレート９０部（共栄社化学製ライトエステルＬ）にポリプロピレングリコールジメタクリレート（共栄社化学製ＮＫエステル９ＰＧ）１０部を混合し、さらに重合触媒としてｔ−ブチルパーオキシ−２−エチルヘキサノエート０．５部を添加した。硬化条件は４０℃×１ｈ＋６０℃×３ｈ＋８０℃×１ｈ＋１００℃×１ｈとした。
【００５２】
＜樹脂３：ポリエステル系低弾性率樹脂＞
撹拌機、コンデンサ、窒素ガス導入管および温度計を取り付けた２リットルの４つ口フラスコにジエチレングリコール４６３部、ネオペンチルグリコール４５４部、アジピン酸９２７部、無水マレイン酸１５６部を仕込み、窒素ガスをゆっくり流しながらマントルヒータを用いて１ｈで１５０℃に昇温し、１ｈ保温後、５ｈかけて２２０℃に昇温した。その温度で６ｈ保温し、酸価３０の不飽和ポリエステルを得た。これにハイドロキノン０．０１％を溶解したスチレンモノマーに不飽和ポリエステル分が７０重量％となるように溶解し、２５℃の粘度が０．１９Ｐａｓの不飽和ポリエステル樹脂液とした。この樹脂液１００部に有機過酸化物として、ビス（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネート０．１５部、クメンハイドロパーオキサイド０．４５部、過酸化ベンゾイル０．８部を添加した。硬化条件は８０℃×３ｈ＋１２５℃×３ｈとした。
【００５３】
＜樹脂４：ジシクロペンタジエン系樹脂１＞
樹脂１と同様の高純度ジシクロペンタジエン１００重量部、およびシランカップリング剤（日本ユニカー製ＦＺ−３７７８）０．１重量部を混合した。次いで平均粒径１５μｍの溶融シリカ（（株）龍森製ヒューズレックスＲＤ−８）を所定量攪拌混合しコンパウンドを得た。図１に示されるメタセシス重合触媒を用いて、樹脂１と同様に硬化させた。
【００５４】
＜樹脂５：ジシクロペンタジエン系樹脂２＞
樹脂１で用いたジシクロペンタジエンにジエチルアルミニウムクロライドを４０ミリモル濃度、ｎ−プロピルアルコールを５２ミリモル濃度および四塩化ケイ素２０ミリモル濃度それぞれを窒素パージしたドライボックス内で添加しＡ液とした。また、Ａ液と同様にジシクロペンタジエンに対しトリデシルアンモニウムモリブデネートを１０ミリモル濃度添加しＢ液を作製した。このＡ液およびＢ液を５０重量部づつ混合し、速やかに平均粒径１５μｍの溶融シリカ（（株）龍森製ヒューズレックスＲＤ−８）１００重量部を混合攪拌し、窒素雰囲気下で等量づつ混合して供試した。硬化条件は５０℃×０．５ｈ＋１２５℃×３ｈとした。
【００５５】
＜樹脂６：エポキシ樹脂＞
ビスフェノールＡ型エポキシ樹脂１００重量部（東都化成（株）製ＹＤ−１２８）にシランカップリング剤０．１重量部（東芝シリコーン製、ＴＳＡ−７２０）を混合してＡ液とした。一方、硬化剤としてメチルテトラヒドロ無水フタル酸（日立化成工業（株）製ＨＮ−２２００）８７重量部に２−エチル−４−メチルイミダゾールを２部配合しＢ液とした。このＡ液５０重量部およびＢ液を４５重量部を混合し、さらに平均粒径１５μｍの溶融シリカ１００重量部（（株）龍森製ヒューズレックスＲＤ−８）を混合し十分に攪拌して供試した。硬化条件は１００℃×１ｈ、１２５℃×２ｈおよび１４０℃×３ｈとした。
【００５６】
＜樹脂７：シリコーン樹脂＞
市販の放熱タイプシリコーン樹脂（信越シリコーン製ＫＥ−１２２３）を供試した。硬化条件は１００℃×１ｈとした。
【００５７】
＜樹脂８：ウレタン樹脂＞
市販の注型用ウレタン樹脂（日立化成工業（株）製ＫＵ−７０７）１００重量部に、シランカップリング剤（日本ユニカー製ＡＺ−６１７１）を０．１重量部混合攪拌し、加熱により付着水分を除去した平均粒径１５μｍの溶融シリカ（（株）龍森製ヒューズレックスＲＤ−８）１００重量部を混合攪拌した。硬化条件は５０℃×３ｈ＋１００℃×２ｈとした。
【００５８】
試験方法
＜粘度＞
Ｂ型粘度計、２３℃、ロータ＃３、６０ｒｐｍの条件で粘度を測定した。
＜曲げ弾性率＞
３ｍｍ厚の注型板を作製しＪＩＳ−Ｋ−７２０３に準拠し測定した。
試験片形状：２５×８０×３ｍｍ、試験スパン：４８ｍｍ、試験速度１００ｍｍ／分
＜モデル含浸試験＞
直径１５ｍｍのポリプロピレン製試験管に１００℃で１時間乾燥したガラスビーズ（平均粒径８０μｍ）を振動させながら試験管内に高さで約６０ｍｍになるように充填した後、秤量してガラスビーズの重量（Ｗ０ｇ）を測定した。次いで、樹脂組成物をガラスビーズ充填済みのポリプロピレン製試験管に高さで約６０ｍｍになるよう注入し、１０ｍｍＨｇに減圧して１０分間放置した後、規定の条件で熱硬化させた。この後、含浸されずに硬化物から分離されるガラスビーズを集めてその重量（Ｗ１ｇ）を測定した。次式よりモデル含浸率を算出した。
モデル含浸率（％）＝｛（Ｗ０−Ｗ１）／Ｗ０｝×１００
【００５９】
＜部品モデル１（イグニッションコイル用封止材）＞
イグニッションコイルの断面構造の一例を図２に示す。
イグニッションコイルは、磁性体の中心コア１、外部コア２、一次ボビン３、一次コイル４、二次ボビン５、二次コイル６、端子７などで構成されている。一次コイルは直径０．５ｍｍ程度のエナメル線を約２００回、二次コイルは直径０．０５ｍｍ程度のエナメル細線を２００００回程度ボビンに巻線されている。一次コイルはバッテリーに接続され直流電流が流れるが、点火タイミング調整電子回路部品およびパワースイッチにより流れる電流を断続させて磁束を変化させ、自己誘導作用により一次電圧を得る。この一次電圧を一次コイルと二次コイルの相互誘導作用により２０〜４０ＫＶの高電圧とし、端子に接続した点火プラグに火花放電を起こさせる。
【００６０】
部品モデル１は、ポリフェニレンサルファイド（ＰＰＳ）製ケース材に磁性体コア、アルミ電極、点火タイミング制御回路部品（構成：ＩＣ付セラミック基板／エポキシ樹脂で部品封止）、変性ポリフェニレンオキサイド（ＰＰＯ）ボビンの１次コイルおよび２次コイルを組み込んだイグニッションコイルに図３の表１に示した供試試料を、５ｔｏｒｒ×１分間の脱泡条件で注型し、３０℃×１ｈ＋５０℃×１ｈ＋８０℃×１ｈ＋１２０×１ｈの硬化条件で硬化した。
【００６１】
＜部品モデル２（イグニッションコイル用一括封止材）＞
点火タイミング制御回路部品（構成：ベアチップＩＣ付セラミック基板／部品未封止）を用いた以外、部品モデル１と同様の部材構成のイグニッションコイルに図３の表１に示した供試試料を、５ｔｏｒｒ×１分間の脱泡条件で注型し、３０℃×１ｈ＋５０℃×１ｈ＋８０℃×１ｈ＋１２０×１ｈの硬化条件で硬化し、電子回路部品とコイルの一括封止イグニッションコイルを得た。
【００６２】
＜部品モデル３（ケースレスイグニッションコイル用一括封止材）＞
磁性体コア、真鍮電極、点火タイミング制御回路部品（構成：ベアチップＩＣ付セラミック基板／部品未封止）および変性ポリフェニレンオキサイド（ＰＰＳ）ボビンの１次コイルおよび２次コイルを金型の中央に配し、表１に示した供試試料を、５ｔｏｒｒ×１分間の脱泡条件で注型し、３０℃×１ｈ＋５０℃×１ｈ＋８０℃×１ｈ＋１２０×１ｈの硬化条件で硬化後、金属ケースより封止部材を取り出して、一括封止ケースレスイグニッションコイルを得た。
【００６３】
＜部品モデル４（ＩＣ部品封止材）＞
２５×２５×５ｍｍの変性ＰＰＯ製凹型ケース材の中央に１５ 角のエポキシ樹脂封止１６ピンＤＩＰ型ＩＣ付セラミック基板を配し、あらかじめ脱泡した供試試料を流し込み成形品を得た。
【００６４】
＜部品モデル５（ＤＩＰ型ＩＣ封止材）＞
５ｍｍの酸化膜を有するシリコンチップにアルミ配線を施したテスト素子を使用し、部分銀メッキを施した４２アロイのリードフレームにエポキシ系銀ペーストで接続し、サーモソニック型ワイヤボンダにより２００℃で素子のボンディングパッドとインナーリードを１０μｍの金線にて接続した。その後、予め脱泡した供試試料をポッティングし、硬化して１６ピン型ＤＩＰ（Ｄｕａｌ Ｉｎｌｉｎｅ Ｐａｃｋａｇｅ）型半導体封止パッケージを得た。
【００６５】
＜出力特性＞
部品モデル１〜３を（−４０℃×３０分＋１２５℃×３０分）を１サイクルとするヒートサイクル試験を４００サイクル行い、試験後に一次電圧として１２Ｖ印加したときに、２次電圧として２０ＫＶ以上の出力が得られるか試験した。また、試験後の部品を切断して剥離の有無を光学顕微鏡により観察した。
＜成形性＞
部品モデル４で、金線ワイヤーの切断状態を軟質Ｘ線で確認し、断線がなかったものを○、断線があったものを×とした。
＜耐はんだリフロー性＞
部品モデル４および５を、８５℃／８５％ＲＨの雰囲気に１６８時間放置した後、２４０℃×１０秒間の加熱を３回行いクラック発生の観察ならびに通電試験を行った。
【００６６】
実施例および比較例の結果を図３の表１に示した。本発明の電気・電子部品は、弾性率の高いエポキシ樹脂やジシクロペンタジエン系樹脂ならびに弾性率の低いシリコーン樹脂、ウレタン樹脂を用いて封止した部品よりも優れた出力特性、成形性および耐はんだリフロー性を有していた。この結果は、本発明の電気・電子部品が優れた信頼性を有していることを示している。
【００６７】
【発明の効果】
本発明の電気・電子部品により、高密度化、高集積化に対応する長寿命、高耐久性の電気・電子機器を広く提供できる。
【図面の簡単な説明】
【図１】 Ｒｕカルベン触媒の化学構造式。
【図２】 イグニッションコイルの断面図。
【図３】 実施例および比較例の結果を示す表１。
【符号の説明】
１．磁性体の中心コア
２．磁性体の外部コア
３．一次ボビン
４．一次コイル
５．二次ボビン
６．二次コイル
７．端子[0001]
BACKGROUND OF THE INVENTION
The present invention encloses an electric / electronic part including a silicon substrate, a transformer, a coil, an LSI, an IC, a transistor, a diode, a power switch, a resistance element, a capacitor, or a supporting substrate on which these parts are mounted. It relates to stopped electrical and electronic parts.
[0002]
[Prior art]
With the miniaturization and thinning of electrical and electronic equipment, the density and high integration of members used have been advanced, and the progress in semiconductor-related members is particularly remarkable. These electrical / electronic components generally improve the reliability of electrical / electronic components such as insulation, moisture resistance, thermal shock resistance, and reflow crack resistance. Height Therefore, an inorganic member such as gold, silver, copper, aluminum, brass, zinc, silicon, germanium, 42 alloy, and stainless steel is sealed with a polymer material. For example, in an IC, a silicon chip is mainly sealed with an epoxy resin, and in an ignition coil, the coil is sealed with an epoxy resin or a silicone resin. An electric / electronic circuit member in which an element member such as an IC or a bare chip is mounted on a ceramic or epoxy resin supporting substrate is sealed with an acrylic resin, a silicone resin, a urethane resin, an epoxy resin, or the like depending on the environment in which it is used. Examples of these sealing resins include thermosetting resins such as epoxy resins, silicone resins, urethane resins, and polyimide resins, and engineering plastics (thermoplastic resins) such as polyethylene, polyethylene terephthalate, polycarbonate, modified polyphenylene oxide, and polyphenylene sulfide. Is mentioned. Among these encapsulating resins, epoxy resins are most representatively used because they are most excellent in adhesion to inorganic materials.
[0003]
The resin used for sealing these electrical / electronic components has a linear expansion coefficient that is close to that of inorganic members such as silicon chips, aluminum electrodes, and copper wires in order to prevent interfacial delamination between the inorganic member and the polymer, that is, low linear expansion. It is generally required to be a coefficient. In addition, heat from the electrical / electronic components, such as Joule heat generated during semiconductor operation and heat generated by the electrical resistance of the copper wire coil, is diffused to improve the durability and reliability of electrical / electronic components. It is generally required to increase conductivity. In general, an inorganic filler such as silica or aluminum hydroxide is added to reduce the linear expansion coefficient and the high thermal conductivity. However, the addition of the filler makes the mechanical properties of the resin hard and brittle, so that cracks are likely to occur and the heat cycle resistance of the component is reduced. In addition, a polymerizable liquid material (resin raw material before polymerization and curing) to which an inorganic filler is added is generally solid at room temperature or has a high viscosity of several tens to several hundred poises, and therefore has poor fluidity and high density. It cannot be applied to sealing of integrated circuits and fine circuits.
[0004]
For example, JP-A-10-218900 proposes a low viscosity epoxy resin prepolymer. This prepolymer achieves a viscosity as low as 29 poise, for example. However, with this level of viscosity, high density integrated circuits and fine circuits still cannot be sufficiently sealed. Furthermore, since the cured product (resin) has a glass transition temperature of 110 ° C. and exhibits mechanically hard and brittle properties under the actual use temperature, there is a problem that cracks are likely to occur in the heat cycle resistance test.
[0005]
Therefore, a method of sealing using an engineering plastic having excellent mechanical toughness has been studied. For example, Japanese Patent Laid-Open No. 10-292118 proposes a method of sealing electronic components such as IC chips by extrusion molding of polyphenylene sulfide at a cylinder temperature of 300 ° C. However, engineering plastics are thermoplastic resins, and generally require high temperatures of 300 ° C or higher for their molding. Even at such high temperatures, they exhibit a high melt viscosity of several hundred poises, so they are sufficiently impregnated with fine circuits. It is extremely difficult to do.
[0006]
On the other hand, in order to prevent the reliability of electrical / electronic parts from being lowered due to peeling or cracking of the sealing resin, a low elastic modulus polymer such as silicone resin or urethane resin may be used as the sealing resin. However, silicone resin and urethane resin prepolymers generally have high viscosity and poor impregnation properties. Moreover, the dielectric constant of these polymers is high compared with an olefin resin, and is inferior to an electrical property. For this reason, JP-A-8-316373 proposes a method for optimizing the resin filling method at the time of molding, and JP-A-10-233472 proposes a method for optimizing the structure of the parts. It cannot be sufficiently impregnated. Japanese Patent Laid-Open No. 5-287077 proposes a silicone resin having a reduced prepolymer viscosity. However, the viscosity is still 3 poises or more, and it still does not reach a level at which a fine circuit can be sufficiently impregnated.
[0007]
On the other hand, cycloolefin resins obtained by metathesis polymerization of norbornene compounds are known to be excellent in mechanical properties, electrical properties, water resistance, etc. In Japanese Patent Publication No. 5-41088, reaction injection molding of norbornene compounds is known. Has proposed a manufacturing method for sealing electrical and electronic components. Japanese Patent Application Laid-Open No. 9-183833 proposes a norbornene-based compound suitable for sealing electric / electronic parts with a new metathesis polymerization catalyst. Furthermore, Japanese Patent Application Laid-Open No. 10-182922 shows that a metathesis polymerizable cycloolefin compound (prepolymer) has a low viscosity even when a filler is added, and is suitable for sealing electric / electronic parts. However, these are all encapsulated by a prepolymer cured product combining a norbornene-based compound such as dicyclopentadiene and an inorganic filler, and the resulting cured product has a high glass transition temperature, but has an adhesive property to an inorganic member. And the elastic modulus is high, there is a problem that peeling easily occurs at the interface with the inorganic member.
[0008]
Further, the metathesis polymerization catalyst system described in JP-B-5-41088 includes a catalyst component selected from organic ammonium salts of tungsten and molybdenum as disclosed in JP-A-59-51911, an alkoxyalkylaluminum halide and an aryloxyaluminum. Since it is the same as that combined with an activator selected from halides and is easily deactivated with oxygen, there is also a problem that molding must be performed in an inert atmosphere.
[0009]
[Problems to be solved by the invention]
As described above, a hard resin having a high elastic modulus such as an epoxy resin is liable to cause a problem of peeling or cracking, and there is a problem in reliability of electric / electronic parts. In addition, a soft resin having a low elastic modulus such as a silicone resin or a urethane resin has a problem that since the prepolymer has a high viscosity, the impregnation property is poor and a high-density integrated circuit or a fine circuit cannot be sufficiently sealed. Further, a polymer obtained by metathesis polymerization of dicyclopentadiene as a cycloolefin resin also has a problem of peeling because of its high elastic modulus. Further, sealing with a cycloolefin resin using a metathesis polymerization catalyst has a problem that it must be completely in an inert gas atmosphere when molding.
[0010]
[Means for Solving the Problems]
As a result of intensive studies on resin sealing of electric / electronic parts, particularly resin sealing of parts including fine circuits, a polymerizable liquid whose viscosity is less than 3 poise and the flexural modulus of the cured resin is 500 MPa or less. The present invention has been completed by finding that the precision casting moldability and solder reflow resistance of electric / electronic parts are improved by sealing with an object. Furthermore, it has been found that when a specific metathesis polymerization catalyst is used to obtain an olefinic resin, it is difficult to be affected by oxygen and moisture in the air, so that an electric / electronic component with little molding variation is provided.
[0011]
That is, the present invention is an electrical / electronic component sealed with a low elastic modulus resin having a flexural modulus of 500 MPa or less at 23 ° C., which is obtained by polymerizing a polymerizable liquid having a viscosity of less than 3 poise at 23 ° C. .
The present invention is also an electrical / electronic component sealed with an olefinic low elastic modulus resin having a flexural modulus at 23 ° C. of 500 MPa or less. It can be a resin obtained by polymerizing a polymerizable liquid having a viscosity of less than 3 poise at 23 ° C.
The low elastic modulus resin has a glass transition temperature of 80 ° C. or less, a linear expansion coefficient of 100 ppm or more at 23 ° C., a water absorption of 23 ° C. and less than 0.1% when immersed in water for 24 hours, and a dielectric constant of 3.0 at 23 ° C. The following is preferable.
The polymerizable liquid can contain a filler, and also includes a modifier, a polymerization rate regulator, a foaming agent, an antifoaming agent, a colorant, a stabilizer, an adhesion-imparting agent, a flame retardant, a coupling agent and At least 1 sort (s) chosen from the additive which consists of organic peroxides can be included.
The polymerizable liquid material preferably contains no solvent.
The polymerizable liquid material is preferably composed of one or more metathesis polymerizable cycloolefin compounds, and is preferably composed of a combination of two or more selected from metathesis polymerizable cycloolefin compounds having a molecular weight of less than 300. .
The polymerizable liquid is polymerized by a metathesis polymerization catalyst, and a catalyst represented by the following general formulas (1), (2), and (3) is used as the metathesis polymerization catalyst.
[0012]
[Formula 4]

(M represents ruthenium or osmium, X and X1 each independently represents an anionic ligand, L and L1 each independently represent a neutral electron donating group, and Q and Q1 each independently represent hydrogen, alkyl. A group, an alkenyl group or an aromatic group, and the alkyl group, the alkenyl group or the aromatic group may have a substituent.)
[0013]
[Chemical formula 5]

(M represents ruthenium or osmium, X and X1 each independently represents an anionic ligand, L and L1 each independently represent a neutral electron donating group, and Q and Q1 each independently represent hydrogen, alkyl. A group, an alkenyl group or an aromatic group, and the alkyl group, the alkenyl group or the aromatic group may have a substituent.)
[0014]
[Chemical 6]

(M represents ruthenium or osmium, X and X1 each independently represents an anionic ligand, L and L1 each independently represent a neutral electron donating group, and R1 and R2 each independently represent 1 carbon atom. -C18 alkyl group, C2-C18 alkenyl group, C2-C18 alkynyl group, aryl group, C1-C18 carboxylate group, C1-C18 alkoxy group, C2-C2 18 alkenyloxy groups, C2-C18 alkynyloxy groups, C2-C18 allyloxy groups, C2-C18 alkoxycarbonyls, C1-C18 alkylthio groups, C1-C18 alkyls A sulfonyl group or a C1-C18 alkylsulfinyl group is shown, R3 shows hydrogen, an aryl group, or a C1-C18 alkyl group.)
Electrical / electronic components can be molded substantially in the presence of oxygen.
As an electrical / electronic component, an ignition coil including a magnetic core, a primary coil wound around the magnetic core, a secondary coil, and a magnetic external core disposed on the outer side can be sealed.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
The electrical / electronic component of the present invention is made of a polymerizable liquid material having a viscosity at 23 ° C. of less than 3 poise and a low elastic modulus resin having a bending elastic modulus at 23 ° C. of 500 MPa or less as defined in JIS-K-7203. Used as a stopping resin.
The polymerizable liquid has a viscosity of less than 3 poise, preferably 0.05 poise to 2.0 poise. In the case of electrical and electronic parts such as flyback transformers and ignition coils, if the viscosity of the polymerizable liquid exceeds 3 poise, the impregnation property inside the winding coil deteriorates and unfilled parts occur, resulting in reduced insulation. It was found to be. Similarly, when a polymerizable liquid having a viscosity exceeding 3 poise is used as a semiconductor element sealing material typified by DIP, the connection wiring between the chip and a substrate such as a lead frame, polyimide film or ceramic is cut. I found out. The bending elastic modulus of the sealing resin is 500 MPa or less, preferably 300 MPa or less, more preferably 100 MPa or less. If it exceeds 500 MPa, peeling and cracking are likely to occur.
[0016]
The type of sealing resin having the above characteristics is not particularly limited. For example, an epoxy resin, a urethane resin, a silicone resin, an acrylic resin and a methacrylic resin, a polyester resin, a phenol resin, an olefin resin, or the like may be used as long as it is liquid at 23 ° C. and a polymerizable liquid less than 3 poise. Acrylic resin, methacrylic resin, polyester resin, and olefin resin are preferable. Particularly preferred is an olefin resin from the viewpoint of excellent electrical characteristics.
[0017]
The glass transition temperature of the resin used for the electric / electronic component of the present invention is preferably 80 ° C. or lower, more preferably 50 ° C. or lower, more preferably 25 ° C. or lower. When the glass transition temperature exceeds 80 ° C., cracks are likely to occur inside the sealing resin. For the same reason, the linear expansion coefficient of the resin is preferably 100 ppm or more. Furthermore, the water absorption of the sealing resin is preferably less than 0.1% when immersed in water at 23 ° C. for 24 hours. If the water absorption is 0.1% or more, the insulation and solder reflow resistance tend to be lowered. In addition, the dielectric constant of the resin is preferably 2.0 to 3.0, more preferably 2.0 to 2.9 so that there is no mutual interference of electromagnetic waves with the increase in density and integration of electric / electronic components. is there.
[0018]
The sealing resin used in the electric / electronic parts of the present invention is considered to have physical properties, appearance, and moldability, and if necessary, a filler, a modifier, a polymerization rate regulator, a foaming agent, an antifoaming agent, A colorant, a stabilizer, an adhesion-imparting agent, a flame retardant, a coupling agent, an organic peroxide, and the like can be optionally added.
[0019]
Examples of the filler used in the present invention include inorganic fillers such as fused silica, crystalline silica, silica sand, calcium carbonate, aluminum hydroxide, magnesium oxide, and clay, and wood flour, polyester, silicone, polystyrene acrylonitrile-butadiene-styrene. Examples thereof include bead-shaped organic fillers such as (ABS). Among these, silica and aluminum hydroxide are preferable from the viewpoint of electrical characteristics and thermal conductivity. As this commercial item, CRT-AA, CRT-D, RD-8 (trade name, manufactured by Tatsumori Co., Ltd.), COX-31 (trade name, manufactured by Micro Corporation), C-303H, C-315H, C- 308 (trade name manufactured by Sumitomo Chemical Co., Ltd.), SL-700 (trade name manufactured by Takehara Chemical Industry Co., Ltd.), and the like. The blending amount of these inorganic fillers is preferably 0 to 95% by weight in the resin, more preferably 10 to 95% by weight, and even more preferably 30 to 95% by weight. If the blending amount exceeds 95% by weight, the dielectric constant of the resin exceeds 3.0, so that the electrical characteristics are likely to deteriorate. More preferably, it is 30 to 75% by weight. The particle size, shape, quality and the like can be appropriately determined depending on the application of the electric / electronic component, but the average particle size is preferably between 0.1 and 100 μm, particularly preferably between 1 and 50 μm. The combination of those having different average particle diameters can improve the fine packing property and fluidity. Furthermore, the shape of the inorganic filler is preferably spherical.
[0020]
In addition, inorganic and organic fibrous fillers such as milled glass, cut fiber, microfiber, microballoon, scaly glass powder, carbon fiber, and aramid fiber can also be used, and these can be used in combination. Select the aspect ratio and shape as appropriate according to the purpose. The blending amount of these fibrous fillers is preferably 0 to 20 parts by weight, more preferably 0 to 10 parts by weight with respect to 100 parts by weight of the low elastic modulus resin.
[0021]
Examples of the modifier used in the present invention include elastomer, natural rubber, butadiene rubber, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), and styrene-maleic acid copolymer. Examples thereof include copolymers, copolymers such as ethylene-vinyl acetate copolymer, and thermoplastic resins such as polymethyl methacrylate, polyvinyl acetate, and polystyrene. Moreover, these copolymers and thermoplastic resins may be esterified, and polar groups may be grafted. In addition, physical properties can be improved by blending an epoxy resin, a urethane resin, a polyester resin, a silicone resin, a phenol resin, a polyimide resin, a polyamide resin, a polyamideimide resin, or a derivative thereof. Further examples include compounds obtained by reacting epoxies with norbornene monocarboxylic acid, compounds obtained by reacting isocyanate compounds with norbornene-ol, highmic acid-modified polyesters, petroleum resins and the like.
[0022]
Petroleum resins include those produced from a known C5 or C9 fraction purified from an ethylene plant, such as Quinton (trade name, manufactured by ZEON) or thermoplastic polynorbornene resin NORSOLEX (Nippon ZEON). Product name). These petroleum resins preferably have a number average molecular weight of 1000 or more, and more preferably have a functional group such as a hydroxyl group or an ester group in the resin skeleton.
[0023]
The amount of these modifiers is generally in the range of 0.2 to 50 parts by weight with respect to 100 parts by weight of the polymerizable liquid, although it depends on the physical properties of the target resin. More preferably, it is the range of 0.5-40 weight part. If the amount is less than 0.2 parts by weight, the effect of the modifier is hardly exhibited, and if the amount is 50 parts by weight or more, the polymerizability tends to decrease.
[0024]
Examples of the polymerization rate regulator used in the present invention include chain transfer agents such as methylstyrene dimer in radically polymerizable resins such as acrylic resins and polyester resins. Examples of the olefin resin include phosphates such as triisopropylphosphine, triphenylphosphine, and tricyclohexylphosphine, and these can be used in an amount of 0.005 to 20 parts by weight with respect to 100 parts by weight of the polymerizable liquid. . The blending amount of these polymerization rate regulators is for the purpose of controlling the pot life for molding. When the pot life may be short, the use amount is reduced, and when it is desired to be longer, it is increased.
[0025]
Examples of the antifoaming agent include known antifoaming agents such as silicone oil, fluorine oil, polycarboxylic acid polymer, and 0.001 to 5 parts by weight are usually added to 100 parts by weight of the polymerizable liquid. it can.
[0026]
Examples of the blowing agent include low-boiling hydrocarbon compounds such as pentane, propane, and hexane, generally known physical blowing agents such as carbon dioxide and water vapor, azobisisobutyronitrile, N′N-dinitrosopentamethylenetetramine, and the like. Commonly known chemical foaming agents such as compounds that generate nitrogen gas by decomposition of azo compounds and nitroso compounds can be mentioned.
[0027]
Examples of the colorant include inorganic pigments such as titanium dioxide, cobalt blue, and cadmium yellow, and organic pigments such as carbon black, aniline black, β-naphthol, phthalocyanine, quinacridone, azo, quinophthalone, and indanthrene blue. Each is blended according to the desired color tone. You may use these in combination of 2 or more types. Usually, the pigment is added in an amount of 0.1 to 50 parts by weight with respect to 100 parts by weight of the polymerizable liquid.
[0028]
Examples of the stabilizer used in the present invention include an ultraviolet absorber, a light stabilizer, and an antioxidant. Examples of the UV absorber include salicylic acid UV absorbers such as phenyl salicylate and para-t-butylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4, Benzophenone ultraviolet absorbers such as 4 ′ dimethoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) Benzotriazole ultraviolet absorbers such as benzotriazole 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole, 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, Cyano such as ethyl-2-cyano-3,3′-diphenyl acrylate Acrylate-based ultraviolet absorbers. These may be used alone or in combination of two or more. The amount of these ultraviolet absorbers to be added is appropriately determined depending on the usage environment of the electric / electronic parts, the presence / absence of the housing, and the required characteristics, but it is usually used in an amount of 0.05 to 20 parts by weight per 100 parts by weight of the polymerizable liquid. it can.
[0029]
Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, dimethyl succinate, Examples include hindered amine light stabilizers such as 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate. This light stabilizer can be added in an amount of 0.05 to 20 parts by weight per 100 parts by weight of the polymerizable liquid.
[0030]
Furthermore, examples of the antioxidant used in the present invention include quinones such as parabenzoquinone, tolquinone, and naphthoquinone, hydroquinones such as hydroquinone, para-t-butylcatechol, 2,5-di-t-butylhydroquinone, and di-t. -Phenols such as butyl paracresol hydroquinone monomethyl ether, pyrogallol, copper salts such as copper naphthenate and copper octenoate, quaternary ammonium salts such as trimethylbenzylammonium chloride, trimethylbenzylammonium maleate, phenyltrimethylammonium chloride, Examples thereof include oximes such as quinone dioxime and methyl ethyl ketoxime, amine hydrochlorides such as triethylamine hydrochloride and dibutylamine hydrochloride, and oils such as mineral oil, essential oil and fatty oil. These antioxidants are added in different types and amounts depending on conditions such as compatibility with the filler, desired molding workability and resin storage stability. Usually, the added amount can be 10 to 10,000 ppm with respect to 100 parts by weight of the polymerizable liquid.
[0031]
Examples of the adhesion-imparting agent used in the present invention include silane coupling agents. The silane coupling agent is usually represented by the formula YSiX (Y is a monovalent group having a functional group and bonded to Si, and X is a monovalent group having hydrolyzability and bonded to Si). Examples of the functional group in Y include groups such as vinyl, amino, epoxy, chloro, mercapto, methacryloxy, cyano, carbamate, pyridine, sulfonyl azide, urea, styryl, chloromethyl, ammonium salt and alcohol. Examples of X include chloro, methoxy, ethoxy, methoxyethoxy and the like. Specific examples include vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxy. Silane, γ-methacryloxypropyltrimethoxysilane, N, N-dimethylaminophenyltriethoxysilane, mercaptoethyltriethoxysilane, methacryloxyethyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, 3- (N-styrylmethyl) -2-aminoethylamino) propyltrimethoxysilane hydrochloride and the like can be mentioned, and these can also be used as a mixture. The silane coupling agent can usually be added in an amount of 0.001 to 5 parts by weight per 100 parts by weight of the polymerizable liquid.
[0032]
As flame retardants, halogen compounds such as hexabromobenzene, tetrabromobisphenol A, decabromodiphenyl oxide, tribromophenol, dibromophenyl glycidyl ether, perchloropentacyclodecane, heptic acid derivatives are used alone or in combination of two or more. The Further, phosphoric acid compounds such as tris phosphate (dichloropropyl) and tris phosphate (dibromopropyl), boric acid compounds, and the like can be used in combination. Further, examples of the auxiliary flame retardant include antimony trioxide, iron oxide, aluminum hydride, and the like. When these are used in combination with the flame retardant, the flame retardant effect is further enhanced. Usually, the halogen-based flame retardant is used in the range of 1 to 50 parts by weight with respect to 100 parts by weight of the cycloolefin compound, and the auxiliary flame retardant such as antimony trioxide is used in the range of 1 to 15 parts by weight. Also, commercially available hydrates such as aluminum hydroxide and magnesium hydroxide can be used as fillers for flame retardancy. These addition amounts are preferably used in the range of 10 to 300 parts by weight with respect to 100 parts by weight of the polymerizable liquid.
[0033]
In addition, in order to improve the wettability of the filler, for example, a commercially available wetting agent such as BYK series manufactured by BYK Chemie Corporation or a coupling agent typified by a dispersing agent can be added. In order to improve workability, a release agent such as silicone oil or zinc stearate can be added.
[0034]
In addition, organic peroxides can also be added. Examples of the organic peroxide include cumene hydroperoxide, tertiary butyl peroxy 2-ethylhexanate, methyl ethyl ketone peroxide, benzoyl peroxide, acetylacetone peroxide, bis-4-tertiarybutylcyclohexane dicarbonate, 2,5- Known materials such as dimethyl-2,5-bis (tertiarybutylperoxy) hexyne-3 may be mentioned, and two or more of these may be used in combination. The addition amount is usually 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymerizable liquid.
[0035]
The polymerizable liquid used in the present invention does not contain a solvent. This solvent is a generally known non-reactive diluent solvent such as benzene, toluene, xylene, ethyl acetate, methyl ethyl ketone. However, among the above-mentioned additives, the solvent contained in the commercial product is ignored. However, even in this case, the solvent is preferably less than 2 parts by weight with respect to the polymerizable liquid material in order to prevent swelling during curing.
To adjust the viscosity of the polymerizable liquid and the mechanical and electrical properties of the low-modulus resin, usually use low-viscosity reactive diluents such as acrylic monomers, methacrylic monomers, vinyl monomers, and diallyl phthalate. These may be used alone or in combination of two or more.
[0036]
Examples of the raw material for the olefin resin used in the present invention include polyethylene, polypropylene, and polybutadiene. Do Although general-purpose general-purpose resins are also exemplified, cycloolefin compounds are preferred, and cycloolefin compounds capable of metathesis polymerization are particularly preferred. The metaolefin-polymerizable cycloolefin compounds are roughly classified into norbornene-based cycloolefin compounds and non-norbornene-based cycloolefin compounds. Examples of the norbornene-based cycloolefin compound include substituted or unsubstituted norbornene, methylnorbornene, dimethylnorbornene, ethylnorbornene, ethylidenenorbornene, butylnorbornene and the like bicyclic norbornene, dicyclopentadiene (cyclopentadiene dimer), and dihydrodiene. Tricyclic norbornene such as cyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene, tetracyclic norbornene such as tetracyclododecene, methyltetracyclododecene, dimethylcyclotetradodecene, tricyclopentadiene (trimer of cyclopentadiene) ), Norbornene having five or more rings such as tetracyclopentadiene (tetramer of cyclopentadiene). Examples of the non-norbornene-based cycloolefin compound include cyclobutene, cyclopentene, cyclooctene, cyclododecene, tetrahydroindene, methyltetrahydroindene, and the like. In addition, a compound having two or more norbornene groups, such as tetracyclododecadiene, symmetric tricyclopentadiene, or the like can also be used as a polyfunctional crosslinking agent. Furthermore, norbornene derivatives such as highmic acid, anhydrous hymic acid, norbornadiene can also be used. These metathesis polymerizable cycloolefin compounds can be used alone or in combination of two or more.
[0037]
Among these, dicyclopentadiene, methyltetracyclododecene, ethylidene norbornene, tricyclopentadiene, cyclooctene, cyclooctadiene, cyclododecatriene and the like are preferable from the viewpoint of availability and economy.
[0038]
Dicyclopentadiene can be heat-treated in advance to convert a part of dicyclopentadiene into a cyclopentadiene oligomer such as tricyclopentadiene or tetracyclopentadiene, or to convert impurities such as vinyl norbornene or methyl vinyl norbornene into tetrahydroindene or methyl tetrahydro. It can be isomerized to indene. The heat treatment is usually 120 to 250 ° C. for about 0.5 to 10 hours.
[0039]
In addition, the raw material of these usual commercially available olefin resins may contain impurities. For example, dicyclopentadiene includes vinyl norbornene, tetrahydroindene, methylvinylnorbornene, methyltetrahydroindene, methyldicyclopentadiene, dimethyldicyclopentadiene, tricyclopentadiene, etc., and cyclooctadiene includes unreacted butadiene and cyclohexane. May contain octane as impurities. Cycloolefin compounds of various purity are commercially available, but there is no need for purification. These raw materials used in the electric / electronic parts of the present invention are usually 90% or more, preferably 95% or more, particularly preferably 98% or more in purity.
[0040]
Among these cycloolefin compounds, the elastic modulus of the resin can be controlled by using two or more cycloolefin compounds having a molecular weight of less than 300 in combination. Resins obtained by polymerizing bicyclic or polycyclic compounds such as dicyclopentadiene and tricyclopentadiene are hard, so monocyclic compounds such as cyclopentene, cyclooctene, cyclooctadiene, cyclododecatriene, and cyclooctatetraene In combination, the elastic modulus can be lowered. These monocyclic cycloolefin compounds used for lowering the elastic modulus are preferably blended in a range of more than 40 mol% and less than 99 mol% with respect to the total number of moles of polycyclic and monocyclic compounds. . If the monocyclic body is less than 40 mol%, the elastic modulus is 500 MPa or more. Moreover, since the crosslinking density is low when 99 mol% or more is used, the toughness of the resin is lowered.
[0041]
The metathesis polymerization catalyst that can be used in the present invention is different from a two-component metathesis catalyst system that combines a catalyst component and an activator as known in the art, and is easily affected by oxygen and moisture in the air. It is a catalyst capable of ring-opening polymerization of a metathesis polymerizable cycloolefin compound by a metathesis reaction without losing catalytic activity. Preferred as such a metathesis polymerization catalyst is the general formula (1) described above.
[0042]
[Chemical 7]

In general formula (A), M represents ruthenium or osmium. X and X1 each independently represent an anionic ligand. An anionic ligand is a group having a negative charge when the coordination to the central metal is removed. Such groups include, for example, hydrogen, halogen, CF _Three CO _Three , CH _Three CO ₂ , CFH ₂ CO ₂ , (CH _Three ) _Three CO,
(CF _Three ) ₂ (CH _Three ) CO, (CF _Three ) (CH _Three ) ₂ CO, C 1-5 alkyl group, terminal prime 1-5 alkoxy group, phenyl group, phenoxy group, tosyl group, mesyl group, trifluoromethanesulfonate group, etc. are particularly preferred. , Chlorine).
[0043]
L and L1 each independently represent a neutral electron donating group. A neutral electron donating group is a group having a neutral charge when coordination with the central metal is removed. Examples of such groups include PR2R3R4 (wherein R2 is a secondary alkyl group or cycloalkyl group, R3 and R4 are each independently an aryl group, a primary alkyl group having 1 to 10 carbon atoms, or a secondary group). A phosphine-based electron donating group represented by formula (1), pyridine, p-fluoropyridine, imidazolylidene compounds, and the like. Preferred L and L 1 are both —P (cyclohexyl) 3, —P (cyclopentyl) 3, or —P (isopropyl) 3.
, L and L1 may be different electron donating groups.
[0044]
Q and Q1 each independently represent hydrogen, an alkyl group, an alkenyl group or an aromatic group. The alkyl group includes an alkyl group having 1 to 20 carbon atoms, the alkenyl group includes an alkenyl group having 2 to 20 carbon atoms, the aromatic group includes an aryl group, and the alkyl group, alkenyl group, or aromatic group is a substituent. You may have.
[0045]
A specific example of such a catalyst is preferably a Ru carbene catalyst shown in FIG.
A synthesis example of the Ru carbene catalyst shown in FIG. 1 is shown below.
<Synthesis example>
In 500 ml of Fisher-Porter bottle, cyclooctadiene ruthenium dichloride (21 mmol), tricyclohexylphosphine (42 mmol), sodium hydroxide (7.2 g), 250 ml of sec-butanol from which oxygen had been removed were placed, and hydrogen was added at 90 ° C. under 2 atmospheres of hydrogen. Heat with. Pressurization is repeated several times until hydrogen absorption is completed, and stirring is continued overnight. Cool to room temperature with hydrogen pressure applied to obtain a pale yellow precipitate. 30 ml of water is added and the precipitate is filtered and dried in a hydrogen stream to give Ru (H) 2 (H2) 2 (Pcy3) 2 (yield about 80%). Next, this Ru (H) 2 (H2) 2 (Pcy3) 2 (1.5 mmol) is dissolved in 30 ml of a dichloroethane solution and cooled to -30 ° C. Add 3-chloro-3-methyl-1-butyne (1.5 mmol). The solution immediately turns reddish purple and is allowed to react for 15 minutes. Remove the cooling bath and add degassed methanol (20 ml) to precipitate purple crystals. Wash with methanol and dry to obtain the desired catalyst (95% yield). (Reference: Organometallics, Vol. 16, No. 18, p. 3867 (1997))
[0046]
The addition amount of the metathesis polymerization catalyst is 0.001 to 20% by weight with respect to the cycloolefin-based polymerizable liquid, but is preferably in the range of 0.01 to 5% by weight for reasons of economy and curing speed. .
[0047]
Usually, the polymerization can be carried out by heating after adding a metathesis polymerization catalyst to a cycloolefin polymerizable liquid. The temperature at which the metathesis polymerization catalyst is added to the polymerizable liquid and dissolved is usually 0 to 80 ° C, preferably room temperature to 50 ° C. The heating operation for obtaining the polymer may be one-step heating, two-step heating or multi-step heating. In the case of one-step heating, the temperature is usually 0 to 250 ° C, preferably 20 to 200 ° C. In the case of two-step heating, the temperature of the first step is usually 0 to 150 ° C, preferably Is 10 to 100 ° C., and the temperature in the second stage is usually 20 to 200 ° C., preferably 30 to 180 ° C. The polymerization time can be appropriately determined depending on the amount of the catalyst and the polymerization temperature, but is usually 1 minute to 50 hours.
[0048]
Examples of the method for molding electrical / electronic parts of the present invention include, for example, a vacuum injection molding method, a pressure injection molding method, an impregnation molding method, an RTM molding method, a lamination molding method such as dipping, hand lay-up and spray-up, and press molding. Method, filament winding method, centrifugal molding method, vacuum or pressure back method, continuous molding method, pultrusion molding method, injection molding method, transfer molding method and the like. When the metathesis polymerization catalyst represented by the general formulas (1) to (3) of the present invention is used, it is not necessary to form an inert atmosphere in these moldings.
[0049]
In the electric / electronic component of the present invention, the electric / electronic member and the housing may be integrally formed. The housing is made of an inorganic material such as SUS, copper, iron, aluminum, ceramics, a thermosetting resin, or a thermoplastic resin. There are no restrictions on organic materials such as biodegradable resins and natural resins that are selected according to the purpose and application. Also, the shape and dimensions of the parts are arbitrarily designed depending on the purpose.
[0050]
【Example】
Hereinafter, the present invention will be described by way of examples. In the examples, “parts” means “parts by weight” unless otherwise specified.
<Resin 1: Olefin-based low elastic modulus resin>
50 parts by weight of high-purity dicyclopentadiene (manufactured by Maruzen Petrochemical, purity 99% or more), 50 parts by weight of cyclooctadiene (purity 98.5% or more, manufactured by HULS), and silane coupling agent (FZ-3778, manufactured by Nippon Unicar) ) 0.1 part by weight was mixed. Next, a predetermined amount of fused silica having an average particle size of 15 μm (Furulex RD-8 manufactured by Tatsumori Co., Ltd.) was added to obtain a compound. In this compound FIG. Then, 0.2 part by weight of a metathesis polymerization catalyst represented by the formula (1) was added immediately before casting, and was tested. The curing conditions were 38 ° C. × 2 hours + 100 ° C. × 1 hour + 125 ° C. × 1 hour.
[0051]
<Resin 2: Acrylic low elastic modulus resin>
90 parts of lauryl methacrylate (light ester L manufactured by Kyoeisha Chemical Co., Ltd.) is mixed with 10 parts of polypropylene glycol dimethacrylate (NK ester 9PG manufactured by Kyoeisha Chemical Co., Ltd.), and t-butylperoxy-2-ethylhexanoate 0.5 is added as a polymerization catalyst. Parts were added. The curing conditions were 40 ° C. × 1 h + 60 ° C. × 3 h + 80 ° C. × 1 h + 100 ° C. × 1 h.
[0052]
<Resin 3: Polyester-based low elastic modulus resin>
A 2-liter four-necked flask equipped with a stirrer, condenser, nitrogen gas inlet tube and thermometer was charged with 463 parts of diethylene glycol, 454 parts of neopentyl glycol, 927 parts of adipic acid, and 156 parts of maleic anhydride, and nitrogen gas was slowly added. While flowing, using a mantle heater, the temperature was raised to 150 ° C. over 1 h, and after keeping warm for 1 h, the temperature was raised to 220 ° C. over 5 h. The mixture was kept at that temperature for 6 hours to obtain an unsaturated polyester having an acid value of 30. This was dissolved in a styrene monomer in which 0.01% of hydroquinone was dissolved so that the unsaturated polyester content would be 70% by weight, and an unsaturated polyester resin solution having a viscosity at 25 ° C. of 0.19 Pas was obtained. To 100 parts of this resin solution, 0.15 part of bis (4-t-butylcyclohexyl) peroxydicarbonate, 0.45 part of cumene hydroperoxide, and 0.8 part of benzoyl peroxide were added as an organic peroxide. The curing conditions were 80 ° C. × 3 h + 125 ° C. × 3 h.
[0053]
<Resin 4: Dicyclopentadiene resin 1>
100 parts by weight of the same high-purity dicyclopentadiene as that of the resin 1 and 0.1 parts by weight of a silane coupling agent (Nippon Unicar FZ-3778) were mixed. Next, a predetermined amount of fused silica (Furulex RD-8, manufactured by Tatsumori Co., Ltd.) having an average particle size of 15 μm was stirred and mixed to obtain a compound. FIG. The resin was cured in the same manner as in the resin 1 using the metathesis polymerization catalyst shown in FIG.
[0054]
<Resin 5: Dicyclopentadiene resin 2>
Liquid A was prepared by adding 40 mmol concentration of diethylaluminum chloride, 52 mmol concentration of n-propyl alcohol and 20 mmol concentration of silicon tetrachloride to dicyclopentadiene used in Resin 1 in a nitrogen-purged dry box. Further, similarly to the liquid A, 10 mmol concentration of tridecyl ammonium molybdenate was added to the dicyclopentadiene to prepare a liquid B. 50 parts by weight of this A liquid and B liquid were mixed, and 100 parts by weight of fused silica (Furex RD-8 manufactured by Tatsumori Co., Ltd.) having an average particle size of 15 μm was immediately mixed and stirred, and the same amount was obtained under a nitrogen atmosphere. Each sample was mixed and tested. The curing conditions were 50 ° C. × 0.5 h + 125 ° C. × 3 h.
[0055]
<Resin 6: Epoxy resin>
A liquid A was prepared by mixing 100 parts by weight of a bisphenol A type epoxy resin (YD-128, manufactured by Tohto Kasei Co., Ltd.) with 0.1 part by weight of a silane coupling agent (TSA-720, manufactured by Toshiba Silicone Co., Ltd.). On the other hand, 2 parts of 2-ethyl-4-methylimidazole was mixed with 87 parts by weight of methyltetrahydrophthalic anhydride (HN-2200, manufactured by Hitachi Chemical Co., Ltd.) as a curing agent to prepare a B solution. 50 parts by weight of this A liquid and 45 parts by weight of B liquid were mixed, and further 100 parts by weight of fused silica having an average particle size of 15 μm (Furex RD-8 manufactured by Tatsumori Co., Ltd.) was mixed and stirred thoroughly. tried. The curing conditions were 100 ° C. × 1 h, 125 ° C. × 2 h, and 140 ° C. × 3 h.
[0056]
<Resin 7: Silicone resin>
A commercially available heat dissipation type silicone resin (KE-1223 made by Shin-Etsu Silicone) was used. The curing conditions were 100 ° C. × 1 h.
[0057]
<Resin 8: Urethane resin>
To 100 parts by weight of a commercially available urethane resin for casting (KU-707, manufactured by Hitachi Chemical Co., Ltd.), 0.1 part by weight of a silane coupling agent (AZ-6171, manufactured by Nihon Unicar Co., Ltd.) was mixed and stirred, and the water content adhered by heating. 100 parts by weight of fused silica (Furex RD-8, manufactured by Tatsumori Co., Ltd.) having an average particle diameter of 15 μm from which the above was removed was mixed and stirred. The curing conditions were 50 ° C. × 3 h + 100 ° C. × 2 h.
[0058]
Test method
<Viscosity>
The viscosity was measured under the conditions of a B-type viscometer, 23 ° C., rotor # 3, 60 rpm.
<Bending elastic modulus>
A cast plate having a thickness of 3 mm was prepared and measured according to JIS-K-7203.
Test piece shape: 25 × 80 × 3 mm, test span: 48 mm, test speed 100 mm / min
<Model impregnation test>
Glass beads dried at 100 ° C. for 1 hour at a temperature of 15 mm in a polypropylene test tube having a diameter of 15 mm (average particle size of 80 μm) were filled in the test tube to a height of about 60 mm, and weighed to determine the weight of the glass beads. (W0g) was measured. Next, the resin composition was poured into a polypropylene test tube filled with glass beads to a height of about 60 mm, decompressed to 10 mmHg, allowed to stand for 10 minutes, and then thermally cured under specified conditions. Thereafter, glass beads that were not impregnated and separated from the cured product were collected and their weight (W1 g) was measured. The model impregnation rate was calculated from the following equation.
Model impregnation rate (%) = {(W0−W1) / W0} × 100
[0059]
<Part model 1 (Ignition coil sealant)>
An example of the cross-sectional structure of the ignition coil is shown in FIG.
The ignition coil includes a magnetic core 1, an outer core 2, a primary bobbin 3, a primary coil 4, a secondary bobbin 5, a secondary coil 6, and a terminal 7. The primary coil is wound about 200 mm of enameled wire with a diameter of about 0.5 mm, and the secondary coil is wound about 20000 times of enameled thin wire with a diameter of about 0.05 mm. The primary coil is connected to the battery and a direct current flows, but the current flowing by the ignition timing adjusting electronic circuit component and the power switch is intermittently changed to change the magnetic flux, and the primary voltage is obtained by the self-induction action. This primary voltage is set to a high voltage of 20 to 40 KV by the mutual induction action of the primary coil and the secondary coil, and spark discharge is caused in the spark plug connected to the terminal.
[0060]
Parts model 1 is made of polyphenylene sulfide (PPS) case material, magnetic core, aluminum electrode, ignition timing control circuit parts (configuration: ceramic substrate with IC / encapsulated parts with epoxy resin), modified polyphenylene oxide (PPO) bobbin The test sample shown in Table 1 in FIG. 3 was cast on the ignition coil incorporating the primary coil and the secondary coil under defoaming conditions of 5 torr × 1 minute, and 30 ° C. × 1 h + 50 ° C. × 1 h + 80 ° C. × 1 h + 120 × Curing was performed under curing conditions of 1 h.
[0061]
<Part model 2 (Batch sealing material for ignition coil)>
The test sample shown in Table 1 in FIG. 3 was placed on the ignition coil having the same member configuration as the component model 1 except that the ignition timing control circuit component (configuration: ceramic substrate with bare chip IC / component unsealed) was used. Casting was performed under defoaming conditions for 1 minute, and curing was performed under curing conditions of 30 ° C. × 1 h + 50 ° C. × 1 h + 80 ° C. × 1 h + 120 × 1 h to obtain a batch sealed ignition coil of electronic circuit components and coils.
[0062]
<Part model 3 (enclosure for caseless ignition coil)>
Magnetic coil, brass electrode, ignition timing control circuit component (configuration: ceramic substrate with bare chip IC / component unsealed) and modified polyphenylene oxide (PPS) bobbin primary and secondary coils are placed in the center of the mold The test sample shown in Table 1 was cast under a defoaming condition of 5 torr × 1 minute, cured under a curing condition of 30 ° C. × 1 h + 50 ° C. × 1 h + 80 ° C. × 1 h + 120 × 1 h, and then a sealing member was attached from a metal case. This was taken out to obtain a batch sealed caseless ignition coil.
[0063]
<Part model 4 (IC part encapsulant)>
A 15-square epoxy resin-sealed 16-pin DIP type IC-attached ceramic substrate was placed in the center of a 25 × 25 × 5 mm modified PPO concave case material, and a test sample defoamed in advance was poured to obtain a molded product.
[0064]
<Part model 5 (DIP type IC encapsulant)>
Using a test element with aluminum wiring on a silicon chip with a 5 mm oxide film, it was connected to a 42 alloy lead frame with partial silver plating with an epoxy-based silver paste, and a thermosonic wire bonder at 200 ° C. The bonding pad and the inner lead were connected with a 10 μm gold wire. Thereafter, the test sample defoamed in advance was potted and cured to obtain a 16-pin DIP (Dual Inline Package) type semiconductor sealed package.
[0065]
<Output characteristics>
400 cycles of the heat cycle test in which the part models 1 to 3 are (-40 ° C. × 30 minutes + 125 ° C. × 30 minutes) and when 12V is applied as the primary voltage after the test, the secondary voltage is 20 KV or more. Tested for output. Moreover, the part after a test was cut | disconnected and the presence or absence of peeling was observed with the optical microscope.
<Moldability>
In the part model 4, the cutting state of the gold wire was confirmed with soft X-rays.
<Solder reflow resistance>
The part models 4 and 5 were left in an atmosphere of 85 ° C./85% 168 for 168 hours, and then heated at 240 ° C. for 10 seconds three times to observe the occurrence of cracks and conduct current tests.
[0066]
The results of Examples and Comparative Examples are shown in Table 1 in FIG. The electrical / electronic parts of the present invention have higher output characteristics, moldability and solder resistance than parts sealed with epoxy resins or dicyclopentadiene resins with high elastic modulus and silicone resins or urethane resins with low elastic modulus. It had reflowability. This result shows that the electrical / electronic component of the present invention has excellent reliability.
[0067]
【The invention's effect】
The electric / electronic component of the present invention can provide a wide range of long-life, high-durability electric / electronic devices corresponding to high density and high integration.
[Brief description of the drawings]
FIG. 1 is a chemical structural formula of a Ru carbene catalyst.
FIG. 2 is a cross-sectional view of an ignition coil.
FIG. 3 is a table 1 showing the results of Examples and Comparative Examples.
[Explanation of symbols]
1. Magnetic core
2. Magnetic outer core
3. Primary bobbin
4). Primary coil
5). Secondary bobbin
6). Secondary coil
7). Terminal

Claims (13)

Comprising a step of sealing with a sealing member obtained by polymerizing a polymerizable composition containing a filler, one or more metathesis polymerizable cycloolefin compounds, and a metathesis polymerization catalyst,
The polymerizable composition is less than 3 poise is polymerizable liquid material in viscosity 23 ° C.,
The sealing member, the manufacturing method of electric and electronic parts, wherein the flexural modulus at 23 ° C. is not more than 500 MPa. The polymerizable composition includes 0.001 to 20% by weight of the metathesis polymerization catalyst with respect to the metathesis polymerizable cycloolefin compound.
The method for producing an electrical / electronic component according to claim 1, wherein the metathesis polymerization catalyst is a compound represented by the following general formula (1).

(M represents ruthenium or osmium, X and X1 each independently represents an anionic ligand, L and L1 each independently represent a neutral electron donating group, and Q and Q1 each independently represent hydrogen, alkyl. A group, an alkenyl group or an aromatic group, and the alkyl group, alkenyl group or aromatic group may have a substituent.) The polymerizable composition includes 0.001 to 20% by weight of the metathesis polymerization catalyst with respect to the metathesis polymerizable cycloolefin compound.
The method for producing an electrical / electronic component according to claim 1, wherein the metathesis polymerization catalyst is a compound represented by the following general formula (2).

(M represents ruthenium or osmium, X and X1 each independently represents an anionic ligand, L and L1 each independently represent a neutral electron donating group, and Q and Q1 each independently represent hydrogen, alkyl. A group, an alkenyl group or an aromatic group, and the alkyl group, the alkenyl group or the aromatic group may have a substituent.) The polymerizable composition includes 0.001 to 20% by weight of the metathesis polymerization catalyst with respect to the metathesis polymerizable cycloolefin compound.
The method for producing an electric / electronic component according to claim 1, wherein the metathesis polymerization catalyst is a compound represented by the following general formula (3).

(M represents ruthenium or osmium, X and X1 each independently represents an anionic ligand, L and L1 each independently represent a neutral electron donating group, and R1 and R2 each independently represent 1 carbon atom. -C18 alkyl group, C2-C18 alkenyl group, C2-C18 alkynyl group, aryl group, C1-C18 carboxylate group, C1-C18 alkoxy group, C2-C2 18 alkenyloxy groups, C2-C18 alkynyloxy groups, C2-C18 allyloxy groups, C2-C18 alkoxycarbonyls, C1-C18 alkylthio groups, C1-C18 alkyls A sulfonyl group or a C1-C18 alkylsulfinyl group is shown, R3 shows hydrogen, an aryl group, or a C1-C18 alkyl group.) The glass transition temperature of the said sealing member is 80 degrees C or less, The manufacturing method of the electrical / electronic component in any one of Claims 1-4 . Method for producing electric and electronic component according to any of the above sealing member of linear expansion coefficient of 23 ° C. in 100 × ¹⁰ -6 / K or more at which claims 1-5 in. The method for producing an electric / electronic component according to any one of claims 1 to 6, wherein the sealing member has a water absorption of less than 0.1% when immersed in water at 23 ° C for 24 hours. The method for manufacturing an electrical / electronic component according to any one of claims 1 to 7 , wherein the sealing member has a dielectric constant of 3.0 or less at 23 ° C. The polymerizable liquid material is selected from an additive comprising a modifier, a polymerization rate modifier, a foaming agent, an antifoaming agent, a colorant, a stabilizer, an adhesion-imparting agent, a flame retardant, a coupling agent, and an organic peroxide. method for producing electric and electronic parts according to any one of claims 1 to 8, comprising at least one compound. The method for producing an electric / electronic component according to any one of claims 1 to 9 , wherein the polymerizable liquid does not contain a solvent. The method for producing an electric / electronic component according to any one of claims 1 to 10 , wherein the polymerizable liquid material comprises a combination of two or more selected from metathesis polymerizable cycloolefin compounds having a molecular weight of less than 300. Method for producing electric and electronic parts according to any substantially oxygen claim 1 to 1 1, which is formed in the presence of. Electric and electronic parts, the central core of the magnetic material, a primary coil wound on the outside thereof, the secondary coil, claim 1 and 1 2 is an ignition coil having a outer core of the disposed outside by a magnetic material The manufacturing method of the electrical / electronic component in any one of .

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