JP3856553B2 - Pressure-sensitive adhesive sheets for silicon oxide-containing materials - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、ガラス、タイルなどＳｉＯ2 を主成分とした無機質材料を被着体とする、ケイ素酸化物含有材用の感圧接着シ―ト類に関する。
【０００２】
【従来の技術】
ガラス板や容器に感圧接着剤層付きのフイルムやラベルを貼ることは、日常的によく見受けられる。たとえば、お店の窓ガラスに意匠性をもたせるために、感圧接着剤層付きの印刷フイルムを貼つたり、ビルの窓ガラスに感圧接着剤層付きの反射防止／遮光フイルムやガラス飛散防止フイルムを貼り付けたり、さらに、屋外に設置されるテレビブラウン管や液晶ガラスパネルプラズマデイスプレ―のガラスパネルに反射防止フイルムを貼り付ける場合がある。
【０００３】
これらフイルムに用いられる感圧接着剤は、耐候性や耐熱性にすぐれていることが必要であり、また雨や結露水にさらされることが多いため、耐水性、耐湿性が必要である。さらに、上述の窓ガラスなどに貼り付けるフイルムのほかに、浴室の無地タイルに意匠性をもたせるため、感圧接着剤層付きの印刷フイルムを貼り付ける場合があるが、この種のフイルムでは温水や高湿下にさらされることになるため、感圧接着剤として耐湿熱性にすぐれたものが求められる。
【０００４】
しかし、このような種々のフイルムの感圧接着剤として、従来では、耐候性や耐熱性にすぐれるアクリル系感圧接着剤が一般に用いられてきたが、アクリル系感圧接着剤は、ガラスやタイルなどのＳｉＯ2 を主成分とした無機質材料に対して十分な耐湿熱性を有しておらず、貼り合せ後に湿熱にさらされると、フイルムが浮いてシワになつたり、剥がれが生じるという問題があつた。
【０００５】
ガラスに対する接着性を改良をするため、ガラス表面にあらかじめシランカツプリング剤を処理する方法が一般的に用いられている。また、アクリル系感圧接着剤中にシランカツプリング剤をブレンドする方法（特公昭６２−３０２３３号公報）も開示されている。しかし、前者は、高温で乾燥処理する必要があり、設備や時間がかかり、また一度施工したガラス窓に適用することが難しく、後者は、シランカツプリング剤中のアルコキシシランのポツトライフが短いため、保存湿度条件・期間に強く制約を受け、いずれも実用的に欠ける。
【０００６】
【発明が解決しようとする課題】
このように、従来の技術では、ガラスやタイルなどの無機質材料に対して、耐水性、とくに耐湿熱性にすぐれた実用的な感圧接着剤層付きフイルムは、ほとんど知られていない。したがつて、本発明は、このような事情に照らし、シランカツプリング剤を用いなくても、ガラスやタイルなどの無機質材料に対して高い接着性を示す、とくに高温多湿下でも高い接着性を示す、耐湿熱性にすぐれた実用的な感圧接着シ―ト類を提供することを目的としている。
【０００７】
【課題を解決するための手段】
本発明者らは、上記の目的を達成するために、鋭意検討するにあたり、まず、従来のアクリル系感圧接着剤がガラスに対して接着力が低くなる、とくにこの現象が多湿下で顕著となることについて、以下のように推察した。ガラスの主成分であるＳｉＯ2 は表面が酸性であることが知られており、一方、従来のアクリル系感圧接着剤は一般にアクリル系単量体と酸性基を有する単量体との共重合体を主成分としており、接着剤としてやはり酸性である。このため、感圧接着剤とガラスとの間で、酸性基同志の電気的斥力が働き、強い接着力を発現できない。とくに水が存在すると、酸性基の解離イオンが増大し電気的斥力がより一層働き、同時に吸水による凝集力の低下も起こり、接着力が低下する。
【０００８】
そこで、本発明者らは、この考察を踏まえ、感圧接着シ―ト類において、感圧接着剤層への吸水を制御し、かつ感圧接着剤の組成に塩基性セグメントを導入することで、上記問題を解決できないかと考え、さらに検討を続けた。その結果、基材として使用するプラスチツクフイルムの透湿度を特定し、かつこのフイルム上に設けるアクリル系感圧接着剤中に特定の塩基性セグメントを導入する組み合せ構成としたときに、ガラスやタイルなどのケイ素酸化物含有材に対して、シランカツプリング剤の処理を施さなくても、すぐれた接着性能を得ることができ、とくに高温多湿下でも高い接着性を示す、耐湿熱性にすぐれた感圧接着シ―ト類が得られることを知り、本発明を完成するに至つた。
【０００９】
すなわち、本発明は、透湿度が５００ｇ以下／m2／２４時間であるプラスチツクフイルムの少なくとも片面に、ａ）一般式（１）：ＣＨ2 ＝Ｃ（Ｒ1 ）ＣＯＯＲ2 （式中、Ｒ1 は水素またはメチル基、Ｒ2 は炭素数４〜１２のアルキル基である）で表されるアクリル系単量体６０〜９５重量％と、ｂ）一般式（２）：ＣＨ2 ＝Ｃ（Ｒ3 ）ＣＯＮＲ4 Ｒ5 （式中、Ｒ3 は水素もしくはメチル基、Ｒ4 ，Ｒ5 はアルキル基であるか、あるいは両者が結合しこれとＮ原子とで複素環を構成する有機基である）で表されるＮ，Ｎ−ジ置換（メタ）アクリルアミド５〜４０重量％と、ｃ）酸性基を含む単量体０〜１０重量％との共重合体を主成分とするアクリル系感圧接着剤からなる層を有し、この層を構成する共重合体成分のゲル分率が５０〜９５重量％の範囲にあることを特徴とするケイ素酸化物含有材用の感圧接着シ―ト類（請求項１）に係るものである。
【００１０】
【発明の実施の形態】
本発明において、基材として用いられるプラスチツクフイルムは、透湿度（ＪＩＳ Ｚ−０２０８法による）が５００ｇ以下／m2／２４時間のものであればよく、材質および厚さはとくに限定されない。用途上、透明性や平滑性が求められる場合が多く、この見地からは、厚さが通常６〜２５０μｍのポリエステルフイルムやポリカ―ボネ―トフイルムなどが適している。上記の透湿度が５００ｇ／m2／２４時間より高いと、多湿下でアクリル系感圧接着剤の吸水量が増大して凝集力の低下、ガラスとの界面接着力の低下を引き起こしやすい。
【００１１】
本発明に用いられるアクリル系感圧接着剤は、ａ）一般式（１）：ＣＨ2 ＝Ｃ（Ｒ1 ）ＣＯＯＲ2 （式中、Ｒ1 は水素またはメチル基、Ｒ2 は炭素数４〜１２のアルキル基である）で表されるアクリル系単量体６０〜９５重量％と、ｂ）一般式（２）：ＣＨ2 ＝Ｃ（Ｒ3 ）ＣＯＮＲ4 Ｒ5 （式中、Ｒ3 は水素またはメチル基、Ｒ4 ，Ｒ5 はアルキル基であるか、あるいは両者が結合しこれとＮ原子とで複素環を構成する有機基である）で表されるＮ，Ｎ−ジ置換（メタ）アクリルアミド５〜４０重量％と、ｃ）酸性基を含む単量体０〜１０重量％との共重合体を主成分とした感圧接着剤である。
【００１２】
ａ成分のアクリル系単量体としては、ブチル（メタ）アクリレ―ト、イソブチル（メタ）アクリレ―ト、イソアミル（メタ）アクリレ―ト、ヘキシル（メタ）アクリレ―ト、ペンチル（メタ）アクリレ―ト、２−エチルヘキシル（メタ）アクリレ―ト、イソオクチル（メタ）アクリレ―ト、イソノニル（メタ）アクリレ―ト、イソデシル（メタ）アクリレ―トなどが挙げられる。一般式（１）のＲ2 の炭素数が４未満では、感圧接着剤の濡れ性が低下して初期接着性が悪くなり、また１２を超えると、接着力に劣る。このａ成分のアクリル系単量体は、単量体全体の６０〜９５重量％の範囲で、その１種または２種以上が用いられる。６０重量％未満では、アクリル系感圧接着剤としての性能を発揮させにくくなり、９５重量％を超えてしまうと、ｂ成分のＮ，Ｎ−ジ置換（メタ）アクリルアミドが不足するため、ガラスなどに対する接着性能が不十分となる。
【００１３】
ｂ成分のＮ，Ｎ−ジ置換（メタ）アクリルアミドは、ガラスなどに対し強接着力を発現させるための必須の単量体成分であり、一般式（２）の中のＲ4 ，Ｒ5 がいずれもアルキル基である非環状の（メタ）アクリルアミドと、同Ｒ4 ，Ｒ5 が結合しこれとＮ原子とで複素環を構成する環状の（メタ）アクリルアミドとが含まれ、そのいずれか一方または両方が用いられる。上記非環状の（メタ）アクリルアミドとしては、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジブチル（メタ）アクリルアミドなどがある。また、上記環状の（メタ）アクリルアミドとしては、Ｎ−（メタ）アクリロイルモルホリン、Ｎ−（メタ）アクリロイルピロリドン、Ｎ−（メタ）アクリロイルピペリジン、Ｎ−（メタ）アクリロイルピロリジン、Ｎ−（メタ）アクリロイル−４−ピペリドンなどがある。このｂ成分のＮ，Ｎ−ジ置換（メタ）アクリルアミドは、単量体全体の５〜４０重量％、好ましくは１０〜３５重量％の範囲で、その１種または２種以上が用いられる。５重量％未満では、ガラスなどに対する接着性が不十分であり、４０重量％を超えると、感圧接着剤の弾性率が増大して、被着体に対して濡れ性が低下する。
【００１４】
ｃ成分の酸性基を含む単量体としては、アクリル酸、メタクリル酸、イタコン酸、マレイン酸、クロトン酸などのカルボキシル基含有単量体や、その他、２−ヒドロキシエチルアクリロイルホスフエ―ト、２−ヒドロキシプロピルアクリロイルホスフエ―トなどのリン酸基含有単量体などが用いられる。このｃ成分の酸性基を含む単量体は、感圧接着剤の凝集力の調整のため必要により用いられる。すなわち、単量体全体の０〜１０重量％、好ましくは２〜８重量％の範囲で、その１種または２種以上が用いられる。１０重量％を超えると、感圧接着剤の酸性成分が増え、ガラスなどに対する耐湿接着力が低下する。
【００１５】
共重合体は、上記のａ成分およびｂ成分からなるか、これらに上記のｃ成分を加えた単量体混合物を、常法により、溶液重合法、乳化重合法、塊状重合法、懸濁重合法などの方法で共重合させることにより、得ることができる。塊状重合法では、紫外線照射による重合方式が好ましい。共重合に際し、ベンゾイルパ―オキサイド、ラウロイルパ―オキサイド、クメンパ―オキサイドなどの有機過酸化物、２，２´−アゾビスイソブチロニトリル、２，２´−アゾビス（２，４−ジメチルバレロニトリル）などのアゾ系化合物、２，２−ジメトキシ−２−フエニルアセトフエノン、２，２−ジエトキシアセトフエノンなどのアセトフエノン系化合物、ベンゾインエチルエ―テル、ベンゾインイソプロピルエ―テルなどのベンゾインエ―テル系化合物、ベンゾフエノン、ベンゾイル安息香酸などのベンゾフエノン系化合物などの熱重合開始剤や光重合開始剤が用いられる。
【００１６】
本発明のアクリル系感圧接着剤において、上記の共重合体成分のゲル分率は、５０〜９５重量％、好ましくは５５〜９０重量％であるのがよい。５０重量％未満となると、多湿下で吸水により凝集力が低下し、接着力が低下しやすい。９５重量％を超えると、ゾル分が少なすぎて、ガラスなどへの濡れ性が悪く、やはり高い接着力を発現できない。ゲル分率の上記設定は、外部架橋剤や内部架橋剤の種類、量などを調整することにより、容易に行うことができる。
【００１７】
外部架橋剤としては、エチレンジイソシアネ―ト、ブチレンジイソシアネ―ト、ヘキサメチレンジイソシアネ―ト、シクロペンチレンジイソシアネ―ト、シクロヘキシレンジイソシアネ―ト、イソホロンジイソシアネ―ト、２，４−トリレンジイソシアネ―ト、４，４´−ジフエニルメタンジイソシアネ―ト、キシリレンジイソシアネ―ト、トリメリロ―ルプロパンのトリレンジイソシアネ―トの付加物などの多官能イソシアネ―ト化合物などが挙げられる。また、内部架橋剤としては、トリメチロ―ルプロパントリ（メタ）アクリレ―ト、ペンタエリスリト―ルテトラ（メタ）アクリレ―ト、１，２−エチレングリコ―ルジ（メタ）アクリレ―ト、１，６−ヘキサンジオ―ルジ（メタ）アクリレ―ト、１，１２−ドデカンジオ―ルジ（メタ）アクリレ―トなどの多官能（メタ）アクリレ―トが挙げられ、これらの内部架橋剤は通常共重合体の合成時に添加される。
【００１８】
本発明のアクリル系感圧接着剤は、このように架橋処理した共重合体成分を主成分とし、これに必要により、粘着付与樹脂、老化防止剤、紫外線吸収剤、着色剤、充填剤、難燃剤、帯電防止剤などの公知の各種の添加剤を加えることができる。これらの添加剤は、その種類に応じた通常の使用量でよい。
【００１９】
本発明の感圧接着シ―ト類は、基材として前記した特定透湿度のプラスチツクフイルムを用い、このフイルムの少なくとも片面に、上記構成の特定のアクリル系感圧接着剤からなる層を設けて、シ―ト状やテ―プ状などの形態としたものである。上記のアクリル系感圧接着剤からなる層の厚さはとくに限定されないが、通常は片面で約５〜２００μｍとすればよい。
【００２０】
このように構成される本発明の感圧接着シ―ト類は、ガラス、タイルなどのＳｉＯ2 を主成分とした無機質材料からなる被着体に対して、すぐれた接着性を示し、とくに高温多湿下の環境においても高い接着性を維持する、すぐれた耐湿熱性を示すことから、実用性にすぐれたケイ素酸化物含有材用の感圧接着シ―ト類として、広範囲の分野で利用することができる。
【００２１】
【実施例】
つぎに、本発明の実施例を記載して、より具体的に説明する。ただし、本発明はこれらの実施例によりなんら限定されるものではない。なお、以下において、部とあるのは重量部を意味するものとする。
なお、また、以下に記載の「実施例１〜８」のうち、「実施例１〜６」が本発明の特許請求の範囲に含まれる感圧接着シートの例を示したものであり、「実施例７，８」は本発明の特許請求の範囲には含まれない対照例としての感圧接着シートを示したものである。
【００２２】
参考例１
ブチルアクリレ―ト７５部、Ｎ，Ｎ−ジエチルアクリルアミド２０部およびアクリル酸５部からなる単量体混合物と、Ｎ，Ｎ´−アゾビスイソブチロニトリル０．２部およびトルエン２００部をフラスコにいれ、窒素置換後、６０℃に加温し、この温度で２０時間攪拌して共重合反応を続け、共重合体溶液Ａを得た。
【００２３】
参考例２
単量体混合物を、ブチルアクリレ―ト５０部、Ｎ，Ｎ−ジエチルアクリルアミド４５部およびアクリル酸５部に変更した以外は、参考例１と同様にして、共重合体溶液Ｂを得た。
【００２４】
参考例３
単量体混合物を、ブチルアクリレ―ト７０部、Ｎ，Ｎ−ジエチルアクリルアミド１５部およびアクリル酸１５部に変更した以外は、参考例１と同様にして、共重合体溶液Ｃを得た。
【００２５】
参考例４
単量体混合物を、ブチルアクリレ―ト９２部およびアクリル酸８部に変更した以外は、参考例１と同様にして、共重合体溶液Ｄを得た。
【００２６】
参考例５
イソオクチルアクリレ―ト８０部、アクリロイルモルホリン１５部およびアクリル酸５部からなる単量体混合物と、２，２−ジメトキシ−２−フエニルアセトフエノン０．１部との混合液を、窒素雰囲気中で紫外線に暴露して部分重合させ、粘度が約２００ポイズのコ―テイング可能なシロツプＥを得た。
【００２７】
参考例６
単量体混合物を、イソオクチルアクリレ―ト８０部およびアクリロイルモルホリン２０部に変更した以外は、参考例５と同様に部分重合させて、粘度が約２００ポイズのコ―テイング可能なシロツプＦを得た。
【００２８】
実施例１
参考例１で得た共重合体溶液Ａに、共重合体１００部に対し、トリメチロ―ルプロパンのトリレンジイソシアネ―ト付加物１．５部を加えて、アクリル系感圧接着剤溶液とした。このアクリル系感圧接着剤溶液を、基材として透湿度が２８ｇ／m2／２４時間、厚さが２５μｍのポリエチレンテレフタレ―トフイルム上に塗布し、１１０℃で８分間乾燥処理して、厚さが５０μｍのアクリル系感圧接着剤からなる層を有する感圧接着シ―トを作製した。なお、上記感圧接着剤からなる層のゲル分率は７２重量％であつた。
【００２９】
実施例２
基材として、透湿度が６０ｇ／m2／２４時間、厚さが２５μｍのポリカ―ボネ―トフイルムを使用した以外は、実施例１と同様にして、厚さが５０μｍのアクリル系感圧接着剤からなる層を有する感圧接着シ―トを作製した。なお、上記感圧接着剤からなる層のゲル分率は、実施例１と同じ７２重量％であつた。
【００３０】
実施例３
参考例５で得たシロツプＥに、シロツプ１００部に対し、トリメチロ―ルプロパントリアクリレ―ト０．０８部を加えて、混合液とした。この混合液を、基材として透湿度が２８ｇ／m2／２４時間、厚さが２５μｍのポリエチレンテレフタレ―トフイルム上に塗布し、窒素ガス雰囲気下で光強度５ｍＷ／cm2 の高圧水銀ランプにより紫外線を９００ｍＪ／cm2 照射して光重合処理し、厚さが５０μｍのアクリル系感圧接着剤からなる層を有する感圧接着シ―トを作製した。なお、上記感圧接着剤からなる層のゲル分率は６８重量％であつた。
【００３１】
実施例４
参考例５で得たシロツプＥに代えて、参考例６で得たシロツプＦを使用した以外は、実施例３と同様にして、厚さが５０μｍのアクリル系感圧接着剤からなる層を有する感圧接着シ―トを作製した。なお、上記感圧接着剤からなる層のゲル分率は６２重量％であつた。
【００３２】
実施例５
基材として、透湿度が８ｇ／m2／２４時間、厚さが２５μｍの延伸ポリプロピレンフイルム（コロナ処理済み）を使用した以外は、実施例３と同様にして、厚さが５０μｍのアクリル系感圧接着剤からなる層を有する感圧接着シ―トを作製した。なお、上記のアクリル系感圧接着剤からなる層のゲル分率は実施例３と同じ６８重量％であつた。
【００３３】
実施例６
参考例５で得たシロツプＥに代えて、参考例６で得たシロツプＦを使用し、かつ基材として透湿度が８ｇ／m2／２４時間、厚さが２５μｍの延伸ポリプロピレンフイルム（コロナ処理済み）を使用した以外は、実施例３と同様にして、厚さが５０μｍのアクリル系感圧接着剤からなる層を有する感圧接着シ―トを作製した。なお、上記感圧接着剤からなる層のゲル分率は６２重量％であつた。
【００３４】
実施例７
トリメチロ―ルプロパンのトリレンジイソシアネ―ト付加物の添加量を０．５部に変更した以外は、実施例１と同様にして、厚さが５０μｍのアクリル系感圧接着剤からなる層を有する感圧接着シ―トを作製した。なお、上記感圧接着剤からなる層のゲル分率は３５重量％であつた。
【００３５】
実施例８
トリメチロ―ルプロパントリアクリレ―トの添加量を０．０３部に変更し、かつ基材として透湿度が８ｇ／m2／２４時間、厚さが２５μｍの延伸ポリプロピレン（コロナ処理済み）を使用した以外は、実施例３と同様にして、厚さが５０μｍのアクリル系感圧接着剤からなる層を有する感圧接着シ―トを作製した。なお、上記感圧接着剤からなる層のゲル分率は４０重量％であつた。
【００３６】
比較例１
参考例１で得た共重合体溶液Ａに代えて、参考例２で得た共重合体溶液Ｂを使用した以外は、実施例１と同様にして、厚さが５０μｍのアクリル系感圧接着剤からなる層を有する感圧接着シ―トを作製した。上記感圧接着剤からなる層のゲル分率は８２重量％であつた。
【００３７】
比較例２
参考例１で得た共重合体溶液Ａに代えて、参考例３で得た共重合体溶液Ｃを使用した以外は、実施例１と同様にして、厚さが５０μｍのアクリル系感圧接着剤からなる層を有する感圧接着シ―トを作製した。上記感圧接着剤からなる層のゲル分率は８４重量％であつた。
【００３８】
比較例３
参考例１で得た共重合体溶液Ａに代えて、参考例４で得た共重合体溶液Ｄを使用した以外は、実施例１と同様にして、厚さが５０μｍのアクリル系感圧接着剤からなる層を有する感圧接着シ―トを作製した。上記感圧接着剤からなる層のゲル分率は７１重量％であつた。
【００３９】
比較例４
参考例１で得た共重合体溶液Ａに代えて、参考例４で得た共重合体溶液Ｄを使用し、かつ基材として透湿度が６０ｇ／m2／２４時間、厚さが２５μｍのポリカ―ボネ―トフイルムを使用した以外は、実施例１と同様にして、厚さが５０μｍのアクリル系感圧接着剤からなる層を有する感圧接着シ―トを作製した。なお、上記感圧接着剤からなる層のゲル分率は７１重量％であつた。
【００４０】
比較例５
参考例１で得た共重合体溶液Ａに、共重合体１００部に対し、トリメチロ―ルプロパンのトリレンジイソシアネ―ト付加物１．５部を加えて、アクリル系感圧接着剤溶液とした。このアクリル系感圧接着剤溶液を剥離紙上に塗布し、１１０℃で８分間乾燥処理して、厚さが５０μｍのアクリル系感圧接着剤からなる層を形成した。ついで、これを、透湿度が７００ｇ／m2／２４時間、厚さが２５μｍのトリアセテ―トフイルムにラミネ―トして、感圧接着シ―トを作製した。なお、上記感圧接着剤からなる層のゲル分率は７２重量％であつた。
【００４１】
比較例６
参考例１で得た共重合体溶液Ａに代えて、参考例４で得た共重合体溶液Ｄを使用した以外は、比較例５と同様にして、厚さが５０μｍのアクリル系感圧接着剤からなる層を有する感圧接着シ―トを作製した。なお、上記感圧接着剤からなる層のゲル分率は７１重量％であつた。
【００４２】
上記の実施例１〜８および比較例１〜６の各感圧接着シ―トについて、下記の方法により、初期接着力、高温放置後（４０℃で７日間放置後）の接着力および高温多湿放置後（４０℃，９２％ＲＨ下で７日間放置後）の接着力を測定した。これらの結果は、後記の表１に示されるとおりであつた。
【００４３】
＜接着力の測定＞
感圧接着シ―トを幅２０mm，長さ１００mmの大きさに裁断し、２３℃，６５％ＲＨ雰囲気下で、厚さが５mmのガラス板に２Kgロ―ラ１往復で圧着して、試験片を作製した。この試験片を、下記（１）〜（３）の条件に放置後、万能引張試験機により速度５０mm／分で１８０度剥離接着力を測定した。
（１）２３℃，６５％ＲＨ雰囲気下２０分間放置後（初期接着力）
（２）（１）の後、４０℃の乾燥機に７日間投入したのち、取り出して２３℃，６５％ＲＨ雰囲気下２０分間放置後（高温放置後の接着力）
（３）（１）の後、４０℃，９２％ＲＨの加熱加湿機に７日間投入したのち、取り出して２３℃，６５％ＲＨ雰囲気下２０分放置後（高温多湿放置後の接着力）
【００４４】
上記の表１から、実施例１〜８の感圧接着シ―トは、ガラスに対し、初期および高温放置後の接着力が大きく、かつ高温多湿放置後でも非常に高い接着力を維持しており、耐湿熱性にすぐれていることがわかる。とくに、アクリル系感圧接着剤を構成する共重合体成分のゲル分率を５０重量％以上に設定した実施例１〜６の感圧接着シ―トは、同ゲル分率が５０重量％未満である実施例７，８の感圧接着シ―トに比べて、耐湿熱性に格段にすぐれている。
【００４６】
なお、実施例８の感圧接着シ―トは、共重合体成分を紫外線照射による塊状重合法で得る場合に、内部架橋剤の量を少なくしてゲル分率を小さくした例を示しているが、この場合初期の接着力がやや低下しているものの、高温多湿放置後の接着力は上記初期の接着力と同等であり、耐湿熱性という面で好結果が得られている。これに対し、比較例１〜６の感圧接着シ―トは、初期の接着力が不足する場合がある以外に、高温多湿放置後に接着力の急激な低下がみられる。
【００４７】
【発明の効果】
以上のように、本発明は、基材として特定透湿度のプラスチツクフイルムを使用するとともに、このフイルムの少なくとも片面に特定のアクリル系感圧接着剤からなる層を設ける構成としたことにより、ガラスやタイルなどのケイ素酸化物含有材に対して、シランカツプリング剤の処理を施さなくても、すぐれた接着性を示す、とくに高温多湿下でも高い接着性を示す、耐湿熱性に格段にすぐれた感圧接着シ―ト類を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a pressure-sensitive adhesive sheet for a silicon oxide-containing material having an inorganic material mainly composed of SiO 2 such as glass and tile as an adherend.
[0002]
[Prior art]
Affixing a film or label with a pressure-sensitive adhesive layer on a glass plate or container is common on a daily basis. For example, in order to give a design to a window glass of a shop, a printing film with a pressure-sensitive adhesive layer is applied, or an anti-reflective / light-shielding film or glass scattering prevention with a pressure-sensitive adhesive layer is applied to a window glass of a building. In some cases, an antireflection film is attached to a glass panel of a TV CRT or a liquid crystal glass panel plasma display installed outdoors.
[0003]
The pressure-sensitive adhesive used for these films needs to be excellent in weather resistance and heat resistance, and is often exposed to rain and dew condensation water, so that it needs water resistance and moisture resistance. Furthermore, in addition to the film to be pasted on the window glass etc. mentioned above, there is a case where a printing film with a pressure sensitive adhesive layer is pasted in order to give a design to a plain tile in the bathroom. Since it is exposed to high humidity, a pressure-sensitive adhesive having excellent moisture and heat resistance is required.
[0004]
However, conventionally, acrylic pressure-sensitive adhesives having excellent weather resistance and heat resistance have been generally used as pressure-sensitive adhesives for various films. It does not have sufficient moisture and heat resistance for inorganic materials mainly composed of SiO 2 such as tiles, and when exposed to wet heat after bonding, the film floats and wrinkles or peels off. Hot.
[0005]
In order to improve the adhesion to glass, a method of treating a glass surface with a silane coupling agent in advance is generally used. Also disclosed is a method of blending a silane coupling agent into an acrylic pressure sensitive adhesive (Japanese Patent Publication No. 62-30233). However, the former needs to be dried at a high temperature, takes equipment and time, and is difficult to apply to a glass window once constructed, and the latter is because the pot life of alkoxysilane in the silane coupling agent is short, There are strong restrictions on storage humidity conditions and duration, both of which are practically lacking.
[0006]
[Problems to be solved by the invention]
As described above, in the prior art, practical pressure-sensitive adhesive layer-attached films having excellent water resistance, particularly moisture and heat resistance, are hardly known for inorganic materials such as glass and tiles. Therefore, in the light of such circumstances, the present invention exhibits high adhesion to inorganic materials such as glass and tiles without using a silane coupling agent, particularly high adhesion under high temperature and high humidity. The purpose of the present invention is to provide practical pressure-sensitive adhesive sheets having excellent resistance to moisture and heat.
[0007]
[Means for Solving the Problems]
In order to achieve the above object, the inventors of the present invention have made extensive studies. First, conventional acrylic pressure-sensitive adhesives have low adhesive strength to glass, and this phenomenon is particularly noticeable under high humidity. I guessed as follows. SiO 2 , the main component of glass, is known to have an acidic surface. On the other hand, conventional acrylic pressure-sensitive adhesives generally use a co-polymer of an acrylic monomer and a monomer having an acidic group. The main component is coalescence, and it is also acidic as an adhesive. For this reason, the electric repulsion between the acidic groups works between the pressure sensitive adhesive and the glass, and a strong adhesive force cannot be expressed. In particular, when water is present, the dissociated ions of the acidic group increase and the electric repulsion further works, and at the same time, the cohesive force is reduced due to water absorption, and the adhesive force is reduced.
[0008]
Based on this consideration, the present inventors have controlled the water absorption into the pressure-sensitive adhesive layer in pressure-sensitive adhesive sheets and introduced a basic segment into the composition of the pressure-sensitive adhesive. I thought that the above problem could be solved, and continued to study. As a result, the moisture permeability of the plastic film used as the base material is specified, and when it is configured to introduce a specific basic segment into the acrylic pressure-sensitive adhesive provided on this film, glass, tile, etc. Excellent silicon oxide-containing materials can be obtained without treatment with a silane coupling agent, especially in high temperature and high humidity, with excellent moisture and heat resistance. Knowing that adhesive sheets can be obtained, the present invention has been completed.
[0009]
That is, the present invention is, on at least one surface of the plastisol stick film is moisture permeability 500g or less / m 2/24 hours, a) the general formula (1): CH 2 = C (R 1) COOR 2 ( In the formula, R 1 Is hydrogen or a methyl group, R 2 is an alkyl group having 4 to 12 carbon atoms), and b) General formula (2): CH 2 = C (R 3 ) CONR 4 R 5 (wherein R 3 is hydrogen or a methyl group, R 4 and R 5 are alkyl groups, or an organic group that forms a heterocyclic ring by combining both with an N atom) ) Acrylic pressure-sensitive material mainly composed of a copolymer of 5 to 40% by weight of N, N-disubstituted (meth) acrylamide represented by formula (c) and 0 to 10% by weight of a monomer containing an acidic group. a layer composed of the adhesive possess a gel fraction of the copolymer component constituting the layer 50 to 95 weight The pressure sensitive Chakushi for silicon oxide-containing material, characterized in that in the range of - in which according to Doo compound (claim 1).
[0010]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, plastisol poke film used as the substrate, as long as the moisture permeability (JIS by Z-0208 method) 500g or less / m 2/24 hours the material and thickness is not particularly limited. Transparency and smoothness are often required for use, and from this viewpoint, a polyester film or a polycarbonate film having a thickness of usually 6 to 250 μm is suitable. When the above moisture permeability is higher than 500g / m 2/24 hours, decrease in water absorption is increased cohesive force of the acrylic pressure-sensitive adhesive under high humidity, likely to cause deterioration of the interfacial adhesion between the glass.
[0011]
The acrylic pressure-sensitive adhesive used in the present invention has a) general formula (1): CH 2 = C (R 1 ) COOR 2 (wherein R 1 is hydrogen or a methyl group, R 2 has 4 to 4 carbon atoms) 60) to 95% by weight of an acrylic monomer represented by the formula (2): CH 2 = C (R 3 ) CONR 4 R 5 (wherein R 3 is A hydrogen or methyl group, R 4 and R 5 are an alkyl group, or an N, N-disubstituted (meta) which is an organic group which is bonded to each other and forms a heterocyclic ring with an N atom. It is a pressure-sensitive adhesive mainly composed of a copolymer of 5) to 40% by weight of acrylamide and c) 0 to 10% by weight of a monomer containing an acidic group.
[0012]
As the acrylic monomer of component a, butyl (meth) acrylate, isobutyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, pentyl (meth) acrylate 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, and the like. When the carbon number of R 2 in the general formula (1) is less than 4, the wettability of the pressure-sensitive adhesive is lowered and the initial adhesiveness is deteriorated, and when it exceeds 12, the adhesive strength is inferior. The acrylic monomer of component a is in the range of 60 to 95% by weight of the whole monomer, and one or more of them are used. If it is less than 60% by weight, it becomes difficult to exhibit the performance as an acrylic pressure-sensitive adhesive, and if it exceeds 95% by weight, N, N-disubstituted (meth) acrylamide of b component is insufficient, so Adhesive performance with respect to is insufficient.
[0013]
The b component N, N-disubstituted (meth) acrylamide is an indispensable monomer component for developing strong adhesion to glass and the like, and R 4 and R 5 in the general formula (2) are Both include acyclic (meth) acrylamide, which is an alkyl group, and cyclic (meth) acrylamide in which the same R 4 and R 5 are combined to form a heterocyclic ring with an N atom. Or both are used. Examples of the acyclic (meth) acrylamide include N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N, N-dibutyl (meth) acrylamide. Examples of the cyclic (meth) acrylamide include N- (meth) acryloylmorpholine, N- (meth) acryloylpyrrolidone, N- (meth) acryloylpiperidine, N- (meth) acryloylpyrrolidine, N- (meth) acryloyl. -4-piperidone and the like. The b component N, N-disubstituted (meth) acrylamide is used in an amount of 5 to 40% by weight, preferably 10 to 35% by weight, based on the whole monomer, and one or more of them are used. If it is less than 5% by weight, the adhesion to glass or the like is insufficient, and if it exceeds 40% by weight, the elastic modulus of the pressure-sensitive adhesive increases and the wettability to the adherend decreases.
[0014]
Examples of the monomer containing an acidic group of component c include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid and crotonic acid, other 2-hydroxyethylacryloyl phosphates, 2 -A phosphate group-containing monomer such as hydroxypropyl acryloyl phosphate is used. The monomer containing an acidic group of component c is used as necessary for adjusting the cohesive force of the pressure-sensitive adhesive. That is, one or more of them are used in the range of 0 to 10% by weight, preferably 2 to 8% by weight of the whole monomer. When it exceeds 10% by weight, the acidic component of the pressure-sensitive adhesive increases, and the moisture-resistant adhesive strength to glass or the like decreases.
[0015]
The copolymer is composed of the above-mentioned components a and b, or a monomer mixture obtained by adding the above-mentioned component c to a solution polymerization method, emulsion polymerization method, bulk polymerization method, suspension weight, It can be obtained by copolymerization by a method such as a combination method. In the bulk polymerization method, a polymerization method by ultraviolet irradiation is preferable. For copolymerization, organic peroxides such as benzoyl peroxide, lauroyl peroxide, cumene peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc. Azo compounds, 2,2-dimethoxy-2-phenylacetophenone, acetophenone compounds such as 2,2-diethoxyacetophenone, benzoin ethers such as benzoin ethyl ether and benzoin isopropyl ether Thermal polymerization initiators and photopolymerization initiators such as benzophenone compounds such as benzophenone and benzophenone and benzoylbenzoic acid are used.
[0016]
In the acrylic pressure-sensitive adhesive of the present invention, the gel fraction of the copolymer component is 50 to 95% by weight, preferably 55 to 90% by weight. When the amount is less than 50% by weight, the cohesive force is reduced due to water absorption under high humidity, and the adhesive force is likely to be reduced. If it exceeds 95% by weight, the sol content is too small, the wettability to glass or the like is poor, and a high adhesive force cannot be expressed. The above setting of the gel fraction can be easily performed by adjusting the type and amount of the external cross-linking agent and the internal cross-linking agent.
[0017]
External crosslinking agents include ethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate. , 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, trimelliol propane tolylene diisocyanate adduct, etc. Examples thereof include isocyanate compounds. Examples of internal cross-linking agents include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, 1,6-hexanediol. -Multifunctional (meth) acrylates such as rudi (meth) acrylate and 1,12-dodecandiol di (meth) acrylate, etc. These internal cross-linking agents are usually added during the synthesis of the copolymer Is done.
[0018]
The acrylic pressure-sensitive adhesive of the present invention comprises the copolymer component thus crosslinked as a main component, and if necessary, tackifying resin, anti-aging agent, ultraviolet absorber, colorant, filler, difficulty Various known additives such as a flame retardant and an antistatic agent can be added. These additives may be used in a usual amount depending on the type.
[0019]
The pressure-sensitive adhesive sheet of the present invention uses the above-described plastic film having a specific moisture permeability as a base material, and a layer made of the specific acrylic pressure-sensitive adhesive having the above-described structure is provided on at least one side of the film. It is in the form of a sheet or tape. The thickness of the layer made of the acrylic pressure-sensitive adhesive is not particularly limited, but it may be usually about 5 to 200 μm on one side.
[0020]
The pressure-sensitive adhesive sheets of the present invention constructed as described above exhibit excellent adhesion to adherends made of inorganic materials mainly composed of SiO 2 such as glass and tiles, especially at high temperatures. Because it exhibits excellent moisture and heat resistance that maintains high adhesion even in humid environments, it can be used in a wide range of fields as a pressure-sensitive adhesive sheet for silicon oxide-containing materials with excellent practicality. Can do.
[0021]
【Example】
Next, examples of the present invention will be described in more detail. However, the present invention is not limited to these examples. In the following, “parts” means parts by weight.
In addition, among "Examples 1 to 8" described below, "Examples 1 to 6" show examples of pressure-sensitive adhesive sheets included in the claims of the present invention. Examples 7 and 8 "show a pressure-sensitive adhesive sheet as a control example not included in the claims of the present invention.
[0022]
Reference example 1
A monomer mixture consisting of 75 parts of butyl acrylate, 20 parts of N, N-diethylacrylamide and 5 parts of acrylic acid, 0.2 part of N, N'-azobisisobutyronitrile and 200 parts of toluene are placed in a flask. After substitution with nitrogen, the mixture was heated to 60 ° C. and stirred at this temperature for 20 hours to continue the copolymerization reaction, whereby a copolymer solution A was obtained.
[0023]
Reference example 2
A copolymer solution B was obtained in the same manner as in Reference Example 1, except that the monomer mixture was changed to 50 parts of butyl acrylate, 45 parts of N, N-diethylacrylamide and 5 parts of acrylic acid.
[0024]
Reference example 3
A copolymer solution C was obtained in the same manner as in Reference Example 1 except that the monomer mixture was changed to 70 parts of butyl acrylate, 15 parts of N, N-diethylacrylamide and 15 parts of acrylic acid.
[0025]
Reference example 4
A copolymer solution D was obtained in the same manner as in Reference Example 1 except that the monomer mixture was changed to 92 parts of butyl acrylate and 8 parts of acrylic acid.
[0026]
Reference Example 5
A mixture of a monomer mixture consisting of 80 parts of isooctyl acrylate, 15 parts of acryloylmorpholine and 5 parts of acrylic acid and 0.1 part of 2,2-dimethoxy-2-phenylacetophenone was added to nitrogen. The coating was partially polymerized by exposure to ultraviolet rays in an atmosphere to obtain a coatable syrup E having a viscosity of about 200 poise.
[0027]
Reference Example 6
Except that the monomer mixture was changed to 80 parts isooctyl acrylate and 20 parts acryloylmorpholine, it was partially polymerized in the same manner as in Reference Example 5 to obtain a coatable syrup F having a viscosity of about 200 poise. Obtained.
[0028]
Example 1
To the copolymer solution A obtained in Reference Example 1, 1.5 parts of a trimethylolpropane tolylene diisocyanate adduct was added to 100 parts of the copolymer to obtain an acrylic pressure-sensitive adhesive solution. . The acrylic pressure sensitive adhesive solution, moisture permeability 28g / m 2/24 hours as the substrate, the thickness is 25μm polyethylene terephthalate of - applying onto the Tofuirumu and dried for 8 minutes at 110 ° C., the thickness A pressure-sensitive adhesive sheet having a layer made of an acrylic pressure-sensitive adhesive having a thickness of 50 μm was prepared. The gel fraction of the pressure-sensitive adhesive layer was 72% by weight.
[0029]
Example 2
As the base material, the moisture permeability is 60g / m 2/24 hours, a thickness of 25μm polycarbonate - BONNET - except using Tofuirumu, the same procedure as in Example 1, a thickness of 50μm of the acrylic pressure-sensitive adhesive A pressure-sensitive adhesive sheet having a layer consisting of was prepared. The gel fraction of the layer made of the pressure-sensitive adhesive was 72% by weight as in Example 1.
[0030]
Example 3
0.08 part of trimethylolpropane triacrylate was added to 100 parts of the syrup E obtained in Reference Example 5 to obtain a mixed solution. The mixture, moisture permeability 28g / m 2/24 hours as the substrate, the thickness of polyethylene terephthalate of 25 [mu] m - was applied onto Tofuirumu, by a high-pressure mercury lamp of light intensity 5 mW / cm 2 in a nitrogen gas atmosphere A pressure-sensitive adhesive sheet having a layer made of an acrylic pressure-sensitive adhesive having a thickness of 50 μm was prepared by irradiating with ultraviolet rays at 900 mJ / cm 2 . The gel fraction of the pressure-sensitive adhesive layer was 68% by weight.
[0031]
Example 4
It has a layer made of an acrylic pressure-sensitive adhesive having a thickness of 50 μm in the same manner as in Example 3 except that the syrup F obtained in Reference Example 6 was used instead of the syrup E obtained in Reference Example 5. A pressure sensitive adhesive sheet was prepared. The gel fraction of the pressure-sensitive adhesive layer was 62% by weight.
[0032]
Example 5
As the base material, the moisture permeability is 8g / m 2/24 hours, except that the thickness was used 25μm oriented polypropylene film of the (already corona treatment), the same procedure as in Example 3, the acrylic feeling of 50μm thickness A pressure sensitive adhesive sheet having a layer made of a pressure adhesive was prepared. The gel fraction of the layer made of the acrylic pressure-sensitive adhesive was 68% by weight as in Example 3.
[0033]
Example 6
Instead of syrup E obtained in Reference Example 5, using the syrup F obtained in Reference Example 6, and moisture permeability of 8g / m 2/24 hours as a substrate, oriented polypropylene film having a thickness of 25 [mu] m (corona treatment A pressure-sensitive adhesive sheet having a layer made of an acrylic pressure-sensitive adhesive having a thickness of 50 μm was prepared in the same manner as in Example 3 except that the above was used. The gel fraction of the pressure-sensitive adhesive layer was 62% by weight.
[0034]
Example 7
It has a layer made of an acrylic pressure-sensitive adhesive having a thickness of 50 μm in the same manner as in Example 1 except that the addition amount of the tolylene diisocyanate adduct of trimethylolpropane was changed to 0.5 part. A pressure sensitive adhesive sheet was prepared. The gel fraction of the pressure-sensitive adhesive layer was 35% by weight.
[0035]
Example 8
Trimethylolpropane - triacrylate - change the amount of bets in 0.03 parts and using moisture permeability 8g / m 2/24 hours, a thickness of 25μm oriented polypropylene (already corona treatment) as a substrate A pressure-sensitive adhesive sheet having a layer made of an acrylic pressure-sensitive adhesive having a thickness of 50 μm was prepared in the same manner as in Example 3 except that. The gel fraction of the layer made of the pressure sensitive adhesive was 40% by weight.
[0036]
Comparative Example 1
An acrylic pressure-sensitive adhesive having a thickness of 50 μm was used in the same manner as in Example 1 except that the copolymer solution B obtained in Reference Example 2 was used instead of the copolymer solution A obtained in Reference Example 1. A pressure-sensitive adhesive sheet having a layer made of an agent was prepared. The gel fraction of the pressure-sensitive adhesive layer was 82% by weight.
[0037]
Comparative Example 2
An acrylic pressure-sensitive adhesive having a thickness of 50 μm was used in the same manner as in Example 1 except that the copolymer solution C obtained in Reference Example 3 was used instead of the copolymer solution A obtained in Reference Example 1. A pressure-sensitive adhesive sheet having a layer made of an agent was prepared. The gel fraction of the layer made of the pressure-sensitive adhesive was 84% by weight.
[0038]
Comparative Example 3
An acrylic pressure-sensitive adhesive having a thickness of 50 μm was used in the same manner as in Example 1 except that the copolymer solution D obtained in Reference Example 4 was used instead of the copolymer solution A obtained in Reference Example 1. A pressure-sensitive adhesive sheet having a layer made of an agent was prepared. The gel fraction of the layer comprising the pressure sensitive adhesive was 71% by weight.
[0039]
Comparative Example 4
Instead of the copolymer solution A obtained in Reference Example 1, using the copolymer solution D obtained in Reference Example 4, and moisture permeability of 60g / m 2/24 hours as a substrate, a thickness of 25μm of A pressure-sensitive adhesive sheet having a layer made of an acrylic pressure-sensitive adhesive having a thickness of 50 μm was prepared in the same manner as in Example 1 except that a polycarbonate film was used. The gel fraction of the pressure-sensitive adhesive layer was 71% by weight.
[0040]
Comparative Example 5
To the copolymer solution A obtained in Reference Example 1, 1.5 parts of a trimethylolpropane tolylene diisocyanate adduct was added to 100 parts of the copolymer to obtain an acrylic pressure-sensitive adhesive solution. . This acrylic pressure-sensitive adhesive solution was applied on release paper and dried at 110 ° C. for 8 minutes to form a layer made of an acrylic pressure-sensitive adhesive having a thickness of 50 μm. Then, this moisture permeability is 700g / m 2/24 hours, of 25μm thickness triacetate - Tofuirumu the laminating - was collected, pressure sensitive Chakushi - to prepare the door. The gel fraction of the pressure-sensitive adhesive layer was 72% by weight.
[0041]
Comparative Example 6
An acrylic pressure-sensitive adhesive having a thickness of 50 μm was used in the same manner as in Comparative Example 5 except that the copolymer solution D obtained in Reference Example 4 was used instead of the copolymer solution A obtained in Reference Example 1. A pressure-sensitive adhesive sheet having a layer made of an agent was prepared. The gel fraction of the pressure-sensitive adhesive layer was 71% by weight.
[0042]
For each of the pressure-sensitive adhesive sheets of Examples 1 to 8 and Comparative Examples 1 to 6, the initial adhesive strength, the adhesive strength after being left at high temperature (after being left at 40 ° C. for 7 days) and the high temperature and humidity are as follows. The adhesive strength after standing (after leaving for 7 days at 40 ° C. and 92% RH) was measured. These results were as shown in Table 1 below.
[0043]
<Measurement of adhesive strength>
A pressure-sensitive adhesive sheet was cut to a size of 20 mm in width and 100 mm in length, and tested in a reciprocating 2 kg roller on a 5 mm thick glass plate in an atmosphere of 23 ° C and 65% RH. A piece was made. The specimen was left under the following conditions (1) to (3), and then the 180 ° peel adhesion was measured at a speed of 50 mm / min with a universal tensile tester.
(1) After standing for 20 minutes in an atmosphere of 23 ° C. and 65% RH (initial adhesive strength)
(2) After (1), after being put into a dryer at 40 ° C. for 7 days, it is taken out and left for 20 minutes in an atmosphere of 23 ° C. and 65% RH (adhesive strength after leaving at high temperature).
(3) After (1), after being put in a heating humidifier at 40 ° C. and 92% RH for 7 days, it is taken out and left in an atmosphere of 23 ° C. and 65% RH for 20 minutes (adhesive strength after leaving at high temperature and high humidity)
[0044]
From Table 1 above, the pressure sensitive in Examples 1-8 Chakushi - TMG, to the glass, initial and adhesion after high temperature exposure is large and to maintain the adhesion very high even after humid standing It can be seen that it has excellent resistance to moisture and heat. In particular, in the pressure-sensitive adhesive sheets of Examples 1 to 6 in which the gel fraction of the copolymer component constituting the acrylic pressure-sensitive adhesive was set to 50% by weight or more, the gel fraction was less than 50% by weight. Compared to the pressure-sensitive adhesive sheets of Examples 7 and 8 as described above, the heat and moisture resistance is remarkably superior.
[0046]
The pressure-sensitive adhesive sheet of Example 8 shows an example in which the gel fraction is reduced by reducing the amount of the internal crosslinking agent when the copolymer component is obtained by a bulk polymerization method by ultraviolet irradiation. However, in this case, although the initial adhesive strength is slightly reduced, the adhesive strength after leaving at high temperature and high humidity is equivalent to the initial adhesive strength, and good results are obtained in terms of moisture and heat resistance. On the other hand, the pressure-sensitive adhesive sheets of Comparative Examples 1 to 6 show a sharp decrease in the adhesive strength after leaving at high temperature and high humidity, in addition to the case where the initial adhesive strength may be insufficient.
[0047]
【The invention's effect】
As described above, the present invention uses a plastic film having a specific moisture permeability as a base material, and has a structure in which a layer made of a specific acrylic pressure-sensitive adhesive is provided on at least one surface of the film. It shows excellent adhesion to silicon oxide-containing materials such as tiles without treatment with a silane coupling agent, especially high humidity under high temperature and high humidity, and excellent resistance to heat and humidity. Pressure bonding sheets can be provided.
Claims (1)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35310297A JP3856553B2 (en) | 1997-12-22 | 1997-12-22 | Pressure-sensitive adhesive sheets for silicon oxide-containing materials |
| US09/210,602 US6337128B1 (en) | 1997-12-16 | 1998-12-15 | Pressure-sensitive adhesion sheets for silicone oxide-containing material |
| DE69815269T DE69815269T2 (en) | 1997-12-16 | 1998-12-16 | Pressure-sensitive films |
| EP19980123911 EP0924060B1 (en) | 1997-12-16 | 1998-12-16 | Pressure-sensitive adhesion sheets |
| US10/005,165 US20020076545A1 (en) | 1997-12-16 | 2001-12-07 | Pressure-sensitive adhesion sheets for silicone oxide-containing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35310297A JP3856553B2 (en) | 1997-12-22 | 1997-12-22 | Pressure-sensitive adhesive sheets for silicon oxide-containing materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11181369A JPH11181369A (en) | 1999-07-06 |
| JP3856553B2 true JP3856553B2 (en) | 2006-12-13 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35310297A Expired - Fee Related JP3856553B2 (en) | 1997-12-16 | 1997-12-22 | Pressure-sensitive adhesive sheets for silicon oxide-containing materials |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3856553B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103403119B (en) * | 2010-12-10 | 2016-01-13 | 日立化成株式会社 | Device used for image display adhesive sheet, image display device and adhesive resin composition |
-
1997
- 1997-12-22 JP JP35310297A patent/JP3856553B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11181369A (en) | 1999-07-06 |
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