JP2005247955A - Adhesive composition and adhesive sheet - Google Patents
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本発明は、粘着性のテープ、ラベル、シートあるいは両面テープ等の各種粘着性加工品における粘着剤に使用される接着剤組成物、及びそれを用いた粘着加工品に関するもので、各種基材、或いは剥離材に対する濡れ性が良好であり、平滑面が得られにくい高速塗工時においてもハジキ、チヂミ、カスレの無い平滑な塗工面を得ることができる接着剤組成物、およびそれを塗工してなる粘着シートに関するものである。 The present invention relates to an adhesive composition used for an adhesive in various adhesive processed products such as an adhesive tape, a label, a sheet or a double-sided tape, and an adhesive processed product using the adhesive composition. Alternatively, an adhesive composition capable of obtaining a smooth coated surface free from cissing, blemishes, and blurring even during high-speed coating with good wettability to a release material and in which a smooth surface is difficult to obtain, and coating the same It is related with the adhesive sheet formed.
現在、水分散型粘着剤組成物は、無有機溶剤型であるため、有機溶剤型粘着剤と比較して、当該有機溶剤が乾燥等により大気中に飛散・分散することがないので、大気汚染が少ないこと、安全衛生に優れていること等の利点があるため、近年広く普及してきている。 At present, since the water-dispersed pressure-sensitive adhesive composition is an organic solvent type, the organic solvent does not scatter or disperse in the atmosphere due to drying or the like compared to the organic solvent-type pressure-sensitive adhesive. In recent years, it has become widespread because it has advantages such as being less in number and being excellent in safety and health.
このような利点をもつ水分散型粘着剤組成物は、紙またはフイルム、シート等の基材に直接塗布するか、あるいは剥離材に塗布した後、各種基材に転写することで、粘着性のテープ、ラベル、シートあるいは両面テープ等の各種粘着性製品に加工される。 The water-dispersed pressure-sensitive adhesive composition having such advantages can be applied directly to a substrate such as paper, film, or sheet, or applied to a release material, and then transferred to various substrates so that the adhesive Processed into various adhesive products such as tape, label, sheet or double-sided tape.
上記の塗布工程においては、従来は比較的低速の塗工速度で行われていたが、粘着加工品の生産性を向上し、製造コストを低下させるためには、各種基材への粘着剤組成物の塗工速度をより高速で行う必要がある。しかしながら、水分散型粘着剤の場合、塗工速度を上げることによって、乾燥効率が低下したり、粘着剤に加わるせん断応力が高くなることにより凝集物が発生しやすくなる、あるいは、塗工剤槽内に気泡が発生しやすくなる等の問題が生じるため、自ずと塗工速度に制限が加わり、十分な生産性の向上に結び付けることは困難であった。 In the above coating process, conventionally, it was performed at a relatively low coating speed, but in order to improve the productivity of adhesive processed products and reduce the manufacturing cost, the composition of the adhesive to various substrates. It is necessary to apply the coating speed at a higher speed. However, in the case of a water-dispersed pressure-sensitive adhesive, by increasing the coating speed, the drying efficiency is reduced, or the shear stress applied to the pressure-sensitive adhesive is increased, so that agglomerates are easily generated, or the coating agent tank Since problems such as easy generation of bubbles occur in the interior, the coating speed is naturally limited, and it has been difficult to achieve sufficient productivity improvement.
この問題を解決する手段として、水分散型粘着剤の固形分を上げ乾燥効率を向上させたり、機械的安定性を向上させる添加剤を加え凝集物の発生を抑える等の方法が挙げられる。しかしながら、これらの方法では、高速塗工性に優れているとは言えないことが明らかとなっている。この課題に関し、特開平８−２１８０４７号公報では、水分散型アクリル系粘着剤組成物に関し、固形分を５０重量％以上、重合体粒子の平均粒子径を０．２μｍ以上、及びせん断速度１．０ｘ１０５（１／ｓ）における粘度を２０ｍｐａ・ｓ以上にすることで高速塗工に適した粘着剤組成物が提案されているが、水分散型粘着剤組成物の塗工性は樹脂の粘性及び、各種基材や剥離材に対する濡れ性にも深く関係するため、固形分、粒子径、粘度の特定のみでは不十分であった。
本発明は、泡立ち等塗工槽内の塗工液の状態が乱れやすく、また、良好な塗工面が得られにくい高速塗工時においても、各種基材、剥離材に対しハジキ、チヂミ、カスレの無い平滑な塗工面を得ることができる接着剤組成物、及び該接着剤組成物を用いて塗工してなる粘着シートを提供しようとするものである。 In the present invention, the state of the coating liquid in the coating tank, such as foaming, is likely to be disturbed, and even during high-speed coating where a good coating surface is difficult to obtain, various substrates and release materials can be repelled, scratched, and scraped. It is intended to provide an adhesive composition capable of obtaining a smooth coated surface having no adhesive, and a pressure-sensitive adhesive sheet coated using the adhesive composition.
本発明者らは、これらの問題を解決するため鋭意検討を行った結果、高剪断速度下での粘度、重合体粒子の体積平均粒子径、粒子径分布、及び動的接触角が特定の値を有する水分散型アクリル樹脂からなる接着剤組成物が優れた塗工性を有し、各種基材、剥離材に対する良好な濡れ性を示し、ハジキ、チヂミ、カスレ起こりやすい高速塗工時においても平滑で良好な塗工面を得ることができることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve these problems, the present inventors have found that the viscosity at a high shear rate, the volume average particle size of the polymer particles, the particle size distribution, and the dynamic contact angle are specific values. Adhesive composition made of water-dispersed acrylic resin with excellent coating properties, good wettability to various base materials and release materials, even during high-speed coating, where repelling, wrinkles and sag are likely to occur The present inventors have found that a smooth and good coated surface can be obtained and have completed the present invention.
すなわち、本発明は以下の［１］〜［５］で特定される。
［１］ （メタ）アクリル酸アルキルエステルを主成分からなり、水分散型アクリル樹脂の剪断速度１０5における粘度が１０〜２００ｍＰａ・ｓの範囲であり、 動的Ｗｉｌｈｅｌｍｙ平板法による動的接触角測定における前進接触角が、９０゜〜１５０゜であることを特徴とする接着剤組成物。
［２］ 水分散型アクリル樹脂の固形分が４０％〜７５％であり、体積平均粒子径が、１５０ｎｍ〜３０００ｎｍの範囲であり、且つその粒子は、バイモーダル或いはブロードな粒子径分布を有していることを特徴とする［１］記載の接着剤組成物。
［３］ アクリル樹脂が、官能基を有するエチレン性不飽和単量体を０．０１質量％〜０．９９質量％共重合していることを特徴とする［１］記載の接着剤組成物。
［４］ 基材又は剥離材上に塗布速度、１００〜１５００ｍ／分の速度で塗布可能な請求項１記載の接着剤組成物。
［５］ ［１］記載の接着剤組成物を用いて、基材或いは剥離材上に塗布された粘着シート。
That is, the present invention is specified by the following [1] to [5].
[1] Consisting of (meth) acrylic acid alkyl ester as the main component, the viscosity of the water-dispersed acrylic resin at a shear rate of 10 5 is in the range of 10 to 200 mPa · s, and the dynamic contact angle measurement by the dynamic Wilhelmy plate method The advancing contact angle in the adhesive composition is 90 ° to 150 °.
[2] The solid content of the water-dispersed acrylic resin is 40% to 75%, the volume average particle size is in the range of 150 nm to 3000 nm, and the particles have a bimodal or broad particle size distribution. The adhesive composition according to [1], wherein
[3] The adhesive composition according to [1], wherein the acrylic resin is copolymerized with 0.01% by mass to 0.99% by mass of an ethylenically unsaturated monomer having a functional group.
[4] The adhesive composition according to claim 1, which can be applied on a substrate or a release material at a coating speed of 100 to 1500 m / min.
[5] A pressure-sensitive adhesive sheet coated on a substrate or a release material using the adhesive composition according to [1].
本発明の接着剤組成物は、各種基材、或いは剥離材に対する濡れ性が良好であり、これを使用して塗工すれば高速塗工時においても、ハジキ、チヂミ、カスレの無い平滑な塗工面を得ることができるので、格段に生産性が向上する。 The adhesive composition of the present invention has good wettability with respect to various substrates or release materials, and when applied using this, a smooth coating free of cissing, wrinkles, and scouring even during high-speed coating. Since the work surface can be obtained, the productivity is remarkably improved.
以下、本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail.
本発明の（メタ）アクリル酸アルキルエステル単量体としては、具体的には、例えばメチル−、エチル−、ｎ−プロピル−、イソプロピル−、ｎ−ブチル−、イソブチル−、ｓｅｃ−ブチル−、ｔｅｒｔ−ブチル−、ｎ−アミル−、イソアミル−、ｎ−ヘキシル−、シクロヘキシル−、ヘプチル−、オクチル−、２−エチルヘキシル−、２−エチルオクチル−、デシル−、ドデシル−、オクタデシル−、ラウリル−、ステアリル−、等のアクリル酸エステル又はメタクリル酸エステルを含む単量体が挙げられ、これらは単独で、或いは２種類以上混合して用いることができる。好ましくはアルキル基の炭素数が１〜１０、より好ましくはアルキル基の炭素数が１〜８の（メタ）アクリル酸アルキルエステル単量体を２種類以上混合して用いる。アルキル基の炭素数が長くなりすぎると、重合反応がスムーズに進行しない傾向がある。 Specific examples of the (meth) acrylic acid alkyl ester monomer of the present invention include, for example, methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl-, isobutyl-, sec-butyl-, tert. -Butyl-, n-amyl-, isoamyl-, n-hexyl-, cyclohexyl-, heptyl-, octyl-, 2-ethylhexyl-, 2-ethyloctyl-, decyl-, dodecyl-, octadecyl-, lauryl-, stearyl -, Etc. The monomer containing acrylic acid ester or methacrylic acid ester is mentioned, These can be used individually or in mixture of 2 or more types. Preferably, two or more types of (meth) acrylic acid alkyl ester monomers having 1 to 10 carbon atoms in the alkyl group, more preferably 1 to 8 carbon atoms in the alkyl group are used. When the carbon number of the alkyl group becomes too long, the polymerization reaction tends not to proceed smoothly.
共重合体中の上記（メタ）アクリル酸エステル単量体の含有量としては９９．０１〜９９．９９質量％が好ましい。９９．０１質量％未満では粘着シートとしての養生後の粘着力変化が大きい傾向にある。また９９．９９質量％を超えると粘着剤として十分な凝集力が得にくくなり易い傾向にある。 As content of the said (meth) acrylic acid ester monomer in a copolymer, 99.01-99.99 mass% is preferable. If it is less than 99.01 mass%, the adhesive force change after curing as an adhesive sheet tends to be large. Moreover, when it exceeds 99.99 mass%, it tends to be difficult to obtain sufficient cohesion as an adhesive.
また上記（メタ）アクリル酸エステル単量体との共重合成分である官能基を有するエチレン性不飽和単量体としては、具体的には水酸基を含有する単量体として例えば２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルアクリレート、２−ヒドロキシプロピルメタクリレート、２−ヒドロキシブチルアクリレート、２−ヒドロキシブチルメタクリレート、２−ヒドロキシビニルエーテル、ポリエチレングリコールモノアクリレート、ポリエチレングリコールモノメタアクリレート、ポリプロピレングリコールモノアクリレート、ポリプロピレングリコールモノメタアクリレート、カルボキシル基を含有する単量体として例えばアクリル酸、メタクリル酸、クロトン酸、マレイン酸、イタコン酸、フマル酸、シトラコン酸、グリシジル基を含有する単量体として例えばグリシジルアクリレート、グリシジルメタクリレート、グリシジルシンナート、アリルグリシジルエーテル、ビニルシクロヘキセンモノエポサイド、アミド基を含有する単量体として例えばアクリルアミド、メタクリルアミド、Ｎ−メチルアクリルアミド、Ｎ−メチルメタアクリルアミド、Ｎ−メチロールアクリルアミド、スルホン酸基を含有する単量体として例えばスチレンスルホン酸及びその塩類、２−アクリルアミド−２−メチルプロパンスルホン酸及びその塩類、アリルスルホン酸及びその塩類、メタアリルスルホン酸及びその塩類、等が挙げられ、これらは単独で、或いは２種類以上混合して用いることができる。 In addition, as the ethylenically unsaturated monomer having a functional group which is a copolymerization component with the (meth) acrylic acid ester monomer, specifically, as a monomer containing a hydroxyl group, for example, 2-hydroxyethyl acrylate 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxyvinyl ether, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol mono Acrylic acid, methacrylic acid, crotonic acid, maleic acid, itacon , Fumaric acid, citraconic acid, glycidyl group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, glycidyl cinnamate, allyl glycidyl ether, vinylcyclohexene monoepoxide, amide group-containing monomers such as acrylamide, methacrylic acid Amide, N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, monomers containing sulfonic acid groups such as styrenesulfonic acid and its salts, 2-acrylamido-2-methylpropanesulfonic acid and its salts, Examples include allyl sulfonic acid and salts thereof, methallyl sulfonic acid and salts thereof, and the like. These may be used alone or in combination of two or more.
共重合体中の上記官能基を有するエチレン性不飽和単量体の配合量としては、（メタ）アクリル酸アルキルエステル単量体１００質量％に対して、０．０１〜０．９９質量％である。 As a compounding quantity of the ethylenic unsaturated monomer which has the said functional group in a copolymer, it is 0.01-0.99 mass% with respect to 100 mass% of (meth) acrylic-acid alkylester monomers. is there.
０．０１質量％未満ではエマルションの重合および機械的安定性が低くなり易いため、重合中の粗大粒子の発生やせん断応力下における凝集物発生の原因となり易い傾向にある。また０．９９質量％を超えると粘着シートの養生後の粘着力変化が大きい傾向にある。 If the amount is less than 0.01% by mass, the polymerization and mechanical stability of the emulsion tend to be low, so that it tends to cause generation of coarse particles during polymerization and generation of aggregates under shear stress. Moreover, when it exceeds 0.99 mass%, there exists a tendency for the adhesive force change after curing of an adhesive sheet to be large.
本発明の接着剤組成物は、上記の主成分の他に、必要に応じて2個以上のエチレン性不飽和二重結合を有する単量体及びその他のモノエチレン性不飽和単量体等を共重合しても良い。 The adhesive composition of the present invention contains, in addition to the above main components, a monomer having two or more ethylenically unsaturated double bonds and other monoethylenically unsaturated monomers as necessary. It may be copolymerized.
まず、２個以上のエチレン性不飽和二重結合を有する単量体としては、具体的には、例えばブタジエン、ジビニルベンゼン、（ポリ）エチレングリコールジアクリレート、（ポリ）エチレングリコールジメタクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパントリメタクリレート等が挙げられ、これらは単独で、或いは２種類以上混合して用いることができる。 First, specific examples of the monomer having two or more ethylenically unsaturated double bonds include butadiene, divinylbenzene, (poly) ethylene glycol diacrylate, (poly) ethylene glycol dimethacrylate, and trimethylol. Examples thereof include propane triacrylate and trimethylolpropane trimethacrylate, and these can be used alone or in combination of two or more.
その他のモノエチレン性不飽和単量体としては、例えば酢酸ビニル、スチレン、α−メチルスチレン、ジビニルベンゼン、アクリロニトリル、メタアクリロニトリル、塩化ビニル、ビニルピロリドン等のビニル系単量体が挙げられる。
これら単量体成分の使用量は、一般的には前記２成分１００質量％に対して、０〜２０質量％の範囲で用いられる。
Examples of other monoethylenically unsaturated monomers include vinyl monomers such as vinyl acetate, styrene, α-methylstyrene, divinylbenzene, acrylonitrile, methacrylonitrile, vinyl chloride, and vinylpyrrolidone.
The amount of these monomer components used is generally in the range of 0 to 20% by mass with respect to 100% by mass of the two components.
本発明の（メタ）アクリル酸アルキルエステルを主成分とし、これに各々異なる官能基を有するエチレン性不飽和単量体を２種以上、必要に応じて2個以上のエチレン性不飽和二重結合を有する単量体及びその他のモノエチレン性不飽和単量体（以下アクリル系単量体と称す）の共重合体を製造する方法としては、特に制限はないが、通常、公知の乳化重合法が採用される。すなわち、水、上記アクリル系単量体混合物、界面活性剤、連鎖移動剤（重合度調節剤）、ラジカル重合開始剤を基本構成とする乳化重合法が採用される。 2 or more types of ethylenically unsaturated monomers each having a different (meth) acrylic acid alkyl ester of the present invention and each having different functional groups, and if necessary, 2 or more ethylenically unsaturated double bonds There is no particular limitation on the method for producing a copolymer of a monomer having a monomer and other monoethylenically unsaturated monomers (hereinafter referred to as acrylic monomers), but generally known emulsion polymerization methods Is adopted. That is, an emulsion polymerization method having water, the above acrylic monomer mixture, a surfactant, a chain transfer agent (polymerization degree modifier), and a radical polymerization initiator as basic components is employed.
まず、界面活性剤としては、具体的には例えば脂肪酸石鹸、ロジン石鹸、アルキルスルホン酸塩、アルキルベンゼンスルホン酸塩、ジアルキルアリールスルホン酸塩、アルキルスルホコハク酸、ポリオキシエチレンアルキル硫酸塩、ポリオキシエチレンアルキルアリール硫酸塩等のアニオン性界面活性剤、ポリオキシエチレンアルキルアリールエーテル、ポリオキシエチレンソルビタン脂肪酸エステル、オキシエチレンオキシプロピレンコポリマー等のノニオン性界面活性剤が挙げられ、通常アニオン性界面活性剤単独またはアニオン性界面活性剤とノニオン性界面活性剤の混合系で用いられる。さらに必要に応じて、ラジカル重合性の界面活性剤またはカチオン性界面活性剤を用いることができる。 First, specific examples of the surfactant include fatty acid soap, rosin soap, alkyl sulfonate, alkyl benzene sulfonate, dialkyl aryl sulfonate, alkyl sulfosuccinic acid, polyoxyethylene alkyl sulfate, and polyoxyethylene alkyl. Nonionic surfactants such as anionic surfactants such as aryl sulfates, polyoxyethylene alkyl aryl ethers, polyoxyethylene sorbitan fatty acid esters, oxyethylene oxypropylene copolymers, etc., usually anionic surfactants alone or anions Used in a mixed system of a surfactant and a nonionic surfactant. Furthermore, a radically polymerizable surfactant or a cationic surfactant can be used as necessary.
また、連鎖移動剤としては、具体的には例えば、ｎ−オクチルメルカプタン、ｎ−ドデシルメルカプタン、ｔ−ドデシルメルカプタン、メルカプトエタノール等のメルカプタン類、四塩化炭素等のハロゲン化炭化水素等が挙げられる。 Specific examples of the chain transfer agent include mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and mercaptoethanol, and halogenated hydrocarbons such as carbon tetrachloride.
また、ラジカル開始剤としては過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の過硫酸塩、過酸化水素、過酸化ベンゾイル、ｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド等の過酸化物、２，２−アゾビスイソブチロニトリル等のアゾビス化合物等が挙げられるが、特に過硫酸塩が好ましい。 Moreover, as radical initiators, persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate, peroxides such as hydrogen peroxide, benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, Examples include azobis compounds such as 2-azobisisobutyronitrile, and persulfate is particularly preferable.
乳化重合において、重合温度は６０〜９０℃の範囲が一般的であるが、重亜硫酸ソーダ、アスコルビン酸（塩）、ロンガリット等の還元剤をラジカル重合開始剤と組み合わせた低温レドックス重合を用いることもできる。また必要に応じて水酸化ナトリウム、水酸化カリウム、炭酸水素ナトリウム、炭酸ナトリウム、りん酸水素ナトリウム等のＰＨ調節剤、あるいはＰＨ緩衝剤等の重合調節剤を添加することもできる。 In the emulsion polymerization, the polymerization temperature is generally in the range of 60 to 90 ° C., but it is also possible to use low temperature redox polymerization in which a reducing agent such as sodium bisulfite, ascorbic acid (salt), Rongalite is combined with a radical polymerization initiator. it can. If necessary, a pH regulator such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, sodium hydrogen phosphate, or a polymerization regulator such as a PH buffer can be added.
また本発明の接着剤組成物は、アルカリ中和を行うことによって安定性を向上させることもできる。中和剤としては例えばアンモニア水溶液、水酸化ナトリウム等の水酸化物、アミン等を用いることができる。 Moreover, the adhesive composition of the present invention can also improve stability by carrying out alkali neutralization. As the neutralizing agent, for example, an aqueous ammonia solution, a hydroxide such as sodium hydroxide, an amine or the like can be used.
本発明の（メタ）アクリル酸アルキルエステルを主成分とする共重合体粒子の体積平均粒子径としては、通常１５０〜３０００ｎｍであり、好ましくは２００〜３０００ｎｍであり、より好ましくは２５０〜３０００ｎｍである。１５０ｎｍ未満では粘度が上昇し、固形分（濃度）が十分に高められず、３０００ｎｍを超えると粒子の沈降等の問題が生じる場合がある。 The volume average particle diameter of the copolymer particles mainly composed of the (meth) acrylic acid alkyl ester of the present invention is usually 150 to 3000 nm, preferably 200 to 3000 nm, more preferably 250 to 3000 nm. . If it is less than 150 nm, the viscosity increases and the solid content (concentration) cannot be sufficiently increased, and if it exceeds 3000 nm, problems such as sedimentation of particles may occur.
更に、粒子径の分布が単一ピークを示す場合は、同一固形分（濃度）であっても樹脂の粘度が高く、高剪断下での粘度低下が大きくなり塗工時のレベリング性が悪化する傾向がある為、本発明では、粒子径分布はバイモーダル或いはブロードであることが好ましい。ここで、バイモーダルとは粒子径測定における粒子径のピークが、２カ所以上存在する（単一ピークではない）事を意味し、ブロードとは、粒子径のピークの広がりを表す標準偏差が、±５０以上の値を示す事を意味する。 Furthermore, when the particle size distribution shows a single peak, the viscosity of the resin is high even at the same solid content (concentration), and the viscosity drop under high shear becomes large, resulting in poor leveling properties during coating. Because of the tendency, in the present invention, the particle size distribution is preferably bimodal or broad. Here, bimodal means that there are two or more particle size peaks in particle size measurement (not a single peak), and broad means that the standard deviation representing the spread of the particle size peak is It means to show a value of ± 50 or more.
本発明の接着剤組成物の固形分（濃度）としては４０質量％〜７５質量％が好ましく、より好ましくは５０質量％〜７５質量％である。４０質量％未満の固形分では乾燥に多くのエネルギーを必要とするため、実用性の面より高速塗工に優れているとはいえない場合がある。７５質量％を超えると乾燥効率はあがるものの製造時の粘度が高くなり過ぎ、操作性が悪い等の問題が生じ易くなるため実用的ではない場合がある。 As solid content (concentration) of the adhesive composition of this invention, 40 mass%-75 mass% are preferable, More preferably, they are 50 mass%-75 mass%. If the solid content is less than 40% by mass, a large amount of energy is required for drying. Therefore, it may not be said that it is excellent in high-speed coating in terms of practicality. If it exceeds 75% by mass, although the drying efficiency is increased, the viscosity at the time of production becomes too high, and problems such as poor operability are likely to occur, which may not be practical.
本発明の接着剤組成物の粘度としては、特に限定はされないが、一般的にはＢ型粘度計で測定される６０回転での粘度が１００〜１５０００ｍＰａ・ｓであり、好ましくは２００〜１２０００ｍＰａ・ｓであり、より好ましくは３００〜１００００ｍＰａ・ｓである。粘度が１００ｍＰａ・ｓ未満では剥離紙に塗工する際にハジキやチヂミ等の現象が生じやすくなり塗工性が悪化する傾向があり、粘度が１５０００ｍＰａ・ｓを超えるとハンドリング性が悪化する傾向がある。 The viscosity of the adhesive composition of the present invention is not particularly limited, but generally the viscosity at 60 rotations measured with a B-type viscometer is 100 to 15000 mPa · s, preferably 200 to 12000 mPa · s. s, more preferably 300 to 10000 mPa · s. When the viscosity is less than 100 mPa · s, a phenomenon such as repellency or wrinkle tends to occur when coating on release paper, and the coating property tends to deteriorate. When the viscosity exceeds 15000 mPa · s, the handling property tends to deteriorate. is there.
本発明の接着剤組成物の高剪断下での粘度は、剪断速度１０5における粘度が１０〜２００ｍＰａ・ｓの範囲であり、２０〜２００ｍＰａ・ｓがより好ましい。剪断速度１０5における粘度が１０ｍＰａ・ｓ未満では剥離紙に塗工する際にハジキやチヂミ等の現象が生じやすくなり塗工性が悪化する傾向があり、剪断速度１０5における粘度が２００ｍＰａ・ｓを超えるとハンドリング性が悪化する傾向がある。 The viscosity of the adhesive composition of the present invention under high shear is in the range of 10 to 200 mPa · s at a shear rate of 10 5 , and more preferably 20 to 200 mPa · s. When the viscosity at a shear rate of 10 5 is less than 10 mPa · s, a phenomenon such as repellency or wrinkles tends to occur when coating on a release paper, and the coating property tends to deteriorate, and the viscosity at a shear rate of 10 5 is 200 mPa · s. If it exceeds 1, the handling property tends to deteriorate.
本発明の接着剤組成物の動的接触角測定は、動的Ｗｉｌｈｅｌｍｙ平板法により測定されるもので、固体表面と液体との濡れ性を過渡的に測定する事が可能であり、特に前進接触角は、液体を固体表面に塗工する際の塗工適正を評価する重要な因子となっている。本発明においては、下記条件により測定される前進接触角が９０゜〜１５０゜である事が必要であるが、好ましくは９０゜〜１３０゜、更には９０゜〜１１０゜がより好ましい。 The dynamic contact angle measurement of the adhesive composition of the present invention is measured by the dynamic Wilhelmy plate method, and it is possible to transiently measure the wettability between the solid surface and the liquid, especially forward contact. Corners are an important factor for evaluating the suitability of coating a liquid on a solid surface. In the present invention, the advancing contact angle measured under the following conditions is required to be 90 ° to 150 °, preferably 90 ° to 130 °, more preferably 90 ° to 110 °.
動的接触角の測定条件として、本発明においては（株）レスカ社製ＷＥＴ−６０００を使用し、液体試料として水分散型粘着剤原液をセットし、厚み０．５ｍｍのシリコンゴムを幅１５ｍｍ長さ２５ｍｍの短冊状にカットしたものを液体への浸漬試料とし、浸漬速度２ｍｍ／ｓｅｃ、浸漬深さ８ｍｍ、浸漬時間１５ｓｅｃで前進接触角を測定した。 As measurement conditions for the dynamic contact angle, WET-6000 manufactured by Reska Co., Ltd. is used in the present invention, a water-dispersed adhesive stock solution is set as a liquid sample, and a 0.5 mm thick silicon rubber is 15 mm wide. A specimen cut into a 25 mm long strip was used as an immersion sample in a liquid, and the advancing contact angle was measured at an immersion speed of 2 mm / sec, an immersion depth of 8 mm, and an immersion time of 15 sec.
本法においては、前進接触角が９０゜の場合は液体と固体が完全に濡れる事を示しており塗工性が非常に良好となるが、角度が大きくなるに従い濡れ性が悪化する為塗工性が悪くなっていく傾向がある。角度が１５０゜以上になると、ハジキやチヂミが生じやすくなる為、実質的には塗工が困難な場合が多い。 In this method, when the advancing contact angle is 90 °, the liquid and the solid are completely wetted and the coating property is very good, but the wettability deteriorates as the angle increases. There is a tendency to get worse. When the angle is 150 ° or more, repelling and squeezing are likely to occur, so that in many cases, coating is practically difficult.
本発明の粒子径や粒子径分布の範囲を制御する条件として、乳化剤の選択と固形分の制御があげられる。乳化剤の選択とは、アニオン系乳化剤とノニオン系乳化剤を併用することで、特にノニオン系乳化剤の比率を増すことにより、粒子径を大きく且つ、ブロード及びバイモーダルな粒子径分布に制御する事が可能となり、固形分を高くすることが可能となる。ブロード及びバイモーダルな粒子径分布に制御するその他の方法としては、２種以上の粒子径の異なる水分散型樹脂をブレンドする事があげられる。上記方法により制御された接着剤組成物の剪断速度１０5における粘度は１０ｍＰａ・ｓに近い値を示し、更に動的Ｗｉｌｈｅｌｍｙ平板法による動的接触角の前進接触角は９０゜に近い値を示す。 Conditions for controlling the particle size and particle size distribution range of the present invention include selection of an emulsifier and control of solid content. The choice of emulsifier means using an anionic emulsifier and a nonionic emulsifier together, and by increasing the ratio of the nonionic emulsifier in particular, it is possible to control the particle size distribution to be large and broad and bimodal. Thus, the solid content can be increased. As another method for controlling the broad and bimodal particle size distribution, blending two or more water-dispersed resins having different particle sizes can be mentioned. The viscosity at the shear rate of 10 5 of the adhesive composition controlled by the above method shows a value close to 10 mPa · s, and the advancing contact angle of the dynamic contact angle by the dynamic Wilhelmy plate method shows a value close to 90 °. .
以上のようにして得られた接着剤組成物には、要求される物性や性能を付与するために、粘着剤の分野で使用されている種類及び量の配合剤を、本発明の効果を損なうことのない範囲で、必要に応じて添加することができる。 In order to impart the required physical properties and performance to the adhesive composition obtained as described above, the kind and amount of compounding agents used in the field of pressure-sensitive adhesives are impaired. It can be added as needed within a range that does not occur.
添加できる配合剤としては、例えば増粘剤、機械的安定性付与剤、粘着付与剤、レベリング剤、濡れ剤、造膜助剤、架橋剤、防腐剤、防錆剤、顔料、充填剤、分散剤、凍結防止剤、消泡剤等が挙げられ、これらは単独で、或いは２種類以上組み合わせて使用する事ができる。 Examples of compounding agents that can be added include thickeners, mechanical stability imparting agents, tackifiers, leveling agents, wetting agents, film-forming aids, crosslinking agents, preservatives, rust preventives, pigments, fillers, and dispersions. Agents, antifreeze agents, antifoaming agents, and the like, and these can be used alone or in combination of two or more.
本発明の接着剤組成物は、１００ｍ／分から１５００ｍ／分まで幅広い塗工速度に対応することができるが、好ましくは１００ｍ／分から１５００ｍ／分、更には３００ｍ／分から１２００ｍ／分がより好ましい。 The adhesive composition of the present invention can cope with a wide range of coating speeds from 100 m / min to 1500 m / min, preferably 100 m / min to 1500 m / min, and more preferably 300 m / min to 1200 m / min.
本発明の粘着加工品の製造方法において、上記水分散型粘着剤組成物の塗工作業は、通常、ロールコーター、リバースロールコーター、グラビアコーター、グラビアリバースコーター、ブレードコーター、コンマコーター、キスコーター、スリットダイコーター、リップコーター、カーテンコーター等の塗工機器によって容易に行うことが出来る。 In the method for producing an adhesive processed article of the present invention, the coating operation of the water-dispersed adhesive composition is usually a roll coater, reverse roll coater, gravure coater, gravure reverse coater, blade coater, comma coater, kiss coater, slit. It can be easily carried out with a coating device such as a die coater, lip coater, curtain coater or the like.
以上、説明した通り、本発明の粘着剤組成物は、幅広い塗工速度での塗工が可能であり、特に高速塗工時においても良好な塗工面を得ることができ、生産性の優れた粘着加工品の製造が可能となる。 As described above, the pressure-sensitive adhesive composition of the present invention can be applied at a wide range of coating speeds, and can obtain a good coating surface even during high-speed coating, and has excellent productivity. Adhesive processed products can be manufactured.
［実施例］
以下に実施例、及び比較例を挙げて、本発明をさらに具体的に説明するが、本発明は実施例に限定されるものではない。なお、例中の部は質量部を、％は質量％をそれぞれ表す。
[Example]
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the examples. In addition, the part in an example represents a mass part and% represents the mass%, respectively.
各物性値の測定は次の方法で行った。
ｉ）固形分（単位：％）
水分散型粘着剤組成物約２ｇをシャーレに精秤し、１０５℃で３時間乾燥後再び精秤し、次式により算出した。
固形分（％）＝（Ａ−Ｂ）／Ａ×１００
ここで、Ａは乾燥前の重量であり、Ｂは１０５℃で３時間乾燥した後の重量である。
ｉｉ）粒子径（μｍ）
大塚電子（株）製ＬＰＡ−３１００を使用し、動的光散乱方式により測定した体積平均粒子径
ｉｉｉ）塗工性
リップコーターにて３５０ｍ／分の速度で塗工し、塗工面の平滑性、ハジキ、チヂミ、カスレを観察した。
ｉｖ）高速剪断粘度
熊谷理機工業（株）製：ハーキュレス高剪断粘度計を使用し、剪断速度１０5における粘度を測定した。
Each physical property value was measured by the following method.
i) Solid content (unit:%)
About 2 g of the water-dispersed pressure-sensitive adhesive composition was precisely weighed in a petri dish, dried at 105 ° C. for 3 hours and then weighed again, and the following formula was calculated.
Solid content (%) = (A−B) / A × 100
Here, A is the weight before drying, and B is the weight after drying at 105 ° C. for 3 hours.
ii) Particle size (μm)
Using LPA-3100 manufactured by Otsuka Electronics Co., Ltd., volume average particle diameter measured by dynamic light scattering method iii) Coating property Coating with a lip coater at a speed of 350 m / min, smoothness of the coated surface, He observed repellency, chijimi, and blur.
iv) High-speed shear viscosity manufactured by Kumagai Riki Kogyo Co., Ltd .: The viscosity at a shear rate of 10 5 was measured using a Hercules high shear viscometer.
また、実施例・比較例中で使用した単量体は、下記の略称で表す。
・２−エチルヘキシルアクリレート…２ＥＨＡ
・メチルメタアクリレート・・・ＭＭＡ
・アクリル酸…ＡＡ
・ｎ−ドデシルメルカプタン…ｎＤＭ
The monomers used in the examples and comparative examples are represented by the following abbreviations.
・ 2-Ethylhexyl acrylate… 2EHA
・ Methyl methacrylate ・ ・ ・ MMA
・ Acrylic acid ... AA
・ N-dodecyl mercaptan ... nDM
窒素導入管、攪拌機を設置した温度調節可能な反応器に蒸留水２０５部、過硫酸カリウム１．８部を仕込み窒素気流下で８０℃まで昇温した後、２ＥＨＡ５４９部、ＭＭＡ５５．６部、ＡＡ２．４部、ｎＤＭ０．２部からなる単量体混合物をアニオン系界面活性剤（ペレックスＳＳＬ：花王（株）製）１０部、ノニオン系界面活性剤（ノイゲンＥＴ１７０：第一工業製薬（株）製）７部、蒸留水１６９部に乳化分散させた単量体乳化物を４時間で連続的に添加し、さらに８０℃で３時間反応を継続し、重合を完結させた後冷却した。完結させたエマルションをアンモニア水にてＰＨを７．５に調整後、金網等で濾過し、固形分６０．９％、粒子径が小粒子１５０ＮＭと大粒子５７０ＮＭの二つの粒子が存在する体積平均粒子径４３０ＮＭのアクリル共重合体エマルジョンを得た。得られたアクリル共重合体エマルジョンに対し、ノプコ８０３４（消泡剤：サンノプコ（株）製）を０．２部、ジアルキルスルホ琥珀酸エステルナトリウム（ネオコールＳＷ−Ｃ：第一工業製薬製）を１．０部加え、会合型増粘剤（アデカノールＵＨ−４２０：旭電化工業（株）製）を２３℃におけるＢ型回転粘度計での６０回転の粘度が３０００ｍＰａ・ｓとなる量を添加し、剪断速度１０5における粘度が５３ｍＰａ・ｓ、前進接触角９８°の水分散型アクリル系接着剤組成物を得た。 A temperature-controllable reactor equipped with a nitrogen introduction tube and a stirrer was charged with 205 parts of distilled water and 1.8 parts of potassium persulfate and heated to 80 ° C. under a nitrogen stream, then 2EHA, 549 parts, MMA, 55.6 parts, AA2 10 parts of an anionic surfactant (Perex SSL: manufactured by Kao Corp.) and a nonionic surfactant (Neugen ET170: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) The monomer emulsion emulsified and dispersed in 7 parts of distilled water and 169 parts of distilled water was continuously added in 4 hours, and the reaction was further continued at 80 ° C. for 3 hours to complete the polymerization, followed by cooling. The completed emulsion is adjusted to pH 7.5 with aqueous ammonia and then filtered through a wire mesh or the like, and the volume average of two particles having a solid content of 60.9%, small particles of 150 NM and large particles of 570 NM is present. An acrylic copolymer emulsion having a particle size of 430 NM was obtained. 0.2 parts of Nopco 8034 (antifoaming agent: manufactured by San Nopco Co., Ltd.) and 1 part of sodium dialkylsulfosuccinate (Neocol SW-C: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) are obtained with respect to the obtained acrylic copolymer emulsion. 0.0 part is added, and an associative thickener (Adecanol UH-420: manufactured by Asahi Denka Kogyo Co., Ltd.) is added in an amount such that the viscosity at 60 rotations at 23 ° C. with a B-type rotational viscometer is 3000 mPa · s. A water-dispersed acrylic adhesive composition having a viscosity at a shear rate of 10 5 of 53 mPa · s and an advancing contact angle of 98 ° was obtained.
窒素導入管、攪拌機を設置した温度調節可能な反応器に蒸留水２０５部、過硫酸カリウム１．８部を仕込み窒素気流下で８０℃まで昇温した後、２ＥＨＡ５４９部、ＭＭＡ５５．６部、ＡＡ２．４部、ｎＤＭ０．２部からなる単量体混合物をアニオン系界面活性剤（ペレックスＳＳＬ：花王（株）製）７部、ノニオン系界面活性剤（ノイゲンＥＴ１７０：第一工業製薬（株）製）１０部、蒸留水１６９部に乳化分散させた単量体乳化物を４時間で連続的に添加し、さらに８０℃で３時間反応を継続し、重合を完結させた後冷却した。完結させたエマルションをアンモニア水にてＰＨを７．５に調整後、金網等で濾過し、固形分６１．１％、体積平均粒子径４３０ＮＭ±３１０ＮＭのアクリル共重合体エマルジョンを得た。得られたアクリル共重合体エマルジョンに対し、ノプコ８０３４（消泡剤：サンノプコ（株）製）を０．２部、ジアルキルスルホ琥珀酸エステルナトリウム（ネオコールＳＷ−Ｃ：第一工業製薬製）を１．０部加え、会合型増粘剤（アデカノールＵＨ−４２０：旭電化工業（株）製）を２３℃におけるＢ型回転粘度計での６０回転の粘度が３０００ｍＰａ・ｓとなる量を添加し、剪断速度１０5における粘度が８０ｍＰａ・ｓ、前進接触角１３８°の水分散型アクリル系接着剤組成物を得た。 A temperature-controllable reactor equipped with a nitrogen introduction tube and a stirrer was charged with 205 parts of distilled water and 1.8 parts of potassium persulfate and heated to 80 ° C. under a nitrogen stream, then 2EHA, 549 parts, MMA, 55.6 parts, AA2 .4 parts, nDM 0.2 parts monomer mixture 7 parts anionic surfactant (Perex SSL: manufactured by Kao Corporation), nonionic surfactant (Neugen ET170: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) The monomer emulsion emulsified and dispersed in 10 parts of distilled water and 169 parts of distilled water was continuously added in 4 hours, and the reaction was continued at 80 ° C. for 3 hours to complete the polymerization, followed by cooling. The completed emulsion was adjusted to pH 7.5 with aqueous ammonia and then filtered through a wire mesh or the like to obtain an acrylic copolymer emulsion having a solid content of 61.1% and a volume average particle size of 430 NM ± 310 NM. 0.2 parts of Nopco 8034 (antifoaming agent: manufactured by San Nopco Co., Ltd.) and 1 part of sodium dialkylsulfosuccinate (Neocol SW-C: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) are obtained with respect to the obtained acrylic copolymer emulsion. 0.0 part is added, and an associative thickener (Adecanol UH-420: manufactured by Asahi Denka Kogyo Co., Ltd.) is added in an amount such that the viscosity at 60 rotations at 23 ° C. with a B-type rotational viscometer is 3000 mPa · s. A water-dispersed acrylic adhesive composition having a viscosity at a shear rate of 10 5 of 80 mPa · s and an advancing contact angle of 138 ° was obtained.
窒素導入管、攪拌機を設置した温度調節可能な反応器に蒸留水２０５部、過硫酸カリウム１．８部を仕込み窒素気流下で８０℃まで昇温した後、２ＥＨＡ５４９部、ＭＭＡ５５．６部、ＡＡ２．４部、ｎＤＭ０．２部からなる単量体混合物をアニオン系界面活性剤（ペレックスＳＳＬ：花王（株）製）２部、ノニオン系界面活性剤（ノイゲンＥＴ１７０：第一工業製薬（株）製）１５部、蒸留水１６９部に乳化分散させた単量体乳化物を６時間で連続的に添加し、さらに８０℃で３時間反応を継続し、重合を完結させた後冷却した。完結させたエマルションをアンモニア水にてＰＨを７．５に調整後、金網等で濾過し、固形分６０．１％、体積平均粒子径１５２５ＮＭ±３５８ＮＭのアクリル共重合体エマルジョンを得た。得られたアクリル共重合体エマルジョンに対し、ノプコ８０３４（消泡剤：サンノプコ（株）製）を０．２部、ジアルキルスルホ琥珀酸エステルナトリウム（ネオコールＳＷ−Ｃ：第一工業製薬製）を１．０部加え、会合型増粘剤（アデカノールＵＨ−４２０：旭電化工業（株）製）を２３℃におけるＢ型回転粘度計での６０回転の粘度が３０００ｍＰａ・ｓとなる量を添加し、剪断速度１０5における粘度が１４６ｍＰａ・ｓ、前進接触角１２２°の水分散型アクリル系接着剤組成物を得た。 A temperature-controllable reactor equipped with a nitrogen introduction tube and a stirrer was charged with 205 parts of distilled water and 1.8 parts of potassium persulfate and heated to 80 ° C. under a nitrogen stream, then 2EHA, 549 parts, MMA, 55.6 parts, AA2 4 parts, nDM 0.2 parts monomer mixture 2 parts anionic surfactant (Perex SSL: manufactured by Kao Corporation), nonionic surfactant (Neugen ET170: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) The monomer emulsion emulsified and dispersed in 15 parts of distilled water and 169 parts of distilled water was continuously added in 6 hours, and the reaction was further continued at 80 ° C. for 3 hours to complete the polymerization, followed by cooling. The completed emulsion was adjusted to pH 7.5 with aqueous ammonia and then filtered through a wire mesh or the like to obtain an acrylic copolymer emulsion having a solid content of 60.1% and a volume average particle size of 1525 NM ± 358 NM. 0.2 parts of Nopco 8034 (antifoaming agent: manufactured by San Nopco Co., Ltd.) and 1 part of sodium dialkylsulfosuccinate (Neocol SW-C: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) are obtained with respect to the obtained acrylic copolymer emulsion. 0.0 part is added, and an associative thickener (Adecanol UH-420: manufactured by Asahi Denka Kogyo Co., Ltd.) is added in an amount such that the viscosity at 60 rotations at 23 ° C. with a B-type rotational viscometer is 3000 mPa · s. A water-dispersed acrylic adhesive composition having a viscosity at a shear rate of 10 5 of 146 mPa · s and an advancing contact angle of 122 ° was obtained.
窒素導入管、攪拌機を設置した温度調節可能な反応器に蒸留水２０５部、過硫酸カリウム１．８部を仕込み窒素気流下で８０℃まで昇温した後、２ＥＨＡ５４９部、ＭＭＡ５４．７部、ＡＡ０．６部、ｎＤＭ０．２部からなる単量体混合物をアニオン系界面活性剤（ペレックスＳＳＬ：花王（株）製）１０部、ノニオン系界面活性剤（ノイゲンＥＴ１７０：第一工業製薬（株）製）７部、蒸留水１６９部に乳化分散させた単量体乳化物を６連続的に添加し、さらに８０℃で３時間反応を継続し、重合を完結させた後冷却した。完結させたエマルションをアンモニア水にてＰＨを７．５に調整後、金網等で濾過し、固形分６１．３％、粒子径が小粒子１３０ＮＭと大粒子６１０ＮＭの二つの粒子が存在する体積平均粒子径４４０ＮＭのアクリル共重合体エマルジョンを得た。得られたアクリル共重合体エマルジョンに対し、ノプコ８０３４（消泡剤：サンノプコ（株）製）を０．２部、ジアルキルスルホ琥珀酸エステルナトリウム（ネオコールＳＷ−Ｃ：第一工業製薬製）を１．０部加え、会合型増粘剤（アデカノールＵＨ−４２０：旭電化工業（株）製）を２３℃におけるＢ型回転粘度計での６０回転の粘度が３０００ｍＰａ・ｓとなる量を添加し、剪断速度１０5における粘度が４７ｍＰａ・ｓ、前進接触角９２°の水分散型アクリル系接着剤組成物を得た。 A temperature-controllable reactor equipped with a nitrogen introduction tube and a stirrer was charged with 205 parts of distilled water and 1.8 parts of potassium persulfate and heated to 80 ° C. under a nitrogen stream, and then 2EHA, 549 parts, MMA, 54.7 parts, AA0. .6 parts, nDM 0.2 part monomer mixture 10 parts anionic surfactant (Perex SSL: manufactured by Kao Corporation), nonionic surfactant (Neugen ET170: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 6) The monomer emulsion emulsified and dispersed in 7 parts and 169 parts of distilled water was continuously added, and the reaction was further continued at 80 ° C. for 3 hours to complete the polymerization, followed by cooling. The completed emulsion is adjusted to pH 7.5 with aqueous ammonia and then filtered through a wire mesh or the like, and the volume average of two particles having a solid content of 61.3% and a small particle size of 130 NM and a large particle of 610 NM is present. An acrylic copolymer emulsion having a particle size of 440 NM was obtained. 0.2 parts of Nopco 8034 (antifoaming agent: manufactured by San Nopco Co., Ltd.) and 1 part of sodium dialkylsulfosuccinate (Neocol SW-C: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) are obtained with respect to the obtained acrylic copolymer emulsion. 0.0 part is added, and an associative thickener (Adecanol UH-420: manufactured by Asahi Denka Kogyo Co., Ltd.) is added in an amount such that the viscosity at 60 rotations at 23 ° C. with a B-type rotational viscometer is 3000 mPa · s. A water-dispersed acrylic adhesive composition having a viscosity at a shear rate of 10 5 of 47 mPa · s and an advancing contact angle of 92 ° was obtained.
窒素導入管、攪拌機を設置した温度調節可能な反応器に蒸留水２０５部、過硫酸カリウム１．８部を仕込み窒素気流下で８０℃まで昇温した後、２ＥＨＡ５４９部、ＭＭＡ５５．６部、ＡＡ２．４部、ｎＤＭ０．２部からなる単量体混合物をアニオン系界面活性剤（ペレックスＳＳＬ：花王（株）製）１５部、ノニオン系界面活性剤（ノイゲンＥＴ１７０：第一工業製薬（株）製）２部、蒸留水２９０部に乳化分散させた単量体乳化物を４連続的に添加し、さらに８０℃で３時間反応を継続し、重合を完結させた後冷却した。完結させたエマルションをアンモニア水にてＰＨを７．５に調整後、金網等で濾過し、固形分５５．６％、粒子径が小粒子８０ＮＭと大粒子２５０ＮＭの二つの粒子が存在する体積平均粒子径１９７ＮＭのアクリル共重合体エマルジョンを得た。得られたアクリル共重合体エマルジョンに対し、ノプコ８０３４（消泡剤：サンノプコ（株）製）を０．２部、ジアルキルスルホ琥珀酸エステルナトリウム（ネオコールＳＷ−Ｃ：第一工業製薬製）を１．０部加え、会合型増粘剤（アデカノールＵＨ−４２０：旭電化工業（株）製）を２３℃におけるＢ型回転粘度計での６０回転の粘度が３０００ｍＰａ・ｓとなる量を添加し、剪断速度１０5における粘度が１７ｍＰａ・ｓ、前進接触角９４°の水分散型アクリル系接着剤組成物を得た。 A temperature-controllable reactor equipped with a nitrogen introduction tube and a stirrer was charged with 205 parts of distilled water and 1.8 parts of potassium persulfate and heated to 80 ° C. under a nitrogen stream, then 2EHA, 549 parts, MMA, 55.6 parts, AA2 .4 parts, nDM 0.2 parts monomer mixture 15 parts anionic surfactant (Perex SSL: Kao Corporation), nonionic surfactant (Neugen ET170: Daiichi Kogyo Seiyaku Co., Ltd.) 4 parts of the monomer emulsion emulsified and dispersed in 2 parts of distilled water and 290 parts of distilled water were continuously added, and the reaction was further continued at 80 ° C. for 3 hours to complete the polymerization, followed by cooling. The completed emulsion is adjusted to pH 7.5 with aqueous ammonia and then filtered through a wire mesh or the like, and the volume average of two particles of solid content 55.6%, small particles 80 NM and large particles 250 NM are present. An acrylic copolymer emulsion having a particle size of 197 NM was obtained. 0.2 parts of Nopco 8034 (antifoaming agent: manufactured by San Nopco Co., Ltd.) and 1 part of sodium dialkylsulfosuccinate (Neocol SW-C: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) are obtained with respect to the obtained acrylic copolymer emulsion. 0.0 part is added, and an associative thickener (Adecanol UH-420: manufactured by Asahi Denka Kogyo Co., Ltd.) is added in an amount such that the viscosity at 60 rotations at 23 ° C. with a B-type rotational viscometer is 3000 mPa · s. A water-dispersed acrylic adhesive composition having a viscosity at a shear rate of 10 5 of 17 mPa · s and an advancing contact angle of 94 ° was obtained.
［比較例１］
実施例同様な装置で、反応器に蒸留水２０５部、過硫酸カリウム１．８部を仕込み窒素気流下で８０℃まで昇温した後、２ＥＨＡ５４９部、ＭＭＡ５５．６部、ＡＡ２．４部、ｎＤＭ０．２部からなる単量体混合物をアニオン系界面活性剤（ペレックスＳＳＬ：花王（株）製）７部、ノニオン系界面活性剤（ノイゲンＥＴ１７０：第一工業製薬（株）製）１０部、蒸留水５９２部に乳化分散させた単量体乳化物を４連続的に添加し、さらに８０℃で３時間反応を継続し、重合を完結させた後冷却した。完結させたエマルションをアンモニア水にてＰＨを７．５に調整後、金網等で濾過し、固形分４４．２％、粒子径が小粒子１２５ＮＭと大粒子７３０ＮＭの二つの粒子が存在する体積平均粒子径５２０ＮＭのアクリル共重合体エマルジョンを得た。得られたアクリル共重合体エマルジョンに対し、ノプコ８０３４（消泡剤：サンノプコ（株）製）を０．２部、ジアルキルスルホ琥珀酸エステルナトリウム（ネオコールＳＷ−Ｃ：第一工業製薬製）を１．０部加え、会合型増粘剤（アデカノールＵＨ−４２０：旭電化工業（株）製）を２３℃におけるＢ型回転粘度計での６０回転の粘度が３０００ｍＰａ・ｓとなる量を添加し、剪断速度１０5における粘度が８ｍＰａ・ｓ、前進接触角９５°の水分散型アクリル系接着剤組成物を得た。
[Comparative Example 1]
In the same apparatus as in the Examples, 205 parts of distilled water and 1.8 parts of potassium persulfate were charged into a reactor, and the temperature was raised to 80 ° C. under a nitrogen stream, and then 2EHA, 549 parts, MMA, 55.6 parts, AA, 2.4 parts, and nDM0. .7 parts of an anionic surfactant (Perex SSL: manufactured by Kao Corporation), 10 parts of a nonionic surfactant (Neugen ET170: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), distillation Four monomer emulsions emulsified and dispersed in 592 parts of water were continuously added, and the reaction was further continued at 80 ° C. for 3 hours to complete the polymerization, followed by cooling. The completed emulsion is adjusted to pH 7.5 with aqueous ammonia and then filtered through a wire mesh or the like, and the volume average of two particles of solid content 44.2%, small particle size 125 NM and large particle 730 NM is present. An acrylic copolymer emulsion having a particle size of 520 NM was obtained. 0.2 parts of Nopco 8034 (antifoaming agent: manufactured by San Nopco Co., Ltd.) and 1 part of sodium dialkylsulfosuccinate (Neocol SW-C: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) are obtained with respect to the obtained acrylic copolymer emulsion. 0.0 part is added, and an associative thickener (Adecanol UH-420: manufactured by Asahi Denka Kogyo Co., Ltd.) is added in an amount such that the viscosity at 60 rotations at 23 ° C. with a B-type rotational viscometer is 3000 mPa · s. A water-dispersed acrylic adhesive composition having a viscosity at a shear rate of 10 5 of 8 mPa · s and an advancing contact angle of 95 ° was obtained.
［比較例２］
実施例同様な装置を用いて、反応器に蒸留水１６５部、過硫酸カリウム１．８部を仕込み窒素気流下で８０℃まで昇温した後、２ＥＨＡ５４９部、ＭＭＡ５５．６部、ＡＡ２．４部、ｎＤＭ０．２部からなる単量体混合物をアニオン系界面活性剤（ペレックスＳＳＬ：花王（株）製）２部、ノニオン系界面活性剤（ノイゲンＥＴ１７０：第一工業製薬（株）製）１５部、蒸留水１５５部に乳化分散させた単量体乳化物を４連続的に添加し、さらに８０℃で３時間反応を継続し、重合を完結させた後冷却した。完結させたエマルションをアンモニア水にてＰＨを７．５に調整後、金網等で濾過し、固形分６５．３％、体積平均粒子径５４０ＮＭ±３５ＮＭのアクリル共重合体エマルジョンを得た。得られたアクリル共重合体エマルジョンに対し、ノプコ８０３４（消泡剤：サンノプコ（株）製）を０．２部、ジアルキルスルホ琥珀酸エステルナトリウム（ネオコールＳＷ−Ｃ：第一工業製薬製）を１．０部加え、２３℃におけるＢ型回転粘度計での６０回転の粘度が１６４００ｍＰａ・ｓ、剪断速度１０5における粘度が２３０ｍＰａ・ｓ、前進接触角１５３°の水分散型アクリル系接着剤組成物を得た。
[Comparative Example 2]
Using the same apparatus as in the Examples, 165 parts of distilled water and 1.8 parts of potassium persulfate were charged into the reactor, and the temperature was raised to 80 ° C. under a nitrogen stream, and then 2EHA, 549 parts, MMA, 55.6 parts, AA, 2.4 parts. , 2 parts of an anionic surfactant (Perex SSL: manufactured by Kao Corporation), 15 parts of a nonionic surfactant (Neugen ET170: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) The monomer emulsion emulsified and dispersed in 155 parts of distilled water was continuously added, and the reaction was further continued at 80 ° C. for 3 hours to complete the polymerization, followed by cooling. The completed emulsion was adjusted to pH 7.5 with aqueous ammonia and then filtered through a wire mesh or the like to obtain an acrylic copolymer emulsion having a solid content of 65.3% and a volume average particle size of 540 NM ± 35 NM. 0.2 parts of Nopco 8034 (antifoaming agent: manufactured by San Nopco Co., Ltd.) and 1 part of sodium dialkylsulfosuccinate (Neocol SW-C: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) are obtained with respect to the obtained acrylic copolymer emulsion. 0.0 part, a water-dispersed acrylic adhesive composition having a viscosity at 60 ° C. of 16400 mPa · s at 23 ° C., a viscosity of 230 mPa · s at a shear rate of 10 5 , and a forward contact angle of 153 ° Got.
上記実施例および比較例で得られた水分散型アクリル系接着剤組成物の塗工性能評価結果を表１及び表２に示した。 Tables 1 and 2 show the coating performance evaluation results of the water-dispersed acrylic adhesive compositions obtained in the above Examples and Comparative Examples.
本発明の接着剤組成物は、幅広い塗工速度での塗工が可能であり、特に高速塗工時においても良好な塗工面を得ることができ、生産性の優れた粘着加工品の製造が可能となる。 The adhesive composition of the present invention can be applied at a wide range of coating speeds, and can obtain a good coated surface even during high-speed coating, making it possible to produce an adhesive processed product with excellent productivity. It becomes possible.
Claims (5)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2010254961A (en) * | 2009-03-30 | 2010-11-11 | Lintec Corp | Acrylic emulsion type adhesive composition, production method thereof, and adhesive sheet |
| KR101426146B1 (en) * | 2011-09-26 | 2014-07-31 | 닛토덴코 가부시키가이샤 | Method for producing pressure-sensitive adhesive layer for optical film, pressure-sensitive adhesive layer for optical film, pressure-sensitive adhesive type optical film and image display device |
| JP2015528047A (en) * | 2012-10-09 | 2015-09-24 | エルジー・ケム・リミテッド | Acrylic emulsion pressure-sensitive adhesive composition containing nano-sized latex particles having a monomodal particle size distribution and method for producing the same |
| JP2016180065A (en) * | 2015-03-24 | 2016-10-13 | トッパン・フォームズ株式会社 | Re-peelable sheet |
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| JP2003277708A (en) * | 2002-03-25 | 2003-10-02 | Dainippon Ink & Chem Inc | Aqueous pressure-sensitive adhesive resin composition, adhesive, method for applying adhesive and adhesive product |
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| JP2010254961A (en) * | 2009-03-30 | 2010-11-11 | Lintec Corp | Acrylic emulsion type adhesive composition, production method thereof, and adhesive sheet |
| KR101426146B1 (en) * | 2011-09-26 | 2014-07-31 | 닛토덴코 가부시키가이샤 | Method for producing pressure-sensitive adhesive layer for optical film, pressure-sensitive adhesive layer for optical film, pressure-sensitive adhesive type optical film and image display device |
| US9181458B2 (en) | 2011-09-26 | 2015-11-10 | Nitto Denko Corporation | Method for manufacturing optical film-forming pressure-sensitive adhesive layer, optical film-forming pressure-sensitive adhesive layer, pressure-sensitive adhesive-type optical film, and image display device |
| JP2015528047A (en) * | 2012-10-09 | 2015-09-24 | エルジー・ケム・リミテッド | Acrylic emulsion pressure-sensitive adhesive composition containing nano-sized latex particles having a monomodal particle size distribution and method for producing the same |
| JP2016180065A (en) * | 2015-03-24 | 2016-10-13 | トッパン・フォームズ株式会社 | Re-peelable sheet |
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