JP2004285138A - Emulsion type adhesive composition - Google Patents
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【０００１】
【発明の属する技術分野】本発明は、フィルム基材用感圧性接着剤、紙基材用感圧接着剤のラベル、シートの用途で使用されるエマルション型粘着剤組成物に関し、詳しくは経時安定性と耐水性に優れたエマルション型粘着剤組成物に関する。
【０００２】
【従来の技術】従来、塗料、粘着剤、感圧接着剤等の分野においては、有機溶剤型樹脂組成物が多く用いられてきた。しかし、近年安全性や衛生性の面から水性への要求が高まってきている。しかし、有機溶剤型に比べ水性のものは、耐水性等が不十分であることが多い。すなわち、水性樹脂組成物の多くは、乳化重合で作られるが、この場合乳化剤を用いることが多く、塗料塗膜や成膜した粘着剤中（以下、まとめて成膜物という。）に存在するこの乳化剤によって耐水性が損なわれやすいという問題点があった。
【０００３】水性樹脂組成物からなる成膜物の耐水性を向上させるために、乳化剤量を減らしたり、反応性乳化剤を用いたり、あるいは水性エマルジョンの平均粒子径（以下粒子径とする）を小さくしたりする試みが検討されている。粒子径を小さくして耐水性を向上させる方法の具体的な例として特許文献１、特許文献２および特許文献３が知られている。
【０００４】乳化剤を低減することは耐水性に対し、一応の効果は認められるが、乳化重合時の系の安定性・安全性・生産性等、また製造後の水性エマルションの貯蔵安定性等を考慮すると、一概に乳化剤量を低減することはできない。ラジカル重合性界面活性剤を用いた系は一定の耐水性の効果はあるが、これだけでは有機溶剤型に匹敵するレベルには達しない。そこで耐水性を保持するためにエマルションの粒子径をコントロール（小さく）し、エマルションが様々な基材へ塗布され成膜する際の成膜性を向上する方法が取られている。
【０００５】一般的に粘着剤分野では塗工時のハジキ等の塗工欠陥を防止するために増粘剤等を用い塗工機械に合わせた適性粘度に粘度調整した物を材料として用いる。水性エマルションの耐水性向上のために粒子径を小さく調整したものは耐水性の効果は見られるものの、経時で粘度が変化し適性粘度領域を外れてしまい、塗工欠陥を生じるという問題点がある。特に粒子径を０．３μｍ以下に設定した系ではこの傾向が多く見られる。
粘着剤のｐＨ調整や予め熱経時しておくという方法が提案されているが、粒子径を小さくし耐水性が良好で且つ経時安定性に優れた水性エマルション型粘着剤を提供することは出来なかった。
【０００６】
【特許文献１】特開平１− １７０６６号公報
【特許文献２】特開昭６３−２８４２８４号公報
【特許文献３】特開昭６３−３１２３６９号公報
【０００７】
【発明が解決しようとする課題】本発明は上記問題点を解決するためになされたもので耐水性を付与するために粒子径を小さくした水性エマルションの経時粘度に関するものである。増粘剤等で粘度を上げた水性エマルションであってもその増粘効果を維持し、経時粘度が安定な水性エマルション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、メタ）アクリル酸エステルを主成分とするエチレン性不飽和単量体をラジカル重合性界面活性剤の存在下にエマルション重合して得られたエマルション型アクリル系組成物と、低級アルキルで置換されてもよい尿素もしくは低級アルキルで置換されてもよいチオ尿素とを含むことを特徴とするエマルション型粘着剤組成物である。
更に本発明はエマルション型アクリル系組成物の平均粒子径が０．３μｍ以下である上記エマルション型粘着剤組成物である。
更に本発明は更に増粘剤を含有する上記エマルション型粘着剤組成物である。
更に本発明は基材もしくはセパレーターに上記エマルション型粘着剤組成物を塗工してなる粘着剤塗工物である。
【０００９】
【発明の実施の形態】以下に本発明の構成を詳しく説明する。
本発明における（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ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ｎ−オクチル、（メタ）アクリル酸ｎ−アミル、（メタ）アクリル酸イソアミルなどの（メタ）アクリル酸アルキルエステルがあり、これらはエチレン性不飽和単量体中８０〜９９重量％が使用される。その他の（メタ）アクリル酸エステルとしてβヒドロキシエチル（メタ）アクリレート、βヒドロキシプロピル（メタ）アクリレート、３−クロロ−２−ヒドロキシプロピルメタアクリレート、トリエチレングリコールモノメタアクリレートなどのヒドロキシル基を有する（メタ）アクリル酸エステルが挙げられる。
【００１０】本発明におけるエチレン性不飽和単量体としてはスチレン、酢酸ビニル、アクリロニトリル等、（メタ）アクリル酸、クロトン酸、イタコン酸、マレイン酸、フマール酸などのα、β不飽和カルボン酸、グリシジル（メタ）アクリレート等のエポキシ基含有不飽和単量体、ダイアセトンアクリルアミド等のカルボニル基含有不飽和単量体、Ｎ−メチロール（メタ）アクリルアマイド等のメチロール基含有不飽和単量体、γ―メタクリロキシプロピルトリメトキシシランやγ―メタクリロキシプロピルトリエトキシシラン、ジビニルベンゼンやエチレングリコールジメタクリレート等が挙げられる。
【００１１】本発明におけるラジカル重合性界面活性剤としては下記一般式（１）〜（４）に示す構造を有するものが知られている。
【化１】
【００１３】本発明の重合はエマルション重合の公知の方法が用いることができる。開始剤種類、反応温度、反応濃度等、通常のエマルション重合の方法が用いられ、特に制限は無い。
【００１４】本発明の低級アルキル基で置換されてもよい尿素もしくはチオ尿素の低級アルキル基は炭素数１〜４のアルキル基であり、具体的には尿素、トリメチル尿素、テトラメチル尿素、チオ尿素、トリメチルチオ尿素等が挙げられる。低級アルキル基で置換されてもよい尿素もしくはチオ尿素の使用量としてはエチレン性不飽和単量体１００重量％に対して０．００１〜５重量％、好ましくは０．０１〜１重量％である。０．００１％以下では目的とする経時安定性が得られない。５重量％以上では耐水性や接着物性に影響を及ぼす。
【００１５】低級アルキル基で置換されてもよい尿素もしくはチオ尿素を添加する時期としては、エマルション重合時でも重合後のブレンド工程でもよい。作業性を考えると重合後のブレンド工程で各種添加剤と同様に添加する方が望ましい。ブレンド工程とはエマルション型粘着剤を形成するに必要な各種添加剤を重合後のエマルションに必要に応じて添加する工程である。
【００１６】本発明におけるエマルション型アクリル組成物中のエマルションの平均粒子径は０．３μｍ以下が望ましい。０．３μｍ以上のエマルションであっても経時粘度変化を抑制する効果はあるが、粒子径が０．３μｍ以上のエマルションでは経時による粒子同士の吸着による経時粘度変化が比較的起こりにくい。粒子径が０．３μｍ以下のエマルションでは粒子同士の吸着による経時減粘や、増粘剤の増粘構造の破壊による粘度変化が見られる。
【００１７】本発明では必要に応じて消泡剤、防腐剤、レベリング剤、増粘剤、架橋剤、粘着付与剤等の各種添加剤を併用する事ができる。
【００１８】本発明のエマルション型粘着剤組成物を塗工してなる粘着剤塗工物はコンマコーター、リバースコーター、スロットダイコーター、リップコーター等のコーティング方式により基材への直接塗工法や、セパレーターへ塗工した後基材を貼り合わせる転写塗工法などにより得ることができる。この場合、エマルション型粘着剤組成物を塗工してなる粘着剤塗工物における粘着剤の塗工量は乾燥重量で５〜３０ｇ／ｍ２が適当である。基材としてはポリエステル、ポリプロピレン、塩化ビニルなどのフィルム状基材もしくは上質紙、アート紙、コート紙などの紙基材が挙げられる。塗工、乾燥、貼り合わせた後は本発明のエマルション型粘着剤組成物を含む粘着シートもしくは粘着テープとして使用することができる。
【００１９】以下に本発明を更に詳細に説明するために、以下に実施例と比較例を示す。
【００２０】実施例１
温度計、撹拌器、冷却コンデンサーを備えた重合用フラスコにイオン交換水７７．４重量％、アクアロンＫＨ−１０（第一工業製薬社製）０．１重量％を仕込み、窒素充填後、８０℃まで内部温度を上げた。次にアクリル酸２−エチルヘキシル８３重量％、メタクリル酸メチル１５重量％、アクリル酸２重量％、ラジカル重合性界面活性剤アクアロンＫＨ−１０（第一工業製薬社製）１．５重量％およびイオン交換水３０．３重量％を混合撹拌して乳化物とした。過硫酸カリウム０．４重量％をイオン交換水１３．３重量％で溶解した約３％の過硫酸カリウム水溶液を作成し、上記乳化物とともに１５０分かけて重合フラスコに均一滴下した。更に１８０分間反応して重合を終えた。出来上がったエマルションは固形分４５．０％、ｐＨ２．０、粘度１００ｍＰａ・ｓ、粒子径０．１６μｍであった。重合したエマルションに２５％アンモニア水を０．６重量％添加して中和し、増粘剤アデカノールＵＨ−４２０（旭電化工業社製）を１．０重量％とチオ尿素０．０２重量％を添加してよく撹拌し、エマルション型粘着剤を得た。
【００２１】実施例２
温度計、撹拌器、冷却コンデンサーを備えた重合用フラスコにイオン交換水７７．４重量％、アクアロンＫＨ−１０（第一工業製薬社製）０．１重量％を仕込み、窒素充填後、８０℃まで内部温度を上げた。次にアクリル酸２−エチルヘキシル８３重量％、メタクリル酸メチル１５重量％、アクリル酸２重量％、ラジカル重合性界面活性剤アクアロンＫＨ−１０（第一工業製薬社製）１．５重量％およびイオン交換水３０．３重量％を混合撹拌して乳化物とした。過硫酸カリウム０．４重量％をイオン交換水１３．３重量％で溶解した約３％の過硫酸カリウム水溶液を作成し、上記乳化物とともに１５０分かけて重合フラスコに均一滴下した。更に１８０分間反応して重合を終えた。出来上がったエマルションは固形分４５．０％、ｐＨ２．０、粘度１００ｍＰａ・ｓ、粒子径０．１６μｍであった。重合したエマルションに２５％アンモニア水を０．６重量％添加して中和し、増粘剤アデカノールＵＨ−４２０（旭電化工業社製）を１．０重量％と尿素０．０２重量％を添加してよく撹拌し、エマルション型粘着剤を得た。
【００２２】実施例３
温度計、撹拌器、冷却コンデンサーを備えた重合用フラスコにイオン交換水７７．４重量％、アデカリアソープＳＲ−１０Ｎ（旭電化工業社製）０．１重量％を仕込み、窒素充填後、８０℃まで内部温度を上げた。次にアクリル酸２−エチルヘキシル８３重量％、メタクリル酸メチル１５重量％、アクリル酸２重量％、ラジカル重合性界面活性剤アデカリアソープＳＲ−１０Ｎ（旭電化工業社製）１．５重量％およびイオン交換水３０．３重量％を混合撹拌して乳化物とした。過硫酸カリウム０．４重量％をイオン交換水１３．３重量％で溶解した約３％の過硫酸カリウム水溶液を作成し、上記乳化物とともに１５０分かけて重合フラスコに均一滴下した。更に１８０分間反応して重合を終えた。出来上がったエマルションは固形分４５．０％、ｐＨ２．０、粘度１２０ｍＰａ・ｓ、粒子径０．１７μｍであった。重合したエマルションに２５％アンモニア水を０．６重量％添加して中和し、増粘剤アデカノールＵＨ−４２０（旭電化工業社製）を１．０重量％とチオ尿素０．０２重量％を添加してよく撹拌し、エマルション型粘着剤を得た。
【００２３】実施例４
温度計、撹拌器、冷却コンデンサーを備えた重合用フラスコにイオン交換水７７．４重量％、アクアロンＫＨ−１０（第一工業製薬社製）０．１重量％を仕込み、窒素充填後、８０℃まで内部温度を上げた。次にアクリル酸２−エチルヘキシル４３重量％、アクリル酸ｎ−ブチル４０重量％、メタクリル酸メチル１５重量％、アクリル酸２重量％、ラジカル重合性界面活性剤アクアロンＫＨ−１０（第一工業製薬社製）１．５重量％およびイオン交換水３０．３重量％を混合撹拌して乳化物とした。過硫酸カリウム０．４重量％をイオン交換水１３．３重量％で溶解した約３％の過硫酸カリウム水溶液を作成し、上記乳化物とともに１５０分かけて重合フラスコに均一滴下した。更に１８０分間反応して重合を終えた。出来上がったエマルションは固形分４４．８％、ｐＨ２．０、粘度９０ｍＰａ・ｓ、粒子径０．１５μｍであった。重合したエマルションに２５％アンモニア水を０．６重量％添加して中和し、増粘剤アデカノールＵＨ−４２０（旭電化工業社製）を１．０重量％とチオ尿素０．０２重量％を添加してよく撹拌し、エマルション型粘着剤を得た。
【００２４】実施例５
温度計、撹拌器、冷却コンデンサーを備えた重合用フラスコにイオン交換水７７．４重量％、アクアロンＫＨ−１０（第一工業製薬社製）０．１重量％を仕込み、窒素充填後、８０℃まで内部温度を上げた。次にアクリル酸２−エチルヘキシル８３重量％、メタクリル酸メチル１５重量％、アクリル酸２重量％、ラジカル重合性界面活性剤アクアロンＫＨ−１０（第一工業製薬社製）１．５重量％およびイオン交換水３０．３重量％を混合撹拌して乳化物とした。過硫酸カリウム０．４重量％をイオン交換水１３．３重量％で溶解した約３％の過硫酸カリウム水溶液を作成し、上記乳化物とともに１５０分かけて重合フラスコに均一滴下した。更に１８０分間反応して重合を終えた。出来上がったエマルションは固形分４５．０％、ｐＨ２．０、粘度１００ｍＰａ・ｓ、粒子径０．１６μｍであった。重合したエマルションに２５％アンモニア水を０．６重量％添加して中和し、増粘剤アデカノールＵＨ−４２０（旭電化工業社製）を１．０重量％とチオ尿素０．２重量％を添加してよく撹拌し、エマルション型粘着剤を得た。
【００２５】比較例１
温度計、撹拌器、冷却コンデンサーを備えた重合用フラスコにイオン交換水７７．４重量％、アクアロンＫＨ−１０（第一工業製薬社製）０．１重量％を仕込み、窒素充填後、８０℃まで内部温度を上げた。次にアクリル酸２−エチルヘキシル８３重量％、メタクリル酸メチル１５重量％、アクリル酸２重量％、ラジカル重合性界面活性剤アクアロンＫＨ−１０（第一工業製薬社製）１．５重量％およびイオン交換水３０．３重量％を混合撹拌して乳化物とした。過硫酸カリウム０．４重量％をイオン交換水１３．３重量％で溶解した約３％の過硫酸カリウム水溶液を作成し、上記乳化物とともに１５０分かけて重合フラスコに均一滴下した。更に１８０分間反応して重合を終えた。出来上がったエマルションは固形分４５．０％、ｐＨ２．０、粘度１００ｍＰａ・ｓ、粒子径０．１６μｍであった。重合したエマルションに２５％アンモニア水を０．６重量％添加して中和し、増粘剤アデカノールＵＨ−４２０（旭電化工業社製）を１．０重量％を添加してよく撹拌し、エマルション型粘着剤を得た。
【００２６】比較例２
温度計、撹拌器、冷却コンデンサーを備えた重合用フラスコにイオン交換水７７．４重量％、ニューコール２３２０ＳＮ（日本乳化剤社製）０．１重量％を仕込み、窒素充填後、８０℃まで内部温度を上げた。次にアクリル酸２−エチルヘキシル８３重量％、メタクリル酸メチル１５重量％、アクリル酸２重量％、非重合性界面活性剤ニューコール２３２０ＳＮ（日本乳化剤社製）８．０重量％およびイオン交換水２４．５重量％を混合撹拌して乳化物とした。過硫酸カリウム０．４重量％をイオン交換水１３．３重量％で溶解した約３％の過硫酸カリウム水溶液を作成し、上記乳化物とともに１５０分かけて重合フラスコに均一滴下した。更に１８０分間反応して重合を終えた。出来上がったエマルションは固形分４４．９％、ｐＨ１．９、粘度３５０ｍＰａ・ｓ、粒子径０．１８μｍであった。重合したエマルションに２５％アンモニア水を０．６重量％添加して中和し、増粘剤アデカノールＵＨ−４２０（旭電化工業社製）を１．０重量％とチオ尿素０．０２重量％を添加してよく撹拌し、エマルション型粘着剤を得た。
【００２７】実施例１〜５、比較例１、２で得られたエマルション型粘着剤の経時安定性を以下の方法で確認した。得られたエマルション型粘着剤を２３℃および４０℃で３ヶ月静置して粘度変化を測定し、粘度変化が経時前と比べて１０％以内のものを◎、１０〜２０％のものを○、２０〜５０％のものを△、５０％以上のものを×とした。
【００２８】実施例１〜５、比較例１，２で得られたエマルション型粘着剤の耐水性を以下の方法で確認した。得られたエマルション型粘着剤を２５μｍのＰＥＴフィルム上に乾燥塗膜が２０μｍになるように塗布した。これを１０５℃のオーブンで７５秒間に入れ乾燥させ、セパレーターと貼りあわせて粘着フィルムを作成した。この粘着フィルムを蒸留水に７２時間浸漬して白化レベルを目視で確認した。
【００２９】
【表１】
【発明の効果】本発明により耐水性良好なエマルションであっても粘度経時安定性に優れたエマルション型粘着剤を得る事が出来た。[0001]
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an emulsion-type pressure-sensitive adhesive composition for use as a pressure-sensitive adhesive for a film base, a label for a pressure-sensitive adhesive for a paper base, and a sheet. The present invention relates to an emulsion-type pressure-sensitive adhesive composition excellent in water resistance and water resistance.
[0002]
2. Description of the Related Art Conventionally, in the fields of paints, pressure-sensitive adhesives and pressure-sensitive adhesives, organic solvent-type resin compositions have been widely used. However, in recent years, the demand for water based on safety and hygiene has been increasing. However, aqueous materials are often insufficient in water resistance and the like as compared with organic solvent types. That is, most of the aqueous resin composition is made by emulsion polymerization. In this case, an emulsifier is often used, and is present in a paint film or a formed pressure-sensitive adhesive (hereinafter, collectively referred to as a film). There was a problem that water resistance was easily impaired by this emulsifier.
In order to improve the water resistance of a film formed from an aqueous resin composition, the amount of an emulsifier is reduced, a reactive emulsifier is used, or the average particle size of the aqueous emulsion (hereinafter referred to as the particle size) is reduced. Or attempts to do so are being considered. Patent Document 1, Patent Document 2, and Patent Document 3 are known as specific examples of a method for improving the water resistance by reducing the particle diameter.
[0004] Although reducing the amount of emulsifier has a certain effect on water resistance, it has been found that the stability, safety and productivity of the system during emulsion polymerization and the storage stability of the aqueous emulsion after production are reduced. Considering this, the amount of emulsifier cannot be reduced unconditionally. The system using the radical polymerizable surfactant has a certain water resistance effect, but does not reach a level comparable to that of the organic solvent type alone. In order to maintain water resistance, a method has been adopted in which the particle size of the emulsion is controlled (small) to improve the film forming property when the emulsion is applied to various substrates to form a film.
In general, in the field of pressure-sensitive adhesives, in order to prevent coating defects such as cissing during coating, a material whose viscosity is adjusted to an appropriate viscosity suitable for a coating machine by using a thickener or the like is used as a material. A water-based emulsion in which the particle size is adjusted small to improve the water resistance has a problem that although the effect of water resistance can be seen, the viscosity changes with time and the viscosity is out of the proper viscosity range, resulting in a coating defect. . In particular, this tendency is often observed in a system in which the particle diameter is set to 0.3 μm or less.
Although a method of adjusting the pH of the pressure-sensitive adhesive or preheating with time has been proposed, it has not been possible to provide a water-based emulsion-type pressure-sensitive adhesive having a small particle diameter, good water resistance, and excellent stability over time. Was.
[0006]
[Patent Document 1] JP-A-1-17066 [Patent Document 2] JP-A-63-284284 [Patent Document 3] JP-A-63-212369
SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and relates to the viscosity over time of an aqueous emulsion having a reduced particle size in order to impart water resistance. It is an object of the present invention to provide a water-based emulsion having a stable viscosity over time even when the viscosity of the water-based emulsion is increased by a thickener or the like.
[0008]
DISCLOSURE OF THE INVENTION The present invention relates to an emulsion type obtained by subjecting an ethylenically unsaturated monomer having a meth) acrylate ester as a main component to emulsion polymerization in the presence of a radically polymerizable surfactant. An emulsion-type pressure-sensitive adhesive composition comprising an acrylic composition and urea which may be substituted with lower alkyl or thiourea which may be substituted with lower alkyl.
Furthermore, the present invention is the above-mentioned emulsion-type pressure-sensitive adhesive composition, wherein the emulsion-type acrylic composition has an average particle size of 0.3 μm or less.
Further, the present invention is the above-mentioned emulsion-type pressure-sensitive adhesive composition further containing a thickener.
Further, the present invention is a pressure-sensitive adhesive coated product obtained by coating the above-mentioned emulsion type pressure-sensitive adhesive composition on a substrate or a separator.
[0009]
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The structure of the present invention will be described below in detail.
Examples of the (meth) acrylate in the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, lauryl (meth) acrylate, ( There are alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, n-amyl (meth) acrylate and isoamyl (meth) acrylate, which are ethylenically unsaturated. 80-99% by weight of the monomers are used. Other (meth) acrylic acid esters having hydroxyl groups such as β-hydroxyethyl (meth) acrylate, β-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl methacrylate, and triethylene glycol monomethacrylate (meth) ) Acrylic esters.
The ethylenically unsaturated monomers in the present invention include styrene, vinyl acetate, acrylonitrile and the like, α-, β-unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid; Epoxy group-containing unsaturated monomers such as glycidyl (meth) acrylate; carbonyl group-containing unsaturated monomers such as diacetone acrylamide; methylol group-containing unsaturated monomers such as N-methylol (meth) acrylamide; —Methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, divinylbenzene, ethylene glycol dimethacrylate and the like.
As the radical polymerizable surfactant in the present invention, those having structures represented by the following general formulas (1) to (4) are known.
Embedded image
For the polymerization of the present invention, a known method of emulsion polymerization can be used. Conventional emulsion polymerization methods such as initiator type, reaction temperature and reaction concentration are used, and there is no particular limitation.
The lower alkyl group of urea or thiourea which may be substituted by a lower alkyl group of the present invention is an alkyl group having 1 to 4 carbon atoms, and specifically includes urea, trimethylurea, tetramethylurea, thiourea. , Trimethylthiourea and the like. The amount of urea or thiourea which may be substituted with a lower alkyl group is 0.001 to 5% by weight, preferably 0.01 to 1% by weight, based on 100% by weight of the ethylenically unsaturated monomer. . If the content is less than 0.001%, the desired temporal stability cannot be obtained. If the content is 5% by weight or more, it affects water resistance and adhesive properties.
The urea or thiourea which may be substituted with a lower alkyl group may be added at the time of emulsion polymerization or at the blending step after polymerization. Considering workability, it is desirable to add the same as various additives in the blending step after polymerization. The blending step is a step of adding various additives necessary for forming an emulsion-type pressure-sensitive adhesive to the emulsion after polymerization as necessary.
The average particle size of the emulsion in the emulsion type acrylic composition of the present invention is desirably 0.3 μm or less. An emulsion having a particle diameter of 0.3 μm or more has an effect of suppressing a change in viscosity over time, but an emulsion having a particle diameter of 0.3 μm or more hardly causes a change in viscosity with time due to adsorption of particles over time. In an emulsion having a particle diameter of 0.3 μm or less, a time-dependent decrease in viscosity due to adsorption between particles and a change in viscosity due to the destruction of the thickening structure of the thickener are observed.
In the present invention, if necessary, various additives such as an antifoaming agent, a preservative, a leveling agent, a thickener, a crosslinking agent and a tackifier can be used in combination.
The pressure-sensitive adhesive coated product obtained by coating the emulsion-type pressure-sensitive adhesive composition of the present invention can be directly coated on a substrate by a coating method such as a comma coater, a reverse coater, a slot die coater, or a lip coater. It can be obtained by a transfer coating method in which a base material is applied after being applied to a separator, or the like. In this case, the coating amount of the pressure-sensitive adhesive in the pressure-sensitive adhesive coated product obtained by coating the emulsion-type pressure-sensitive adhesive composition is appropriately 5 to 30 g / m 2 in terms of dry weight. Examples of the substrate include film substrates such as polyester, polypropylene, and vinyl chloride, and paper substrates such as high-quality paper, art paper, and coated paper. After coating, drying and laminating, it can be used as a pressure-sensitive adhesive sheet or pressure-sensitive adhesive tape containing the emulsion-type pressure-sensitive adhesive composition of the present invention.
In order to explain the present invention in more detail below, examples and comparative examples are shown below.
Embodiment 1
A polymerization flask equipped with a thermometer, a stirrer, and a cooling condenser was charged with 77.4% by weight of ion-exchanged water and 0.1% by weight of Aqualon KH-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and after filling with nitrogen, 80 ° C. The internal temperature was raised until. Next, 83% by weight of 2-ethylhexyl acrylate, 15% by weight of methyl methacrylate, 2% by weight of acrylic acid, 1.5% by weight of a radical polymerizable surfactant Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.) and ion exchange 30.3% by weight of water was mixed and stirred to obtain an emulsion. An aqueous solution of about 3% potassium persulfate was prepared by dissolving 0.4% by weight of potassium persulfate in 13.3% by weight of ion-exchanged water, and was uniformly added dropwise to the polymerization flask over 150 minutes together with the emulsion. The reaction was continued for another 180 minutes to complete the polymerization. The resulting emulsion had a solid content of 45.0%, a pH of 2.0, a viscosity of 100 mPa · s, and a particle size of 0.16 μm. 0.6% by weight of 25% aqueous ammonia was added to the polymerized emulsion to neutralize it, and 1.0% by weight of a thickener Adecanol UH-420 (manufactured by Asahi Denka Kogyo KK) and 0.02% by weight of thiourea were added. The mixture was added and stirred well to obtain an emulsion-type adhesive.
Embodiment 2
A polymerization flask equipped with a thermometer, a stirrer, and a cooling condenser was charged with 77.4% by weight of ion-exchanged water and 0.1% by weight of Aqualon KH-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and after filling with nitrogen, 80 ° C. The internal temperature was raised until. Next, 83% by weight of 2-ethylhexyl acrylate, 15% by weight of methyl methacrylate, 2% by weight of acrylic acid, 1.5% by weight of a radical polymerizable surfactant Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.) and ion exchange 30.3% by weight of water was mixed and stirred to obtain an emulsion. An aqueous solution of about 3% potassium persulfate was prepared by dissolving 0.4% by weight of potassium persulfate in 13.3% by weight of ion-exchanged water, and was uniformly added dropwise to the polymerization flask over 150 minutes together with the emulsion. The reaction was continued for another 180 minutes to complete the polymerization. The resulting emulsion had a solid content of 45.0%, a pH of 2.0, a viscosity of 100 mPa · s, and a particle size of 0.16 μm. The polymerized emulsion was neutralized by adding 0.6% by weight of 25% aqueous ammonia and adding 1.0% by weight of a thickener Adecanol UH-420 (manufactured by Asahi Denka Kogyo KK) and 0.02% by weight of urea. After stirring well, an emulsion-type pressure-sensitive adhesive was obtained.
Embodiment 3
A polymerization flask equipped with a thermometer, a stirrer, and a cooling condenser was charged with 77.4% by weight of ion-exchanged water and 0.1% by weight of Adecaria Soap SR-10N (manufactured by Asahi Denka Kogyo Co., Ltd.). The internal temperature was raised to ° C. Next, 83% by weight of 2-ethylhexyl acrylate, 15% by weight of methyl methacrylate, 2% by weight of acrylic acid, 1.5% by weight of radical polymerizable surfactant Adecaria Soap SR-10N (manufactured by Asahi Denka Kogyo KK) and ions Emulsion was obtained by mixing and stirring 30.3% by weight of exchanged water. An aqueous solution of about 3% potassium persulfate was prepared by dissolving 0.4% by weight of potassium persulfate in 13.3% by weight of ion-exchanged water, and was uniformly added dropwise to the polymerization flask over 150 minutes together with the emulsion. The reaction was continued for another 180 minutes to complete the polymerization. The resulting emulsion had a solid content of 45.0%, a pH of 2.0, a viscosity of 120 mPa · s, and a particle size of 0.17 μm. 0.6% by weight of 25% aqueous ammonia was added to the polymerized emulsion to neutralize it, and 1.0% by weight of a thickener Adecanol UH-420 (manufactured by Asahi Denka Kogyo KK) and 0.02% by weight of thiourea were added. The mixture was added and stirred well to obtain an emulsion-type adhesive.
Embodiment 4
A polymerization flask equipped with a thermometer, a stirrer, and a cooling condenser was charged with 77.4% by weight of ion-exchanged water and 0.1% by weight of Aqualon KH-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and after filling with nitrogen, 80 ° C. The internal temperature was raised until. Next, 43% by weight of 2-ethylhexyl acrylate, 40% by weight of n-butyl acrylate, 15% by weight of methyl methacrylate, 2% by weight of acrylic acid, a radical polymerizable surfactant Aqualon KH-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) ) 1.5% by weight and 30.3% by weight of ion-exchanged water were mixed and stirred to obtain an emulsion. An aqueous solution of about 3% potassium persulfate was prepared by dissolving 0.4% by weight of potassium persulfate in 13.3% by weight of ion-exchanged water, and was uniformly added dropwise to the polymerization flask over 150 minutes together with the emulsion. The reaction was continued for another 180 minutes to complete the polymerization. The resulting emulsion had a solid content of 44.8%, a pH of 2.0, a viscosity of 90 mPa · s, and a particle size of 0.15 μm. 0.6% by weight of 25% aqueous ammonia was added to the polymerized emulsion to neutralize it, and 1.0% by weight of a thickener Adecanol UH-420 (manufactured by Asahi Denka Kogyo KK) and 0.02% by weight of thiourea were added. The mixture was added and stirred well to obtain an emulsion-type adhesive.
Embodiment 5
A polymerization flask equipped with a thermometer, a stirrer, and a cooling condenser was charged with 77.4% by weight of ion-exchanged water and 0.1% by weight of Aqualon KH-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and after filling with nitrogen, 80 ° C. The internal temperature was raised until. Next, 83% by weight of 2-ethylhexyl acrylate, 15% by weight of methyl methacrylate, 2% by weight of acrylic acid, 1.5% by weight of a radical polymerizable surfactant Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.) and ion exchange 30.3% by weight of water was mixed and stirred to obtain an emulsion. An aqueous solution of about 3% potassium persulfate was prepared by dissolving 0.4% by weight of potassium persulfate in 13.3% by weight of ion-exchanged water, and was uniformly added dropwise to the polymerization flask over 150 minutes together with the emulsion. The reaction was continued for another 180 minutes to complete the polymerization. The resulting emulsion had a solid content of 45.0%, a pH of 2.0, a viscosity of 100 mPa · s, and a particle size of 0.16 μm. The polymerized emulsion was neutralized by adding 0.6% by weight of 25% aqueous ammonia, and 1.0% by weight of a thickener Adecanol UH-420 (manufactured by Asahi Denka Kogyo KK) and 0.2% by weight of thiourea. The mixture was added and stirred well to obtain an emulsion-type adhesive.
Comparative Example 1
A polymerization flask equipped with a thermometer, a stirrer, and a cooling condenser was charged with 77.4% by weight of ion-exchanged water and 0.1% by weight of Aqualon KH-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and after filling with nitrogen, 80 ° C. The internal temperature was raised until. Next, 83% by weight of 2-ethylhexyl acrylate, 15% by weight of methyl methacrylate, 2% by weight of acrylic acid, 1.5% by weight of a radical polymerizable surfactant Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.) and ion exchange 30.3% by weight of water was mixed and stirred to obtain an emulsion. An aqueous solution of about 3% potassium persulfate was prepared by dissolving 0.4% by weight of potassium persulfate in 13.3% by weight of ion-exchanged water, and was uniformly added dropwise to the polymerization flask over 150 minutes together with the emulsion. The reaction was continued for another 180 minutes to complete the polymerization. The resulting emulsion had a solid content of 45.0%, a pH of 2.0, a viscosity of 100 mPa · s, and a particle size of 0.16 μm. The polymerized emulsion was neutralized by adding 0.6% by weight of 25% aqueous ammonia, and 1.0% by weight of a thickener Adecanol UH-420 (manufactured by Asahi Denka Kogyo Co., Ltd.) was added thereto, followed by stirring well. A mold adhesive was obtained.
Comparative Example 2
A polymerization flask equipped with a thermometer, a stirrer, and a cooling condenser was charged with 77.4% by weight of ion-exchanged water and 0.1% by weight of Newcol 2320SN (manufactured by Nippon Emulsifier Co.), and filled with nitrogen. Raised. Next, 83% by weight of 2-ethylhexyl acrylate, 15% by weight of methyl methacrylate, 2% by weight of acrylic acid, 8.0% by weight of non-polymerizable surfactant Newcol 2320SN (manufactured by Nippon Emulsifier Co.) and 24. 5% by weight was mixed and stirred to obtain an emulsion. An aqueous solution of about 3% potassium persulfate was prepared by dissolving 0.4% by weight of potassium persulfate in 13.3% by weight of ion-exchanged water, and was uniformly added dropwise to the polymerization flask over 150 minutes together with the emulsion. The reaction was continued for another 180 minutes to complete the polymerization. The resulting emulsion had a solid content of 44.9%, a pH of 1.9, a viscosity of 350 mPa · s, and a particle size of 0.18 μm. 0.6% by weight of 25% aqueous ammonia was added to the polymerized emulsion to neutralize it, and 1.0% by weight of a thickener Adecanol UH-420 (manufactured by Asahi Denka Kogyo KK) and 0.02% by weight of thiourea were added. The mixture was added and stirred well to obtain an emulsion-type adhesive.
The stability over time of the emulsion-type pressure-sensitive adhesives obtained in Examples 1 to 5 and Comparative Examples 1 and 2 was confirmed by the following method. The obtained emulsion-type pressure-sensitive adhesive was allowed to stand at 23 ° C. and 40 ° C. for 3 months, and the viscosity change was measured. △: 20 to 50%, ×: 50% or more
The water resistance of the emulsion type pressure-sensitive adhesives obtained in Examples 1 to 5 and Comparative Examples 1 and 2 was confirmed by the following method. The obtained emulsion-type pressure-sensitive adhesive was applied on a 25-μm PET film so that the dry coating film became 20 μm. This was placed in an oven at 105 ° C. for 75 seconds and dried, and bonded to a separator to form an adhesive film. This adhesive film was immersed in distilled water for 72 hours to visually check the whitening level.
[0029]
[Table 1]
According to the present invention, an emulsion-type pressure-sensitive adhesive having excellent stability over time can be obtained even with an emulsion having good water resistance.
Claims (4)
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|---|---|---|---|---|
| JPS4751808B1 (en) * | 1969-07-12 | 1972-12-26 | ||
| JPS4996078A (en) * | 1972-12-18 | 1974-09-11 | ||
| JPH0885777A (en) * | 1994-07-18 | 1996-04-02 | Sekisui Chem Co Ltd | Adhesive composition and paper tube produced by using the same |
| JPH11181297A (en) * | 1997-12-25 | 1999-07-06 | Kuraray Co Ltd | Aqueous emulsion composition |
| JP2002080809A (en) * | 2000-09-05 | 2002-03-22 | Showa Highpolymer Co Ltd | Aqueous emulsion pressure-sensitive adhesive |
| JP2004197028A (en) * | 2002-12-20 | 2004-07-15 | Aica Kogyo Co Ltd | Aqueous adhesive composition |
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2003
- 2003-03-20 JP JP2003077105A patent/JP2004285138A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4751808B1 (en) * | 1969-07-12 | 1972-12-26 | ||
| JPS4996078A (en) * | 1972-12-18 | 1974-09-11 | ||
| JPH0885777A (en) * | 1994-07-18 | 1996-04-02 | Sekisui Chem Co Ltd | Adhesive composition and paper tube produced by using the same |
| JPH11181297A (en) * | 1997-12-25 | 1999-07-06 | Kuraray Co Ltd | Aqueous emulsion composition |
| JP2002080809A (en) * | 2000-09-05 | 2002-03-22 | Showa Highpolymer Co Ltd | Aqueous emulsion pressure-sensitive adhesive |
| JP2004197028A (en) * | 2002-12-20 | 2004-07-15 | Aica Kogyo Co Ltd | Aqueous adhesive composition |
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