JP4097454B2 - Surface-reactive functional group-modified adhesive and adhesive tape or sheet - Google Patents

Description

（反応式（１）において、Ｒは水素原子又は有機基を示す）
【００４６】
反応式（１）において、Ｒの有機基としては、アルキル基（例えば、メチル基、エチル基、プロピル基、ブチル基など）、シクロアルキル基、アリール基などの炭化水素基などが挙げられる。なお、アミノ基が第１級アミノ基である場合［例えば、反応式（１）において、Ｒが水素原子である場合］、２つのビニル基が第１級アミノ基と反応されていてもよいが、第１級アミノ基には、１つのビニル基のみが反応していることが好ましい。
【００４７】
アミノ基反応性官能基含有化合物（ｃ）としてのビニル基含有化合物としては、ビニル基を構成する炭素原子の少なくとも一方の炭素原子に、電子吸引性基が結合したビニル基を含有する化合物を好適に用いることができる。ビニル基含有化合物としては、例えば、アクリル酸エステル、メタクリル酸エステル、クロトン酸エステル、イソクロトン酸エステル、２−ブテン酸エステル、３−メチル−２−ブテン酸エステル、２−ペンテン酸エステル、２−ヘキセン酸エステル、２−オクテン酸エステル、オレイン酸エステル、桂皮酸エステル等のビニル基含有モノカルボン酸エステル類；マレイン酸ジエステル、フマル酸ジエステル、イタコン酸ジエステル等のビニル基含有ジカルボン酸ジエステル類などのビニル基含有カルボン酸エステル系化合物を用いることができる。該ビニル基含有カルボン酸エステル系化合物において、エステル部位としては、メチルエステル、エチルエステル、プロピルエステル、イソプロピルエステル、ブチルエステル、イソブチルエステル、ｓ−ブチルエステル、ｔ−ブチルエステル、ペンチルエステル、イソペンチルエステル、ヘキシルエステル、ヘプチルエステル、２−エチルヘキシルエステル、オクチルエステル、イソオクチルエステル、ノニルエステル、イソノニルエステル、デシルエステル、イソデシルエステル、ラウリルエステル、ステアリルエステル等のＣ_1-30アルキルエステル（好ましくはＣ_1-20アルキルエステル）；シクロヘキシルエステル等のシクロアルキルエステル；フェニルエステル、ベンジルエステル等のアリールエステルなどが挙げられる。なお、エステル部位を複数有する場合、それぞれのエステル部位は、同一であってもよく異なっていてもよい。
【００４８】
ビニル基含有化合物としては、アクリル酸エステル、メタクリル酸エステル［これらを「（メタ）アクリル酸エステル」と称する場合がある］が好ましい。具体的には、（メタ）アクリル酸エステルとしては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓ−ブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸イソペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ステアリルなどが挙げられる。
【００４９】
ビニル基含有化合物としては、（メタ）アクリル酸エステルのなかでも、アクリル酸Ｃ_1-20アルキルエステル（さらにはアクリル酸Ｃ_2-10アルキルエステル）が好ましく、特に、アクリル酸ブチル、アクリル酸２−エチルヘキシル、アクリル酸イソオクチルおよびアクリル酸イソノニルから選択された少なくとも一種のアクリル酸アルキルエステルが好適である。
【００５０】
アミノ基含有ポリマー（Ａ）の調製方法（１）において、アミノ基を有する高分子（ｂ）と、アミノ基反応性官能基含有化合物（ｃ）（例えば、ビニル基含有化合物）とを反応させる際の、アミノ基を有する高分子（ｂ）と、アミノ基反応性官能基含有化合物（ｃ）との割合としては、アミノ基を有する高分子（ｂ）における少なくとも一部のアミノ基が、アミノ基反応性官能基含有化合物（ｃ）におけるアミノ基反応性官能基（例えば、ビニル基）と反応する割合であればよいが、アミノ基を有する高分子（ｂ）におけるアミノ基が残存するような割合であることが好ましい。例えば、アミノ基を有する高分子（ｂ）における全アミノ基に対して、アミノ基反応性官能基含有化合物（ｃ）（ビニル基含有化合物など）におけるアミノ基反応性官能基（ビニル基など）が０．０５〜１．０当量であってもよく、また、０．２〜０．８当量（さらに好ましくは０．４〜０．６当量）となるような割合であることが望ましい。
【００５１】
なお、アミノ基を有する高分子（ｂ）と、アミノ基反応性官能基含有化合物（ｃ）とを混合し、必要に応じて加熱等を行うことにより、アミノ基を有する高分子（ｂ）におけるアミノ基と、アミノ基反応性官能基含有化合物（ｃ）のアミノ基反応性官能基との反応を行うことができる。
【００５２】
また、アミノ基含有ポリマー（Ａ）の調製方法（２）において、分子内におけるアミノ基の水素原子が、原子数が５以上の有機基で置換されているアミノ基含有モノマーとしては、例えば、前記アミノ基を有する高分子（ｂ）のモノマー成分としてのアミノ基含有モノマー［例えば、アリルアミン、ビニルアミン等の第１級又は第２級アミノ基含有ビニルモノマー；エチレンイミン等のアジリジン化合物；アミノエチルアクリレート、アミノプロピルアクリレート、アミノエチルメタクリレート、アミノプロピルメタクリレート等のアミノアルキル基含有（メタ）アクリレートなど］のアミノ基と、前記アミノ基反応性官能基含有化合物（ｃ）（例えば、アクリル酸エステル、メタクリル酸エステル、クロトン酸エステル、イソクロトン酸エステル、２−ブテン酸エステル、３−メチル−２−ブテン酸エステル、２−ペンテン酸エステル、２−ヘキセン酸エステル、２−オクテン酸エステル、オレイン酸エステル、桂皮酸エステル等のビニル基含有モノカルボン酸エステル類；マレイン酸ジエステル、フマル酸ジエステル、イタコン酸ジエステル等のビニル基含有ジカルボン酸ジエステル類などのビニル基含有カルボン酸エステル系化合物など）のアミノ基反応性官能基（例えば、ビニル基など）との反応により得られるアミノ基含有モノマーを用いることができる。
【００５３】
他のアミノ基含有モノマーとしては、例えば、前記アミノ基を有する高分子（ｂ）のモノマー成分としてのアミノ基含有モノマー［例えば、アリルアミン、ビニルアミン等の第１級又は第２級アミノ基含有ビニルモノマー；エチレンイミン等のアジリジン化合物；アミノエチルアクリレート、アミノプロピルアクリレート、アミノエチルメタクリレート、アミノプロピルメタクリレート等のアミノアルキル基含有（メタ）アクリレートなど］を用いることができる。
【００５４】
従って、本発明では、アミノ基含有ポリマー（Ａ）としては、ポリアリルアミン、ポリビニルアミン又はポリエチレンイミンにおけるアミノ基と、（メタ）アクリル酸エステルなどのビニル基含有化合物におけるビニル基との反応により得られる、原子数が５以上の有機基を有するアミノ基を含有しているポリアリルアミン、ポリビニルアミン又はポリエチレンイミンを好適に用いることができる。
【００５５】
アミノ基修飾層４を形成するための界面接触反応は、例えば、粘着剤層３を構成するベースポリマーや反応性官能基含有化合物等を含む固体相又は液体相（粘着剤相）と、アミノ基修飾層４を構成するアミノ基含有ポリマー（Ａ）を含有する液体相との間で行わせることができる。粘着剤相と、アミノ基修飾層４を構成するアミノ基含有ポリマー（Ａ）を含有する液体相とを界面接触反応させる方法としては、両相をディッピング、浸漬により接触させる方法、グラビア、キスなどのロールコーティング、ファンテンなどのダイスコーティング、スクイズコーティング、スピンコーティングなどの公知乃至慣用の塗布方式により粘着剤相に前記液体相を塗布する方法、スプレーなどで粘着剤相に前記液体相を噴霧塗布する方法などの何れの方法であってもよい。
【００５６】
なお、粘着剤表面に高密度にアミノ基を導入するためには、アミノ基修飾層４を構成するアミノ基含有ポリマー（Ａ）を含有する液体相の媒体が粘着剤相を溶解又は膨潤させるのは好ましくなく、例えば、粘着剤がアクリル系の場合には、水やアルコール、ヘキサン、ヘプタンのような粘着剤相を溶解又は膨潤させない溶媒を適宜選択して使用することが望ましい。
【００５７】
このようにして粘着剤層３の表面に形成されるアミノ基修飾層４の厚さとしては、粘着剤層３の粘着特性等を損なわない範囲で適宜選択できるが、一般には１μｍ以下（例えば０．００１〜１μｍ程度）、好ましくは０．１μｍ以下（例えば０．００１〜０．１μｍ程度）である。
【００５８】
このように、アミノ基修飾層４を粘着剤層３の表面に導入することにより、被着体、特に、酸性の表面状態を有する被着体に対して強い接着性を示すようになる。また、粘着剤層３の表面に導入されたアミノ基修飾層４のアミノ基の高反応性を利用して、さらに、界面接触反応を施して、別種（又は他種）の反応性官能基を導入することも可能である。このように、別種の反応性官能基を導入することにより、被着体の種類に応じて、所望の接着強度に容易に調整することができる。別種の反応性官能基としては、被着体に対する接着反応性を示す官能基であることが好ましい。
【００５９】
図２は本発明の表面反応性官能基修飾粘着剤からなる粘着剤層を備えた粘着テープ又はシートの他の例を示す概略断面図である。この粘着テープ又はシート１１では、基材２の一方の面に粘着剤層３が設けられており、該粘着剤層３の表面を、アミノ基含有ポリマー（Ａ）で界面接触反応により被覆することによって、アミノ基を含有するアミノ基修飾層４が形成され、さらにこの上に、アミノ基修飾層４のアミノ基を利用した界面接触反応により、アミノ基以外の（別種の）反応性官能基を含有する第２の反応性官能基修飾層（第２官能基修飾層）５が形成されている。図２において、基材２、粘着剤層３およびアミノ基修飾層（アミノ基含有ポリマー（Ａ）層）４については前記図１と同様である。
【００６０】
前記別種の反応性官能基（すなわち、第２官能基修飾層５中の反応性官能基）の具体的な例としては、例えば、カルボキシル基、ヒドロシリル基、ヒドロキシル基、アルコキシシリル基、シラノール基、ビニル基などが挙げられる。被着体がガラス等の場合、粘着剤表面がアルコキシシリル基やシラノール基で修飾されると、それらが経時的にガラス表面のシラノール基と反応して化学結合を形成し、大きな接着強度が発現する。また、被着体がステンレス等の金属やメラミン樹脂塗膜などの場合、接着反応性官能基としてカルボキシル基などを用いると、経時により大きな接着強度が発現する。
【００６１】
界面接触反応が可能な２つの反応性官能基の組み合わせは前記と同様である。第２官能基修飾層５を形成するのに用いる反応性官能基含有化合物としては、前記アミノ基修飾層４のアミノ基含有ポリマー（Ａ）と界面接触反応が可能な反応性基と、アミノ基以外の反応性官能基（別種の反応性官能基）とを含有する反応性官能基含有化合物を用いることができる。さらに、この第２官能基修飾層５の形成に用いる反応性官能基含有化合物としては、粘着剤層３の粘着特性（初期粘着特性）を損なわない化合物であることも重要である。なお、第２官能基修飾層５を形成するのに用いる反応性官能基含有化合物において、前記２つの反応性官能基（すなわち、界面接触反応が可能な反応性官能基と、別種の反応性官能基と）は同一であっても異なっていてもよい。第２官能基修飾層５の形成に用いる反応性官能基含有化合物としては、アミノ基に対して高い反応性を示すイソシアネート基、酸ハライド基（酸クロライド基など）、エポキシ基、酸無水物基又はカルボキシル基を含有し、且つカルボキシル基、ヒドロキシル基、アルコキシシリル基、シラノール基、ビニル基などの被着体表面と反応可能な所望の接着反応性官能基を含有するポリマーを用いることができる。
【００６２】
なお、アミノ基修飾層４上に第２官能基修飾層５を形成する方法は、前記粘着剤層３の上にアミノ基修飾層４を形成する方法に準じて行うことができる。従って、第２官能基修飾層５の形成に用いる反応性官能基含有化合物と、アミノ基修飾層４の形成に用いるアミノ基含有ポリマー（Ａ）と界面接触反応は、前記の方法に準じて行うことができる。このように、アミノ基修飾層４に含まれるアミノ基の高い反応性を利用して、再度界面接触反応を施すことにより、別種の反応性官能基を最表層に固定することができる。最表層である第２官能基修飾層５の厚さとしては、粘着剤層３の粘着特性等を損なわない範囲で適宜選択できるが、一般には０．００１〜１０μｍ、好ましくは０．００１〜５μｍ程度である。
【００６３】
上記の図１及び図２の例では、アミノ基修飾層４や第２官能基修飾層５などの反応性官能基を含む官能基修飾層は１層又は２層で構成されているが、界面接触反応を同様にして繰り返すことにより、必要に応じて官能基修飾層を３層以上の層で構成することも可能である。また、上記の各例では、基材２の片面に粘着剤層及び官能基修飾層が形成されているが、基材２の他方の面にも粘着剤層、又は粘着剤層と官能基修飾層を設けて両面粘着テープ又はシートとしてもよい。
【００６４】
本発明の粘着剤、及び粘着テープ又はシートによれば、もとの粘着剤が有する初期の高い粘着性を効果的に保持しているので貼り付け作業を確実にできるとともに、粘着剤の最表面が界面接触反応により接着反応性を示す官能基（アミノ基など）で修飾されているので、該官能基が内部拡散することなく被着体表面と化学的に結合し、経時的に接着力がさらに上昇していき、最終的には極めて強固な接着となる。なお、本発明では、被着体に貼り付け後は室温で放置しておくだけで接着力を経時的に上昇させることができるので、加熱やＵＶ（紫外線）等の外部エネルギーを印加する必要はないが、接着力の経時上昇を加速させたい場合には、加熱など熱エネルギー等を印加してもよい。また、本発明では、基材やベース粘着剤（ベースポリマー）として適切なものを選択することにより、充分な耐久性、耐熱性を有する粘着テープ又はシートとすることができる。
【００６５】
本発明は、あらゆる種類の粘着テープ又はシート全般に適用可能であるが、その中でも特に、金属、ガラス、プラスチック材料等に用いる接合用両面テープなど、強固な接合力（大きな接着強度）が必要とされ且つ貼り付け初期から高い接着強度が求められる用途に使用される強接着性粘着テープ又はシートとして有用である。
【００６６】
【実施例】
以下に実施例を挙げて本発明を具体的に説明するが、本発明はこれら実施例により何ら限定されるものではない。
【００６７】
製造例１（アクリル系粘着剤溶液の調製）
フラスコに、ブチルアクリレート１９０ｇ、アクリル酸１０ｇ、重合開始剤としてアゾビスイソブチロニトリル０．４ｇ、溶媒として酢酸エチル３００．６ｇを仕込み、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の温度を６０℃に上げた。数分後、発熱が始まり、フラスコ内の温度を６０℃に保つよう外浴をコントロールした。重合開始約３時間後、８３．５ｇの酢酸エチルをフラスコ内に滴下し、３時間重合を続けた。その後、さらに８３．５ｇの酢酸エチルをフラスコ内に滴下してから、フラスコ内の温度を８０℃まで上げて、２時間重合し、固形分濃度３０重量％のアクリル系粘着剤溶液を調製した。ＧＰＣ（ゲルパーミエーションクロマトグラフィー）により測定した結果、得られたポリマーの重量平均分子量（Ｍｗ）はポリスチレン換算で１３０万であった。
【００６８】
製造例２（アクリル系粘着テープＡの作製）
製造例１で得られたアクリル系粘着剤溶液に対し、その固形分１００重量部あたり、商品名「コロネートＬ」［日本ポリウレタン工業（株）製、トリメチロールプロパンへの２，４−トリレンジイソシアネート付加化合物７５重量％酢酸エチル溶液］を３重量部（固形分換算）配合した。これをコロナ処理を施した厚さ３８μｍのポリエステルフィルム上に、乾燥後の厚さが４０μｍとなるようにアプリケーターを用いて塗布し、乾燥機にて８０℃で５分間乾燥させて溶媒を揮散させて粘着テープを作製した。この粘着テープを“粘着テープＡ”とする。
【００６９】
製造例３（原子数が５以上の有機基を有するアミノ基を含有しているアミノ基含有ポリマーの調製）
商品名「ＰＡＡ−１０Ｃ」（日東紡績社製；ポリアリルアミンの濃度が１０重量％であるポリアリルアミン水溶液）５０重量部に、イソプロピルアルコール（溶剤）５０．８重量部を添加し攪拌して希釈したところに、ポリアリルアミンのアミノ基の１／２当量に相当するビニル基を有するブチルアクリレート５．７重量部を、攪拌しながら約１０分かけて滴下した。滴下終了後、室温で１日間放置して、ブチルアクリレートのビニル基へのポリアリルアミンのアミノ基の付加反応（マイケル付加反応）を行った。該付加反応終了後、反応生成物の¹Ｈ−ＮＭＲ分析を行ったところ、図３に示されるスペクトル（ＮＭＲスペクトル）が得られた。この図３に示されるＮＭＲスペクトルでは、ブチルアクリレートの二重結合はすべて消失していた。また、２．８３ｐｐｍと、２．５６ｐｐｍとの積分値から、ブチルアクリレート単位と、アリルアミン単位とのモル比を定量したところ、ブチルアクリレート単位：アリルアミン単位＝５２：４８（モル比）であった。これにより、前記式（１）で表されるアミノ基と、ビニル基との反応（付加反応）が定量的に進行したことが確認された。従って、前記反応により、２−ブトキシカルボニルエチルアミノ基および第１級アミノ基を含有しているポリアリルアミンが調製された。すなわち、原子数が５以上の有機基を有するアミノ基および第１級アミノ基を含有しているポリアリルアミンが調製された。
【００７０】
なお、¹Ｈ−ＮＭＲ分析の条件は次のとおりである。
装置：日本電子社製「ＥＸ−４００」
観測周波数：４００ＭＨｚ
パルス幅：４５°
ケミカルシフト基準：３．３ｐｐｍ
測定溶媒：ＣＤ₃ＯＤ
測定温度：室温（２０〜２５℃）
測定方法：ダブルホモゲートデカップリング法
【００７１】
そして、この反応混合物溶液１重量部に対して、イソプロピルアルコール１５０重量部と、水３４９重量部とを加えて攪拌することにより、２−ブトキシカルボニルエチルアミノ基を含有しているポリアリルアミンの濃度が０．０２重量％の溶液を調製した。この２−ブトキシカルボニルエチルアミノ基および第１級アミノ基を含有しているポリアリルアミンの濃度が０．０２重量％の溶液を、“ブチルアクリレート付加ポリアリルアミン溶液Ａ”とする。
【００７２】
実施例１
粘着テープＡを作製し、その直後に（粘着剤中のイソシアネート基が活性なうちに）続けて、製造例３で得られたブチルアクリレート付加ポリアリルアミン溶液Ａ中に１分間浸漬した後、６０ｍｍ／ｍｉｎの速度で垂直方向に引き上げ、表面を４０℃のオーブンで乾燥させた後、その粘着剤面が他の物質に触れないように室温で７日間以上放置した。この粘着テープを、“粘着テープＢ”とする。
【００７３】
比較例１
“粘着テープＡ”を作製した後、何の表面処理も施さず、その粘着剤面が他の物質に触れないように室温で７日間放置した。
【００７４】
比較例２
粘着テープＡを作製し、その直後に（粘着剤中のイソシアネート基が活性なうちに）続けて、ポリアリルアミン（商品名「ＰＡＡ−１０Ｃ」日東紡績社製）の０．０２重量％水溶液中に１分間浸漬した後、６０ｍｍ／ｍｉｎの速度で垂直方向に引き上げ、表面を室温で自然乾燥させた後、その粘着剤面が他の物質に触れないように室温で７日間以上放置した。この粘着テープを、“粘着テープＣ”とする。
【００７５】
以下に、粘着テープとしての接着力評価の結果を示す。
（初期接着強度評価）
実施例１及び比較例１〜２における粘着テープＡ、Ｂ、Ｃについて、それぞれ、対ＳＵＳ３０４ＢＡ板、および対ポリエステルワニス塗装スズメッキ鉄板（ポリエステルワニス塗装板）についての初期接着強度評価を行った。なお、ＳＵＳ３０４ＢＡ板としては、市販のＳＵＳ３０４ＢＡ板を使用した。また、ポリエステルワニス塗装板としては、スズメッキ鉄板の表面を日東電工社製の商品名「ポリエステルワニスＮＶ−５４３」で塗装したものを用いた。
【００７６】
ＳＵＳ３０４ＢＡ板、ポリエステルワニス塗装板に、それぞれ、幅２０ｍｍに切り出した粘着テープを貼り付け、２ｋｇのゴムローラーを用いて一往復圧着した。このサンプルを貼り付け３０分後に、引張試験機にて３００ｍｍ／ｍｉｎの引き剥がし速度で、１８０°剥離強度（Ｎ／２０ｍｍ）を測定した。結果を表１に示した。
【００７７】
【表１】

【００７８】
本発明に該当する、２−ブトキシカルボニルエチルアミノ基および第１級アミノ基を含有しているポリアリルアミンを用いてアミノ基修飾処理を施した“粘着テープＢ”（実施例１）は、もとの“粘着テープＡ”（比較例１）の初期接着能力と比べて、７０％以上の初期接着能力を有することがわかる。一方、２−ブトキシカルボニルエチルアミノ基を含有していないポリアリルアミンを用いてアミノ基修飾処理を施した“粘着テープＣ”（比較例２）では、低い初期接着能力を示している。
【００７９】
（経時後接着強度評価）
実施例１及び比較例１〜２における粘着テープＡ、Ｂ、Ｃについて、それぞれ、対ＳＵＳ３０４ＢＡ板、および対ポリエステルワニス塗装スズメッキ鉄板（ポリエステルワニス塗装板）についての経時後接着強度評価を行った。なお、ＳＵＳ３０４ＢＡ板としては、市販のＳＵＳ３０４ＢＡ板を使用し、ポリエステルワニス塗装板としては、スズメッキ鉄板の表面を日東電工社製の商品名「ポリエステルワニスＮＶ−５４３」で塗装したものを用いた。
ＳＵＳ３０４ＢＡ板、ポリエステルワニス塗装板に、それぞれ、幅２０ｍｍに切り出した粘着テープを貼り付け、２ｋｇのゴムローラーを用いて一往復圧着した。このサンプルを貼り付け後、経日促進試験として５０℃で３日間加熱したのちに、引張試験機にて３００ｍｍ／ｍｉｎの引き剥がし速度で、１８０°剥離強度を測定した。結果を表２に示した。
【００８０】
【表２】

【００８１】
本発明に該当する、２−ブトキシカルボニルエチルアミノ基および第１級アミノ基を含有しているポリアリルアミンを用いてアミノ基修飾処理を施した“粘着テープＢ”（実施例１）の経日促進試験後の対ＳＵＳ３０４ＢＡ板および対ポリエステルワニス塗装板の接着強度は、表面未処理の“粘着テープＡ”（比較例１）のそれに比べて同等（対ＳＵＳ３０４ＢＡ板）または非常に大きい値（対ポリエステルワニス塗装板）を示した。なお、表中の対ポリエステルワニス塗装板の接着強度に関する欄で、＞２４．５とは、測定値が２４．５Ｎ／２０ｍｍを超えた時点で、粘着剤とポリエステルワニス塗装板との界面が剥がれないで、粘着剤とポリエステル基材の界面で投錨破壊したことを示すものである。つまり、粘着剤とポリエステルワニス塗装板とがそれらの値以上の力で強固に接着していることを表している。これは、ポリエステルワニス塗装板表面に残存する官能基と、粘着剤表面のアミノ基が化学的に反応して、強固な結合を形成していることを示唆するものである。
【００８２】
これら前述のすべての結果を考えあわせると、実施例１の“粘着テープＢ”は、もとの“粘着テープＡ”表面に柔軟性に富むアミノ基修飾層が固定されており、さらには、もとの“粘着テープＡ”の初期粘着力を維持し、しかも、経時でポリエステルワニス塗装板に対して高い接着強度を発揮することができる。
【００８３】
【発明の効果】
本発明によれば、粘着剤の最表面の柔軟性のため、もとの粘着剤が有する初期の高い粘着性を保持しているので貼り付け作業を確実にできる。また、粘着剤表面が接着反応性を示すアミノ基で修飾されているので、該アミノ基と被着体表面とが化学的に結合し、経時的に接着力がさらに上昇していき、最終的には極めて高い接着強度が得られる。
【図面の簡単な説明】
【図１】本発明の粘着テープ又はシートの一例を示す概略断面図である。
【図２】本発明の粘着テープ又はシートの他の例を示す概略断面図である。
【図３】製造例３において、反応終了後の反応生成物の¹Ｈ−ＮＭＲ分析により得られたＮＭＲスペクトルを示す図である。
【符号の説明】
１，11 粘着テープ又はシート
２ 基材
３ 粘着剤層
４ 官能基修飾層
５ 第２官能基修飾層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a pressure-sensitive adhesive and a pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet provided with a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive. More specifically, the present invention relates to a pressure-sensitive adhesive and pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet that has been subjected to amino group modification exhibiting high reactivity on the pressure-sensitive adhesive surface without impairing the initial adhesive force of the pressure-sensitive adhesive. In addition, the present invention relates to a pressure-sensitive adhesive and a pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet that exhibit a strong bonding force by increasing the adhesive strength with the elapse of time after being attached to a specific adherend.
[0002]
[Prior art]
Adhesive tape or adhesive sheet can be easily attached to an adherend by simply applying pressure at the time of bonding, so it can be applied to various adherends such as metal, glass, resin coating, wood, paper, and plastic materials. Widely used for bonding. In these pressure-sensitive adhesive tapes or pressure-sensitive adhesive sheets, a pressure-sensitive adhesive showing an adhesive strength suitable for the intended use is used. For example, in the case of a masking tape, a surface protection tape, and the like, the adhesive is re-peeled after being applied, so that an adhesive having low adhesive strength is used. Further, in the case of a double-sided adhesive tape such as metal, glass, wood, and plastic material, a strong adhesive force (high adhesive strength) is required, and thus a pressure-sensitive adhesive having high adhesive strength is used.
[0003]
On the other hand, an amino group is a functional group rich in reactivity, and shows high adhesiveness or low adhesiveness depending on the type of adherend, so that it has a desired adhesive strength depending on the type of adherend. It is a functional group suitable for adjustment. Further, by utilizing the high reactivity of the amino group introduced on the adhesive surface, it is possible to modify it to other (other) functional groups. Since the adhesive strength can be adjusted, the functional group is also suitable from this point.
[0004]
As a method of modifying the surface of the pressure-sensitive adhesive with an amino group, the inside of the bulk layer of the pressure-sensitive adhesive itself, such as a method of copolymerizing a monomer containing an amino group in the main component of the pressure-sensitive adhesive, or a method of compounding a compound containing an amino group There is a method of introducing an amino group. However, these methods have problems such as insufficient concentration of amino groups on the surface and contamination of the adherend due to bleeding of compounding components (compounds containing amino groups).
[0005]
Also known are a method of applying a dilute solution of an amino group-containing compound to the pressure-sensitive adhesive surface, a method using means for modifying the plastic film surface such as corona discharge treatment, plasma treatment, and radiation treatment. Even in the method, there is a problem that the concentration of amino groups on the surface becomes insufficient, or the amino groups are not fixed on the surface and are internally diffused over time, and the effect is lost.
[0006]
As a method for solving these problems, Japanese Patent Application Laid-Open No. 10-46112 proposes a method of stably introducing a desired functional group only on the pressure-sensitive adhesive surface of the pressure-sensitive adhesive tape and sheet using an interfacial contact reaction. .
[0007]
[Problems to be solved by the invention]
However, the pressure-sensitive adhesive tape or sheet modified with the surface-reactive functional group by the method described in, for example, the example of the above-mentioned document can finally obtain a strong adhesive strength due to the change over time after the application, but the pressure-sensitive adhesive layer Since the outermost surface is covered with a thin layer of the functional group-containing compound, the adhesive strength of the surface is reduced, and the initial adhesive strength is weakened. This property is very effective in applications that require so-called reworkability that can be temporarily fixed and reattached, but on the other hand, it cannot be applied in applications that require high adhesiveness from the beginning of application. There was a problem.
[0008]
Further, as a method for solving this problem, for example, a method described in JP 2001-323247 A has been proposed. JP-A-2001-323247 discloses an acrylic monomer, a primary or secondary amino group which can be copolymerized with the acrylic monomer and contains a primary or secondary amino group or is polymerized. A method is described in which a pressure-sensitive adhesive surface is functionally modified with a copolymer with a monomer capable of generating a group. However, there is a demand for a pressure-sensitive adhesive that can be more effectively maintained without impairing the high pressure-sensitive adhesive properties that the pressure-sensitive adhesive originally has.
[0009]
The present invention overcomes such problems of the prior art, effectively maintains the high adhesive properties of the adhesive initially possessed by the adhesive, and exhibits strong adhesion to the adherend after application. It aims at providing an adhesive and an adhesive tape or an adhesive sheet. In particular, it is an object of the present invention to provide a pressure-sensitive adhesive, a pressure-sensitive adhesive tape, or a pressure-sensitive adhesive sheet that adheres strongly to a specific adherend as the adhesive force further increases with time.
[0010]
[Means for Solving the Problems]
As a result of diligent studies to achieve the above object, the present inventors made use of an interfacial contact reaction between a pressure-sensitive adhesive phase and a phase containing an amino group-containing compound to modify the surface of the pressure-sensitive adhesive with an amino group. As an amino group-containing compound, by performing an interface contact reaction using an amino group-containing polymer containing an amino group having a specific organic group and coating with the amino group-containing polymer, Adhesive reactivity is compatible, and it is possible to stably and easily introduce highly reactive amino groups on the surface of the pressure-sensitive adhesive while maintaining a high level without damaging the adhesive strength of the initial adhesive. I found it. The present invention has been completed based on these findings.
[0011]
  That is, in the present invention, hydrogen atoms of at least some amino groups in the molecule areoverallSubstituted with an organic group of 5 or more atomsAnd obtained by a reaction between the amino group in the polymer (b) having an amino group and the vinyl group that is the amino group-reactive functional group of the vinyl group-containing compound as the amino group-reactive functional group-containing compound (c).A surface-reactive functional group-modified pressure-sensitive adhesive in which the pressure-sensitive adhesive surface is modified with an amino group is provided by coating the surface of the pressure-sensitive adhesive with an amino group-containing polymer (A) by an interfacial contact reaction. The surface-reactive functional group-modified pressure-sensitive adhesive includes a pressure-sensitive adhesive whose adhesive force increases with time with respect to a specific adherend after being attached.
[0012]
The organic group substituted on the amino group in the amino group-containing polymer (A) is preferably a hydrocarbon group which may have a substituent.
[0013]
  in frontAs the polymer (b) having an amino group, a polymer having at least one primary or secondary amino group selected from polyallylamine, polyvinylamine and polyethyleneimine can be used. on the other hand,in frontAs the vinyl group-containing compound, (meth) acrylic acid esters are suitable.
[0014]
In the present invention, the second reaction having a reactive functional group other than an amino group on the amino group-containing polymer (A) layer by an interfacial contact reaction utilizing an amino group in the amino group-containing polymer (A) layer. A functional functional group modification layer may be formed. The reactive functional group other than the amino group in the second reactive functional group modification layer is preferably a functional group selected from a carboxyl group, a hydroxyl group, an alkoxysilyl group, a silanol group, and a vinyl group.
[0015]
The present invention also provides a pressure-sensitive adhesive tape or sheet provided with a pressure-sensitive adhesive layer composed of the above-mentioned surface-reactive functional group-modified pressure-sensitive adhesive.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
A feature of the surface-reactive functional group-modified pressure-sensitive adhesive of the present invention is that the pressure-sensitive adhesive surface is modified with a functional group that exhibits adhesion reactivity by an interfacial contact reaction, and is a hydrogen atom of at least some amino groups in the molecule. A pressure-sensitive adhesive in which the pressure-sensitive adhesive surface is modified with an amino group by coating the surface of the pressure-sensitive adhesive with an amino group-containing polymer (A) substituted with an organic group having 5 or more atoms by an interfacial contact reaction Is in the point of using.
[0017]
According to such a pressure-sensitive adhesive, since the amino group-containing polymer (A) is used, the flexibility of the pressure-sensitive adhesive surface and the adhesion reactivity are compatible, and as a result, the original pressure-sensitive adhesive is essentially The adhesive strength at the initial stage of application is effectively maintained at a higher level with little or no loss of adhesion. That is, in the surface-reactive functional group-modified pressure-sensitive adhesive of the present invention, the initial adhesive strength of the pressure-sensitive adhesive having an unmodified surface is maintained.
[0018]
In addition, highly reactive amino groups can be stably and easily introduced on the surface of the pressure-sensitive adhesive. Specifically, since an amino group is immobilized on the pressure-sensitive adhesive surface by an interfacial contact reaction using the amino group-containing polymer (A), for example, this is reacted with an amino group immobilized on the pressure-sensitive adhesive surface. When attached to an adherend having a surface state that is easy to wear (for example, an adherend having an acidic surface state), the adhesive initially physically wets and spreads to exhibit adhesive strength equivalent to that of a normal adhesive tape. At the same time, the amino group on the pressure-sensitive adhesive surface and the surface of the adherend are chemically bonded to each other over time, and the adhesive force further increases, and finally extremely strong bonding similar to what is called an adhesive becomes possible.
[0019]
Such surface-reactive functional group-modified pressure-sensitive adhesives have, for example, an initial adhesive force (for example, 180 ° peel strength after 1 minute after being attached to an adherend) corresponding to the unmodified surface. The pressure-sensitive adhesive has an adhesive strength of 70% or more (for example, about 70 to 300%), preferably 90% or more (for example, about 90 to 300%) of the initial adhesive strength of the adhesive.
[0020]
With the preferred surface-reactive functional group-modified pressure-sensitive adhesive, the adhesive force to the adherend increases with time. For example, the 180 ° peel strength after 1 minute after being attached to the adherend is P₀And the 180 ° peel strength when heated at 100 ° C. for 60 minutes as P₁The ratio P between the two₁/ P₀Is preferably 2 or more. P₁/ P₀Is preferably 2.5 or more, more preferably 4 or more. The 180 ° peel strength is a value measured according to JIS Z 0237 (tensile speed: 300 mm / min).
[0021]
The pressure-sensitive adhesive of the present invention may be in any form, and for example, can constitute a pressure-sensitive adhesive layer in various pressure-sensitive adhesive products such as pressure-sensitive adhesive tapes, pressure-sensitive adhesive sheets, and pressure-sensitive adhesive labels.
[0022]
Hereinafter, the present invention will be described in more detail with reference to the drawings. In addition, the same code | symbol is attached | subjected to the same member or the same part.
FIG. 1 is a schematic cross-sectional view showing an example of a pressure-sensitive adhesive tape or sheet provided with a pressure-sensitive adhesive layer made of the surface-reactive functional group-modified pressure-sensitive adhesive of the present invention. In this pressure-sensitive adhesive tape or sheet 1, the pressure-sensitive adhesive layer 3 is provided on one surface of the substrate 2, and the surface of the pressure-sensitive adhesive layer 3 is covered with an amino group-containing polymer (A) by an interfacial contact reaction. An amino group-modified layer [amino group-containing polymer (A) layer] 4 containing amino groups is formed.
[0023]
The substrate 2 is not particularly limited as long as it has a self-supporting property. For example, a polyester film such as polyethylene terephthalate; an olefin resin such as polyethylene and polypropylene; a plastic film made of a polymer such as polyvinyl chloride, paper, Examples thereof include cloth, metal foil, release paper, release film, and composites thereof. The base material may have a single-layer form or a multi-layer form.
[0024]
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 3 is not particularly limited, and any of known pressure-sensitive adhesives such as an acrylic pressure-sensitive adhesive and a rubber-based pressure-sensitive adhesive can be used. Acrylic pressure-sensitive adhesives generally contain acrylic acid alkyl esters such as butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isononyl acrylate, and ethyl acrylate as main monomers, and cyano group-containing vinyl compounds such as acrylonitrile, acetic acid. Vinyl esters such as vinyl, aromatic vinyl compounds such as styrene, alkyl methacrylate esters such as methyl methacrylate, carboxyl compounds containing carboxyl groups such as acrylic acid, vinyl compounds containing acid anhydride groups such as maleic anhydride, vinyl pyrrolidone, etc. Vinyl group-containing heterocyclic compounds, epoxy group-containing vinyl compounds such as glycidyl methacrylate, amino group-containing vinyl compounds such as dimethylaminoethyl methacrylate, hydroxyethyl alcohol Hydroxyl group-containing vinyl compound such relations, in which the copolymer base polymer of the monomer mixture was added modifying monomer, such as an amide group-containing vinyl compound such as acrylamide.
[0025]
Rubber adhesives are generally natural rubber, styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-butadiene rubber, polybutadiene, The base polymer is a rubber polymer such as isoprene, polyisobutylene, butyl rubber, chloroprene rubber, or silicone rubber.
[0026]
These adhesives include rosin-based, terpene-based, styrene-based, aliphatic petroleum-based, aromatic petroleum-based, xylene-based, phenol-based, coumarone-indene-based, and hydrogenated products such as these, and liquids. Additives such as resins, liquid rubbers, polybutenes, process oils, dioctyl phthalates, and other softening agents, antioxidants, fillers, pigments, crosslinking agents, and the like can be appropriately blended.
[0027]
The pressure-sensitive adhesive layer 3 is formed by, for example, applying the above-mentioned pressure-sensitive adhesive as a solution or an aqueous dispersion on the substrate 2 and then drying and removing the solvent or water, or applying the above-mentioned pressure-sensitive adhesive by hot-melt coating or It can be formed by calendar coating. Alternatively, the pressure-sensitive adhesive layer 3 can also be formed by coating a monomer or oligomer, which is a precursor of the pressure-sensitive adhesive, on the substrate 2 and then performing photopolymerization by irradiating ultraviolet rays.
[0028]
The thickness of the pressure-sensitive adhesive layer 3 can be selected in a wide range depending on the purpose of use and the type of adherend, but is generally about 1 to 3000 μm, preferably about 10 to 1000 μm.
[0029]
In the pressure-sensitive adhesive layer 3, a compound containing a reactive functional group capable of interfacial contact reaction when the amino group-modified layer 4 is formed (hereinafter referred to as “reactive functional group”). It may be referred to as “containing compound”). As a method of containing such a compound, the reactive functional group is chemically added to the base polymer such as the acrylic pressure-sensitive adhesive or rubber-based pressure sensitive adhesive by copolymerization, graft reaction, side chain modification reaction, or the like. Any method such as a method of introducing, a method of adding and mixing the reactive functional group-containing compound in the pressure-sensitive adhesive composition before coating may be used.
[0030]
Any reactive functional group capable of interfacial contact reaction with an amino group may be used as long as it is a group that reacts with an amino group, but it is preferable that the interfacial contact reaction proceeds in a short time. It is desirable that the combination be highly specific. From this point of view, an isocyanate group, an acid halide group (such as an acid chloride group), an epoxy group, an acid anhydride group, or a carboxyl group is preferable as the reactive functional group capable of interfacial contact with an amino group.
[0031]
Therefore, as the reactive functional group-containing compound (compound having a reactive functional group capable of interfacial contact reaction when forming the amino group-modified layer 4) to be contained in the pressure-sensitive adhesive layer 3 in advance, the pressure-sensitive adhesive layer 3 is an isocyanate group, for example, diisocyanate compounds such as tolylene diisocyanate (TDI), diphenylmethane-4,4′-diisocyanate (MDI), hexamethylene diisocyanate (HDI) preferable. These diisocyanate compounds also have an effect as a crosslinking agent for pressure-sensitive adhesives.
[0032]
In addition, the amino group-containing polymer (A) used to form the amino group-modified layer [amino group-containing polymer (A) layer] 4 has at least some of the amino group hydrogen atoms in the molecule having the number of atoms. An amino group-containing polymer substituted with 5 or more organic groups. An amino group containing polymer (A) can be used individually or in combination of 2 or more types. It is also important that the amino group-containing polymer (A) is a polymer that does not impair the adhesive properties (initial adhesive properties) of the pressure-sensitive adhesive layer 3.
[0033]
Such an amino group-containing polymer (A) is capable of interfacial contact reaction with the pressure-sensitive adhesive layer 3 and exhibits adhesion reactivity with respect to the adherend. Characteristic) is not impaired. The adhesion reactivity refers to a chemical reaction with respect to atoms, molecules, functional groups, functional segments existing on the adherend surface, such as covalent bonds, coordinate bonds, hydrogen bonds, ionic bonds, metal bonds, etc. A property that develops a large bond strength by forming a chemical bond or exerting strong electrostatic interaction or non-bonded interatomic interaction such as van der Waals force on atoms etc. present on the adherend surface. Say.
[0034]
In the present invention, the type of amino group having an organic group having 5 or more atoms and the arrangement site of the nitrogen atom of the amino group in the amino group-containing polymer (A) (for example, atoms constituting the side chain or main chain) And the ratio to the total amino groups is adjusted as appropriate without damaging the initial high adhesive strength of the original adhesive (adhesive constituting the adhesive layer 3). Amino groups can be introduced on the surface of the layer.
[0035]
In the amino group-containing polymer (A), the nitrogen atom of the amino group (amino group having no organic group having 5 or more atoms or amino group having 5 or more organic groups) is the main chain of the polymer. The atom which comprises may be sufficient and the atom which comprises the side chain of a polymer may be sufficient. When the amino group-containing polymer (A) has an amino group in the side chain, the nitrogen atom of the amino group may be directly bonded to an atom (such as a carbon atom) constituting the main chain of the polymer. It does not have to be. When the nitrogen atom of the amino group in the side chain is not directly bonded to the atom constituting the main chain of the polymer, the nitrogen atom is a chain (or organic group) having 10 or less (preferably 5 or less) atoms. It is desirable to bond to atoms constituting the main chain of the polymer via
[0036]
In the amino group-containing polymer (A), the organic group having 5 or more atoms substituted on the amino group may have 5 or more atoms as a whole, but it constitutes the main chain of the organic group. It is desirable that the number of atoms is 5 or more (preferably 8 or more). On the other hand, the upper limit of the number of atoms of the organic group is not particularly limited, but may be, for example, 30 or less (preferably 20 or less). In addition, when the organic group contains a cyclic group (for example, an aryl group, a cycloalkyl group, a heterocyclic group, etc.) (for example, when the cyclic group constitutes the main chain of the organic group), the organic group The number of atoms in can include half of the number of atoms constituting the cyclic group.
[0037]
  As such an organic group having 5 or more atoms, a hydrocarbon group which may have a substituent is suitable. Examples of the hydrocarbon group which may have a substituent include an alkyl group, an alkoxycarbonylalkyl group, an aryloxycarbonylalkyl group, a cycloalkyloxycarbonylalkyl group, an alkoxyalkyl group, an aryloxyalkyl group, and a cycloalkyloxy group. An alkyl group that may have an inert substituent such as an alkyl group (particularly a substituent that is non-reactive with an amino group) and other hydrocarbon groups corresponding to these alkyl groups (for example, , Aryl group, cycloalkyl group, etc.). When the hydrocarbon group has a substituent constituting the main chain of the organic group, in the main chain of the organic group, the ratio of the number of atoms of the hydrocarbon group and the number of atoms of the substituent is Not limited.
[0038]
In the amino group-containing polymer (A), the amino group in which a hydrogen atom is substituted with an organic group having 5 or more atoms may be at least a part of the amino group in the polymer molecule. The proportion of amino groups substituted with 5 or more organic groups is 5 to 100 mol% (preferably 20 to 80 mol%, more preferably 40 to 60 mol%) with respect to all amino groups in the molecule. It may be. Even if all amino groups in the molecule have an organic group having 5 or more atoms, at least a part of the amino group having an organic group having 5 or more atoms may be a secondary amino group. In this case, the adhesion reactivity can be effectively exhibited.
[0039]
The method for preparing the amino group-containing polymer (A) is not particularly limited. For example, (1) the amino group in the polymer (b) having an amino group and the amino group-reactive functional group-containing compound (c) Monomer containing at least an amino group-containing monomer in which a hydrogen atom of an amino group in the molecule is substituted with an organic group having 5 or more atoms in the molecule, and a preparation method by reaction with a group-reactive functional group Examples thereof include a preparation method by polymerization (including copolymerization) using components (for example, other amino group-containing monomers and amino group-free copolymerizable monomers may be included). In the present invention, the amino group-containing polymer (A) is obtained by reacting the amino group in the polymer (b) having an amino group with the amino group-reactive functional group of the amino group-reactive functional group-containing compound (c). An amino group-containing polymer in which at least some of the amino group hydrogen atoms in the resulting molecule are substituted with an organic group having 5 or more atoms can be suitably used.
[0040]
In addition, in the preparation method (1) of the amino group-containing polymer (A), the polymer (b) having an amino group and the amino group-reactive functional group-containing compound (c) should be used alone or in combination of two or more. Can do. In addition, in the preparation method (2) of the amino group-containing polymer (A), an amino group-containing monomer in which the hydrogen atom of the amino group in the molecule is substituted with an organic group having 5 or more atoms, Other amino group-containing monomers and non-amino group-containing copolymerizable monomers may be used alone or in combination of two or more.
[0041]
In the preparation method (1) of the amino group-containing polymer (A), the polymer (b) having an amino group includes a primary amino group (unsubstituted amino group) or a secondary group in the side chain or main chain. It preferably has at least one amino group (mono-substituted amino group). These primary and / or secondary amino groups may have a tertiary amino group (disubstituted amino group).
[0042]
Examples of the polymer (b) having an amino group include primary or secondary amino group-containing vinyl monomers such as allylamine and vinylamine; aziridine compounds such as ethyleneimine; aminoethyl acrylate, aminopropyl acrylate, and aminoethyl. A polymer having an amino group that contains an amino group-containing monomer such as an aminoalkyl group-containing (meth) acrylate such as methacrylate or aminopropyl methacrylate as a monomer component can be used. Moreover, the monomer component in the polymer (b) having an amino group can be used alone or in combination of two or more.
[0043]
The monomer component in the polymer (b) having an amino group is preferably at least one amino group-containing monomer selected from allylamine, vinylamine and ethyleneimine. Therefore, in the present invention, the polymer (b) having an amino group is preferably a polymer having at least one primary or secondary amino group selected from polyallylamine, polyvinylamine and polyethyleneimine. .
[0044]
On the other hand, the amino group-reactive functional group-containing compound (c) is not particularly limited as long as it is a compound containing an amino group-reactive functional group that is a functional group having reactivity with an amino group. Examples of such amino group-reactive functional groups include vinyl groups, isocyanate groups, carboxyl groups, acid halide groups, acid anhydride groups, and epoxy groups. The amino group-reactive functional groups may be used alone or in combination of two or more. Preferred amino group reactive functional groups include vinyl groups. Therefore, in the present invention, a vinyl group-containing compound can be suitably used as the amino group-reactive functional group-containing compound (c).
[0045]
The reaction (addition reaction) between the amino group of the polymer (b) having an amino group and the vinyl group in the vinyl group-containing compound as the amino group-reactive functional group-containing compound (c) is, for example, the following reaction It can be represented by Formula (1).
[Chemical 1]

(In Reaction Formula (1), R represents a hydrogen atom or an organic group)
[0046]
In the reaction formula (1), examples of the organic group R include hydrocarbon groups such as alkyl groups (for example, methyl group, ethyl group, propyl group, butyl group), cycloalkyl groups, and aryl groups. When the amino group is a primary amino group [for example, when R is a hydrogen atom in the reaction formula (1)], two vinyl groups may be reacted with the primary amino group. It is preferable that only one vinyl group is reacted with the primary amino group.
[0047]
As the vinyl group-containing compound as the amino group-reactive functional group-containing compound (c), a compound containing a vinyl group in which an electron-withdrawing group is bonded to at least one carbon atom constituting the vinyl group is suitable. Can be used. Examples of the vinyl group-containing compound include acrylic acid ester, methacrylic acid ester, crotonic acid ester, isocrotonic acid ester, 2-butenoic acid ester, 3-methyl-2-butenoic acid ester, 2-pentenoic acid ester, and 2-hexene. Vinyl group-containing monocarboxylic acid esters such as acid esters, 2-octenoic acid esters, oleic acid esters, and cinnamic acid esters; vinyls such as maleic acid diesters, fumaric acid diesters, itaconic acid diesters, and other vinyl group-containing dicarboxylic acid diesters A group-containing carboxylic acid ester compound can be used. In the vinyl group-containing carboxylic acid ester compound, the ester moiety may be methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester, pentyl ester, isopentyl ester. Hexyl ester, heptyl ester, 2-ethylhexyl ester, octyl ester, isooctyl ester, nonyl ester, isononyl ester, decyl ester, isodecyl ester, lauryl ester, stearyl ester, etc._1-30Alkyl esters (preferably C_1-20Alkyl esters); cycloalkyl esters such as cyclohexyl esters; aryl esters such as phenyl esters and benzyl esters. In addition, when it has multiple ester site | parts, each ester site | part may be the same and may differ.
[0048]
As the vinyl group-containing compound, acrylic acid esters and methacrylic acid esters [these may be referred to as “(meth) acrylic acid esters”] are preferable. Specifically, (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, ( Isobutyl acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic acid Heptyl, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylic Isodecyl acid, lauryl (meth) acrylate, stearyl (meth) acrylate, etc. It is.
[0049]
As the vinyl group-containing compound, among (meth) acrylic acid esters, acrylic acid C_1-20Alkyl esters (and acrylic acid C_2-10Alkyl esters) are preferred, and in particular, at least one alkyl acrylate selected from butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate and isononyl acrylate is preferred.
[0050]
In the preparation method (1) of the amino group-containing polymer (A), the polymer (b) having an amino group is reacted with the amino group-reactive functional group-containing compound (c) (for example, a vinyl group-containing compound). The ratio of the polymer (b) having an amino group to the amino group-reactive functional group-containing compound (c) is such that at least a part of the amino group in the polymer (b) having an amino group is an amino group. A ratio that reacts with an amino group-reactive functional group (for example, vinyl group) in the reactive functional group-containing compound (c) may be used, but a ratio at which an amino group in the polymer (b) having an amino group remains. It is preferable that For example, the amino group-reactive functional group (vinyl group, etc.) in the amino group-reactive functional group-containing compound (c) (vinyl group-containing compound, etc.) with respect to all amino groups in the polymer (b) having an amino group. 0.05-1.0 equivalent may be sufficient and it is desirable that it is a ratio which will be 0.2-0.8 equivalent (more preferably 0.4-0.6 equivalent).
[0051]
In addition, in the polymer (b) having an amino group, the polymer (b) having an amino group and the amino group-reactive functional group-containing compound (c) are mixed and heated as necessary. Reaction of an amino group and the amino group reactive functional group of an amino group reactive functional group containing compound (c) can be performed.
[0052]
In addition, in the preparation method (2) of the amino group-containing polymer (A), as the amino group-containing monomer in which the hydrogen atom of the amino group in the molecule is substituted with an organic group having 5 or more atoms, for example, An amino group-containing monomer as a monomer component of the polymer (b) having an amino group [for example, primary or secondary amino group-containing vinyl monomers such as allylamine and vinylamine; aziridine compounds such as ethyleneimine; aminoethyl acrylate, An amino group of aminoalkyl group-containing (meth) acrylate such as aminopropyl acrylate, aminoethyl methacrylate, aminopropyl methacrylate, etc.] and the amino group-reactive functional group-containing compound (c) (for example, acrylic ester, methacrylic ester) , Crotonic acid ester, isocrotonic acid ester Ter, 2-butenoic acid ester, 3-methyl-2-butenoic acid ester, 2-pentenoic acid ester, 2-hexenoic acid ester, 2-octenoic acid ester, oleic acid ester, cinnamic acid ester, etc. Amino group-reactive functional groups (for example, vinyl groups) of acid esters; vinyl group-containing carboxylic acid ester compounds such as maleic acid diesters, fumaric acid diesters, itaconic acid diesters, and the like. An amino group-containing monomer obtained by the reaction with can be used.
[0053]
Other amino group-containing monomers include, for example, amino group-containing monomers as monomer components of the polymer (b) having an amino group [for example, primary or secondary amino group-containing vinyl monomers such as allylamine and vinylamine. Aziridine compounds such as ethyleneimine; aminoalkyl group-containing (meth) acrylates such as aminoethyl acrylate, aminopropyl acrylate, aminoethyl methacrylate, aminopropyl methacrylate, etc.] can be used.
[0054]
Therefore, in the present invention, the amino group-containing polymer (A) is obtained by a reaction between an amino group in polyallylamine, polyvinylamine or polyethyleneimine and a vinyl group in a vinyl group-containing compound such as (meth) acrylic acid ester. Polyallylamine, polyvinylamine or polyethyleneimine containing an amino group having an organic group having 5 or more atoms can be preferably used.
[0055]
The interfacial contact reaction for forming the amino group-modified layer 4 includes, for example, a solid phase or a liquid phase (adhesive phase) containing a base polymer or a reactive functional group-containing compound constituting the adhesive layer 3, an amino group It can be performed between the liquid phase containing the amino group-containing polymer (A) constituting the modification layer 4. Examples of a method for interfacial contact reaction between the pressure-sensitive adhesive phase and the liquid phase containing the amino group-containing polymer (A) constituting the amino group-modified layer 4 are methods of contacting both phases by dipping and dipping, gravure, kiss, etc. The liquid phase is applied to the adhesive phase by spraying or the like by spraying, etc., by a known or conventional application method such as roll coating, die coating such as phantom, squeeze coating, spin coating, etc. Any method may be used.
[0056]
In order to introduce amino groups at high density onto the pressure-sensitive adhesive surface, the liquid phase medium containing the amino group-containing polymer (A) constituting the amino group-modified layer 4 dissolves or swells the pressure-sensitive adhesive phase. For example, when the pressure-sensitive adhesive is acrylic, it is desirable to appropriately select and use a solvent that does not dissolve or swell the pressure-sensitive adhesive phase, such as water, alcohol, hexane, and heptane.
[0057]
The thickness of the amino group-modified layer 4 thus formed on the surface of the pressure-sensitive adhesive layer 3 can be appropriately selected within a range that does not impair the pressure-sensitive adhesive properties of the pressure-sensitive adhesive layer 3, but is generally 1 μm or less (for example, 0 0.001 to about 1 μm), preferably 0.1 μm or less (for example, about 0.001 to 0.1 μm).
[0058]
As described above, by introducing the amino group-modified layer 4 to the surface of the pressure-sensitive adhesive layer 3, strong adhesion to an adherend, particularly, an adherend having an acidic surface state is exhibited. Further, by utilizing the high reactivity of the amino group of the amino group modification layer 4 introduced on the surface of the pressure-sensitive adhesive layer 3, an interfacial contact reaction is further performed, so that another kind (or another kind) of reactive functional group is formed. It is also possible to introduce. In this manner, by introducing another type of reactive functional group, it is possible to easily adjust the desired adhesive strength according to the type of adherend. Another type of reactive functional group is preferably a functional group that exhibits adhesion reactivity to the adherend.
[0059]
FIG. 2 is a schematic cross-sectional view showing another example of a pressure-sensitive adhesive tape or sheet provided with a pressure-sensitive adhesive layer made of the surface-reactive functional group-modified pressure-sensitive adhesive of the present invention. In this pressure-sensitive adhesive tape or sheet 11, the pressure-sensitive adhesive layer 3 is provided on one surface of the substrate 2, and the surface of the pressure-sensitive adhesive layer 3 is coated with an amino group-containing polymer (A) by an interfacial contact reaction. As a result, an amino group-modified layer 4 containing an amino group is formed, and a reactive functional group other than the amino group (another kind) is further formed thereon by an interfacial contact reaction using the amino group of the amino group-modified layer 4. A second reactive functional group modification layer (second functional group modification layer) 5 to be contained is formed. In FIG. 2, the substrate 2, the pressure-sensitive adhesive layer 3, and the amino group-modified layer (amino group-containing polymer (A) layer) 4 are the same as those in FIG.
[0060]
Specific examples of the different types of reactive functional groups (that is, reactive functional groups in the second functional group modification layer 5) include, for example, carboxyl group, hydrosilyl group, hydroxyl group, alkoxysilyl group, silanol group, A vinyl group etc. are mentioned. When the adherend is glass, etc., if the pressure-sensitive adhesive surface is modified with alkoxysilyl groups or silanol groups, they react with the silanol groups on the glass surface over time to form chemical bonds, resulting in high adhesive strength. To do. In addition, when the adherend is a metal such as stainless steel or a melamine resin coating film, when a carboxyl group or the like is used as an adhesion-reactive functional group, a greater adhesive strength is developed over time.
[0061]
The combination of two reactive functional groups capable of interfacial contact reaction is the same as described above. Examples of the reactive functional group-containing compound used to form the second functional group-modified layer 5 include a reactive group capable of interfacial contact reaction with the amino group-containing polymer (A) of the amino group-modified layer 4, and an amino group. A reactive functional group-containing compound containing a reactive functional group other than (reactive functional group of another type) can be used. Furthermore, it is important that the reactive functional group-containing compound used for forming the second functional group modification layer 5 is a compound that does not impair the adhesive properties (initial adhesive properties) of the adhesive layer 3. In the reactive functional group-containing compound used to form the second functional group modification layer 5, the two reactive functional groups (that is, a reactive functional group capable of interfacial contact reaction and another reactive functional group). And groups) may be the same or different. Examples of the reactive functional group-containing compound used for forming the second functional group modification layer 5 include isocyanate groups, acid halide groups (such as acid chloride groups), epoxy groups, and acid anhydride groups that are highly reactive with amino groups. Alternatively, a polymer containing a carboxyl group and a desired adhesion-reactive functional group capable of reacting with an adherend surface such as a carboxyl group, a hydroxyl group, an alkoxysilyl group, a silanol group, or a vinyl group can be used.
[0062]
The method for forming the second functional group modification layer 5 on the amino group modification layer 4 can be performed in accordance with the method for forming the amino group modification layer 4 on the pressure-sensitive adhesive layer 3. Therefore, the reactive functional group-containing compound used for forming the second functional group-modified layer 5 and the amino group-containing polymer (A) used for forming the amino group-modified layer 4 are subjected to the interfacial contact reaction according to the method described above. be able to. In this way, by using the high reactivity of the amino group contained in the amino group modification layer 4 and performing the interface contact reaction again, another type of reactive functional group can be fixed to the outermost layer. The thickness of the second functional group modification layer 5 that is the outermost layer can be appropriately selected within a range that does not impair the adhesive properties of the pressure-sensitive adhesive layer 3, but is generally 0.001 to 10 μm, preferably 0.001 to 5 μm. Degree.
[0063]
In the example of FIG. 1 and FIG. 2 described above, the functional group-modified layer containing reactive functional groups such as the amino group-modified layer 4 and the second functional group-modified layer 5 is composed of one or two layers. By repeating the contact reaction in the same manner, the functional group modification layer can be composed of three or more layers as required. In each of the above examples, the pressure-sensitive adhesive layer and the functional group modification layer are formed on one surface of the base material 2, but the pressure-sensitive adhesive layer or the pressure-sensitive adhesive layer and the functional group modification are also formed on the other surface of the base material 2. It is good also as a double-sided adhesive tape or a sheet | seat by providing a layer.
[0064]
According to the pressure-sensitive adhesive of the present invention, and the pressure-sensitive adhesive tape or sheet, since the initial high-adhesiveness of the original pressure-sensitive adhesive is effectively retained, the pasting operation can be ensured and the outermost surface of the pressure-sensitive adhesive Is modified with a functional group (such as an amino group) that exhibits adhesive reactivity by interfacial contact reaction, so that the functional group chemically binds to the surface of the adherend without internal diffusion, and the adhesive strength increases over time. It will rise further and will eventually become a very strong bond. In the present invention, the adhesive force can be increased with time by simply leaving it at room temperature after being attached to the adherend, so it is necessary to apply external energy such as heating or UV (ultraviolet). However, if it is desired to accelerate the increase in the adhesive force over time, heat energy such as heating may be applied. Moreover, in this invention, it can be set as the adhesive tape or sheet | seat which has sufficient durability and heat resistance by selecting a suitable thing as a base material or a base adhesive (base polymer).
[0065]
The present invention can be applied to all kinds of adhesive tapes or sheets in general, and among them, particularly, a strong bonding force (high adhesive strength) is required, such as a double-sided adhesive tape used for metal, glass, plastic materials and the like. In addition, it is useful as a strong adhesive pressure-sensitive adhesive tape or sheet used for applications requiring high adhesive strength from the beginning of application.
[0066]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[0067]
Production Example 1 (Preparation of acrylic adhesive solution)
A flask was charged with 190 g of butyl acrylate, 10 g of acrylic acid, 0.4 g of azobisisobutyronitrile as a polymerization initiator, and 300.6 g of ethyl acetate as a solvent. Nitrogen gas was introduced while gently stirring, and the temperature in the flask Was raised to 60 ° C. After a few minutes, an exotherm began and the outer bath was controlled to keep the temperature in the flask at 60 ° C. About 3 hours after the start of the polymerization, 83.5 g of ethyl acetate was dropped into the flask, and the polymerization was continued for 3 hours. Thereafter, 83.5 g of ethyl acetate was further dropped into the flask, the temperature in the flask was raised to 80 ° C., and polymerization was performed for 2 hours to prepare an acrylic pressure-sensitive adhesive solution having a solid content concentration of 30% by weight. As a result of measurement by GPC (gel permeation chromatography), the weight average molecular weight (Mw) of the obtained polymer was 1.3 million in terms of polystyrene.
[0068]
Production Example 2 (Production of Acrylic Adhesive Tape A)
For the acrylic pressure-sensitive adhesive solution obtained in Production Example 1, the product name “Coronate L” [manufactured by Nippon Polyurethane Industry Co., Ltd., 2,4-tolylene diisocyanate to trimethylolpropane per 100 parts by weight of the solid content. 3 parts by weight (in terms of solid content) of an addition compound 75% by weight ethyl acetate solution] was added. This was applied onto a 38 μm thick polyester film subjected to corona treatment using an applicator so that the thickness after drying would be 40 μm, and dried at 80 ° C. for 5 minutes to evaporate the solvent. An adhesive tape was prepared. This adhesive tape is referred to as “adhesive tape A”.
[0069]
Production Example 3 (Preparation of an amino group-containing polymer containing an amino group having an organic group having 5 or more atoms)
50.8 parts by weight of isopropyl alcohol (solvent) was added to 50 parts by weight of a trade name “PAA-10C” (manufactured by Nitto Boseki; polyallylamine aqueous solution having a polyallylamine concentration of 10% by weight) and diluted by stirring. Then, 5.7 parts by weight of butyl acrylate having a vinyl group corresponding to 1/2 equivalent of the amino group of polyallylamine was dropped over about 10 minutes with stirring. After completion of the dropwise addition, the reaction was allowed to stand at room temperature for 1 day to carry out an addition reaction (Michael addition reaction) of the polyallylamine amino group to the vinyl group of butyl acrylate. After completion of the addition reaction,¹When H-NMR analysis was performed, the spectrum (NMR spectrum) shown in FIG. 3 was obtained. In the NMR spectrum shown in FIG. 3, all the double bonds of butyl acrylate disappeared. Moreover, when the molar ratio of a butyl acrylate unit and an allylamine unit was quantified from the integral value of 2.83 ppm and 2.56 ppm, it was butyl acrylate unit: allylamine unit = 52: 48 (molar ratio). This confirmed that the reaction (addition reaction) between the amino group represented by the formula (1) and the vinyl group proceeded quantitatively. Therefore, polyallylamine containing 2-butoxycarbonylethylamino group and primary amino group was prepared by the above reaction. That is, a polyallylamine containing an amino group having an organic group having 5 or more atoms and a primary amino group was prepared.
[0070]
In addition,¹The conditions for H-NMR analysis are as follows.
Apparatus: “EX-400” manufactured by JEOL Ltd.
Observation frequency: 400 MHz
Pulse width: 45 °
Chemical shift standard: 3.3ppm
Measuring solvent: CD_ThreeOD
Measurement temperature: room temperature (20-25 ° C.)
Measurement method: Double homogate decoupling method
[0071]
Then, by adding 150 parts by weight of isopropyl alcohol and 349 parts by weight of water to 1 part by weight of this reaction mixture solution, the concentration of polyallylamine containing 2-butoxycarbonylethylamino group is increased. A 0.02 wt% solution was prepared. A solution in which the concentration of polyallylamine containing 2-butoxycarbonylethylamino group and primary amino group is 0.02% by weight is referred to as “butyl acrylate-added polyallylamine solution A”.
[0072]
Example 1
An adhesive tape A was prepared and immediately after that (while the isocyanate group in the adhesive was active), after being immersed in the butyl acrylate-added polyallylamine solution A obtained in Production Example 3 for 1 minute, 60 mm / After pulling up in the vertical direction at a rate of min and drying the surface in an oven at 40 ° C., it was allowed to stand at room temperature for 7 days or more so that the pressure-sensitive adhesive surface did not touch other substances. This adhesive tape is referred to as “adhesive tape B”.
[0073]
Comparative Example 1
After the “adhesive tape A” was prepared, no surface treatment was performed, and the adhesive surface was left for 7 days at room temperature so that the adhesive surface did not touch other substances.
[0074]
Comparative Example 2
An adhesive tape A was prepared and immediately thereafter (while the isocyanate group in the adhesive was active), in a 0.02% by weight aqueous solution of polyallylamine (trade name “PAA-10C” manufactured by Nitto Boseki Co., Ltd.) After being immersed for 1 minute, it was pulled up in the vertical direction at a speed of 60 mm / min, and the surface was naturally dried at room temperature, and then left for 7 days or more at room temperature so that the adhesive surface did not touch other substances. This pressure-sensitive adhesive tape is referred to as “pressure-sensitive adhesive tape C”.
[0075]
Below, the result of adhesive strength evaluation as an adhesive tape is shown.
(Initial bond strength evaluation)
About adhesive tape A, B, and C in Example 1 and Comparative Examples 1-2, initial adhesive strength evaluation about a SUS304BA board and a polyester varnish coating tin plating iron plate (polyester varnish coating board) was performed, respectively. In addition, as a SUS304BA board, the commercially available SUS304BA board was used. Moreover, as a polyester varnish coating board, what coated the surface of the tin plating iron plate with the brand name "polyester varnish NV-543" by Nitto Denko Corporation was used.
[0076]
Each of the SUS304BA plate and the polyester varnish coating plate was pasted with an adhesive tape cut out to a width of 20 mm, and was subjected to one reciprocal pressure bonding using a 2 kg rubber roller. 30 minutes after attaching this sample, 180 ° peel strength (N / 20 mm) was measured at a peeling speed of 300 mm / min with a tensile tester. The results are shown in Table 1.
[0077]
[Table 1]

[0078]
“Adhesive tape B” (Example 1), which was subjected to amino group modification treatment using polyallylamine containing 2-butoxycarbonylethylamino group and primary amino group, corresponding to the present invention, was originally It can be seen that it has an initial adhesive ability of 70% or more as compared with the initial adhesive ability of “Adhesive Tape A” (Comparative Example 1). On the other hand, “adhesive tape C” (Comparative Example 2) subjected to amino group modification using polyallylamine not containing 2-butoxycarbonylethylamino group shows low initial adhesion ability.
[0079]
(Evaluation of adhesive strength after time)
About adhesive tape A, B, and C in Example 1 and Comparative Examples 1-2, the adhesive strength evaluation with time about SUS304BA board and the polyester varnish coating tin plating iron plate (polyester varnish coating board) was performed, respectively. As the SUS304BA plate, a commercially available SUS304BA plate was used, and as the polyester varnish coated plate, a surface of a tin-plated iron plate coated with a trade name “Polyester Varnish NV-543” manufactured by Nitto Denko Corporation was used.
Each of the SUS304BA plate and the polyester varnish coating plate was pasted with an adhesive tape cut out to a width of 20 mm, and was subjected to one reciprocal pressure bonding using a 2 kg rubber roller. After pasting this sample, it was heated at 50 ° C. for 3 days as an aging acceleration test, and then the 180 ° peel strength was measured at a peeling rate of 300 mm / min with a tensile tester. The results are shown in Table 2.
[0080]
[Table 2]

[0081]
Promotion of aging of “adhesive tape B” (Example 1) subjected to amino group modification treatment using polyallylamine containing 2-butoxycarbonylethylamino group and primary amino group corresponding to the present invention The adhesive strength of the SUS304BA plate and the polyester varnish coated plate after the test is equivalent (vs. SUS304BA plate) or very large value (vs. polyester varnish) compared to that of the untreated “adhesive tape A” (Comparative Example 1). Painted plate). In addition, in the column regarding the adhesive strength of the polyester varnish coating plate in the table,> 24.5 means that when the measured value exceeds 24.5 N / 20 mm, the interface between the pressure-sensitive adhesive and the polyester varnish coating plate is peeled off. It indicates that the anchor was broken at the interface between the pressure-sensitive adhesive and the polyester base material. That is, it represents that the pressure-sensitive adhesive and the polyester varnish coating plate are firmly bonded with a force greater than those values. This suggests that the functional group remaining on the polyester varnish coated plate surface and the amino group on the pressure-sensitive adhesive surface chemically react to form a strong bond.
[0082]
Considering all the above-mentioned results, the “adhesive tape B” of Example 1 has a flexible amino group-modified layer fixed on the surface of the original “adhesive tape A”. The initial adhesive strength of the “adhesive tape A” can be maintained, and high adhesive strength can be exerted with respect to the polyester varnish coated plate over time.
[0083]
【The invention's effect】
According to the present invention, because of the flexibility of the outermost surface of the pressure-sensitive adhesive, the initial high pressure-sensitive adhesive property of the original pressure-sensitive adhesive is maintained, so that the pasting operation can be ensured. In addition, since the surface of the pressure-sensitive adhesive is modified with an amino group that exhibits adhesion reactivity, the amino group and the adherend surface are chemically bonded, and the adhesive force further increases over time. Has an extremely high adhesive strength.
[Brief description of the drawings]
FIG. 1 is a schematic sectional view showing an example of an adhesive tape or sheet of the present invention.
FIG. 2 is a schematic sectional view showing another example of the pressure-sensitive adhesive tape or sheet of the present invention.
FIG. 3 shows the reaction product after completion of the reaction in Production Example 3.¹It is a figure which shows the NMR spectrum acquired by the H-NMR analysis.
[Explanation of symbols]
1,11 Adhesive tape or sheet
2 Base material
3 Adhesive layer
4 Functional group modification layer
5 Second functional group modification layer

Claims (8)

The hydrogen group of at least a part of the amino group in the molecule is substituted with an organic group having a total number of atoms of 5 or more, and the amino group in the polymer (b) having an amino group and an amino group-reactive functional group By covering the pressure-sensitive adhesive surface by an interfacial contact reaction with an amino group-containing polymer (A) obtained by reaction with a vinyl group which is an amino group-reactive functional group of the vinyl group-containing compound as the containing compound (c) , A surface-reactive functional group-modified pressure-sensitive adhesive whose surface is modified with an amino group.   The surface-reactive functional group-modified pressure-sensitive adhesive according to claim 1, wherein the adhesive force increases with time with respect to a specific adherend after pasting.   The surface-reactive functional group-modified pressure-sensitive adhesive according to claim 1 or 2, wherein the organic group substituted on the amino group in the amino group-containing polymer (A) is a hydrocarbon group which may have a substituent. The polymer (b) having an amino group is a polymer having at least one primary or secondary amino group selected from polyallylamine, polyvinylamine and polyethyleneimine. The surface-reactive functional group-modified pressure-sensitive adhesive according to Item . The surface-reactive functional group-modified pressure-sensitive adhesive according to any one of claims 1 to 4, wherein the vinyl group-containing compound is a (meth) acrylic acid ester. Furthermore, the second reactive functional group modification having a reactive functional group other than the amino group on the amino group-containing polymer (A) layer by an interfacial contact reaction using an amino group in the amino group-containing polymer (A) layer The surface-reactive functional group-modified pressure-sensitive adhesive according to any one of claims 1 to 5, wherein a layer is formed. 7. The surface reactivity according to claim 6, wherein the reactive functional group other than the amino group in the second reactive functional group modification layer is a functional group selected from a carboxyl group, a hydroxyl group, an alkoxysilyl group, a silanol group, and a vinyl group. Functional group modified adhesive. The adhesive tape or sheet provided with the adhesive layer which consists of a surface-reactive functional group modification adhesive in any one of Claims 1-7.

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