JP4516632B2 - Acrylic pressure-sensitive adhesive composition and its adhesive sheets - Google Patents
Acrylic pressure-sensitive adhesive composition and its adhesive sheets Download PDFInfo
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- JP4516632B2 JP4516632B2 JP11160299A JP11160299A JP4516632B2 JP 4516632 B2 JP4516632 B2 JP 4516632B2 JP 11160299 A JP11160299 A JP 11160299A JP 11160299 A JP11160299 A JP 11160299A JP 4516632 B2 JP4516632 B2 JP 4516632B2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
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Description
【０００１】
【発明の属する技術分野】
本発明は、電子部品などの固定用途に有用なアクリル系感圧性接着剤組成物とこれを用いたシ―ト状やテ―プ状などの接着シ―ト類に関する。
【０００２】
【従来の技術】
近年、電子部品などの固定用途に、種々の接合材料が使用されている。
この種の用途では、強接着性とともに、電子部品を基板に実装するときのハンダリフロ―に耐えうる高耐熱性が必要である。また、電子部品の高信頼性に伴い、含有不純物や揮発成分などによる電子部品の誤作動や腐食の問題があり、使用される接合材料としても、高純度のものが求められている。
【０００３】
このような電子部品などの固定用途に好適な接合材料として、本発明者らは、先に、常温で粘着性がなく、加熱により接着性を示す熱接着性組成物を提案した（特願平１０−２６８８５４号）。この熱接着性組成物によれば、低圧、短時間の加熱により強接着性、高耐熱性を発揮させることができるが、常温での粘着性（感圧接着性やタツクともいう）がないため、接着使用に際して、粘着性が必要とされる用途には使用することができなかつた。
【０００４】
常温で粘着性を示す感圧性接着剤には種々のものが知られ、電子部品などの接着用途にも、種々のアクリル系感圧性接着剤が用いられている。アクリル系感圧性接着剤は、通常、アルキル基の炭素数が平均２〜１４個のアルキル（メタ）アクリレ―トを主成分とし、これに凝集力の向上のためにアクリル酸などを加えた単量体混合物の粘着性共重合物を主剤成分としたものである。
【０００５】
しかしながら、このようなアクリル系感圧性接着剤では、接着性や凝集力（耐熱性）を満足させることができたとしても、アクリル酸などの酸成分が電子部品を腐食させるという問題があつた。また、アクリル酸などの酸成分を使用しないで、水酸基やアミド基などを有する単量体を凝集力向上成分として用いた粘着性共重合物を主剤成分としたものも提案されているが、これでは接着性が不足し、また凝集力や耐熱性なども不十分であるという問題があつた。
【０００６】
【発明が解決しようとする課題】
本発明は、上記従来の事情に照らし、電子部品などの固定用途に有用な常温で粘着性を有する接合材料として、接着性にすぐれ、実装時のハンダリフロ―に耐えうる耐熱性を有し、しかも電子部品を腐食させることのないアクリル系感圧性接着剤組成物とその接着シ―ト類を提供することを目的とする。
【０００７】
【課題を解決するための手段】
本発明者らは、上記目的に対する鋭意検討の過程において、まず、アクリル系共重合体の合成に際し、アルキル基の炭素数が平均２〜１４個のアルキル（メタ）アクリレ―トを主成分とする限り、これに凝集力向上成分としてカルボキシル基を含有しない単量体を加えて共重合させるようにしても、凝集力不足となつて耐熱性に乏しいものとなり、また接着性も低下し、電子部品などの固定用途に適した接合材料を得ることが難しいことがわかつた。
【０００８】
本発明者らは、この知見を踏まえて、さらに検討を続けた結果、アルキル基の炭素数が平均２〜１４個のアルキル（メタ）アクリレ―トを主成分とする代わりに、ホモポリマ―自体が大きな凝集力を発揮する特定の分子構造を持つアクリル系単量体を主成分とし、これにさらに粘着性を発現させるための特定の単量体成分を加えて共重合させることにより、常温で粘着性を示す接合材料として、可撓性、柔軟性、凝集性に富み、電子部品に用いられる各種被着体に対して強固な接着性を示すとともに、耐熱性にもすぐれており、しかも電子部品の腐食を発生させることのないアクリル系感圧性接着剤組成物とその接着シ―ト類が得られることを見い出し、本発明を完成するに至つた。
【０００９】
すなわち、本発明は、つぎの式（１）；
【化２】
で表される（メタ）アクリル酸エステル５０〜８０重量％と、これと共重合可能でかつ分子内にカルボキシル基を含有しないモノエチレン性不飽和単量体５０〜２０重量％とからなり、かつ上記のモノエチレン性不飽和単量体がホモポリマーのガラス転移温度が−３０℃以下となるアルキル（メタ）アクリレートを必須成分として含む単量体混合物の粘着性共重合物を含有することを特徴とするアクリル系感圧性接着剤組成物（請求項１）、とくに上記の粘着性共重合物が紫外線などの放射線の照射による共重合物である上記構成のアクリル系感圧性接着剤組成物（請求項２）に係るものである。
また、本発明は、基材の片面または両面に上記構成のアクリル系感圧性接着剤組成物からなる層を有することを特徴とする接着シート類（請求項３）、とくにアルミニウム板に対する１８０°剥離接着強度が１，１００ｇ／２０ｍｍ幅以上である上記構成の接着シート類（請求項４）、また電子部品の固定用途に用いられる上記構成の接着シート類（請求項５）に係るものである。
【００１０】
【発明の実施の形態】
本発明において、式（１）で表される（メタ）アクリル酸エステルは、ホモポリマ―が高いガラス転移点（Ｔｇ）を示すものであつて、代表的なものとして、フエノキシエチル（メタ）アクリレ―ト、フエノキシプロピル（メタ）アクリレ―ト、ノニルフエノキシエチル（メタ）アクリレ―ト、ノニルフエノキシプロピル（メタ）アクリレ―トなどが挙げられる。また、フエノ―ル、クレゾ―ル、ノニルフエノ―ルなどのエチレンオキシド付加物、プロピレンオキシド付加物（付加モル数は３まで）とアクリル酸またはメタクリル酸とのエステルも好ましく用いられる。これらは、その１種または２種以上が用いられる。
【００１１】
本発明において、上記の（メタ）アクリル酸エステルと共重合可能でかつ分子内にカルボキシル基を含有しないモノエチレン性不飽和単量体としては、エチル（メタ）アクリレ―ト、ブチル（メタ）アクリレ―ト、イソアミル（メタ）アクリレ―ト、ｎ−ヘキシル（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、デシル（メタ）アクリレ―ト、ドデシル（メタ）アクリレ―トなどのアルキル（メタ）アクリレ―トが挙げられる。その他、ヒドロキシアルキル（メタ）アクリレ―ト、シアノアルキル（メタ）アクリレ―ト、（メタ）アクリルアミド、置換（メタ）アクリルアミド、Ｎ−ビニルカプロラクタム、（メタ）アクリロニトリル、２−メトキシエチル（メタ）アクリレ―ト、（メタ）アクリル酸グリシジル、酢酸ビニルなどを使用することもできる。
【００１２】
このようなモノエチレン性不飽和単量体の中でも、共重合物のガラス転移温度を低下させて、粘着性を発現させるという観点から、ブチル（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―トなどのホモポリマ―のガラス転移温度が−３０℃以下となるアルキル（メタ）アクリレ―トがとくに好ましい。これらのモノエチレン性不飽和単量体は、その１種または２種以上が用いられる。なお、このような分子内にカルボキシル基を含有しないモノエチレン性不飽和単量体に代え、分子内にカルボキシル基を含有するモノエチレン性不飽和単量体として、アクリル酸、メタクリル酸、イタコン酸、クロトン酸などを用いると、電子部品の腐食などの問題が起こるため、本発明には使用できない。
【００１３】
本発明においては、上記の式（１）で表される（メタ）アクリル酸エステルとこれと共重合可能でかつ分子内にカルボキシル基を含有しないモノエチレン性不飽和単量体とからなる単量体混合物を使用するが、両成分の使用割合としては、主成分である前者の（メタ）アクリル酸エステルが５０〜８０重量％、好ましくは６０〜７５重量％で、後者のモノエチレン性不飽和単量体が５０〜２０重量％、好ましくは４０〜２５重量％であるのがよい。主成分である前者の（メタ）アクリル酸エステルが５０重量％未満となり、後者のモノエチレン性不飽和単量体が５０重量％を超えると、電子部品実装時のハンダリフロ―などにおける耐熱性を保持することができなくなる。また、後者のモノエチレン性不飽和単量体が２０重量％未満となり、前者の（メタ）アクリル酸エステルが８０重量％を超えると、常温での粘着性を発現できなくなる。
【００１４】
本発明においては、上記の単量体混合物を共重合させて、粘着性共重合物とする。共重合は、溶液重合法、乳化重合法、塊状重合法、これらの併用法などの適宜の重合方式を採用できる。共重合には、重合触媒として、熱重合開始剤や光重合開始剤が用いられ、また過硫酸カリウム、過硫酸アンモニウム、過酸化水素などや、これらと還元剤とからなるレドツクス系開始剤などが用いられる。
【００１５】
なお、上記の重合法の中でも、紫外線や電子線などの放射線の照射による塊状重合法が最も好ましい。これによれば、有機溶剤の残存による電子部品の腐食、高温での気化膨張による膨れ、剥がれ、ずれ、乳化剤のブリ―ドによる汚染、接着不良、耐湿性低下などの心配がなく、また比較的弱い強度の紫外線などを照射することで共重合物の分子量を高くでき、高い架橋度と大きな凝集力を有する耐熱性のとくにすぐれた粘着性共重合物とすることができる。
【００１６】
本発明のアクリル系感圧性接着剤組成物は、上記のようにして得られる粘着性共重合物を必須成分とし、これに任意成分として、粘着付与剤、可塑剤、軟化剤、充填剤、顔料、染料、老化防止剤などの従来公知の各種添加剤を含有させることができる。また、接着剤の保持特性を向上させるために、交叉結合剤として、イソシアネ―ト系化合物、エポキシ系化合物などの公知の架橋剤や、光重合を行う場合などには、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―トなどの多官能（メタ）アクリレ―トを含有させるようにしてもよい。
【００１７】
上記の架橋剤や多官能（メタ）アクリレ―トからなる交叉結合剤の使用量は、前記の単量体混合物１００重量部に対し、通常０．０５〜５重量部、好ましくは０．１〜３重量部の範囲とするのがよい。多官能（メタ）アクリレ―トでは、上記範囲内で、２官能の場合は多く、３官能それ以上の多官能の場合は少なくするのがよい。上記使用量が０．０５重量部未満では、共重合後の架橋度を十分に高くできず、保持特性の低下を招きやすく、逆に５重量部を超えると、弾性率が極端に高くなり、接着不良などの接着性の低下を引き起こしやすい。
【００１８】
本発明の接着シ―ト層は、基材の片面または両面に、上記の粘着性共重合物を含有するアクリル系感圧性接着剤組成物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。上記の層は、あらかじめ適宜の重合法で粘着性共重合物を得、これに架橋剤などを加えてアクリル系感圧性接着剤組成物を調製し、この組成物を基材上に塗工し、必要に応じて加熱などにより架橋処理する方式により、形成できる。また、より好ましくは、重合前の単量体混合物またはその部分重合物に多官能（メタ）アクリレ―トなどを加えた放射線重合性組成物を調製し、これを基材上に塗工し、紫外線などの放射線を照射して共重合させる方式、つまり粘着性共重合物の合成と同時に層形成する方式を採用するのがよく、これによれば接着剤の耐熱性により好結果が得られる。
【００１９】
基材には、ポリエステルフイルムなどの合成樹脂フイルムや繊維基材などの非剥離性基材のほか、剥離紙などの剥離性基材を使用できる。剥離性基材の場合、この上に形成したアクリル系感圧性接着剤組成物からなる層を最終的に非剥離性基材の上に転写してもよい。本発明の接着シ―ト類には、基材としてこのような非剥離基材を用いたものと剥離性基材を用いたものとの両方が含まれる。
【００２０】
本発明のアクリル系感圧性接着剤組成物とその接着シ―ト類は、常温で粘着性を示す接合材料として、可撓性、柔軟性、凝集性に富み、各種被着体に対して強固な接着性を示すとともに、実装時のハンダリフロ―に耐えうる耐熱性を有し、しかもアクリル酸などの腐食成分を含まないため、電子部品などの固定用途に使用でき、その他、上記特徴を生かした各種用途に使用できる。
【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。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。
【００２２】
実施例１
冷却管、窒素導入管、温度計、撹拌機を備えた反応容器に、酢酸エチル２１０部を溶媒として、フエノキシエチルアクリレ―ト７０部、ブチルアクリレ―ト２０部、ヒドロキシエチルアクリレ―ト３部、過酸化ベンゾイル０．３部を入れ、窒素気流中で重合処理して、固形分が約３０重量％である粘着性共重合物の溶液を得た。この溶液に、その固形分１００部あたり、多官能イソシアネ―ト系架橋剤３部を均一に混合して、アクリル系感圧性接着剤組成物の溶液を調製した。つぎに、この溶液をセパレ―タ上に塗布し、１３０℃で５分間乾燥処理して、厚さが５０μｍの接着剤層を形成し、接着シ―トを作製した。
【００２３】
実施例２
四つ口フラスコに、フエノキシエチルアクリレ―ト７０部、ブチルアクリレ―ト２０部、アクリロイルモルフオリン１０部、２，２−ジメトキシ−２−フエニルアセトフエノン０．０５部を投入し、窒素雰囲気下で紫外線に暴露して部分的に光重合させ、粘度が約３０ポイズのシロツプを得た。この部分重合したシロツプ１００部に、交叉結合剤として１，６−ヘキサンジオ―ルジアクリレ―ト０．３部を均一に混合して、光重合性組成物を調製した。つぎに、この光重合性組成物をセパレ―タ上に塗布し、９００ｍｊ／cm2 の紫外線を照射して光重合させ、厚さが５０μｍのアクリル系感圧性接着剤組成物からなる層を形成して、接着シ―トを作製した。
【００２４】
実施例３
フエノキシエチルアクリレ―ト７０部の代わりに、クレゾ―ルのエチレンオキシド付加物（付加モル数１）とアクリル酸とのエステル７０部を用いた以外は、実施例２と同様にして、厚さが５０μｍのアクリル系感圧性接着剤組成物からなる層を形成して、接着シ―トを作製した。
【００２５】
実施例４
四つ口フラスコに、フエノキシエチルアクリレ―ト８０部、イソノニルアクリレ―ト２０部、２，２−ジメトキシ−２−フエニルアセトフエノン０．０５部を投入し、窒素雰囲気下で紫外線に暴露して部分的に光重合させ、粘度が約３０ポイズのシロツプを得た。この部分重合したシロツプ１００部に、交叉結合剤としてトリメチロ―ルプロパントリアクリレ―ト０．２部を均一に混合し、光重合性組成物を調製した。つぎに、この光重合性組成物をセパレ―タ上に塗布し、９００ｍｊ／cm2 の紫外線を照射して光重合させ、厚さが５０μｍのアクリル系感圧性接着剤組成物からなる層を形成して、接着シ―トを作製した。
【００２６】
比較例１
冷却管、窒素導入管、温度計、撹拌機を備えた反応容器に、酢酸エチル２１０部を溶媒として、ブチルアクリレ―ト６０部、アクリロニトリル３０部、ヒドロキシエチルアクリレ―ト１０部、過酸化ベンゾイル０．３部を入れ、窒素気流中で重合処理して、固形分が約３０重量％のアクリル系共重合体の溶液を得た。この溶液に、その固形分１００部あたり、多官能イソシアネ―ト系架橋剤３部を均一に混合して、アクリル系感圧性接着剤組成物の溶液を調製した。つぎに、この溶液をセパレ―タ上に塗布し、１３０℃で５分間乾燥処理して、厚さが５０μｍの接着剤層を形成し、接着シ―トを作製した。
【００２７】
比較例２
四つ口フラスコに、イソオクチルアクリレ―ト６０部、アクリロイルモルフオリン４０部、２，２−ジメトキシ−２−フエニルアセトフエノン０．０５部を投入し、窒素雰囲気下で紫外線に暴露して部分的に光重合させ、粘度が約３０ポイズのシロツプを得た。この部分重合したシロツプ１００部に、交叉結合剤として１，６−ヘキサンジオ―ルジアクリレ―ト０．３部を均一に混合し、光重合性組成物を調製した。つぎに、この光重合性組成物をセパレ―タ上に塗布し、９００ｍｊ／cm2 の紫外線を照射して光重合させ、厚さが５０μｍのアクリル系感圧性接着剤組成物からなる層を形成して、接着シ―トを作製した。
【００２８】
比較例３
四つ口フラスコに、エチルアクリレ―ト８０部、アクリロイルモルフオリン２０部、２，２−ジメトキシ−２−フエニルアセトフエノン０．０５部を投入し、窒素雰囲気下で紫外線に暴露して部分的に光重合させ、粘度が約３０ポイズのシロツプを得た。この部分重合したシロツプ１００部に、交叉結合剤として１，６−ヘキサンジオ―ルジアクリレ―ト０．３部を均一に混合し、光重合性組成物を調製した。つぎに、この光重合性組成物を、セパレ―タ上に塗布し、９００ｍｊ／cm2 の紫外線を照射して光重合させ、厚さが５０μｍのアクリル系感圧性接着剤組成物からなる層を形成して、接着シ―トを作製した。
【００２９】
比較例４
四つ口フラスコに、フエノキシエチルアクリレ―ト４０部、ブチルアクリレ―ト５０部、アクリロイルモルフオリン１０部、２，２−ジメトキシ−２−フエニルアセトフエノン０．０５部を投入し、窒素雰囲気下で紫外線に暴露して部分的に光重合させ、粘度が約３０ポイズのシロツプを得た。この部分重合したシロツプ１００部に、交叉結合剤として１，６−ヘキサンジオ―ルジアクリレ―ト０．３部を均一に混合し、光重合性組成物を調製した。つぎに、この光重合性組成物をセパレ―タ上に塗布し、９００ｍｊ／cm2 の紫外線を照射して光重合させ、厚さが５０μｍのアクリル系感圧性接着剤組成物からなる層を形成して、接着シ―トを作製した。
【００３０】
比較例５
四つ口フラスコに、フエノキシエチルアクリレ―ト９０部、ブチルアクリレ―ト１０部、２，２−ジメトキシ−２−フエニルアセトフエノン０．０５部を投入し、窒素雰囲気下で紫外線に暴露して部分的に光重合させ、粘度が約３０ポイズのシロツプを得た。この部分重合したシロツプ１００部に、交叉結合剤として１，６‐ヘキサンジオ―ルジアクリレ―ト０．３部を均一に混合し、光重合性組成物を調製した。つぎに、この光重合性組成物をセパレ―タ上に塗布し、９００ｍｊ／cm2 の紫外線を照射して光重合させ、厚さが５０μｍのアクリル系感圧性接着剤組成物からなる層を形成して、接着シ―トを作製した。
【００３１】
上記の実施例１〜４および比較例１〜５の各接着シ―トについて、下記の方法により、１８０°剥離接着強度、保持力およびハンダ耐熱性を調べた。これらの結果は、表１に示されるとおりであつた。
【００３２】
＜１８０°剥離接着強度＞
幅２０mm、長さ５０mmの接着シ―トを、厚さが２５μｍのポリエチレンテレフタレ―トフイルム（以下、ＰＥＴフイルムという）にハンドロ―ラにて貼り合わせ、これを各被着体に２kgロ―ラ１往復で貼り合わせた。このサンプルを、温度２３℃、湿度６５％ＲＨの雰囲気下で、３０分放置後、引張り速度３００mm／分で１８０°方向に引張り、その中心値を１８０°剥離接着強度とした。
【００３３】
＜保持力＞
１５mm角に切断した接着シ―トを、アルミニウム／アルミニウム（２５mm×５０mm）の両端部間に５kgロ―ラ１往復で貼り合わせて、試験片を作製し、これを８０℃雰囲気中に３０分放置した。その後、この試験片を垂下して、一方のアルミニウムの下端部に８０℃雰囲気中で１kgの荷重をかけ、２時間後のずれ距離を測定した。なお、落下したものはその時間を測定した。
【００３４】
＜ハンダ耐熱性＞
接着シ―トを、厚さが７５μｍのポリイミドフイルムに、ラミネ―タ（温度：１００℃、圧力：５kg／cm、速度：２ｍ／分）で貼り合わせ、これを、５０mm角に切断し、セパレ―タを剥がし、２６０℃に溶融したハンダ浴に接着剤層面が上になるように浮かせた状態で６０秒間処理した。処理後の接着剤層面の状態を、目視にて観察し、接着剤層の発泡および流動の有無を判別し、〇：変化・異常なし、×：変化・異常あり、と評価した。
【００３５】
上記の表１の結果から、本発明の実施例１〜４の各接着シ―トは、接着強度、保持力（凝集力）およびハンダ耐熱性のいずれにもすぐれていることがわかる。これに対し、比較例１〜３の各接着シ―ト〔アクリル系共重合体の合成に際し、アルキル（メタ）アクリレ―トを主成分として使用〕は、電子部品用途での過酷な条件に用いるには、耐熱性および接着性ともに満足させることができない。また、比較例４の接着シ―ト（フエノキシエチルアクリレ―トの使用量が少なすぎる）は、電子部品用途での過酷な条件に用いるには、耐熱性を満足させることができない。さらに、比較例５の接着シ―ト（フエノキシエチルアクリレ―トの使用量が多すぎる）は、常温で粘着性を発現させることができない。
【００３７】
【発明の効果】
以上のように、本発明は、ホモポリマ―自体が大きな凝集力を発揮する特定の分子構造を持つアクリル系単量体と粘着性を発現させるための特定の単量体成分とからなる単量体混合物の粘着性共重合物を主剤成分として用いたことにより、常温で粘着性を示す接合材料として、電子部品に用いられる各種被着体に対して強固な接着性を示すとともに、実装時のハンダリフロ―に耐えうるすぐれた耐熱性を有し、しかも電子部品の腐食を発生させることのないアクリル系感圧性接着剤組成物とその接着シ―ト類を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an acrylic pressure-sensitive adhesive composition that is useful for fixing electronic parts and the like, and sheet and tape-like adhesive sheets using the same.
[0002]
[Prior art]
In recent years, various bonding materials have been used for fixing electronic parts and the like.
This type of application requires high heat resistance that can withstand solder reflow when mounting electronic components on a substrate, as well as strong adhesion. Further, along with the high reliability of electronic components, there are problems of malfunction and corrosion of electronic components due to contained impurities, volatile components, etc., and high-purity bonding materials are required.
[0003]
As a bonding material suitable for fixing such electronic parts, the present inventors have previously proposed a heat-adhesive composition that is not sticky at room temperature and exhibits adhesiveness upon heating (Japanese Patent Application No. Hei. 10-268854). According to this heat-adhesive composition, strong adhesiveness and high heat resistance can be exhibited by low pressure and short time heating, but there is no stickiness at room temperature (also called pressure-sensitive adhesiveness or tack). The adhesive cannot be used for applications that require stickiness.
[0004]
Various pressure-sensitive adhesives exhibiting tackiness at room temperature are known, and various acrylic pressure-sensitive adhesives are also used for bonding applications such as electronic parts. Acrylic pressure-sensitive adhesives are usually composed of an alkyl (meth) acrylate having an alkyl group having an average of 2 to 14 carbon atoms as the main component, and acrylic acid or the like added to improve the cohesive strength. An adhesive copolymer of a monomer mixture is used as a main ingredient component.
[0005]
However, such an acrylic pressure-sensitive adhesive has a problem that an acid component such as acrylic acid corrodes an electronic component even if the adhesiveness and cohesive force (heat resistance) can be satisfied. In addition, an adhesive copolymer using a monomer having a hydroxyl group or an amide group as a cohesive strength improving component without using an acid component such as acrylic acid as a main component has also been proposed. However, there was a problem that adhesiveness was insufficient, and cohesion and heat resistance were insufficient.
[0006]
[Problems to be solved by the invention]
In light of the above-described conventional circumstances, the present invention is a bonding material having adhesiveness at room temperature that is useful for fixing electronic parts and the like, has excellent adhesion, and has heat resistance that can withstand solder reflow during mounting. An object of the present invention is to provide an acrylic pressure-sensitive adhesive composition and an adhesive sheet thereof that do not corrode electronic components.
[0007]
[Means for Solving the Problems]
In the process of earnestly examining the above object, the present inventors first have an alkyl (meth) acrylate having an alkyl group having an average of 2 to 14 carbon atoms as a main component in the synthesis of an acrylic copolymer. As long as the copolymer does not contain a carboxyl group-containing monomer as a cohesive strength improving component, the cohesive strength is insufficient and the heat resistance is poor. It has been found that it is difficult to obtain a bonding material suitable for fixing applications such as.
[0008]
Based on this finding, the present inventors have continued further studies. As a result, instead of the alkyl (meth) acrylate having an alkyl group having an average of 2 to 14 carbon atoms as the main component, the homopolymer itself is used. Adhesive at room temperature by copolymerizing acrylic monomer with a specific molecular structure that exhibits a large cohesive force, and adding a specific monomer component to develop adhesiveness. As a bonding material that exhibits high flexibility, it is rich in flexibility, flexibility, and cohesiveness, and exhibits strong adhesion to various adherends used in electronic components, as well as excellent heat resistance, and electronic components The inventors have found that an acrylic pressure-sensitive adhesive composition and its adhesive sheet that do not cause corrosion are obtained, and the present invention has been completed.
[0009]
That is, the present invention provides the following formula (1);
[Chemical 2]
(Meth) acrylic acid ester represented by: 50 to 80% by weight, monoethylenically unsaturated monomer that is copolymerizable therewith and does not contain a carboxyl group in the molecule , and The monoethylenically unsaturated monomer is characterized by containing a cohesive copolymer of a monomer mixture containing an alkyl (meth) acrylate as an essential component so that the homopolymer has a glass transition temperature of −30 ° C. or lower. Acrylic pressure-sensitive adhesive composition (Claim 1), in particular, the above-mentioned pressure-sensitive adhesive composition is an acrylic pressure-sensitive adhesive composition having the above-described structure, which is a copolymer obtained by irradiation with radiation such as ultraviolet rays (claim) Item 2).
The present invention also provides adhesive sheets characterized by having a layer made of an acrylic pressure-sensitive adhesive composition having the above-described structure on one side or both sides of a base material (Claim 3) , particularly 180 ° peeling to an aluminum plate. The present invention relates to an adhesive sheet having the above-described configuration having an adhesive strength of 1,100 g / 20 mm width or more (Claim 4) and an adhesive sheet having the above-described configuration used for fixing electronic components (Claim 5) .
[0010]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the (meth) acrylic acid ester represented by the formula (1) is a homopolymer having a high glass transition point (Tg), and a typical example thereof is phenoxyethyl (meth) acrylate. Phenoxypropyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, nonylphenoxypropyl (meth) acrylate, and the like. Further, esters of ethylene oxide adducts such as phenol, cresol and nonylphenol, propylene oxide adducts (up to 3 addition moles) and acrylic acid or methacrylic acid are also preferably used. One or more of these are used.
[0011]
In the present invention, monoethylenically unsaturated monomers that can be copolymerized with the above (meth) acrylic acid ester and do not contain a carboxyl group in the molecule include ethyl (meth) acrylate and butyl (meth) acrylate. -Too, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, decyl (meta And alkyl (meth) acrylates such as acrylate and dodecyl (meth) acrylate. In addition, hydroxyalkyl (meth) acrylate, cyanoalkyl (meth) acrylate, (meth) acrylamide, substituted (meth) acrylamide, N-vinylcaprolactam, (meth) acrylonitrile, 2-methoxyethyl (meth) acrylate , Glycidyl (meth) acrylate, vinyl acetate and the like can also be used.
[0012]
Among such monoethylenically unsaturated monomers, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate are used from the viewpoint of reducing the glass transition temperature of the copolymer and exhibiting adhesiveness. Alkyl (meth) acrylates having a glass transition temperature of −30 ° C. or less of homopolymers such as —to, isooctyl (meth) acrylate, isononyl (meth) acrylate and the like are particularly preferable. One or more of these monoethylenically unsaturated monomers are used. Instead of such a monoethylenically unsaturated monomer that does not contain a carboxyl group in the molecule, monoethylenically unsaturated monomers that contain a carboxyl group in the molecule, acrylic acid, methacrylic acid, itaconic acid When crotonic acid or the like is used, problems such as corrosion of electronic parts occur, and thus cannot be used in the present invention.
[0013]
In the present invention, a monomer comprising the (meth) acrylic acid ester represented by the above formula (1) and a monoethylenically unsaturated monomer copolymerizable therewith and containing no carboxyl group in the molecule. A mixture of both components is used, but the proportion of both components is 50-80% by weight, preferably 60-75% by weight of the former (meth) acrylic acid ester as the main component, and the latter monoethylenically unsaturated The monomer should be 50 to 20% by weight, preferably 40 to 25% by weight. When the former (meth) acrylic acid ester, which is the main component, is less than 50% by weight, and the latter monoethylenically unsaturated monomer is more than 50% by weight, heat resistance is maintained in solder reflow when mounting electronic components. Can not do. On the other hand, if the latter monoethylenically unsaturated monomer is less than 20% by weight and the former (meth) acrylic acid ester is more than 80% by weight, adhesiveness at normal temperature cannot be expressed.
[0014]
In the present invention, the above monomer mixture is copolymerized to form an adhesive copolymer. For the copolymerization, an appropriate polymerization method such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, or a combination thereof can be adopted. In the copolymerization, a thermal polymerization initiator or a photopolymerization initiator is used as a polymerization catalyst, and potassium persulfate, ammonium persulfate, hydrogen peroxide, or a redox initiator composed of these and a reducing agent is used. It is done.
[0015]
Among the above polymerization methods, the bulk polymerization method by irradiation with radiation such as ultraviolet rays or electron beams is most preferable. According to this, there is no concern about corrosion of electronic components due to remaining organic solvent, swelling, peeling, slippage due to vaporization and expansion at high temperature, contamination due to emulsifier blades, poor adhesion, reduced moisture resistance, etc. By irradiating with weak ultraviolet light or the like, the molecular weight of the copolymer can be increased, and an adhesive copolymer having a high degree of crosslinking and a large cohesive force and having excellent heat resistance can be obtained.
[0016]
The acrylic pressure-sensitive adhesive composition of the present invention comprises a tacky copolymer obtained as described above as an essential component, and as an optional component, a tackifier, a plasticizer, a softener, a filler, a pigment Various conventionally known additives such as dyes and anti-aging agents can be contained. In addition, in order to improve the retention properties of the adhesive, a known cross-linking agent such as an isocyanate compound or an epoxy compound as a cross-linking agent, or trimethylolpropane tri (meth) when photopolymerization is performed. Multifunctional (meta) such as acrylate, pentaerythritol tetra (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate ) An acrylate may be contained.
[0017]
The amount of the crosslinking agent comprising the above-mentioned crosslinking agent or polyfunctional (meth) acrylate is usually 0.05 to 5 parts by weight, preferably 0.1 to 100 parts by weight of the monomer mixture. The range is preferably 3 parts by weight. In the polyfunctional (meth) acrylate, within the above range, it is preferable that the number of difunctionals is large, and the number of trifunctional or higher polyfunctionals is small. If the amount used is less than 0.05 parts by weight, the degree of cross-linking after copolymerization cannot be sufficiently increased, and the retention characteristics are liable to decrease. Conversely, if it exceeds 5 parts by weight, the elastic modulus becomes extremely high, It tends to cause poor adhesion such as poor adhesion.
[0018]
The adhesive sheet layer of the present invention is provided with a layer made of an acrylic pressure-sensitive adhesive composition containing the above-mentioned adhesive copolymer on one side or both sides of a base material, so It has a shape such as a cup. For the above layer, an adhesive copolymer is obtained in advance by an appropriate polymerization method, an acrylic pressure-sensitive adhesive composition is prepared by adding a cross-linking agent, etc., and this composition is applied onto a substrate. If necessary, it can be formed by a method of crosslinking by heating or the like. More preferably, a radiation-polymerizable composition prepared by adding a polyfunctional (meth) acrylate or the like to a monomer mixture before polymerization or a partial polymer thereof, is coated on a substrate, It is preferable to employ a method of irradiating and irradiating radiation such as ultraviolet rays, that is, a method of forming a layer at the same time as the synthesis of the adhesive copolymer. According to this, good results are obtained due to the heat resistance of the adhesive.
[0019]
As the base material, a synthetic resin film such as a polyester film, a non-peelable base material such as a fiber base material, and a peelable base material such as a release paper can be used. In the case of a peelable substrate, the layer made of the acrylic pressure-sensitive adhesive composition formed thereon may be finally transferred onto the non-peelable substrate. The adhesive sheets of the present invention include both those using such a non-peeling substrate as a substrate and those using a peelable substrate.
[0020]
The acrylic pressure-sensitive adhesive composition of the present invention and its adhesive sheet are a bonding material that exhibits tackiness at room temperature, and is rich in flexibility, flexibility, and cohesion, and strong against various adherends. In addition to exhibiting excellent adhesiveness, it has heat resistance that can withstand solder reflow during mounting, and does not contain corrosive components such as acrylic acid, so it can be used for fixing applications such as electronic parts. Can be used for various purposes.
[0021]
【Example】
Next, examples of the present invention will be described in more detail. In the following, “parts” means parts by weight.
[0022]
Example 1
In a reaction vessel equipped with a cooling tube, a nitrogen introducing tube, a thermometer, and a stirrer, 210 parts of ethyl acetate as a solvent, 70 parts of phenoxyethyl acrylate, 20 parts of butyl acrylate, hydroxyethyl acrylate 3 parts and 0.3 part of benzoyl peroxide were added and polymerized in a nitrogen stream to obtain a solution of an adhesive copolymer having a solid content of about 30% by weight. To this solution, 3 parts of a polyfunctional isocyanate crosslinking agent was uniformly mixed per 100 parts of the solid content to prepare a solution of an acrylic pressure-sensitive adhesive composition. Next, this solution was applied on a separator and dried at 130 ° C. for 5 minutes to form an adhesive layer having a thickness of 50 μm, thereby producing an adhesive sheet.
[0023]
Example 2
Into a four-necked flask, 70 parts of phenoxyethyl acrylate, 20 parts of butyl acrylate, 10 parts of acryloylmorpholine, 0.05 part of 2,2-dimethoxy-2-phenylacetophenone were added, The film was partially photopolymerized by exposure to ultraviolet light in a nitrogen atmosphere to obtain a syrup having a viscosity of about 30 poise. To 100 parts of this partially polymerized syrup, 0.3 part of 1,6-hexanediol diacrylate as a cross-linking agent was uniformly mixed to prepare a photopolymerizable composition. Next, this photopolymerizable composition is applied onto a separator and photopolymerized by irradiating with 900 mj / cm 2 of ultraviolet rays to form a layer made of an acrylic pressure-sensitive adhesive composition having a thickness of 50 μm. Thus, an adhesive sheet was produced.
[0024]
Example 3
In the same manner as in Example 2, except that 70 parts of phenoxyethyl acrylate was used, 70 parts of an ester of cresol with an ethylene oxide adduct (added mole number 1) and acrylic acid was used. A layer made of an acrylic pressure-sensitive adhesive composition having a thickness of 50 μm was formed to prepare an adhesive sheet.
[0025]
Example 4
Into a four-necked flask, 80 parts of phenoxyethyl acrylate, 20 parts of isononyl acrylate, 0.05 part of 2,2-dimethoxy-2-phenylacetophenone were added, and the atmosphere was nitrogen. Was partially exposed to UV light and partially photopolymerized to obtain a syrup having a viscosity of about 30 poise. To 100 parts of the partially polymerized syrup, 0.2 parts of trimethylolpropane triacrylate as a cross-linking agent was uniformly mixed to prepare a photopolymerizable composition. Next, this photopolymerizable composition is applied onto a separator and photopolymerized by irradiating with 900 mj / cm 2 of ultraviolet rays to form a layer made of an acrylic pressure-sensitive adhesive composition having a thickness of 50 μm. Thus, an adhesive sheet was produced.
[0026]
Comparative Example 1
In a reaction vessel equipped with a condenser, a nitrogen inlet tube, a thermometer, and a stirrer, 210 parts of ethyl acetate as a solvent, 60 parts of butyl acrylate, 30 parts of acrylonitrile, 10 parts of hydroxyethyl acrylate, benzoyl peroxide 0 .3 parts were added and polymerized in a nitrogen stream to obtain an acrylic copolymer solution having a solid content of about 30% by weight. To this solution, 3 parts of a polyfunctional isocyanate crosslinking agent was uniformly mixed per 100 parts of the solid content to prepare a solution of an acrylic pressure-sensitive adhesive composition. Next, this solution was applied on a separator and dried at 130 ° C. for 5 minutes to form an adhesive layer having a thickness of 50 μm, thereby producing an adhesive sheet.
[0027]
Comparative Example 2
In a four-necked flask, 60 parts of isooctyl acrylate, 40 parts of acryloyl morpholine, 0.05 part of 2,2-dimethoxy-2-phenylacetophenone are added and exposed to ultraviolet light in a nitrogen atmosphere. And partially photopolymerized to obtain a syrup having a viscosity of about 30 poise. To 100 parts of the partially polymerized syrup, 0.3 part of 1,6-hexanediol diacrylate as a cross-linking agent was uniformly mixed to prepare a photopolymerizable composition. Next, this photopolymerizable composition is applied onto a separator and photopolymerized by irradiating with 900 mj / cm 2 of ultraviolet rays to form a layer made of an acrylic pressure-sensitive adhesive composition having a thickness of 50 μm. Thus, an adhesive sheet was produced.
[0028]
Comparative Example 3
A four-necked flask was charged with 80 parts of ethyl acrylate, 20 parts of acryloylmorpholine, and 0.05 parts of 2,2-dimethoxy-2-phenylacetophenone, and partially exposed to ultraviolet light in a nitrogen atmosphere. To obtain a syrup having a viscosity of about 30 poise. To 100 parts of the partially polymerized syrup, 0.3 part of 1,6-hexanediol diacrylate as a cross-linking agent was uniformly mixed to prepare a photopolymerizable composition. Next, this photopolymerizable composition is applied onto a separator, photopolymerized by irradiating with 900 mj / cm 2 of ultraviolet rays, and a layer made of an acrylic pressure-sensitive adhesive composition having a thickness of 50 μm is formed. The adhesive sheet was formed.
[0029]
Comparative Example 4
Into a four-necked flask, 40 parts of phenoxyethyl acrylate, 50 parts of butyl acrylate, 10 parts of acryloylmorpholine, 0.05 part of 2,2-dimethoxy-2-phenylacetophenone are added, The film was partially photopolymerized by exposure to ultraviolet light in a nitrogen atmosphere to obtain a syrup having a viscosity of about 30 poise. To 100 parts of the partially polymerized syrup, 0.3 part of 1,6-hexanediol diacrylate as a cross-linking agent was uniformly mixed to prepare a photopolymerizable composition. Next, this photopolymerizable composition is applied onto a separator and photopolymerized by irradiating with 900 mj / cm 2 of ultraviolet rays to form a layer made of an acrylic pressure-sensitive adhesive composition having a thickness of 50 μm. Thus, an adhesive sheet was produced.
[0030]
Comparative Example 5
Into a four-necked flask, 90 parts of phenoxyethyl acrylate, 10 parts of butyl acrylate, 0.05 part of 2,2-dimethoxy-2-phenylacetophenone were added and exposed to ultraviolet light in a nitrogen atmosphere. Exposure and partial photopolymerization resulted in a syrup having a viscosity of about 30 poise. To 100 parts of the partially polymerized syrup, 0.3 part of 1,6-hexanediol diacrylate as a cross-linking agent was uniformly mixed to prepare a photopolymerizable composition. Next, this photopolymerizable composition is applied onto a separator and photopolymerized by irradiating with 900 mj / cm 2 of ultraviolet rays to form a layer made of an acrylic pressure-sensitive adhesive composition having a thickness of 50 μm. Thus, an adhesive sheet was produced.
[0031]
About each adhesive sheet of said Examples 1-4 and Comparative Examples 1-5, 180 degree peeling adhesive strength, holding power, and solder heat resistance were investigated with the following method. These results were as shown in Table 1.
[0032]
<180 ° peel strength>
An adhesive sheet with a width of 20 mm and a length of 50 mm is attached to a polyethylene terephthalate film (hereinafter referred to as PET film) with a thickness of 25 μm with a hand roller, and this is attached to each adherend with a 2 kg roller. Bonded in one round trip. The sample was allowed to stand for 30 minutes in an atmosphere at a temperature of 23 ° C. and a humidity of 65% RH, and then pulled in the 180 ° direction at a pulling speed of 300 mm / min.
[0033]
<Retention force>
Adhesive sheet cut to 15mm square was bonded between aluminum / aluminum (25mm x 50mm) at both ends with a 5kg roller, making a test piece, which was placed in an 80 ° C atmosphere for 30 minutes. I left it alone. Then, this test piece was suspended, a 1 kg load was applied to the lower end of one aluminum in an 80 ° C. atmosphere, and the shift distance after 2 hours was measured. In addition, the time was measured for those that fell.
[0034]
<Solder heat resistance>
The adhesive sheet is bonded to a 75 μm thick polyimide film with a laminator (temperature: 100 ° C., pressure: 5 kg / cm, speed: 2 m / min), cut into 50 mm squares, and separated. -The film was peeled off and treated for 60 seconds in a state where the adhesive layer surface was floated in a solder bath melted at 260 ° C. The state of the surface of the adhesive layer after the treatment was visually observed, and the presence or absence of foaming and flow of the adhesive layer was discriminated.
[0035]
From the results of Table 1 above, it can be seen that each of the adhesive sheets of Examples 1 to 4 of the present invention is excellent in all of adhesive strength, holding power (cohesive force) and solder heat resistance. In contrast, each of the adhesive sheets of Comparative Examples 1 to 3 (using an alkyl (meth) acrylate as a main component in the synthesis of an acrylic copolymer) is used for severe conditions in electronic component applications. However, neither heat resistance nor adhesiveness can be satisfied. Further, the adhesive sheet of Comparative Example 4 (the amount of phenoxyethyl acrylate used is too small) cannot satisfy the heat resistance when used in severe conditions for electronic parts. Furthermore, the adhesive sheet of Comparative Example 5 (the amount of phenoxyethyl acrylate used is too large) cannot exhibit tackiness at room temperature.
[0037]
【The invention's effect】
As described above, the present invention is a monomer composed of an acrylic monomer having a specific molecular structure in which the homopolymer itself exhibits a large cohesive force and a specific monomer component for expressing adhesiveness. By using the adhesive co-polymer of the mixture as the main ingredient component, it exhibits strong adhesion to various adherends used in electronic components as a bonding material that exhibits adhesiveness at room temperature, and solder reflow during mounting. It is possible to provide an acrylic pressure-sensitive adhesive composition and an adhesive sheet thereof that have excellent heat resistance that can withstand-and that does not cause corrosion of electronic components.
Claims (5)
で表される（メタ）アクリル酸エステル５０〜８０重量％と、これと共重合可能でかつ分子内にカルボキシル基を含有しないモノエチレン性不飽和単量体５０〜２０重量％とからなり、かつ上記のモノエチレン性不飽和単量体がホモポリマーのガラス転移温度が−３０℃以下となるアルキル（メタ）アクリレートを必須成分として含む単量体混合物の粘着性共重合物を含有することを特徴とするアクリル系感圧性接着剤組成物。The following formula (1);
(Meth) acrylic acid ester represented by: 50 to 80% by weight, monoethylenically unsaturated monomer that is copolymerizable therewith and does not contain a carboxyl group in the molecule , and The monoethylenically unsaturated monomer is characterized by containing a cohesive copolymer of a monomer mixture containing an alkyl (meth) acrylate as an essential component so that the homopolymer has a glass transition temperature of −30 ° C. or lower. An acrylic pressure-sensitive adhesive composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11160299A JP4516632B2 (en) | 1999-04-20 | 1999-04-20 | Acrylic pressure-sensitive adhesive composition and its adhesive sheets |
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| Application Number | Priority Date | Filing Date | Title |
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| JP11160299A JP4516632B2 (en) | 1999-04-20 | 1999-04-20 | Acrylic pressure-sensitive adhesive composition and its adhesive sheets |
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| Publication Number | Publication Date |
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| JP2000303045A JP2000303045A (en) | 2000-10-31 |
| JP4516632B2 true JP4516632B2 (en) | 2010-08-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP11160299A Expired - Fee Related JP4516632B2 (en) | 1999-04-20 | 1999-04-20 | Acrylic pressure-sensitive adhesive composition and its adhesive sheets |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004128457A (en) * | 2002-10-02 | 2004-04-22 | Atotech Deutsche Gmbh | Micro-structure cooler and its usage |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100707745B1 (en) * | 1999-10-28 | 2007-04-17 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | High refractive index pressure sensitive adhesive |
| JP2008297419A (en) * | 2007-05-31 | 2008-12-11 | Daio Paper Corp | Adhesive sheet for electronic display |
| JP5209947B2 (en) * | 2007-12-13 | 2013-06-12 | 東京応化工業株式会社 | Adhesive treatment method |
| JP5480477B2 (en) | 2008-05-23 | 2014-04-23 | 日東電工株式会社 | Adhesive composition, adhesive sheet and method for producing the same |
| JP5281318B2 (en) | 2008-05-23 | 2013-09-04 | 日東電工株式会社 | Adhesive composition and adhesive sheet for metal surface sticking |
| JP5342174B2 (en) | 2008-05-23 | 2013-11-13 | 日東電工株式会社 | Adhesive composition and use thereof |
| JP2010229246A (en) * | 2009-03-26 | 2010-10-14 | Daio Paper Corp | Pressure-sensitive adhesive sheet |
| WO2011090090A1 (en) * | 2010-01-21 | 2011-07-28 | 日本合成化学工業株式会社 | Adhesive agent, adhesive agent for optical member, optical member having adhesive layer attached thereto, image display device, active-energy-ray- and/or heat-curable adhesive agent composition, and adhesive agent composition |
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| JP2602888B2 (en) * | 1988-04-04 | 1997-04-23 | ミネソタ マイニング アンド マニユフアクチユアリング カンパニー | Adhesive sheet |
| WO1997043352A1 (en) * | 1996-05-16 | 1997-11-20 | Minnesota Mining And Manufacturing Company | Adhesive compositions and methods of use |
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| JPH0230353B2 (en) * | 1982-05-11 | 1990-07-05 | Kanzaki Paper Mfg Co Ltd | KANATSUSETSUCHAKUZAISOSEIBUTSU |
| JPH02248482A (en) * | 1989-03-23 | 1990-10-04 | Fujikura Kasei Co Ltd | Photocurable pressure-sensitive adhesive composition |
| JPH06340851A (en) * | 1993-06-02 | 1994-12-13 | Sekisui Chem Co Ltd | Pressure-sensitive adhesive tape or sheet having thin metal layer |
| JP3385869B2 (en) * | 1996-09-10 | 2003-03-10 | 東洋インキ製造株式会社 | Radiation-curable liquid resin composition |
| JPH10287823A (en) * | 1997-04-15 | 1998-10-27 | Kansai Paint Co Ltd | Active energy beam-curable resin composition and coating formation of the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2602888B2 (en) * | 1988-04-04 | 1997-04-23 | ミネソタ マイニング アンド マニユフアクチユアリング カンパニー | Adhesive sheet |
| WO1997043352A1 (en) * | 1996-05-16 | 1997-11-20 | Minnesota Mining And Manufacturing Company | Adhesive compositions and methods of use |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004128457A (en) * | 2002-10-02 | 2004-04-22 | Atotech Deutsche Gmbh | Micro-structure cooler and its usage |
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| JP2000303045A (en) | 2000-10-31 |
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