JP3580437B2 - Curable resin composition - Google Patents

Description

【００１１】
（Ｘは、ハロゲン原子、Ｒ_１は水素または炭素数１〜２０の１価の炭化水素基、Ｒ_２は、−Ｒ_３−，−Ｒ_３−ＯＣ（＝Ｏ）−または−Ｒ_３−Ｃ（＝Ｏ）−〔Ｒ_３は炭素数１〜２０までの２価の炭化水素基で、好ましい具体例としては、アルキレン基、シクロアルキレン基、アリーレン基、アラルキレン基が挙げられる〕で示される２価の有機基である。）
で示される有機ハロゲン化合物を反応させることにより、不飽和基を有する有機重合体が製造される。
【００１２】
主鎖または側鎖の水酸基をオキシメタル基にする方法としては、Ｎａ，Ｋのようなアルカリ金属、ＮａＨのような金属水素化物、ＮａＯＣＨ_３ のような金属アルコキシド、ＮａＯＨ，ＫＯＨのようなアルカリなどと反応させる方法が挙げられる。
上記方法では、出発原料として用いた水酸基含有有機重合体とほぼ同じ分子量をもつ不飽和基含有有機重合体が得られるが、より高分子量の重合体を得たい場合には一般式（Ｉ）の化合物と反応させる前にオキシメタル化物と多価有機ハロゲン化物例えば塩化メチレン、ビス（クロロメチル）ベンゼン等を反応させて分子量を増大させた後、（Ｉ）と反応させると良い。
【００１３】
上記一般式（Ｉ）で示される有機ハロゲン化物の具体例としては、アリルクロライド、アリルブロマイド、ビニル（クロロメチル）ベンゼン、アリル（クロロメチル）ベンゼン、アリル（ブロモメチル）ベンゼン、アリル（クロロメチル）エーテル、アリル（クロロメトキシ）ベンゼン、１−ブテニル（クロロメチル）エーテル、１−ヘキセニル（クロロメトキシ）ベンゼン、アリルオキシ（クロロメチル）ベンゼン等が挙げられるが、これらに限定されるものではない。この中で最も好ましいものは、コスト、反応性の点からアリルクロライドである。
【００１４】
重合中に不飽和基を導入する方法としては、例えば開始剤兼連鎖移動剤を用いるＵＳＰ４３１６９７３に示す方法や、特開昭６３−１０５００５に示す方法等を用いることができる。
本発明の（Ｂ）成分である、分子中に少なくとも２個のヒドロシリル基を有する有機化合物としては特に制限はない。ここで、ヒドロシリル基１個とはＳｉＨ基１個をさす。従って、同一Ｓｉに水素原子が２個結合している場合はヒドロシリル基２個と計算する。この有機化合物において、ヒドロシリル基を含む基を具体的に例示するならば、−Ｓｉ（Ｈ）_ｎ（ＣＨ_３）_３−ｎ ，−Ｓｉ（Ｈ）_ｎ（Ｃ_２Ｈ_５）_３−ｎ，−Ｓｉ（Ｈ）_ｎ（Ｃ_６Ｈ_５）_３−ｎ （ｎ＝１〜３）、−ＳｉＨ_２（Ｃ_６Ｈ_１３）などのケイ素原子１個だけ含有する基、−Ｓｉ（ＣＨ_３ ）_２Ｓｉ（ＣＨ_３）_２Ｈ，−Ｓｉ（ＣＨ_３）_２ＣＨ_２ＣＨ_２Ｓｉ（ＣＨ_３）_２Ｈ，−Ｓｉ（ＣＨ_３）_２ＳｉＣＨ_３Ｈ_２、
【００１５】
【化２】

【００１６】
などのケイ素原子を２個含む基、
【００１７】
【化３】

【００１８】
（式中、ＲはＨ，ＯＳｉ（ＣＨ_３）_３および炭素数が１〜１０の有機基より選ばれる基であり各々のＲは同じでも異なっていてもよい。ｍ，ｎは正の整数で且つ、２≦ｍ＋ｎ≦５０）
【００１９】
【化４】

【００２０】
（Ｒ，ｍ，ｎは上記に同じ）
【００２１】
【化５】

【００２２】
（式中、Ｒは上記に同じ、ｍは正の整数、ｎ、ｐ、ｑは０または正の整数で、且つ１≦ｍ＋ｎ＋ｐ＋ｑ≦５０）
【００２３】
【化６】

【００２４】
（式中Ｒは上記に同じ、ｍは正の整数、ｎは０または正の整数で、且つ２≦ｍ＋ｎ≦５０）などで示される鎖状、枝分かれ状、環状の各種の多価ハイドロジェンシロキサンより誘導された基などが挙げられる。
上記の各種のヒドロシリル基含有基のうち、本発明のヒドロシリル基含有化合物の、（Ａ）成分に対する相溶性を損なう可能性が少ないという点から、ヒドロシリル基を構成する基の部分の分子量は５００以下が望ましく、さらにヒドロシリル基の反応性も考慮すれば、下記のものが好ましい。
【００２５】
【化７】

【００２６】
（式中、ｐは正の整数、ｑは０または正の整数であり、かつ２≦ｐ＋ｑ≦４）
【００２７】
【化８】

【００２８】
【化９】

【００２９】
同一分子中にヒドロシリル基含有基が２個以上存在する場合には、それらは互いに同一でも異なっても構わない。（Ｂ）成分中に含まれるトータルのヒドロシリル基の個数については、少なくとも、１分子中に２個あれば良いが、２〜１５個が好ましく、３〜１２個が特に好ましい。本発明のヒドロシリル基含有化合物を、ヒドロシリル化触媒存在下に、アルケニル基を含有する化合物（（Ａ）成分）と混合してヒドロシリル化反応により硬化させる場合には、該ヒドロシリル基の個数が２より少ないと硬化不良を起こす場合が多い。また、該ヒドロシリル基の個数が１５より多くなると、（Ｂ）成分の安定性が悪くなり、そのうえ、硬化後も多量のヒドロシリル基が硬化物中に残存し、ボイドやクラックの原因となる。
【００３０】
（Ｂ）成分のヒドロシリル基含有化合物としては特に制限はないが、上記ヒドロシリル基含有基を有する有機化合物が挙げられ、低分子量のものから重合体にいたる各種の化合物を用いることができる。
具体的に例示すると、式（ＩＩ）
【００３１】
【化１０】

【００３２】
（式中、Ｘは上記のヒドロシリル基含有基、Ｒ^１は水素またはメチル、Ｒ^２は炭素数１〜２０の２価の炭化水素基で１個以上のエーテル結合が含有されていてもよい。Ｒ^３は脂肪族または芳香族の有機基、ａは正の整数。）で表されるエーテル結合を有する化合物、
式（ＩＩＩ ）
【００３３】
【化１１】

【００３４】
（式中、Ｘは上記のヒドロシリル基含有基、Ｒ^１は水素またはメチル基、Ｒ^２は炭素数１〜２０の２価の炭化水素基で１個以上のエーテル結合を含有していてもよい。Ｒ^４は脂肪族または芳香族の有機基、ａは正の整数。）で表されるエステル結合を有する化合物、
式（ＩＶ）
【００３５】
【化１２】

【００３６】
（式中、Ｘは上記のヒドロシリル基含有基、Ｒ^１は水素またはメチル基、Ｒ^５は脂肪族または芳香族の有機基、ａは正の整数）で表される炭化水素系の化合物、 さらに、式（Ｖ）
【００３７】
【化１３】

【００３８】
（式中、Ｘは上記のヒドロシリル基含有基、Ｒ^１は水素またはメチル基、Ｒ^２は炭素数１〜２０の２価の炭化水素基で１個以上のエーテル結合を含有していてもよい。Ｒ^６は脂肪族または芳香族の有機基、ａは正の整数）で表されるカーボネート結合を有する化合物が挙げられる。
（Ｂ）成分として有機重合体を用いる場合、式（ＩＩ）〜（Ｖ）のＲ^３ 〜Ｒ^６ の有機基は重合体残基となるが、この残基は、線状でも枝分かれ状でもよく、分子量は５００００以下の任意のものが好適に使用できるが、２００００以下のものが特に好ましい。
【００３９】
（Ｂ）成分のヒドロシリル基は、分子末端にあっても分子中にあっても良いが、本発明の組成物を用いてゴム状硬化物を作製する場合には、分子末端にある方が有効網目鎖長が長くなるので好ましい。
（Ｂ）成分の製造方法としては特に制限はなく、任意の方法を用いればよい。例えば、（ｉ）分子内にＳｉ−Ｃｌ基をもつ有機化合物をＬｉＡｌＨ_４，ＮａＢＨ_４などの還元剤で処理して該化合物中のＳｉ−Ｃｌ基をＳｉ−Ｈ基に還元する方法、（ｉｉ）分子内にある官能基Ｘを持つ有機化合物と分子内に上記官能基と反応する官能基Ｙ及びヒドロシリル基を同時にもつ化合物とを反応させる方法、（ｉｉｉ）アルケニル基を持つ有機化合物に対してヒドロシリル基を持つポリヒドロシラン化合物を選択ヒドロシリル化することにより、反応後もヒドロシリル基を該化合物の分子中に残存させる方法などが考えられる。これらのうち（ｉｉｉ）の方法が特に好ましい。
【００４０】
本発明の（Ｃ）成分であるヒドロシリル化触媒については、特に制限はなく、任意のヒドロシリル化触媒を用いることができる。具体的に例示すれば
白金の単体、アルミナ、シリカ、カーボンブラック等の単体に固体白金を担持させたもの；
白金−ビニルシロキサン錯体（例えば
Ｐｔ_ｎ（ＶｉＭｅ_２ＳｉＯＳｉＭｅ_２Ｖｉ）_ｍ 、
Ｐｔ［（ＭｅＶｉＳｉＯ）_４〕_ｍ 、）；
白金−ホスフィン錯体（例えば、
Ｐｔ（ＰＰｈ_３）_４ 、Ｐｔ（ＰＢｕ_３）_４）；
白金−ホスファイト錯体（例えば、
Ｐｔ［Ｐ（ＯＰｈ）_３］_４ 、Ｐｔ［Ｐ（ＯＢｕ）_３ ］_４ ；
（式中、Ｍｅはメチル基、Ｂｕはブチル基、Ｖｉはビニル基、Ｐｈはフェニル基を表し、ｎ、ｍは整数を表す）
Ｐｔ（ａｃａｃ）_２ 、またＡｓｈｂｙの米国特許第３１５９６０１及び３１５９６６２号明細書中に記載された白金−炭化水素複合体、並びにＬａｍｏｒｅａｕｘの米国特許第３２２０９７２号明細書中に記載された白金アルコラート触媒も挙げられる。
【００４１】
また、白金化合物以外の触媒の例としては、Ｒｈ／Ａｌ₂Ｏ₃等が挙げられる。これらの触媒は単独で使用してもよく、２極以上併用することもできる。触媒活性の点から、白金−オレフィン錯体、白金−ビニルシロキサン錯体、Ｐｔ（ａｃａｃ）₂等が好ましい。本発明の（Ｃ）成分であるヒドロシリル化触媒の量としては（Ａ）成分中の不飽和基１ｍｏｌに対して１０^-1〜１０^-8ｍｏｌの範囲で用いる。好ましくは１０^-3〜１０^-6ｍｏｌの範囲で用いるのがよい。
【００４２】
本発明の（Ｄ）成分である芳香族ジイソシアナート化合物については、より具体的には、
【００４３】
【化１４】

【００４４】
に挙げる化合物やそれらの２量体、３量体、プレポリマー等を使用する事ができる。接着性付与効果を十分に出すためには（Ｄ）成分中にイソシアナート基が２個以上あることが必要である。添加量は、（Ａ）成分重合体１００重量部に対して０．０１〜２０重量部、好ましくは０．１〜５重量部の割合で使用される。（Ｄ）成分は単独で使用しても、２種以上併用しても良い。
【００４５】
本発明の（Ｅ）成分であるビニル基、エポキシ基及びイソシアナート基からなる群から選択される少なくとも１種を含有するシランカップリング剤についても付加型硬化させる際に硬化阻害の問題なく使用できる。（Ｅ）成分については、より具体的には、
【００４６】
【化１５】

【００４７】
に挙げる化合物を使用する事ができる。（Ｅ）成分はビニル基、エポキシ基及びイソシアナート基からなる群から選択される少なくとも１種を含有するが、その他、アリル基、メタクリロキシ基、メタクリロイル基等を含有していてもよい。
（Ｅ）成分は単独で使用しても、２種以上併用しても良い。添加量は、（Ａ）成分重合体１００重量部に対して０．０１〜２０重量部、好ましくは０．１〜５重量部の割合で使用される。
【００４８】
本発明の（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）及び（Ｅ）成分を混合した液状樹脂組成物を加熱すると硬化物が得られる。硬化条件については特に制限はないが、一般に３０〜２００℃、好ましくは５０〜１５０℃で１０秒〜２時間程度で硬化させる。ただし、１００℃以下で硬化させた場合は１３０℃以上で１時間程度後硬化させると好ましい。１５０℃以上で後硬化させるとさらに好ましい。
【００４９】
本発明の熱硬化性液状樹脂組成物には、必要に応じて各種配合物を添加することができる。添加成分の例としては、可塑剤、接着性改良剤、保存安定性改良剤、充填剤、老化防止剤、紫外線吸収刑、金属不活性化剤、オゾン劣化防止剤、耐光安定化剤、ラジカル重合禁止剤、過酸化物分解剤、滑剤、顔料、発泡剤等を挙げることができる。
【００５０】
可塑剤としては、一般に用いられている可塑剤を用いることができるが、本発明に用いる炭化水素系重合体と相溶性のよいものが好ましい。可塑剤の具体例としては、ポリブテン、水添ポリブテン、α−メチルスチレンオリゴマー、ポリブタジエン、水添ポリブタジエン、部分水素添加ターフェニル、パラフィン油、ナフテン油、アタクティックポリプロピレンなどであり、これらのなかでも不飽和結合を含まない水添ポリブテン、水添ポリブタジエン、パラフィン油、ナフテン油、アタクティックポリプロピレンなどの炭化水素系化合物が好ましい。
【００５１】
また、前述の接着性付与剤と併用して他の接着性付与剤を添加しても良い。クマロン−インデン樹脂、ロジンエステル樹脂、テルペン−フェノール樹脂等の粘着付与剤やα−メチルスチレン−ビニルトルエン共重合体、ポリエチルメチルスチレン、アルキルチタネート類等も併用して用いることができる。
保存安定性改良剤としては、（Ｃ）成分の触媒活性を室温保存時のみ制御するものが好ましく、２−ベンゾチアゾリルサルファイド、ベンゾチアゾール、チアゾール、ジメチルアセチレンジカルボキシレート、ジエチルアセチレンジカルボキシレート、ＢＨＴ、ブチルヒドロキシアニソール、ビタミンＥ、３−メチル−１−ブテン−３−オール、アセチレン性不飽和基含有オルガノシロキサン、アセチレンアルコール、３−メチル−１−ブチン−３−オール、３−メチル−１−ペンチン−３−オール、ジアリルフマレート、ジアリルマレート、ジエチルフマレート、ジエチルマレート、ジメチルマレート等を用いることができる。保存安定性改良剤を用いる場合の使用量は、触媒１ｍｏｌ に対し０．１〜１０００ｍｏｌ、好ましくは１〜２００ｍｏｌである。保存安定性改良剤の使用量が上記の量の上限を越えた場合には、硬化遅延が起こるばかりでなく、硬化不良を起こし、硬化物に要求される物性を満足させることができない。逆に保存安定性改良剤の使用量が上記の量の下限を下回った場合には、組成物の保存安定性を改良するという目的を達成することができない。
【００５２】
【実施例】
以下、実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらに限定されるものではない。
〔製造例１〕
アリル基末端水添ポリイソプレンオリゴマーの合成
両末端に水酸基を有する水素添加ポリイソプレン（出光石油化学（株）製、商品名：エポール）３００ｇにトルエン５０ｍｌを加え共沸脱気により脱水した。ｔ−ＢｕＯＫ４８ｇをトルエン２００ｍｌに溶解したものを添加し、８０℃で３時間反応させた。温度を６０℃に下げ、アリルクロライド４７ｍｌを約３０分間かけて滴下した。滴下終了後、そのままの温度で２時間反応させた。反応終了後、生成した塩を吸着させるために反応溶液にケイ酸アルミニウム３０ｇを加え、２時間撹拌した。濾過精製により約２５０ｇのアリル末端水添ポリイソプレンを粘稠な液体として得た。^１Ｈ−ＮＭＲ分析により末端の９０％にアリル基が導入されている事が確認された。ヨウ素価より求めたオレフィンのモル数は０．１１ｍｏｌ／１００ｇであった。元素分析より求めた塩素含量は０．１％未満であった。またＥ型粘度計による粘度は約３３０ポイズ（２３℃）であった。
【００５３】
○エポールの代表的物性値（エポール技術資料より）
；水酸基含有量（ｍｅｑ／ｇ） ０．９０
；粘度（ｐｏｉｓｅ／３０℃） ７００
；平均分子量（ＶＰＯ測定） ２５００
〔製造例２〕 アリル基末端水添ポリブタジエンオリゴマーの合成
両末端に水酸基を有する水素添加ポリブタジエン（三菱化成（株）製、商品名：ポリテール）３００ｇにトルエン５０ｍｌを加え共沸脱気により脱水した。ｔ−ＢｕＯＫ４１ｇをトルエン２００ｍｌに溶解したものを注入し、８０℃で３時間反応させた。温度を６０℃に下げ、アリルクロライド４０ｍｌを約３０分間かけて滴下した。滴下終了後、そのままの温度で２時間反応させた。反応終了後、生成した塩を吸着させるために反応溶液にケイ酸アルミニウム３０ｇを加え、２時間撹拌した。濾過精製により約２４０ｇのアリル末端水添ポリブタジエンを粘調な液体として得た。^１Ｈ−ＮＭＲ分析により末端の８５％にアリル基が導入されている事が確認された。ヨウ素価より求めたオレフィンのモル数は０．１０ｍｏｌ／１００ｇであった。元素分析より求めた塩素含量は０．１％未満であった。またＥ型粘度計による粘度は約３００ポイズ（２３℃）であった。
【００５４】
○ポリテールの代表的物性値（ポリテール技術資料より）
；水酸基含有量（ｍｅｑ／ｇ） ０．７３〜０．９８
；粘度（ｐｏｉｓｅ／３０℃） ５００〜１５００
；粘度（ｐｏｉｓｅ／８０℃） ６〜１９
；密度（ｇ／ｃｍ^３） ０．８７（２５℃）
〔製造例３〕 不飽和末端ポリイソブテンオリゴマーの合成
１Ｌの耐圧ガラスオートクレーブに撹拌用羽根、三方コック及び真空ラインを取り付けて、真空ラインで真空にしながら重合容器を１００℃で１時間加熱することにより乾燥させ、室温まで冷却後、三方コックを用いて窒素で常圧に戻した。その後、三方コックの一方から窒素を流しながら注射器を用いてオートクレーブに水素化カルシウム処理により乾燥させた主溶媒である１，１−ジクロロエタン４０ｍｌを導入した。つぎに蒸留、精製したアリルトリメチルシラン５ｍｍｏｌを添加し、更にトリクミルクロライド２ｍｍｏｌを溶解させた１０ｍｌの１，１−ジクロロエタン溶液を添加した。
【００５５】
次に酸化バリウムを充填したカラムを通過させることにより脱水したイソブテン７ｇが入っているニードルバルブ付き耐圧ガラス製液化ガス採取管を三方コックに接続した後、容器本体を−７０℃のドライアイス−アセトンバスに浸漬し、重合容器内部を撹拌しながら１時間冷却した。冷却後、真空ラインにより内部を減圧した後、ニードルバルブを開け、イソブテンを耐圧ガラス製液化ガス採取管から重合容器に導入した。その後三方コックの一方から窒素を流すことにより常圧に戻し、更に撹拌下１時間冷却を続け重合容器内を−１０℃まで昇温した。
【００５６】
次にＴｉＣｌ_４ ３．２ｇ（１０ｍｍｏｌ）を注射器を用いて三方コックから添加して重合を開始させ、６０分経過した時点で予め０℃以下に冷却しておいたメタノールを添加することにより反応を終了させた。その後反応混合物をナス型フラスコに取り出し、未反応のイソブテン、１，１−ジクロロエタン、アリルトリメチルシラン及びメタノールを留去し、残ったオリゴマーを１００ｍｌのｎ−へキサンに溶解後、中性になるまでこの溶液の水洗を繰り返した。その後、このｎ−へキサン溶液を２０ｍｌまで濃縮し、３００ｍｌのアセトンにこの濃縮溶液をそそぎ込むことによりオリゴマーを沈澱分離させた。
【００５７】
こうして得られたオリゴマーを再び１００ｍｌのｎ−へキサンに溶解させ、無水硫酸マグネシウムで乾燥させ、濾過し、ｎ−へキサンを減圧留去することにより末端にアリル基を有するポリイソブテンオリゴマーを得た。
〔製造例４〕 ヒドロシリル基含有炭化水素系硬化剤の合成
撹拌可能な２Ｌのガラス製反応容器中に１，３，５，７−テトラメチルシクロテトラシロキサン５００ｇ（２．０８ｍｏｌ）、トルエン６００ｇ、ビス（１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン）白金錯体触媒（８．０×１０^−７ｍｏｌ）を入れ、窒素下８０℃に加熱した。十分な撹拌を加えながら１，９−デカジエン２８．７ｇ（０．２０８ｍｏｌ）とトルエン５８ｇの混合物を１時間かけて添加した。全量添加後、ガスクロマトグラフィーで１，９−デカジエンの残存量を定量し、消失するまで８０℃で撹拌を続けた。反応混合物を濃縮し、残留物として１１０ｇのＳｉ−Ｈ基含有炭化水素系硬化剤を得た。
〔製造例５〕 アリル基末端ポリオキシプロピレンオリゴマーの合成
特開昭５３−１３４０９５に開示された方法に従って、アリル基末端ポリオキシプロピレンオリゴマーを合成した。平均分子量３０００である市販のポリオキシプロピレングリコールと粉末苛性ソーダを６０℃撹拌し、ブロモクロロメタンを加えて反応を行い、ジャンプ反応により分子量を増大させた。次に、アリルクロライドを加えて、１１０℃で末端の水酸基をアリルエーテル化した。これを珪酸アルミニウムにより処理して、アリル基末端ポリオキシプロピレンオリゴマーを得た。このオリゴマーの数平均分子量は、７８５０であり、ヨウ素価から求めた末端のアリル化率は９１％であった。また、Ｂ型粘度計による粘度は、４００ポイズ（２５℃）であった。
〔製造例６〕 アリル基末端ポリカプロラクトンオリゴマーの合成
３０３ｇ（０．１モル）の末端水酸基ポリカプロラクトン（数平均分子量３０３０、水酸基当量１５３０）、２４．４ｇのピリジン、３００ｍｌのＴＨＦを、撹拌棒、温度計、滴下ロート、窒素吹き込み管、冷却器を付設した４つ口フラスコに仕込み、室温下、滴下ロートより３２ｇのクロルギ酸アリルを徐々に滴下した。滴下終了後、５０℃に加熱して、３時間撹拌した。生成した塩を濾別した後、１５０ｍｌのトルエンを添加し、２００ｍｌの塩酸水溶液で洗浄、中和、濃縮することによりアリル基末端ポリカプロラクトンを得た。得られたオリゴマーの数平均分子量は、ＶＰＯ測定で３２００であった。ヨウ素化の測定より、末端のアリル化率は９８％であった。
〔製造例７〕 側鎖にアリル基をもつアクリルオリゴマーの合成
撹拌棒、滴下ロート、温度計、３方コック、冷却器を備えた１Ｌの４つ口フラスコを準備した。次に窒素雰囲気下でトルエン２０ｍｌを仕込んだ。２５．６ｇのｎ−ブチルアクリレート、２．５２ｇのアリルメタクリレート、０．８１ｇのｎ−ドデシルメルカプタン、１．０ｇのアゾビスイソブチロニトリル、１００ｍｌのトルエンからなるモノマーのトルエン溶液を滴下ロートに仕込み、トルエン還流条件下で、約１時間かけて滴下した。滴下終了後、さらに２時間撹拌反応させた。反応終了後、珪酸アルミニウムで処理した後、濾過助剤を用いて吸引濾過することにより透明な溶液を得た。これより、溶媒を加熱減圧留去して淡黄色の粘ちょうなオリゴマー２６ｇを得た。分子量は、ＶＰＯで３９００、ヨウ素価によるアリル基のモル数は、０．１５４ｍｏｌ／１００ｇであり、重合体１分子中のアリル基は平均６個であるアクリルオリゴマーが合成できた。
〔実施例１〕
製造例１で得られた（Ａ）成分及び製造例４で得られた（Ｂ）成分を（Ａ）成分の不飽和基量と（Ｂ）成分中のＳｉ−Ｈ基量とが同じになるように秤量し、更に（Ｃ）成分として白金−ビニルシロキサン触媒（キシレン溶液）を白金が（Ａ）成分中の不飽和基のモル数に対して３×１０^−４モルｅｑになるように秤量し、更に（Ｄ）成分としてジイソシアン酸−４，４′−ジフェニルメタン（和光純薬（株）製、以下ＭＤＩと略する）を（Ａ）成分１００重量部に対して３重量部添加し、更に（Ｅ）成分としてγ−イソシアナートプロピルトリエトキシシラン（チッソ（株）製、商品名：Ｉ−７８４０）を（Ａ）成分１００重量部に対して３重量部添加し、均一に混合した後、該組成物を各種基材の上に塗布し、１３０℃で１０分間更に１５０℃で６０分間加熱して硬化させた。
【００５８】
こうして得られた試験片について常態及びプレッシャークッカー（ＰＣＴ）処理後（１２１℃、２気圧、２０時間処理後）の接着性を評価した。
なお、接着性評価はＪＩＳＫ６８５０規定の引張剪断接着強さ試験方法及びＪＩＳＫ５４００規定の付着性評価方法の中の碁盤目テープ法により評価した。被着体としては銅（厚み：１．６ｍｍ）、アルミニウム（厚み：１．６ｍｍ）、ガラス（厚み：２．８ｍｍ）、ポリイミド（厚み：０．１ｍｍ）を用いた。なお、それぞれの被着体はＪＩＳＫ６８４８規定の方法で表面処理した。
〔実施例２〕
実施例１と同様にして、ただし（Ｄ）成分をＭＤＩとし、（Ｅ）成分をビニルトリス（β−メトキシエトキシ）シラン（日本ユニカー（株）製、商品名：Ａ−１７２）として試験片を作製し、接着性を評価した。
〔実施例３〕
実施例１と同様にして、ただし（Ｄ）成分をＭＤＩとし、（Ｅ）成分をγ−グリシドキシプロピルトリメトキシシラン（日本ユニカー（株）製、商品名：Ａ−１８７）として試験片を作製し、接着性を評価した。
〔実施例４〕
実施例１と同様にして、ただし（Ｄ）成分を２，４−ジイソシアン酸トリレン（和光純薬（株）製、以下ＴＤＩと略する）とし、（Ｅ）成分をγ−イソシアナートプロピルトリエトキシシラン（チッソ（株）製、商品名：Ｉ−７８４０）として試験片を作製し、接着性を評価した。
〔実施例５〕
実施例１と同様にして、ただし（Ｄ）成分をＴＤＩとし、（Ｅ）成分をビニルトリス（β−メトキシエトキシ）シラン（日本ユニカー（株）製、商品名：Ａ−１７２）として試験片を作製し、接着性を評価した。
〔実施例６〕
実施例１と同様にして、ただし（Ｄ）成分をＴＤＩとし、（Ｅ）成分をγ−グリシドキシプロピルトリメトキシシラン（日本ユニカー（株）製、商品名：Ａ−１８７）として試験片を作製し、接着性を評価した。
【００５９】
実施例１〜６の結果を表１に示す。
〔比較例１〕
実施例１と同様にして、ただし（Ｄ）及び（Ｅ）成分を配合せずに試験片を作製し、接着性を評価した。
〔比較例２〕
実施例１と同様にして、ただし（Ｄ）成分をＭＤＩとし、（Ｅ）成分を配合せずに試験片を作製し、接着性を評価した。
〔比較例３〕
実施例１と同様にして、ただし（Ｄ）成分をＴＤＩとし、（Ｅ）成分を配合せずに試験片を作製し、接着性を評価した。
〔比較例４〕
実施例１において（Ｄ）成分を配合せず、（Ｅ）成分をγ−イソシアナートプロピルトリエトキシシラン（チッソ（株）製、商品名：Ｉ−７８４０）として試験片を作製し、接着性を評価した。
〔比較例５〕
実施例１と同様にして、ただし（Ｄ）成分を配合せず、（Ｅ）成分をビニルトリス（β−メトキシエトキシ）シラン（日本ユニカー（株）製、商品名：Ａ−１７２）として試験片を作製し、接着性を評価した。
〔比較例６〕
実施例１と同様にして、ただし（Ｄ）成分を配合せず、（Ｅ）成分をγ−グリシドキシプロピルトリメトキシシラン（日本ユニカー（株）製、商品名：Ａ−１８７）として試験片を作製し、接着性を評価した。
【００６０】
比較例１〜６の結果を表２に示す
接着性評価は（Ａ）成分として、製造例１で得られたオリゴマー以外に製造例２及び３で得られたオリゴマーについても実施した。なお、（Ｂ）成分としては共通で製造例４で得られた硬化剤を用いた。
〔実施例７〕
実施例１と同様にして、ただし（Ａ）成分を製造例２で得られたオリゴマーとし、（Ｄ）成分をＭＤＩとし、（Ｅ）成分をγ−イソシアナートプロピルトリエトキシシラン（チッソ（株）製、商品名：Ｉ−７８４０）として試験片を作製し、接着性を評価した。
〔実施例８〕
実施例１と同様にして、ただし（Ａ）成分を製造例２で得られたオリゴマーとし、（Ｄ）成分をＭＤＩとし、（Ｅ）成分をビニルトリス（β−メトキシエトキシ）シラン（日本ユニカー（株）製、商品名：Ａ−１７２）として試験片を作製し、接着性を評価した。
〔実施例９〕
実施例１と同様にして、ただし（Ａ）成分を製造例２で得られたオリゴマーとし、（Ｄ）成分をＭＤＩとし、（Ｅ）成分をγ−グリシドキシプロピルトリメトキシシラン（日本ユニカー（株）製、商品名：Ａ−１８７）として試験片を作製し、接着性を評価した。
〔実施例１０〕
実施例１と同様にして、ただし（Ａ）成分を製造例３で得られたオリゴマーとし、（Ｄ）成分をＭＤＩとし、（Ｅ）成分をγ−イソシアナートプロピルトリエトキシシラン（チッソ（株）製、商品名：Ｉ−７８４０）として試験片を作製し、接着性を評価した。
〔実施例１１〕
実施例１と同様にして、ただし（Ａ）成分を製造例３で得られたオリゴマーとし、（Ｄ）成分をＭＤＩとし、（Ｅ）成分をビニルトリス（β−メトキシエトキシ）シラン（日本ユニカー（株）製、商品名：Ａ−１７２）として試験片を作製し、接着性を評価した。
〔実施例１２〕
実施例１と同様にして、ただし（Ａ）成分を製造例３で得られたオリゴマーとし、（Ｄ）成分をＭＤＩとし、（Ｅ）成分をγ−グリシドキシプロピルトリメトキシシラン（日本ユニカー（株）製、商品名：Ａ−１８７）として試験片を作製し、接着性を評価した。
【００６１】
実施例７〜１２の結果を表３に示す。
〔比較例７〕
実施例１と同様にして、ただし（Ａ）成分を製造例２で得られたオリゴマーとし、（Ｄ）及び（Ｅ）成分を配合せずに試験片を作製し、接着性を評価した。
〔比較例８〕
実施例１と同様にして、ただし（Ａ）成分を製造例２で得られたオリゴマーとし、（Ｄ）成分をＭＤＩとし、（Ｅ）成分を配合せずに試験片を作製し、接着性を評価した。
〔比較例９〕
実施例１と同様にして、ただし（Ａ）成分を製造例２で得られたオリゴマーとし、（Ｄ）成分を配合せず、（Ｅ）成分をビニルトリス（β−メトキシエトキシ）シラン（日本ユニカー（株）製、商品名：Ａ−１７２）として試験片を作製し、接着性を評価した。
〔比較例１０〕
実施例１と同様にして、ただし（Ａ）成分を製造例３で得られたオリゴマーとし、（Ｄ）及び（Ｅ）成分を配合せずに試験片を作製し、接着性を評価した。
〔比較例１１〕
実施例１と同様にして、ただし（Ａ）成分を製造例３で得られたオリゴマーとし、（Ｄ）成分をＭＤＩとし、（Ｅ）成分を配合せずに試験片を作製し、接着性を評価した。
〔比較例１２〕
実施例１と同様にして、ただし（Ａ）成分を製造例３で得られたオリゴマーとし、（Ｄ）成分を配合せず、（Ｅ）成分をビニルトリス（β−メトキシエトキシ）シラン（日本ユニカー（株）製、商品名：Ａ−１７２）として試験片を作製し、接着性を評価した。
【００６２】
比較例７〜１２の結果を表４に示す。
〔実施例１３〕
実施例１と同様にして、ただし（Ａ）成分として製造例５のポリオキシプロピレンオリゴマーを使用し、（Ｄ）成分をＭＤＩ、（Ｅ）成分をγ−イソシアナートプロピルシラン（チッソ（株）製、商品名：Ｉ−７８４０）として試験片を作製し、接着性を評価した。
〔比較例１３〕
実施例１３から（Ｄ）、（Ｅ）成分を除いた組成物を用いて試験片を作製し、接着性を評価した。
〔比較例１４〕
実施例１３から（Ｅ）成分のみを除いた組成物を用いて試験片を作製し、接着性を評価した。
〔比較例１５〕
実施例１３から（Ｄ）成分のみを除いた組成物を用いて試験片を作製し、接着性を評価した。
〔実施例１４〕
実施例１と同様にして、ただし（Ａ）成分として製造例６のポリカプロラクトンオリゴマーを使用し、（Ｄ）成分をＴＤＩ、（Ｅ）成分をγ−グリシドキシプロピルトリメトキシシラン（日本ユニカー（株）製、商品名：Ａ−１８７）として試験片を作製し、接着性を評価した。
〔比較例１６〕
実施例１４から（Ｄ）、（Ｅ）成分を除いた組成物を用いて試験片を作製し、接着性を評価した。
〔比較例１７〕
実施例１４から（Ｅ）成分のみを除いた組成物を用いて試験片を作製し、接着性を評価した。
〔比較例１８〕
実施例１４から（Ｄ）成分のみを除いた組成物を用いて試験片を作製し、接着性を評価した。
〔実施例１５〕
実施例１と同様にして、ただし、（Ａ）成分として製造例７のアクリルオリゴ−マーを使用し、（Ｄ）成分としてＭＤＩ、（Ｅ）成分としてビニルトリス（β−メトキシエトキシ）シラン（日本ユニカー（株）製、商品名：Ａ−１７２）を使用して試験片を作製し、接着性を評価した。
〔比較例１９〕
実施例１５から（Ｄ）、（Ｅ）成分を除いた組成物を用いて試験片を作製し、接着性を評価した。
〔比較例２０〕
実施例１５から（Ｅ）成分のみを除いた組成物を用いて試験片を作製し、接着性を評価した。
〔比較例２１〕
実施例１５から（Ｄ）成分のみを除いた組成物を用いて試験片を作製し、接着性を評価した。
【００６３】
【表１】

【００６４】
【表２】

【００６５】
【表３】

【００６６】
【表４】

【００６７】
【表５】

【００６８】
実施例１３から１５及び比較例１３から２０の接着性測定結果を表５に示す。
表１〜５の結果より以下のことが明らかとなった。
〔１〕（Ａ）、（Ｂ）、（Ｃ）成分のみでは接着性がなく、これに（Ｄ）成分または（Ｅ）成分のいずれか一方のみを添加した場合は接着性の改良効果は見られるが不十分であった。
〔２〕（Ａ）、（Ｂ）、（Ｃ）成分に（Ｄ）成分と（Ｅ）成分の両方を添加することによって常態及びプレッシャークッカー処理後の接着性を大幅に改良することが可能であった。
【００６９】
以上のよう本発明の硬化性樹脂組成物は各種の被着体に対して優れた接着性を示した。
【００７０】
【発明の効果】
以上の説明及び表１〜５の比較からも明らかなように本発明の硬化性樹脂組成物は、高い硬化性を有することに加え、各種基材との接着性が良く湿熱処理後でも接着性がほとんど低下しないため、従来接着力及び接着保持力が不足して使用できなかった分野にも使用できるようになった。該硬化物はゴム状弾性体であるために低熱応力性であり、産業上の利用分野としては、電気・電子部品等の封止材用組成物や各種コーティング材、ガスケット材料、シーリング材、成型材料、塗料用の組成物として用いることができる。中でも炭化水素系重合体骨格のものは、さらに低透湿性、低吸湿性、耐熱性、耐候性等を有し、半導体素子のドリップコーティングやポッティング用液状封止材、コンデンサー等の各種電子部品のポッティング材、コーティング材、太陽電池裏面封止材の電子部品用の封止材等の組成物として用いることができる。[0001]
[Industrial applications]
The present invention relates to a curable resin composition which is excellent in curability, the cured product of which is a rubber-like substance, has excellent low stress properties and excellent adhesiveness, and which is addition-curable by a hydrosilylation reaction. As an industrial application field, it can be used as a composition for a sealing material for electric / electronic parts, various coating materials, a gasket material, a sealing material, a molding material, and a coating material. Among them, those having a hydrocarbon polymer skeleton further have low moisture permeability, low moisture absorption, heat resistance, weather resistance, etc., and are used for drip coating of semiconductor elements, liquid sealing materials for potting, various electronic components such as capacitors. It can be used as a composition such as a potting material, a coating material, and a sealing material for electronic components such as a solar cell back surface sealing material.
[0002]
[Problems to be solved by the invention]
Conventionally, various types of curable compositions that cure to form a rubber-like substance have been developed. Above all, as a curing system with excellent deep curing properties, a polyorganosiloxane having an average of two or more vinyl groups in one molecule at the terminal or in the molecular chain, and a hydrogen atom bonded to a silicon atom in one molecule Crosslinkable polyorganohydrogensiloxanes having two or more polyorganohydrogensiloxanes have been developed, and are used as silicon-based sealing materials and potting materials by utilizing their excellent weather resistance, heat resistance, and water resistance. However, this system is limited in its use due to its high cost, poor adhesion, and easy mold generation. Further, as a system which does not use such expensive polyorganosiloxane, an organic polymer having at least one alkenyl group in a molecule is crosslinked with a hydrocarbon-based curing agent having at least two hydrosilyl groups in a molecule. Materials are disclosed in JP-A-3-200807, JP-A-3-95266, and the like. However, although these materials are excellent in curability, mechanical strength as a rubber, low stress property, and the like, they have a problem that their adhesiveness to metals, glass, plastic materials, and the like is insufficient. For the purpose of improving the adhesion, a tacky composition obtained by adding a tackifier resin to the above composition (Japanese Patent Application Laid-Open No. 4-145188) or an adhesive composition containing a silane coupling agent (Japanese Patent Application Laid-Open No. 185687) are disclosed, but they have an effect of improving the adhesiveness but cannot be said to be sufficient.
[0003]
[Means for Solving the Problems]
The curable resin composition of the present invention has been intensively studied to solve the above problems, and as a result, the following components (A), (B), (C), (D) and (E) are essential components. The present inventors have found that such a curable resin composition solves the above problems, and have completed the present invention.
[0004]
That is, the present invention
(A) containing at least one unsaturated group in the molecule,The skeleton is at least one selected from the group consisting of hydrocarbons, polyethers, polyesters, and acrylics,Organic polymer having a number average molecular weight of 500 to 60,000
(B)The ratio of the hydrosilyl group of the component (B) to the unsaturated group of the component (A) is 0.02 to 2 in a molar ratio,Contains at least two hydrosilyl groups in the moleculeAnd the skeleton is mainly composed of hydrocarbonsOrganic compounds
(C)The molar ratio of the component (C) to 1 mol of the unsaturated group in the component (A) is 10 ^-1 -10 ^-8 mol ofHydrosilylation catalyst
(D)0.01 to 20 parts by weight of aromatic diisocyanate based on 100 parts by weight of component (A)Compound
(E)0.01 to 20 parts by weight based on 100 parts by weight of component (A), containing at least one selected from the group consisting of vinyl groups, epoxy groups and isocyanate groups.Silane coupling agent
And a curable resin composition containing, as an essential component. The present invention aims at improving the adhesiveness of a curable composition containing (A), (B) and (C),Aromatic diisocyanateCompound and (E)Contains at least one selected from the group consisting of a vinyl group, an epoxy group and an isocyanate groupBy adding an adhesion-imparting agent in combination with a silane coupling agent, it is characteristic that an adhesion-improving effect that cannot be achieved by adding each alone is obtained.
[0005]
Hereinafter, the present invention will be described in detail.
As the organic polymer having at least one unsaturated group in the molecule as the component (A) used in the present invention and having a number average molecular weight of 500 to 60,000, those having various main chain skeletons can be used. Can be. First, as the hydrocarbon polymer, an olefin compound having 1 to 6 carbon atoms, that is, ethylene, propylene, 1-butene, isobutene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, Polymers obtained by homopolymerizing or copolymerizing olefinic compounds such as pentene, 4-methyl-1-pentene, hexene, and vinylcyclohexane, for example, polyisobutylene, ethylene-propylene copolymers, and diene-based polymers Homopolymer or copolymer of compound, ie, polyisoprene or hydrogenated product thereof, polybutadiene or hydrogenated product thereof, copolymer of isobutylene and isoprene or hydrogenated product thereof, copolymer of isoprene and butadiene or hydrogenated product thereof Things and the like can be used. Among these polymers, polyisoprene, polybutadiene, and polyisobutylene polymers are preferable because they can easily introduce a functional group into the terminal and control the molecular weight.
[0006]
As the polyether polymer, for example, polyoxyethylene, polyoxypropylene, polyoxytetramethylene, a polyoxyethylene-polyoxypropylene copolymer, or the like is suitably used. Examples of polyester-based polymers include polycondensation of dibasic acids such as adipic acid and azelaic acid with diols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and lactones such as ε-caprolactone. Polymerized polyester or the like can be used. Examples of the acrylic polymer include polymers obtained by radical copolymerization of acrylic monomers such as ethyl acrylate, butyl acrylate, and allyl acrylate, and polymers obtained by copolymerizing these acrylic monomers with methyl methacrylate, styrene, acrylonitrile, and the like. Can be used.
[0007]
Examples of the other organic polymer include a nylon polymer, a polysulfide polymer, a polyphenylene oxide polymer, a polycarbonate polymer, and a diallyl phthalate polymer.
The number average molecular weight of the organic polymer is from 500 to 60,000. In particular, about 700 to 15,000 is preferable in terms of handling. If the number average molecular weight is less than 500, elongation of the cured product will be poor, and if it exceeds 60,000, workability will be poor and it is not practical.
[0008]
The component (A) of the present invention requires at least one unsaturated group per molecule. In order to satisfy the curability and the mechanical properties of the cured product, the number is preferably 1.2 or more. In order to obtain a sufficient curing rate and a high gel fraction, it is most preferable to use 1.5 or more.
As a method for introducing an unsaturated group, various methods have been proposed. These methods can be roughly classified into a method introduced after polymerization and a method introduced during polymerization.
[0009]
As a method for introducing an unsaturated group after the polymerization, for example, an organic polymer having a hydroxyl group at a terminal or a side chain is used as a starting material, and the hydroxyl group is converted into an oxymetal group such as -ONa or -OK, and then the general formula ( I)
[0010]
Embedded image

[0011]
(X is a halogen atom, R₁Is hydrogen or a monovalent hydrocarbon group having 1 to 20 carbon atoms, R₂Is -R₃-, -R₃-OC (= O)-or -R₃-C (= O)-[R₃Is a divalent hydrocarbon group having 1 to 20 carbon atoms, and specific preferred examples thereof include an alkylene group, a cycloalkylene group, an arylene group, and an aralkylene group. )
An organic polymer having an unsaturated group is produced by reacting an organic halogen compound represented by the formula (1).
[0012]
Examples of a method for converting a hydroxyl group in the main chain or side chain into an oxymetal group include alkali metals such as Na and K, metal hydrides such as NaH, and NaOCH.₃And an alkali such as NaOH and KOH.
According to the above method, an unsaturated group-containing organic polymer having substantially the same molecular weight as the hydroxyl group-containing organic polymer used as a starting material can be obtained. Before reacting with the compound, the oxymetalated compound may be reacted with a polyvalent organic halide such as methylene chloride, bis (chloromethyl) benzene or the like to increase the molecular weight, and then reacted with (I).
[0013]
Specific examples of the organic halide represented by the general formula (I) include allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl) ether , Allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy) benzene, allyloxy (chloromethyl) benzene, and the like, but are not limited thereto. The most preferred of these is allyl chloride in terms of cost and reactivity.
[0014]
As a method for introducing an unsaturated group during polymerization, for example, a method described in US Pat. No. 4,316,973 using an initiator and a chain transfer agent, a method described in JP-A-63-105005, and the like can be used.
The organic compound having at least two hydrosilyl groups in the molecule, which is the component (B) of the present invention, is not particularly limited. Here, one hydrosilyl group refers to one SiH group. Therefore, when two hydrogen atoms are bonded to the same Si, it is calculated as two hydrosilyl groups. In this organic compound, a specific example of a group containing a hydrosilyl group is -Si (H)_n(CH₃)_3-n, -Si (H)_n(C₂H₅)_3-n, -Si (H)_n(C₆H₅)_3-n(N = 1 to 3), -SiH₂(C₆H_Thirteen) Or a group containing only one silicon atom, such as -Si (CH₃)₂Si (CH₃)₂H, -Si (CH₃)₂CH₂CH₂Si (CH₃)₂H, -Si (CH₃)₂SiCH₃H₂,
[0015]
Embedded image

[0016]
A group containing two silicon atoms, such as
[0017]
Embedded image

[0018]
(Wherein R is H, OSi (CH₃)₃And a group selected from organic groups having 1 to 10 carbon atoms, and each R may be the same or different. m and n are positive integers and 2 ≦ m + n ≦ 50)
[0019]
Embedded image

[0020]
(R, m, n are the same as above)
[0021]
Embedded image

[0022]
(Where R is the same as above, m is a positive integer, n, p, and q are 0 or positive integers, and 1 ≦ m + n + p + q ≦ 50)
[0023]
Embedded image

[0024]
(Wherein R is the same as above, m is a positive integer, n is 0 or a positive integer, and 2 ≦ m + n ≦ 50), and various chain, branched and cyclic polyvalent hydrogensiloxanes And groups derived therefrom.
Among the above-mentioned various hydrosilyl group-containing groups, the molecular weight of the group constituting the hydrosilyl group is 500 or less from the viewpoint that the compatibility of the hydrosilyl group-containing compound of the present invention with the component (A) is unlikely to be impaired. The following are preferable in consideration of the reactivity of the hydrosilyl group.
[0025]
Embedded image

[0026]
(Where p is a positive integer, q is 0 or a positive integer, and 2 ≦ p + q ≦ 4)
[0027]
Embedded image

[0028]
Embedded image

[0029]
When two or more hydrosilyl group-containing groups are present in the same molecule, they may be the same or different. The number of the total hydrosilyl groups contained in the component (B) should be at least two in one molecule, but is preferably 2 to 15, and particularly preferably 3 to 12. When the hydrosilyl group-containing compound of the present invention is mixed with an alkenyl group-containing compound (component (A)) in the presence of a hydrosilylation catalyst and cured by a hydrosilylation reaction, the number of hydrosilyl groups is preferably less than 2. If the amount is small, curing failure often occurs. On the other hand, when the number of the hydrosilyl groups is more than 15, the stability of the component (B) deteriorates, and a large amount of the hydrosilyl groups remains in the cured product even after curing, which causes voids and cracks.
[0030]
The hydrosilyl group-containing compound as the component (B) is not particularly limited, and examples thereof include an organic compound having the above-mentioned hydrosilyl group-containing group, and various compounds ranging from low molecular weight compounds to polymers can be used.
Illustrating specifically, Formula (II)
[0031]
Embedded image

[0032]
(Wherein X is the above-mentioned hydrosilyl group-containing group, R¹Is hydrogen or methyl, R²Is a divalent hydrocarbon group having 1 to 20 carbon atoms and may contain one or more ether bonds. R³Is an aliphatic or aromatic organic group, and a is a positive integer. A) a compound having an ether bond represented by
Formula (III)
[0033]
Embedded image

[0034]
(Wherein X is the above-mentioned hydrosilyl group-containing group, R¹Is hydrogen or methyl, R²Is a divalent hydrocarbon group having 1 to 20 carbon atoms and may contain one or more ether bonds. R⁴Is an aliphatic or aromatic organic group, and a is a positive integer. A) a compound having an ester bond represented by
Formula (IV)
[0035]
Embedded image

[0036]
(Wherein X is the above-mentioned hydrosilyl group-containing group, R¹Is hydrogen or methyl, R⁵Is an aliphatic or aromatic organic group, a is a positive integer), and a hydrocarbon compound represented by the formula (V)
[0037]
Embedded image

[0038]
(Wherein X is the above-mentioned hydrosilyl group-containing group, R¹Is hydrogen or methyl, R²Is a divalent hydrocarbon group having 1 to 20 carbon atoms and may contain one or more ether bonds. R⁶Is an aliphatic or aromatic organic group, and a is a positive integer) and has a carbonate bond.
When an organic polymer is used as the component (B), R represented by the formulas (II) to (V)³~ R⁶Is a polymer residue, and this residue may be linear or branched, and any having a molecular weight of 50,000 or less can be suitably used, and those having a molecular weight of 20,000 or less are particularly preferred.
[0039]
The hydrosilyl group of the component (B) may be present at the molecular terminal or in the molecule, but when a rubber-like cured product is produced using the composition of the present invention, it is more effective at the molecular terminal. This is preferable because the length of the network chain becomes longer.
The method for producing the component (B) is not particularly limited, and any method may be used. For example, (i) an organic compound having a Si—Cl group in a molecule is LiAlH₄, NaBH₄A method of reducing the Si—Cl group in the compound to a Si—H group by treating with a reducing agent such as (ii) reacting the organic compound having a functional group X in the molecule with the above functional group in the molecule A method of reacting a compound having a functional group Y and a hydrosilyl group at the same time, and (iii) selectively hydrosilylating a polyhydrosilane compound having a hydrosilyl group with respect to an organic compound having an alkenyl group, so that the hydrosilyl group can be converted after the reaction. A method of allowing the compound to remain in the molecule of the compound can be considered. Of these, the method (iii) is particularly preferred.
[0040]
There is no particular limitation on the hydrosilylation catalyst which is the component (C) of the present invention, and any hydrosilylation catalyst can be used. To give a concrete example
Platinum simple substance, solid platinum supported on simple substance such as alumina, silica, carbon black, etc .;
Platinum-vinylsiloxane complex (for example,
Pt_n(ViMe₂SiOSiMe₂Vi)_m,
Pt [(MeViSiO)₄]_m,);
Platinum-phosphine complexes (e.g.,
Pt (PPh₃)₄, Pt (PBu₃)₄);
Platinum-phosphite complexes (e.g.,
Pt [P (OPh)₃]₄, Pt [P (OBu)₃]₄;
(In the formula, Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent integers.)
Pt (acac)₂And platinum-hydrocarbon complexes described in Ashby U.S. Pat. Nos. 3,159,601 and 3,159,662, and platinum alcoholate catalysts described in Lamoreaux U.S. Pat. No. 3,220,972.
[0041]
Examples of catalysts other than platinum compounds include Rh / Al_TwoO_ThreeAnd the like. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, platinum-olefin complex, platinum-vinylsiloxane complex, Pt (acac)_TwoAre preferred. As the amount of the hydrosilylation catalyst which is the component (C) of the present invention,Is (A) 10 moles per mole of unsaturated group in component^-1-10^-8Use in mol rangeYou.Preferably 10^-3-10^-6It is good to use in the range of mol.
[0042]
Component (D) of the present inventionAromatic diisocyanateAbout compoundsIsMore specifically,
[0043]
Embedded image

[0044]
And their dimers, trimers, prepolymers, and the like. In order to sufficiently exert the effect of imparting adhesiveness, the component (D) must have two or more isocyanate groups.is necessary. Addition amountIs(A) 0.01 to 20 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the component polymer. The component (D) may be used alone or in combination of two or more.
[0045]
Component (E) of the present inventionContains at least one selected from the group consisting of a vinyl group, an epoxy group and an isocyanate groupThe silane coupling agent can also be used without any problem of curing inhibition during addition-type curing. (E) About the componentIsMore specifically,
[0046]
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[0047]
The following compounds can be used.The component (E) contains at least one selected from the group consisting of a vinyl group, an epoxy group, and an isocyanate group, and may further contain an allyl group, a methacryloxy group, a methacryloyl group, and the like.
The component (E) may be used alone or in combination of two or more. Addition amountIs(A) 0.01 to 20 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the component polymer.
[0048]
When the liquid resin composition obtained by mixing the components (A), (B), (C), (D) and (E) of the present invention is heated, a cured product is obtained. The curing conditions are not particularly limited, but curing is generally performed at 30 to 200 ° C, preferably 50 to 150 ° C, for about 10 seconds to 2 hours. However, when curing is performed at 100 ° C. or lower, it is preferable to perform post-curing at 130 ° C. or higher for about 1 hour. It is more preferable to perform post-curing at 150 ° C. or higher.
[0049]
Various compounds can be added to the thermosetting liquid resin composition of the present invention as needed. Examples of the additional components include a plasticizer, an adhesion improver, a storage stability improver, a filler, an antioxidant, an ultraviolet absorbing agent, a metal deactivator, an ozone deterioration inhibitor, a light stabilizer, and a radical polymerization. Examples include an inhibitor, a peroxide decomposer, a lubricant, a pigment, and a foaming agent.
[0050]
As the plasticizer, a commonly used plasticizer can be used, but a plasticizer having good compatibility with the hydrocarbon polymer used in the present invention is preferable. Specific examples of the plasticizer include polybutene, hydrogenated polybutene, α-methylstyrene oligomer, polybutadiene, hydrogenated polybutadiene, partially hydrogenated terphenyl, paraffin oil, naphthenic oil, atactic polypropylene, and the like. Hydrocarbon compounds containing no saturated bond, such as hydrogenated polybutene, hydrogenated polybutadiene, paraffin oil, naphthenic oil, and atactic polypropylene, are preferred.
[0051]
Further, another adhesiveness-imparting agent may be added in combination with the aforementioned adhesiveness-imparting agent. Tackifiers such as coumarone-indene resin, rosin ester resin, and terpene-phenol resin, α-methylstyrene-vinyltoluene copolymer, polyethylmethylstyrene, and alkyl titanates can also be used in combination.
As the storage stability improver, one that controls the catalytic activity of the component (C) only at the time of storage at room temperature is preferable. , BHT, butylhydroxyanisole, vitamin E, 3-methyl-1-buten-3-ol, an organosiloxane containing an acetylenically unsaturated group, acetylene alcohol, 3-methyl-1-butyn-3-ol, 3-methyl- 1-pentyn-3-ol, diallyl fumarate, diallyl malate, diethyl fumarate, diethyl malate, dimethyl malate and the like can be used. When the storage stability improver is used, the amount used is 0.1 to 1000 mol, preferably 1 to 200 mol, per 1 mol of the catalyst. When the amount of the storage stability improver exceeds the upper limit of the above amount, not only curing delay occurs but also curing failure occurs, and physical properties required for a cured product cannot be satisfied. Conversely, if the amount of the storage stability improver falls below the lower limit of the above amount, the object of improving the storage stability of the composition cannot be achieved.
[0052]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
[Production Example 1]
Synthesis of hydrogenated allyl group-terminated polyisoprene oligomer
50 ml of toluene was added to 300 g of hydrogenated polyisoprene having hydroxyl groups at both terminals (trade name: Epole, manufactured by Idemitsu Petrochemical Co., Ltd.), and the mixture was dehydrated by azeotropic degassing. A solution prepared by dissolving 48 g of t-BuOK in 200 ml of toluene was added, and reacted at 80 ° C. for 3 hours. The temperature was lowered to 60 ° C., and 47 ml of allyl chloride was added dropwise over about 30 minutes. After the completion of the dropwise addition, the reaction was carried out at the same temperature for 2 hours. After completion of the reaction, 30 g of aluminum silicate was added to the reaction solution to adsorb the generated salt, and the mixture was stirred for 2 hours. Filtration and purification yielded about 250 g of allyl-terminated hydrogenated polyisoprene as a viscous liquid.¹H-NMR analysis confirmed that 90% of the terminals had an allyl group introduced. The number of moles of the olefin determined from the iodine value was 0.11 mol / 100 g. The chlorine content determined by elemental analysis was less than 0.1%. The viscosity measured by an E-type viscometer was about 330 poise (23 ° C.).
[0053]
○ Typical physical properties of Epole (from Epole technical data)
A hydroxyl group content (meq / g) 0.90;
Viscosity (poise / 30 ° C.) 700
Average molecular weight (VPO measurement) 2500
[Production Example 2] Synthesis of hydrogenated allyl group-terminated polybutadiene oligomer
50 ml of toluene was added to 300 g of hydrogenated polybutadiene having hydroxyl groups at both ends (manufactured by Mitsubishi Kasei Corporation, trade name: Polytail), and the mixture was dehydrated by azeotropic degassing. A solution prepared by dissolving 41 g of t-BuOK in 200 ml of toluene was injected and reacted at 80 ° C. for 3 hours. The temperature was lowered to 60 ° C., and 40 ml of allyl chloride was added dropwise over about 30 minutes. After the completion of the dropwise addition, the reaction was carried out at the same temperature for 2 hours. After completion of the reaction, 30 g of aluminum silicate was added to the reaction solution to adsorb the generated salt, and the mixture was stirred for 2 hours. About 240 g of allyl-terminated hydrogenated polybutadiene was obtained as a viscous liquid by filtration and purification.¹H-NMR analysis confirmed that 85% of the terminals had an allyl group introduced. The number of moles of the olefin determined from the iodine value was 0.10 mol / 100 g. The chlorine content determined by elemental analysis was less than 0.1%. The viscosity measured by an E-type viscometer was about 300 poise (23 ° C.).
[0054]
○ Representative physical properties of polytail (from polytail technical data)
A hydroxyl group content (meq / g) 0.73 to 0.98;
A viscosity (poise / 30 ° C.) of 500 to 1500;
Viscosity (poise / 80 ° C) 6-19
Density (g / cm³) 0.87 (25 ° C)
[Production Example 3] Synthesis of unsaturated terminal polyisobutene oligomer
A stirring blade, a three-way cock and a vacuum line were attached to a 1 L pressure-resistant glass autoclave, and the polymerization vessel was dried by heating at 100 ° C. for 1 hour while evacuating with a vacuum line. After cooling to room temperature, a three-way cock was used. The pressure was returned to normal pressure with nitrogen. Thereafter, 40 ml of 1,1-dichloroethane, which was the main solvent dried by calcium hydride treatment, was introduced into the autoclave using a syringe while flowing nitrogen from one of the three-way cocks. Next, 5 mmol of distilled and purified allyltrimethylsilane was added, and 10 ml of a 1,1-dichloroethane solution in which 2 mmol of tricumyl chloride was dissolved was further added.
[0055]
Next, a liquefied gas sampling tube made of pressure-resistant glass with a needle valve containing 7 g of isobutene dehydrated by passing through a column filled with barium oxide was connected to a three-way cock, and the container body was dried at -70 ° C. in dry ice-acetone. It was immersed in a bath and cooled for 1 hour while stirring the inside of the polymerization vessel. After cooling, the inside of the reactor was depressurized by a vacuum line, and then the needle valve was opened, and isobutene was introduced into the polymerization vessel from a pressure-resistant glass liquefied gas sampling tube. Thereafter, the pressure was returned to normal pressure by flowing nitrogen from one of the three-way cocks. Further, cooling was continued for 1 hour with stirring, and the temperature inside the polymerization vessel was raised to -10 ° C.
[0056]
Next, TiCl₄3.2 g (10 mmol) was added from a three-way cock using a syringe to start polymerization, and when 60 minutes had passed, methanol, which had been cooled to 0 ° C. or lower in advance, was added to terminate the reaction. Thereafter, the reaction mixture was taken out into an eggplant-shaped flask, unreacted isobutene, 1,1-dichloroethane, allyltrimethylsilane and methanol were distilled off.The remaining oligomer was dissolved in 100 ml of n-hexane, and then neutralized. This solution was repeatedly washed with water. Thereafter, the n-hexane solution was concentrated to 20 ml, and the concentrated solution was poured into 300 ml of acetone to precipitate and separate oligomers.
[0057]
The oligomer thus obtained was again dissolved in 100 ml of n-hexane, dried over anhydrous magnesium sulfate, filtered, and the n-hexane was distilled off under reduced pressure to obtain a polyisobutene oligomer having an allyl group at the terminal.
[Production Example 4] Synthesis of hydrosilyl group-containing hydrocarbon-based curing agent
500 g (2.08 mol) of 1,3,5,7-tetramethylcyclotetrasiloxane, 600 g of toluene, and bis (1,3-divinyl-1,1,3,3- Tetramethyldisiloxane) platinum complex catalyst (8.0 × 10^-7mol)) and heated to 80 ° C. under nitrogen. While adding sufficient stirring, a mixture of 28.7 g (0.208 mol) of 1,9-decadiene and 58 g of toluene was added over 1 hour. After addition of the entire amount, the remaining amount of 1,9-decadiene was quantified by gas chromatography, and stirring was continued at 80 ° C until disappearance. The reaction mixture was concentrated to obtain 110 g of a Si-H group-containing hydrocarbon-based curing agent as a residue.
[Production Example 5] Synthesis of allyl group-terminated polyoxypropylene oligomer
An allyl group-terminated polyoxypropylene oligomer was synthesized according to the method disclosed in JP-A-53-134095. A commercially available polyoxypropylene glycol having an average molecular weight of 3,000 and powdered caustic soda were stirred at 60 ° C., bromochloromethane was added to carry out a reaction, and the molecular weight was increased by a jump reaction. Next, allyl chloride was added, and the terminal hydroxyl group was allyl etherified at 110 ° C. This was treated with aluminum silicate to obtain an allyl group-terminated polyoxypropylene oligomer. The number average molecular weight of this oligomer was 7,850, and the terminal allylation ratio determined from the iodine value was 91%. The viscosity measured by a B-type viscometer was 400 poise (25 ° C.).
[Production Example 6] Synthesis of allyl-terminated polycaprolactone oligomer
303 g (0.1 mol) of terminal hydroxyl group polycaprolactone (number average molecular weight 3030, hydroxyl equivalent 1530), 24.4 g of pyridine and 300 ml of THF were added to a stirring bar, a thermometer, a dropping funnel, a nitrogen blowing tube, and a cooler. The mixture was charged into an attached four-necked flask, and at room temperature, 32 g of allyl chloroformate was gradually dropped from a dropping funnel. After completion of the dropwise addition, the mixture was heated to 50 ° C. and stirred for 3 hours. After the generated salt was separated by filtration, 150 ml of toluene was added, washed with 200 ml of hydrochloric acid aqueous solution, neutralized and concentrated to obtain an allyl-terminated polycaprolactone. The number average molecular weight of the obtained oligomer was 3,200 as measured by VPO. From the measurement of iodination, the terminal allylation ratio was 98%.
[Production Example 7] Synthesis of acrylic oligomer having allyl group in side chain
A 1-L four-necked flask equipped with a stirring rod, a dropping funnel, a thermometer, a three-way cock, and a condenser was prepared. Next, 20 ml of toluene was charged in a nitrogen atmosphere. A monomer solution consisting of 25.6 g of n-butyl acrylate, 2.52 g of allyl methacrylate, 0.81 g of n-dodecyl mercaptan, 1.0 g of azobisisobutyronitrile, and 100 ml of toluene was charged into a dropping funnel. The mixture was added dropwise over about 1 hour under reflux conditions of toluene. After the completion of the dropwise addition, the reaction was further stirred for 2 hours. After completion of the reaction, the mixture was treated with aluminum silicate, and then subjected to suction filtration using a filter aid to obtain a transparent solution. The solvent was distilled off by heating under reduced pressure to obtain 26 g of a pale yellow viscous oligomer. The molecular weight was 3900 by VPO, the number of moles of allyl groups based on iodine value was 0.154 mol / 100 g, and an acrylic oligomer having an average of 6 allyl groups in one polymer molecule was synthesized.
[Example 1]
In the component (A) obtained in Production Example 1 and the component (B) obtained in Production Example 4, the amount of the unsaturated group in the component (A) is the same as the amount of the Si—H group in the component (B). Then, a platinum-vinylsiloxane catalyst (xylene solution) as the component (C) was added in an amount of 3 × 10 3 based on the number of moles of the unsaturated group in the component (A).^-4And weighed to give a molar eq, and further, as component (D), 4,4'-diphenylmethane diisocyanate (manufactured by Wako Pure Chemical Industries, Ltd .; hereinafter abbreviated as MDI) based on 100 parts by weight of component (A) 3 parts by weight, and 3 parts by weight of γ-isocyanatopropyltriethoxysilane (trade name: I-7840, manufactured by Chisso Corporation) as the component (E) are added to 100 parts by weight of the component (A). After the mixture was uniformly mixed, the composition was applied on various substrates, and cured by heating at 130 ° C. for 10 minutes and further at 150 ° C. for 60 minutes.
[0058]
The test pieces thus obtained were evaluated for adhesion under normal conditions and after pressure cooker (PCT) treatment (121 ° C., 2 atm, 20 hours).
The adhesion was evaluated by the cross cut tape method in the tensile shear adhesion strength test method specified in JIS K6850 and the adhesion evaluation method specified in JIS K5400. Copper (thickness: 1.6 mm), aluminum (thickness: 1.6 mm), glass (thickness: 2.8 mm), and polyimide (thickness: 0.1 mm) were used as the adherend. In addition, each adherend was surface-treated by a method specified in JIS K6848.
[Example 2]
A test piece was prepared in the same manner as in Example 1 except that the component (D) was MDI and the component (E) was vinyltris (β-methoxyethoxy) silane (trade name: A-172, manufactured by Nippon Unicar Co., Ltd.). Then, the adhesiveness was evaluated.
[Example 3]
A test piece was prepared in the same manner as in Example 1 except that the component (D) was MDI and the component (E) was γ-glycidoxypropyltrimethoxysilane (trade name: A-187, manufactured by Nippon Unicar Co., Ltd.). It was prepared and the adhesion was evaluated.
[Example 4]
In the same manner as in Example 1, except that the component (D) was tolylene 2,4-diisocyanate (manufactured by Wako Pure Chemical Industries, Ltd .; hereinafter, abbreviated as TDI), and the component (E) was γ-isocyanatopropyltriethoxy. Test pieces were prepared as silane (trade name: I-7840, manufactured by Chisso Corporation), and the adhesion was evaluated.
[Example 5]
A test piece was prepared in the same manner as in Example 1, except that the component (D) was TDI and the component (E) was vinyltris (β-methoxyethoxy) silane (trade name: A-172, manufactured by Nippon Unicar Co., Ltd.). Then, the adhesiveness was evaluated.
[Example 6]
A test piece was prepared in the same manner as in Example 1, except that the component (D) was TDI and the component (E) was γ-glycidoxypropyltrimethoxysilane (manufactured by Nippon Unicar Co., Ltd., trade name: A-187). It was prepared and the adhesion was evaluated.
[0059]
Table 1 shows the results of Examples 1 to 6.
[Comparative Example 1]
Test pieces were prepared in the same manner as in Example 1 except that the components (D) and (E) were not blended, and the adhesion was evaluated.
[Comparative Example 2]
A test piece was prepared in the same manner as in Example 1 except that the component (D) was MDI and the component (E) was not blended, and the adhesion was evaluated.
[Comparative Example 3]
A test piece was prepared in the same manner as in Example 1 except that the component (D) was TDI and the component (E) was not blended, and the adhesion was evaluated.
[Comparative Example 4]
In Example 1, a test piece was prepared without using the component (D) and using the component (E) as γ-isocyanatopropyltriethoxysilane (trade name: I-7840, manufactured by Chisso Corporation), and the adhesion was evaluated. evaluated.
[Comparative Example 5]
A test piece was prepared in the same manner as in Example 1 except that the component (D) was not blended and the component (E) was vinyltris (β-methoxyethoxy) silane (trade name: A-172, manufactured by Nippon Unicar Co., Ltd.). It was prepared and the adhesion was evaluated.
[Comparative Example 6]
A test piece was prepared in the same manner as in Example 1 except that the component (D) was not used and the component (E) was changed to γ-glycidoxypropyltrimethoxysilane (trade name: A-187, manufactured by Nippon Unicar Co., Ltd.). Was prepared, and the adhesiveness was evaluated.
[0060]
Table 2 shows the results of Comparative Examples 1 to 6.
The evaluation of adhesiveness was carried out on the oligomers obtained in Production Examples 2 and 3 as well as the oligomer obtained in Production Example 1 as the component (A). The curing agent obtained in Production Example 4 was commonly used as the component (B).
[Example 7]
Example 1 was repeated except that component (A) was the oligomer obtained in Production Example 2, component (D) was MDI, and component (E) was γ-isocyanatopropyltriethoxysilane (manufactured by Chisso Corporation). Manufactured under the trade name of I-7840), and the adhesion was evaluated.
Example 8
Example 1 was repeated except that component (A) was the oligomer obtained in Production Example 2, component (D) was MDI, and component (E) was vinyltris (β-methoxyethoxy) silane (Nihon Unicar Co., Ltd. ), Trade name: A-172), a test piece was prepared, and the adhesion was evaluated.
[Example 9]
In the same manner as in Example 1, except that the component (A) is the oligomer obtained in Production Example 2, the component (D) is MDI, and the component (E) is γ-glycidoxypropyltrimethoxysilane (Nihon Unicar ( Co., Ltd., trade name: A-187), a test piece was prepared, and the adhesion was evaluated.
[Example 10]
In the same manner as in Example 1, except that the component (A) was the oligomer obtained in Production Example 3, the component (D) was MDI, and the component (E) was γ-isocyanatopropyltriethoxysilane (Chisso Corporation). Manufactured under the trade name of I-7840), and the adhesion was evaluated.
[Example 11]
In the same manner as in Example 1, except that the component (A) was the oligomer obtained in Production Example 3, the component (D) was MDI, and the component (E) was vinyltris (β-methoxyethoxy) silane (Nihon Unicar Co., Ltd. ), Trade name: A-172), a test piece was prepared, and the adhesion was evaluated.
[Example 12]
In the same manner as in Example 1, except that the component (A) is the oligomer obtained in Production Example 3, the component (D) is MDI, and the component (E) is γ-glycidoxypropyltrimethoxysilane (Nihon Unicar ( Co., Ltd., trade name: A-187), a test piece was prepared, and the adhesion was evaluated.
[0061]
Table 3 shows the results of Examples 7 to 12.
[Comparative Example 7]
A test piece was prepared in the same manner as in Example 1 except that the component (A) was the oligomer obtained in Production Example 2, and the components (D) and (E) were not blended, and the adhesion was evaluated.
[Comparative Example 8]
A test piece was prepared in the same manner as in Example 1 except that component (A) was the oligomer obtained in Production Example 2, component (D) was MDI, and component (E) was not blended. evaluated.
[Comparative Example 9]
In the same manner as in Example 1, except that the component (A) was the oligomer obtained in Production Example 2, the component (D) was not blended, and the component (E) was vinyltris (β-methoxyethoxy) silane (Nihon Unicar ( Co., Ltd., trade name: A-172), a test piece was prepared, and the adhesion was evaluated.
[Comparative Example 10]
A test piece was prepared in the same manner as in Example 1 except that the component (A) was the oligomer obtained in Production Example 3, and the components (D) and (E) were not blended, and the adhesion was evaluated.
[Comparative Example 11]
A test piece was prepared in the same manner as in Example 1 except that component (A) was the oligomer obtained in Production Example 3, component (D) was MDI, and component (E) was not blended. evaluated.
[Comparative Example 12]
In the same manner as in Example 1, except that the component (A) is the oligomer obtained in Production Example 3, the component (D) is not blended, and the component (E) is vinyltris (β-methoxyethoxy) silane (Nippon Unicar ( Co., Ltd., trade name: A-172), a test piece was prepared, and the adhesion was evaluated.
[0062]
Table 4 shows the results of Comparative Examples 7 to 12.
[Example 13]
In the same manner as in Example 1, except that the polyoxypropylene oligomer of Production Example 5 was used as the component (A), the component (D) was MDI, and the component (E) was γ-isocyanatopropylsilane (manufactured by Chisso Corporation). , Trade name: I-7840), and the adhesion was evaluated.
[Comparative Example 13]
A test piece was prepared using the composition excluding the components (D) and (E) from Example 13, and the adhesion was evaluated.
[Comparative Example 14]
Test pieces were prepared from the composition of Example 13 except for the component (E) alone, and the adhesion was evaluated.
[Comparative Example 15]
Test pieces were prepared from the composition of Example 13 except for the component (D) alone, and the adhesion was evaluated.
[Example 14]
In the same manner as in Example 1, except that the polycaprolactone oligomer of Production Example 6 was used as the component (A), the component (D) was TDI, and the component (E) was γ-glycidoxypropyltrimethoxysilane (Nihon Unicar ( Co., Ltd., trade name: A-187), a test piece was prepared, and the adhesion was evaluated.
[Comparative Example 16]
Test pieces were prepared using the composition excluding the components (D) and (E) from Example 14, and the adhesion was evaluated.
[Comparative Example 17]
Test pieces were prepared from the composition of Example 14 except for the component (E) alone, and the adhesion was evaluated.
[Comparative Example 18]
A test piece was prepared from the composition of Example 14 except that only the component (D) was removed, and the adhesion was evaluated.
[Example 15]
Same as Example 1, except that the acrylic oligomer of Production Example 7 was used as the component (A), MDI was used as the component (D), and vinyltris (β-methoxyethoxy) silane was used as the component (E) (Nihon Unicar Test pieces were prepared using the product name (A-172, manufactured by Co., Ltd.), and the adhesion was evaluated.
[Comparative Example 19]
A test piece was prepared using the composition excluding the components (D) and (E) from Example 15, and the adhesion was evaluated.
[Comparative Example 20]
Test pieces were prepared from the composition of Example 15 except for the component (E) alone, and the adhesion was evaluated.
[Comparative Example 21]
A test piece was prepared from the composition of Example 15 except for the component (D) alone, and the adhesion was evaluated.
[0063]
[Table 1]

[0064]
[Table 2]

[0065]
[Table 3]

[0066]
[Table 4]

[0067]
[Table 5]

[0068]
Table 5 shows the measurement results of the adhesiveness of Examples 13 to 15 and Comparative Examples 13 to 20.
From the results of Tables 1 to 5, the following became clear.
[1] There is no adhesiveness only with the components (A), (B) and (C), and when only one of the component (D) or the component (E) is added thereto, the effect of improving the adhesiveness is not seen. Was insufficient.
[2] By adding both the component (D) and the component (E) to the components (A), (B) and (C), it is possible to greatly improve the adhesiveness under normal conditions and after pressure cooker treatment. there were.
[0069]
As described above, the curable resin composition of the present invention exhibited excellent adhesion to various adherends.
[0070]
【The invention's effect】
As is clear from the above description and the comparison of Tables 1 to 5, the curable resin composition of the present invention has high curability, good adhesion to various substrates, and good adhesion even after wet heat treatment. , Is hardly reduced, so that it can be used in a field where the conventional adhesive power and adhesive holding power were insufficient and could not be used. Since the cured product is a rubber-like elastic material, it has low thermal stress, and as an industrial application field, a composition for sealing materials for electric and electronic parts, various coating materials, a gasket material, a sealing material, a molding material, and the like. It can be used as a composition for materials and paints. Among them, those having a hydrocarbon polymer skeleton further have low moisture permeability, low moisture absorption, heat resistance, weather resistance, etc., and are used for drip coating of semiconductor elements, liquid sealing materials for potting, various electronic components such as capacitors. It can be used as a composition such as a potting material, a coating material, and a sealing material for electronic components such as a solar cell back surface sealing material.

Claims (1)

A curable resin composition comprising the following components (A), (B), (C), (D) and (E) as essential components;
(A) the molecule contains at least one unsaturated group, and the skeleton is at least one selected from the group consisting of hydrocarbons, polyethers, polyesters and acrylics, and has a number average molecular weight A molar ratio of the hydrosilyl group of the component (B) to the unsaturated group of the organic polymer (B) of the component (A) of from 500 to 60,000 is from 0.02 to 2; containing, backbone organic compound consisting mainly of hydrocarbons (C) in a ratio molar ratio of component (a) component (C) the unsaturated group 1mol in 10 ^-1 to 10 ^-8 mol hydrosilylation 0.01 to 20 parts by weight of the aromatic diisocyanate compound (E) per 100 parts by weight of the catalyst (D) component (A) 0.01 to 20 parts by weight per 100 parts by weight of the component (A) Vinyl group, epoxy And a silane coupling agent containing at least one selected from the group consisting of isocyanate group