JP2004168920A - Thermally conductive silicone elastomer composition - Google Patents
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、熱伝導性シリコーンエラストマー組成物に関し、詳しくは、貯蔵中に硬化性の経時変化が小さく、硬化して、熱伝導率の高いシリコーンエラストマーを形成する熱伝導性シリコーンエラストマー組成物に関する。
【０００２】
【従来の技術】
硬化して、熱伝導性のシリコーンゴムを形成する熱伝導性シリコーンゴム組成物は公知であり、例えば、特開平３−１７０５８１号公報および特開平７−１３３４３２号公報には、一分子中に少なくとも２個のアルケニル基を有するオルガノポリシロキサン、一分子中に少なくとも２個のケイ素原子結合水素原子を有するオルガノポリシロキサン、銀微粉末、および白金系触媒からなるシリコーンゴム組成物が提案されているが、このようなシリコーンゴム組成物は、長期間の保管中に、硬化性が低下し、やがては硬化不良を生じるという問題があった。
【０００３】
【発明が解決しようとする課題】
本発明者らは、上記の問題を解決するために鋭意検討した結果、本発明に到達した。
すなわち、本発明の目的は、貯蔵中に硬化性の経時変化が小さく、硬化して、熱伝導率の高いシリコーンエラストマーを形成する熱伝導性シリコーンエラストマー組成物を提供することにある。
【０００４】
【課題を解決するための手段】
本発明の熱伝導性シリコーンエラストマー組成物は、
（Ａ）一分子中に少なくとも２個のアルケニル基を有するオルガノポリシロキサン１００重量部、
（Ｂ）一分子中に少なくとも２個のケイ素原子結合水素原子を有するオルガノポリシロキサン｛（Ａ）成分中のアルケニル基１モルに対して、本成分中のケイ素原子結合水素原子が０．３〜１０モルとなる量｝、
（Ｃ）熱伝導性フィラー ５０〜５，０００重量部、
（Ｄ）フェノール系化合物および／またはベンゾトリアゾール系化合物（本組成物中に重量単位で１０〜１０，０００ｐｐｍとなる量）、
（Ｅ）白金系触媒（本成分中の白金金属が、本組成物に対して重量単位で１０〜１０，０００ｐｐｍとなる量）、および
（Ｆ）エン−イン化合物および／またはアルキンアルコール（本組成物中に重量単位で１０〜１０，０００ｐｐｍとなる量）
からなることを特徴とする。
【０００５】
【発明の実施の形態】
本発明の熱伝導性シリコーンエラストマー組成物を詳細に説明する。
（Ａ）成分は本組成物の主剤であり、一分子中に少なくとも２個のアルケニル基を有するオルガノポリシロキサンである。（Ａ）成分中のアルケニル基としては、ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基が例示され、特に、ビニル基、ヘキセニル基が好ましい。（Ａ）成分中のアルケニル基の結合位置としては、分子鎖末端および／または分子鎖側鎖が例示される。また、（Ａ）成分中のアルケニル基以外のケイ素原子に結合している有機基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等のアルキル基；フェニル基、トリル基、キシリル基等のアリール基；ベンジル基、フェネチル基等のアラルキル基；３−クロロプロピル基、３，３，３−トリフロロプロピル基等のハロゲン化アルキル基等のアルケニル基を除く置換もしくは非置換の一価炭化水素基が例示され、特に、メチル基、フェニル基が好ましい。このような（Ａ）成分の分子構造としては、直鎖状、一部分枝を有する直鎖状、分枝鎖状、網状が例示される。（Ａ）成分は、これらの分子構造を有するオルガノポリシロキサンの二種以上の混合物であってもよい。また、（Ａ）成分の２５℃における粘度は限定されず、５０〜５００，０００ｍＰａ・ｓの範囲内であることが好ましく、特に、１００〜５０，０００ｍＰａ・ｓの範囲内であることが好ましい。
【０００６】
このような（Ａ）成分のオルガノポリシロキサンとしては、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖メチルビニルポリシロキサン、分子鎖両末端トリメチルシロキシ基封鎖メチルビニルシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端ジメチルビニルシロキシ基封鎖メチルビニルポリシロキサン、分子鎖両末端ジメチルビニルシロキシ基封鎖メチルフェニルポリシロキサン、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、分子鎖両末端ジメチルビニルシロキシ基封鎖メチルビニルシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端ジメチルビニルシロキシ基封鎖メチルビニルシロキサン・ジフェニルシロキサン共重合体等のジオルガノポリシロキサン；式：Ｒ１ ３ＳｉＯ１／２で示されるシロキサン単位と式：ＳｉＯ４／２で示されるシロキサン単位からなるシリコーンレジン、式：Ｒ１ＳｉＯ３／２で示されるシロキサン単位からなるシリコーンレジン、式：Ｒ１ ２ＳｉＯ２／２で示されるシロキサン単位と式：Ｒ１ＳｉＯ３／２で示されるシロキサン単位からなるシリコーンレジン、式：Ｒ１ ２ＳｉＯ２／２で示されるシロキサン単位と式：Ｒ１ＳｉＯ３／２で示されるシロキサン単位と式：ＳｉＯ４／２で示されるシロキサン単位からなるシリコーンレジン等のシリコーンレジン、およびこれらの２種以上の混合物が例示される。上式中のＲ１は置換もしくは非置換の一価炭化水素基であり、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等のアルキル基；ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基等のアルケニル基；フェニル基、トリル基、キシリル基等のアリール基；ベンジル基、フェネチル基等のアラルキル基；３−クロロプロピル基、３，３，３−トリフロロプロピル基等のハロゲン化アルキル基が例示される。但し、上記シリコーンレジンの一分子中の少なくとも２個のＲ１は前記アルケニル基である。
【０００７】
（Ｂ）成分は、上記（Ａ）成分を架橋して、本組成物を硬化させるための成分であり、一分子中に少なくとも２個のケイ素原子結合水素原子を有するオルガノポリシロキサンである。（Ｂ）成分中のケイ素原子結合水素原子の結合位置としては、分子鎖末端および／または分子鎖側鎖が例示される。また、（Ｂ）成分中の水素原子以外のケイ素原子に結合している有機基としては、前記と同様のアルケニル基を除く置換もしくは非置換の一価炭化水素基が例示され、特に、メチル基、フェニル基が好ましい。このような（Ｂ）成分の分子構造としては、直鎖状、一部分枝を有する直鎖状、分枝鎖状、網状が例示される。（Ｂ）成分は、これらの分子構造を有するオルガノポリシロキサンの二種以上の混合物であってもよい。また、（Ｂ）成分の２５℃における粘度は限定されず、１〜５００，０００ｍＰａ・ｓの範囲内であることが好ましく、特に、５〜１，０００ｍＰａ・ｓの範囲内であることが好ましい。
【０００８】
このような（Ｂ）成分のオルガノポリシロキサンとしては、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサン、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖メチルハイドロジェンポリシロキサン、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン・メチルフェニルシロキサン共重合体等のジオルガノポリシロキサン；式：Ｒ２ ３ＳｉＯ１／２で示されるシロキサン単位と式：ＳｉＯ４／２で示されるシロキサン単位からなるシリコーンレジン、式：Ｒ２ＳｉＯ３／２で示されるシロキサン単位からなるシリコーンレジン、式：Ｒ２ ２ＳｉＯ２／２で示されるシロキサン単位と式：Ｒ２ＳｉＯ３／２で示されるシロキサン単位からなるシリコーンレジン、式：Ｒ２ ２ＳｉＯ２／２で示されるシロキサン単位と式：Ｒ２ＳｉＯ３／２で示されるシロキサン単位と式：ＳｉＯ４／２で示されるシロキサン単位からなるシリコーンレジン等のシリコーンレジン、およびこれらの２種以上の混合物が例示される。上式中のＲ２は水素原子、またはアルケニル基を除く置換もしくは非置換の一価炭化水素基である。Ｒ２の一価炭化水素基としては、前記と同様の基が例示される。但し、上記シリコーンレジンの一分子中の少なくとも２個のＲ２は水素原子である。
【０００９】
本組成物において、（Ｂ）成分の含有量は、上記（Ａ）成分中のアルケニル基１モルに対して、（Ｂ）成分中のケイ素原子結合水素原子が０．３〜１０モルの範囲内となる量である。これは、（Ｂ）成分の含有量が上記範囲の下限未満となる量であると、得られる組成物が十分に硬化しなくなる傾向があり、一方、上記範囲の上限をこえると、得られるシリコーンエラストマーの耐熱性が低下したりする傾向があるからである。
【００１０】
（Ｃ）成分は本組成物を硬化して得られるシリコーンエラストマーに熱伝導性を付与するための熱伝導性フィラーである。この（Ｃ）成分としては、金、銀、ニッケル、銅等の金属微粉末；セラミック、ガラス、石英、有機樹脂等の微粉末表面に金、銀、ニッケル、銅等の金属を蒸着またはメッキした微粉末；酸化アルミニウム、窒化アルミニウム、酸化亜鉛等の金属化合物、およびこれらの２種以上の混合物が例示される。本組成物において、熱伝導率が３Ｗ／ｍＫ以上である高熱伝導性のシリコーンエラストマーを得るためには、（Ｃ）成分として銀微粉末を用いることが好ましい。この銀微粉末の形状としては、球状、フレーク状、フレーク樹枝状が例示される。このような（Ｃ）成分の平均粒子径としては、１〜１００μｍの範囲内であることが好ましく、特に、１〜５０μｍの範囲内であることが好ましい。
【００１１】
本組成物において、（Ｃ）成分の含有量は、（Ａ）成分１００重量部に対して５０〜５，０００重量部の範囲内であり、好ましくは、３００〜３，０００重量部の範囲内である。これは、（Ｃ）成分の含有量が上記範囲の下限未満であると、得られるシリコーンエラストマーに十分な熱伝導性を付与できなくなる傾向があり、一方、上記範囲の上限をこえると、均一な組成物を調製することが困難であったり、得られる組成物の取扱作業性が悪化する傾向があるからである。
【００１２】
（Ｄ）成分は、本組成物の貯蔵中に、本組成物の硬化性の経時変化を抑制するためのフェノール系化合物および／またはベンゾトリアゾール系化合物である。このフェノール系化合物としては、２，６−ジ−ｔｅｒｔ−ブチルフェノール、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール、２，６−ジ−ｔｅｒｔ−ブチル−４−エチルフェノール、２，６−ジ−ｔｅｒｔ−ブチル−４−ｓｅｃ−ブチルフェノール、２−（１−メチルシクロヘキシル）−４，６−ジメチルフェノール、２，６−ジ−ｔｅｒｔ−ブチル−α−ジメチルアミノ−ｐ−クレゾール等のモノフェノール化合物；２，２’−メチレン−ビス−（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、２，２’−メチレン−ビス−（４−メチル−６−シクロヘキシルフェノール）、２，２’−メチレン−ビス−（４−エチル−６−ｔｅｒｔ−ブチルフェノール）、４，４’−メチレン−ビス−（２，６−ジ−ｔｅｒｔ−ブチルフェノール）、２，２’−メチレン−ビス−（６−α−メチルベンジル−ｐ−クレゾール）、２，２’−メチレン−ビス−（６−ｔｅｒｔ−ブチル−４−メチルフェノール）等のビスフェノール化合物；４，４’−チオビス−（６−ｔｅｒｔ−ブチル−３−メチルフェノール）、４，４’−チオビス−（６−ｔｅｒｔ−ブチル−ｏ−クレゾール）等のチオビスフェノール化合物；１，１，３−トリス−（２−メチル−４−ヒドロキシ−５−ｔｅｒｔ−ブチルフェニル）ブタン、４，４’−ブチリデンビス−（３−メチル−６−ｔｅｒｔ−ブチルフェノール）、２，２−チオビス−（４−メチル−６−ｔｅｒｔ−ブチルフェノール）等のヒンダートフェノール化合物が例示される。また、このベンゾトリアゾール系化合物としては、１Ｈ−ベンゾトリアゾール、４−メチル−１Ｈ−ベンゾトリアゾール、５−メチル−１Ｈ−ベンゾトリアゾール、２−（２’−ヒドロキシ−５’−メチル−フェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔｅｒｔ−ブチル−フェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’−ｔｅｒｔ−ブチル−５’−メチル−フェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔｅｒｔ−ブチル−フェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−５’−ｔｅｒｔ−オクチル−フェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔｅｒｔ−アミル−フェニル）ベンゾトリアゾール、２−［２’−ヒドロキシ−３’−（３”，４”，５”，６”−テトラヒドロフタ
ルイミドメチル）−５’−メチル−フェニル］ベンゾトリアゾール、２，２’−メチレンビス［４−（１，１，３，３−テトラメチルブチル）−６−（２Ｈ−ベンゾトリアゾール−２−イル）フェノール］、２−［２−ヒドロキシ−３，５−ビス（α，α−ジメチルベンジル）フェニル］−２Ｈ−ベンゾトリアゾール、２−（２−ヒドロキシ−４−オクチルオキシフェニル）−２Ｈ−ベンゾトリアゾール、２−（２Ｈ−ベンゾトリアゾール−２−イル）−４−メチル−６−（３，４，５，６−テトラヒドロフタルイミジルメチル）フェノールが例示される。
【００１３】
本組成物において、（Ｄ）成分の含有量は、本組成物に対して重量単位で１０〜１０，０００ｐｐｍの範囲内となる量である。これは、（Ｄ）成分の含有量が上記範囲の下限未満であると、得られる組成物の硬化性の経時変化を抑制することが困難であるからであり、一方、上記範囲の上限をこえると、得られる組成物の硬化が著しく遅くなるからである。
【００１４】
（Ｅ）成分は本組成物の硬化を促進するための白金系触媒である。（Ｅ）成分の白金系触媒としては、白金黒、白金担持アルミナ粉末、白金担持シリカ粉末、白金担持カーボン粉末、塩化白金酸、塩化白金酸のアルコール溶液、白金のオレフィン錯体、白金のアルケニルシロキサン錯体、これらの白金系触媒を、メチルメタクリレート樹脂、ポリカーボネート樹脂、ポリスチレン樹脂、シリコーン樹脂などの熱可塑性樹脂中に分散させて微粒子化した触媒が例示される。
【００１５】
本組成物において、（Ｅ）成分の含有量は、本成分に含まれる白金金属が本組成物中に重量単位で０．１〜１，０００ｐｐｍの範囲内となる量である。これは、（Ｅ）成分の含有量が上記範囲の下限未満であると、得られる組成物が十分に硬化しなくなるからであり、一方、上記範囲の上限をこえると、得られるシリコーンエラストマーに着色等の問題を生じるからである。
【００１６】
（Ｆ）成分は本組成物の硬化性を調節し、取扱作業性を向上させるためのエン−イン化合物および／またはアルキンアルコールである。このエン−イン化合物としては、３−メチル−３−ペンテン−１−イン、３，５−ジメチル−３−ヘキセン−１−インが例示される。また、このアルキンアルコールとしては、２−メチル−３−ブチン−２−オール、３，５−ジメチル−１−ヘキシン−３−オール、２−フェニル−３−ブチン−２−オールが例示される。
【００１７】
本組成物において、（Ｆ）成分の含有量は、本組成物に対して重量単位で１０〜１０，０００ｐｐｍの範囲内となる量である。これは、（Ｆ）成分の含有量が上記範囲の下限未満であると、得られる組成物の硬化性を調節することが困難となり、取扱作業性が悪化するからであり、一方、上記範囲の上限をこえると、得られる組成物の硬化が著しく遅くなるからである。
【００１８】
本組成物は、上記（Ａ）成分〜（Ｆ）成分を均一に混合することにより調製することができるが、本組成物を硬化して得られる熱伝導性シリコーンエラストマーに良好な接着性を付与するため接着促進剤を含有することが好ましい。この接着促進剤としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、アリルトリメトキシシラン、アリルトリエトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン等のアルコキシシラン化合物；式：
【化１】
【化２】
【化３】
【化４】
【化５】
で表されるシロキサンオリゴマー等の一分子中にケイ素原子結合水素原子またはアルケニル基、およびケイ素原子結合アルコキシ基を有するシロキサンオリゴマーが例示される。
【００１９】
本組成物において、この接着促進剤は任意の成分であるが、これを含有する場合には、その含有量は、（Ａ）成分１００重量部に対して２０重量部以下であることが好ましく、特に、０．５〜１０重量部の範囲内であることが好ましい。これは、接着促進剤を含有しない場合には、得られるシリコーンエラストマー組成物は接着性が乏しかったり、これを硬化して得られるシリコーンエラストマーの接触抵抗や体積抵抗率の経時変化を招来する可能性があるためであり、一方、接着促進剤の含有量が上記範囲の上限を超えると、得られるシリコーンエラストマー組成物の貯蔵安定性が低下したり、これを硬化して得られるシリコーンエラストマーの物理的特性が経時的に変化するようになるからである。
【００２０】
また、本組成物には、硬化して得られる熱伝導性シリコーンエラストマーに適当な硬度と強度を付与するための任意の成分として無機質充填剤を含有してもよい。この無機質充填剤としては、例えば、ヒュームドシリカ、結晶性シリカ、焼成シリカ、湿式シリカ、カーボンブラックおよび無機質充填剤をオルガノアルコキシシラン、オルガノクロロシラン、オルガノジシラザン等の有機ケイ素化合物により表面処理した無機質充填剤が挙げられる。これらの無機質充填剤の含有量は、（Ａ）成分１００重量部に対して５０重量部以下であることが好ましい。
【００２１】
本組成物は、硬化してシリコーンゴム、シリコーンゲル等のシリコーンエラストマーを形成することができる。このような本組成物は、放熱性接着剤、放熱性ダイボンディング剤、放熱性ペースト、電磁波シールド剤等として好適であり、また、、放熱性シート、電磁波吸収シートの原料としても好適である。
【００２２】
【実施例】
本発明の熱伝導性シリコーンエラストマー組成物を実施例により詳細に説明する。なお、実施例中の粘度は２５℃における値である。また、熱伝導性シリコーンエラストマー組成物を硬化して得られるシリコーンエラストマーの特性を次のように測定した。
［熱伝導率］
熱伝導性シリコーンエラストマー組成物を１５０℃で３０分間加熱することにより硬化して、厚さ１ｃｍのシート状シリコーンエラストマーを作製した。このシート状シリコーンエラストマーの熱伝導率を定常法熱伝導測定装置（アンター社製のＵＮＩＴＨＥＲＭ ＭＯＤＥＬ ２０２２）を用いて測定した。
［硬さ］
熱伝導性シリコーンエラストマー組成物を１５０℃で３０分加熱することにより硬化して得られたシリコーンエラストマーの硬さをＪＩＳ Ｋ ６２５３に規定のタイプＡデュロメーターにより測定した。
【００２３】
［実施例１］
粘度５００ｍＰａ・ｓの分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン（ビニル基の含有量＝０．４３重量％）９９重量部、粘度１０ｍＰａ・ｓの分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体（ケイ素原子結合水素原子の含有量＝０．７６重量％）１重量部（上記のジメチルポリシロキサン中のビニル基１モルに対して、本成分中のケイ素原子結合水素原子が０．５モルとなる量）、平均粒子径５μｍのフレーク状銀微粉末９００重量部、１Ｈ−ベンゾトリアゾール（本組成物において重量単位で１００ｐｐｍとなる量）、白金の１，３−ジビニルテトラメチルジシロキサン錯体を軟化点８０〜９０℃の熱可塑性シリコーン樹脂に分散して微粒子化した白金系触媒（本組成物において、触媒中の白金金属が重量単位で１５ｐｐｍとなる量）、および２−フェニル−３−ブチン−２−オール（本組成物において重量単位で２００ｐｐｍとなる量）を均一に混合して熱伝導性シリコーンゴム組成物を調製した。
【００２４】
次に、この熱伝導性シリコーンゴム組成物を二つに分けた。一方は、１５０℃で３０分加熱することにより硬化させ、得られたシリコーンゴムの硬さおよび熱伝導率を測定した。残りは、冷蔵保管し、１ヶ月後に取り出し、１５０℃で３０分間加熱することにより硬化させ、得られたシリコーンゴムの硬さおよび熱伝導率を測定した。これらの結果を表１に示した。
【００２５】
［実施例２］
実施例１において、１Ｈ−ベンゾトリアゾールの代わりに２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノールを用いた以外は実施例１と同様にして熱伝導性シリコーンゴム組成物を調製した。この熱伝導性シリコーンゴム組成物について、実施例１と同様に評価し、その結果を表１に示した。
【００２６】
［比較例１］
実施例１において、１Ｈ−ベンゾトリアゾールを添加しない以外は実施例１と同様にして熱伝導性シリコーンゴム組成物を調製した。この熱伝導性シリコーンゴム組成物についても、実施例１と同様に評価し、その結果を表１に示した。
【００２７】
【表１】
［実施例３］
粘度が５００ｍＰａ・ｓの分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン（ビニル基の含有量＝０．４３重量％）９０重量部、粘度１０ｍＰａ・ｓの分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体（ケイ素原子結合水素原子の含有量＝０．７６重量％）１重量部（上記のジメチルポリシロキサン中のビニル基１モルに対して、本成分中のケイ素原子結合水素原子が０．５モルとなる量）、粘度１５ｍＰａ・ｓの分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルポリシロキサン（ケイ素原子結合水素原子の含有量＝０．１２重量％）９重量部（上記ジメチルポリシロキサン中のビニル基１モルに対して、本成分中のケイ素原子結合水素原子が０．７モルとなる量）、平均粒子径５μｍの球状銀微粉末９００重量部、１Ｈ−ベンゾトリアゾール（本組成物中、重量単位で１００ｐｐｍとなる量）、白金の１，３−ジビニルテトラメチルジシロキサン錯体を軟化点８０〜９０℃の熱可塑性シリコーン樹脂に分散して微粒子化した白金系触媒（本組成物において、本触媒中の白金金属が重量単位で１５ｐｐｍとなる量）、および２−フェニル−３−ブチン−２−オール（本組成物中、重量単位で２００ｐｐｍとなる量）を均一に混合して熱伝導性シリコーンゴム組成物を調製した。
【００２９】
次に、この熱伝導性シリコーンゴム組成物を二つに分けた。一方は、１５０℃で３０分加熱することにより硬化させ、得られたシリコーンゴムの硬さおよび熱伝導率を測定した。残りは、冷蔵保管し、１ヶ月後に取り出し、１５０℃で３０分間加熱することにより硬化させ、得られたシリコーンゴムの硬さおよび熱伝導率を測定した。これらの結果を表２に示した。
【００３０】
［実施例４］
実施例３において、１Ｈ−ベンゾトリアゾールの代わりに２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノールを用いた以外は実施例３と同様にして熱伝導性シリコーンゴム組成物を調製した。この熱伝導性シリコーンゴム組成物について、実施例３と同様に評価し、その結果を表２に示した。
【００３１】
［比較例２］
実施例３において、１Ｈ−ベンゾトリアゾールを添加しない以外は実施例３と同様にして熱伝導性シリコーンゴム組成物を調製した。この熱伝導性シリコーンゴム組成物についても、実施例３と同様に評価し、その結果を表２に示した。
【００３２】
【表２】
【発明の効果】
本発明の熱伝導性シリコーンエラストマー組成物は、貯蔵中に硬化性の経時変化が小さく、硬化して熱伝導率の高いシリコーンエラストマーを形成するという特徴がある。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a thermally conductive silicone elastomer composition, and more particularly to a thermally conductive silicone elastomer composition that hardens over time during storage and cures to form a silicone elastomer having a high thermal conductivity.
[0002]
[Prior art]
A thermally conductive silicone rubber composition which cures to form a thermally conductive silicone rubber is known. For example, JP-A-3-170581 and JP-A-7-133432 disclose at least one molecule per molecule. A silicone rubber composition comprising an organopolysiloxane having two alkenyl groups, an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, fine silver powder, and a platinum-based catalyst has been proposed. However, such a silicone rubber composition has a problem in that the curability of the composition during storage for a long period of time is reduced, and eventually curing failure occurs.
[0003]
[Problems to be solved by the invention]
The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention.
That is, an object of the present invention is to provide a thermally conductive silicone elastomer composition which hardens over time during storage and hardens to form a silicone elastomer having a high thermal conductivity.
[0004]
[Means for Solving the Problems]
The thermally conductive silicone elastomer composition of the present invention comprises
(A) 100 parts by weight of an organopolysiloxane having at least two alkenyl groups in one molecule,
(B) an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule {the silicon-bonded hydrogen atoms in the component (A) are in the range of 0.3 to 1 mol per alkenyl group in the component (A); An amount of 10 moles,
(C) a thermally conductive filler of 50 to 5,000 parts by weight,
(D) a phenolic compound and / or a benzotriazole-based compound (an amount of 10 to 10,000 ppm by weight in the present composition),
(E) a platinum-based catalyst (the amount of platinum metal in this component is 10 to 10,000 ppm by weight based on the present composition), and (F) an ene-yne compound and / or an alkyne alcohol (this composition Amount of 10 to 10,000 ppm by weight in the product)
It is characterized by comprising.
[0005]
BEST MODE FOR CARRYING OUT THE INVENTION
The heat conductive silicone elastomer composition of the present invention will be described in detail.
The component (A) is a main component of the present composition and is an organopolysiloxane having at least two alkenyl groups in one molecule. Examples of the alkenyl group in the component (A) include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group, and a vinyl group and a hexenyl group are particularly preferable. Examples of the bonding position of the alkenyl group in the component (A) include a molecular chain terminal and / or a molecular chain side chain. The organic group bonded to a silicon atom other than the alkenyl group in the component (A) includes an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; a phenyl group and a tolyl group. Aryl or aralkyl such as benzyl or phenethyl; substituted or unsubstituted except alkenyl such as halogenated alkyl such as 3-chloropropyl or 3,3,3-trifluoropropyl. A substituted monovalent hydrocarbon group is exemplified, and a methyl group and a phenyl group are particularly preferred. Examples of the molecular structure of the component (A) include a straight chain, a partially branched straight chain, a branched chain, and a network. The component (A) may be a mixture of two or more kinds of organopolysiloxanes having these molecular structures. The viscosity of the component (A) at 25 ° C. is not limited, but is preferably in the range of 50 to 500,000 mPa · s, and particularly preferably in the range of 100 to 50,000 mPa · s.
[0006]
Examples of the organopolysiloxane of the component (A) include a dimethylsiloxane / methylvinylsiloxane copolymer having trimethylsiloxy groups at both ends of molecular chains, methylvinylpolysiloxane having trimethylsiloxy groups at both ends of molecular chains, and trimethyl at both ends of molecular chains. Siloxy group-blocked methyl vinyl siloxane / methyl phenyl siloxane copolymer, molecular chain terminal trimethyl siloxy group-blocked dimethyl siloxane / methyl vinyl siloxane / methyl phenyl siloxane copolymer, molecular chain terminal dimethyl vinyl siloxy group-blocked dimethyl polysiloxane, molecule Methylvinylpolysiloxane with dimethylvinylsiloxy group blocked at both ends of the chain, methylphenylpolysiloxane with dimethylvinylsiloxy group blocked at both ends of the molecular chain, dimethylvinylsiloxane with dimethylvinylsiloxy group at both ends of the molecular chain Xan / methyl vinyl siloxane copolymer, molecular chain dimethylvinylsiloxy group-blocked methylvinylsiloxane / methylphenylsiloxane copolymer, molecular chain dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane coalesce diorganopolysiloxane such as both ends of the molecular chain blocked by dimethylvinylsiloxy groups methylvinylsiloxane-diphenylsiloxane copolymers; formula siloxane units of the formula R 1 3 SiO 1/2: represented by SiO 4/2 silicone resin consisting of siloxane units of the formula: silicone resin composed of siloxane units represented by R 1 SiO 3/2, wherein: the siloxane units represented by the formula R 1 2 SiO 2/2: with R 1 SiO 3/2 Shown siloxane unit Ranaru silicone resin, wherein: the siloxane units represented by the formula R 1 2 SiO 2/2: siloxane units of the formula R 1 SiO 3/2: silicone resin or the like consisting of siloxane units represented by SiO 4/2 And mixtures of two or more thereof. R 1 in the above formula is a substituted or unsubstituted monovalent hydrocarbon group, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group; a vinyl group, an allyl group, a butenyl group Alkenyl groups such as pentenyl group, hexenyl group and heptenyl group; aryl groups such as phenyl group, tolyl group and xylyl group; aralkyl groups such as benzyl group and phenethyl group; 3-chloropropyl group, 3,3,3-tri Examples thereof include a halogenated alkyl group such as a fluoropropyl group. However, at least two R 1 in one molecule of the silicone resin are the alkenyl groups.
[0007]
The component (B) is a component for curing the present composition by crosslinking the component (A), and is an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule. Examples of the bonding position of the silicon-bonded hydrogen atom in the component (B) include a molecular chain terminal and / or a molecular chain side chain. Examples of the organic group bonded to a silicon atom other than a hydrogen atom in the component (B) include the same substituted or unsubstituted monovalent hydrocarbon group as described above, excluding an alkenyl group. And a phenyl group is preferred. Examples of the molecular structure of the component (B) include a straight chain, a partially branched straight chain, a branched chain, and a network. The component (B) may be a mixture of two or more organopolysiloxanes having these molecular structures. The viscosity of the component (B) at 25 ° C. is not limited, but is preferably in the range of 1 to 500,000 mPa · s, and particularly preferably in the range of 5 to 1,000 mPa · s.
[0008]
Examples of the organopolysiloxane of the component (B) include methylhydrogenpolysiloxane having trimethylsiloxy groups at both ends of molecular chains, dimethylsiloxane / methylhydrogensiloxane copolymer having trimethylsiloxy groups at both ends of molecular chains, Trimethylsiloxy terminal-blocked methyl hydrogen siloxane / methyl phenyl siloxane copolymer, molecular chain bi-terminal trimethyl siloxy-group dimethyl siloxane / methyl hydrogen siloxane / methyl phenyl siloxane copolymer, molecular chain both-terminal dimethyl hydrogen siloxy group Dimethylpolysiloxane, dimethylhydrogensiloxy group-blocked at both molecular chain terminals Methylhydrogenpolysiloxane, dimethylhydroxylene-blocked dimethylhydrogensiloxy group at both molecular chain terminals・ Methyl hydrogen siloxane copolymer, dimethyl hydrogen siloxane blocked at both ends of molecular chain dimethyl siloxane ・ Methyl phenyl siloxane copolymer, dimethyl siloxane blocked at both ends of dimethyl hydrogen siloxy, methyl hydrogen siloxane ・ Methyl phenyl siloxane diorganopolysiloxane such copolymer; formula siloxane units represented by the formula R 2 3 SiO 1/2: silicone resins comprising siloxane units represented by SiO 4/2, wherein: in R 2 SiO 3/2 silicone resin composed of siloxane units represented by the formula: siloxane units represented by the formula R 2 2 SiO 2/2: silicone resins comprising siloxane units represented by R 2 SiO 3/2, wherein: R 2 2 SiO 2 / siloxane single represented by 2 Preparative formula siloxane units represented by the formula R 2 SiO 3/2: silicone resin silicone resin or the like consisting of siloxane units represented by SiO 4/2, and mixtures of two or more of the above. R 2 in the above formula is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group excluding an alkenyl group. Examples of the monovalent hydrocarbon group for R 2 include the same groups as described above. However, at least two R 2 in one molecule of the silicone resin are hydrogen atoms.
[0009]
In the present composition, the content of the component (B) is such that the silicon-bonded hydrogen atom in the component (B) is in the range of 0.3 to 10 mol per 1 mol of the alkenyl group in the component (A). Is the amount If the content of the component (B) is less than the lower limit of the above range, the obtained composition tends to be insufficiently cured, while if it exceeds the upper limit of the above range, the obtained silicone will not be cured. This is because the heat resistance of the elastomer tends to decrease.
[0010]
The component (C) is a thermally conductive filler for imparting thermal conductivity to a silicone elastomer obtained by curing the present composition. As the component (C), a metal fine powder such as gold, silver, nickel, and copper; and a metal such as gold, silver, nickel, and copper are deposited or plated on the surface of fine powder such as ceramic, glass, quartz, and organic resin. Fine powder; metal compounds such as aluminum oxide, aluminum nitride, and zinc oxide; and mixtures of two or more thereof. In the present composition, in order to obtain a highly thermally conductive silicone elastomer having a thermal conductivity of 3 W / mK or more, it is preferable to use fine silver powder as the component (C). Examples of the shape of the fine silver powder include a spherical shape, a flake shape, and a flake dendritic shape. The average particle diameter of the component (C) is preferably in the range of 1 to 100 μm, and particularly preferably in the range of 1 to 50 μm.
[0011]
In the present composition, the content of the component (C) is within a range from 50 to 5,000 parts by weight, and preferably from 300 to 3,000 parts by weight, based on 100 parts by weight of the component (A). It is. This is because if the content of the component (C) is less than the lower limit of the above range, the obtained silicone elastomer tends to be unable to have sufficient thermal conductivity. This is because it is difficult to prepare the composition or the handling efficiency of the obtained composition tends to deteriorate.
[0012]
The component (D) is a phenolic compound and / or a benzotriazole-based compound for suppressing a change over time in the curability of the present composition during storage of the present composition. The phenolic compounds include 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6 Mono-di-tert-butyl-4-sec-butylphenol, 2- (1-methylcyclohexyl) -4,6-dimethylphenol, and 2,6-di-tert-butyl-α-dimethylamino-p-cresol Phenol compound; 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis- (4-methyl-6-cyclohexylphenol), 2,2'-methylene -Bis- (4-ethyl-6-tert-butylphenol), 4,4'-methylene-bis- (2,6-di-tert-butylphenol) ), 2,2'-methylene-bis- (6-α-methylbenzyl-p-cresol), bisphenol compounds such as 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol); Thiobisphenol compounds such as 4,4'-thiobis- (6-tert-butyl-3-methylphenol) and 4,4'-thiobis- (6-tert-butyl-o-cresol); 1,1,3- Tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4,4'-butylidenebis- (3-methyl-6-tert-butylphenol), 2,2-thiobis- (4-methyl- Hindered phenol compounds such as 6-tert-butylphenol). Examples of the benzotriazole-based compound include 1H-benzotriazole, 4-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole, and 2- (2′-hydroxy-5′-methyl-phenyl) benzotriazole. 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methyl-phenyl) -5 -Chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-tert-octyl-phenyl ) Benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amyl-phenyl) benzotriazole, 2- [2′- Droxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methyl-phenyl] benzotriazole, 2,2'-methylenebis [4- (1,1,3,3 -Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, -(2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole, 2- (2H-benzotriazol-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalimidyl Methyl) phenol is exemplified.
[0013]
In the present composition, the content of the component (D) is an amount within the range of 10 to 10,000 ppm by weight based on the present composition. This is because, if the content of the component (D) is less than the lower limit of the above range, it is difficult to suppress the change over time in the curability of the composition to be obtained, while the amount exceeds the upper limit of the above range. This is because curing of the obtained composition becomes extremely slow.
[0014]
The component (E) is a platinum-based catalyst for accelerating the curing of the composition. Examples of the platinum catalyst as the component (E) include platinum black, platinum-supported alumina powder, platinum-supported silica powder, platinum-supported carbon powder, chloroplatinic acid, an alcohol solution of chloroplatinic acid, an olefin complex of platinum, and an alkenylsiloxane complex of platinum. Examples thereof include catalysts obtained by dispersing these platinum-based catalysts in a thermoplastic resin such as a methyl methacrylate resin, a polycarbonate resin, a polystyrene resin, and a silicone resin to form fine particles.
[0015]
In the present composition, the content of the component (E) is such that the platinum metal contained in the present component is in the range of 0.1 to 1,000 ppm by weight in the present composition. This is because if the content of the component (E) is less than the lower limit of the above range, the obtained composition will not be sufficiently cured, while if it exceeds the upper limit of the above range, the obtained silicone elastomer will be colored. This causes problems such as the following.
[0016]
The component (F) is an ene-yne compound and / or an alkyne alcohol for controlling the curability of the composition and improving the handling efficiency. Examples of the ene-yne compound include 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne. Examples of the alkyne alcohol include 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, and 2-phenyl-3-butyn-2-ol.
[0017]
In the present composition, the content of the component (F) is an amount within the range of 10 to 10,000 ppm by weight with respect to the present composition. This is because if the content of the component (F) is less than the lower limit of the above range, it becomes difficult to adjust the curability of the obtained composition, and the handling workability is deteriorated. If the upper limit is exceeded, the curing of the obtained composition becomes extremely slow.
[0018]
The present composition can be prepared by uniformly mixing the above components (A) to (F), but imparts good adhesion to a thermally conductive silicone elastomer obtained by curing the present composition. In order to achieve this, it is preferable to contain an adhesion promoter. Examples of the adhesion promoter include alkoxysilane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane. ;formula:
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A siloxane oligomer having a silicon-bonded hydrogen atom or alkenyl group and a silicon-bonded alkoxy group in one molecule such as a siloxane oligomer represented by
[0019]
In the present composition, the adhesion promoter is an optional component, and when it is contained, its content is preferably 20 parts by weight or less based on 100 parts by weight of the component (A). In particular, the content is preferably in the range of 0.5 to 10 parts by weight. This is because, when the silicone elastomer composition does not contain an adhesion promoter, the resulting silicone elastomer composition may have poor adhesion, or may cause a change with time in the contact resistance and volume resistivity of the silicone elastomer obtained by curing the composition. On the other hand, when the content of the adhesion promoter exceeds the upper limit of the above range, the storage stability of the obtained silicone elastomer composition is reduced, or the physical properties of the silicone elastomer obtained by curing this are reduced. This is because the characteristics change over time.
[0020]
The composition may contain an inorganic filler as an optional component for imparting appropriate hardness and strength to the thermally conductive silicone elastomer obtained by curing. Examples of the inorganic filler include fumed silica, crystalline silica, calcined silica, wet silica, carbon black, and inorganic fillers that have been surface-treated with an organosilicon compound such as organoalkoxysilane, organochlorosilane, or organodisilazane. Fillers. The content of these inorganic fillers is preferably 50 parts by weight or less based on 100 parts by weight of the component (A).
[0021]
The composition can be cured to form a silicone elastomer such as a silicone rubber or silicone gel. Such a composition is suitable as a heat dissipating adhesive, a heat dissipating die bonding agent, a heat dissipating paste, an electromagnetic wave shielding agent and the like, and is also suitable as a raw material for a heat dissipating sheet and an electromagnetic wave absorbing sheet.
[0022]
【Example】
The heat conductive silicone elastomer composition of the present invention will be described in more detail with reference to examples. In addition, the viscosity in an Example is a value in 25 degreeC. The properties of the silicone elastomer obtained by curing the thermally conductive silicone elastomer composition were measured as follows.
[Thermal conductivity]
The thermally conductive silicone elastomer composition was cured by heating at 150 ° C. for 30 minutes to produce a 1 cm thick sheet-like silicone elastomer. The thermal conductivity of this sheet-shaped silicone elastomer was measured using a steady-state thermal conductivity measuring device (UNITHERM MODEL 2022 manufactured by Anter Co.).
[Hardness]
The hardness of the silicone elastomer obtained by curing the heat conductive silicone elastomer composition by heating it at 150 ° C. for 30 minutes was measured with a type A durometer specified in JIS K6253.
[0023]
[Example 1]
99 parts by weight of a dimethylvinylsiloxane-blocked dimethylvinylsiloxy group at both ends of a molecular chain having a viscosity of 500 mPa · s (vinyl group content = 0.43% by weight), 1 part by weight of a methylhydrogensiloxane copolymer (content of silicon-bonded hydrogen atoms = 0.76% by weight) (1 mole of vinyl groups in the above-mentioned dimethylpolysiloxane, 1 mole of silicon-bonded hydrogen in this component) 900 parts by weight of flake silver fine powder having an average particle diameter of 5 μm, 1H-benzotriazole (an amount of 100 ppm by weight in the present composition), 1,3-divinyl of platinum Platinum system in which a tetramethyldisiloxane complex is dispersed in a thermoplastic silicone resin having a softening point of 80 to 90 ° C to form fine particles. The medium (in the present composition, the amount of platinum metal in the catalyst is 15 ppm by weight) and the 2-phenyl-3-butyn-2-ol (in the present composition, the amount is 200 ppm by weight) are uniformly mixed. The mixture was mixed to prepare a thermally conductive silicone rubber composition.
[0024]
Next, this thermally conductive silicone rubber composition was divided into two parts. One was cured by heating at 150 ° C. for 30 minutes, and the hardness and thermal conductivity of the obtained silicone rubber were measured. The remainder was stored in a refrigerator, taken out one month later, cured by heating at 150 ° C. for 30 minutes, and the hardness and thermal conductivity of the obtained silicone rubber were measured. Table 1 shows the results.
[0025]
[Example 2]
A heat conductive silicone rubber composition was prepared in the same manner as in Example 1 except that 2,6-di-tert-butyl-4-methylphenol was used instead of 1H-benzotriazole. This heat conductive silicone rubber composition was evaluated in the same manner as in Example 1, and the results are shown in Table 1.
[0026]
[Comparative Example 1]
A heat conductive silicone rubber composition was prepared in the same manner as in Example 1 except that 1H-benzotriazole was not added. This thermally conductive silicone rubber composition was evaluated in the same manner as in Example 1, and the results are shown in Table 1.
[0027]
[Table 1]
[Example 3]
90 parts by weight of a dimethylvinylsiloxane-blocked dimethylvinylsiloxy group at both ends of a molecular chain having a viscosity of 500 mPa · s (vinyl group content = 0.43% by weight), and a dimethylsiloxane having a trimethylsiloxy group at both ends of a molecular chain having a viscosity of 10 mPa · s 1 part by weight of methyl hydrogen siloxane copolymer (content of silicon-bonded hydrogen atoms = 0.76% by weight) 9 parts by weight of a dimethylpolysiloxane endblocked by dimethylhydrogensiloxy groups at both ends of the molecular chain having a viscosity of 15 mPa · s (content of silicon-bonded hydrogen atoms = 0.12% by weight) having an amount of 0.5 mol of hydrogen atoms). The silicon-bonded hydrogen atom in this component is 0.7 mole per 1 mole of the vinyl group in the dimethylpolysiloxane. ), 900 parts by weight of spherical silver fine powder having an average particle diameter of 5 µm, 1H-benzotriazole (an amount of 100 ppm by weight in the present composition), and 1,3-divinyltetramethyldisiloxane complex of platinum. A platinum-based catalyst dispersed in a thermoplastic silicone resin having a softening point of 80 to 90 ° C. and made into fine particles (in the present composition, the amount of platinum metal in the catalyst becomes 15 ppm by weight), and 2-phenyl-3- Butyn-2-ol (in the present composition, an amount of 200 ppm by weight) was uniformly mixed to prepare a thermally conductive silicone rubber composition.
[0029]
Next, this thermally conductive silicone rubber composition was divided into two parts. One was cured by heating at 150 ° C. for 30 minutes, and the hardness and thermal conductivity of the obtained silicone rubber were measured. The remainder was stored in a refrigerator, taken out one month later, cured by heating at 150 ° C. for 30 minutes, and the hardness and thermal conductivity of the obtained silicone rubber were measured. Table 2 shows the results.
[0030]
[Example 4]
A heat conductive silicone rubber composition was prepared in the same manner as in Example 3, except that 2,6-di-tert-butyl-4-methylphenol was used instead of 1H-benzotriazole. This heat conductive silicone rubber composition was evaluated in the same manner as in Example 3, and the results are shown in Table 2.
[0031]
[Comparative Example 2]
A heat-conductive silicone rubber composition was prepared in the same manner as in Example 3 except that 1H-benzotriazole was not added. This heat conductive silicone rubber composition was evaluated in the same manner as in Example 3, and the results are shown in Table 2.
[0032]
[Table 2]
【The invention's effect】
The heat conductive silicone elastomer composition of the present invention is characterized in that the change of the curability with time during storage is small, and the composition is cured to form a silicone elastomer having a high heat conductivity.
Claims (4)
（Ｂ）一分子中に少なくとも２個のケイ素原子結合水素原子を有するオルガノポリシロキサン｛（Ａ）成分中のアルケニル基１モルに対して、本成分中のケイ素原子結合水素原子が０．３〜１０モルとなる量｝、
（Ｃ）熱伝導性フィラー ５０〜５，０００重量部、
（Ｄ）フェノール系化合物および／またはベンゾトリアゾール系化合物（本組成物中に重量単位で１０〜１０，０００ｐｐｍとなる量）、
（Ｅ）白金系触媒（本成分中の白金金属が、本組成物に対して重量単位で１０〜１０，０００ｐｐｍとなる量）、および
（Ｆ）エン−イン化合物および／またはアルキンアルコール（本組成物中に重量単位で１０〜１０，０００ｐｐｍとなる量）
からなる熱伝導性シリコーンエラストマー組成物。(A) 100 parts by weight of an organopolysiloxane having at least two alkenyl groups in one molecule,
(B) an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule {the silicon-bonded hydrogen atoms in the component (A) are in the range of 0.3 to 1 mol per alkenyl group in the component (A); An amount of 10 moles,
(C) a thermally conductive filler of 50 to 5,000 parts by weight,
(D) a phenolic compound and / or a benzotriazole-based compound (an amount of 10 to 10,000 ppm by weight in the present composition),
(E) a platinum-based catalyst (the amount of platinum metal in this component is 10 to 10,000 ppm by weight based on the present composition), and (F) an ene-yne compound and / or an alkyne alcohol (this composition Amount of 10 to 10,000 ppm by weight in the product)
A thermally conductive silicone elastomer composition comprising:
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| PCT/JP2003/011457 WO2004046233A1 (en) | 2002-11-21 | 2003-09-08 | Thermally-conductive silicone elastomer composition |
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| EP0647682B1 (en) * | 1993-10-06 | 1997-12-03 | Dow Corning Toray Silicone Company, Limited | Silver-filled electrically conductive organosiloxane compositions |
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- 2002-11-21 JP JP2002337566A patent/JP4676671B2/en not_active Expired - Fee Related
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2003
- 2003-09-08 WO PCT/JP2003/011457 patent/WO2004046233A1/en active Application Filing
- 2003-09-08 AU AU2003260954A patent/AU2003260954A1/en not_active Abandoned
- 2003-10-13 TW TW092128292A patent/TW200416258A/en unknown
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| JPH07150048A (en) * | 1993-10-06 | 1995-06-13 | Toray Dow Corning Silicone Co Ltd | Electrically conductive silicone rubber composition |
| JPH08319425A (en) * | 1995-05-25 | 1996-12-03 | Toray Dow Corning Silicone Co Ltd | Heat-conductive silicone rubber composition |
| JPH08325457A (en) * | 1995-05-29 | 1996-12-10 | Toray Dow Corning Silicone Co Ltd | Thermally conductive silicone rubber composition |
| JPH09111124A (en) * | 1995-10-17 | 1997-04-28 | Toray Dow Corning Silicone Co Ltd | Heat-conductive silicone rubber and its composition |
Cited By (24)
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| JP2007224102A (en) * | 2006-02-22 | 2007-09-06 | Shin Etsu Chem Co Ltd | Thermal conductive silicone composition, thermal conductive silicone molded article, and its manufacturing method |
| JP2013010862A (en) * | 2011-06-29 | 2013-01-17 | Shin-Etsu Chemical Co Ltd | Curable and grease-like thermoconductive silicone composition and semiconductor device |
| JP2014051606A (en) * | 2012-09-07 | 2014-03-20 | Dow Corning Toray Co Ltd | Curable silicone composition and photosemiconductor device |
| WO2014088115A1 (en) * | 2012-12-07 | 2014-06-12 | 東レ・ダウコーニング株式会社 | Curable silicone composition and optical semiconductor device |
| JPWO2014088115A1 (en) * | 2012-12-07 | 2017-01-05 | 東レ・ダウコーニング株式会社 | Curable silicone composition and optical semiconductor device |
| JP2017071659A (en) * | 2015-10-05 | 2017-04-13 | 三菱マテリアル株式会社 | Heat radiation sheet |
| WO2018079309A1 (en) * | 2016-10-26 | 2018-05-03 | 信越化学工業株式会社 | Thermally-conductive silicone composition |
| TWI764949B (en) * | 2016-10-26 | 2022-05-21 | 日商信越化學工業股份有限公司 | Thermally Conductive Silicon Oxygen Composition |
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| KR102203924B1 (en) * | 2016-10-31 | 2021-01-18 | 다우 도레이 캄파니 리미티드 | One component curable thermally conductive silicone grease composition and electronic/electronic parts |
| JPWO2018079215A1 (en) * | 2016-10-31 | 2018-11-01 | 東レ・ダウコーニング株式会社 | One-component curable thermally conductive silicone grease composition and electronic / electrical parts |
| CN109890900B (en) * | 2016-10-31 | 2022-01-14 | 陶氏东丽株式会社 | One-component curable heat-conductive silicone grease composition and electronic/electrical component |
| US11319412B2 (en) | 2016-10-31 | 2022-05-03 | Dow Toray Co., Ltd. | Thermally conductive silicone compound |
| WO2018079215A1 (en) * | 2016-10-31 | 2018-05-03 | 東レ・ダウコーニング株式会社 | One-pack curable type thermally conductive silicone grease composition and electronic/electrical component |
| JP2019001900A (en) * | 2017-06-15 | 2019-01-10 | 信越化学工業株式会社 | Thermally conducive silicone composition |
| WO2018230189A1 (en) * | 2017-06-15 | 2018-12-20 | 信越化学工業株式会社 | Thermally-conductive silicone composition |
| WO2019155846A1 (en) * | 2018-02-09 | 2019-08-15 | 信越化学工業株式会社 | Thermoconductive silicone composition, cured product, semiconductor device, and semiconductor device production method |
| JPWO2019155846A1 (en) * | 2018-02-09 | 2020-12-03 | 信越化学工業株式会社 | Thermally Conductive Silicone Compositions, Cured Products, Semiconductor Devices, and Methods for Manufacturing Semiconductor Devices |
| WO2023145438A1 (en) * | 2022-01-31 | 2023-08-03 | 信越化学工業株式会社 | Thermally-conductive addition-curable silicone composition and cured product thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2004046233A1 (en) | 2004-06-03 |
| TW200416258A (en) | 2004-09-01 |
| JP4676671B2 (en) | 2011-04-27 |
| AU2003260954A1 (en) | 2004-06-15 |
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