JP3670049B2 - Delayed tack type pressure-sensitive adhesive composition - Google Patents
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Description
【０００１】
【産業上の利用分野】
本発明は、エマルジョン型粘着剤組成物に関するものであり、詳細には常温では粘着性を示さないが、一定温度以上に加熱することによって粘着性を発現する、取扱性に優れたディレードタック型粘着剤組成物に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
従来、粘着剤組成物は、その組成物をシートに塗工した後、乾燥させてシート状粘着剤とされ、その粘着剤を塗工されたシートはロール状にして保管されることが多い。保管の際に、基材の裏面と粘着剤塗工面とを接着させない目的のために剥離紙が使用されているのが現状であるが、剥離紙の使用は、作業が煩雑になり、粘着剤使用後に不要となる剥離紙が高価である等の問題があり、できるだけ剥離紙を使用せずとも基材の裏面と粘着剤塗工面とが接着しないように、種々工夫がなされている。
【０００３】
例えば、熱可塑性樹脂及び粘着付与樹脂からなるディレードタック型粘着剤組成物に、常温での粘着性の抑制の目的で結晶性可塑剤を配合することによって、加熱した時にのみ溶融した結晶性可塑剤が熱可塑性樹脂を軟化させ、その結果粘着性が発現されるようにした方法がある。
しかしながら、結晶性可塑剤はその融点以下でも徐々に粘着剤中に拡散して熱可塑性樹脂を軟化させるため、時間の経過と共に粘着性が生じ、依然として保管中に基材の裏面と粘着剤塗工面との接着を引き起こしてしまうという問題が残っていた。
【０００４】
一方、上記問題を解決せんとして、結晶性可塑剤にかえてワックスを添加する方法も試みられているが、経時により生じる粘着性の発現を抑制することが不十分であるばかりか、最終的な加熱後の粘着性を損なうという問題が生じた。
また、現在使用又は提案されているディレードタック型粘着剤は、どれも比較的低温で粘着性が発現してしまうため、粘着剤を基材に塗工後に乾燥させる際の乾燥温度を低くする必要があり、生産効率が著しく低いものであった。
【０００５】
【課題を解決するための手段】
本発明者らは、前記の課題を解決するために種々研究を重ねた結果、以下の構成を採ることにより本発明の目的を達成できることを見出し、本発明を完成した。
すなわち、本発明のディレードタック型粘着剤組成物は、（Ａ）カルボキシル基を有する不飽和単量体（ａ）３〜６０重量％、疎水性単量体（ｂ）４０〜９７重量％およびその他の単量体（ｃ）０〜５０重量％を共重合させて得られるガラス転移温度が２０℃以上の樹脂であって、且つその５重量％以上が可溶化されてなる樹脂を含有する樹脂含有溶液、及び、（Ｂ）ガラス転移温度が−３０℃以下の樹脂からなるアクリル系樹脂水性エマルジョンからなり、前記各成分の不揮発分の重量比（Ａ）／（Ｂ）が１５／８５〜５０／５０であるディレードタック型粘着剤組成物にある。
【０００６】
本発明のディレードタック型粘着剤組成物を構成する樹脂含有溶液（Ａ）を構成する樹脂は、カルボキシル基を有する不飽和単量体（ａ）３〜６０重量％、疎水性単量体（ｂ）４０〜９７重量％およびその他の単量体（ｃ）０〜５０重量％を共重合させて得られる樹脂である。
【０００７】
カルボキシル基を有する不飽和単量体（ａ）としては、アクリル酸（１０５℃）、メタクリル酸（１３０℃）、イタコン酸（１６０℃）等が挙げられる（尚、括弧内の値はその単独重合体のガラス転移温度であり、以下同様。）。この（ａ）成分は、本発明における樹脂含有溶液（Ａ）を構成する樹脂の３〜６０重量％、好ましくは５〜５０重量％を占めるように使用される。３重量％未満であると、得られた樹脂を十分に水に可溶化させることが難しく、その結果後述する（Ｂ）成分のアクリル系樹脂水性エマルジョンとの混和性が低下するという問題が生じ、逆に６０重量％を超えると樹脂含有溶液の粘度が経時と共に高くなるという問題が生じる。
【０００８】
また疎水性単量体（ｂ）としては、例えばメチルメタクリレート（１０５℃）、エチルアクリレート（−２２℃）、ブチルアクリレート（−５４℃）、２-エチルヘキシルアクリレート（−８５℃）、スチレン（１００℃）等のビニル芳香族化合物、塩化ビニル（８０℃）、塩化ビニリデン（−２０℃）等のハロゲン化ビニル、酢酸ビニル（３０℃）、プロピオン酸ビニル（１０℃）等のビニルエステル、エチレン（−１２５℃）、ブタジエン（−１０９℃）等のオレフィン系単量体及びその他アクリロニトリル（１３０℃）等が挙げられる。
【０００９】
この（ｂ）成分は、本発明における樹脂含有溶液（Ａ）を構成する樹脂の４０〜９７重量％、好ましくは５０〜９５重量％を占めるように使用される。４０重量％未満であると、樹脂含有溶液（Ａ）の樹脂とアクリル系樹脂水性エマルジョン（Ｂ）の樹脂との親和力が確保できず、貯蔵中に増粘し易く、また加熱後の充分な粘着特性の発現が得られず、逆に９７重量％を超えると、相対的に（ａ）成分の割合が減ることになり、引いては 樹脂含有溶液（Ａ）の樹脂の凝集、沈殿が生じることとなる。
【００１０】
尚、ここにいう疎水性とは２０℃における水への溶解度が８ｇ／１００ｍｌ以下であることを意味する。
更にその他の単量体（ｃ）としては、具体的には、アクリルアミド（１５３℃）、２−ヒドロキシエチルアクリレート（−１５℃）、ジアセトンアクリルアミド（６５℃）等が挙げられる。
【００１１】
この（ｃ）成分は、樹脂の水溶性の確保又は、後述するガラス転移温度の調製のために、本発明における樹脂含有溶液（Ａ）を構成する樹脂の０〜５０重量％、好ましくは０〜４０重量％を占めるように使用される。５０重量％を超えると、相対的に（ａ）成分及び／又は（ｂ）成分の割合が減ることになり、水性エマルジョン（Ｂ）との混和性が低下したり、経時と共に粘度が上昇するという問題が生じる。
【００１２】
尚、該樹脂含有溶液（Ａ）は、粘着剤組成物を塗工・乾燥時及び塗工したシートをロール状にして保管する際に、粘着性の発現を抑制させるための成分であり、従って常温で粘着性を示さないように、樹脂のガラス転移温度を２０℃以上、好ましくは３０℃〜１３０℃にする必要がある。ガラス転移温度が２０℃未満であると、粘着剤組成物の塗工・乾燥時にすでに粘着性が発現してしまうという問題があり、また、ガラス転移温度が高くなりすぎると、粘着性を発現させるための加熱温度が高くなり、高エネルギーの消費につながる。
【００１３】
また、本願発明の（Ａ）成分は、５重量％以上、好ましくは１０重量％が可溶化されてなる樹脂を含有する樹脂含有溶液である必要がある。本願発明において、可溶化率とは後述する重合法によって重合して得られた樹脂含有溶液を不揮発分が１５重量％になるように水で希釈した後に、その希釈液を遠心加速度１．８×１０5 ｇで６０分間遠心処理し、得られた上澄液中の不揮発分量を測定してｗ重量部とし、また遠心分離に使用した前記の希釈液中の不揮発分量を測定してＷ重量部としたときの下記式で表わされる可溶化率をいう。
【００１４】
可溶化率＝ｗ／Ｗ×１００（重量％）
【００１５】
従って、例えば樹脂含有溶液を製造するための重合前、又は重合中の重合系にアルカリ及び／又は有機溶剤を添加して共重合を行なわせたような場合であって、その重合によって得られた生成共重合体樹脂を含有する重合生成物が、そのままで既に可溶化率が５重量％以上になっているときには、改めて可溶化処理のためのアルカリ及び／又は有機溶剤の添加を行わなくてもよい。
【００１６】
その可溶化処理に使用されるアルカリとしては、無機の水溶性アルカリ、たとえば水酸化ナトリウム、水酸化カリウムなど；又は水に溶解してアルカリ性を示す無機塩類、たとえば炭酸水素ナトリウム、ピロリン酸ナトリウムなど；その他アンモニア水や有機アミンなどが挙げられる。アルカリの添加は、前述のとおり、必ずしも樹脂含有溶液の重合後である必要がなく、場合によっては重合前の単量体にアルカリを添加して中和させてから、共重合を行なわせてもよい。使用されるアルカリの量は、共重合体樹脂中のカルボキシル基を完全に中和する量であってもよいし、部分的に中和する量であってもよい。
【００１７】
可溶化処理に使用される有機溶剤は、アルカリ添加のみでは充分に水可溶化できない場合に補助的に添加してもよいし、有機溶剤のみの添加で可溶化させてもよい。
使用される有機溶剤としては、特に限定されないが、テキサノール、エチレングリコールモノブチルエーテル、エチレングリコールモノエチルエーテル及びそれらのアセテート、ベンジルアルコール、ブチルカルビトールアセテート、２，２，４−トリメチル−１，３−ペンタンジオールなどが挙げられる。
【００１８】
また更に、前記（Ａ）成分の樹脂含有溶液を構成する樹脂の重量平均分子量（Ｍｗ）が、３０００〜３００００であるのが、アクリル系水性エマルジョン（Ｂ）との混和性に優れ、また加熱時の粘着性に優れるので望ましい。Ｍｗが３０００以下であると、低温で乾燥させても粘着性が生じやすく、経時と共にその粘着性が強くなる傾向にある。またＭｗが３００００以上になると（Ｂ）成分の樹脂水性エマルジョンと混合する際の安定性が低下し、また加熱時の粘着性が低下したり、粘着性発現までに長時間要するようになる傾向にある。
【００１９】
前記した（Ａ）成分である樹脂含有溶液の製造方法としては、例えば有機溶媒中で常法にしたがって各構成単量体混合物を重合開始剤、たとえば過酸化ベンゾイルやｔ−ブチルハイドロパーオキシド等の有機過酸化物やアゾビスイソブチロニトリル等のアゾ系開始剤等を用いて溶液重合する方法が挙げられる。この際分子量調節剤として有機ハロゲン化物やアルキルメルカプタン類といった連鎖移動剤を用いることも可能である。こうして得られた樹脂溶液から減圧によって溶媒を留去後、水を加え又必要に応じてさらにアルカリ及び／又は溶剤を添加して、前記した可溶化率を有する樹脂の樹脂含有溶液（Ａ）とする。
【００２０】
また、（Ａ）成分である樹脂含有溶液の他の製造方法としては、常法のエマルジョン重合に従って、即ち乳化剤を用い共重合を構成する単量体混合物を乳化共重合させ、これにアルカリを加えて水溶化する方法もあるが、この方法の場合には、分子量制御のための連鎖移動剤を用いることが必須となる。尚、ここにいうアルカリとは、アンモニア、トリエチルアミン、エタノールアミン等の有機アミン又は水酸化ナトリウム等の無機のアルカリも使用できるがアンモニアを用いるのが最も好ましい。
【００２１】
尚、使用される乳化剤としては、ジアルキルスルホコハク酸ナトリウム、アルキルスルホン酸のアルカリ塩、オキシアルキル化されたアルコールまたはアルキルフェノールのアルカリ金属塩、脂肪酸のアルカリ塩などアニオン性界面活性剤、ノニオン性界面活性剤の各種のものが単独もしくは併用して使用できる。その使用量は、通常樹脂分に対し０．１〜１０重量％の割合である。又、目的によっては、カチオン性界面活性剤を単独で、あるいはノニオン性界面活性剤と併用して使用することもできる。
【００２２】
乳化重合において用いる重合開始剤は、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム、過酸化水素などの無機過酸化物が好ましいが、その他アゾビスイソブチロニトリル、アゾビスバレロニトリルなどのアゾ系開始剤；ベンゾイルパーオキサイド、ラウロイルパーオキサイド、ｔーブチルパーオキサイドなどの有機過酸化物系開始剤も使用できる。また、これらの開始剤に、ロンガリット、Ｌーアスコルビン酸、有機アミン、金属塩などの還元剤を併用してレドックス開始剤として用いてもよい。
【００２３】
また、本発明のディレードタック型粘着剤組成物を構成するアクリル系樹脂水性エマルジョン（Ｂ）を構成する樹脂は、ガラス転移温度が−３０℃以下、好ましくは−４０℃以下であることが必要である。この成分（Ｂ）は、粘着性を発現させるためのものである。
【００２４】
該ガラス転移温度が−３０℃以下の樹脂からなるアクリル系樹脂水性エマルジョンは、例えばブチルアクリレート（−５４℃）、２−エチルヘキシルアクリレート（−８５℃）、ラウリルアクリレート（−６５℃）等の、単独重合体のガラス転移温度が低い単量体から主として構成される。又、ガラス転移温度を調製するために、エチレン（−１２５℃）やブタジエン（−１０９℃）を共重合させることも可能である。
【００２５】
この（Ｂ）の樹脂水性エマルジョンの製造方法としては、エマルジョン重合の常法に従って、即ち乳化剤を用い共重合を構成する単量体混合物を乳化共重合させる方法（詳細は（Ａ）を製造する際のエマルジョン重合の方法と同様。）が挙げられる。
【００２６】
保護コロイド剤としては、たとえばヒドロキシエチルセルロースやポリエチレンオキサイドプロピレンオキサイドブロックポリマー、不飽和カルボン酸共重合体のアルカリ可溶物等がある。
前記各成分の不揮発分の重量比（Ａ）／（Ｂ）は１５／８５〜５０／５０、好ましくは２０／８０〜５０／５０である。（Ａ）成分の割合が１５未満であると、常温で粘着性を示すこととなり、ディレードタック型粘着剤とは成りえず、また、（Ａ）成分の割合が５０を超えると、加熱しても粘着性を有するようにならない。
【００２７】
また、前記（Ａ）成分を構成する樹脂のガラス転移温度が２０〜６０℃である場合は、前記各成分の不揮発分の重量比（Ａ）／（Ｂ）が２５／７５〜５０／５０であるのが好ましく、前記（Ａ）成分を構成する樹脂のガラス転移温度が６０〜１１０℃である場合は、前記各成分の不揮発分の重量比（Ａ）／（Ｂ）が１５／８５〜２５／７５であるのが、好ましい。
【００２８】
本ディレードタック型粘着剤組成物は、特に接着力を向上させる目的で、粘着付与性樹脂、たとえば、ロジン誘導体、テルペン樹脂、石油樹脂などを添加したり、或は、粘着物性を損なわない程度で、パラフィンや長鎖脂肪酸やそのアミド等のワックス類、酸化チタンやタルク等の無機フィラーを添加することも可能である。
【００２９】
尚、本ディレードタック型粘着剤組成物は、紙などの支持体に塗布、乾燥させておき、接着時に加熱により粘着性を発現させ、ラベル、テープ、包装物のシール等に用いられる。
【００３０】
本ディレードタック型粘着剤組成物の基材への塗布後の乾燥温度及び粘着性を発現させる加熱温度は、本発明の（Ａ）成分の樹脂含有溶液を構成する樹脂のガラス転移温度に強く依存する。即ち、乾燥温度は（Ａ）成分中の樹脂のガラス転移温度の＋３０℃以下が好ましく、その温度を超えると乾燥時にすでに粘着性を有することとなり易い。また、粘着性を発現させる加熱温度は、乾燥温度以上の温度が必要であり、好ましくは（Ａ）成分中の樹脂のガラス転移温度の＋３０℃以上である。
【００３１】
【実施例】
次に本発明を実施例および比較例を挙げて詳細に説明する。例中の部および％は特に記載しない限り重量部および重量％である。
製造例１
温度調節器、撹拌機、還流冷却器、供給容器および窒素導入管の付いた反応器にメチルセロソルブ１５０部を仕込み窒素置換した。
反応器を８０℃に加熱後、表１に記載したモノマー混合溶液１００部とｔ−ドデシルメルカプタン０．１部の混合物を供給容器Ｉから、またアゾビスイソブチロニトリル２部をメチルセロソルブ５０部に溶解したものを供給容器ＩＩから各各４時間かけて均一に添加した。
【００３２】
添加終了後、反応器を８０℃に保ってさらに２時間熟成し、均一な重合体溶液を得た。次いで、ロータリーエバポレーターを使って減圧により、メチルセロソルブをほぼ完全に留去した後、脱イオン水を加え、更にアンモニアを加えて中和し、ｐＨ８、不揮発分２５％の樹脂含有溶液を得た。
【００３３】
尚、この樹脂樹脂含有溶液の樹脂の可溶化率は１００％であり、重量平均分子量はゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定したところ約５０００であった。
【００３４】
【表１】
製造例２〜８
製造例１と同一の装置を用い、モノマー組成、溶媒、開始剤などを表１に示すように変更して、各々均一な重合体溶液を得た後、溶媒を留去水置換及び中和によって各々表１に示すような樹脂含有溶液を得た。
製造例９
製造例１と同一装置を用い反応器内に水４０部及び過硫酸ナトリウム０．０６部を装入した。別に供給物Ｉとして下記のものを用意した。
【００３６】
【００３７】
上記の予め開始剤溶液を装入した反応器内を窒素ガス置換した後、同反応器内に上記供給物Ｉの１０％を加え、その混合物を９０℃に加熱した。次いで、供給物ＩＩの１０％を同反応器内に投入してから、供給物Ｉと供給物ＩＩの残りを３〜３．５時間かけて均一に同反応器に供給した。その供給終了後なお１．５時間９０℃に保持して乳化重合させ、樹脂水性エマルジョンを得た。この樹脂水性エマルジョンの不揮発分は約５２％であった。
【００３８】
単量体の組成及び生成したエマルジョンの不揮発分及び樹脂のガラス転移温度（計算値）を表２に示した。
【００３９】
【表２】
製造例１０及び１１
製造例９と同一装置を用い、単量体組成を表２に示すようにそれぞれ変更したほかは、製造例９にしたがって樹脂水性エマルジョンを得た。その結果を表２に示した。
【００４１】
製造例１２
製造例９と同一装置を用い、反応器内に製造例１で製造した樹脂含有溶液１００部装入した。別に供給物Ｉとして下記のものを用意した。
【００４２】
供給物Ｉ
アクリル酸ブチル ９０部
メタクリル酸メチル ９．５部
イタコン酸 ０．５部
また別に、供給物ＩＩとして、水２０部に過硫酸ナトリウム０．６部及び水酸化ナトリウム０．１５部を溶解した開始剤溶液を調製した。
【００４３】
上記の反応容器内を窒素ガス置換した後、同反応容器内に上記供給物Ｉ及びＩＩ各々の１０％を加え、その混合物を９０℃に加熱した。次いで、供給物Ｉ及びＩＩの残りを３時間かけて均一に同反応容器に供給した。その供給終了後なお１．５時間９０℃に保持して乳化重合させ、樹脂水性エマルジョンを得た。この樹脂水性エマルジョンの不揮発分は約４５％であった。結果を表２に示した。
【００４４】
実施例１〜７及び比較例１〜７
上記製造例で製造した樹脂含有溶液と樹脂水性エマルジョンを表３及び表４に記載の割合で混合し、撹拌してディレードタック型粘着剤組成物を調製した。
そして得られた組成物をポリエステルフィルムの表面にアプリケーターを用いて乾燥塗布膜が２５±１ｇ／ｍ2 となるように塗布し、５０℃で１０分間乾燥させて試験片Ａを作成した。
また、これとは別に、同様な塗布条件で塗布し、８０℃で５分間乾燥させて試験片Ｂを作成した。
【００４５】
上記試験片Ａ及びＢについて、以下に示す試験方法及び評価基準で評価を行ない、結果を表３及び表４に示した。
尚、比較例３は、混合安定性が悪く一日静置後に水層とエマルジョン層の２層に分離してしまった。また、比較例６は、均一に混合するのが難しく、乾燥塗布膜は不均一であった。
【００４６】
接着力試験；上記の試験片（２．５×１０cm）を１４０℃で３０秒間加熱した後、表面を研磨したステンレス板（ＳＵＳ）に接着させ、引っ張り試験機（インストロン社製）を用いて１８０°の引っ張り強度（引っ張り速度: ３００mm／分）を測定し、以下の基準で評価した。
【００４７】
◎・・・１０００ｇ／２５mm超
○・・・７５０〜１０００ｇ／２５mm
△・・・５００〜７５０ｇ／２５mm
×・・・５００ｇ／２５mm未満
【００４８】
保持力試験；上記の試験片（２．０×２．０cm）を１４０℃で３０秒間加熱した後、表面研磨したステンレス板（ＳＵＳ）に接着させ、１Ｋｇの荷重をかけ、２０℃、湿度６５％の条件下で保持力（剥離するまでの時間）を測定し、以下の基準で評価した。
【００４９】
◎・・・６０分超
○・・・３０〜６０分
△・・・１０〜３０分
× ・・１０分未満
【００５０】
ブロッキング試験；上記の試験片Ａ及びＢの粘着剤組成物塗布面を重ね、その上から０．５ｋｇ／ｃｍ2 の荷重で４０℃１日放置後剥離させた時の状態を、以下の基準で評価した。
【００５１】
◎・・・全く抵抗なく引き剥がせる
○・・・１０ｇ／２５mm未満の強度で引き剥がせる
△・・・１０〜２０ｇ／２５mmの強度で引き剥がせる
×・・・２０ｇ／２５mm以上の引き剥がし強度が必要である
【００５２】
【表３】
【表４】
【発明の効果】
本発明のディレードタック型粘着剤組成物は、常温では粘着性を示さず、一定温度以上に加熱することによって粘着性を発現するので、取扱性に優れ、また加熱後の粘着特性即ち接着力、保持力とも優れていると共に、本粘着剤組成物を塗工したシートは耐ブロッキング性に優れているので、ディレードタック型粘着剤として有用であり、また剥離紙の不要な粘着シートを提供することが可能である。剥離紙の不要は省資源化の面からも極めて有益である。[0001]
[Industrial application fields]
The present invention relates to an emulsion-type pressure-sensitive adhesive composition, and in particular, does not exhibit adhesiveness at normal temperature, but develops adhesiveness when heated to a certain temperature or higher, and has a delayed tack-type adhesive with excellent handling properties. The agent composition.
[0002]
[Prior art and problems to be solved by the invention]
Conventionally, a pressure-sensitive adhesive composition is applied to a sheet and then dried to form a sheet-like pressure-sensitive adhesive, and the sheet coated with the pressure-sensitive adhesive is often stored in a roll shape. Release paper is currently used for the purpose of preventing the back surface of the base material and the adhesive-coated surface from adhering to each other during storage. There are problems such that the release paper that is unnecessary after use is expensive, and various measures have been taken so that the back surface of the substrate and the adhesive-coated surface are not adhered even if the release paper is not used as much as possible.
[0003]
For example, a crystalline plasticizer that melts only when heated by blending a crystalline plasticizer with a purpose of suppressing adhesiveness at room temperature into a delayed tack type adhesive composition comprising a thermoplastic resin and a tackifying resin. There is a method in which a thermoplastic resin is softened and, as a result, adhesiveness is developed.
However, since the crystalline plasticizer gradually diffuses into the adhesive even below its melting point and softens the thermoplastic resin, it becomes sticky over time, and the back surface of the substrate and the adhesive coated surface still remain during storage. The problem of causing the adhesion with was left.
[0004]
On the other hand, as a solution to the above problem, a method of adding wax in place of the crystalline plasticizer has also been tried, but it is not only insufficient to suppress the expression of tackiness caused by the passage of time. There was a problem that the adhesiveness after heating was impaired.
In addition, since all of the delayed tack type adhesives currently used or proposed exhibit adhesiveness at a relatively low temperature, it is necessary to lower the drying temperature when the adhesive is dried on the base material. The production efficiency was extremely low.
[0005]
[Means for Solving the Problems]
As a result of repeating various studies to solve the above-mentioned problems, the present inventors have found that the object of the present invention can be achieved by adopting the following configuration, and have completed the present invention.
That is, the delayed tack-type pressure-sensitive adhesive composition of the present invention comprises (A) an unsaturated monomer having a carboxyl group (a) 3 to 60% by weight, a hydrophobic monomer (b) 40 to 97% by weight, and others. A resin containing a resin having a glass transition temperature of 20 ° C. or higher obtained by copolymerizing 0 to 50% by weight of the monomer (c), and a resin in which 5% by weight or more is solubilized And (B) an acrylic resin aqueous emulsion composed of a resin having a glass transition temperature of −30 ° C. or lower, and the weight ratio (A) / (B) of the non-volatile components of each component is 15 / 85-50 / It is in the delayed tack type adhesive composition which is 50.
[0006]
The resin constituting the resin-containing solution (A) constituting the delayed tack-type pressure-sensitive adhesive composition of the present invention is composed of 3 to 60% by weight of unsaturated monomer (a) having a carboxyl group, hydrophobic monomer (b ) A resin obtained by copolymerizing 40 to 97% by weight and other monomer (c) 0 to 50% by weight.
[0007]
Examples of the unsaturated monomer (a) having a carboxyl group include acrylic acid (105 ° C.), methacrylic acid (130 ° C.), itaconic acid (160 ° C.) and the like. This is the glass transition temperature of the coalescence, and so on.) This component (a) is used so as to occupy 3 to 60% by weight, preferably 5 to 50% by weight of the resin constituting the resin-containing solution (A) in the present invention. If it is less than 3% by weight, it is difficult to sufficiently solubilize the obtained resin in water, and as a result, there arises a problem that the miscibility with the aqueous acrylic resin emulsion of the component (B) described later is reduced. Conversely, if it exceeds 60% by weight, there arises a problem that the viscosity of the resin-containing solution increases with time.
[0008]
Examples of the hydrophobic monomer (b) include methyl methacrylate (105 ° C.), ethyl acrylate (−22 ° C.), butyl acrylate (−54 ° C.), 2-ethylhexyl acrylate (−85 ° C.), styrene (100 ° C. Vinyl aromatic compounds such as vinyl chloride (80 ° C.), vinyl halides such as vinylidene chloride (−20 ° C.), vinyl esters such as vinyl acetate (30 ° C.), vinyl propionate (10 ° C.), ethylene (− 125 ° C.), olefinic monomers such as butadiene (−109 ° C.), and other acrylonitrile (130 ° C.).
[0009]
This component (b) is used so as to occupy 40 to 97% by weight, preferably 50 to 95% by weight of the resin constituting the resin-containing solution (A) in the present invention. If it is less than 40% by weight, the affinity between the resin of the resin-containing solution (A) and the resin of the acrylic resin aqueous emulsion (B) cannot be ensured, the viscosity tends to increase during storage, and sufficient adhesion after heating. If the expression of the characteristics is not obtained, and if the content exceeds 97% by weight, the proportion of the component (a) is relatively decreased, and the resin in the resin-containing solution (A) is aggregated and precipitated. It becomes.
[0010]
In addition, the hydrophobicity here means that the solubility in water at 20 ° C. is 8 g / 100 ml or less.
Specific examples of the other monomer (c) include acrylamide (153 ° C.), 2-hydroxyethyl acrylate (−15 ° C.), diacetone acrylamide (65 ° C.), and the like.
[0011]
This component (c) is 0 to 50% by weight, preferably 0 to 0% by weight of the resin constituting the resin-containing solution (A) in the present invention in order to ensure the water solubility of the resin or to adjust the glass transition temperature described later. Used to account for 40% by weight. When it exceeds 50% by weight, the proportion of the component (a) and / or the component (b) is relatively decreased, the miscibility with the aqueous emulsion (B) is decreased, and the viscosity is increased with time. Problems arise.
[0012]
The resin-containing solution (A) is a component for suppressing the expression of adhesiveness when the pressure-sensitive adhesive composition is coated and dried and when the coated sheet is stored in the form of a roll. The glass transition temperature of the resin needs to be 20 ° C. or higher, preferably 30 ° C. to 130 ° C. so as not to exhibit tackiness at normal temperature. If the glass transition temperature is less than 20 ° C., there is a problem that the tackiness is already developed at the time of coating / drying of the pressure-sensitive adhesive composition, and if the glass transition temperature is too high, the tackiness is developed. Because of this, the heating temperature increases, leading to high energy consumption.
[0013]
Further, the component (A) of the present invention needs to be a resin-containing solution containing a resin in which 5% by weight or more, preferably 10% by weight, is solubilized. In the present invention, the solubilization rate is a resin-containing solution obtained by polymerization by a polymerization method described later, diluted with water so that the non-volatile content is 15% by weight, and then the diluted solution is subjected to a centrifugal acceleration of 1.8 × Centrifugation at 10 5 g for 60 minutes, the amount of non-volatile content in the resulting supernatant was measured to be w parts by weight, and the amount of non-volatile content in the diluent used for centrifugation was measured to be W parts by weight The solubilization rate represented by the following formula.
[0014]
Solubilization rate = w / W x 100 (wt%)
[0015]
Therefore, for example, in the case where copolymerization is carried out by adding an alkali and / or organic solvent to a polymerization system during polymerization for producing a resin-containing solution, and obtained by the polymerization. When the solubilization rate of the polymerization product containing the produced copolymer resin is already 5% by weight or more as it is, there is no need to newly add an alkali and / or organic solvent for the solubilization treatment. Good.
[0016]
Examples of the alkali used for the solubilization treatment include inorganic water-soluble alkalis such as sodium hydroxide and potassium hydroxide; or inorganic salts which show alkalinity when dissolved in water, such as sodium bicarbonate and sodium pyrophosphate; Other examples include ammonia water and organic amines. As described above, it is not always necessary to add the alkali after the polymerization of the resin-containing solution. In some cases, the alkali may be added to neutralize the monomer before the polymerization, and then copolymerization may be performed. Good. The amount of alkali used may be an amount that completely neutralizes the carboxyl groups in the copolymer resin, or may be an amount that partially neutralizes.
[0017]
The organic solvent used for the solubilization treatment may be supplementarily added when water cannot be sufficiently solubilized only by addition of alkali, or may be solubilized by addition of only the organic solvent.
The organic solvent used is not particularly limited, but texanol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether and their acetates, benzyl alcohol, butyl carbitol acetate, 2,2,4-trimethyl-1,3- Examples include pentanediol.
[0018]
Furthermore, the resin constituting the resin-containing solution of the component (A) has a weight average molecular weight (Mw) of 3000 to 30000, which is excellent in miscibility with the acrylic aqueous emulsion (B) and when heated. It is desirable because of its excellent adhesiveness. When Mw is 3000 or less, even if it is dried at a low temperature, tackiness tends to occur, and the tackiness tends to increase with time. Moreover, when Mw becomes 30000 or more, the stability at the time of mixing with the resin aqueous emulsion of the component (B) is lowered, the adhesiveness at the time of heating is lowered, or it tends to take a long time to develop the adhesiveness. is there.
[0019]
As a method for producing the resin-containing solution which is the component (A), for example, each constituent monomer mixture is polymerized in an organic solvent according to a conventional method, for example, benzoyl peroxide or t-butyl hydroperoxide. Examples thereof include a solution polymerization method using an azo initiator such as an organic peroxide or azobisisobutyronitrile. In this case, a chain transfer agent such as an organic halide or an alkyl mercaptan can be used as a molecular weight modifier. After distilling off the solvent from the resin solution thus obtained under reduced pressure, water is added and, if necessary, an alkali and / or solvent is further added, and the resin-containing solution (A) of the resin having the above-described solubilization rate and To do.
[0020]
In addition, as another method for producing the resin-containing solution which is the component (A), according to a conventional emulsion polymerization, that is, an emulsifier is used to emulsion-copolymerize a monomer mixture constituting the copolymer, and an alkali is added thereto. However, in this method, it is essential to use a chain transfer agent for controlling the molecular weight. In addition, although an alkali alkali such as ammonia, an organic amine such as triethylamine or ethanolamine, or an inorganic alkali such as sodium hydroxide can be used, it is most preferable to use ammonia.
[0021]
Examples of the emulsifier used include sodium dialkylsulfosuccinate, alkali salts of alkylsulfonic acid, alkali metal salts of oxyalkylated alcohols or alkylphenols, alkali salts of fatty acids, nonionic surfactants, and the like. These can be used alone or in combination. The amount used is usually 0.1 to 10% by weight based on the resin content. Depending on the purpose, a cationic surfactant can be used alone or in combination with a nonionic surfactant.
[0022]
The polymerization initiator used in the emulsion polymerization is preferably an inorganic peroxide such as potassium persulfate, sodium persulfate, ammonium persulfate or hydrogen peroxide, but other azo initiators such as azobisisobutyronitrile and azobisvaleronitrile. Agents: Organic peroxide initiators such as benzoyl peroxide, lauroyl peroxide, and t-butyl peroxide can also be used. These initiators may be used as a redox initiator in combination with a reducing agent such as Rongalite, L-ascorbic acid, an organic amine, or a metal salt.
[0023]
Further, the resin constituting the acrylic resin aqueous emulsion (B) constituting the delayed tack-type pressure-sensitive adhesive composition of the present invention needs to have a glass transition temperature of −30 ° C. or lower, preferably −40 ° C. or lower. is there. This component (B) is for expressing adhesiveness.
[0024]
The acrylic resin aqueous emulsion composed of a resin having a glass transition temperature of −30 ° C. or lower is, for example, butyl acrylate (−54 ° C.), 2-ethylhexyl acrylate (−85 ° C.), lauryl acrylate (−65 ° C.), or the like. The polymer is mainly composed of monomers having a low glass transition temperature. In order to adjust the glass transition temperature, ethylene (-125 ° C) or butadiene (-109 ° C) can be copolymerized.
[0025]
As the method for producing the aqueous resin emulsion (B), a method of emulsion copolymerization according to a conventional method of emulsion polymerization, that is, a monomer mixture constituting copolymerization using an emulsifier (for details, when producing (A) The same as in the emulsion polymerization method.).
[0026]
Examples of the protective colloid agent include hydroxyethyl cellulose, polyethylene oxide propylene oxide block polymer, and an alkali-soluble material of unsaturated carboxylic acid copolymer.
The weight ratio (A) / (B) of the non-volatile content of each component is 15/85 to 50/50, preferably 20/80 to 50/50. When the proportion of the component (A) is less than 15, it will exhibit adhesiveness at room temperature and cannot be a delayed tack type adhesive, and when the proportion of the component (A) exceeds 50, it is heated. Does not become sticky.
[0027]
Moreover, when the glass transition temperature of resin which comprises the said (A) component is 20-60 degreeC, weight ratio (A) / (B) of the non volatile matter of each said component is 25 / 75-50 / 50. Preferably, when the glass transition temperature of the resin constituting the component (A) is 60 to 110 ° C., the weight ratio (A) / (B) of the non-volatile content of each component is 15/85 to 25 / 75 is preferred.
[0028]
This delayed tack-type pressure-sensitive adhesive composition is added to a tackifying resin, for example, a rosin derivative, a terpene resin, a petroleum resin, etc. for the purpose of particularly improving the adhesive strength, or the adhesive physical properties are not impaired. It is also possible to add waxes such as paraffin, long chain fatty acids and amides thereof, and inorganic fillers such as titanium oxide and talc.
[0029]
The delayed tack-type pressure-sensitive adhesive composition is applied to a support such as paper and dried, and exhibits adhesiveness by heating at the time of adhesion, and is used for sealing labels, tapes, packages, and the like.
[0030]
The drying temperature after application of the delayed tack-type pressure-sensitive adhesive composition to the base material and the heating temperature at which the adhesiveness is developed strongly depend on the glass transition temperature of the resin constituting the resin-containing solution of the component (A) of the present invention. To do. That is, the drying temperature is preferably + 30 ° C. or less of the glass transition temperature of the resin in the component (A), and if it exceeds that temperature, it tends to already have tackiness during drying. In addition, the heating temperature for developing the adhesive property needs to be a temperature equal to or higher than the drying temperature, and is preferably + 30 ° C. or higher of the glass transition temperature of the resin in the component (A).
[0031]
【Example】
Next, the present invention will be described in detail with reference to examples and comparative examples. Parts and% in the examples are parts by weight and% by weight unless otherwise specified.
Production Example 1
A reactor equipped with a temperature controller, a stirrer, a reflux condenser, a supply container, and a nitrogen introduction tube was charged with 150 parts of methyl cellosolve and purged with nitrogen.
After the reactor was heated to 80 ° C., a mixture of 100 parts of the monomer mixed solution described in Table 1 and 0.1 part of t-dodecyl mercaptan was supplied from the supply vessel I, and 2 parts of azobisisobutyronitrile was added to 50 parts of methyl cellosolve. The product dissolved in was added uniformly from the supply container II over 4 hours each.
[0032]
After completion of the addition, the reactor was kept at 80 ° C. and further aged for 2 hours to obtain a uniform polymer solution. Subsequently, after the methyl cellosolve was almost completely distilled off under reduced pressure using a rotary evaporator, deionized water was added and neutralized by adding ammonia to obtain a resin-containing solution having a pH of 8 and a nonvolatile content of 25%.
[0033]
In addition, the resin solubilization rate of this resin resin-containing solution was 100%, and the weight average molecular weight was about 5000 as measured by gel permeation chromatography (GPC).
[0034]
[Table 1]
Production Examples 2-8
Using the same apparatus as in Production Example 1, the monomer composition, solvent, initiator, etc. were changed as shown in Table 1 to obtain uniform polymer solutions, respectively, and then the solvent was distilled off with water and neutralized. Resin-containing solutions as shown in Table 1 were obtained.
Production Example 9
Using the same apparatus as in Production Example 1, 40 parts of water and 0.06 part of sodium persulfate were charged into the reactor. Separately, the following was prepared as feed I.
[0036]
[0037]
After the inside of the reactor charged with the initiator solution was replaced with nitrogen gas, 10% of the feed I was added to the reactor, and the mixture was heated to 90 ° C. Then, 10% of Feed II was charged into the reactor, and Feed I and the remainder of Feed II were fed uniformly into the reactor over 3 to 3.5 hours. After the completion of the supply, the mixture was held at 90 ° C. for 1.5 hours for emulsion polymerization to obtain an aqueous resin emulsion. The non-volatile content of this aqueous resin emulsion was about 52%.
[0038]
Table 2 shows the composition of the monomer, the nonvolatile content of the produced emulsion, and the glass transition temperature (calculated value) of the resin.
[0039]
[Table 2]
Production Examples 10 and 11
A resin aqueous emulsion was obtained according to Production Example 9, except that the same apparatus as in Production Example 9 was used and the monomer composition was changed as shown in Table 2. The results are shown in Table 2.
[0041]
Production Example 12
Using the same apparatus as in Production Example 9, 100 parts of the resin-containing solution produced in Production Example 1 was charged into the reactor. Separately, the following was prepared as feed I.
[0042]
Supply I
Butyl acrylate 90 parts Methyl methacrylate 9.5 parts Itaconic acid 0.5 parts In addition, as feed II, an initiator in which 0.6 parts of sodium persulfate and 0.15 parts of sodium hydroxide were dissolved in 20 parts of water A solution was prepared.
[0043]
After replacing the inside of the reaction vessel with nitrogen gas, 10% of each of the feeds I and II was added to the reaction vessel, and the mixture was heated to 90 ° C. The remainder of feeds I and II were then fed uniformly to the reaction vessel over 3 hours. After the completion of the supply, the mixture was held at 90 ° C. for 1.5 hours for emulsion polymerization to obtain an aqueous resin emulsion. The non-volatile content of this aqueous resin emulsion was about 45%. The results are shown in Table 2.
[0044]
Examples 1-7 and Comparative Examples 1-7
The resin-containing solution and aqueous resin emulsion produced in the above production examples were mixed at the ratios shown in Tables 3 and 4 and stirred to prepare a delayed tack-type pressure-sensitive adhesive composition.
And the obtained composition was apply | coated to the surface of the polyester film using the applicator so that a dry application film | membrane might be 25 +/- 1g / m < 2 >, and it was made to dry at 50 degreeC for 10 minutes, and the test piece A was created.
Separately, it was coated under the same coating conditions and dried at 80 ° C. for 5 minutes to prepare a test piece B.
[0045]
The test pieces A and B were evaluated according to the following test methods and evaluation criteria, and the results are shown in Tables 3 and 4.
In Comparative Example 3, the mixing stability was poor and the mixture was separated into two layers, an aqueous layer and an emulsion layer, after standing for one day. In Comparative Example 6, it was difficult to mix uniformly, and the dry coating film was non-uniform.
[0046]
Adhesive strength test: The above test piece (2.5 × 10 cm) was heated at 140 ° C. for 30 seconds, then adhered to a polished stainless steel plate (SUS), and a tensile tester (Instron) was used. The 180 ° tensile strength (tensile speed: 300 mm / min) was measured and evaluated according to the following criteria.
[0047]
◎ ... More than 1000g / 25mm ○ ... 750-1000g / 25mm
△ ... 500-750g / 25mm
× ・ ・ ・ less than 500g / 25mm
Holding power test: The above test piece (2.0 × 2.0 cm) was heated at 140 ° C. for 30 seconds, then adhered to a surface-polished stainless steel plate (SUS), applied with a load of 1 kg, 20 ° C., humidity 65 The holding power (time until peeling) was measured under the condition of% and evaluated according to the following criteria.
[0049]
◎ ... More than 60 minutes ○ ... 30-60 minutes △ ... 10-30 minutes × ・ ・ Less than 10 minutes [0050]
Blocking test: The above-mentioned test pieces A and B were coated with the pressure-sensitive adhesive composition-coated surface, and the state when peeled after standing at 40 ° C. for 1 day with a load of 0.5 kg / cm 2 was measured according to the following criteria. evaluated.
[0051]
◎ ・ ・ ・ Peel off without resistance ○ ・ ・ ・ Peel off with strength less than 10g / 25mm △ ・ ・ ・ Peel off with strength of 10-20g / 25mm × ・ ・ ・ Peel off over 20g / 25mm Strength is required [0052]
[Table 3]
[Table 4]
【The invention's effect】
The delayed tack-type pressure-sensitive adhesive composition of the present invention does not exhibit tackiness at room temperature, and exhibits tackiness by heating to a certain temperature or higher, so that it is easy to handle and also has adhesive properties after heating, that is, adhesive strength, A sheet coated with this pressure-sensitive adhesive composition is also excellent in holding power, and is excellent in anti-blocking property. Therefore, it is useful as a delayed tack-type pressure-sensitive adhesive and provides a pressure-sensitive adhesive sheet that does not require a release paper. Is possible. The need for release paper is extremely beneficial from the viewpoint of resource saving.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07565995A JP3670049B2 (en) | 1995-03-31 | 1995-03-31 | Delayed tack type pressure-sensitive adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07565995A JP3670049B2 (en) | 1995-03-31 | 1995-03-31 | Delayed tack type pressure-sensitive adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08269420A JPH08269420A (en) | 1996-10-15 |
| JP3670049B2 true JP3670049B2 (en) | 2005-07-13 |
Family
ID=13582587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07565995A Expired - Fee Related JP3670049B2 (en) | 1995-03-31 | 1995-03-31 | Delayed tack type pressure-sensitive adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3670049B2 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08269431A (en) * | 1995-03-31 | 1996-10-15 | Mitsubishi Chem Basf Co Ltd | Pressure-sensitive adhesive composition |
| WO1998003602A1 (en) * | 1996-07-19 | 1998-01-29 | Toagosei Co., Ltd. | Heat-sensitive and pressure-sensitive adhesive sheet |
| JP4580484B2 (en) * | 1999-05-19 | 2010-11-10 | 大日本印刷株式会社 | Lid material |
| JP2002226823A (en) * | 2001-01-31 | 2002-08-14 | Mitsubishi Chemicals Corp | Heat-sensitive tacky adhesive agent composition and heat- sensitive tacky adhesive sheet or label |
| JP2003063539A (en) * | 2001-08-23 | 2003-03-05 | Dainippon Printing Co Ltd | Re-sealable pillow type bag |
| JP5230884B2 (en) * | 2001-09-21 | 2013-07-10 | 大日本印刷株式会社 | Resealable packaging bag. |
| JP4629406B2 (en) * | 2004-10-25 | 2011-02-09 | 大日本印刷株式会社 | Resealable pillow type bag and gusset pillow type bag |
| JP5551850B2 (en) * | 2006-08-08 | 2014-07-16 | 高圧ガス工業株式会社 | Thermal adhesive and thermal label using the same |
| CN103261251B (en) * | 2010-09-17 | 2016-08-03 | 科思创德国股份有限公司 | For the method manufacturing the goods of binding agent coating, the goods that can be obtained by it and their purposes |
| US9290682B2 (en) * | 2011-11-18 | 2016-03-22 | 3M Innovative Properties Company | Pressure-sensitive adhesive composition |
| JP6196538B2 (en) * | 2013-11-14 | 2017-09-13 | 旭化成株式会社 | Cover material for press-through pack packaging body, manufacturing method thereof, and packaging body |
| JP6315946B2 (en) * | 2013-11-14 | 2018-04-25 | 旭化成株式会社 | Press-through pack packaging lid and packaging |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54137031A (en) * | 1978-04-17 | 1979-10-24 | Mitsui Toatsu Chem Inc | Vinyl polymer emulsion for adhesives |
| JPH07107150B2 (en) * | 1987-03-27 | 1995-11-15 | 日本合成ゴム株式会社 | Emulsion type pressure sensitive adhesive |
| EP0303430B1 (en) * | 1987-08-14 | 1993-12-22 | Minnesota Mining And Manufacturing Company | Pressure-sensitive adhesive |
| EP0357229B1 (en) * | 1988-08-01 | 1994-01-05 | E.I. Du Pont De Nemours And Company | Acrylic hot melt pressure sensitive adhesive compositions |
| US5095065A (en) * | 1989-06-02 | 1992-03-10 | Exxon Chemical Patents Inc. | Internal resin-tackified acrylic polymers |
| DE4219651A1 (en) * | 1992-06-16 | 1993-12-23 | Basf Ag | Use of aqueous dispersions as a heat seal adhesive |
| JPH07173436A (en) * | 1992-12-28 | 1995-07-11 | Mitsui Toatsu Chem Inc | Hot-melt pressure-sensitive adhesive composition curable with active energy ray |
| JPH06346026A (en) * | 1993-06-10 | 1994-12-20 | Mitsui Toatsu Chem Inc | Composition for activating energy ray curing type hot-melt pressure sensitive adhesive and adhesive product using this composition and production of adhesive product |
| JPH08269431A (en) * | 1995-03-31 | 1996-10-15 | Mitsubishi Chem Basf Co Ltd | Pressure-sensitive adhesive composition |
-
1995
- 1995-03-31 JP JP07565995A patent/JP3670049B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08269420A (en) | 1996-10-15 |
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