JP4744568B2 - Water dispersion type adhesive sheet - Google Patents
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- JP4744568B2 JP4744568B2 JP2008204819A JP2008204819A JP4744568B2 JP 4744568 B2 JP4744568 B2 JP 4744568B2 JP 2008204819 A JP2008204819 A JP 2008204819A JP 2008204819 A JP2008204819 A JP 2008204819A JP 4744568 B2 JP4744568 B2 JP 4744568B2
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本発明は、水分散型の粘着シート、さらに詳細には、室温粘着性の水分散型アクリル系粘着剤により粘着剤層が形成された水分散型粘着シートに関する。 The present invention relates to a water-dispersed pressure-sensitive adhesive sheet, and more particularly to a water-dispersed pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer is formed of a room-temperature-sensitive water-dispersible acrylic pressure-sensitive adhesive.
水分散型のアクリル系粘着剤を用いた粘着シートは、溶剤を用いないため、環境衛生上望ましく、耐溶剤性の点でも優れるなどの利点を有している。しかし、その一方で、溶剤型の粘着剤を用いた粘着シートと比較した場合、粗面接着性と保持性の２つの性能を両立できないという欠点を有していた。 The pressure-sensitive adhesive sheet using the water-dispersed acrylic pressure-sensitive adhesive does not use a solvent, and therefore has an advantage that it is desirable for environmental hygiene and is excellent in solvent resistance. However, on the other hand, when compared with a pressure-sensitive adhesive sheet using a solvent-type pressure-sensitive adhesive, there was a drawback that the two performances of rough surface adhesion and retention were not compatible.
したがって、本発明の目的は、水分散型のアクリル系粘着剤を用いた粘着シートであって、優れた粗面接着性と保持性とを併せ持つ水分散型粘着シートを提供することにある。 Accordingly, an object of the present invention is to provide a water-dispersed pressure-sensitive adhesive sheet that is a pressure-sensitive adhesive sheet using a water-dispersed acrylic pressure-sensitive adhesive and has both excellent rough surface adhesion and retainability.
本発明者らは、上記の目的を達成するため鋭意検討した結果、粘着剤層を形成するために用いる水分散型のアクリル系粘着剤の固形分に占める溶剤不溶分、及び該粘着剤を基材に塗布し乾燥させたときの塗膜（粘着剤層）中の溶剤不溶分を一定の値以下に制御すると、溶剤型粘着剤と比較して同等以上の優れた粗面接着性及び保持性が得られることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that the solvent-insoluble matter in the solid content of the water-dispersed acrylic pressure-sensitive adhesive used to form the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive When the solvent insoluble content in the coating film (adhesive layer) is controlled to a certain value or less when applied to the material and dried, it has excellent rough surface adhesiveness and retainability equivalent to or better than that of the solvent-type adhesive. Has been found, and the present invention has been completed.
すなわち、本発明は、（メタ）アクリル酸エステルを主単量体成分とする室温粘着性の水分散型アクリル系粘着剤により粘着剤層が形成された水分散型粘着シートであって、固形分中の溶剤不溶分が２０重量％以下の水分散型アクリル系粘着剤を基材上に塗布して粘着剤層を形成し、水蒸発工程終了時における粘着剤層の溶剤不溶分が２０重量％以下となるように水蒸発を行い、その後該粘着剤層を架橋させて得られ、架橋後の粘着剤層中の溶剤不溶分が２５〜７０重量％である水分散型粘着シートを提供する。前記水分散型粘着シートでは、水分散型アクリル系粘着剤に、ポリイソシアネート、メラミン樹脂、尿素樹脂、エポキシ樹脂、金属酸化物、金属過酸化物、金属塩、金属水酸化物、カルボキシル基含有ポリマー、酸無水物、ポリアミンから選択される架橋剤が添加されていることが好ましい。また、前記水分散型粘着シートでは、粒度２８０番の研磨紙に対する粗面接着力が８０ｇｆ／２０ｍｍ幅以上であって、保持力（垂下したフェノール樹脂板に１０ｍｍ×２０ｍｍの接着面積で貼り付け、自由端に６００ｇの均一加重を負荷した際の８０℃での落下時間）が１２０分を超えることが好ましい。さらに、前記水分散型粘着シートでは、特に架橋後の粘着剤層中の溶剤不溶分が、３０〜５０重量％であることが好ましい。
That is, the present invention is a water-dispersed pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer is formed of a room-temperature-adhesive water-dispersed acrylic pressure-sensitive adhesive having (meth) acrylic acid ester as a main monomer component, A water-dispersed acrylic pressure-sensitive adhesive having a solvent insoluble content of 20% by weight or less is coated on a substrate to form a pressure-sensitive adhesive layer, and the solvent-insoluble content of the pressure-sensitive adhesive layer at the end of the water evaporation step is 20% by weight. A water-dispersed pressure-sensitive adhesive sheet obtained by evaporating water to the following and then crosslinking the pressure-sensitive adhesive layer and having a solvent-insoluble content in the crosslinked pressure-sensitive adhesive layer of 25 to 70% by weight is provided. In the water-dispersed pressure-sensitive adhesive sheet, the water-dispersed acrylic pressure-sensitive adhesive is added to polyisocyanate, melamine resin, urea resin, epoxy resin, metal oxide, metal peroxide, metal salt, metal hydroxide, carboxyl group-containing polymer. Preferably, a crosslinking agent selected from acid anhydrides and polyamines is added. Further, the water-dispersed pressure-sensitive adhesive sheet has a rough surface adhesive strength of 80 gf / 20 mm width or more to abrasive paper having a particle size of No. 280, and has a holding power (adhered to a suspended phenol resin plate with an adhesive area of 10 mm × 20 mm. It is preferable that the dropping time at 80 ° C. when a uniform load of 600 g is applied to the end exceeds 120 minutes. Further, in the water-dispersible pressure-sensitive adhesive sheet, solvent-insoluble fraction in the pressure-sensitive adhesive layer after crosslinking especially is preferably 30 to 50 wt%.
なお、本明細書において、「溶剤不溶分」とは、所定量（約５００ｍｇ）の試料を精秤し（そのうち固形分の重量をＷ1ｍｇとする）、これを酢酸エチル中に室温で３日間浸漬した後、不溶の固体を濾過し、１００℃で２時間乾燥させて重量（Ｗ2ｍｇ）を測定し、下記式に従って算出したものである。
溶剤不溶分（重量％）＝（Ｗ2／Ｗ1）×１００。
In the present specification, the “solvent insoluble matter” means that a predetermined amount (about 500 mg) of a sample is precisely weighed (of which the solid content is W 1 mg), and this is placed in ethyl acetate at room temperature. After soaking for days, the insoluble solid was filtered, dried at 100 ° C. for 2 hours, the weight (W 2 mg) was measured, and calculated according to the following formula.
Solvent insoluble content (% by weight) = (W 2 / W 1 ) × 100.
本発明によれば、水分散型のアクリル系共重合体を用いるので、環境衛生上望ましいだけでなく、水分散型であるにもかかわらず、粗面接着性と保持性の２つの特性を両立できる。 According to the present invention, since a water-dispersible acrylic copolymer is used, it is desirable not only for environmental hygiene, but also has two characteristics of rough surface adhesion and retainability despite being water-dispersible. it can.
本発明において、粘着シートの粘着剤層を構成するアクリル系粘着剤は、（メタ）アクリル酸エステルを主単量体成分とするアクリル系共重合体からなる。前記（メタ）アクリル酸エステルとしては、一般式（１）
ＣＨ2＝Ｃ（Ｒ1）ＣＯＯＲ2 （１）
（式中、Ｒ1は水素原子又はメチル基、Ｒ2は炭素数２〜１４のアルキル基を示す）
で表される化合物が挙げられる。
In this invention, the acrylic adhesive which comprises the adhesive layer of an adhesive sheet consists of an acrylic copolymer which has (meth) acrylic acid ester as a main monomer component. As said (meth) acrylic acid ester, general formula (1)
CH 2 = C (R 1 ) COOR 2 (1)
(Wherein R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 2 to 14 carbon atoms)
The compound represented by these is mentioned.
前記Ｒ2として、例えば、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、イソアミル基、ヘキシル基、へプチル基、２−エチルヘキシル基、イソオクチル基、イソノニル基、イソデシル基などが例示できる。これらの（メタ）アクリル酸エステルは単独でまたは２種以上混合して使用できる。 Examples of R 2 include ethyl, propyl, isopropyl, butyl, isobutyl, isoamyl, hexyl, heptyl, 2-ethylhexyl, isooctyl, isononyl, and isodecyl. These (meth) acrylic acid esters can be used alone or in admixture of two or more.
前記アクリル系共重合体は、後架橋するための架橋点を導入したり、被着体への接着力を向上させたり、粘着剤の凝集力を高めたりするため、コモノマーとして適量の官能基含有単量体やその他の共重合性単量体を用いることができる。 The acrylic copolymer contains an appropriate amount of functional group as a comonomer in order to introduce a cross-linking point for post-crosslinking, to improve the adhesion to the adherend, or to increase the cohesive strength of the pressure-sensitive adhesive. Monomers and other copolymerizable monomers can be used.
前記官能基含有単量体としては、例えば、アクリル酸、メタクリル酸、イタコン酸、マレイン酸、クロトン酸、無水マレイン酸などのカルボキシル基含有単量体又はその酸無水物；（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル、（メタ）アクリル酸２−ヒドロキシブチルなどの水酸基含有単量体；（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−メトキシメチル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミドなどのアミド基含有単量体；（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸ｔ−ブチルアミノエチルなどのアミノ基含有単量体；（メタ）アクリル酸グリシジルなどのグリシジル基含有単量体；（メタ）アクリロイルプロピルトリメトキシシラン、（メタ）アクリロイルプロピルジメトキシシラン、（メタ）アクリロイルプロピルトリエトキシシランなどの多官能性アルコキシシラン；（メタ）アクリロニトリル、Ｎ−（メタ）アクリロイルモルホリン、Ｎ−ビニル−２−ピロリドンなどが挙げられる。これらの官能基含有単量体は１種または２種以上使用することができる。 Examples of the functional group-containing monomer include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, and maleic anhydride, or acid anhydrides thereof; (meth) acrylic acid 2 Hydroxyl group-containing monomers such as hydroxyethyl, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methylol ( Amide group-containing monomers such as (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide; dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, etc. Amino group-containing monomers; glycidyl such as glycidyl (meth) acrylate Containing monomer; Multifunctional alkoxysilane such as (meth) acryloylpropyltrimethoxysilane, (meth) acryloylpropyldimethoxysilane, (meth) acryloylpropyltriethoxysilane; (meth) acrylonitrile, N- (meth) acryloylmorpholine , N-vinyl-2-pyrrolidone and the like. These functional group-containing monomers can be used alone or in combination of two or more.
前記その他の共重合性単量体としては、例えば、（メタ）アクリル酸メチル：酢酸ビニルなどのビニルエステル類；スチレン、ビニルトルエンなどの芳香族ビニル化合物；シクロペンチル（メタ）アクリレート、イソボルニル（メタ）アクリレートなどの環式アルコールの（メタ）アクリル酸エステル類；ネオペンチルグリコールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレートなどの多価アルコールの（メタ）アクリル酸エステル類などが挙げられる。これらの共重合性単量体も１種または２種以上使用できる。 Examples of the other copolymerizable monomers include, for example, methyl (meth) acrylate: vinyl esters such as vinyl acetate; aromatic vinyl compounds such as styrene and vinyl toluene; cyclopentyl (meth) acrylate, isobornyl (meth) (Meth) acrylic esters of cyclic alcohols such as acrylates; neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetra And (meth) acrylic acid esters of polyhydric alcohols such as methylolmethane tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate. These copolymerizable monomers can also be used alone or in combination of two or more.
本発明では粘着剤として水分散型のアクリル系粘着剤を用いる。水分散型アクリル系粘着剤は、前記（メタ）アクリル酸エステル、官能基含有単量体、その他の共重合性単量体を含む単量体混合物を慣用の乳化重合に付すことにより得ることができる。重合方法としては、一般的な一括重合、連続滴下重合、分割滴下重合などを採用でき、重合温度は、例えば２０〜１００℃程度である。 In the present invention, a water-dispersed acrylic pressure-sensitive adhesive is used as the pressure-sensitive adhesive. The water-dispersed acrylic pressure-sensitive adhesive can be obtained by subjecting a monomer mixture containing the (meth) acrylic acid ester, functional group-containing monomer, and other copolymerizable monomer to conventional emulsion polymerization. it can. As the polymerization method, general batch polymerization, continuous dropping polymerization, divided dropping polymerization, or the like can be employed, and the polymerization temperature is, for example, about 20 to 100 ° C.
重合に用いる重合開始剤としては、例えば、２，２′−アゾビスイソブチロニトリル、２，２′−アゾビス（２−アミジノプロパン）ジヒドロクロライド、２，２′−アゾビス［２−（５−メチル−２−イミダゾリン−２−イル）プロパン］ジヒドロクロライド、２，２′−アゾビス（Ｎ，Ｎ′−ジメチレンイソブチルアミジン）などのアゾ系開始剤；過硫酸カリウム、過硫酸アンモニウムなどの過硫酸塩；ベンゾイルパーオキサイド、ｔ−ブチルハイドロパーオキサイドなどの過酸化物系開始剤；過硫酸塩と亜硫酸水素ナトリウムなどのレドックス系開始剤などが挙げられる。重合開始剤の使用量は、モノマーの総量１００重量部に対して、例えば０．００５〜１重量部程度である。 Examples of the polymerization initiator used for the polymerization include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5- Methyl-2-imidazolin-2-yl) propane] dihydrochloride, azo initiators such as 2,2′-azobis (N, N′-dimethyleneisobutylamidine); persulfates such as potassium persulfate and ammonium persulfate And peroxide initiators such as benzoyl peroxide and t-butyl hydroperoxide; redox initiators such as persulfate and sodium hydrogen sulfite. The amount of the polymerization initiator used is, for example, about 0.005 to 1 part by weight with respect to 100 parts by weight of the total amount of monomers.
また、重合には連鎖移動剤を用いてもよい。連鎖移動剤としては、慣用の連鎖移動剤、例えば、ドデカンチオール等のメルカプタン類等が例示できる。連鎖移動剤の使用量は、モノマーの総量１００重量部に対して、例えば０．００１〜０．５重量部程度である。 Moreover, you may use a chain transfer agent for superposition | polymerization. Examples of chain transfer agents include conventional chain transfer agents such as mercaptans such as dodecanethiol. The amount of chain transfer agent used is, for example, about 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the total amount of monomers.
また、乳化剤として、ラウリル硫酸ナトリウム、ラウリル硫酸アンモニウム、ドデシルベンゼンスルホン酸ナトリウム、ポリオキシエチレンアルキルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルフェニルエーテル硫酸アンモニウムなどのアニオン系乳化剤；ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテルなどのノニオン系乳化剤などを使用できる。これらの乳化剤は単独で用いてもよく、２種以上を併用してもよい。乳化剤の使用量は、モノマーの総量１００重量部に対して、例えば０．２〜１０重量部、好ましくは０．５〜５重量部程度である。 In addition, as an emulsifier, anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium polyoxyethylene alkyl ether sulfate, ammonium polyoxyethylene alkylphenyl ether sulfate; polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl Nonionic emulsifiers such as ether can be used. These emulsifiers may be used independently and may use 2 or more types together. The amount of the emulsifier used is, for example, about 0.2 to 10 parts by weight, preferably about 0.5 to 5 parts by weight with respect to 100 parts by weight of the total amount of monomers.
水分散型アクリル系粘着剤は、上記方法のほか、前記アクリル系共重合体を乳化重合以外の方法で得た後、乳化剤により水に分散させて調製してもよい。 In addition to the above method, the water-dispersed acrylic pressure-sensitive adhesive may be prepared by obtaining the acrylic copolymer by a method other than emulsion polymerization and then dispersing it in water using an emulsifier.
また、本発明では、粘着剤を基材上に塗布して形成した塗膜を架橋させるため、多くの場合、前記水分散型アクリル系粘着剤に架橋剤を添加する。該架橋剤としては、前記コモノマーとして用いる官能基含有単量体の種類などに応じ、慣用の架橋剤、例えば、ポリイソシアネート、メラミン樹脂、尿素樹脂、エポキシ樹脂、金属（過）酸化物、金属塩、金属水酸化物、カルボキシル基含有ポリマー、酸無水物、ポリアミンなどの中から適宜選択して使用できる。また、水蒸発工程後、ＵＶ（紫外線）架橋法やＥＢ（電子線）架橋法等により粘着剤層を架橋させる場合には、例えば、トリメチロールプロパンアクリレート、ネオペンチルグリコールジアクリレートなどの多官能性アクリレート等を架橋剤として使用することもできる。また、ＵＶ架橋法を採用する場合、前記水分散型アクリル系粘着剤に、ベンゾフェノン類、アセトフェノン類、ベンジルアルキルケタール類、ベンゾインエーテル類などの光反応開始剤を添加してもよい。 Moreover, in this invention, in order to bridge | crosslink the coating film formed by apply | coating an adhesive on a base material, in many cases, a crosslinking agent is added to the said water dispersion type acrylic adhesive. The crosslinking agent may be a conventional crosslinking agent such as polyisocyanate, melamine resin, urea resin, epoxy resin, metal (per) oxide, metal salt, depending on the type of functional group-containing monomer used as the comonomer. , Metal hydroxide, carboxyl group-containing polymer, acid anhydride, polyamine, and the like. In addition, when the pressure-sensitive adhesive layer is crosslinked by a UV (ultraviolet ray) crosslinking method or an EB (electron beam) crosslinking method after the water evaporation step, for example, polyfunctionality such as trimethylolpropane acrylate or neopentyl glycol diacrylate. Acrylate or the like can also be used as a crosslinking agent. In the case of adopting the UV crosslinking method, a photoreaction initiator such as benzophenones, acetophenones, benzyl alkyl ketals, and benzoin ethers may be added to the water-dispersed acrylic pressure-sensitive adhesive.
水分散型アクリル系粘着剤には、その他、必要に応じて、ｐＨを調整するための塩基（アンモニア水など）や酸、粘着剤に通常使用される添加剤、例えば、粘着付与樹脂、界面活性剤、老化防止剤、充填剤、顔料、着色剤などが添加されていてもよい。 For water-dispersed acrylic pressure-sensitive adhesives, other bases (such as ammonia water) and acids for adjusting pH, acids, and additives commonly used for pressure-sensitive adhesives, such as tackifier resins, surface activity, etc. Agents, anti-aging agents, fillers, pigments, colorants and the like may be added.
本発明の重要な特徴は、固形分中の溶剤不溶分が２０重量％以下の水分散型アクリル系粘着剤を基材上に塗布して粘着剤層を形成し、水蒸発工程終了時における粘着剤層中の溶剤不溶分が２０重量％以下となるように水蒸発を行い、その後該粘着剤層を架橋させる点にある。 An important feature of the present invention is that a water-dispersed acrylic pressure-sensitive adhesive having a solvent insoluble content of solid content of 20% by weight or less is applied on a substrate to form a pressure-sensitive adhesive layer. Water evaporation is performed so that the solvent-insoluble content in the agent layer is 20% by weight or less, and then the pressure-sensitive adhesive layer is crosslinked.
水分散型アクリル系粘着剤における固形分中の溶剤不溶分は、重合条件、例えば、反応温度、反応時間、モノマー組成、重合開始剤の種類及び使用量、連鎖移動剤の種類及び使用量などを適宜選択することにより調整できる。前記溶剤不溶分は、好ましくは１５重量％以下、さらに好ましくは１２重量％以下である。 The solvent-insoluble content in the solid content of the water-dispersed acrylic pressure-sensitive adhesive is determined based on the polymerization conditions, such as reaction temperature, reaction time, monomer composition, type and amount of polymerization initiator, type and amount of chain transfer agent. It can adjust by selecting suitably. The solvent-insoluble content is preferably 15% by weight or less, more preferably 12% by weight or less.
基材としては、例えば、ポリプロピレンフィルム、エチレン−プロピレン共重合体フィルム、ポリエステルフィルム、ポリ塩化ビニルなどのプラスチックフィルム；クラフト紙などの紙；金属箔などを使用できる。前記プラスチックフィルムは、無延伸フィルム及び延伸（一軸延伸又は二軸延伸）フィルムの何れであってもよい。また、基材のうち粘着剤を塗布する面には、通常使用される下塗剤やコロナ放電方式などによる表面処理が施されていてもよい。基材の厚みは、目的に応じて適宜選択できるが、一般には１０〜５００μｍ程度である。 As the substrate, for example, a polypropylene film, an ethylene-propylene copolymer film, a polyester film, a plastic film such as polyvinyl chloride, paper such as kraft paper, metal foil, or the like can be used. The plastic film may be an unstretched film or a stretched (uniaxially stretched or biaxially stretched) film. Further, the surface of the base material to which the pressure-sensitive adhesive is applied may be subjected to a surface treatment such as a commonly used primer or a corona discharge method. Although the thickness of a base material can be suitably selected according to the objective, generally it is about 10-500 micrometers.
水分散型アクリル系粘着剤の塗布は、慣用のコーター、例えば、グラビヤロールコーター、リバースロールコーター、キスロールコーター、ディップロールコーター、バーコーター、ナイフコーター、スプレーコーターなどを用いて行うことができる。前記粘着剤は、乾燥（水蒸発）後の粘着剤層の厚みが、例えば１０〜１００μｍ程度となるように塗布される。 The water-dispersed acrylic pressure-sensitive adhesive can be applied using a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, or a spray coater. The pressure-sensitive adhesive is applied so that the thickness of the pressure-sensitive adhesive layer after drying (water evaporation) is, for example, about 10 to 100 μm.
水蒸発工程終了時における粘着剤層中の溶剤不溶分を２０重量％以下に抑制する方法としては、例えば、（ｉ）前記アクリル系粘着剤に熱架橋を起こす架橋剤を実質的に添加することなく基材に塗布した後、水蒸発（乾燥）を行い、その後、ＵＶ架橋法やＥＢ架橋法により架橋させる方法、（ii）前記アクリル系粘着剤に熱架橋を起こす架橋剤を添加するが、水蒸発を実質的に架橋を起こさせない温度、又は架橋速度の遅い温度で行い、次いで架橋が進行する温度で架橋させる方法等が挙げられる。 As a method for suppressing the solvent insoluble content in the pressure-sensitive adhesive layer to 20% by weight or less at the end of the water evaporation step, for example, (i) substantially adding a crosslinking agent that causes thermal crosslinking to the acrylic pressure-sensitive adhesive After applying to the substrate without evaporation, water evaporation (drying) and then crosslinking by UV crosslinking method or EB crosslinking method, (ii) adding a crosslinking agent that causes thermal crosslinking to the acrylic pressure-sensitive adhesive, Examples include a method in which water evaporation is performed at a temperature at which crosslinking is not substantially caused, or at a temperature at which the crosslinking rate is slow, and then crosslinked at a temperature at which crosslinking proceeds.
水蒸発工程終了時における粘着剤層中の溶剤不溶分は、好ましくは１５重量％以下、さらに好ましくは１２重量％以下である。 The solvent-insoluble content in the pressure-sensitive adhesive layer at the end of the water evaporation step is preferably 15% by weight or less, more preferably 12% by weight or less.
水蒸発工程後の架橋は、慣用の方法、例えば、熱架橋法、ＵＶ架橋法、ＥＢ架橋法などにより行うことができる。架橋後の粘着剤層中の溶剤不溶分は、粘着性等を損なわない範囲で選択できるが、一般には２５〜７０重量％程度、好ましくは３０〜５０重量％程度である。 Crosslinking after the water evaporation step can be performed by a conventional method such as a thermal crosslinking method, a UV crosslinking method, an EB crosslinking method, or the like. The solvent-insoluble content in the pressure-sensitive adhesive layer after crosslinking can be selected within a range that does not impair the adhesiveness, but is generally about 25 to 70% by weight, preferably about 30 to 50% by weight.
本発明では、水分散型のアクリル系粘着剤を用いているにもかかわらず、粗面に対する接着力が良好で且つ保持性能にも優れる。このような効果が奏される詳細な理由は明らかでないが、水が蒸発し水分散型粘着剤の粒子同士が融着する際、溶剤不溶分を低く抑えることで粒子がより融着しやすくなることに起因するものと推測される。 In the present invention, despite the use of the water-dispersed acrylic pressure-sensitive adhesive, the adhesive force to the rough surface is good and the holding performance is also excellent. Although the detailed reason for such an effect is not clear, when water evaporates and the water-dispersed pressure-sensitive adhesive particles are fused to each other, the particles are more easily fused by keeping the solvent insoluble content low. It is presumed to be caused by this.
以下、実施例により本発明をさらに詳細に説明するが、本発明はこれらに限定されるものではない。なお、「部」は、特に断りがない限り重量基準である。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. “Parts” are based on weight unless otherwise specified.
実施例１
冷却管、窒素導入管、温度計及び攪拌機を備えた反応容器に、アクリル酸ブチル９８部、アクリル酸２部、２，２′−アゾビス（２−アミジノプロパン）ジヒドロクロライド（開始剤）０．１部、ドデカンチオール（連鎖移動剤）０．０３部を、ポリオキシエチレンノニルフェニルエーテル硫酸アンモニウム（乳化剤）２部を添加した水１００部に加えて乳化重合したのち、１０重量％アンモニウム水を添加してｐＨ８に調整した。得られた水分散型アクリル系粘着剤の固形分中の溶剤不溶分は０重量％であった。この粘着剤を厚さ４０μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムに塗布し、１２０℃で３分乾燥（水蒸発）させて厚さ５０μｍの粘着剤層を設けた。その後、ＥＢを３Ｍｒａｄ照射することによって架橋させ、粘着シートを得た。乾燥終了時の粘着剤層の溶剤不溶分は０重量％、架橋後の粘着剤層の溶剤不溶分は４０重量％であった。
Example 1
In a reaction vessel equipped with a cooling tube, a nitrogen introducing tube, a thermometer and a stirrer, 98 parts of butyl acrylate, 2 parts of acrylic acid, 2,2′-azobis (2-amidinopropane) dihydrochloride (initiator) 0.1 Part, 0.03 part of dodecanethiol (chain transfer agent) was added to 100 parts of water to which 2 parts of polyoxyethylene nonylphenyl ether ammonium sulfate (emulsifier) was added, and after emulsion polymerization, 10% by weight ammonium water was added. The pH was adjusted to 8. The solvent-insoluble content in the solid content of the obtained water-dispersed acrylic pressure-sensitive adhesive was 0% by weight. This pressure-sensitive adhesive was applied to a polyethylene terephthalate (PET) film having a thickness of 40 μm and dried at 120 ° C. for 3 minutes (water evaporation) to provide a pressure-sensitive adhesive layer having a thickness of 50 μm. Thereafter, EB was crosslinked by irradiation with 3 Mrad to obtain an adhesive sheet. The solvent-insoluble content of the pressure-sensitive adhesive layer at the end of drying was 0% by weight, and the solvent-insoluble content of the pressure-sensitive adhesive layer after crosslinking was 40% by weight.
実施例２
実施例１と同様の反応容器に、アクリル酸ブチル９８部、アクリル酸２部、２，２′−アゾビス［２−（５−メチル−２−イミダゾリン−２−イル）プロパン］ジヒドロクロライド（開始剤）０．１部、ドデカンチオール（連鎖移動剤）０．０１部を、ポリオキシエチレンノニルフェニルエーテル硫酸アンモニウム（乳化剤）２部を添加した水１００部に加えて乳化重合したのち、１０重量％アンモニウム水を添加してｐＨ８に調整した。得られた水分散型アクリル系粘着剤の固形分中の溶剤不溶分は１０重量％であった。この粘着剤を厚さ４０μｍのＰＥＴフィルムに塗布し、１２０℃で３分乾燥（水蒸発）させて厚さ５０μｍの粘着剤層を設けた。その後、ＥＢを２．７Ｍｒａｄ照射することによって架橋させ、粘着シートを得た。乾燥終了時の粘着剤層の溶剤不溶分は１０重量％、架橋後の粘着剤層の溶剤不溶分は４０重量％であった。
Example 2
In a reaction vessel similar to Example 1, 98 parts of butyl acrylate, 2 parts of acrylic acid, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride (initiator) ) 0.1 part, 0.01 part of dodecanethiol (chain transfer agent) is added to 100 parts of water to which 2 parts of polyoxyethylene nonylphenyl ether ammonium sulfate (emulsifier) is added, and after emulsion polymerization, 10% by weight ammonium water Was added to adjust the pH to 8. The solvent-insoluble content in the solid content of the obtained water-dispersed acrylic pressure-sensitive adhesive was 10% by weight. This pressure-sensitive adhesive was applied to a PET film having a thickness of 40 μm and dried at 120 ° C. for 3 minutes (water evaporation) to provide a pressure-sensitive adhesive layer having a thickness of 50 μm. Thereafter, EB was crosslinked by 2.7 Mrad irradiation to obtain an adhesive sheet. The solvent-insoluble content of the pressure-sensitive adhesive layer at the end of drying was 10% by weight, and the solvent-insoluble content of the pressure-sensitive adhesive layer after crosslinking was 40% by weight.
実施例３
実施例１と同様にして得られた水分散型アクリル系粘着剤に、ブロックイソシアネート型架橋剤（商品名：コロネート２５１３、日本ポリウレタン工業株式会社製）を４部添加し、これを厚さ４０μｍのＰＥＴフィルムに塗布し、８０℃で３分乾燥（水蒸発）させて厚さ５０μｍの粘着剤層を設けた。その後、１５０℃で３分間熱処理することによって架橋させ、厚さ５０μｍの粘着剤層を有する粘着シートを得た。乾燥終了時の粘着剤層の溶剤不溶分は５重量％、架橋後の粘着剤層の溶剤不溶分は４０重量％であった。
Example 3
To the water-dispersed acrylic pressure-sensitive adhesive obtained in the same manner as in Example 1, 4 parts of a blocked isocyanate type cross-linking agent (trade name: Coronate 2513, manufactured by Nippon Polyurethane Industry Co., Ltd.) was added. It was applied to a PET film and dried at 80 ° C. for 3 minutes (water evaporation) to provide an adhesive layer having a thickness of 50 μm. Then, it crosslinked by heat-processing for 3 minutes at 150 degreeC, and obtained the adhesive sheet which has a 50-micrometer-thick adhesive layer. The solvent-insoluble content of the pressure-sensitive adhesive layer at the end of drying was 5% by weight, and the solvent-insoluble content of the pressure-sensitive adhesive layer after crosslinking was 40% by weight.
比較例１
実施例１と同様にして得られた水分散型アクリル系粘着剤に、ブロックイソシアネート型架橋剤（商品名：コロネート２５１３、日本ポリウレタン工業株式会社製）を４部添加し、これを厚さ４０μｍのＰＥＴフィルムに塗布し、１５０℃で３分乾燥させて厚さ５０μｍの粘着剤層を有する粘着シートを得た。この時の粘着剤層の溶剤不溶分は４０重量％であった。
Comparative Example 1
To the water-dispersed acrylic pressure-sensitive adhesive obtained in the same manner as in Example 1, 4 parts of a blocked isocyanate type cross-linking agent (trade name: Coronate 2513, manufactured by Nippon Polyurethane Industry Co., Ltd.) was added. It was applied to a PET film and dried at 150 ° C. for 3 minutes to obtain an adhesive sheet having an adhesive layer having a thickness of 50 μm. The solvent-insoluble content of the pressure-sensitive adhesive layer at this time was 40% by weight.
比較例２
実施例１と同様にして得られた水分散型アクリル系粘着剤に、エポキシ型架橋剤（商品名：テトラッド−Ｃ、三菱瓦斯化学株式会社製）を０．１部添加し、これを厚さ４０μｍのＰＥＴフィルムに塗布し、８０℃で３分乾燥（水蒸発）させて厚さ５０μｍの粘着剤層を設けた。その後、１３０℃で３分間熱処理することによって架橋させ、厚さ５０μｍの粘着剤層を有する粘着シートを得た。乾燥終了時の粘着剤層の溶剤不溶分は３０重量％、架橋後の粘着剤層の溶剤不溶分は４０重量％であった。
Comparative Example 2
0.1 part of an epoxy type cross-linking agent (trade name: Tetrad-C, manufactured by Mitsubishi Gas Chemical Co., Inc.) was added to the water-dispersed acrylic pressure-sensitive adhesive obtained in the same manner as in Example 1, and the thickness was reduced. It was applied to a 40 μm PET film and dried at 80 ° C. for 3 minutes (water evaporation) to provide a 50 μm thick adhesive layer. Then, it crosslinked by heat-processing at 130 degreeC for 3 minute (s), and obtained the adhesive sheet which has a 50-micrometer-thick adhesive layer. The solvent-insoluble content of the pressure-sensitive adhesive layer at the end of drying was 30% by weight, and the solvent-insoluble content of the pressure-sensitive adhesive layer after crosslinking was 40% by weight.
比較例３
実施例１と同様にして得られた水分散型アクリル系粘着剤に、エポキシ型架橋剤（商品名：テトラッド−Ｃ、三菱瓦斯化学株式会社製）を０．０５部添加し、これを厚さ４０μｍのＰＥＴフィルムに塗布し、１３０℃で３分乾燥させて厚さ５０μｍの粘着剤層を有する粘着シートを得た。この時の粘着剤層の溶剤不溶分は２５重量％であった。
Comparative Example 3
0.05 parts of an epoxy type cross-linking agent (trade name: Tetrad-C, manufactured by Mitsubishi Gas Chemical Co., Inc.) was added to the water-dispersed acrylic pressure-sensitive adhesive obtained in the same manner as in Example 1, and the thickness was increased. It was applied to a 40 μm PET film and dried at 130 ° C. for 3 minutes to obtain a pressure sensitive adhesive sheet having a 50 μm thick pressure sensitive adhesive layer. At this time, the solvent-insoluble content of the pressure-sensitive adhesive layer was 25% by weight.
比較例４
実施例１と同様の反応容器に、アクリル酸ブチル９８部、アクリル酸２部、過硫酸アンモニウム（開始剤）０．１部、ドデカンチオール（連鎖移動剤）０．０３部を、ポリオキシエチレンノニルフェニルエーテル硫酸アンモニウム（乳化剤）２部を添加した水１００部に加えて乳化重合したのち、１０重量％アンモニウム水を添加してｐＨ８に調整した。得られた水分散型アクリル系粘着剤の固形分中の溶剤不溶分は３０重量％であった。この粘着剤を厚さ４０μｍのＰＥＴフィルムに塗布し、１２０℃で３分乾燥して厚さ５０μｍの粘着剤層を設けた。その後、ＥＢを１Ｍｒａｄ照射することによって架橋させ、粘着シートを得た。この時の粘着剤層の溶剤不溶分は４０重量％であった。
Comparative Example 4
In a reaction vessel similar to Example 1, 98 parts of butyl acrylate, 2 parts of acrylic acid, 0.1 part of ammonium persulfate (initiator), 0.03 part of dodecanethiol (chain transfer agent) were added to polyoxyethylene nonylphenyl. The emulsion was added to 100 parts of water to which 2 parts of ether ammonium sulfate (emulsifier) was added, and then emulsion polymerization was performed, and then 10% by weight ammonium water was added to adjust the pH to 8. The solvent-insoluble content in the solid content of the obtained water-dispersed acrylic pressure-sensitive adhesive was 30% by weight. This pressure-sensitive adhesive was applied to a PET film having a thickness of 40 μm and dried at 120 ° C. for 3 minutes to provide a pressure-sensitive adhesive layer having a thickness of 50 μm. Then, it was made to crosslink by irradiating 1Mrad of EB, and the adhesive sheet was obtained. The solvent-insoluble content of the pressure-sensitive adhesive layer at this time was 40% by weight.
評価試験
実施例及び比較例で得た粘着シートについて次の特性を調べた。
（粗面接着力）
幅２０ｍｍ、長さ１００ｍｍの大きさの粘着シートを粒度２８０番の研磨紙に２ｋｇのゴムローラを１往復させる方法にて圧着し、２３℃下に２０分放置後、２３℃、６５％ＲＨ雰囲気中にて剥離に要する力を測定した（１８０度ピール、剥離速度３００ｍｍ／分）。
Evaluation test The following characteristics were investigated about the adhesive sheet obtained by the Example and the comparative example.
(Rough surface adhesion)
A pressure-sensitive adhesive sheet having a width of 20 mm and a length of 100 mm is pressure-bonded by a method in which a 2 kg rubber roller is reciprocated once on abrasive paper having a particle size of 280, and left at 23 ° C. for 20 minutes, and then in an atmosphere of 23 ° C. and 65% RH. The force required for peeling was measured at 180 degrees peel (peeling speed 300 mm / min).
（保持力試験）
幅１０ｍｍの粘着シートをフェノール樹脂板に対し１０ｍｍ×２０ｍｍの接着面積で貼り付け、２０分経過後８０℃下で２０分放置した後、フェノール樹脂板を垂下し、粘着テープの自由端に６００ｇの均一荷重を負荷して、８０℃での粘着シートの落下時間（落下するまでに要した時間）を測定した。
結果を表１に示す。
(Retention force test)
An adhesive sheet with a width of 10 mm was attached to the phenolic resin plate with an adhesive area of 10 mm × 20 mm. After 20 minutes, the adhesive sheet was left at 80 ° C. for 20 minutes, then the phenolic resin plate was suspended, and 600 g of free adhesive tape was attached to the free end. A uniform load was applied, and the dropping time of the pressure-sensitive adhesive sheet at 80 ° C. (time required for dropping) was measured.
The results are shown in Table 1.
Claims (4)
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| JPS61101584A (en) * | 1984-10-25 | 1986-05-20 | Nitto Electric Ind Co Ltd | Preparation of pressure-sensitive adhesive tape |
| JP3288476B2 (en) * | 1993-05-07 | 2002-06-04 | 日東電工株式会社 | Removable adhesive and its adhesive member |
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