JP2004256609A - Epoxy group-having silicon compound, method for producing the same and thermosetting resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy group-having silicon compound which gives highly heat-resistant cured products. <P>SOLUTION: This epoxy group-having silicon compound is obtained by hydrolyzing an alkoxysilane having an epoxy group in the molecule or the alkoxysilane having an epoxy group in the molecule and a substituted alkoxysilicon compound in the presence of an acid catalyst and then condensing the hydrolysates in the presence of a basic catalyst. The thermosetting resin composition comprises the silicon compound, a curing agent, and, if necessary, a curing accelerator and an organic solvent. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【０００９】
（式中Ｒ_１は、エポキシ基を有する置換基、炭素数１０以下のアルキル基、アリール基又は不飽和脂肪族残基を示し、複数個あるＲ_１はそれぞれ互いに同一でも異なっていても良いが、少なくとも１つはエポキシ基を含む置換基である。）
（２）式（１ａ）の化合物がＲ_１ａとして、炭素数３以下のグシシドキシアルキル基および／又はオキシラン基を持った炭素数５〜８のシクロアルキル基で置換されたアルキル基を有する化合物であり、式（１ｂ）の化合物がＲ_{１ ｂ}として、炭素数６以下のアルキル基又はアリール基を有する化合物である（１）記載のエポキシ基を有するケイ素化合物、
（３）全ての縮合成分が、式（１ａ）においてＲ_１ａが炭素数３以下のグシシドキシアルキル基である化合物である請求項１記載のエポキシ基を有するケイ素化合物、（４）全ての縮合成分が、式（１ａ）においてＲ_１ａがオキシラン基を持った炭素数５〜８のシクロアルキル基で置換されたアルキル基である（１）記載のエポキシ基を有するケイ素化合物、
（５）１）（１）〜（４）のいずれか一項に記載のエポキシ基を有するケイ素化合物、２）硬化剤並びに必要に応じて３）硬化促進剤及び４）有機溶剤を含有する熱硬化性樹脂組成物、
（６）（１）の式（１ａ）及び／又は式（１ｂ）で表される置換アルコキシケイ素化合物以外のエポキシ樹脂を含有する（５）記載の熱硬化性樹脂組成物、
（７）（５）又は（６）記載の熱硬化性樹脂組成物を硬化してなる硬化物、
に関する。
【００１０】
【発明の実施の形態】
本発明で使用する式（１ａ）のエポキシ基を有するアルコキシケイ素化合物中のエポキシ基を有する基Ｒ１ａとしては、エポキシ基を有する置換基であれば特に制限はないが、β−グリシドキシエチル基、γ−グリシドキシプロピル基、γ−グリシドキシブチル基等の炭素数４以下、好ましくは３以下のグシシドキシアルキル基、グリシジル基、β−（３，４−エポキシシクロヘキシル）エチル基、γ−（３，４−エポキシシクロヘキシル）プロピル基、β−（３，４−エポキシシクロヘプチル）エチル基、β−（３，４エポキシシクロヘキシル）プロピル基、β−（３，４エポキシシクロヘキシル）ブチル基、β−（３，４エポキシシクロヘキシル）ペンチル基等のオキシラン基を持った炭素数５〜８のシクロアルキル基で置換されたアルキル基等が挙げられ、好ましいものとしてはオキシラン基を持った炭素数５〜８のシクロアルキル基で置換された炭素数３以下のアルキル基等が挙げられる。これらの中でβ−グリシドキシエチル基、γ−グリシドキシプロピル基、β−（３，４エポキシシクロヘキシル）エチル基が好ましい。これらの置換基Ｒ１ａを有する式（１ａ）の化合物として用いる事のできる化合物の好ましい具体例としては、β−グリシドキシエチルトリメトキシシラン、β−グリシドキシエチルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリエトキシシラン等が挙げられる。
Ｒ_２としてはメチル基、エチル基、プロピル基、ブチル基が例示される。
【００１１】
また、式（１ｂ）で表される置換アルコキシケイ素化合物としては、置換基Ｒ_{１ ｂ}が、炭素数１０以下のアルキル基、アリール基又は不飽和脂肪族残基、好ましくは、組成物の相溶性、硬化物の物性の点から炭素数６以下のアルキル基又はアリール基であり、Ｒ_３が、炭素数４以下のアルキル基である組み合わせの化合物が好ましい。具体的にはメチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリプロポキシシラン、メチルトリブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、イソブチルトリメトキシシラン、イソブチルトリエトキシシラン、ｎ−プロピルトリメトキシシラン、ｎ−プロピルトリエトキシシラン、イソプロピルトリメトキシシラン、イソプロピルトリエトキシシラン、デシルトリメトキシシラン、デシルトリエトキシシラン等のアルキルトリアルコキシシラン類、フェニルトリメトキシシラン、フェニルトリエトキシシラン等のアリールトリアルコキシシラン類等が挙げられる。Ｒ_３としてはメチル基、エチル基、プロピル基、ブチル基が例示される。
なお、前記エポキシ基を有するアルコキシケイ素化合物及び置換アルコキシケイ素化合物中のアルコキシ基としては、反応条件の点でメトキシ基又はエトキシ基が好ましい。
【００１２】
本発明のエポキシ基を有するケイ素化合物を得る前記縮合反応においては、式（１ａ）のエポキシ基を有するアルコキシケイ素化合物を必須成分とし、式（１ａ）の化合物単独、または必要に応じ、式（１ａ）の化合物と式（１ｂ）の置換アルコキシケイ素化合物とを酸触媒で加水分解後、塩基性触媒の存在下、（共）縮合させることにより得る事が出来る。また、（共）縮合を促進するため、必要に応じ水を添加することができる。水の添加量としては、系全体のアルコキシ基１モルに対し０．０５〜１．５モル、好ましくは０．０７〜１．２モルである。
【００１３】
上記加水分解反応に使用する触媒は、酸であれば特に限定されないが、塩酸、硫酸、硝酸等の無機酸や蟻酸、酢酸、蓚酸等の有機酸が挙げられる。これらの中でも、反応性制御の点から蟻酸、酢酸が好ましい。触媒の添加量としては、エポキシ基を有するアルコキシケイ素化合物（式（１ａ））と置換アルコキシケイ素化合物（式（１ｂ））の合計に対し、０．００１〜１０重量％が好ましく、０．０１〜７．５重量％がより好ましい。
この加水分解反応における反応条件は、使用する触媒の種類、使用量にもよるが、通常５〜８０℃、好ましくは１０〜５０℃であり、反応時間は通常１〜１２時間である。
【００１４】
上記縮合反応に使用する触媒は塩基性であれば特に限定されないが、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化セシウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウムなどの無機塩基、アンモニア、トリエチルアミン、ジエチレントリアミン、ｎ−ブチルアミン、ジメチルアミノエタノール、トリエタノールアミン、テトラメチルアンモニウムハイドロオキサイドなどの有機塩基を使用することが出来る。これらの中でも、特に生成物からの触媒除去が容易である点で無機塩基又はアンモニアが好ましい。触媒の添加量としては、加水分解に使用した酸の中和に必要な量に加えてエポキシ基を有するアルコキシケイ素化合物（式（１ａ））と置換アルコキシケイ素化合物（式（１ｂ））の合計に対して、０．０５〜７重量％が好ましく、０．１〜５重量％がより好ましい。
この縮合反応における反応条件は、単独縮合、共縮合いずれの場合も、使用する触媒の種類、使用量にもよるが、通常１０〜１４０℃、好ましくは１５〜１２０℃であり、反応時間は通常１〜１２時間である。
【００１５】
上記反応は、無溶剤または溶剤中で行うことができる。溶剤としては、エポキシ基を有するアルコキシケイ素化合物及び置換アルコキシケイ素化合物を溶解する溶剤であれば特に制限はない。このような溶剤としては、例えばジメチルホルムアミド、ジメチルアセトアミド、テトラヒドロフラン、メチルエチルケトン、メチルイソブチルケトンなどの非プロトン性極性溶媒、トルエン、キシレン等の芳香族炭化水素等が例示できる。
このようにして得られる本発明のエポキシ基を有するケイ素化合物の分子量は、重量平均分子量で４００〜５００００のものが好ましく、７５０〜３００００のものがより好ましい。重量平均分子量で４００未満の場合、耐熱性向上効果に乏しく、５００００より大きい場合、組成物にした場合の相溶性の低下、粘度の上昇といった組成物としての物性が低下し好ましくない。
【００１６】
本発明のエポキシ基を有するケイ素化合物は、各種用途に供されるが、好ましい態様においては、通常、硬化剤を組み合わせた、熱硬化性樹脂組成物として使用される。また各種用途へ適用するにあたっては、用途に応じて各種のエポキシ樹脂を併用することも出来る。
【００１７】
本発明の熱硬化性樹脂組成物を調製するに当たり、硬化剤としては、通常、エポキシ樹脂の硬化剤として使用されている、アミン系化合物、酸無水物系化合物、アミド系化合物、フェノール系化合物等を特に制限無く使用できる。具体的には、ジアミノジフェニルメタン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルスルホン、イソホロンジアミン、ジシアンジアミド、テトラエチレンペンタミン、ジメチルベンジルアミン、ケチミン化合物、リノレン酸の２量体とエチレンジアミンより合成されるポリアミド樹脂、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、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、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、ビスフェノール類、フェノール類（フェノール、アルキル置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン、ジヒドロキシナフタレン等）と各種アルデヒドとの重縮合物、フェノール類と各種ジエン化合物との重合物、フェノール類と芳香族ジメチロールとの重縮合物、又はビスメトキシメチルビフェニルとナフトール類若しくはフェノール類との縮合物等、ビフェノール類及びこれらの変性物、イミダゾール、３フッ化硼素−アミン錯体、グアニジン誘導体などが挙げられる。硬化剤の使用量は、組成物中のエポキシ基１当量に対して０．２〜１．５当量が好ましく、０．３〜１．２当量が特に好ましい。また、硬化剤としてベンジルジメチルアミン等の３級アミンを使用する場合の硬化剤の使用量としては、組成物中のエポキシ基を有する化合物に対し、０．３〜２０重量％使用することが好ましく、０．５〜１０重量％が特に好ましい。
【００１８】
本発明の熱硬化性樹脂組成物中には必要により硬化促進剤をを有するさせることができる。硬化促進剤としては、例えば２−メチルイミダゾール、２−エチルイミダゾール、２−エチルー４−メチルイミダゾール、等のイミダゾール類、２−（ジメチルアミノメチル）フェノール、１，８−ジアザ−ビシクロ（５，４，０）ウンデセン−７等の第３級アミン類、トリフェニルフォスフィン等のホスフィン類、オクチル酸スズなどの金属化合物、第４級ホスホニウム塩などが挙げられる。硬化促進剤は、組成物中のエポキシ基を有する化合物１００重量部に対して０．０１〜１５重量部が必要に応じ用いられる。
【００１９】
本発明の熱硬化性樹脂組成物において、本発明のエポキシ基を有するケイ素化合物を他のエポキシ樹脂と併用する場合、本発明のエポキシ基を有するケイ素化合物が全エポキシ基を有する化合物中に占める割合は、１０重量％以上が好ましい。使用することができる他のエポキシ樹脂としては、通常、電気・電子部品に使用されるエポキシ樹脂でであれば特に制限はないが、用いうるエポキシ樹脂の具体例としては、フェノール性水酸基を２個以上有する化合物をグリシジル化したもの、例えばテトラブロモビスフェノールＡ、テトラブロモビスフェノールＦ、ビスフェノールＡ、テトラメチルビスフェノールＦ、ビスフェノールＦ、ビスフェノールＳ若しくはビスフェノールＫ等のビスフェノール類、又はビフェノール若しくはテトラメチルビフェノール等のビフェノール類、又はハイドロキノン、メチルハイドロキノン、ジメチルハイドロキノン、トリメチルハイドロキノン若しくはジ−ｔｅｒ．ブチルハイドロキノン等のハイドロキノン類、又はレゾルシノール若しくはメチルレゾルシノール等のレゾルシノール類、又はカテコール若しくはメチルカテコール等のカテコール類、又はジヒドロキシナフタレン、ジヒドロキシメチルナフタレン若しくはジヒドロキシジメチルナフタレン等のジヒドロキシナフタレン類のグリシジル化物やフェノール類若しくはナフトール類とアルデヒド類との縮合物、又はフェノール類若しくはナフトール類とキシリレングリコールとの縮合物又はフェノール類とイソプロペニルアセトフェノンとの縮合物又はフェノール類とジシクロペンタジエンとの反応物又はビスメトキシメチルビフェニルとナフトール類若しくはフェノール類との縮合物のグリシジル化物等が挙げられる。これらは、市販若しくは公知の方法により得ることが出来る。その他ＥＨＰＥ−３１５０、セロキサイド２０２１（ダイセル化学工業（株）製）、水添ビスフェノールＡ型エポキシ樹脂等の脂環式エポキシ樹脂、ＴＥＰＩＣ、ＴＥＰＩＣ−Ｌ、ＴＥＰＩＣ−Ｈ、ＴＥＰＩＣ−Ｓ（いずれも日産化学工業（株）製）等の複素環式エポキシ樹脂が挙げられる。これらは単独で用いてもよく、２種以上を用いても良い。
【００２０】
更に、本発明の熱硬化性樹脂組成物には、必要に応じてシリカ、アルミナ、ガラスファイバー、タルク等の充填材や離型剤、顔料、表面処理剤、粘度調整材、可塑剤、安定剤、カップリング剤等、種々の配合剤を添加することができる。
本発明の熱硬化性樹脂組成物は、各成分を均一に混合することにより得られる。
【００２１】
本発明の熱硬化性樹脂組成物を、溶剤に溶解し、ワニスとして使用することも出来る。溶剤としては、組成物の各成分を溶解する物であれば特に限定されないが、例えばトルエン、キシレン、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジメチルホルムアミド等が挙げられる。これら溶剤の溶解したワニスを、ガラス繊維、カーボン繊維、ポリエステル繊維、ポリアミド繊維、アルミナ繊維、紙などの基材に含浸させ、加熱乾燥して得たプリプレグを熱プレス成形して本発明の硬化物を得ることも出来る。
その際溶剤は、本発明の熱硬化性樹脂組成物と溶剤の合計重量に対し溶剤の占める割合が、通常１０〜７０重量％、好ましくは１５〜６５重量％となる量使用する。
【００２２】
本発明の熱硬化性樹脂組成物は従来知られている方法と同様の方法で容易にその硬化物とすることができる。例えばエポキシ基を有する化合物と硬化剤並びに必要により硬化促進剤及び配合剤とを必要に応じて押出機、ニ−ダ、ロ−ル等を用いて均一になるまで充分に混合してエポキシ樹脂組成物を得、そのエポキシ樹脂組成物を溶融後注型あるいはトランスファ−成型機などを用いて成型し、さらに８０〜２００℃で２〜１０時間加熱することにより硬化物を得ることができる。
【００２３】
【実施例】
以下、本発明を実施例により更に詳細に説明する。尚、本発明はこれら実施例に限定されるものではない。また、実施例中特に断りがない限り、部は重量部を示す。なお、実施例中の各物性値は以下の方法で測定した。
（１）重量平均分子量：ＧＰＣ（ゲルパーミエーションクロマトグラフィー）法により測定。
（２）エポキシ当量：ＪＩＳ Ｋ−７２３６に準じた方法で測定。
（３）核磁気共鳴スペクトル：日本電子（株）製 ＪＮＭ−ＡＬ４００を使用し、^２９Ｓｉの核磁気共鳴スペクトル（ＮＭＲ）を測定。
【００２４】
実施例１
γ−グリシドキシプロピルトリメトキシシラン４６．７部、水１０．８部、蟻酸２．３部を室温で１時間撹拌することによりアルコキシ基を加水分解した。次いでこれにメチルエチルケトン４０部、７．２重量％水酸化カリウム水溶液４０部を反応容器に仕込み、室温で５時間反応させた。反応終了後、洗浄液が中性になるまで水洗を繰り返した。次いで減圧下で溶媒を除去することにより本発明のエポキシ基を有するケイ素化合物（Ａ）３３ｇを得た。得られた化合物のエポキシ当量は１７２ｇ／ｅｑ、重量平均分子量は３０００であった。得られた化合物の２９Ｓｉ−ＮＭＲを測定した結果、−６５ｐｐｍ付近に、Ｓｉに３つの−Ｏ−Ｓｉ≡が結合した構造（Ｑ３構造）に帰属されるピークが観測された。また、赤外吸収スペクトルを測定したところ、１０３５ｃｍ^−１付近に鎖状−Ｏ−Ｓｉ−Ｏ−、１０６５ｃｍ^−１付近に大環状−Ｏ−Ｓｉ−Ｏ−、１０９５ｃｍ^−１付近に４員環−Ｏ−Ｓｉ−Ｏ−に起因する吸収ピークがそれぞれ認められた。
【００２５】
実施例２
実施例１で得られたエポキシ基を有するケイ素化合物（Ａ）１７．９部、ビスフェノールＡ型エポキシ樹脂（エポキシ当量１８６ｇ／ｅｑ、ジャパンエポキシレジン（株）製、エピコート８２８）１０部、ジアミノジフェニルメタン７．９部を均一に混合し本発明の熱硬化性樹脂組成物を調製した。得られた樹脂組成物をアルミカップに流し込み、６０℃、１００℃、１５０℃、１９０℃各４時間加熱することによってその硬化物を得た。また得られた硬化物にボイド等の欠陥は認められなかった。
【００２６】
比較例１
ビスフェノールＡ型エポキシ樹脂（エポキシ当量１８６ｇ／ｅｑ、ジャパンエポキシレジン（株）製、エピコート８２８）１０部、ジアミノジフェニルメタン２．６部を均一に混合し熱硬化性樹脂組成物を調製した。得られた樹脂組成物を実施例２と同様な方法で硬化させることにより、その硬化物を得た。
【００２７】
（耐熱性評価）
実施例２及び比較例１で得られた硬化物を幅４ｍｍ、厚さ３ｍｍ、長さ４０ｍｍの大きさに成形し、動的粘弾性測定装置（ＴＡインスツルメンツ社製、ＤＭＡ２９８０、測定条件：振幅１５μｍ、振動数１０Ｈｚ、昇温速度２℃／分）を用いて動的貯蔵弾性率を測定することにより耐熱性を評価した。測定結果を図１に示す。
【００２８】
図１より、比較例１では温度の上昇に伴い弾性率の大幅な低下が認められるのに対し、実施例２では弾性率の低下が小さく、高温時の弾性率が高く耐熱性に優れていることが認められる。
【００２９】
（線膨張係数評価）
実施例２及び比較例１で得られた硬化物を縦４ｍｍ、横４ｍｍ、高さ１０ｍｍの大きさに成形し、熱機械分析装置（ＴＡインスツルメンツ社製、ＴＭＡ２９４０、昇温速度２℃／分）を用いて線膨張係数の測定を行った。測定結果を図２に示す。
【００３０】
図２より、全ての測定範囲において、比較例１より実施例２の方が線膨張係数が低く、特に高温領域（１５０℃以上）における線膨張係数が著しく低いことが認められる。
【００３１】
【発明の効果】
本発明のエポキシ基を有するケイ素化合物を使用することにより、高温時の弾性率および線膨張係数に関し大幅な改善が認められ、耐熱性に優れた硬化物を得ることができる。
【図面の簡単な説明】
【図１】実施例２及び比較例１で得られた硬化物の動的貯蔵弾性率の測定結果を示すグラフ。
図１において、横軸は温度を、縦軸は動的貯蔵弾性率をそれぞれ示す。
【図２】実施例２及び比較例１で得られた硬化物の線膨張係数の測定結果を示すグラフ。
図２において、横軸は温度を、縦軸は線膨張係数をそれぞれ示す。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel silicon compound, various insulating materials for electric and electronic parts containing the same, various composite materials including laminates (printed wiring boards) and FRP (fiber reinforced plastics), adhesives, paints, and the like. The present invention relates to a thermosetting resin composition having excellent heat resistance.
[0002]
[Prior art]
Epoxy resins are widely used in the fields of various electric / electronic parts, structural materials, adhesives, paints, etc. because of their excellent heat resistance, electric properties, mechanical properties, and the like. Further, with the recent development of the electric and electronic fields, demands for epoxy resins have become higher, and in particular, improvements in heat resistance have been required.
[0003]
Methods for improving the heat resistance of the epoxy resin include increasing the crosslink density of the cured product by increasing the functional group density in the epoxy resin, and introducing a rigid skeleton into the resin skeleton. There are methods for improving the structure and filling with fillers such as glass fibers, silica particles and mica. However, a sufficient improvement effect has not been obtained by such a method of improving the structure of the epoxy resin itself or adding a filler or the like.
[0004]
As a method for improving the heat resistance other than the structural improvement of the epoxy resin itself and the addition of a filler, etc., a method using a silane-modified epoxy resin having an alkoxy group obtained by subjecting a bisphenol A type epoxy resin and a hydrolyzable alkoxysilane to a dealcoholization reaction. (Patent Document 1) has been proposed, but it has been pointed out that a problem such as voids or the like easily occurs in a cured product due to alcohol and water generated as by-products.
In addition, as a compound having a silicon and an epoxy group in a molecule as in the case of the silane-modified epoxy resin having an alkoxy group, a polyorganosiloxane having an epoxy group and a method for producing the same have been proposed (Patent Document 2). It is necessary to end-cap the hydroxyl group and / or the alkoxy group at the terminal of the main chain in order to improve the stability. In order to obtain the desired product, a mercapto group is introduced in advance and the ethylenically unsaturated group having an epoxy group A multi-step process of obtaining an organopolysiloxane having an epoxy group by subjecting the compound to a Michael addition reaction in the presence of a radical initiator is necessary and inefficient. No mention is made of the heat resistance of the resulting polyorganosiloxane having epoxy groups.
[0005]
[Patent Document 1]
JP 2001-59013 A [Patent Document 2]
Japanese Patent Application Laid-Open No. Hei 10-324749
[Problems to be solved by the invention]
An object of the present invention is to provide a silicon compound having an epoxy group that can obtain a cured product having excellent heat resistance without depending on a conventional heat resistance improving method.
[0007]
[Means for Solving the Problems]
Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention provides (1) the following formula (1a)
R _1a Si (OR ₂ ) ₃ (1a)
(In the formula, R _1a represents a substituent having an epoxy group. R ₂ represents an alkyl group having 4 or less carbon atoms.)
Or an alkoxysilicon compound having an epoxy group represented by the following formula (1b)
R _{1 b} Si (OR ₃ ) ₃ (1b)
(Wherein R _{1 b,} the number 10 following an alkyl group having a carbon or an aryl group or an unsaturated aliphatic residue, R ₃ denotes a alkyl group having 4 or less carbon atoms.)
A silicon having an epoxy group, having a skeletal structure represented by the following formula (1), obtained by hydrolyzing a substituted alkoxysilicon compound represented by the formula (1) with an acid catalyst and then condensing in the presence of a basic catalyst: Compound,
[0008]
Embedded image

[0009]
(Wherein R ₁ represents a substituent having an epoxy group, an alkyl group having 10 or less carbon atoms, an aryl group or an unsaturated aliphatic residue, and a plurality of R _{1 s} may be the same or different from each other. , At least one of which is a substituent containing an epoxy group.)
(2) A compound in which the compound of the formula (1a) has, as R _1a , an alkyl group substituted with a glycidoxyalkyl group having 3 or less carbon atoms and / or a cycloalkyl group having 5 to 8 carbon atoms having an oxirane group. , and the as compound R _{1 b} of formula (1b), a compound having an alkyl group or an aryl group having 6 or less carbon atoms (1) a silicon compound having an epoxy group described,
(3) The silicon compound having an epoxy group according to (1), wherein all the condensed components are compounds in which R _1a in the formula (1a) is a glycidoxyalkyl group having 3 or less carbon atoms. The silicon compound having an epoxy group according to (1), wherein the component is a compound in which R _1a in the formula (1a) is an alkyl group substituted with a cycloalkyl group having 5 to 8 carbon atoms having an oxirane group,
(5) 1) a silicon compound having an epoxy group according to any one of (1) to (4), 2) a curing agent, and if necessary, 3) a curing accelerator and 4) heat containing an organic solvent. Curable resin composition,
(6) The thermosetting resin composition according to (5), which contains an epoxy resin other than the substituted alkoxysilicon compound represented by Formula (1a) and / or Formula (1b) in (1).
(7) a cured product obtained by curing the thermosetting resin composition according to (5) or (6),
About.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
The group R1a having an epoxy group in the alkoxysilicon compound having an epoxy group of the formula (1a) used in the present invention is not particularly limited as long as it is a substituent having an epoxy group, but a β-glycidoxyethyl group A glycidoxyalkyl group having 4 or less, preferably 3 or less carbon atoms, such as a γ-glycidoxypropyl group or a γ-glycidoxybutyl group, a glycidyl group, a β- (3,4-epoxycyclohexyl) ethyl group, γ- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycyclohexyl) ethyl group, β- (3,4 epoxycyclohexyl) propyl group, β- (3,4 epoxycyclohexyl) butyl group , An alkyl group substituted with a cycloalkyl group having 5 to 8 carbon atoms and having an oxirane group such as β- (3,4 epoxycyclohexyl) pentyl group And the like, an alkyl group having 3 or less carbon atoms substituted with a cycloalkyl group having a carbon number of 5-8 having an oxirane group is as preferred. Among these, a β-glycidoxyethyl group, a γ-glycidoxypropyl group, and a β- (3,4 epoxycyclohexyl) ethyl group are preferred. Preferred specific examples of the compound which can be used as the compound of the formula (1a) having the substituent R1a include β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidyl Examples thereof include xypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane.
Examples of R ₂ include a methyl group, an ethyl group, a propyl group, and a butyl group.
[0011]
Examples of the substituent alkoxy silicon compound represented by the formula (1b), the substituents R _{1 b} is an alkyl group having 10 or less carbon atoms, an aryl group or an unsaturated aliphatic residue, preferably, the compatibility of the composition In view of the physical properties of the cured product, a compound having a combination of an alkyl group or an aryl group having 6 or less carbon atoms and R ₃ being an alkyl group having 4 or less carbon atoms is preferable. Specifically, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-propyltrimethoxysilane , Alkyltrialkoxysilanes such as n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, and aryltrialkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane And the like. Examples of R ₃ include a methyl group, an ethyl group, a propyl group, and a butyl group.
The alkoxy group in the alkoxysilicon compound having an epoxy group and the substituted alkoxysilicon compound is preferably a methoxy group or an ethoxy group in terms of reaction conditions.
[0012]
In the condensation reaction for obtaining a silicon compound having an epoxy group of the present invention, an alkoxysilicon compound having an epoxy group of the formula (1a) is an essential component, and the compound of the formula (1a) alone or, if necessary, a compound of the formula (1a) ) And the substituted alkoxysilicon compound of the formula (1b) are hydrolyzed with an acid catalyst and then (co) condensed in the presence of a basic catalyst. In order to promote (co) condensation, water can be added as necessary. The amount of water to be added is 0.05 to 1.5 mol, preferably 0.07 to 1.2 mol, per 1 mol of the alkoxy group in the entire system.
[0013]
The catalyst used in the hydrolysis reaction is not particularly limited as long as it is an acid, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, and organic acids such as formic acid, acetic acid, and oxalic acid. Among them, formic acid and acetic acid are preferable from the viewpoint of controlling the reactivity. The amount of the catalyst to be added is preferably 0.001 to 10% by weight, and more preferably 0.01 to 10% by weight, based on the total of the alkoxysilicon compound having an epoxy group (formula (1a)) and the substituted alkoxysilicon compound (formula (1b)). 7.5% by weight is more preferred.
The reaction conditions in this hydrolysis reaction are usually 5 to 80 ° C., preferably 10 to 50 ° C., and the reaction time is usually 1 to 12 hours, although it depends on the type and amount of the catalyst used.
[0014]
The catalyst used in the above condensation reaction is not particularly limited as long as it is basic, and inorganic catalysts such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate Organic bases such as a base, ammonia, triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide can be used. Among these, an inorganic base or ammonia is particularly preferred in that the catalyst can be easily removed from the product. The amount of the catalyst added is the amount required for neutralization of the acid used for the hydrolysis and the total of the alkoxysilicon compound having an epoxy group (formula (1a)) and the substituted alkoxysilicon compound (formula (1b)). On the other hand, 0.05 to 7% by weight is preferable, and 0.1 to 5% by weight is more preferable.
The reaction conditions in this condensation reaction are usually 10 to 140 ° C., preferably 15 to 120 ° C., depending on the type and amount of the catalyst used, in either case of single condensation or co-condensation. 1 to 12 hours.
[0015]
The above reaction can be performed without a solvent or in a solvent. The solvent is not particularly limited as long as it dissolves the alkoxysilicon compound having an epoxy group and the substituted alkoxysilicon compound. Examples of such a solvent include aprotic polar solvents such as dimethylformamide, dimethylacetamide, tetrahydrofuran, methyl ethyl ketone and methyl isobutyl ketone, and aromatic hydrocarbons such as toluene and xylene.
The molecular weight of the silicon compound having an epoxy group of the present invention thus obtained is preferably 400 to 50,000, more preferably 750 to 30,000 in terms of weight average molecular weight. When the weight average molecular weight is less than 400, the heat resistance improving effect is poor, and when the weight average molecular weight is more than 50,000, the physical properties of the composition such as a decrease in the compatibility and an increase in the viscosity of the composition are unfavorably reduced.
[0016]
The silicon compound having an epoxy group of the present invention is used for various applications. In a preferred embodiment, it is generally used as a thermosetting resin composition in which a curing agent is combined. When applied to various applications, various epoxy resins can be used in combination depending on the application.
[0017]
In preparing the thermosetting resin composition of the present invention, as a curing agent, amine-based compounds, acid anhydride-based compounds, amide-based compounds, phenol-based compounds, etc., which are usually used as curing agents for epoxy resins Can be used without particular limitation. Specifically, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, tetraethylenepentamine, dimethylbenzylamine, ketimine compound, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenols, phenol Of phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with various aldehydes Products, polymers of phenols and various diene compounds, polycondensates of phenols and aromatic dimethylol, or condensates of bismethoxymethylbiphenyl with naphthols or phenols, biphenols and modified products thereof, Examples include imidazole, boron trifluoride-amine complex, and guanidine derivatives. The amount of the curing agent used is preferably 0.2 to 1.5 equivalents, and particularly preferably 0.3 to 1.2 equivalents, per equivalent of the epoxy group in the composition. When a tertiary amine such as benzyldimethylamine is used as the curing agent, the amount of the curing agent used is preferably 0.3 to 20% by weight based on the epoxy group-containing compound in the composition. , 0.5 to 10% by weight is particularly preferred.
[0018]
The thermosetting resin composition of the present invention may have a curing accelerator if necessary. Examples of the curing accelerator include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, and 1,8-diaza-bicyclo (5,4). , 0) tertiary amines such as undecene-7, phosphines such as triphenylphosphine, metal compounds such as tin octylate, and quaternary phosphonium salts. The curing accelerator is used as needed in an amount of 0.01 to 15 parts by weight based on 100 parts by weight of the compound having an epoxy group in the composition.
[0019]
In the thermosetting resin composition of the present invention, when the silicon compound having an epoxy group of the present invention is used in combination with another epoxy resin, the proportion of the silicon compound having an epoxy group of the present invention in the total compound having an epoxy group Is preferably 10% by weight or more. The other epoxy resin that can be used is not particularly limited as long as it is an epoxy resin that is usually used for electric / electronic parts. Specific examples of the epoxy resin that can be used include two phenolic hydroxyl groups. Glycidylated compounds having the above, for example, bisphenols such as tetrabromobisphenol A, tetrabromobisphenol F, bisphenol A, tetramethylbisphenol F, bisphenol F, bisphenol S or bisphenol K, or biphenols such as biphenol or tetramethylbiphenol Or hydroquinone, methylhydroquinone, dimethylhydroquinone, trimethylhydroquinone or di-ter. Hydroquinones such as butylhydroquinone, or resorcinols such as resorcinol or methylresorcinol, or catechols such as catechol or methylcatechol, or dihydroxynaphthalene, glycidylated phenols of dihydroxynaphthalenes such as dihydroxymethylnaphthalene or dihydroxydimethylnaphthalene or phenols or Condensates of naphthols and aldehydes, or phenols or condensates of naphthols and xylylene glycol, or condensates of phenols and isopropenyl acetophenone or reactants of phenols and dicyclopentadiene or bismethoxymethyl Glycidylated products of condensates of biphenyl and naphthols or phenols are exemplified. These can be obtained commercially or by a known method. In addition, EHPE-3150, Celloxide 2021 (manufactured by Daicel Chemical Industries, Ltd.), alicyclic epoxy resins such as hydrogenated bisphenol A type epoxy resin, TEPIC, TEPIC-L, TEPIC-H, and TEPIC-S (all are Nissan Chemical Industries, Ltd.) (Manufactured by Kogyo Co., Ltd.). These may be used alone or in combination of two or more.
[0020]
Further, the thermosetting resin composition of the present invention may optionally contain fillers such as silica, alumina, glass fiber, and talc, release agents, pigments, surface treatment agents, viscosity modifiers, plasticizers, and stabilizers. Various additives such as a coupling agent and the like can be added.
The thermosetting resin composition of the present invention is obtained by uniformly mixing the components.
[0021]
The thermosetting resin composition of the present invention can be dissolved in a solvent and used as a varnish. The solvent is not particularly limited as long as it dissolves each component of the composition, and examples thereof include toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, and dimethylformamide. A varnish in which these solvents are dissolved is impregnated into a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and prepreg obtained by heating and drying is subjected to hot press molding to obtain a cured product of the present invention. You can also get
In this case, the solvent is used in such an amount that the ratio of the solvent to the total weight of the thermosetting resin composition of the present invention and the solvent is usually 10 to 70% by weight, preferably 15 to 65% by weight.
[0022]
The thermosetting resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, a compound having an epoxy group, a curing agent, and, if necessary, a curing accelerator and a compounding agent are sufficiently mixed as required using an extruder, a kneader, a roll, or the like until the mixture becomes uniform, thereby forming an epoxy resin composition. After curing the epoxy resin composition, the epoxy resin composition is molded using a casting or transfer molding machine, and then heated at 80 to 200 ° C. for 2 to 10 hours to obtain a cured product.
[0023]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples. Note that the present invention is not limited to these examples. In the examples, unless otherwise specified, parts are parts by weight. In addition, each physical property value in an Example was measured by the following method.
(1) Weight average molecular weight: measured by GPC (gel permeation chromatography) method.
(2) Epoxy equivalent: measured by a method according to JIS K-7236.
(3) Nuclear magnetic resonance spectrum: A nuclear magnetic resonance spectrum (NMR) of ²⁹ Si was measured using JNM-AL400 manufactured by JEOL Ltd.
[0024]
Example 1
The alkoxy group was hydrolyzed by stirring 46.7 parts of γ-glycidoxypropyltrimethoxysilane, 10.8 parts of water, and 2.3 parts of formic acid at room temperature for 1 hour. Next, 40 parts of methyl ethyl ketone and 40 parts of a 7.2% by weight aqueous solution of potassium hydroxide were charged into the reaction vessel and reacted at room temperature for 5 hours. After the completion of the reaction, washing with water was repeated until the washing solution became neutral. Then, the solvent was removed under reduced pressure to obtain 33 g of the silicon compound (A) having an epoxy group of the present invention. The epoxy equivalent of the obtained compound was 172 g / eq, and the weight average molecular weight was 3000. As a result of measuring 29Si-NMR of the obtained compound, a peak belonging to a structure in which three -O-Si≡ were bonded to Si (Q3 structure) was observed at about -65 ppm. The measured infrared absorption spectrum, 1035 cm chain -O-Si-O-around ^-1 macrocyclic -O-Si-O- around 1065 cm ^-1, 4-membered ring in the vicinity of 1095 cm ^-1 - Absorption peaks attributed to O-Si-O- were observed respectively.
[0025]
Example 2
17.9 parts of an epoxy group-containing silicon compound (A) obtained in Example 1, 10 parts of a bisphenol A type epoxy resin (epoxy equivalent: 186 g / eq, manufactured by Japan Epoxy Resin Co., Ltd., Epicoat 828), diaminodiphenylmethane 7 .9 parts were uniformly mixed to prepare a thermosetting resin composition of the present invention. The obtained resin composition was poured into an aluminum cup and heated at 60 ° C., 100 ° C., 150 ° C. and 190 ° C. for 4 hours to obtain a cured product. No defects such as voids were found in the obtained cured product.
[0026]
Comparative Example 1
10 parts of a bisphenol A epoxy resin (epoxy equivalent: 186 g / eq, manufactured by Japan Epoxy Resin Co., Ltd., Epicoat 828) and 2.6 parts of diaminodiphenylmethane were uniformly mixed to prepare a thermosetting resin composition. The obtained resin composition was cured in the same manner as in Example 2 to obtain a cured product.
[0027]
(Heat resistance evaluation)
The cured products obtained in Example 2 and Comparative Example 1 were formed into a size of 4 mm in width, 3 mm in thickness, and 40 mm in length, and were measured with a dynamic viscoelasticity measuring device (TA Instruments, DMA2980, measurement condition: amplitude 15 μm). The heat resistance was evaluated by measuring the dynamic storage modulus using a vibration frequency of 10 Hz and a heating rate of 2 ° C./min. FIG. 1 shows the measurement results.
[0028]
From FIG. 1, it can be seen that in Comparative Example 1, a large decrease in the elastic modulus was observed with an increase in temperature, whereas in Example 2, the decrease in the elastic modulus was small, and the elastic modulus at a high temperature was high and the heat resistance was excellent. It is recognized that.
[0029]
(Evaluation of linear expansion coefficient)
The cured products obtained in Example 2 and Comparative Example 1 were formed into a size of 4 mm in length, 4 mm in width, and 10 mm in height, and a thermomechanical analyzer (manufactured by TA Instruments, TMA2940, heating rate 2 ° C./min) Was used to measure the linear expansion coefficient. FIG. 2 shows the measurement results.
[0030]
From FIG. 2, it can be seen that the coefficient of linear expansion of Example 2 is lower than that of Comparative Example 1 in all the measurement ranges, and particularly the coefficient of linear expansion in a high-temperature region (150 ° C. or higher) is remarkably low.
[0031]
【The invention's effect】
By using the silicon compound having an epoxy group of the present invention, a significant improvement in the elastic modulus and linear expansion coefficient at a high temperature is recognized, and a cured product having excellent heat resistance can be obtained.
[Brief description of the drawings]
FIG. 1 is a graph showing the measurement results of the dynamic storage modulus of the cured products obtained in Example 2 and Comparative Example 1.
In FIG. 1, the horizontal axis represents temperature, and the vertical axis represents dynamic storage modulus.
FIG. 2 is a graph showing the measurement results of the coefficient of linear expansion of the cured products obtained in Example 2 and Comparative Example 1.
In FIG. 2, the horizontal axis represents temperature, and the vertical axis represents linear expansion coefficient.

Claims (7)

The following formula (1a)
R _1a Si (OR ₂ ) ₃ (1a)
(In the formula, R _1a represents a substituent having an epoxy group. R ₂ represents an alkyl group having 4 or less carbon atoms.)
Or an alkoxysilicon compound having an epoxy group represented by the following formula (1b)
R _{1 b} Si (OR ₃ ) ₃ (1b)
(Wherein R _{1 b,} the number 10 following an alkyl group having a carbon or an aryl group or an unsaturated aliphatic residue, R ₃ denotes a alkyl group having 4 or less carbon atoms.)
A silicon having an epoxy group, having a skeletal structure represented by the following formula (1), obtained by hydrolyzing a substituted alkoxysilicon compound represented by the formula (1) with an acid catalyst and then condensing in the presence of a basic catalyst: Compound.

(Wherein R ₁ represents a substituent having an epoxy group, an alkyl group having 10 or less carbon atoms, an aryl group or an unsaturated aliphatic residue, and a plurality of R _{1 s} may be the same or different from each other. , At least one of which is a substituent containing an epoxy group.) The compound of the formula (1a) is a compound having, as R _1a , an alkyl group substituted with a glycidoxyalkyl group having 3 or less carbon atoms and / or a cycloalkyl group having 5 to 8 carbon atoms having an oxirane group, The epoxy compound-containing silicon compound according to claim 1, wherein the compound of the formula (1b) is a compound having an alkyl group or an aryl group having 6 or less carbon atoms as R _{1 b} . The silicon compound having an epoxy group according to claim 1, wherein all the condensation components are compounds in which R _1a in the formula (1a) is a glycidoxyalkyl group having 3 or less carbon atoms. All condensation component, a silicon compound having an epoxy group according to claim 1, wherein R _1a is an alkyl group substituted with a cycloalkyl group having a carbon number of 5-8 having an oxirane group in the formula (1a). 1) a silicon compound having an epoxy group according to any one of claims 1 to 4; 2) a curing agent and, if necessary, 3) a curing accelerator and 4) a thermosetting resin composition containing an organic solvent. . The thermosetting resin composition according to claim 5, further comprising an epoxy resin other than the substituted alkoxysilicon compound represented by the formula (1a) and / or the formula (1b). A cured product obtained by curing the thermosetting resin composition according to claim 5.

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