JP2004091703A - Conductive silicone self-adhesive composition and self-adhesive tape - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、金属腐食の問題がなく，高温での耐熱性に優れた導電性接点部材の接着，電磁波シールド材，帯電防止のための除電用などに好適な導電性シリコーン粘着剤組成物を提供することにある。
【０００２】
【従来の技術及び発明が解決しようとする課題】
シリコーン粘着剤を使用した粘着テープや粘着ラベルは、シリコーン粘着剤層が耐熱性、耐寒性、耐候性、電気絶縁性、耐薬品性に優れることから、アクリル系粘着剤、ゴム系粘着剤、ウレタン系粘着剤、エポキシ系粘着剤などでは変質・劣化してしまうような厳しい環境下での使用が可能である。また、シリコーン系材料の表面に対して粘着することから、撥水、離型などの目的でシリコーン処理された物品やシリコーン系剥離紙、シリコーンゴムへの粘着も可能である。
【０００３】
シリコーン粘着剤を用いた粘着テープなどを製造するには、シリコーン粘着剤をプラスチックフィルムなどの基材に塗工し、粘着特性を向上させるため架橋反応を行い硬化させる。
【０００４】
このような粘着テープの用途には、耐熱性のある基材にシリコーン粘着剤を塗工して製造した、耐熱粘着テープ、耐熱マスキングテープ、耐薬品マスキングテープ、電気絶縁テープ、シリコーン剥離紙どうしを連結するためのスプライシングテープなどがある。
【０００５】
シリコーン粘着剤はそれ自体が電気絶縁性を有しているため，導電性を付与するためには，導電性微粒子を添加することが知られている。特許２９２８９４４号公報には，過酸化物硬化型シリコーン粘着剤に導電性フィラーを添加した導電性感圧粘着剤付き耐熱型導電性テープが示されている。しかし，架橋触媒に有機過酸化物を用いるため，硬化後に副生成物である有機酸が粘着剤層に残留する場合があり、この有機酸により組成物に導電性微粒子として添加される金属微粒子や，金属箔基材，さらに被着体を腐食させるという欠点がある。
【０００６】
特開２００１−１４６５７８号公報には，ゲル分率が１０〜４０％となるシリコーン系粘着剤に粘着剤樹脂あたり３０〜８０ＰＨＲの導電性微粒子を添加した導電性シリコーン系粘着剤組成物が開示されている。このものはゲル分率が低く，さらに導電性微粒子の含有量が多いために，高温（例えば２００℃を越える温度）での耐熱性、特に耐熱保持力に劣るという問題があった。
【０００７】
本発明は、かかる欠点を克服した金属腐食の問題がなく，高温での耐熱性に優れた導電性接点部材の接着，電磁波シールド材，帯電防止のための除電用などに好適な導電性シリコーン粘着剤組成物を提供することを目的とする。
【０００８】
【課題を解決するための手段及び発明の実施の形態】
本発明者は、上記目的を改善するため鋭意検討を重ねた結果、特定のシリコーン粘着剤に特定の導電性微粒子を配合した付加反応硬化型シリコーン粘着剤組成物が、有効であることを見出し知見し、本発明をなすに至った。
【０００９】
付加反応硬化型シリコーン粘着剤組成物の組成としては、次のものが好適に用いられる。
（Ａ）１分子中に２個以上のアルケニル基を有するポリジオルガノシロキサン
（Ｂ）Ｒ１ ３ＳｉＯ０．５単位（Ｒ１は炭素数１〜１０の脂肪族不飽和結合を含有しない１価炭化水素基である。）及びＳｉＯ２単位を含有し、Ｒ１ ３ＳｉＯ０．５単位／ＳｉＯ２単位のモル比が０．６〜１．７であるポリオルガノシロキサン
（Ｃ）ＳｉＨ基を含有するポリオルガノシロキサン
（Ｄ）制御剤
（Ｅ）白金触媒
（Ｆ）導電性微粒子
【００１０】
ここで、（Ａ）成分は、１分子中に２個以上のアルケニル基を有するポリジオルガノシロキサンであり、このようなアルケニル基含有ポリジオルガノシロキサンとしては、下記式で示されるものが例示できる。
Ｒ（３−ａ）ＸａＳｉＯ−（ＲＸＳｉＯ）ｍ−（Ｒ２ＳｉＯ）ｎ−ＳｉＲ（３−ａ）Ｘａ
Ｒ２（ＨＯ）ＳｉＯ−（ＲＸＳｉＯ）ｐ−（Ｒ２ＳｉＯ）ｑ−ＳｉＲ２（ＯＨ）
（式中、Ｒは炭素数１〜１０の１価炭化水素基であり、Ｘはアルケニル基含有有機基である。ａは０〜３の整数で１が好ましく、ｍは０以上であるが、ａ＝０の場合、ｍは２以上であり、ｍは、１００≦ｍ＋ｎ≦２０，０００を満足する数であり、ｐは２以上、ｑは、１００≦ｐ＋ｑ≦２０，０００を満足する数である。
【００１１】
Ｒは炭素数１〜１０の１価炭化水素基であり、具体的にはメチル基，エチル基，プロピル基，ブチル基などのアルキル基，シクロヘキシル基などのシクロアルキル基，フェニル基，トリル基などのアリール基，などがあげられるが、特にメチル基，フェニル基が好ましい。
【００１２】
Ｘはアルケニル基含有有機基で炭素数２から１０のものが好ましく、具体的にはビニル基，アリル基，ヘキセニル基，オクテニル基，アクリロイルプロピル基，アクリロイルメチル基，メタクリロイルプロピル基，シクロヘキセニルエチル基，ビニルオキシプロピル基，などがあげられるが、特にビニル基，ヘキセニル基などが好ましい。
【００１３】
このポリジオルガノシロキサンの性状は、オイル状、生ゴム状であればよく、（Ａ）成分の粘度は、２５℃において１００ｍＰａ・ｓ以上、特に１，０００ｍＰａ・ｓ以上が好ましい。なお、上限としては、特に限定されないが、重合度が２０，０００以下となるように選定することが好ましい。また、（Ａ）成分は１種を単独で又は２種以上を併用してもよい。
【００１４】
（Ｂ）成分はＲ１ ３ＳｉＯ０．５単位（Ｒ１は炭素数１〜６の脂肪族不飽和結合を含有しない１価炭化水素基である。）及びＳｉＯ２単位を含有し、Ｒ１ ３ＳｉＯ０．５単位／ＳｉＯ２単位のモル比が０．６〜１．７であるポリオルガノシロキサンである。Ｒ１ ３ＳｉＯ０．５単位／ＳｉＯ２単位のモル比が０．６未満では粘着力やタックが低下することがあり、１．７を越えると粘着力や保持力が低下することがある。特には０．６〜１．０が好ましい。この時（Ｂ）成分は、ＳｉＯＨ基を含有していてもよく、ＯＨ基含有量は０〜４．０重量％であればよい。また、（Ｂ）成分は２種以上を併用してもよい。なお、Ｒ１は、メチル基、エチル基、プロピル基、ブチル基などのアルキル基、シクロヘキシル基などのシクロアルキル基、フェニル基等が挙げられ、メチル基が好ましい。
【００１５】
（Ａ），（Ｂ）成分は単純に混合したものを使用してもよいし、（Ａ）成分の分子鎖の両末端にＳｉＯＨ基を有する次式のものを含有する場合、
Ｒ２（ＨＯ）ＳｉＯ−（ＲＸＳｉＯ）ｐ−（Ｒ２ＳｉＯ）ｑ−ＳｉＲ２（ＯＨ）
（Ａ），（Ｂ）成分を縮合反応物として使用してもよい。縮合反応を行うには、トルエンなどの溶剤に溶解した（Ａ），（Ｂ）成分の混合物を、アルカリ性触媒を用い、室温乃至還流下で反応させればよい。
【００１６】
（Ｂ）成分はアルケニル基を含有しないので、付加反応による架橋に関与せず、架橋成分は主として（Ａ）成分と架橋剤の（Ｃ）成分である。硬化後の粘着剤層のゲル分率は架橋成分の割合に相当する。耐熱保持力などの耐熱性を向上させるためには、組成物中の架橋成分の割合を増やせばよいが、過剰に増やすと粘着力が低下するなどの影響が発生する場合がある。このような点から、（Ａ），（Ｂ）成分の配合重量比は２０／８０〜８０／２０とすればよく、特に４５／５５〜７０／３０とすることが好ましい。（Ａ）成分の配合割合が２０／８０より少ないと十分な耐熱性が得られない。また、８０／２０より多いと粘着力、タックなどの粘着特性が低下することがある。
【００１７】
（Ｃ）成分は架橋剤で、１分子中にケイ素原子に結合した水素原子を少なくとも２個、好ましくは３個以上有するオルガノヒドロポリシロキサンで、直鎖状、分岐状、環状のものなどを使用することができる。
【００１８】
（Ｃ）成分としては、下記式のものを例示することができるが、これらのものには限定されない。
【化１】
【００１９】
このオルガノヒドロポリシロキサンの２５℃における粘度は、１〜５，０００ｍＰａ・ｓ、特に５〜５００ｍＰａ・ｓであることが好ましく、また２種以上の混合物でもよい。
【００２０】
（Ｃ）成分の使用量は、（Ａ）成分中のアルケニル基に対する（Ｃ）成分中のＳｉＨ基のモル比が０．５〜２０、特に０．８〜１５の範囲となるように配合することが好ましい。０．５未満では架橋密度が低くなり、これにともない保持力が低くなることがあり、２０を越えると粘着力及びタックが低下したり、処理液の使用可能時間が短くなる場合がある。
【００２１】
（Ｄ）成分は付加反応制御剤であり、シリコーン粘着剤組成物を調合乃至基材に塗工する際、加熱硬化の以前に処理液が増粘やゲル化をおこさないようにするために添加するものである。
【００２２】
（Ｄ）成分の具体例としては、
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、
３，５−ジメチル−１−ヘキシン−３−オール、
１−エチニルシクロヘキサノール、
３−メチル−３−トリメチルシロキシ−１−ブチン、
３−メチル−３−トリメチルシロキシ−１−ペンチン、
３，５−ジメチル−３−トリメチルシロキシ−１−ヘキシン、
１−エチニル−１−トリメチルシロキシシクロヘキサン、
ビス（２，２−ジメチル−３−ブチノキシ）ジメチルシラン、
１，３，５，７−テトラメチル−１，３，５，７−テトラビニルシクロテトラシロキサン、
１，１，３，３−テトラメチル−１，３−ジビニルジシロキサン
などが挙げられる。
【００２３】
（Ｄ）成分の配合量は、（Ａ），（Ｂ）成分の合計１００重量部に対して０〜５．０重量部の範囲であることが好ましく、特に０．０５〜２．０重量部が好ましい。５．０重量部を越えると硬化性が低下することがある。
【００２４】
（Ｅ）成分は白金系触媒であり、塩化白金酸、塩化白金酸のアルコール溶液、塩化白金酸とアルコールとの反応物、塩化白金酸とオレフィン化合物との反応物、塩化白金酸とビニル基含有シロキサンとの反応物などがあげられる。
【００２５】
（Ｅ）成分の添加量は、（Ａ），（Ｂ）成分の合計に対し、白金分として１〜５，０００ｐｐｍ、特に５〜２，０００ｐｐｍとすることが好ましい。１ｐｐｍ未満では硬化性が低下し、架橋密度が低くなり、保持力が低下することがあり、５，０００ｐｐｍを越えると処理浴の使用可能時間が短くなる場合がある。
【００２６】
上記の付加反応硬化型シリコーン粘着剤に，（Ｆ）成分の導電性微粒子を添加する。具体的には，銀粉、銅粉、金粉、ニッケル粉、アルミニウム粉、鉄粉、はんだ粉等の金属粉、カーボンブラック、カーボンナノチューブ、フラーレン、ポリアセチレンなどの導電性樹脂．さらに中空ガラスビーズ、シリカ、酸化チタン等の無機粒子やポリアクリレート、エポキシ樹脂、シリコーン樹脂、フッ素樹脂等の樹脂粒子の表面を金属メッキした銀メッキシリカ、金メッキシリカ、金メッキガラスビーズ、銀メッキポリアクリレート微粒子などの導電化粒子があげられる。その中でも銀粉、銅粉、カーボンブラック、金メッキシリカ、銀メッキシリカが好ましい。
【００２７】
（Ｆ）成分の導電性微粒子の形状は，球状，樹枝状，針状など特に制限はない。また、粒径は特に制限はないが，最大粒径が粘着剤の塗工厚みの１．５倍を越えないことが好ましく，これを越えると粘着剤塗工表面に導電性微粒子の突出が大きくなりすぎて，この部分を起点に被着体からの浮きなどが発生しやすくなる．
【００２８】
本発明の導電性シリコーン粘着剤組成物に使用する導電性粒子が銀粉の場合、平均粒径は０．１〜１５０μｍ、好ましくは０．１５〜８０μｍである。平均粒径が０．１μｍ未満の場合は、導電性が極端に低下するため好ましくなく、１５０μｍを超える場合には、良好な接着性が得られないために好ましくない。
【００２９】
（Ｆ）成分の添加量は（Ａ）、（Ｂ）成分の合計／（Ｆ）成分の比が９７／３〜５０／５０とすることが好ましい。（Ｆ）成分の配合割合が９７／３より少ないと十分な導電性が得られない。５０／５０より多いと粘着力が小さくなるなど粘着特性が低下することがある。
【００３０】
上記の導電性を有する付加反応硬化型シリコーン粘着剤の耐熱性を向上させるためには、硬化後の粘着剤層のゲル分率を４５％以上にすることが好ましい。ゲル分率が４５％未満の場合、粘着剤層の凝集性が低下するため、十分な耐熱保持力が得られないことがある。 ゲル分率の上限は特に限定されないが、十分な粘着力が得られなくなるため、７０％以下とすることが好ましい。
【００３１】
本発明のシリコーン粘着剤組成物には、上記各成分以外に任意成分を添加することができる。例えば、ポリジメチルシロキサン、ポリジメチルジフェニルシロキサンなどの非反応性のポリオルガノシロキサン、塗工の際の粘度を下げるためのトルエン、キシレン等の芳香族系溶剤、ヘキサン、オクタン、イソパラフィンなどの脂肪族系溶剤、メチルエチルケトン、メチルイソブチルケトンなどのケトン系溶剤、酢酸エチル、酢酸イソブチルなどのエステル系溶剤、ジイソプロピルエーテル、１，４−ジオキサンなどのエーテル系溶剤、又はこれらの混合溶剤、酸化防止剤、染料、顔料などが挙げられる。なお、通常、組成物の粘度を下げ、塗工を容易にするために溶剤が使用される。
【００３２】
上記のように配合されたシリコーン粘着剤組成物を、種々の基材に塗工し、所定の条件にて硬化させることにより、粘着層を得ることができる。
【００３３】
シリコーン粘着剤組成物を塗工する基材として、具体的には、ポリエステル、ポリテトラフルオロエチレン、ポリイミド、ポリフェニレンスルフィド、ポリアミド、ポリカーボネート、ポリスチレン、ポリプロピレン、ポリエチレン、ポリ塩化ビニルなどのプラスチックフィルム、和紙、合成紙、ポリエチレンラミネート紙などの紙、布、ガラス繊維、アルミニウム、銅などの金属箔、これらのうちの複数を積層してなる複合基材などが例示できる。
【００３４】
これらの基材と粘着層の密着性を向上させるために、基材面にプライマー処理、コロナ処理、エッチング処理、あるいはプラズマ処理したものを用いてもよい。
【００３５】
塗工方法は、公知の塗工方式を用いて塗工すればよく、コンマコーター、リップコーター、ロールコーター、ダイコーター、ナイフコーター、ブレードコーター、ロッドコーター、キスコーター、グラビアコーター、ワイヤーバーコーターなどによる塗工、スクリーン塗工、浸漬塗工、キャスト塗工などが例示できる。
【００３６】
塗工量としては、硬化した後の粘着層の厚みとして２〜２００μｍ、特に３〜１００μｍとすることができる。
【００３７】
硬化条件としては、８０〜１５０℃で１５秒〜３分、好ましくは１００〜 １３０℃で３０秒〜２分とすればよいが、この限りではない。
【００３８】
上記のように基材に直接塗工して粘着テープを製造してもよいし、剥離コーティングをおこなった剥離フィルムや剥離紙に塗工し、粘着剤の硬化をおこなったのち、上記の基材に貼り合わせる転写法により粘着テープを製造してもよい。
【００３９】
【発明の効果】
本発明により，金属腐食の問題がなく，高温での耐熱性，特に耐熱保持力に優れた導電性シリコーン粘着剤組成物および粘着テープを得ることができる。
【００４０】
【実施例】
以下、調製例及び実施例と比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、下記例中の部は重量部を示したものであり、特性値は下記の試験方法による測定値である。また、Ｍｅはメチル基、Ｐｈはフェニル基、Ｖｉはビニル基を表す。
【００４１】
導電性
シリコーン粘着剤組成物溶液を、厚み１８μｍ，幅２５ｍｍの銅箔基材に硬化後の厚みが４０μｍとなるようにアプリケータを用いて塗工したのち、１３０℃×１分の条件で加熱し硬化させ粘着テープを作成した。この粘着テープの粘着面に直径１０ｍｍの円柱状電極の底面を貼りつけた。この電極と銅箔基材の背面（粘着剤を塗工しない面）との電気抵抗を抵抗計を用いて測定した。
【００４２】
粘着力
導電性評価と同様の方法で粘着テープを作成し、この粘着テープをステンレス板に貼りつけ、ゴム層で被覆された重さ２ｋｇ のローラーを１往復させることにより圧着した。室温で約２０時間放置したのち、引っ張り試験機を用いて３００ｍｍ／分の速度で１８０°の角度でテープをステンレス板から引き剥がすのに要する力（Ｎ／２５ｍｍ）を測定した。
【００４３】
耐熱保持力
導電性評価と同様の方法で粘着テープを作成した。この粘着テープをステンレス板の端部に粘着面積が２５×２５ｍｍ となるように貼りつけ、粘着テープの下端に重さ１ｋｇの荷重をかけ、ステンレス板を垂直に支持し２５０℃で１時間放置したあとのずれ距離を読みとり顕微鏡で測定した。
【００４４】
ゲル分率
導電性微粒子を添加しない粘着剤組成物を導電性評価と同様の方法で塗工し粘着テープを作成した。この粘着テープの２５ｍｍ×１５ｍｍを秤量し５０ｍＬのトルエンに浸漬し２４時間放置した。この粘着テープを取り出し、１００℃の乾燥器中で３０分間乾燥させ秤量した。浸漬前の粘着テープの重量をＷ１、浸漬後乾燥させた粘着テープの重量をＷ２，テープ基材の重量をＢとし、次式によってゲル分率を求めた。
ゲル分率（％）＝１００×（Ｗ２−Ｂ）／（Ｗ１−Ｂ）
【００４５】
実施例１
次式のアルケニル基含有ポリジメチルシロキサン（４５部），
Ｍｅ２ＶｉＳｉＯ−［ＭｅＶｉＳｉＯ］６−［Ｐｈ２ＳｉＯ］１５０−［Ｍｅ２ＳｉＯ］４８５０−ＳｉＭｅ２Ｖｉ
Ｍｅ３ＳｉＯ０．５単位、ＳｉＯ２単位からなる（Ｍｅ３ＳｉＯ０．５単位／ＳｉＯ２単位＝０．８５）ポリシロキサンの６０％トルエン溶液 （９２部）、トルエン（６３部）、次式の架橋剤（０．２９部）、
Ｍｅ３ＳｉＯ−［ＭｅＨＳｉＯ］４０−ＳｉＭｅ３
エチニルシクロヘキサノール（０．２０部）、銀粉（三井金属社製、平均粒径１．８μｍ）（２５部）を混合した。白金触媒ＣＡＴ−ＰＬ−５０Ｔ（信越化学工業社製）（０．８部）を添加してさらに混合し、シリコーン粘着剤組成物溶液を調整した。このシリコーン粘着剤の導電性、粘着力、耐熱保持力を測定した。結果を表に示す。
【００４６】
実施例２
実施例１のアルケニル基含有ポリジメチルシロキサンを次式のものとしたシリコーン粘着剤組成物溶液を調整した。
Ｍｅ２ＶｉＳｉＯ−［ＭｅＶｉＳｉＯ］５−［Ｍｅ２ＳｉＯ］５０００−ＳｉＭｅ２Ｖｉ
このシリコーン粘着剤の導電性、粘着力、保持力を測定した。結果を表に示す。（「糊残り性」の定義及びデータがありませんが？）
【００４７】
実施例３
実施例１で銀粉を銅粉（三井金属社製、最大粒径４５μｍ以下）としたシリコーン粘着剤組成物溶液を調整した。 このシリコーン粘着剤の導電性、粘着力、保持力を測定した。結果を表に示す。
【００４８】
実施例４
実施例１で銀粉をカーボンブラック（電気化学社製、一次粒径４８μｍ）としたシリコーン粘着剤組成物溶液を調整した。 このシリコーン粘着剤の導電性、粘着力、保持力を測定した。結果を表に示す。
【００４９】
実施例５
実施例１の銀粉（２０部）をカーボンブラック（１１部）としたシリコーン粘着剤組成物溶液を調整した。 このシリコーン粘着剤の導電性、粘着力、耐熱保持力を測定した。結果を表に示す。
【００５０】
実施例６
実施例１のアルケニル基含有ポリジメチルシロキサン（５０部）、Ｍｅ３ＳｉＯ０．５単位、ＳｉＯ２単位からなる（Ｍｅ３ＳｉＯ０．５単位／ＳｉＯ２単位＝０．８５）ポリシロキサンの６０％トルエン溶液 （８３部）、トルエン（６７部）、実施例１の架橋剤（０．３２部）、エチニルシクロヘキサノール（０．２０部）、銀粉（６７部）を混合した。白金触媒ＣＡＴ−ＰＬ−５０Ｔ（信越化学工業社製）（０．８部）を添加してさらに混合し、シリコーン粘着剤組成物溶液を調整した。このシリコーン粘着剤の導電性、粘着力、保持力を測定した。結果を表に示す。
【００５１】
実施例７
実施例６で銀粉の量を２５部としたシリコーン粘着剤組成物溶液を調整した。このシリコーン粘着剤の導電性、粘着力、保持力を測定した。結果を表に示す。
【００５２】
実施例８
実施例６で銀粉の量を５．３部としたシリコーン粘着剤組成物溶液を調整した。 このシリコーン粘着剤の導電性、粘着力、保持力を測定した。結果を表に示す。
【００５３】
比較例１
実施例６で銀粉の量を２．０４部としたシリコーン粘着剤組成物溶液を調整した。 このシリコーン粘着剤の導電性、粘着力、耐熱保持力を測定した。結果を表に示す。
【００５４】
比較例２
付加反応硬化型シリコーン粘着剤ＫＲ−３７００（シリコーン分６０％）（信越化学工業社製）（８３．５部）、過酸化物硬化型シリコーン粘着剤ＫＲ−１３０（シリコーン分６０％）（信越化学工業社製）（８３．５部）、トルエン（８３．５部）、銀粉（６７部）を混合したのち白金触媒ＣＡＴ−ＰＬ−５０Ｔ（信越化学工業社製）（０．８部）を添加しさらに混合し，シリコーン粘着剤組成物溶液を調整した．このシリコーン粘着剤の導電性，粘着力，耐熱保持力を測定した．結果を表に示す．
【００５５】
【表１】
TECHNICAL FIELD OF THE INVENTION
The present invention provides a conductive silicone pressure-sensitive adhesive composition suitable for adhesion of a conductive contact member excellent in heat resistance at a high temperature without problem of metal corrosion, electromagnetic wave shielding material, and static elimination for antistatic. Is to do.
[0002]
Problems to be solved by the prior art and the invention
Adhesive tapes and labels using silicone adhesives include acrylic adhesives, rubber adhesives, and urethanes because the silicone adhesive layer has excellent heat resistance, cold resistance, weather resistance, electrical insulation, and chemical resistance. It can be used in a severe environment where the quality of the adhesive or epoxy adhesive is deteriorated or deteriorated. In addition, since it adheres to the surface of the silicone-based material, it is possible to adhere to silicone-treated articles, silicone-based release paper, and silicone rubber for the purpose of water repellency, mold release, and the like.
[0003]
In order to manufacture an adhesive tape or the like using a silicone adhesive, the silicone adhesive is applied to a base material such as a plastic film and cured by a crosslinking reaction to improve the adhesive properties.
[0004]
For applications of such adhesive tapes, heat-resistant adhesive tapes, heat-resistant masking tapes, chemical-resistant masking tapes, electrical insulating tapes, and silicone release papers manufactured by applying a silicone adhesive to a heat-resistant base material are used. There are splicing tapes for connection.
[0005]
Since the silicone adhesive itself has electrical insulation properties, it is known to add conductive fine particles in order to impart conductivity. Japanese Patent No. 2928944 discloses a heat-resistant conductive tape with a conductive pressure-sensitive adhesive in which a conductive filler is added to a peroxide-curable silicone adhesive. However, since an organic peroxide is used as a cross-linking catalyst, an organic acid which is a by-product may remain in the pressure-sensitive adhesive layer after curing, and the organic acid may cause metal fine particles to be added to the composition as conductive fine particles. There is a disadvantage that the metal foil substrate and the adherend are corroded.
[0006]
JP-A-2001-146578 discloses a conductive silicone-based pressure-sensitive adhesive composition in which 30 to 80 PHR of conductive fine particles per pressure-sensitive adhesive resin are added to a silicone-based pressure-sensitive adhesive having a gel fraction of 10 to 40%. ing. Since this has a low gel fraction and a large content of conductive fine particles, there is a problem that heat resistance at high temperatures (for example, a temperature exceeding 200 ° C.), particularly heat resistance, is poor.
[0007]
The present invention overcomes the above-mentioned drawbacks and has no problem of metal corrosion, and has excellent heat resistance at high temperatures, and is suitable for bonding conductive contact members, electromagnetic wave shielding material, and antistatic charge-removing conductive silicone adhesive. It is intended to provide an agent composition.
[0008]
Means for Solving the Problems and Embodiments of the Invention
The present inventors have conducted intensive studies to improve the above object, and as a result, have found that an addition reaction-curable silicone pressure-sensitive adhesive composition in which specific conductive fine particles are blended with a specific silicone pressure-sensitive adhesive is effective. Thus, the present invention has been accomplished.
[0009]
The following are suitably used as the composition of the addition reaction-curable silicone pressure-sensitive adhesive composition.
(A) a polydiorganosiloxane having at least two alkenyl groups in one molecule (B) R 1 3 SiO 0.5 units (R 1 is a monovalent hydrocarbon free of aliphatic unsaturation having 1 to 10 carbon atoms is a hydrogen group.) and contain SiO 2 units, the molar ratio of R 1 3 SiO 0.5 units / SiO 2 units containing polyorganosiloxane (C) SiH group is 0.6 to 1.7 Polyorganosiloxane (D) controlling agent (E) platinum catalyst (F) conductive fine particles
Here, the component (A) is a polydiorganosiloxane having two or more alkenyl groups in one molecule, and examples of such an alkenyl group-containing polydiorganosiloxane include those represented by the following formula.
R (3-a) X a SiO- (RXSiO) m - (R 2 SiO) n -SiR (3-a) X a
R 2 (HO) SiO- (RXSiO ) p - (R 2 SiO) q -SiR 2 (OH)
(In the formula, R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, X is an alkenyl group-containing organic group. A is an integer of 0 to 3, preferably 1, and m is 0 or more. When a = 0, m is 2 or more, m is a number satisfying 100 ≦ m + n ≦ 20,000, p is 2 or more, and q is a number satisfying 100 ≦ p + q ≦ 20,000. is there.
[0011]
R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a cycloalkyl group such as a cyclohexyl group, a phenyl group, a tolyl group, and the like. And a methyl group and a phenyl group are particularly preferable.
[0012]
X is an alkenyl group-containing organic group having preferably 2 to 10 carbon atoms, specifically, a vinyl group, an allyl group, a hexenyl group, an octenyl group, an acryloylpropyl group, an acryloylmethyl group, a methacryloylpropyl group, and a cyclohexenylethyl group. , A vinyloxypropyl group, and the like, with a vinyl group and a hexenyl group being particularly preferred.
[0013]
The properties of the polydiorganosiloxane may be oil-like or raw rubber-like, and the viscosity of the component (A) at 25 ° C. is preferably 100 mPa · s or more, particularly preferably 1,000 mPa · s or more. The upper limit is not particularly limited, but is preferably selected so that the degree of polymerization is 20,000 or less. The component (A) may be used alone or in combination of two or more.
[0014]
Component (B) R 1 3 SiO 0.5 units (R 1 is a monovalent hydrocarbon radical free of aliphatic unsaturation having 1 to 6 carbon atoms.) And containing SiO 2 units, R 1 It is a polyorganosiloxane having a molar ratio of 3 SiO 0.5 units / SiO 2 units of 0.6 to 1.7. In R 1 3 molar ratio of SiO 0.5 units / SiO 2 units is less than 0.6 may adhesive strength or tackiness is lowered, it is possible to decrease the adhesive strength and holding power exceeds 1.7. Particularly, 0.6 to 1.0 is preferable. At this time, the component (B) may contain a SiOH group, and the OH group content may be 0 to 4.0% by weight. Further, two or more types of component (B) may be used in combination. Note that R 1 includes an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group; a cycloalkyl group such as a cyclohexyl group; a phenyl group; and a methyl group is preferable.
[0015]
The components (A) and (B) may be used as a simple mixture, or when the component (A) contains the following formula having SiOH groups at both ends of the molecular chain,
R 2 (HO) SiO- (RXSiO ) p - (R 2 SiO) q -SiR 2 (OH)
The components (A) and (B) may be used as a condensation reaction product. To carry out the condensation reaction, a mixture of the components (A) and (B) dissolved in a solvent such as toluene may be reacted at room temperature to reflux using an alkaline catalyst.
[0016]
Since the component (B) does not contain an alkenyl group, it does not participate in crosslinking by an addition reaction, and the crosslinking components are mainly the component (A) and the component (C) of the crosslinking agent. The gel fraction of the pressure-sensitive adhesive layer after curing corresponds to the ratio of the crosslinking component. In order to improve heat resistance such as heat resistance, the proportion of the crosslinking component in the composition may be increased, but an excessive increase may cause an effect such as a decrease in adhesive strength. From such a point, the mixing weight ratio of the components (A) and (B) may be set to 20/80 to 80/20, and particularly preferably set to 45/55 to 70/30. If the mixing ratio of the component (A) is less than 20/80, sufficient heat resistance cannot be obtained. On the other hand, if it is more than 80/20, the adhesive properties such as adhesive strength and tackiness may be reduced.
[0017]
The component (C) is a cross-linking agent, which is an organohydropolysiloxane having at least two, preferably at least three, hydrogen atoms bonded to silicon atoms in one molecule, and may be a linear, branched, or cyclic organohydropolysiloxane. can do.
[0018]
Examples of the component (C) include those of the following formulas, but are not limited thereto.
Embedded image
[0019]
The viscosity of this organohydropolysiloxane at 25 ° C. is preferably from 1 to 5,000 mPa · s, particularly preferably from 5 to 500 mPa · s, or a mixture of two or more.
[0020]
The amount of the component (C) used is such that the molar ratio of the SiH group in the component (C) to the alkenyl group in the component (A) is in the range of 0.5 to 20, especially 0.8 to 15. Is preferred. If it is less than 0.5, the crosslink density becomes low, and the holding power may decrease accordingly. If it exceeds 20, the adhesive strength and tack may be reduced, or the usable time of the treatment liquid may be shortened.
[0021]
The component (D) is an addition reaction control agent, which is added in order to prevent the treatment liquid from thickening or gelling before heat curing when preparing or applying the silicone pressure-sensitive adhesive composition to a substrate. Is what you do.
[0022]
As specific examples of the component (D),
3-methyl-1-butyn-3-ol,
3-methyl-1-pentyn-3-ol,
3,5-dimethyl-1-hexyn-3-ol,
1-ethynylcyclohexanol,
3-methyl-3-trimethylsiloxy-1-butyne,
3-methyl-3-trimethylsiloxy-1-pentyne,
3,5-dimethyl-3-trimethylsiloxy-1-hexyne,
1-ethynyl-1-trimethylsiloxycyclohexane,
Bis (2,2-dimethyl-3-butynoxy) dimethylsilane,
1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane,
Examples thereof include 1,1,3,3-tetramethyl-1,3-divinyldisiloxane.
[0023]
The amount of the component (D) is preferably in the range of 0 to 5.0 parts by weight, particularly 0.05 to 2.0 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). Is preferred. If it exceeds 5.0 parts by weight, the curability may decrease.
[0024]
The component (E) is a platinum-based catalyst, which contains chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reactant of chloroplatinic acid and an alcohol, a reactant of chloroplatinic acid and an olefin compound, and containing chloroplatinic acid and a vinyl group. Reaction products with siloxane and the like can be mentioned.
[0025]
The added amount of the component (E) is preferably 1 to 5,000 ppm, particularly preferably 5 to 2,000 ppm, as platinum, based on the total of the components (A) and (B). If the amount is less than 1 ppm, the curability is reduced, the crosslinking density is reduced, and the holding power may be reduced. If the amount exceeds 5,000 ppm, the usable time of the treatment bath may be shortened.
[0026]
The conductive fine particles of the component (F) are added to the above addition reaction-curable silicone pressure-sensitive adhesive. Specifically, metal powders such as silver powder, copper powder, gold powder, nickel powder, aluminum powder, iron powder, and solder powder; conductive resins such as carbon black, carbon nanotube, fullerene, and polyacetylene; Furthermore, silver-plated silica, gold-plated silica, gold-plated glass beads, and silver-plated polyacrylate in which the surfaces of inorganic particles such as hollow glass beads, silica, and titanium oxide, and resin particles such as polyacrylate, epoxy resin, silicone resin, and fluororesin are metal-plated. Examples include conductive particles such as fine particles. Among them, silver powder, copper powder, carbon black, gold-plated silica, and silver-plated silica are preferable.
[0027]
The shape of the conductive fine particles of the component (F) is not particularly limited, such as a sphere, a tree, or a needle. Although the particle size is not particularly limited, it is preferable that the maximum particle size does not exceed 1.5 times the coating thickness of the pressure-sensitive adhesive. It becomes too easy to float from the adherend starting from this part.
[0028]
When the conductive particles used in the conductive silicone pressure-sensitive adhesive composition of the present invention are silver powder, the average particle size is 0.1 to 150 μm, preferably 0.15 to 80 μm. When the average particle size is less than 0.1 μm, the conductivity is extremely reduced, which is not preferable. When the average particle size is more than 150 μm, good adhesion is not obtained, which is not preferable.
[0029]
The added amount of the component (F) is preferably such that the ratio of the sum of the components (A) and (B) / the component (F) is 97/3 to 50/50. If the compounding ratio of the component (F) is less than 97/3, sufficient conductivity cannot be obtained. If the ratio is more than 50/50, the adhesive properties may be reduced, for example, the adhesive strength may be reduced.
[0030]
In order to improve the heat resistance of the above-mentioned addition-curable silicone pressure-sensitive adhesive having conductivity, it is preferable that the gel fraction of the pressure-sensitive adhesive layer after curing is 45% or more. If the gel fraction is less than 45%, the cohesiveness of the pressure-sensitive adhesive layer is reduced, so that sufficient heat-resistant holding power may not be obtained. The upper limit of the gel fraction is not particularly limited, but is preferably 70% or less because sufficient adhesive strength cannot be obtained.
[0031]
In the silicone pressure-sensitive adhesive composition of the present invention, optional components other than the above components can be added. For example, non-reactive polyorganosiloxanes such as polydimethylsiloxane and polydimethyldiphenylsiloxane, aromatic solvents such as toluene and xylene for decreasing the viscosity during coating, and aliphatic solvents such as hexane, octane, and isoparaffin. Solvent, methyl ethyl ketone, ketone solvents such as methyl isobutyl ketone, ethyl acetate, ester solvents such as isobutyl acetate, diisopropyl ether, ether solvents such as 1,4-dioxane, or a mixed solvent thereof, antioxidant, dye, Pigments and the like. In addition, usually, a solvent is used to lower the viscosity of the composition and to facilitate coating.
[0032]
An adhesive layer can be obtained by applying the silicone adhesive composition compounded as described above to various substrates and curing it under predetermined conditions.
[0033]
As a substrate for applying the silicone pressure-sensitive adhesive composition, specifically, polyester, polytetrafluoroethylene, polyimide, polyphenylene sulfide, polyamide, polycarbonate, polystyrene, polypropylene, polyethylene, plastic films such as polyvinyl chloride, Japanese paper, Examples include paper such as synthetic paper and polyethylene laminated paper, cloth, glass fiber, metal foil such as aluminum and copper, and a composite base material obtained by laminating a plurality of these materials.
[0034]
In order to improve the adhesion between these substrates and the pressure-sensitive adhesive layer, a substrate that has been subjected to a primer treatment, a corona treatment, an etching treatment, or a plasma treatment may be used.
[0035]
The coating method may be applied using a known coating method, such as a comma coater, a lip coater, a roll coater, a die coater, a knife coater, a blade coater, a rod coater, a kiss coater, a gravure coater, a wire bar coater, or the like. Examples include coating, screen coating, dip coating, and cast coating.
[0036]
The coating amount can be 2 to 200 μm, particularly 3 to 100 μm, as the thickness of the pressure-sensitive adhesive layer after curing.
[0037]
The curing conditions may be set at 80 to 150 ° C. for 15 seconds to 3 minutes, preferably at 100 to 130 ° C. for 30 seconds to 2 minutes, but are not limited thereto.
[0038]
The adhesive tape may be manufactured by directly applying to the substrate as described above, or may be applied to a release film or a release paper that has been subjected to release coating, and after the adhesive is cured, the above-described base material may be used. A pressure-sensitive adhesive tape may be manufactured by a transfer method in which the adhesive tape is adhered to the adhesive tape.
[0039]
【The invention's effect】
According to the present invention, it is possible to obtain a conductive silicone pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape which have no problem of metal corrosion and have excellent heat resistance at high temperature, particularly excellent heat resistance.
[0040]
【Example】
Hereinafter, the present invention will be specifically described with reference to Preparation Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples. The parts in the following examples are parts by weight, and the characteristic values are measured by the following test methods. Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group.
[0041]
Conductivity The silicone pressure-sensitive adhesive composition solution is applied to a copper foil substrate having a thickness of 18 μm and a width of 25 mm using an applicator so that the thickness after curing becomes 40 μm, and then 130 ° C. for 1 minute. The mixture was heated and cured under the conditions described above to prepare an adhesive tape. The bottom surface of a cylindrical electrode having a diameter of 10 mm was attached to the adhesive surface of the adhesive tape. The electrical resistance between this electrode and the back surface of the copper foil substrate (the surface not coated with the adhesive) was measured using a resistance meter.
[0042]
Adhesive force An adhesive tape was prepared in the same manner as in the evaluation of conductivity, and the adhesive tape was stuck on a stainless steel plate, and pressed by reciprocating a 2 kg roller covered with a rubber layer once. After leaving at room temperature for about 20 hours, the force (N / 25 mm) required to peel the tape from the stainless steel plate at a rate of 300 mm / min and at an angle of 180 ° was measured using a tensile tester.
[0043]
Heat-resistant holding power An adhesive tape was prepared in the same manner as in the evaluation of conductivity. This adhesive tape was attached to the end of the stainless steel plate so that the adhesive area was 25 × 25 mm, a load of 1 kg was applied to the lower end of the adhesive tape, the stainless steel plate was supported vertically, and left at 250 ° C. for 1 hour. The remaining displacement distance was read and measured with a microscope.
[0044]
Gel fraction A pressure-sensitive adhesive composition to which no conductive fine particles were added was applied in the same manner as in the evaluation of conductivity to prepare a pressure-sensitive adhesive tape. 25 mm × 15 mm of this adhesive tape was weighed, immersed in 50 mL of toluene, and left for 24 hours. The adhesive tape was taken out, dried in a dryer at 100 ° C. for 30 minutes, and weighed. The weight of the pressure-sensitive adhesive tape before immersion was W1, the weight of the pressure-sensitive adhesive tape dried after immersion was W2, and the weight of the tape substrate was B, and the gel fraction was determined by the following equation.
Gel fraction (%) = 100 × (W2-B) / (W1-B)
[0045]
Example 1
An alkenyl group-containing polydimethylsiloxane of the following formula (45 parts),
Me 2 ViSiO- [MeViSiO] 6 - [Ph 2 SiO] 150 - [Me 2 SiO] 4850 -SiMe 2 Vi
A 60% toluene solution of polysiloxane composed of 0.5 unit of Me 3 SiO and 2 units of SiO 2 ( 0.5 unit of Me 3 SiO / 0.82 units of SiO 2 ) (92 parts), toluene (63 parts), and the following formula Crosslinking agent (0.29 parts),
Me 3 SiO— [MeHSiO] 40 —SiMe 3
Ethynylcyclohexanol (0.20 part) and silver powder (Mitsui Metals, average particle size 1.8 μm) (25 parts) were mixed. Platinum catalyst CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) (0.8 parts) was added and further mixed to prepare a silicone pressure-sensitive adhesive composition solution. The electrical conductivity, adhesive strength, and heat resistance of this silicone adhesive were measured. The results are shown in the table.
[0046]
Example 2
A silicone adhesive composition solution was prepared using the alkenyl group-containing polydimethylsiloxane of Example 1 as the following formula.
Me 2 ViSiO- [MeViSiO] 5 - [Me 2 SiO] 5000 -SiMe 2 Vi
The conductivity, adhesive strength and holding power of this silicone adhesive were measured. The results are shown in the table. (There is no definition and data of "glue residue".)
[0047]
Example 3
In Example 1, a silicone pressure-sensitive adhesive composition solution containing silver powder as copper powder (Mitsui Metals Co., Ltd., maximum particle size of 45 μm or less) was prepared. The conductivity, adhesive strength and holding power of this silicone adhesive were measured. The results are shown in the table.
[0048]
Example 4
In Example 1, a silicone pressure-sensitive adhesive composition solution in which silver powder was made of carbon black (Primary particle size: 48 μm, manufactured by Denki Kagaku Co., Ltd.) was prepared. The conductivity, adhesive strength and holding power of this silicone adhesive were measured. The results are shown in the table.
[0049]
Example 5
A silicone pressure-sensitive adhesive composition solution containing silver powder (20 parts) of Example 1 and carbon black (11 parts) was prepared. The electrical conductivity, adhesive strength, and heat resistance of this silicone adhesive were measured. The results are shown in the table.
[0050]
Example 6
Example 1 of the alkenyl group-containing polydimethylsiloxane (50 parts), Me 3 SiO 0.5 units, consisting of SiO 2 units (Me 3 SiO 0.5 units / SiO 2 units = 0.85) 60% of a polysiloxane A toluene solution (83 parts), toluene (67 parts), the crosslinking agent of Example 1 (0.32 parts), ethynylcyclohexanol (0.20 parts), and silver powder (67 parts) were mixed. Platinum catalyst CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) (0.8 parts) was added and further mixed to prepare a silicone pressure-sensitive adhesive composition solution. The conductivity, adhesive strength and holding power of this silicone adhesive were measured. The results are shown in the table.
[0051]
Example 7
In Example 6, a silicone pressure-sensitive adhesive composition solution was prepared in which the amount of silver powder was 25 parts. The conductivity, adhesive strength and holding power of this silicone adhesive were measured. The results are shown in the table.
[0052]
Example 8
In Example 6, a silicone pressure-sensitive adhesive composition solution was prepared in which the amount of silver powder was 5.3 parts. The conductivity, adhesive strength and holding power of this silicone adhesive were measured. The results are shown in the table.
[0053]
Comparative Example 1
In Example 6, a silicone pressure-sensitive adhesive composition solution was prepared in which the amount of silver powder was 2.04 parts. The electrical conductivity, adhesive strength, and heat resistance of this silicone adhesive were measured. The results are shown in the table.
[0054]
Comparative Example 2
Addition reaction-curable silicone adhesive KR-3700 (silicone content 60%) (Shin-Etsu Chemical Co., Ltd.) (83.5 parts), peroxide-curable silicone adhesive KR-130 (silicone content 60%) (Shin-Etsu Chemical (83.5 parts), toluene (83.5 parts), silver powder (67 parts), and then a platinum catalyst CAT-PL-50T (Shin-Etsu Chemical Co., Ltd.) (0.8 parts) was added. The mixture was further mixed to prepare a silicone adhesive composition solution. The conductivity, adhesive strength, and heat retention of this silicone adhesive were measured. The results are shown in the table.
[0055]
[Table 1]
Claims (4)
（Ａ）１分子中に２個以上のアルケニル基を有するポリジオルガノシロキサン２０〜８０重量部
（Ｂ）Ｒ１ ３ＳｉＯ０．５単位（Ｒ１は炭素数１〜１０の脂肪族不飽和結合を含有しない１価炭化水素基である。）及びＳｉＯ２単位を含有し、Ｒ１ ３ＳｉＯ０．５単位／ＳｉＯ２単位のモル比が０．６〜１．７であるポリオルガノシロキサン ８０〜２０重量部
（Ｃ）ＳｉＨ基を含有するポリオルガノシロキサン（Ａ）成分中のアルケニル基に対する（Ｃ）成分中のＳｉＨ基のモル比が０．５〜２０となる量
（Ｄ）制御剤（Ａ），（Ｂ）成分の合計１００重量部に対して０〜５．０重量部
（Ｅ）白金系触媒（Ａ），（Ｂ）成分の合計に対して白金分として１〜５０００ｐｐｍ
（Ｆ）導電性微粒子 （Ａ），（Ｂ）成分の合計／（Ｆ）の比が，９７／３〜５０／５０
を含有する導電性を有する付加反応硬化型シリコーン粘着剤組成物。Silicone pressure-sensitive adhesive composition,
(A) polydiorganosiloxane 20-80 parts by weight of at least two alkenyl groups in one molecule (B) R 1 3 SiO 0.5 units (R 1 is an aliphatic unsaturation having 1 to 10 carbon atoms is a monovalent hydrocarbon radical containing no.) and containing SiO 2 units, a polyorganosiloxane 80 to 20 molar ratio of R 1 3 SiO 0.5 units / SiO 2 units is 0.6 to 1.7 (C) The amount by which the molar ratio of the SiH group in the component (C) to the alkenyl group in the component (A) is 0.5 to 20 (D) the controlling agent (A) 0 to 5.0 parts by weight based on 100 parts by weight of the total of components (B) and (E) 1 to 5000 ppm in terms of platinum based on the total of the platinum-based catalysts (A) and (B)
(F) Conductive fine particles The ratio of the sum of components (A) and (B) / (F) is 97/3 to 50/50.
A conductive addition-curable silicone pressure-sensitive adhesive composition comprising:
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