JP3964264B2 - Synthetic resin water-based emulsion type pressure-sensitive adhesive and method for producing the same - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、耐熱性、耐候性に優れているアクリル系感圧接着剤の内、ポリオレフィン系樹脂に対する強い粘着性と耐水白化性が優れ、有機溶媒を含まないため大気汚染防止、作業環境保全性に好ましいとされた合成樹脂水性エマルジョン型感圧接着剤に関する。
【０００２】
【従来の技術】
家電品、日用品、建材等の用途に、感圧接着剤を加工して得られる粘着テープ、粘着ラベル、両面粘着テープ等の粘着製品が広く用いられている。これらの粘着製品に用いられる感圧接着剤として、物性バランスのほか耐熱性、耐候性等の耐久性が優れたアクリル系感圧接着剤が普及している。なかでも大気汚染防止、作業環境改善の観点から合成樹脂水性エマルジョン型アクリル系感圧接着剤が広く用いられ、ポリオレフィン類に対する粘着力を向上させるために炭化水素系、テルペン系、ロジン系等の粘着付与樹脂を添加するのが一般的である。
しかし、従来の合成樹脂水性エマルジョン型アクリル系感圧接着剤は高湿度環境下や水浸漬時において白濁を生じ、耐水白化性が悪くなるために、透明ラベルなど意匠性が要求される分野では殆ど使用されていない。
【０００３】
例えば、特許２５９９５８９号（特開昭６３−２５６６７２号、荒川化学工業（株））には、通常アニオン系界面活性剤を用いて粘着付与樹脂をエマルジョン化した粘着付与樹脂エマルジョンに合成樹脂水性アクリル系重合体エマルジョンとをブレンドしてなる感圧接着剤が開示されている。しかしこの感圧接着剤は粘着付与樹脂をエマルジョン化するために界面活性剤を使用しているために耐水白化性の低下を引き起こし易く、更に粘着付与樹脂をエマルジョン化したとき、粘着付与樹脂エマルジョン粒子を０．２μｍ以下まで分散にすることが困難なために透明性と耐水白化性の低下が避けられない。
【０００４】
また特許１８３２４５５号（特開昭５８−１８５６６８号、特公平２−３０３５１号、ヘキスト合成（株））、特開平８−２３１９３７号（積水化学工業（株））及び特開平９−１１１２１８号公報（旭化成工業（株））等には、粘着付与樹脂をモノマーに溶解させ、更にはそれに界面活性剤水溶液を加えてモノマーを乳化させて、通常の乳化重合を行う方法が開示されているが、通常モノマー乳化で得られるモノマー油滴の平均粒子径は１〜５μｍと大きく、且つ、モノマーは界面活性剤ミセルやポリマー重合体粒子に水相を介して拡散されて重合が行われるが、粘着付与樹脂は水相を介しての拡散は困難なので、重合後、最終生成ポリマー粒子と粘着付与樹脂の巨大粒子とが個別に存在したり、粘着付与樹脂が凝集物となることが多い。従って、これらの方法ではエマルジョン中に１μｍ以上の粘着付与樹脂の巨大粒子が生成して、ポリオレフィン類に対する粘着性の低下とと耐水白化性が低下を引き起こすことが避けられなかった。
【０００５】
また特開２０００−３１３８６５号公報（東洋インキ製造（株））には、アルキル基の炭素数が９〜１４の（メタ）アクリル酸エステルに粘着付与樹脂と油溶性開始剤を溶解させ、平均粒子径が１μｍ以下のモノマー油滴を形成させた後、モノマー油滴内で乳化重合を行う方法が開示されている。この方法では粘着付与樹脂の巨大粒子の生成が抑制され、ポリオレフィン類に対する粘着性は向上するが、モノマー油滴の平均粒子径を０．１５μｍ以下まで小さくしないとポリマー粒子の平均粒子径を０．０５〜０．１５μｍまで小さくすることが困難である。しかしこの方法でモノマー油滴の平均粒子径を０．１５μｍ以下にすることが困難であるために、この方法を用いてもポリオレフィン類に対する粘着性と耐水白化性を両立させることは困難であった。
【０００６】
本発明者らは上記の問題を解決するため、従来のアクリル系水性エマルジョン型感圧接着剤のポリオレフィン系樹脂に対する粘着性と耐水白化性を検討した結果、水性エマルジョン粒子径サイズ（粘着付与樹脂およびアクリル共重合体）は小さいほど好ましいだけでなく、エマルジョン粒子の構成が強く影響することを見出した。即ちメカニズムまでは解明できなかったが、結果的に粘着付与樹脂とアクリル共重合体が同一粒子内にあるのではなく、できるだけ別個に存在する方が粘着性を低下させずに耐水白化性に優れた水性エマルジョン型感圧接着剤となることを見出した。このため粒子サイズの小さい粘着付与樹脂粒子およびアクリル共重合体粒子をいかにして製造するかが問題となる。
【０００７】
【発明が解決しようとする課題】
本発明は、耐熱性、耐候性に優れたアクリル系感圧接着剤の内で、ポリオレフィン系樹脂に対する強い粘着性及び耐水白化性に優れ、大気汚染防止、環境保全性に優れた水性エマルジョン型感圧接着剤を提供することを目的とする。
【０００８】
【課題を解決するための手段】
本発明は、
［１］ アルキル基の炭素数が４〜８の（メタ）アクリル酸アルキルエステルを主成分とするモノマー（Ａ）と粘着付与樹脂（Ｂ）からなる成分をアニオン性界面活性剤（Ｃ）を含有する水溶液を用いて乳化分散し、平均粒子径が０．４μｍ以下となるモノマー乳化液（Ｄ）となし、これを水溶性重合開始剤及びアニオン性界面活性剤（Ｅ）を含有する重合用水溶液（Ｆ）中に滴下しながら重合してポリマー粒子の平均粒子径が０．０５〜０．１５μｍの合成樹脂水性エマルジョンとすることを特徴とする水性エマルジョン型感圧接着剤の製造方法、
［２］ モノマー（Ａ）が、アルキル基の炭素数が４〜８の（メタ）アクリル酸アルキルエステルを５０〜９９．４９重量％、カルボキシル基を有するモノマーを０．５〜５．０重量％、アルコキシシリル基を有するモノマーを０．０１〜１．０重量％を必須成分として含有するモノマーの混合物である上記［１］に記載の水性エマルジョン型感圧接着剤の製造方法、
［３］ モノマー乳化液（Ｄ）が、モノマー（Ａ）１００重量部に対し、粘着付与樹脂（Ｂ）４〜２０重量部、ポリオキシアルキレン構造と不飽和二重結合を有するアニオン性界面活性剤（Ｃ）０．５〜２．０重量部を含有する水溶液である上記［１］に記載の水性エマルジョン型感圧接着剤の製造方法、
［４］ 重合用水溶液（Ｆ）が、モノマー（Ａ）１００重量部に対し、水溶性重合開始剤及びポリオキシアルキレン構造と不飽和二重結合を有するアニオン性界面活性剤（Ｅ）０．１〜２．０重量部を含有する水溶液である上記［１］に記載の合成樹脂水性エマルジョン型感圧接着剤の製造方法、
［５］ 粘着付与樹脂（Ｂ）として、脂環族石油樹脂を用いることを特徴とする上記［１］または［３］に記載の合成樹脂水性エマルジョン型感圧接着剤の製造方法、及び
【０００９】
［６］ 粘着付与樹脂の存在下に、アルキル基の炭素数が４〜８の（メタ）アクリル酸アルキルエステルを５０〜９９．４９重量％、カルボキシル基を有するモノマーを０．５〜５．０重量％、アルコキシシリル基を有するモノマーを０．０１〜１．０重量％を必須成分として含有するモノマーの混合物と、ポリオキシアルキレン構造と不飽和二重結合を有するアニオン性界面活性剤からなる平均粒子径０．４μｍ以下のモノマー乳化液を、水溶性重合開始剤と不飽和二重結合を有するアニオン性界面活性剤を含有する重合用水溶液中で共重合して得られたポリマー粒子の平均粒子径が０．０５〜０．１５μｍの合成樹脂水性エマルジョンからなる水性エマルジョン型感圧接着剤、を開発することにより上記の課題を解決した。
【００１０】
【発明の実施の形態】
本発明者らは上記の課題、即ち結果的に粘着付与樹脂とアクリル共重合体が同一粒子内にあるのではなく、できるだけ別個に形成するべく、モノマーとして粘着付与樹脂を溶解可能で、且つ重合用水溶液（Ｆ）の水相を通して界面活性剤ミセルへ拡散するように、アルキル基の炭素数が４〜８の（メタ）アクリル酸アルキルエステルを主成分とするモノマー（Ａ）を選び、これで粘着付与樹脂（Ｂ）を溶解したモノマー油滴成分を、アニオン性界面活性剤水溶液（Ｃ）中に機械的に強制乳化分散して平均粒子径が０．４μｍ以下となるモノマー乳化液（Ｄ）を製造し、次にこれを、水溶性重合開始剤とアニオン性界面活性剤（Ｅ）を含有する重合用水溶液（Ｆ）中に滴下しながら重合する。
【００１１】
かくして重合用水溶液（Ｆ）中の界面活性剤ミセルで重合が開始され、重合核となる粒子数が格段に多くなり、モノマー乳化液（Ｄ）中の（モノマー＋粘着付与樹脂）粒子からモノマー（Ａ）が重合用水溶液（Ｆ）中に溶解して重合用水溶液（Ｆ）中のアニオン性界面活性剤（Ｅ）で安定化された共重合体粒子を形成するものと考えられる。このためモノマー乳化液（Ｄ）中の（モノマー＋粘着付与樹脂）粒子は、モノマーの溶解流出に伴いそのサイズを小さくなる。そして粘着付与樹脂とアクリル共重合体とが別個の粒子として、ポリマー粒子の平均粒子径が０．０５〜０．１５μｍとして存在するエマルジョンとなるものと推定している。この結果粘着付与樹脂が微細に分散し、且つ、ポリマー粒子の平均粒子径が０．０５〜０．１５μｍとなるポリオレフィン類に対する粘着性と耐水白化性が優れた合成樹脂水性エマルジョン型感圧接着剤が得られた。
【００１２】
一般の粘着付与剤成分（Ｂ）は、アクリル酸２エチルヘキシルやアクリル酸ｎ−ブチル等の通常の乳化重合可能なモノマーに比べ、水に対する溶解度が極めて小さいので、水相を通してはミセルに拡散できない。そのために通常の乳化重合や滴下乳化重合法では合成樹脂水性エマルジョン中に粘着付与樹脂を微細に分散させることができない。しかし、粘着付与剤を溶解したモノマーのモノマー油滴の平均粒子径を０．４μｍ以下まで小さくし、好ましくは０．２〜０．３μｍとし、水溶性重合開始剤の存在下に、アニオン性界面活性剤水溶液（Ｆ）中に滴下しながら重合すると、粘着付与樹脂の分散が向上することできる。粘着付与剤を溶解したモノマーのモノマー乳化液の平均粒子径を０．４μｍ以上にすると、粘着付与樹脂の分散が低下し、透明性と耐水白化性の低下を引き起こす。
【００１３】
本発明において粘着付与樹脂を溶解したモノマーの乳化分散に用いる乳化機として、例えば超音波乳化機、高圧ホモゲナイザー等を挙げることができる。
また、モノマー乳化液（Ｄ）のモノマー油滴を小さくするとモノマー油滴の総表面積が増大し、界面活性剤がモノマー油滴表面に殆ど吸着し、界面活性剤ミセルが生成しなくなる。そのために、モノマー油滴を０．４μｍ以下まで小さくすると、界面活性剤ミセルでの重合開始が起こり難くなり、モノマー油滴内でモノマーが重合し、粘着付与剤とポリマーが含まれたポリマー粒子が得られてしまう。そのために、モノマー油滴内で重合させる場合、モノマー油滴の平均粒子径を小さくしないと、ポリマー粒子の平均粒子径を小さくすることが困難である。しかし、水溶性重合開始剤の存在下に界面活性剤ミセルを多量に存在させた界面活性剤水溶液（Ｆ）中に、モノマー油滴の平均粒子径が０．４μｍ以下となるモノマー乳化液（Ｄ）を滴下重合させると、モノマー油滴よりモノマーが重合用水溶液中に溶解し、界面活性剤ミセルでも重合反応が開始する事により、ポリマー粒子数が格段に増え、ポリマー粒子の平均粒子径が０．０５〜０．１５μｍとなり、耐水白化性が格段に向上することを見出した。
【００１４】
この場合に、重合を容易に進ませるために、モノマー油滴の平均粒子径が０．４μｍ以下となるモノマー乳化液（Ｄ）を予め少量加えてから滴下重合を開始しても良いが、モノマー乳化液（Ｄ）を重合用水溶液（Ｆ）中に予め加えると、モノマー乳化液（Ｄ）中のモノマー油滴に、重合用水溶液（Ｆ）中の界面活性剤（Ｅ）が吸着し、開始剤ミセルが減少するために、予め界面活性剤（Ｅ）を含む重合用水溶液（Ｆ）中に加えるモノマー乳化液（Ｄ）の割合はモノマー乳化液（Ｄ）の５重量％以内が望ましい。
このとき重合反応が抑制されないよう窒素、アルゴン等の不活性ガスで重合系を置換しておくことが好ましい。重合温度は、４０〜９０℃の範囲が適当であり、重合時間は１〜１０時間が適当である。
【００１５】
本発明で使用されるアルキル基の炭素数が４〜８である（メタ）アクリル酸アルキルエステルは、モノマーの混合物に粘着付与樹脂を溶解させることが必要であるために、アルキル基の炭素数が４以上であることが必要である。アルキル基の炭素数が３以下であると粘着付与樹脂をモノマーの混合物に溶解させることが難しくなる。また、アルキル基の炭素数が９以上であると水に対する溶解度が極めて小さくなり、モノマ−油滴中の不飽和和単量体が界面活性剤ミセルに移動しなくなるために、合成樹脂水性エマルジョンの平均粒子径を小さくすることが困難になる。
【００１６】
本発明で使用されるアルキル基の炭素数が４〜８である（メタ）アクリル酸アルキルとして、例えばアクリル酸又はメタクリル酸のブチル、イソブチル、ｔ−ブチル、ペンチル、シクロヘキシル、ヘプチル、オクチル、２エチルヘキシル等のアルキルエステルが挙げられ、その中でもアクリル酸２エチルヘキシル、アクリル酸ｎ−ブチルが好ましい。モノマー全量中の含有量は、粘着力と粘着付与樹脂の溶解性を向上させる観点から、５０重量％以上、好ましくは７０重量％以上である。これらは単独でも、２種以上組み合わせて用いてもよい。
【００１７】
本発明で使用されるカルボキシル基を有するモノマーは、合成樹脂水性エマルジョンの機械的な安定性を付与させるために使用する。カルボキシル基を有するモノマーを共重合して合成樹脂水性エマルジョンの機械的な安定性を付与させるためには、アンモニア水等で合成樹脂水性エマルジョンを中和してｐＨを７以上にすることが望ましい。その結果として、耐水性を低下させる界面活性剤を少なくすることができる。
【００１８】
本発明で使用されるカルボキシル基を有するモノマーとして、例えばメタクリル酸、アクリル酸、マレイン酸、イタコン酸等が挙げられ、メタクリル酸、アクリル酸が好ましい。これらは単独でも、２種以上組み合わせて用いてもよい。不飽和単量体全量中の含有量は、合成樹脂水性エマルジョンの機械的安定性を向上させる観点から０．５重量％以上、好ましくは１．０重量％以上であり、耐水白化性を向上させる観点から５重量％以下、好ましくは３重量％以下である。
【００１９】
本発明で使用されるアルコシキシシリル基を有するモノマーは、乾燥皮膜の膨潤を抑制し、耐水白化性を更に向上させるために使用する。本発明で使用されるアルコキシシリル基を有する不飽和単量体としては、ビニルトリス（β―メトキシエトキシ）シラン、γ―メタクリロキシプロピルトリメトキシシラン、γ―メタクリロキシプロピルジメトキシシラン、γ―アクリロキシプロピルトリメトキシシラン、γ―アクリロキシプロピルジメトキシシラン等があり、単独或いは併用して用いることができる。中でも、γ―メタクリロキシプロピルトリメトキシシラン、γ―メタクリロキシプロピルジメトキシシラン、γ―アクリロキシプロピルトリメトキシシラン、γ―アクリロキシプロピルジメトキシシランが好ましい。使用量は０．０１〜１．０重量％、好ましくは０．０５〜０．５重量％が望ましい。使用量が０．０１重量％より少なくなると、耐水白化性の向上効果が少なくなり、１．０重量％より多くなると逆に乾燥皮膜の成膜性が低下して耐水白化性が低下する。
【００２０】
本発明では、粘着付与樹脂のモノマーの混合物への溶解を損なわない程度、アルキル基の炭素数が４〜８である（メタ）アクリル酸アルキル及びカルボキシル基を有する不飽和単量体と共重合可能な各種モノマーも用いることができ、例えば（メタ）アクリル酸のメチル、エチル、プロピル、ベンジル、デシル、イソデシル、ドデシル、イソドデシル、ラウリル、トリデシル、イソトリデシル、テトラデシル等のエステル、アクリロニトリル、スチレン、ジビニルベンセン、酢酸ビニル等の極性基をもたない不飽和単量体や（メタ）アクリル酸のヒドロキシエチル、ヒドロキシプロピル等のエステル、パラスチレンスルホン酸ナトリル等の極性基を有する不飽和単量体が挙げられる。更にはモノマー全量中の含有量は４９．５重量％以下が好ましい。
【００２１】
本発明で使用される粘着付与脂は、例えば脂肪族系石油樹脂、脂環族系石油樹脂、水添ロジン系樹脂等が挙げられる。特に軟化点が８０℃以上の水相に拡散し難い粘着付与樹脂や、酸価及び水酸基価が０．１以下の水相に拡散し難い粘着付与樹脂が望ましい。
中でも脂環族系石油樹脂が望ましい。本製造方法ではモノマーの重合の場から粘着付与剤を隔離することができるために粘着付与剤によるモノマーの重合阻害を少なくすることができるが、未水添のロジン系樹脂、フェノール系樹脂、キシレン系樹脂等は、不飽和単量体の重合阻害を起こやすく、更に凝集力の低下が起こし易いために、保持力と粘着力のバランスをとることが難しく好ましくない。粘着付与樹脂樹脂の使用量は、全モノマー１００重量部に対して、ポリオレフィン被着体に対する粘着力を向上させる観点から ４重量部以上であり、透明性を保持するために２０量部以下である。
【００２２】
これらは単独でも、２種以上をブレンド又は変性等で組み合わせて用いてもよい。脂環族系石油樹脂としては、荒川化学工業（株）製のアルコンＰ−１４０、Ｐ−１２５、Ｐ−１１５、アルコンＭ−１３５、Ｍ−１１５、Ｍ−１００、等が上げられる。水添ロジン系樹脂としては、荒川化学工業（株）製のパインクリスタルＫＥ−６５６等が上げられる。
本発明で乳化剤で使用されるポリオキシアルキレン構造と不飽和二重結合を有するアニオン性界面活性剤としては、式（１）〜式（３）で示されるような界面活性剤が望ましい。
【００２３】
【化１】
ここで、Ｒ1、Ｒ3，Ｒ4，Ｒ5は水素又はアルキル基、Ｒ2はアルキル基或いはアルキルフェニル基等であり、Ａは−ＣＨ2ＣＨ2−などのアルキレン基、Ｍはアンモニウム塩又はカリウム、ナトリウム等の金属塩、ｎは２〜２０の整数、ｍは０〜２０の整数を示す。
【００２７】
式（１）で表させる化合物としては、アクアロンＫＨ−１０、ＫＨ−５（第一工業製薬（株）製）等があり、式（２）で表される化合物としては、アデカリアソープＳＥ−１０Ｎ（旭電化工業（株）製）等があり、式（３）で表される化合物としては、アクアロンＨＳ−１０（第一工業製薬（株）製）等がある。
本発明ではアニオン性界面活性剤にポリオキシアルキレン構造を持たせることによりモノマー乳化液の安定性が大幅に向上する。また不飽和二重結合を持たせることにより重合体エマルジョンの機械的な安定性が大幅に向上する。そのために界面活性剤の使用量を大幅に減らすことができる。
【００２８】
使用量は乳化分散して平均粒子径が０．４μｍ以下のモノマー油滴を形成させたモノマー乳化液（Ｃ）には、不飽和単量体混合物１００重量部に対して、０．５〜２．０重量部が用いられる。また、界面活性剤水溶液中（Ｆ）には、０．１〜２．０重量部用いられる。また、耐水白化性及び耐水密着性を低下させない範囲でポリアルキレン構造と不飽和二重結合を分子内に持たないイオン性界面活性剤、或いは、非イオン性界面活性剤を併用することもできるが、極力併用しない方が望ましい。
【００２９】
本乳化重合には通常の水溶性開始剤を用いて重合することができる。本発明で使用される水溶性開始剤としては、過硫酸ナトリルム、過硫酸カリウム、過硫酸アンモニウム、過酸化水素、ターシャリーブチルハイドロパーオキサイド等を使用することができ、還元剤を併用してレドックスにしても良い。また、モノマー乳化液（Ｃ）のモノマー油滴内で重合を防ぐために、油溶性開始剤は併用しない方が良い。
【００３０】
更に、耐水性に影響の少ない範囲で、目的に応じて、中和剤、防腐剤、消泡剤、増粘剤、架橋剤、粘着付与剤等の各種添加剤を乳化重合時または乳化重合物に併用することができる。
本発明において、全仕込み量に対する粘着付与樹脂を溶解した不飽和単量体混合物の比率は、乾燥効率の観点から３５重量％以上が好ましく、製造時の重合熱除去、撹拌効率の観点から５５重量％以下が好ましい。
【００３１】
本発明の粘着製品は、本発明の合成樹脂水性エマルジョン型感圧接着剤を基材に塗工し乾燥することにより得られる。塗工には、ワイヤーコーター、アプリケーター、ダイコーター、ロールコーター、コンマコーター、リップコーター、カーテンコーター等が用いられる。基材は、透明基材、特に透明フィルムテープが好ましく、ＯＰＰ （二軸延伸ポリプロピレン）フィルムや ＰＥＴ（ポリエチレンテレフタレート）フィルム、更にはＰＥ（ポリエチレン）フィルムや塩化ビニルフィルム等が用いられる。エマルジョンを直接塗工する場合には、コロナ処理をフィルム表面に施してあるものや表面コートしてあるものを用いることもでき、また、増粘剤等を添加した高粘度のエマルジョンに対しては、剥離紙や剥離フィルムへ塗工して乾燥し、透明基材を張り合わせることによる転写塗工をすることもできる。粘着剤の塗工厚は、マイクロメーターで測定することができ、一般的には約２０〜３０μｍ程度の塗工厚となるように塗工される。塗工後の粘着剤の乾燥には、熱風乾燥機が用いられ、塗工面が透明で平滑になる条件（例えば、９０〜１１０ ℃で１〜５分程度）で乾燥が行われる。
【００３２】
本発明の合成樹脂水性エマルジョン型感圧接着剤は、水浸漬時でも白濁が殆どなく、加えて強粘着性と保持力が共に優れ、ポリオレフィン被着体に対する良好な粘着性を示す。更に透明性の低下が少ない。従って、一般的な感圧接着剤としてのみならず、透明ラベルなど意匠性が要求される分野の感圧接着剤としても利用できる。
【００３３】
【実施例】
実施例及び比較例におけるエマルジョン及びそのフィルムの物性等は以下に示す方法で測定した。
（１）．平均粒径
Ｈｏｎｅｙｗｅｌｌ社の粒子径分布測定器（Ｍｉｃｒｏｔｒａｃ（ＵＰＡ１５０））を使用して測定した。（５０％頻度値を採用）
（２）．耐水白化性
粘着フィルム片を２５ｍｍ×５０ｍｍの大きさに切り取り、離型ＰＥＴフィルムを剥がして粘着剤層を露出させ、４３０ｎｍの透過率を測定した。（粘着剤を塗工していないフィルムの透過率を１００％とした。）次に２３℃の水で満たされたビーカーで７日間浸漬し、４３０ｎｍの透過率を測定した。耐水白化性は７日間水中浸漬前後の透過率の差で表され、透過率の差が小さいほど白化が少なく耐水白化性が良好である。
【００３４】
（３）．ポリオレフィン類に対する粘着性
粘着フィルム片を２５ｍｍ幅に切断し、エタノールで脱脂処理した低密度ポリエチレン板に、２３℃×５０％ＲＨの雰囲気下で２ｋｇのローラーを１往復させて圧着した試験体を、同雰囲気下で２４時間放置した後、テンシロン型定速引っ張り試験機を用い、３００ｍｍ／ｍｉｎの引っ張り速度で引き剥がし、１８０°剥離力を測定した。
（４）．保持力
ＪＩＳ ６２５３に規定されるステンレス鋼板に、粘着フィルムを、貼付け面積２５ｍｍ×２５ｍｍとなるよう貼付し、４０℃雰囲気下２０分間静置した。続いて１ｋｇの荷重をかけ、２４時間後のズレ幅を測定した。２４時間保持できなかったものは落下時間を記録した。
【００３５】
また、実施例及び比較例における粘着フィルムは以下に示す方法で作製した。内面コロナ処理した５０μＰＥＴフィルムに乾燥膜厚が３０μｍになるように水性エマルジョン型感圧接着剤を塗工し、１１０℃のオーブン中で５分間乾燥させた後、離型処理したＰＥＴフィルムを張り合わせ、
２３℃×５０％ＲＨの雰囲気下で２４時間以上放置したのものを粘着フィルムとした。
【００３６】
（実施例１）
容器に、アクリル酸２エチルヘキシル ８０ｇ、メタクリル酸メチル １７．４４ｇ、アクリル酸 ２．４ｇ 、γ―メタクリロキシプロピルトリメトキシシラン ０．１６ｇ、アルコンＭ−１３５ １０ｇ（荒川化学工業（株）脂環族系石油樹脂）を仕込み、混合物が均一になるまで室温で撹拌した。これにアクアロンＫＨ−１０（第一工業製薬（株）製アニオン性反応性界面活性剤） １．２ｇと水 ９２ｇ加え、高圧ホモゲナイザー（ＡＰＶ ＧＡＵＬＩＮ社）で４００ｋｇ／ｃｍ2の圧力で乳化分散して平均粒子径が０．２５μｍのモノマー乳化液（Ｄ）を得た。
【００３７】
セパラブルフラスコにアクアロンＫＨ−１０（第一工業製薬（株）製アニオン性反応性界面活性剤） ０．８ｇと水 ３４ｇからなる界面活性剤水溶液（Ｆ）を仕込み攪拌しながら８０℃に昇温した。更に、モノマー乳化液（Ｄ）の３％と過硫酸カリウム ０．０６ｇを添加し乳化重合を開始した。その後、モノマー乳化液（Ａ）の９７％と過硫酸カリウム ０．２ｇと水８ｇを３時間かけてゆっくり添加し、更に８０℃で２時間熟成し、室温に冷却後、２５％アンモニア水でｐＨを８．５に調製し。１８０メッシュの金網で濾過して重合体エマルジョンを得た。重合体エマルジョンの平均粒径は０．１１μｍ、固型分は４５．１％であった。
得られた合成樹脂水性エマルジョン型感圧接着剤を内面コロナ処理した５０μｍＰＥＴ（ポリエチレンテレフタレート）フィルムにアプリケーターで乾燥厚みが２５〜３５μｍとなるよう塗布し、１１０℃に調製した熱風乾燥器中で５分間乾燥後、離型処理したＰＥＴ（ポリエチレンテレフタレート）フィルムを貼りあわせ、１日間エージングすることで粘着フィルムを作製した。配合比及びエマルジョンの物性値を表１に示す。
【００３８】
（実施例２）
実施例１において、容器に、アクリル酸２エチルヘキシル ８０．０ｇ、メタクリル酸メチル １７．４４ｇ、アクリル酸 ２．４ｇ 、γ―メタクリロキシプロピルトリメトキシシラン ０．１６ｇ、アルコンＭ−１３５ ５ｇ（荒川化学工業（株）脂環族系石油樹脂）を仕込み、混合物が均一になるまで室温で撹拌した。これにアクアロンＫＨ−１０（第一工業製薬（株）製アニオン性反応性界面活性剤） １．２ｇと水 ８６ｇ加え、高圧ホモゲナイザー（ＡＰＶ ＧＡＵＬＩＮ社）で４００ｋｇ／ｃｍ2の圧力で乳化分散して平均粒子径が０．２６μｍのモノマー乳化液（Ｃ）を得た。重合体エマルジョンの平均粒径は０．１１μｍ、固型分は４５．２％であった。実施例１と同様に粘着フィルムを作製した。配合比及びエマルジョンの物性値を表１に示す。
【００３９】
（実施例３）
実施例１において、アルコンＭ−１３５をアルコンＰ−１４０（荒川化学工業（株）脂環族系石油樹脂）に変更した以外は同様にした。重合体エマルジョンの平均粒径は０．１１μｍ、固型分は４４．９％であった。実施例１と同様に粘着フィルムを作製した。配合比及びエマルジョンの物性値を表１に示す。
【００４０】
（実施例４）
実施例１において、界面活性剤水溶液（Ｆ）をアクアロンＫＨ−１０（第一工業製薬（株）製アニオン性反応性界面活性剤） ０．４ｇと水 ３４．４ｇにした以外は同様にした。重合体エマルジョンの平均粒径は０．１３μｍ、固型分は４５．０％であった。実施例１と同様に粘着フィルムを作製した。配合比及びエマルジョンの物性値を表１に示す。
【００４１】
（実施例５）
実施例１において、アクリル酸２エチルヘキシル９０．０ｇ、メタクリル酸メチル７．４４ｇとした以外は同様に反応を行った。重合体エマルジョンの平均粒径は０．１１μｍ、固型分は４５．２％であった。実施例１と同様に粘着フィルムを作製した。配合比及びエマルジョンの物性値を表２に示す。
【００４２】
（実施例６）
実施例１において、アクリル酸２エチルヘキシル４５．０ｇ、アクリル酸ｎ−ブチル４５．０ｇ、アクリル酸メチル７．４４ｇとした以外は同様に反応を行った。重合体エマルジョンの平均粒径は０．１２μｍ、固型分は４５．２％であった。実施例１と同様に粘着フィルムを作製した。配合比及びエマルジョンの物性値を表２に示す。
【００４３】
（実施例７）
実施例１において、メタクリル酸メチル１７．１ｇ、γ−メタクリロキシプロピルトリメトキシシラン０．５ｇとした以外は同様に反応を行った。重合体エマルジョンの平均粒径は０．１１μｍ、固型分は４５．０％であった。実施例１と同様に粘着フィルムを作製した。配合比及びエマルジョンの物性値を表２に示す。
【００４４】
（実施例８）
メタクリル酸メチルを１７．６ｇとし、γ−メタクリロキシプロピルトリメトキシシランを使用しないで実施例１と同様に反応を行った。重合体エマルジョンの平均粒径は０．１１μｍ、固型分は４５．１％であった。実施例１と同様に粘着フィルムを作製した。配合比及びエマルジョンの物性値を表２に示す。
【００４５】
（比較例１）
実施例１において、界面活性剤水溶液（Ｂ）のアクアロンＫＨ−１０モノマー乳化液（Ｂ）の平均粒子径を０．４８μｍにした以外は同様にした。重合体エマルジョンの平均粒径は０．１２μｍ、固型分は４４．７％であった。実施例１と同様に粘着フィルムを作製した。配合比及びエマルジョンの物性値を表３に示す。
【００４６】
（比較例２）
実施例１において、界面活性剤水溶液（Ｆ）をアクアロンＫＨ−１０（第一工業製薬（株）製アニオン性反応性界面活性剤） ０ｇと水 ３４．８ｇにした以外は同様にした。重合体エマルジョンの平均粒径は０．２４μｍ、固型分は４４．８％であった。実施例１と同様に粘着フィルムを作製した。配合比及びエマルジョンの物性値を表３に示す。
【００４７】
（比較例３）
実施例１において、アクリル酸２エチルヘキシルをアクリル酸ｎ−ラウリルにした以外は実施例１と同様にした。重合体エマルジョンの平均粒径は０．２０μｍ、固型分は４４．４％であった。実施例１と同様に粘着フィルムを作製した。配合比及びエマルジョンの物性値を表３に示す。
【００４８】
（比較例４）
実施例１において、容器に、アクリル酸２エチルヘキシル ８０ｇ、メタクリル酸メチル １７．４４ｇ、アクリル酸 ２．４ｇ 、γ―メタクリロキシプロピルトリメトキシシラン ０．１６ｇを仕込み、混合物が均一になるまで室温で撹拌した。これにアクアロンＫＨ−１０（第一工業製薬（株）製アニオン性反応性界面活性剤） １．２ｇと水 ８０ｇ加え、高圧ホモゲナイザー（ＡＰＶ ＧＡＵＬＩＮ社）で４００ｋｇ／ｃｍ2の圧力で乳化分散して平均粒子径が０．２４μｍのモノマー乳化液（Ｃ）を得た。重合体エマルジョンの平均粒径は０．１０μｍ、固型分は４５．２％であった。実施例１と同様に粘着フィルムを作製した。配合比及びエマルジョンの物性値を表３に示す。
【００４９】
【表１】
【表２】
【表３】
【発明の効果】
本発明の合成樹脂水性エマルジョン型感圧接着剤は、耐熱性、耐候性に優れ、有機溶媒を含まないため大気汚染防止、環境保全性に優れ、且つ作業環境保全性に好ましい上、ポリオレフィン類に対する粘着性が優れ一般的な感圧接着剤としてのみならず、特に水浸漬時での白濁が少ないため透明ラベルなど意匠性が要求される分野の従来エマルジョン型感圧接着剤では置き換えられなかった分野の感圧接着剤としても利用可能となった。[0001]
BACKGROUND OF THE INVENTION
The present invention is an acrylic pressure-sensitive adhesive having excellent heat resistance and weather resistance, and is excellent in strong tackiness and water whitening resistance to polyolefin resins, and does not contain an organic solvent. The present invention relates to a water-based emulsion-type pressure-sensitive adhesive which is considered to be preferable for the above.
[0002]
[Prior art]
Adhesive products such as pressure-sensitive adhesive tapes, pressure-sensitive adhesive labels, and double-sided pressure-sensitive adhesive tapes obtained by processing a pressure-sensitive adhesive are widely used in applications such as home appliances, daily necessities, and building materials. As pressure-sensitive adhesives used in these pressure-sensitive adhesive products, acrylic pressure-sensitive adhesives that are excellent in durability such as heat resistance and weather resistance in addition to the balance of physical properties are widespread. Of these, synthetic resin water-emulsion acrylic pressure sensitive adhesives are widely used from the viewpoint of preventing air pollution and improving the working environment. Adhesives such as hydrocarbons, terpenes, and rosins are used to improve adhesion to polyolefins. It is common to add an imparting resin.
However, the conventional synthetic resin water-based emulsion type acrylic pressure-sensitive adhesives cause white turbidity in high humidity environments or when immersed in water, and the water whitening resistance deteriorates. not being used.
[0003]
For example, in Japanese Patent No. 2599589 (Japanese Patent Laid-Open No. Sho 63-256672, Arakawa Chemical Industries, Ltd.), a tackifying resin emulsion obtained by emulsifying a tackifying resin using a normal anionic surfactant is used as a synthetic resin aqueous acrylic system. A pressure sensitive adhesive blended with a polymer emulsion is disclosed. However, since this pressure-sensitive adhesive uses a surfactant to emulsify the tackifying resin, it tends to cause a decrease in water whitening resistance. Further, when the tackifying resin is emulsified, the tackifying resin emulsion particles Is difficult to disperse to 0.2 μm or less, and thus a decrease in transparency and water whitening resistance is inevitable.
[0004]
Also, Japanese Patent No. 1832455 (Japanese Patent Laid-Open No. 58-185668, Japanese Patent Publication No. 2-30351, Hoechst Synthesis Co., Ltd.), Japanese Patent Laid-Open No. 8-231937 (Sekisui Chemical Co., Ltd.) and Japanese Patent Laid-Open No. 9-111218 ( Asahi Kasei Kogyo Co., Ltd.) and the like disclose a method of dissolving a tackifier resin in a monomer and further emulsifying the monomer by adding a surfactant aqueous solution thereto, and performing ordinary emulsion polymerization. The average particle size of monomer oil droplets obtained by monomer emulsification is as large as 1 to 5 μm, and the monomer is diffused through the aqueous phase into the surfactant micelles and polymer polymer particles, and polymerization is performed. Since it is difficult to diffuse through the aqueous phase, the final product polymer particles and the giant particles of the tackifying resin are present individually after polymerization or the tackifying resin often becomes an aggregate. Therefore, in these methods, it is inevitable that huge particles of a tackifying resin having a size of 1 μm or more are formed in the emulsion, resulting in a decrease in the adhesion to polyolefins and a decrease in water whitening resistance.
[0005]
JP 2000-313865 A (Toyo Ink Manufacturing Co., Ltd.) discloses that an average particle size is obtained by dissolving a tackifier resin and an oil-soluble initiator in a (meth) acrylic acid ester having 9 to 14 carbon atoms in an alkyl group. A method is disclosed in which after formation of monomer oil droplets having a diameter of 1 μm or less, emulsion polymerization is performed in the monomer oil droplets. This method suppresses the formation of giant particles of tackifying resin and improves the adhesion to polyolefins. However, the average particle size of the polymer particles is reduced to 0.005 unless the average particle size of the monomer oil droplets is reduced to 0.15 μm or less. It is difficult to reduce it to 05 to 0.15 μm. However, since it is difficult to make the average particle diameter of the monomer oil droplets 0.15 μm or less by this method, it is difficult to achieve both adhesion to polyolefins and water whitening resistance even if this method is used. .
[0006]
In order to solve the above problems, the present inventors have studied the tackiness and water whitening resistance of conventional acrylic water-based emulsion-type pressure-sensitive adhesives to polyolefin resins. It has been found that the smaller the (acrylic copolymer) is, the more preferable it is, and that the composition of the emulsion particles is strongly influenced. That is, the mechanism could not be elucidated, but as a result, the tackifying resin and the acrylic copolymer are not in the same particle, but if they exist as separately as possible, the water whitening resistance is excellent without reducing the adhesiveness. It was found to be a water-based emulsion type pressure-sensitive adhesive. For this reason, it becomes a problem how to produce tackifying resin particles and acrylic copolymer particles having a small particle size.
[0007]
[Problems to be solved by the invention]
The present invention is an aqueous pressure sensitive adhesive that is excellent in heat resistance and weather resistance, has excellent adhesion to polyolefin resins and water whitening resistance, is excellent in air pollution prevention and environmental conservation. An object is to provide a pressure-sensitive adhesive.
[0008]
[Means for Solving the Problems]
The present invention
[1] An anionic surfactant (C) containing a monomer (A) and a tackifier resin (B) mainly composed of (meth) acrylic acid alkyl ester having 4 to 8 carbon atoms in the alkyl group A monomer emulsion (D) having an average particle diameter of 0.4 μm or less is obtained by emulsifying and dispersing using an aqueous solution to be polymerized, and this aqueous solution for polymerization contains a water-soluble polymerization initiator and an anionic surfactant (E). (F) A method for producing a water-based emulsion-type pressure-sensitive adhesive, characterized by being polymerized while being dropped into a synthetic resin aqueous emulsion having an average particle size of 0.05 to 0.15 μm.
[2] The monomer (A) is 50 to 99.49% by weight of a (meth) acrylic acid alkyl ester having 4 to 8 carbon atoms in the alkyl group, and 0.5 to 5.0% by weight of a monomer having a carboxyl group. The method for producing an aqueous emulsion-type pressure-sensitive adhesive according to the above [1], which is a mixture of monomers containing 0.01 to 1.0% by weight of an alkoxysilyl group-containing monomer as an essential component,
[3] Anionic surfactant in which monomer emulsion (D) has 4 to 20 parts by weight of tackifier resin (B), 100 parts by weight of monomer (A), polyoxyalkylene structure and unsaturated double bond (C) The method for producing an aqueous emulsion-type pressure-sensitive adhesive according to the above [1], which is an aqueous solution containing 0.5 to 2.0 parts by weight,
[4] Water-soluble polymerization initiator and anionic surfactant (E) 0.1 having an unsaturated double bond with water-soluble polymerization initiator and 100 parts by weight of monomer (A) The method for producing a synthetic resin aqueous emulsion-type pressure-sensitive adhesive according to the above [1], which is an aqueous solution containing ~ 2.0 parts by weight,
[5] A method for producing a synthetic resin aqueous emulsion-type pressure-sensitive adhesive according to [1] or [3] above, wherein an alicyclic petroleum resin is used as the tackifying resin (B);
[0009]
[6] In the presence of the tackifying resin, 50 to 99.49% by weight of a (meth) acrylic acid alkyl ester having 4 to 8 carbon atoms in the alkyl group and a monomer having a carboxyl group of 0.5 to 5.0 An average consisting of a mixture of monomers containing 0.01% to 1.0% by weight of a monomer having an alkoxysilyl group as an essential component, and an anionic surfactant having a polyoxyalkylene structure and an unsaturated double bond Average particle size of polymer particles obtained by copolymerizing a monomer emulsion having a particle size of 0.4 μm or less in an aqueous solution for polymerization containing a water-soluble polymerization initiator and an anionic surfactant having an unsaturated double bond The above-mentioned problems have been solved by developing an aqueous emulsion type pressure-sensitive adhesive comprising a synthetic resin aqueous emulsion having a diameter of 0.05 to 0.15 μm.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The present inventors have solved the above-mentioned problem, that is, the tackifier resin and the acrylic copolymer are not in the same particle, but can be dissolved as a monomer and polymerized so as to be formed as separately as possible. The monomer (A) mainly composed of (meth) acrylic acid alkyl ester having 4 to 8 carbon atoms in the alkyl group is selected so as to diffuse into the surfactant micelle through the aqueous phase of the aqueous solution (F). Monomer emulsion liquid (D) in which the monomer oil droplet component in which the tackifier resin (B) is dissolved is mechanically compulsorily emulsified and dispersed in the anionic surfactant aqueous solution (C) to have an average particle size of 0.4 μm or less. Next, this is polymerized while dropping into an aqueous solution (F) for polymerization containing a water-soluble polymerization initiator and an anionic surfactant (E).
[0011]
Thus, the polymerization is initiated by the surfactant micelle in the aqueous solution for polymerization (F), the number of particles serving as polymerization nuclei is remarkably increased, and the monomer (monomer + tackifier resin) in the monomer emulsion (D) is changed from the monomer ( It is considered that A) dissolves in the aqueous solution for polymerization (F) to form copolymer particles stabilized with the anionic surfactant (E) in the aqueous solution for polymerization (F). For this reason, the (monomer + tackifier resin) particles in the monomer emulsion (D) are reduced in size as the monomer dissolves and flows out. And it is estimated that the tackifier resin and the acrylic copolymer will become an emulsion in which the average particle diameter of the polymer particles is 0.05 to 0.15 μm as separate particles. As a result, the pressure-sensitive adhesive is a synthetic resin aqueous emulsion having excellent tackiness and water whitening resistance to polyolefins in which the tackifying resin is finely dispersed and the average particle size of the polymer particles is 0.05 to 0.15 μm. was gotten.
[0012]
Since the general tackifier component (B) has a very low solubility in water as compared with ordinary emulsion-polymerizable monomers such as 2-ethylhexyl acrylate and n-butyl acrylate, it cannot diffuse into micelles through the aqueous phase. For this reason, ordinary emulsion polymerization or drop emulsion polymerization cannot finely disperse the tackifying resin in the synthetic resin aqueous emulsion. However, the average particle diameter of the monomer oil droplets of the monomer in which the tackifier is dissolved is reduced to 0.4 μm or less, preferably 0.2 to 0.3 μm, and an anionic interface is present in the presence of a water-soluble polymerization initiator. Polymerization while dropping into the aqueous activator solution (F) can improve the dispersion of the tackifying resin. When the average particle size of the monomer emulsion of the monomer in which the tackifier is dissolved is 0.4 μm or more, the dispersion of the tackifier resin is lowered, and the transparency and water whitening resistance are lowered.
[0013]
Examples of the emulsifier used for emulsifying and dispersing the monomer in which the tackifying resin is dissolved in the present invention include an ultrasonic emulsifier and a high-pressure homogenizer.
Further, when the monomer oil droplets in the monomer emulsion (D) are made smaller, the total surface area of the monomer oil droplets increases, the surfactant is almost adsorbed on the surface of the monomer oil droplets, and surfactant micelles are not generated. Therefore, when the monomer oil droplets are reduced to 0.4 μm or less, polymerization in the surfactant micelles hardly occurs, the monomer is polymerized in the monomer oil droplets, and polymer particles containing the tackifier and the polymer are formed. Will be obtained. Therefore, when polymerizing in the monomer oil droplets, it is difficult to reduce the average particle size of the polymer particles unless the average particle size of the monomer oil droplets is reduced. However, in the surfactant aqueous solution (F) in which a large amount of surfactant micelles are present in the presence of a water-soluble polymerization initiator, a monomer emulsion (D) having an average particle diameter of monomer oil droplets of 0.4 μm or less. ) Is dissolved in the aqueous solution for polymerization from the monomer oil droplets, and the polymerization reaction starts even in the surfactant micelles, so that the number of polymer particles is remarkably increased and the average particle size of the polymer particles is 0. It was found to be 0.05 to 0.15 μm, and the water whitening resistance was remarkably improved.
[0014]
In this case, in order to facilitate the polymerization, dropwise polymerization may be started after adding a small amount of the monomer emulsion (D) in which the average particle diameter of the monomer oil droplets is 0.4 μm or less in advance. When the emulsion (D) is added in advance to the polymerization aqueous solution (F), the surfactant (E) in the polymerization aqueous solution (F) is adsorbed to the monomer oil droplets in the monomer emulsion (D), and starts. In order to reduce the agent micelle, the ratio of the monomer emulsion (D) added in advance to the aqueous solution for polymerization (F) containing the surfactant (E) is preferably within 5% by weight of the monomer emulsion (D).
At this time, it is preferable to replace the polymerization system with an inert gas such as nitrogen or argon so that the polymerization reaction is not suppressed. The polymerization temperature is suitably in the range of 40 to 90 ° C., and the polymerization time is suitably 1 to 10 hours.
[0015]
The (meth) acrylic acid alkyl ester having 4 to 8 carbon atoms of the alkyl group used in the present invention requires the tackifier resin to be dissolved in the monomer mixture. It must be 4 or more. When the carbon number of the alkyl group is 3 or less, it is difficult to dissolve the tackifier resin in the monomer mixture. Further, when the alkyl group has 9 or more carbon atoms, the solubility in water becomes extremely small, and the unsaturated sum monomer in the monomer oil droplet does not move to the surfactant micelle. It becomes difficult to reduce the average particle size.
[0016]
Examples of the alkyl (meth) acrylate having 4 to 8 carbon atoms of the alkyl group used in the present invention include acrylic acid or methacrylic acid butyl, isobutyl, t-butyl, pentyl, cyclohexyl, heptyl, octyl, and 2-ethylhexyl. Among them, 2-ethylhexyl acrylate and n-butyl acrylate are preferable. The content in the total amount of the monomers is 50% by weight or more, preferably 70% by weight or more, from the viewpoint of improving the adhesive strength and the solubility of the tackifying resin. These may be used alone or in combination of two or more.
[0017]
The monomer having a carboxyl group used in the present invention is used for imparting mechanical stability of the synthetic resin aqueous emulsion. In order to copolymerize the monomer having a carboxyl group and impart mechanical stability of the synthetic resin aqueous emulsion, it is desirable to neutralize the synthetic resin aqueous emulsion with ammonia water or the like to make the pH 7 or more. As a result, it is possible to reduce the surfactant that lowers the water resistance.
[0018]
Examples of the monomer having a carboxyl group used in the present invention include methacrylic acid, acrylic acid, maleic acid, itaconic acid and the like, and methacrylic acid and acrylic acid are preferable. These may be used alone or in combination of two or more. The content in the total amount of unsaturated monomers is 0.5% by weight or more, preferably 1.0% by weight or more from the viewpoint of improving the mechanical stability of the synthetic resin aqueous emulsion, and improves the water whitening resistance. From the viewpoint, it is 5% by weight or less, preferably 3% by weight or less.
[0019]
The monomer having an alkoxysilyl group used in the present invention is used for suppressing swelling of the dried film and further improving water whitening resistance. Examples of the unsaturated monomer having an alkoxysilyl group used in the present invention include vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyldimethoxysilane, and γ-acryloxypropyl. Examples thereof include trimethoxysilane and γ-acryloxypropyldimethoxysilane, which can be used alone or in combination. Of these, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyldimethoxysilane, γ-acryloxypropyltrimethoxysilane, and γ-acryloxypropyldimethoxysilane are preferable. The amount used is 0.01 to 1.0% by weight, preferably 0.05 to 0.5% by weight. When the amount used is less than 0.01% by weight, the effect of improving the water whitening resistance is reduced, and when it is more than 1.0% by weight, the film formability of the dry film is lowered and the water whitening resistance is lowered.
[0020]
In the present invention, it is possible to copolymerize with alkyl (meth) acrylate having 4 to 8 carbon atoms and an unsaturated monomer having a carboxyl group to such an extent that dissolution of the tackifier resin in the monomer mixture is not impaired. Various monomers such as methyl, ethyl, propyl, benzyl, decyl, isodecyl, dodecyl, isododecyl, lauryl, tridecyl, isotridecyl, tetradecyl and the like, acrylonitrile, styrene, divinyl benzene, (meth) acrylic acid, Examples thereof include unsaturated monomers having no polar group such as vinyl acetate, esters of hydroxyethyl and hydroxypropyl of (meth) acrylic acid, and unsaturated monomers having a polar group such as sodium parastyrene sulfonate. . Further, the content in the total amount of monomers is preferably 49.5% by weight or less.
[0021]
Examples of the tackifying fat used in the present invention include aliphatic petroleum resins, alicyclic petroleum resins, and hydrogenated rosin resins. In particular, a tackifying resin that is difficult to diffuse into an aqueous phase having a softening point of 80 ° C. or higher, or a tackifying resin that is difficult to diffuse into an aqueous phase having an acid value and a hydroxyl value of 0.1 or less are desirable.
Of these, alicyclic petroleum resins are desirable. In this production method, since the tackifier can be isolated from the monomer polymerization site, the inhibition of monomer polymerization by the tackifier can be reduced. However, unhydrogenated rosin resin, phenol resin, xylene Resins such as those tend to cause polymerization inhibition of unsaturated monomers and also tend to cause a decrease in cohesive force, making it difficult to balance holding force and adhesive strength. The amount of the tackifying resin used is 4 parts by weight or more from the viewpoint of improving the adhesive strength to the polyolefin adherend with respect to 100 parts by weight of all monomers, and 20 parts by weight or less in order to maintain transparency. .
[0022]
These may be used alone or in combination of two or more by blending or modification. Examples of the alicyclic petroleum resin include Arcon P-140, P-125, P-115, Alcon M-135, M-115, M-100, etc. manufactured by Arakawa Chemical Industries, Ltd. Examples of the hydrogenated rosin resin include Pine Crystal KE-656 manufactured by Arakawa Chemical Industries, Ltd.
As the anionic surfactant having a polyoxyalkylene structure and an unsaturated double bond used as an emulsifier in the present invention, surfactants represented by the formulas (1) to (3) are desirable.
[0023]
[Chemical 1]
Where R 1 , R Three , R Four , R Five Is hydrogen or an alkyl group, R 2 Is an alkyl group or an alkylphenyl group, and A is -CH 2 CH 2 An alkylene group such as-, M is an ammonium salt or a metal salt such as potassium or sodium, n is an integer of 2 to 20, and m is an integer of 0 to 20.
[0027]
Examples of the compound represented by the formula (1) include Aqualon KH-10 and KH-5 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and the compound represented by the formula (2) includes Adekari Soap SE- 10N (manufactured by Asahi Denka Kogyo Co., Ltd.) and the like, and examples of the compound represented by the formula (3) include Aqualon HS-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
In the present invention, the stability of the monomer emulsion is greatly improved by providing the anionic surfactant with a polyoxyalkylene structure. In addition, the mechanical stability of the polymer emulsion is greatly improved by providing an unsaturated double bond. Therefore, the amount of surfactant used can be greatly reduced.
[0028]
The amount used is 0.5 to 2 with respect to 100 parts by weight of the unsaturated monomer mixture in the monomer emulsified liquid (C) emulsified and dispersed to form monomer oil droplets having an average particle size of 0.4 μm or less. 0.0 parts by weight are used. Moreover, 0.1-2.0 weight part is used in surfactant aqueous solution (F). In addition, an ionic surfactant having no polyalkylene structure and unsaturated double bond in the molecule or a nonionic surfactant can be used in combination as long as the water whitening resistance and water adhesion resistance are not lowered. It is desirable not to use as much as possible.
[0029]
In this emulsion polymerization, polymerization can be carried out using a normal water-soluble initiator. As the water-soluble initiator used in the present invention, sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, tertiary butyl hydroperoxide, and the like can be used. May be. In order to prevent polymerization in the monomer oil droplets of the monomer emulsion (C), it is better not to use an oil-soluble initiator in combination.
[0030]
Furthermore, various additives such as neutralizers, preservatives, antifoaming agents, thickeners, cross-linking agents, tackifiers, and the like are used during emulsion polymerization or in the form of emulsion polymers, depending on the purpose within a range that does not affect water resistance. Can be used together.
In the present invention, the ratio of the unsaturated monomer mixture in which the tackifier resin is dissolved with respect to the total charged amount is preferably 35% by weight or more from the viewpoint of drying efficiency, and 55% by weight from the viewpoint of removal of polymerization heat during production and stirring efficiency. % Or less is preferable.
[0031]
The pressure-sensitive adhesive product of the present invention is obtained by applying the synthetic resin aqueous emulsion type pressure-sensitive adhesive of the present invention to a substrate and drying it. For coating, a wire coater, applicator, die coater, roll coater, comma coater, lip coater, curtain coater, or the like is used. The substrate is preferably a transparent substrate, particularly a transparent film tape, and an OPP (biaxially stretched polypropylene) film, a PET (polyethylene terephthalate) film, a PE (polyethylene) film, a vinyl chloride film, or the like is used. When the emulsion is applied directly, the film surface can be corona-treated or the surface-coated film can be used. For high-viscosity emulsions with thickeners added, etc. Alternatively, it can be applied to a release paper or a release film, dried, and a transfer coating can be performed by laminating a transparent substrate. The coating thickness of the pressure-sensitive adhesive can be measured with a micrometer, and is generally applied so as to have a coating thickness of about 20 to 30 μm. For drying the pressure-sensitive adhesive after coating, a hot air dryer is used, and drying is performed under the condition that the coated surface is transparent and smooth (for example, at about 90 to 110 ° C. for about 1 to 5 minutes).
[0032]
The synthetic resin water-based emulsion type pressure-sensitive adhesive of the present invention has almost no white turbidity even when immersed in water, and is excellent in both strong adhesiveness and holding power, and exhibits good adhesiveness to polyolefin adherends. Furthermore, there is little decrease in transparency. Accordingly, it can be used not only as a general pressure-sensitive adhesive but also as a pressure-sensitive adhesive in fields where design properties such as transparent labels are required.
[0033]
【Example】
The physical properties of the emulsions and their films in the examples and comparative examples were measured by the following methods.
(1). Average particle size
It measured using the particle diameter distribution measuring device (Microtrac (UPA150)) of Honeywell. (50% frequency value is used)
(2). Water whitening resistance
The adhesive film piece was cut into a size of 25 mm × 50 mm, the release PET film was peeled off to expose the adhesive layer, and the transmittance at 430 nm was measured. (The transmittance of the film not coated with the adhesive was 100%.) Next, the film was immersed in a beaker filled with water at 23 ° C. for 7 days, and the transmittance at 430 nm was measured. Water whitening resistance is represented by the difference in transmittance before and after immersion in water for 7 days. The smaller the difference in transmittance, the less whitening and the better the water whitening resistance.
[0034]
(3). Adhesion to polyolefins
A test piece obtained by cutting a pressure-sensitive adhesive film piece to a width of 25 mm and depressurizing and degreasing with ethanol by reciprocating a 2 kg roller in a 23 ° C. × 50% RH atmosphere once in a reciprocating manner was obtained under the same atmosphere. After standing for a period of time, using a Tensilon type constant speed tensile tester, the sample was peeled off at a pulling speed of 300 mm / min, and the 180 ° peeling force was measured.
(4). Holding power
An adhesive film was stuck on a stainless steel plate defined in JIS 6253 so that the pasting area was 25 mm × 25 mm, and was allowed to stand in a 40 ° C. atmosphere for 20 minutes. Subsequently, a load of 1 kg was applied, and the deviation width after 24 hours was measured. For those that could not be held for 24 hours, the drop time was recorded.
[0035]
Moreover, the adhesive film in an Example and a comparative example was produced with the method shown below. An aqueous emulsion-type pressure-sensitive adhesive was applied to a 50 μPET film that had been subjected to internal corona treatment so that the dry film thickness was 30 μm, dried in an oven at 110 ° C. for 5 minutes, and then the PET film that had been subjected to the release treatment was bonded together.
An adhesive film was allowed to stand for 24 hours or more in an atmosphere of 23 ° C. × 50% RH.
[0036]
Example 1
In a container, 80 g of 2-ethylhexyl acrylate, 17.44 g of methyl methacrylate, 2.4 g of acrylic acid, 0.16 g of γ-methacryloxypropyltrimethoxysilane, 10 g of Alcon M-135 (Arakawa Chemical Industries, Ltd., alicyclic group) Petroleum resin) was added and stirred at room temperature until the mixture was uniform. To this, 1.2 g of Aqualon KH-10 (an anionic reactive surfactant manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 92 g of water were added, and 400 kg / cm using a high-pressure homogenizer (APV GAULIN). 2 The monomer emulsified liquid (D) having an average particle diameter of 0.25 μm was obtained by emulsifying and dispersing at a pressure of 5 μm.
[0037]
Aqualon KH-10 (anionic reactive surfactant manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) in a separable flask was charged with an aqueous surfactant solution (F) consisting of 0.8 g and 34 g of water, and the temperature was raised to 80 ° C. while stirring. did. Furthermore, 3% of the monomer emulsion (D) and 0.06 g of potassium persulfate were added to start emulsion polymerization. Thereafter, 97% of the monomer emulsion (A), 0.2 g of potassium persulfate and 8 g of water were slowly added over 3 hours, and further aged at 80 ° C. for 2 hours. After cooling to room temperature, pH was adjusted with 25% aqueous ammonia. To 8.5. Filtration through a 180 mesh wire mesh gave a polymer emulsion. The average particle size of the polymer emulsion was 0.11 μm, and the solid content was 45.1%.
The obtained synthetic resin aqueous emulsion pressure sensitive adhesive was applied to a 50 μm PET (polyethylene terephthalate) film that had been corona-treated on the inner surface with an applicator so that the dry thickness would be 25 to 35 μm, and 5 minutes in a hot air drier prepared at 110 ° C. After drying, a release film-treated PET (polyethylene terephthalate) film was bonded and aged for 1 day to prepare an adhesive film. Table 1 shows the compounding ratio and the physical property values of the emulsion.
[0038]
(Example 2)
In Example 1, 80.0 g of 2-ethylhexyl acrylate, 17.44 g of methyl methacrylate, 2.4 g of acrylic acid, 0.16 g of γ-methacryloxypropyltrimethoxysilane, 5 g of Alcon M-135 (Arakawa Chemical Industries) (Alicyclic petroleum resin) was added and stirred at room temperature until the mixture was uniform. To this was added Aqualon KH-10 (an anionic reactive surfactant manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 86 g of water, and 400 kg / cm using a high-pressure homogenizer (APV GAULIN). 2 The monomer emulsified liquid (C) having an average particle diameter of 0.26 μm was obtained by emulsifying and dispersing at a pressure of 5 μm. The average particle size of the polymer emulsion was 0.11 μm, and the solid content was 45.2%. An adhesive film was produced in the same manner as in Example 1. Table 1 shows the compounding ratio and the physical property values of the emulsion.
[0039]
(Example 3)
In Example 1, it carried out similarly except having changed Alcon M-135 to Alcon P-140 (Arakawa Chemical Industries Co., Ltd. alicyclic petroleum resin). The average particle size of the polymer emulsion was 0.11 μm, and the solid content was 44.9%. An adhesive film was produced in the same manner as in Example 1. Table 1 shows the compounding ratio and the physical property values of the emulsion.
[0040]
Example 4
In Example 1, the surfactant aqueous solution (F) was the same except that 0.4 g of Aqualon KH-10 (an anionic reactive surfactant manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 34.4 g of water were used. The average particle size of the polymer emulsion was 0.13 μm, and the solid content was 45.0%. An adhesive film was produced in the same manner as in Example 1. Table 1 shows the compounding ratio and the physical property values of the emulsion.
[0041]
(Example 5)
The reaction was conducted in the same manner as in Example 1 except that 90.0 g of 2-ethylhexyl acrylate and 7.44 g of methyl methacrylate were used. The average particle size of the polymer emulsion was 0.11 μm, and the solid content was 45.2%. An adhesive film was produced in the same manner as in Example 1. Table 2 shows the compounding ratio and the physical property values of the emulsion.
[0042]
(Example 6)
In Example 1, the reaction was conducted in the same manner except that 45.0 g of 2-ethylhexyl acrylate, 45.0 g of n-butyl acrylate, and 7.44 g of methyl acrylate were used. The average particle size of the polymer emulsion was 0.12 μm, and the solid content was 45.2%. An adhesive film was produced in the same manner as in Example 1. Table 2 shows the compounding ratio and the physical property values of the emulsion.
[0043]
(Example 7)
In Example 1, the reaction was performed in the same manner except that 17.1 g of methyl methacrylate and 0.5 g of γ-methacryloxypropyltrimethoxysilane were used. The average particle size of the polymer emulsion was 0.11 μm, and the solid content was 45.0%. An adhesive film was produced in the same manner as in Example 1. Table 2 shows the compounding ratio and the physical property values of the emulsion.
[0044]
(Example 8)
The reaction was carried out in the same manner as in Example 1 except that 17.6 g of methyl methacrylate was used and γ-methacryloxypropyltrimethoxysilane was not used. The average particle size of the polymer emulsion was 0.11 μm, and the solid content was 45.1%. An adhesive film was produced in the same manner as in Example 1. Table 2 shows the compounding ratio and the physical property values of the emulsion.
[0045]
(Comparative Example 1)
In Example 1, it carried out similarly except having made the average particle diameter of the Aqualon KH-10 monomer emulsion (B) of surfactant aqueous solution (B) into 0.48 micrometer. The average particle size of the polymer emulsion was 0.12 μm, and the solid content was 44.7%. An adhesive film was produced in the same manner as in Example 1. Table 3 shows the compounding ratio and the physical property values of the emulsion.
[0046]
(Comparative Example 2)
In Example 1, the surfactant aqueous solution (F) was the same except that Aqualon KH-10 (an anionic reactive surfactant manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was changed to 0 g and water 34.8 g. The average particle size of the polymer emulsion was 0.24 μm, and the solid content was 44.8%. An adhesive film was produced in the same manner as in Example 1. Table 3 shows the compounding ratio and the physical property values of the emulsion.
[0047]
(Comparative Example 3)
Example 1 was the same as Example 1 except that 2-ethylhexyl acrylate was changed to n-lauryl acrylate. The average particle size of the polymer emulsion was 0.20 μm, and the solid content was 44.4%. An adhesive film was produced in the same manner as in Example 1. Table 3 shows the compounding ratio and the physical property values of the emulsion.
[0048]
(Comparative Example 4)
In Example 1, a container was charged with 80 g of 2-ethylhexyl acrylate, 17.44 g of methyl methacrylate, 2.4 g of acrylic acid, and 0.16 g of γ-methacryloxypropyltrimethoxysilane, and stirred at room temperature until the mixture became uniform. did. To this, 1.2 g Aqualon KH-10 (an anionic reactive surfactant manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 80 g water were added, and 400 kg / cm using a high-pressure homogenizer (APV GAULIN). 2 The monomer emulsified liquid (C) having an average particle size of 0.24 μm was obtained by emulsifying and dispersing at a pressure of 5 μm. The average particle diameter of the polymer emulsion was 0.10 μm, and the solid content was 45.2%. An adhesive film was produced in the same manner as in Example 1. Table 3 shows the compounding ratio and the physical property values of the emulsion.
[0049]
[Table 1]
[Table 2]
[Table 3]
【The invention's effect】
The synthetic resin aqueous emulsion type pressure-sensitive adhesive of the present invention is excellent in heat resistance and weather resistance, and does not contain an organic solvent, so it is excellent in air pollution prevention, environmental conservation, and work environment conservation. Fields that have not been replaced by conventional emulsion-type pressure-sensitive adhesives not only as general pressure-sensitive adhesives with excellent tackiness, but also in fields where design properties are required, such as transparent labels, especially because they are less cloudy when immersed in water It can also be used as a pressure sensitive adhesive.
Claims (5)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4481020B2 (en) * | 2004-01-22 | 2010-06-16 | 日東電工株式会社 | Optical member adhesive composition, optical member adhesive layer, optical member adhesive sheet, and optical member |
| JP2005213341A (en) * | 2004-01-29 | 2005-08-11 | Lintec Corp | Pressure sensitive adhesive composition and pressure sensitive adhesive optical member |
| JP4522405B2 (en) | 2004-04-22 | 2010-08-11 | 積水化成品工業株式会社 | Gel adhesive composition |
| JP4800722B2 (en) * | 2005-09-26 | 2011-10-26 | 日東電工株式会社 | Optical pressure-sensitive adhesive composition, optical pressure-sensitive adhesive layer, optical member with a pressure-sensitive adhesive layer, method for producing the same, and image display device |
| JP5419320B2 (en) * | 2006-08-11 | 2014-02-19 | 日東電工株式会社 | Adhesive tape |
| JP2011063665A (en) * | 2009-09-15 | 2011-03-31 | Showa Denko Kk | Water-based emulsion adhesive composition for lapping processing |
| JP4824839B1 (en) * | 2011-06-20 | 2011-11-30 | 株式会社イーテック | Aqueous pressure-sensitive adhesive composition and method for producing the same |
| KR101546659B1 (en) | 2012-10-09 | 2015-08-24 | 주식회사 엘지화학 | Acrylic Emulsion Pressure Sensitive Adhesive Composition Comprising Nano-Sized Latex of Monomodal Particle Size Distribution and Manufacturing Process thereof |
| JP5916782B2 (en) * | 2014-03-28 | 2016-05-11 | 昭和電工株式会社 | An aqueous emulsion adhesive composition for lapping. |
| JP6390894B2 (en) * | 2014-06-17 | 2018-09-19 | Dic株式会社 | Adhesive tape |
| US11696975B2 (en) | 2016-09-30 | 2023-07-11 | Sekisui Plastics Co., Ltd. | Hydrogel |
| JP6948277B2 (en) * | 2018-03-14 | 2021-10-13 | リンテック株式会社 | Adhesive sheet and manufacturing method of adhesive sheet |
| WO2024062954A1 (en) * | 2022-09-22 | 2024-03-28 | 株式会社レゾナック | Composite particles, binder composition for non-aqueous secondary battery and non-aqueous secondary battery electrode |
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