JP2004059851A - Composition for heat conductive, electric insulative pressure sensitive adhesive agent and adhesive sheet using same - Google Patents
Composition for heat conductive, electric insulative pressure sensitive adhesive agent and adhesive sheet using same Download PDFInfo
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【０００１】
【発明の属する技術分野】
本発明は難燃性熱伝導性感圧接着剤用組成物、難燃性熱伝導電気絶縁感圧接着剤及び難燃性熱伝導電気絶縁粘着シートに関する。
【０００２】
【従来技術】
近年、エレクトロニクス技術の格段なる進歩により電気、電子機器の高集積化・高性能化が進むに伴い、半導体やＣＰＵ等の電子部品や、プラズマディスプレイ等の家電製品では、それ自身が発生する熱による温度上昇で電子部品が機能障害を生じる恐れがあることから、熱放散の必要性が高まっている。そのため電子部品や家電製品には、ヒートシンク等の熱対策部品を接合部材による接着、又は機械的に固定して熱放散を行い、機能障害を予防する対策が講じられている。この接合部材には、高い熱伝導性と電気絶縁性の他、安全性の面から万一の発火にたいして着火・延焼の危険性が無いように高い難燃性が要求される。
【０００３】
特開平６−８８０６１号公報は、アルキル基中に１〜１２個の炭素原子を有する（メタ）アルキルアクリレートと共重合可能な極性モノマーから調整されるポリマーにランダムに分散された熱伝導電気絶縁粒子を含有する熱伝導電気絶縁感圧接着剤及びそれを使用した接着テープが記載されている。しかし、該発明には、本用途に対して難燃性を付与すべき認識がなく、記載もされていない。
【０００４】
特開平１０−３３０６９２号公報には、アルキル基の炭素数が２〜１４個である（メタ）アルキルアクリレートを主成分とする単量体と分子内に極性基を有する共重合可能な単量体からなるアクリル系共重合体に対して熱伝導性充填剤を配合する際に、分子内にラジカル重合性の炭素−炭素二重結合を有する反応性界面活性剤を配合することにより、熱伝導充填剤の種類の制約を受けることのない熱伝導性感圧接着剤と、これを用いた熱伝導性感圧接着シートを提案している。しかしながら、該発明も本用途に対して難燃性を付与すべき認識がなく、記載もされていない。
【０００５】
特開平１１−２６９４３８号公報には、アルキル基の炭素数が４〜１４個である（メタ）アルキルアクリレートと共重合可能な極性ビニルモノマーからなるアクリル系共重合体と、金属水酸化物からなる難燃性熱伝導性感圧接着剤が記載されている。しかしながら、より高い熱伝導性（１．０Ｗ／ｍ・Ｋ以上）と優れた難燃性（ＵＬ９４−ＶＴＭ０）を満足するために、金属水酸化物をアクリル系共重合体１００質量部に対して１８０質量部を越えて添加すると、ＵＶ硬化型の感圧接着剤組成物の場合は粘度が著しく上昇するため、塗工適性が低下する問題があった。
【０００６】
【発明が解決しようとする課題】
本発明者らは、特開平１０−３３０６９２号公報記載の技術に従い、市場で求められる高い熱伝導性と優れた難燃性を有する難燃性熱伝導電気絶縁粘着シートを得るために、金属水酸化物の添加量を増やした系の作製を試みた。しかしその結果、粘着剤用組成物の流動性が非常に乏しいため、塗工ができないものしか得られなかった。また、塗工適性を付与するために粘着剤用組成物を部分重合する事によりシロップ状にしたものは、金属水酸化物をアクリル系共重合体１００質量部に対して１８０質量部を越えて配合した際には増粘が著しく、塗工する事ができなかった。
【０００７】
本発明は、上記のような従来技術の欠点を解消した、すなわち塗工適性に優れる難燃性熱伝導電気絶縁感圧接着剤用組成物、及び熱伝導性や難燃性に優れる難燃性熱伝導電気絶縁感圧接着剤および難燃性熱伝導電気絶縁粘着シートを提供することを目的とするものである。
【０００８】
【課題を解決するための手段】
本発明者らは鋭意検討の結果、炭素数が１〜１４個のアルキル基を有する（メタ）アルキルアクリレートに対して、光重合開始剤、難燃性熱伝導電気絶縁粒子、特定の分散剤を配合した組成物にすることにより、塗工適性に優れる難燃性熱伝導電気絶縁感圧接着剤用組成物が得られることを見出し、本発明を完成するに至った。
【０００９】
すなわち本発明は、
ａ）炭素数が１〜１４個のアルキル基を有する（メタ）アルキルアクリレート単量体と、
ｂ）光重合性開始剤と、
ｃ）熱伝導電気絶縁粒子３００〜７００質量部を含有し、かつ該熱伝導電気絶縁粒子のうち２００質量部以上が難燃性を有し、
ｄ）高分子系分散剤を、熱伝導電気絶縁粒子に対して０．０５〜５．０質量％、
を含有することを特徴とする、難燃性熱伝導電気絶縁感圧接着剤用組成物を提供する。さらに、それを使用した熱伝導率、電気絶縁性および難燃性に優れた難燃性熱伝導電気絶縁感圧接着剤、及びその感圧接着剤層を有する難燃性熱伝導電気絶縁粘着シートを提供する。
【００１０】
【発明の実施の形態】
本発明の組成物において、ａ）成分の炭素数が１〜１４個のアルキル基を有する（メタ）アルキルアクリレート単量体としては、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸イソブチル、アクリル酸イソアミル、アクリル酸ヘキシル、アクリル酸２−エチルヘキシル、アクリル酸オクチル、アクリル酸イソオクチル、アクリル酸イソノニル、アクリル酸イソデシル、アクリル酸ラウリル、エタクリル酸メチル、メタクリル酸ブチル、メタクリル酸ヘキシル、メタクリル酸２−エチルヘキシル、メタクリル酸イソデシル、メタクリル酸ラウリル等が挙げられるが、これに限定されるものではない。これらは単量体混合物中７０〜１００質量％、好ましくは９０〜９９質量％の割合で用いられる。（メタ）アルキルアクリレートの量が７０質量％未満であると、初期接着性などが低下する。
【００１１】
（分子内に極性基を有する共重合性単量体）
本発明の熱伝導電気絶縁感圧接着剤用組成物に、分子内に極性基を有する共重合性単量体を加えてもよい。この共重合性単量体は、上記（メタ）アルキルアクリレート単量体と共重合してアクリル共重合体を生成して凝集力や接着力を向上することができる。特に限定されるものではないが、例として、アクリル酸、イタコン酸、（無水）マレイン酸、（無水）フマル酸、カプロラクタン変性の（メタ）アクリレート、アクリル酸ダイマー等の酸基含有単量体、（メタ）アクリルアミド、置換アクリルアミド、Ｎ−ビニルピロリドン、Ｎ−ビニルカプロラクタム、（メタ）アクリロイルモルフォリン、（メタ）アクリルアミド等の窒素含有単量体、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート等の水酸基含有単量体などが挙げられるがこれに限定されるものではない。これら共重合性単量体は、全単量体の３０〜０．５質量％、好ましくは１０〜１質量％の割合で用いられる。３０質量％を越えると、初期接着性が低下する。
【００１２】
（光重合開始剤）
本発明の組成物において、ｂ）成分の光重合開始剤としては、ベンゾインメチルエーテル、ベンゾインエチルエーテルなどのベンゾインエーテル類、２，２−ジエトキシアセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノンなどの置換アセトフェノン類、２−メチル−２−ヒドロキシプロピオフェノンなどの置換−α−ケトール類、ベンジルケタール類、アシルフォスフィンオキサイド類、ベンゾイン類、ベンゾフェノン類など公知のものが挙げられる。また、分子内に開裂点が２つ以上ある光重合開始剤、例えば、ビスアシルフォスフィンオキサイド類、ビスマレイミド誘導体を用いると、光重合物の分子量を大きくしやすいので好ましい。
【００１３】
これらの光重合開始剤の使用量は種類や光源の波長にもよるが、単量体１００質量部に対して、０．０１〜３質量部、好ましくは０．１〜１質量部の割合で用いる。０．０１質量部より少ないと、未反応の単量体が残存する。また、３質量部より多いと、光重合によって生成する光重合物の分子量が低下して感圧接着剤の凝集力不足を招く。また、後述する熱伝導性電気絶縁粒子の配合量が多い場合は、２種以上の光重合開始剤の併用が好ましい。
【００１４】
（熱伝導性電気絶縁粒子）
本発明の組成物において、ｃ）成分の熱伝導性電気絶縁性粒子としては、熱伝導性が高く、電気的に絶縁性である充填剤であれば、特に限定されないが、例えば金属酸化物、金属窒化物、炭化珪素、金属水酸化物、樹脂をコーティングした金属の群から選ばれた少なくとも１種を挙げることができる。
【００１５】
かかる金属酸化物としては、特に限定されないが、例えば酸化アルミニウムや酸化チタン、酸化マグネシウムなどの金属酸化物、窒化アルミニウムなどの金属窒化物、窒化珪素、水酸化アルミニウムや水酸化マグネシウムなどの金属水酸化物などが挙げられる。
【００１６】
（熱伝導電気絶縁粒子の含有量）
本発明で使用するｃ）成分である熱伝導電気絶縁粒子は、単量体１００質量部に対して３００〜７００質量部、好ましくは３００〜５００質量部である。熱伝導電気絶縁粒子が３００質量部未満であると、高い熱伝導性が発揮できない。７００質量部を越えると、粘着シートの柔軟性が損なわれるので、凹凸面への追従性が低下するため熱伝導効率が低下する。
【００１７】
本発明で使用するｃ）成分の熱伝導電気絶縁粒子の平均粒径は、特に限定されないが、０．５〜７０μｍが好ましく、更に好ましくは１〜３０μｍである。形状は、球状、針状、フレーク状などいかなる形状でもよい。熱伝導電気絶縁粒子は、１種又は化合物種類や平均粒径、形状が異なる２種以上の粒子を組み合わせて使用してもよい。また、粒子表面には必要に応じてカップリング処理、ステアリン処理、樹脂被覆処理、シリカ被覆処理などの表面処理を適宜行っても良い。
【００１８】
本発明で使用するＣ）成分のうち２００質量部以上は難燃性熱伝導電気絶縁粒子を使用する。難燃性熱伝導電気絶縁粒子としては、特に限定されないが、例えば金属水酸化物が挙げられる。金属水酸化物としては、水酸化アルミニウム、水酸化マグネシウムなどが挙げられる。２００質量部未満では、これのみでＵＬ−９４のＶＴＭ−０を達成する難燃性が発揮できない。
【００１９】
難燃性熱伝導電気絶縁粒子を、難燃性を有さない熱伝導電気絶縁粒子と併用する場合は、難燃性を有する粒子の平均粒径は難燃性を有さない粒子の平均粒径より小さいものが好ましい。好ましくは、平均粒径は１０μｍ以下である。難燃性を有する粒子の平均粒径が小さいと、同一添加量の場合、表面積の増加や粘着シート全体に均一に分散するので難燃性が向上する。また、難燃性熱伝導電気絶縁粒子は、１種又は化合物種類や平均粒径、形状が異なる２種以上の粒子を組み合わせて使用してもよい。
【００２０】
（高分子系分散剤）
本発明のｄ）成分である高分子系分散剤は、炭化水素鎖を主体とした疎水基を主鎖と親水基を側鎖に有する、界面活性剤の機能と高分子の特性を兼ね備えた両親媒性の高分子である。高分子系の分散剤を使用すると、単量体に熱伝導電気絶縁粒子を配合した際の分散性が改善され、さらに本発明記載の配合量において適度な流動性を発現するため、シロップ化などの手法を用いる事なく良好な塗工適性を付与できる。
使用される高分子系分散剤の重量平均分子量は、５００〜２万であることが好ましく、１０００〜１万であることが更に好ましい。
【００２１】
高分子系分散剤に利用されるものとしては、天然系や合成系があり一般の界面活性剤と同様アニオン系、カチオン系、ノニオン系に分類される。スチレン−無水マレイン酸共重合物、オレフィン−無水マレイン酸共重合物、ナフタレンスルホン酸塩のホルマリン縮合物、ポリアクリル酸ナトリウム、ポリアクリルアミド部分加水分解物、アクリルアミド・アクリル酸ナトリウム共重合物、（メタ）アクリレート・アクリル酸共重合物、アルギン酸ナトリウム、ポリエステル酸のアミドアミン塩、ポリエーテルリン酸エステルのアミン塩などのアニオン系や、ポリエチレンイミン、ポリビニルイミダゾリン、アミノアルキル（メタ）アクリレート・アクリルアミド共重合物、ポリアクリルアミドマンニッヒ変性物、キトサン類などのカチオン系や、ポリビニルアルコール、ポリオキシエチレンエーテルエステル共重合体、ポリアクリルアミド、アクリレート・ビニルピロリドン共重合物、でんぷんなどのノニオン系が挙げられる。
【００２２】
高分子系分散剤の選択と配合量は、ｃ）成分の熱伝導電気絶縁粒子の種類や形状、配合量などによって適宜選択されるが、高分子系分散剤の配合量は、ｃ）成分の熱伝導電気絶縁粒子１００質量部に対して０．０５〜５．０質量％を好ましくは０．１〜２．０質量％の割合で用いられる。高分子系分散剤が０．０５質量％未満では、充分な分散性が得られない。５．０質量％を越えると耐熱性が阻害され、高温下での接着性が低下しやすい。
【００２３】
本発明の熱伝導電気絶縁感圧接着剤用組成物の調整においては、ａ）成分を含む単量体成分にｄ）成分の分散剤を配合して十分溶解させたのちに、ｃ）成分を配合し、その他成分を順次配合することが好ましい。更に好ましくは、ａ）にｄ）を溶解させｃ）を配合後１〜８時間撹拌すると、高分子系分散剤と粒子とが吸着平衡に達する。
【００２４】
（その他の添加剤）
この組成物には、粘着シートの凝集性や剪断強度を増加させるため、架橋剤を添加することができる。さらに必要により顔料、充填剤、酸化防止剤、紫外線吸収剤、粘着付与樹脂などの公知の各種添加剤を、紫外線などの照射による光重合を妨げない範囲内で添加してもよい。
【００２５】
（架橋剤）
架橋剤としては、ａ）成分と共重合が可能な多官能（メタ）アクリレートや、分子内にカルボキシル基や水酸基などの極性基を有する共重合性単量体がある場合は、これと反応する官能基を有する架橋剤を用いることができる。本発明では光重合法を用いて粘着シートを作成するので、共重合可能な多官能（メタ）アクリレートとの共重合による架橋は、熟成工程が不要となるので好ましい。極性基と反応する官能基を有する架橋剤を使用する場合は、組成物を塗工する８時間前、好ましくは４時間前に配合する。
【００２６】
共重合可能な多官能（メタ）アクリレートとしては、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、１，２−エチレングリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレートなどの多官能（メタ）アクリレートがある。また、極性基と反応する官能基を有する架橋剤には、トリレンジイソシアネート、トリメチロールプロパントリレンジイソシアネート、ジフエニルメタントリイソシアネートなどの多官能イソシアネート系架橋剤、ポリエチレングリコールジグリシジルエーテル、ジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテルなどのエポキシ系架橋剤、メラミン樹脂系架橋剤、アミノ樹脂系架橋剤、過酸化物系架橋剤、カルボジイミド系架橋剤などが挙げられる。
【００２７】
（粘着付与樹脂）
本発明で使用する粘着剤層に用いられる上記アクリル共重合体には、必要に応じ粘着付与樹脂を添加しても良い。粘着付与樹脂としては、テルペン系樹脂、テルペンフェノール樹脂、ロジン系樹脂、石油系樹脂、クマロン−インデン樹脂、フェノール系樹脂等が挙げられる。本発明では光重合法を用いて粘着シートを作成するので、粘着付与樹脂中の二重結合による重合阻害を防止するために、二重結合が少なく阻害を起こしにくい粘着付与樹脂を用いる。例えば、高度に不均化したロジンエステルや、高度に水素添加をして二重結合を少なくしたロジンエステルやクマロン−インデン樹脂、テルペンフェノール樹脂、分子骨格に二重結合部位をもたないアクリル系樹脂、飽和脂肪族樹脂等が挙げられる。
【００２８】
本発明においては、上記の組成物に紫外線や放射線などを照射して、光重合物とする。紫外線の照射は、窒素ガスなどの不活性ガスで置換した酸素のない雰囲気中で行うか、ポリエチレンテレフタレートなどの紫外線透過性フィルムによる被覆で空気を遮断した状態で行う。紫外線は、波長範囲が１８０〜４６０ｎｍの電磁放射線であるが、これより長波長または短波長の電磁放射線を用いてもよい。紫外線源には、水銀アーク、炭素アーク、低圧水銀ランプ、中・高圧水銀ランプ、マイクロウェーブ励起水銀灯、メタルハライドランプ、蛍光ケミカルランプ、ブラックライトランプなどの通常の照射装置が用いられる。紫外線の強度は、使用する光重合開始剤の種類や被照射体までの距離や電圧の調整により適宜設定できるが、通常は、被照射体面で０．１〜１００ｍＷ／ｃｍ２、好ましくは０．３〜２０ｍＷ／ｃｍ２の紫外線を用いるのが望ましい。紫外線の照射は被照射体面の片側または両側から照射するが、熱伝導性粒子が配合されているので、生産性などの面から両側から照射することが好ましい。また、放射線としては、活性エネルギ―線で、α線、β線、γ線、中性子線、加速電子線のような電離性放射線が用いられ、照射量は１〜１０Ｍｒａｄ程度が好ましい。なお、紫外線と放射線を併用してもよい。光重合後に生成する光重合物とｄ）成分の樹脂との混合物の分子量は、ゲルパーミエッションクロマトグラフ（ＧＰＣ）で測定される重量平均分子量（ポリスチレン換算）で５０万以上、好ましくは８０万以上である。分子量が５０万未満では、凝集性が低下する。
【００２９】
【００３０】
（塗工法・厚さ）
本発明は、このように形成される光重合物を、常態で感圧接着性を有し、かつ熱伝導性や難燃性などが良好なアクリル系の熱伝導電気絶縁粘着シートとしたものである。本発明の粘着シートは、剥離ライナ上に前記の組成物を塗布し、紫外線や放射線を照射して、光重合物からなる熱伝導電気絶縁粘着シートを形成することにより製造できる。粘着シートを形成するには、組成物をロールコーターやダイコーター等で剥離処理したポリエチレンテレフタレート製のフィルム（セパレーター）等に塗布する方法で行う。粘着シートの厚さは、０．１ｍｍ〜５ｍｍ、好ましくは０．５〜２ｍｍである。なお、本発明の粘着シートは、ポリエチレンテレフタレートやポリイミドなどのフィルムを支持体として使用することもできる。
【００３１】
本発明に使用する粘着剤層の９０°ピール接着力は、０．５Ｎ／２５ｍｍ以上であることが好ましい。０．５Ｎ／２５ｍｍ未満であると、例えば、ＣＰＵ等の電子部品とヒートシンク等との接合界面に、せん断方向や割裂方向に負荷が掛かるような装着をした場合、経時で剥がれが発生する。このような場合、ＣＰＵ等の発熱体からシートシンクへの熱伝導が阻害される。
【００３２】
（熱伝導率・難燃性）
本発明の熱伝導電気絶縁粘着シートの熱伝導率は、熱の放散性を十分発現させるために、１Ｗ／ｍ・Ｋ以上、好ましくは１．５Ｗ／ｍ・Ｋである。難燃性は、着火・延焼の危険性を排除する面からＵＬ９４ＶＴＭ−０ を満足する事が好ましい。
【００３３】
（用途）
本発明の熱伝導電気絶縁粘着シートは、半導体やＣＰＵ等の電子部品やプラズマディスプレイパネル等の発熱体と、アルミ製ヒートシンクやヒートパイプ等の放熱部品との接着固定をする用途に使用することができる。
【００３４】
【実施例】
以下に実施例について具体的に説明するが、本願発明はこれらの実施例に限定されるものではない。
【００３５】
（実施例１）
［難燃性熱伝導電気絶縁感圧接着剤用組成物の調整］
２−エチルヘキシルアクリレート９７質量部、アクリル酸３質量部に対して、高分子系分散剤［ＢＹＫ１８０：ビックケミー（株）社製］を３．０質量部（粒子に対して１．０質量％）添加して撹拌したのち、難燃性を有する熱伝導電気絶縁粒子として水酸化アルミニウム［昭和電工（株）製、ハイジライトＨ−３２］３００質量部を添加して１時間撹拌した。これに、光重合開始剤イルガキュア２０２０［チバスペシャリティケミカル社製］０．３質量部、トリメチロールプロパントリアクリレート０．０５質量部、酸化防止剤イルガノックス１０１０［チバスペシャリティケミカル社製］１．０質量部を添加し、均一になるまで充分攪拌して組成物を調整した。
【００３６】
［難燃性熱伝導電気絶縁粘着シートの作成］
この組成物を脱泡処理後、シリコーン離型処理した厚さ７５μｍのポリエステルフィルムに硬化後の厚さが１ｍｍになるように塗工し、シリコーン離型処理した厚さ３８μｍのポリエステルフィルムで被覆したのち、２０Ｗの蛍光ケミカルランプで塗工面の両側から、それぞれ被照射面での照射強度が１．０ｍＷ／ｃｍ２の紫外線を５分間照射し粘着シート状態で重合させ、難燃性熱伝導電気絶縁粘着シートを得た。
【００３７】
（実施例２）
熱伝導電気絶縁粒子を水酸化アルミニウム［住友化学（株）製 Ｃ−３０８］４００質量部、高分子系分散剤［ＢＹＫ１８０］の添加量を１．０質量部（粒子に対して０．２５質量％）に変更した以外は、実施例１と同様に難燃性熱伝導電気絶縁感圧接着剤用組成物および難燃性熱伝導電気絶縁粘着シートを作成した。
【００３８】
（実施例３）
高分子系分散剤をＤＡ２３４［楠本化成（株）製］２．０質量部（粒子に対して０．６７質量％）に変更した以外は、実施例１と同様に難燃性熱伝導電気絶縁感圧接着剤用組成物および難燃性熱伝導電気絶縁粘着シートを作成した。
【００３９】
（実施例４）
熱伝導電気絶縁粒子を水酸化アルミニウム［昭和電工（株）製 Ｈ−３２］２００質量部、酸化アルミニウム［昭和電工（株）製 Ａ−１２］２５０質量部、高分子系分散剤［ＢＹＫ１８０］を６．８質量部（粒子に対して１．５質量％）に変更した以外は、実施例１と同様に難燃性熱伝導電気絶縁感圧接着剤用組成物および難燃性熱伝導電気絶縁粘着シートを作製した。
【００４０】
（比較例１）
アクリル酸イソオクチル７５質量部、アクリル酸ブチル１５質量部、アクリル酸１０質量部に対して、光重合開始剤としてダロキュア１１７３［チバスペシャリティケミカル社製］０．１質量部を添加した混合物を、窒素雰囲気中室温で２０Ｗのブラックライト蛍光ランプで紫外線を照射して、重量平均分子量８０万、酸価７７．９ｍｇＫＯＨ／ｇのアクリル共重合体を４質量部含有する部分重合体（粘度５０００ｍＰａ・ｓ）を得た。これに、難燃性熱伝導電気絶縁性粒子として水酸化アルミニウム［昭和電工（株）製、ハイジライトＨ−３２］３００質量部、反応性界面活性剤［第一工業製薬（株）製、ＲＮ−２０］０．１質量部を添加し均一になるまで充分攪拌し組成物を調整した。しかし、得られた組成物は粘度上昇が著しく、塗工できなかった。
【００４１】
（比較例２）
比較例１のプレミックス工程を省略し、反応性界面活性剤［第一工業製薬（株）製、ＲＮ−２０］２．０質量部を添加した以外は、比較例１と同様に難燃性熱伝導電気絶縁感圧接着剤用組成物を調整した。しかし、この組成物は流動性がないため塗工できなかった。
【００４２】
実施例１〜４、比較例１，２で得られた組成物の塗工性、及び粘着シートの熱伝導率、接着力、体積固有抵抗値、難燃性、実装試験の評価結果を表１に記した。
【００４３】
〔塗工性〕
調整した難燃性熱伝導電気絶縁感圧接着剤用組成物を、脱泡処理を終了して１時間放置した後に、シリコーン離型処理した厚さ７５μｍのポリエステルフィルムに硬化後の厚さが１ｍｍになるように塗工する際作業性を評価した。
【００４４】
評価基準 ○：良、×：塗工不可
【００４５】
〔熱伝導率〕
シリコーン離型処理したポリエステルフィルムを剥がしたシートサンプルを５ｃｍ×１５ｃｍの大きさに切断し、厚みが約２ｃｍになるまで積層し試験片とした。２３℃±２℃の雰囲気温度で、迅速熱伝導率計ＱＴＭ５００（京都電子工業社製）を使用して測定した。
【００４６】
〔接着力〕
厚さ５０μｍのアルミ箔で一方の粘着面を裏打ちした２５ｍｍ×１００ｍｍのシートサンプルを、アルミ板に２ｋｇローラー１往復加圧貼付し、室温で１時間放置後、９０°方向に剥離速度３００ｍｍ／ｍｉｎで引き剥がし接着力を測定した。
【００４７】
〔難燃性〕
ＵＬ規格（ＵＬ９４「機器の部品用プラスチック材料の燃焼試験方法」）に準じ、燃焼性試験を行い判断した。「ＶＴＭ−０」「ＶＴＭ−１」は以下の燃焼程度を示す基準である。
【００４８】
フィルム状の試料を円筒型に保持し、１組５枚の試料に対して各試料につき３秒間の接炎を２回行い、その場合の燃焼時間の合計、燃焼距離、熱による貫通の有無により下記の如く、クラス分類する。ＶＴＭ−０ は、ＶＴＭ−１ よりも燃焼しにくいことを意味する。
【００４９】
燃焼クラス判定基準 ＶＴＭ−１ ＶＴＭ−０
各試料の残炎燃焼時間−−−−−−−−−− ≦３０秒 ≦１０秒
５枚の試料の燃焼時間合計 −−−−−−−− ≦２５０秒 ≦５０秒
第２回接炎後の残炎時間＋無炎燃焼時間 −− ≦６０秒 ≦３０秒
滴下物による綿への着火の有無−−−−−− なし なし
クランプまでの残炎又は無炎燃焼の有無−− なし なし
【００５０】
〔体積固有抵抗値〕
超絶縁／微少電流計 ＴＲ８６０１（タケダ理研（株）製）で測定した。測定温度は３０℃、測定電圧は５００Ｖ・６０秒とした。
【００５１】
〔実装試験〕
難燃性熱伝導電気絶縁粘着シート２５ｍｍ×２５ｍｍを、ＣＰＵと重さ１００ｇのアルミニウムヒートシンクとの間に挟み、一定の圧力をかけてＣＰＵに押しつけて、アルミニウムヒートシンクの荷重が熱伝導粘着シートのせん断方向にかかるように垂直方向に設置し、ＣＰＵに７．０Ｖの電圧を印加した。２４時間後、アルミニウムヒートシンクの装着状態を確認した。
【００５２】
評価基準
○：剥がれ無し、△：５０％剥がれ、×：アルミヒートシンクが脱落
【００５３】
実施例１〜４で得られた難燃性熱伝導電気絶縁感圧接着剤用組成物は、塗工性に優れていた。また、この組成物を使用した難燃性熱伝導電気絶縁粘着シートは、高い熱伝導性や優れた難燃性、接着力、電気絶縁性を示した。また、粘着剤層の接着力が十分なため、実装試験においても剥がれが生じなかった。
【００５４】
【表１】
一方、比較例では組成物の塗工性が劣るため、評価サンプルが作成出来なかった。
【００５６】
【発明の効果】
本発明の難燃性熱伝導電気絶縁感圧接着剤用組成物は、塗工性に優れ、かつ粘着シートに加工した際は高い熱伝導性や優れた難燃性、電気絶縁性と充分な接着性を併せ持つため、電子部品やプラズマディスプレイ等の家電製品の発熱体と、ヒートシンクやヒートパイプ等の放熱体との接合用に好適な難燃性熱伝導電気絶縁粘着シートを作成するのに有用である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a flame-retardant heat-conductive pressure-sensitive adhesive composition, a flame-retardant heat-conductive electrically insulating pressure-sensitive adhesive, and a flame-retardant heat-conductive electrically insulating pressure-sensitive adhesive sheet.
[0002]
[Prior art]
In recent years, with the remarkable progress in electronics technology, the integration and performance of electric and electronic devices have been increasing, and electronic components such as semiconductors and CPUs and home appliances such as plasma displays have been generated by the heat generated by themselves. The need to dissipate heat is increasing because electronic components can malfunction at elevated temperatures. For this reason, in electronic parts and home electric appliances, measures for preventing functional failure are taken by bonding or mechanically fixing a heat countermeasure component such as a heat sink or dissipating the heat to prevent the functional failure. This joint member is required to have high thermal conductivity and electrical insulation, and also high flame retardancy from the viewpoint of safety so that there is no danger of ignition or fire spread in the event of ignition.
[0003]
JP-A-6-88061 discloses heat conductive and electrically insulating particles randomly dispersed in a polymer prepared from a polar monomer copolymerizable with a (meth) alkyl acrylate having 1 to 12 carbon atoms in an alkyl group. And an adhesive tape using the same. However, the invention has no recognition that flame retardancy should be imparted to the present application and does not describe it.
[0004]
JP-A-10-330892 discloses a copolymerizable monomer having a polar group in a molecule and a monomer mainly containing a (meth) alkyl acrylate having an alkyl group having 2 to 14 carbon atoms. When blending a thermally conductive filler with the acrylic copolymer consisting of, by blending a reactive surfactant having a radically polymerizable carbon-carbon double bond in the molecule, the thermal conductive filler We have proposed a heat-conductive pressure-sensitive adhesive that is not restricted by the type of agent, and a heat-conductive pressure-sensitive adhesive sheet using the same. However, the invention also does not recognize that flame retardancy should be imparted to the present application and is not described.
[0005]
JP-A-11-269438 discloses an acrylic copolymer composed of a polar vinyl monomer copolymerizable with a (meth) alkyl acrylate having an alkyl group having 4 to 14 carbon atoms and a metal hydroxide. A flame retardant heat conductive pressure sensitive adhesive is described. However, in order to satisfy higher thermal conductivity (1.0 W / m · K or more) and excellent flame retardancy (UL94-VTM0), metal hydroxide is added to 100 parts by mass of the acrylic copolymer. If it is added in excess of 180 parts by mass, the viscosity of the UV-curable pressure-sensitive adhesive composition is significantly increased, so that there is a problem that the suitability for coating is reduced.
[0006]
[Problems to be solved by the invention]
The present inventors, in accordance with the technology described in Japanese Patent Application Laid-Open No. H10-330792, used a metal water in order to obtain a flame-retardant heat-conductive electrically insulating pressure-sensitive adhesive sheet having high heat conductivity and excellent flame retardancy required in the market. An attempt was made to produce a system in which the amount of oxide added was increased. However, as a result, the fluidity of the pressure-sensitive adhesive composition was very poor, and only those which could not be coated were obtained. In addition, in order to impart coating suitability, the composition for syrup by partially polymerizing the pressure-sensitive adhesive composition exceeds 180 parts by mass of the metal hydroxide with respect to 100 parts by mass of the acrylic copolymer. When blended, the viscosity was remarkably increased and coating could not be performed.
[0007]
The present invention has solved the above-mentioned drawbacks of the prior art, that is, a flame-retardant heat-conductive electrically insulating pressure-sensitive adhesive composition having excellent coating suitability, and a flame-retardant composition having excellent heat conductivity and flame retardancy. It is an object of the present invention to provide a heat conductive electric insulating pressure-sensitive adhesive and a flame-retardant heat conductive electric insulating pressure-sensitive adhesive sheet.
[0008]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that a (meth) alkyl acrylate having an alkyl group having 1 to 14 carbon atoms is added with a photopolymerization initiator, a flame-retardant heat-conductive electrically insulating particle, and a specific dispersant. The present inventors have found that a composition for a flame-retardant heat-conductive and electrically-insulating pressure-sensitive adhesive excellent in coating suitability can be obtained by using the compounded composition, and the present invention has been completed.
[0009]
That is, the present invention
a) a (meth) alkyl acrylate monomer having an alkyl group having 1 to 14 carbon atoms;
b) a photopolymerizable initiator;
c) containing 300 to 700 parts by mass of the heat conductive electric insulating particles, and 200 parts by mass or more of the heat conductive electric insulating particles have flame retardancy;
d) a polymer dispersant in an amount of 0.05 to 5.0% by mass based on the heat conductive and electrically insulating particles;
The composition for a flame-retardant heat-conductive and electrically-insulating pressure-sensitive adhesive, characterized by containing: Further, a flame-retardant heat-conductive electrically insulating pressure-sensitive adhesive having excellent heat conductivity, electrical insulation and flame retardancy using the same, and a flame-retardant heat-conductive electrically insulating pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer I will provide a.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
In the composition of the present invention, the (meth) alkyl acrylate monomer having an alkyl group having 1 to 14 carbon atoms in the component a) includes methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, Isobutyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isooctyl acrylate, isononyl acrylate, isodecyl acrylate, lauryl acrylate, methyl ethacrylate, butyl methacrylate, hexyl methacrylate, Examples include, but are not limited to, 2-ethylhexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, and the like. These are used in a proportion of 70 to 100% by mass, preferably 90 to 99% by mass in the monomer mixture. When the amount of the (meth) alkyl acrylate is less than 70% by mass, the initial adhesiveness and the like are reduced.
[0011]
(Copolymerizable monomer having a polar group in the molecule)
A copolymerizable monomer having a polar group in the molecule may be added to the composition for heat-conductive and electrically-insulating pressure-sensitive adhesive of the present invention. This copolymerizable monomer can be copolymerized with the (meth) alkyl acrylate monomer to form an acrylic copolymer and improve cohesion and adhesion. Although not particularly limited, examples include acrylic acid, itaconic acid, (anhydrous) maleic acid, (anhydrous) fumaric acid, caprolactan-modified (meth) acrylate, acid group-containing monomers such as acrylic acid dimer, Nitrogen-containing monomers such as (meth) acrylamide, substituted acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, (meth) acryloylmorpholine, (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl Examples include, but are not limited to, hydroxyl group-containing monomers such as (meth) acrylate and 4-hydroxybutyl (meth) acrylate. These copolymerizable monomers are used in a proportion of 30 to 0.5% by mass, preferably 10 to 1% by mass of all the monomers. If it exceeds 30% by mass, the initial adhesiveness is reduced.
[0012]
(Photopolymerization initiator)
In the composition of the present invention, as the photopolymerization initiator of the component b), benzoin ethers such as benzoin methyl ether and benzoin ethyl ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone and the like And substituted α-ketols such as 2-methyl-2-hydroxypropiophenone, benzyl ketals, acylphosphine oxides, benzoins and benzophenones. It is preferable to use a photopolymerization initiator having two or more cleavage points in the molecule, for example, a bisacylphosphine oxide or a bismaleimide derivative, since the molecular weight of the photopolymer can be easily increased.
[0013]
The use amount of these photopolymerization initiators depends on the type and the wavelength of the light source, but is 0.01 to 3 parts by mass, preferably 0.1 to 1 part by mass, based on 100 parts by mass of the monomer. Used. If the amount is less than 0.01 parts by mass, unreacted monomers remain. On the other hand, if the amount is more than 3 parts by mass, the molecular weight of the photopolymer produced by the photopolymerization is reduced, and the cohesive force of the pressure-sensitive adhesive is insufficient. When the amount of the thermally conductive electrically insulating particles described later is large, it is preferable to use two or more photopolymerization initiators in combination.
[0014]
(Heat conductive electrically insulating particles)
In the composition of the present invention, the thermally conductive electrically insulating particles of the component c) are not particularly limited as long as they are high heat conductive and electrically insulating fillers. At least one selected from the group consisting of metal nitride, silicon carbide, metal hydroxide, and resin-coated metal can be given.
[0015]
Such metal oxides are not particularly limited, but include, for example, metal oxides such as aluminum oxide, titanium oxide, and magnesium oxide; metal nitrides such as aluminum nitride; silicon nitride; and metal hydroxides such as aluminum hydroxide and magnesium hydroxide. Things.
[0016]
(Content of heat conductive and electrically insulating particles)
The heat conductive and electrically insulating particles as the component (c) used in the present invention are 300 to 700 parts by mass, preferably 300 to 500 parts by mass, per 100 parts by mass of the monomer. When the heat conductive electric insulating particles are less than 300 parts by mass, high heat conductivity cannot be exhibited. If the amount exceeds 700 parts by mass, the flexibility of the pressure-sensitive adhesive sheet is impaired, and the ability to follow the uneven surface is reduced, so that the heat transfer efficiency is reduced.
[0017]
The average particle size of the heat conductive and electrically insulating particles of the component (c) used in the present invention is not particularly limited, but is preferably 0.5 to 70 μm, more preferably 1 to 30 μm. The shape may be any shape such as a spherical shape, a needle shape, and a flake shape. The heat conductive and electrically insulating particles may be used alone or in combination of two or more kinds of particles having different types, average particle diameters, and shapes. Further, the surface of the particles may be appropriately subjected to a surface treatment such as a coupling treatment, a stearin treatment, a resin coating treatment, or a silica coating treatment, if necessary.
[0018]
More than 200 parts by mass of the component C) used in the present invention uses flame-retardant heat conductive and electrically insulating particles. The flame-retardant heat-conductive electrically insulating particles are not particularly limited, and include, for example, metal hydroxides. Examples of the metal hydroxide include aluminum hydroxide and magnesium hydroxide. If the amount is less than 200 parts by mass, the flame retardancy that achieves VTM-0 of UL-94 alone cannot be exhibited.
[0019]
When the flame-retardant heat conductive electrical insulating particles are used in combination with the heat conductive electrical insulating particles having no flame retardancy, the average particle diameter of the particles having flame retardancy is the average particle diameter of the particles having no flame retardancy. Those smaller than the diameter are preferred. Preferably, the average particle size is no more than 10 μm. If the average particle size of the particles having flame retardancy is small, the same addition amount increases the surface area and is uniformly dispersed throughout the pressure-sensitive adhesive sheet, so that the flame retardancy is improved. Further, the flame-retardant heat conductive and electrically insulating particles may be used alone or in combination of two or more kinds of particles having different types of compounds, average particle diameters and shapes.
[0020]
(Polymer dispersant)
The polymer-based dispersant, which is the component d) of the present invention, has a hydrophobic group mainly composed of a hydrocarbon chain in a main chain and a hydrophilic group in a side chain, and has both functions of a surfactant and characteristics of a polymer. It is a medium polymer. The use of a polymer-based dispersant improves the dispersibility when the heat conductive and electrically insulating particles are blended with the monomer, and furthermore, exhibits an appropriate fluidity in the blending amount according to the present invention. Good coating suitability can be imparted without using the method of (1).
The weight average molecular weight of the polymer dispersant used is preferably from 500 to 20,000, more preferably from 1,000 to 10,000.
[0021]
As the polymer dispersant, there are a natural dispersant and a synthetic dispersant, which are classified into anionic, cationic and nonionic like general surfactants. Styrene-maleic anhydride copolymer, olefin-maleic anhydride copolymer, formalin condensate of naphthalene sulfonate, sodium polyacrylate, polyacrylamide partial hydrolyzate, acrylamide / sodium acrylate copolymer, ) Acrylate / acrylic acid copolymers, sodium alginate, amidoamine salts of polyester acids, amine salts of polyether phosphate esters, etc., polyethyleneimine, polyvinylimidazoline, aminoalkyl (meth) acrylate / acrylamide copolymers, Modified polyacrylamide Mannich, cationic such as chitosans, polyvinyl alcohol, polyoxyethylene ether ester copolymer, polyacrylamide, acrylate vinylpyrrolidone copolymer, Nonionic Npun'nado and the like.
[0022]
The selection and blending amount of the polymer dispersant is appropriately selected depending on the type, shape, and blending amount of the heat conductive and electrically insulating particles of the component c). It is used in an amount of 0.05 to 5.0% by mass, preferably 0.1 to 2.0% by mass, based on 100 parts by mass of the heat conductive and electrically insulating particles. If the amount of the polymer dispersant is less than 0.05% by mass, sufficient dispersibility cannot be obtained. If it exceeds 5.0% by mass, heat resistance is impaired, and the adhesiveness at high temperatures tends to decrease.
[0023]
In the preparation of the composition for heat-conductive and electrically-insulating pressure-sensitive adhesive of the present invention, the dispersant of the component (d) is mixed with the monomer component including the component (a) and sufficiently dissolved. It is preferable to mix the other components sequentially. More preferably, when d) is dissolved in a) and stirring is carried out for 1 to 8 hours after blending c), the polymer dispersant and the particles reach the adsorption equilibrium.
[0024]
(Other additives)
A crosslinking agent can be added to this composition in order to increase the cohesiveness and shear strength of the pressure-sensitive adhesive sheet. Further, if necessary, various known additives such as a pigment, a filler, an antioxidant, an ultraviolet absorber, and a tackifier resin may be added as long as the photopolymerization by irradiation with ultraviolet rays or the like is not hindered.
[0025]
(Crosslinking agent)
As a cross-linking agent, if there is a polyfunctional (meth) acrylate copolymerizable with the component a) or a copolymerizable monomer having a polar group such as a carboxyl group or a hydroxyl group in the molecule, it reacts therewith. A crosslinking agent having a functional group can be used. In the present invention, since the pressure-sensitive adhesive sheet is prepared using a photopolymerization method, crosslinking by copolymerization with a copolymerizable polyfunctional (meth) acrylate is preferable because an aging step becomes unnecessary. When a cross-linking agent having a functional group that reacts with a polar group is used, it is blended 8 hours before coating the composition, preferably 4 hours.
[0026]
Examples of the copolymerizable polyfunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, and 1,6-hexanediol di ( There are polyfunctional (meth) acrylates such as (meth) acrylate. The crosslinking agent having a functional group that reacts with a polar group includes polyfunctional isocyanate-based crosslinking agents such as tolylene diisocyanate, trimethylolpropane tolylene diisocyanate, diphenylmethane triisocyanate, polyethylene glycol diglycidyl ether, and diglycidyl ether. And epoxy-based crosslinking agents such as trimethylolpropane triglycidyl ether, melamine resin-based crosslinking agents, amino resin-based crosslinking agents, peroxide-based crosslinking agents, and carbodiimide-based crosslinking agents.
[0027]
(Tackifying resin)
If necessary, a tackifier resin may be added to the acrylic copolymer used in the pressure-sensitive adhesive layer used in the present invention. Examples of the tackifying resin include terpene resins, terpene phenol resins, rosin resins, petroleum resins, cumarone-indene resins, and phenol resins. In the present invention, since the pressure-sensitive adhesive sheet is prepared using a photopolymerization method, in order to prevent polymerization inhibition due to a double bond in the tackifying resin, a tackifying resin having a small number of double bonds and hardly causing inhibition is used. For example, highly disproportionated rosin esters, highly hydrogenated rosin esters with reduced double bonds, coumarone-indene resins, terpene phenol resins, acrylics without double bond sites in the molecular skeleton Resins and saturated aliphatic resins.
[0028]
In the present invention, the above composition is irradiated with ultraviolet light, radiation, or the like to obtain a photopolymer. Irradiation with ultraviolet rays is performed in an oxygen-free atmosphere replaced with an inert gas such as nitrogen gas, or in a state where air is blocked by coating with an ultraviolet-permeable film such as polyethylene terephthalate. Ultraviolet rays are electromagnetic radiation having a wavelength range of 180 to 460 nm, but electromagnetic radiation having a longer or shorter wavelength may be used. Usable irradiation devices such as a mercury arc, a carbon arc, a low-pressure mercury lamp, a medium / high-pressure mercury lamp, a microwave-excited mercury lamp, a metal halide lamp, a fluorescent chemical lamp, and a black light lamp are used as the ultraviolet light source. The intensity of the ultraviolet light can be appropriately set by adjusting the type of the photopolymerization initiator to be used, the distance to the object to be irradiated, and the voltage, but is usually 0.1 to 100 mW / cm 2 , preferably 0.1 to 100 mW / cm 2 on the surface of the object to be irradiated. It is desirable to use ultraviolet rays of 3 to 20 mW / cm 2 . Irradiation with ultraviolet rays is performed from one side or both sides of the surface of the irradiation object, but it is preferable to irradiate from both sides in terms of productivity and the like because heat conductive particles are blended. As the radiation, ionizing radiation such as α-rays, β-rays, γ-rays, neutron rays, and accelerating electron beams is used as the active energy ray, and the irradiation amount is preferably about 1 to 10 Mrad. Note that ultraviolet rays and radiation may be used in combination. The molecular weight of the mixture of the photopolymerized product formed after the photopolymerization and the resin of component d) is 500,000 or more, preferably 800,000 in terms of weight average molecular weight (in terms of polystyrene) measured by gel permeation chromatography (GPC). That is all. If the molecular weight is less than 500,000, the cohesiveness decreases.
[0029]
[0030]
(Coating method / thickness)
The present invention is based on the photopolymer formed as described above, which has a pressure-sensitive adhesive property in a normal state, and is a heat-conductive and electrically insulating pressure-sensitive adhesive sheet having good heat conductivity and flame retardancy. is there. The pressure-sensitive adhesive sheet of the present invention can be produced by applying the composition on a release liner and irradiating the composition with ultraviolet light or radiation to form a heat conductive and electrically insulating pressure-sensitive adhesive sheet made of a photopolymer. The pressure-sensitive adhesive sheet is formed by applying the composition to a polyethylene terephthalate film (separator) or the like that has been subjected to a release treatment using a roll coater, a die coater, or the like. The thickness of the pressure-sensitive adhesive sheet is 0.1 mm to 5 mm, preferably 0.5 to 2 mm. The pressure-sensitive adhesive sheet of the present invention can use a film such as polyethylene terephthalate or polyimide as a support.
[0031]
The 90 ° peel adhesive strength of the pressure-sensitive adhesive layer used in the present invention is preferably 0.5 N / 25 mm or more. If the thickness is less than 0.5 N / 25 mm, for example, if the mounting is performed such that a load is applied in a shearing direction or a splitting direction on a bonding interface between an electronic component such as a CPU and a heat sink or the like, peeling occurs with time. In such a case, heat conduction from the heating element such as the CPU to the sheet sink is hindered.
[0032]
(Thermal conductivity / flame retardant)
The heat conductivity of the heat conductive and electrically insulating pressure-sensitive adhesive sheet of the present invention is 1 W / m · K or more, preferably 1.5 W / m · K, in order to sufficiently exhibit heat dissipation. The flame retardancy preferably satisfies UL94VTM-0 from the viewpoint of eliminating the risk of ignition and fire spread.
[0033]
(Application)
The heat conductive and electrically insulating pressure-sensitive adhesive sheet of the present invention can be used for bonding and fixing electronic components such as semiconductors and CPUs and heating elements such as plasma display panels and heat radiating components such as aluminum heat sinks and heat pipes. it can.
[0034]
【Example】
Examples will be specifically described below, but the present invention is not limited to these examples.
[0035]
(Example 1)
[Preparation of composition for flame-retardant heat-conductive insulating pressure-sensitive adhesive]
To 97 parts by mass of 2-ethylhexyl acrylate and 3 parts by mass of acrylic acid, 3.0 parts by mass (1.0% by mass with respect to the particles) of a polymer dispersant [BYK180: manufactured by BYK Chemie Co., Ltd.] was added. After stirring, 300 parts by mass of aluminum hydroxide [Higilite H-32, manufactured by Showa Denko KK] was added as heat-conductive and electrically insulating particles having flame retardancy, and the mixture was stirred for 1 hour. 0.3 parts by mass of a photopolymerization initiator Irgacure 2020 [manufactured by Ciba Specialty Chemical Co.], 0.05 parts by mass of trimethylolpropane triacrylate, and 1.0 mass of an antioxidant Irganox 1010 [manufactured by Ciba Specialty Chemical Co.] Was added, and the mixture was sufficiently stirred until it became uniform to prepare a composition.
[0036]
[Preparation of flame-retardant heat conductive and electrically insulating adhesive sheet]
After defoaming, the composition was coated on a silicone release-treated polyester film having a thickness of 75 μm so as to have a cured thickness of 1 mm, and covered with a silicone release-treated polyester film having a thickness of 38 μm. Thereafter, ultraviolet rays having an irradiation intensity of 1.0 mW / cm 2 on each of the surfaces to be irradiated are irradiated from both sides of the coated surface with a 20 W fluorescent chemical lamp for 5 minutes to polymerize in a pressure-sensitive adhesive sheet state, thereby producing a flame-retardant heat conductive electrical insulator. An adhesive sheet was obtained.
[0037]
(Example 2)
400 parts by mass of aluminum hydroxide [C-308 manufactured by Sumitomo Chemical Co., Ltd.] and 1.0 part by mass of the polymer dispersant [BYK180] were added to the heat conductive electric insulating particles (0.25 mass with respect to the particles). %), Except that a flame-retardant heat-conductive and electrically-insulating pressure-sensitive adhesive composition and a flame-retardant heat-conductive and electrically-insulating pressure-sensitive adhesive sheet were prepared in the same manner as in Example 1.
[0038]
(Example 3)
Except that the polymer dispersant was changed to DA234 (manufactured by Kusumoto Kasei Co., Ltd.) to 2.0 parts by mass (0.67% by mass based on the particles), the flame-retardant heat conductive electrical insulation was carried out in the same manner as in Example 1. A composition for a pressure-sensitive adhesive and a flame-retardant heat-conductive and electrically insulating pressure-sensitive adhesive sheet were prepared.
[0039]
(Example 4)
200 parts by mass of aluminum hydroxide [H-32 manufactured by Showa Denko KK], 250 parts by mass of aluminum oxide [A-12 manufactured by Showa Denko KK], and a polymer dispersant [BYK180] were used. Except for changing to 6.8 parts by mass (1.5% by mass based on the particles), the composition for a flame-retardant heat-conductive and pressure-sensitive adhesive and the flame-retardant heat-conductive electric insulating material were the same as in Example 1. An adhesive sheet was produced.
[0040]
(Comparative Example 1)
A mixture of 75 parts by mass of isooctyl acrylate, 15 parts by mass of butyl acrylate, and 10 parts by mass of acrylic acid and 0.1 part by mass of Darocur 1173 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator was added to a nitrogen atmosphere. A 20 W black light fluorescent lamp was used to irradiate ultraviolet rays at a medium room temperature to obtain a partial polymer (viscosity 5000 mPa · s) containing 4 parts by mass of an acrylic copolymer having a weight average molecular weight of 800,000 and an acid value of 77.9 mgKOH / g. Obtained. In addition, 300 parts by mass of aluminum hydroxide (manufactured by Showa Denko KK, Heidilite H-32) as a flame-retardant heat conductive and electrically insulating particle, and a reactive surfactant [manufactured by Daiichi Kogyo Seiyaku Co., Ltd., RN -20], and the mixture was sufficiently stirred until it became uniform to prepare a composition. However, the obtained composition had a remarkable increase in viscosity and could not be applied.
[0041]
(Comparative Example 2)
Flame retardancy similar to Comparative Example 1 except that the premixing step of Comparative Example 1 was omitted, and 2.0 parts by mass of a reactive surfactant [RN-20 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] was added. A composition for a heat conducting, electrically insulating, pressure sensitive adhesive was prepared. However, this composition could not be applied because of its lack of fluidity.
[0042]
Table 1 shows the coating properties of the compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2, and the evaluation results of the thermal conductivity, adhesive strength, volume resistivity, flame retardancy, and mounting test of the pressure-sensitive adhesive sheet. It was noted in.
[0043]
(Coating property)
After finishing the defoaming treatment, the adjusted flame-retardant heat-conductive and electrically insulating pressure-sensitive adhesive composition was left for 1 hour, and then cured into a silicone release-treated 75 μm-thick polyester film having a thickness of 1 mm. The workability was evaluated when coating so as to obtain.
[0044]
Evaluation criteria ○: good, ×: coating impossible [0045]
〔Thermal conductivity〕
The sheet sample from which the polyester film subjected to the silicone release treatment was peeled was cut into a size of 5 cm × 15 cm, and laminated to a thickness of about 2 cm to obtain a test piece. It was measured at a temperature of 23 ° C. ± 2 ° C. using a rapid thermal conductivity meter QTM500 (manufactured by Kyoto Electronics Industry Co., Ltd.).
[0046]
(Adhesive strength)
A 25 mm x 100 mm sheet sample lined with a 50 µm-thick aluminum foil on one adhesive side was pasted on an aluminum plate with a 2-kg roller and reciprocatingly pressed, left at room temperature for 1 hour, and peeled at a speed of 300 mm / min in the 90 ° direction. And the peel strength was measured.
[0047]
〔Flame retardance〕
A flammability test was performed in accordance with UL standard (UL94 "Method of testing combustion of plastic materials for equipment parts") to make a judgment. “VTM-0” and “VTM-1” are standards indicating the following degrees of combustion.
[0048]
The sample in the form of a film is held in a cylindrical shape, and a set of five samples is subjected to flame contact twice for 3 seconds for each sample. The total burning time, the burning distance, and the presence or absence of penetration by heat Classify as follows. VTM-0 means that it is less likely to burn than VTM-1.
[0049]
Combustion class judgment criteria VTM-1 VTM-0
Residual flame burning time of each sample---------------------------------------------------------------------------------------------------------------------- After-flame time after flame + non-flame combustion time --- ≤ 60 seconds ≤ 30 seconds Presence or absence of ignition of cotton by dripping --- ----None None Presence of residual flame or flameless combustion up to clamp--None None [0050]
[Volume resistivity]
It was measured with a super insulation / micro ammeter TR8601 (manufactured by Takeda Riken Co., Ltd.). The measurement temperature was 30 ° C., and the measurement voltage was 500 V for 60 seconds.
[0051]
(Mounting test)
A flame-retardant heat-conductive electrically insulating adhesive sheet 25 mm x 25 mm is sandwiched between a CPU and an aluminum heat sink weighing 100 g, and is pressed against the CPU with a certain pressure. It was installed in the vertical direction so as to cover the direction, and a voltage of 7.0 V was applied to the CPU. After 24 hours, the mounting state of the aluminum heat sink was confirmed.
[0052]
Evaluation criteria ○: No peeling, Δ: 50% peeling, ×: Aluminum heat sink falls off.
The compositions for flame-retardant heat-conductive and electrically-insulating pressure-sensitive adhesives obtained in Examples 1 to 4 were excellent in coatability. In addition, the flame-retardant heat-conductive and electrically insulating pressure-sensitive adhesive sheet using this composition exhibited high heat conductivity, excellent flame-retardancy, adhesive strength, and electrical insulation. Further, since the adhesive force of the pressure-sensitive adhesive layer was sufficient, no peeling occurred even in the mounting test.
[0054]
[Table 1]
On the other hand, in Comparative Examples, evaluation samples could not be prepared because of poor coating properties of the composition.
[0056]
【The invention's effect】
The flame-retardant heat-conductive electrically insulating pressure-sensitive adhesive composition of the present invention has excellent coatability, and when processed into a pressure-sensitive adhesive sheet, has high heat conductivity and excellent flame retardancy, and has sufficient electric insulation. Since it has adhesiveness, it is useful for making a flame-retardant heat-conductive electrically insulating adhesive sheet suitable for joining heating elements of home appliances such as electronic components and plasma displays to heat sinks and heat pipes. It is.
Claims (3)
ｂ）光重合性開始剤と、
ｃ）熱伝導電気絶縁粒子３００〜７００質量部を含有し、かつ該熱伝導電気絶縁粒子のうち２００質量部以上が難燃性を有し、
ｄ）高分子系分散剤を、熱伝導電気絶縁粒子に対して０．０５〜５．０質量％
を含有することを特徴とする難燃性熱伝導電気絶縁感圧接着剤用組成物。a) a (meth) alkyl acrylate monomer having an alkyl group having 1 to 14 carbon atoms;
b) a photopolymerizable initiator;
c) containing 300 to 700 parts by mass of the thermally conductive electrically insulating particles, and at least 200 parts by mass of the thermally conductive electrically insulating particles have flame retardancy;
d) 0.05 to 5.0% by mass of the polymer dispersant based on the heat conductive and electrically insulating particles.
A composition for a flame-retardant, heat-conductive, electrically-insulating pressure-sensitive adhesive, comprising:
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| JP2002223297A JP4385573B2 (en) | 2002-07-31 | 2002-07-31 | Composition for heat-conducting electrical insulation pressure-sensitive adhesive and pressure-sensitive adhesive sheet using the same |
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| JP2002223297A JP4385573B2 (en) | 2002-07-31 | 2002-07-31 | Composition for heat-conducting electrical insulation pressure-sensitive adhesive and pressure-sensitive adhesive sheet using the same |
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| JP4385573B2 JP4385573B2 (en) | 2009-12-16 |
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