JP2007146170A - Water dispersion type pressure-sensitive adhesive composition, method for producing the same and adhesive sheet - Google Patents
Water dispersion type pressure-sensitive adhesive composition, method for producing the same and adhesive sheet Download PDFInfo
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Abstract
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本発明はアクリル系の水分散型感圧性接着剤（粘着剤）とその製造方法及び粘着シートに関する。 The present invention relates to an acrylic water-dispersed pressure-sensitive adhesive (pressure-sensitive adhesive), a method for producing the same, and a pressure-sensitive adhesive sheet.
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。一般に、この粘着シートは、粘着剤層の保持力等に影響を及ぼす溶剤不溶分を調整するため、アクリル系モノマーを主成分とする単量体混合物の重合終了後に架橋剤を添加して粘着剤組成物を調製し、これを基材上に塗布することにより製造している。しかし、このようにして得られた粘着シートでは、粘着剤層を構成する粘着剤の溶剤不溶分及び該粘着剤の溶剤可溶部の分子量が経時的に変化し、それに伴って端末剥がれ性（被着体貼付後において端部が剥がれにくい性質）も変化するという問題があった。また、溶剤型の粘着剤を用いた粘着シートと比較した場合、上記の水分散型粘着剤を用いた粘着シートは端末剥がれ性と保持性の２つの性能を両立することが困難である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. In general, this pressure-sensitive adhesive sheet is prepared by adding a cross-linking agent after the polymerization of a monomer mixture containing an acrylic monomer as a main component in order to adjust the solvent insoluble matter that affects the holding power and the like of the pressure-sensitive adhesive layer. It is manufactured by preparing a composition and applying it onto a substrate. However, in the pressure-sensitive adhesive sheet thus obtained, the solvent insoluble content of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer and the molecular weight of the solvent-soluble part of the pressure-sensitive adhesive change with time, and accordingly, the terminal peelability ( There is also a problem that the property that the end portion is difficult to peel off after the adherend is pasted also changes. In addition, when compared with a pressure-sensitive adhesive sheet using a solvent-type pressure-sensitive adhesive, the above-mentioned pressure-sensitive adhesive sheet using a water-dispersed pressure-sensitive adhesive has a drawback that it is difficult to achieve both the terminal peelability and the holding performance. Had.
従って、本発明の目的は、粘着シートとした際に、溶剤不溶分、溶剤可溶部の分子量及び端末剥がれ性の経時安定性に優れた水分散型感圧性接着剤組成物とその製造方法、及び前記の優れた特性を有する粘着シートを提供することにある。また、本発明の他の目的は、溶剤型粘着剤と同等か又はそれ以上に優れた端末剥がれ性及び保持性を示す水分散型感圧性接着剤組成物とその製造方法、及び前記特性を有する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 composition excellent in temporal stability of solvent-insoluble content, solvent-soluble part molecular weight and terminal peelability when used as a pressure-sensitive adhesive sheet, and a method for producing the same. And it is providing the adhesive sheet which has the said outstanding characteristic. Another object of the present invention is to provide a water-dispersed pressure-sensitive adhesive composition exhibiting terminal peelability and retention that is equal to or better than that of a solvent-type pressure-sensitive adhesive, a method for producing the same, and the above-described characteristics. It is to provide an adhesive sheet.
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、水分散型の（メタ）アクリル酸アルキルエステルを主成分とする単量体混合物において、シラン系単量体と必要に応じて連鎖移動剤を添加して重合すると、溶剤不溶分、溶剤可溶部の分子量及び端末剥がれ性の経時安定性が良好な粘着剤組成物が得られることを見出した。また、特に、ポリマーとしたときの溶剤不溶分が特定値以下となるような（メタ）アクリル酸アルキルエステルを主成分とする単量体混合物に対しシラン系単量体を特定の割合で添加して共重合させると、水分散型粘着剤であっても、優れた端末剥がれ性と高い保持性とを両立できることを見出した。本発明はこれらの知見に基づいて完成されたものである。 As a result of intensive studies to achieve the above object, the present inventors have found that in a monomer mixture mainly composed of water-dispersed (meth) acrylic acid alkyl ester, a silane monomer and, if necessary, It has been found that when a chain transfer agent is added for polymerization, a pressure-sensitive adhesive composition having good solvent-insoluble content, molecular weight of the solvent-soluble part and terminal peelability over time can be obtained. In particular, a silane-based monomer is added at a specific ratio to a monomer mixture mainly composed of (meth) acrylic acid alkyl ester whose solvent-insoluble content in the polymer is below a specific value. As a result, it has been found that even when a water-dispersed pressure-sensitive adhesive is used, both excellent terminal peelability and high retainability can be achieved. The present invention has been completed based on these findings.
すなわち、本発明は、（メタ）アクリル酸アルキルエステルを主成分とし、且つシラン系単量体を含む単量体混合物を共重合して得られる高分子を含有する水分散型感圧性接着剤組成物を提供する。 That is, the present invention provides a water-dispersed pressure-sensitive adhesive composition comprising a polymer obtained by copolymerizing a monomer mixture containing a (meth) acrylic acid alkyl ester as a main component and containing a silane monomer. Offer things.
この組成物は、（メタ）アクリル酸アルキルエステルを主成分とし、且つシラン系単量体を含まない組成で重合した場合に溶剤不溶分が５％以下となる樹脂組成物が得られる単量体混合物と、該単量体混合物１００重量部に対して０．００５〜１重量部のシラン系単量体とを前記と同一条件下で共重合して得られる高分子を含有する水分散型感圧性接着剤組成物であってもよい。 This composition is a monomer from which a resin composition having a solvent insoluble content of 5% or less when polymerized with a composition containing (meth) acrylic acid alkyl ester as a main component and not containing a silane monomer. A water-dispersed sensation containing a polymer obtained by copolymerizing a mixture and 0.005 to 1 part by weight of a silane-based monomer with respect to 100 parts by weight of the monomer mixture under the same conditions as above. It may be a pressure-sensitive adhesive composition.
本発明は、また、（メタ）アクリル酸アルキルエステルを主成分とし、且つシラン系単量体を含む単量体混合物を乳化重合に付す水分散型感圧性接着剤組成物の製造方法を提供する。乳化重合は連鎖移動剤の存在下で行ってもよい。 The present invention also provides a method for producing a water-dispersed pressure-sensitive adhesive composition in which a monomer mixture containing a (meth) acrylic acid alkyl ester as a main component and containing a silane monomer is subjected to emulsion polymerization. . Emulsion polymerization may be performed in the presence of a chain transfer agent.
本発明は、さらに、（メタ）アクリル酸アルキルエステルを主成分とし、且つシラン系単量体を含む単量体混合物の共重合体からなる粘着剤層を備えた粘着シートを提供する。 The present invention further provides a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer comprising a copolymer of a monomer mixture containing (meth) acrylic acid alkyl ester as a main component and containing a silane monomer.
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（そのうち不揮発分の重量を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、不溶物を取り出し、この不溶物を１００℃で２時間乾燥させて重量（Ｗ2ｍｇ）を測定し、下記式
溶剤不溶分（重量％）＝（Ｗ2／Ｗ1）×１００
に従って算出したものである。
In the present specification, “solvent insoluble matter” means that a predetermined amount (about 500 mg) of a sample is precisely weighed (of which the weight of non-volatile matter is W 1 mg), and this is placed in ethyl acetate at room temperature. After soaking for days, the insoluble matter was taken out, this insoluble matter was dried at 100 ° C. for 2 hours, and the weight (W 2 mg) was measured. Solvent insoluble matter (wt%) = (W 2 / W 1 ) × 100
It is calculated according to
本発明によれば、水分散型のアクリル系粘着剤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、溶剤不溶分、溶剤可溶部の分子量及び端末剥がれ性の経時安定性に優れる。
また、特に、ポリマーとしたときの溶剤不溶分が特定値以下となるような単量体混合物に対してシラン系単量体を特定の割合で共重合させた場合には、極めて優れた端末剥がれ性と保持性とが発現する。
According to the present invention, a water-dispersed acrylic pressure-sensitive adhesive is used, which is not only environmentally hygienic. Excellent stability over time.
In particular, when the silane monomer is copolymerized at a specific ratio with respect to the monomer mixture in which the solvent-insoluble content in the polymer is below a specific value, extremely excellent terminal peeling is achieved. And retentivity are expressed.
本発明において主構成単量体として用いる（メタ）アクリル酸アルキルエステルとしては、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。
The (meth) acrylic acid alkyl ester used as the main constituent monomer in the present invention is represented by the 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。なかでも、Ｒ2として、ブチル基、２−エチルヘキシル基などの炭素数２〜１０のアルキル基が好ましい。上記（メタ）アクリル酸アルキルエステルは単独でまたは２種以上混合して使用できる。例えば、アクリル酸アルキルエステルとして、アクリル酸ブチル単独、又はアクリル酸ブチルとアクリル酸２−エチルヘキシルとを組み合わせて使用できる。この場合、アクリル酸２−エチルヘキシルとアクリル酸ブチルとの割合は、前者／後者＝０／１００〜５５／４５（例えば、５／９５〜６０／４０）程度である。 Examples of R 2 include ethyl, propyl, isopropyl, butyl, isobutyl, isoamyl, hexyl, heptyl, 2-ethylhexyl, isooctyl, isononyl, and isodecyl. Among these, R 2 is preferably an alkyl group having 2 to 10 carbon atoms such as a butyl group or a 2-ethylhexyl group. The above (meth) acrylic acid alkyl esters can be used alone or in admixture of two or more. For example, butyl acrylate alone or a combination of butyl acrylate and 2-ethylhexyl acrylate can be used as the alkyl acrylate ester. In this case, the ratio of 2-ethylhexyl acrylate to butyl acrylate is about the former / the latter = 0/100 to 55/45 (for example, 5/95 to 60/40).
（メタ）アクリル酸アルキルエステルを主成分とする単量体混合物中の該（メタ）アクリル酸アルキルエステル［例えば、上記（メタ）アクリル酸Ｃ2-14アルキルエステル］の比率は、一般に８０重量％以上（例えば８０〜９９．８重量％程度）、好ましくは８５重量％以上（例えば８５〜９９．５重量％程度）、さらに好ましくは９０重量％以上（例えば９０〜９９重量％程度）である。 The proportion of the (meth) acrylic acid alkyl ester [for example, the above (meth) acrylic acid C 2-14 alkyl ester] in the monomer mixture mainly composed of (meth) acrylic acid alkyl ester is generally 80% by weight. It is more than (for example, about 80 to 99.8% by weight), preferably 85% by weight or more (for example, about 85 to 99.5% by weight), and more preferably 90% by weight or more (for example, about 90 to 99% by weight).
前記単量体混合物は、熱架橋するための架橋点を導入するため、通常、官能基含有単量体（熱架橋性官能基含有単量体）を含んでいる。該官能基含有単量体をコモノマー成分として用いることにより被着体に対する接着力も向上する。 The monomer mixture usually contains a functional group-containing monomer (thermally crosslinkable functional group-containing monomer) in order to introduce a crosslinking point for thermal crosslinking. By using the functional group-containing monomer as a comonomer component, adhesion to an adherend is also improved.
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。これらの中でも、アクリル酸などのカルボキシル基含有単量体又はその酸無水物などが好ましい。上記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 monomers; (meth) acrylonitrile, N- (meth) acryloyl morpholine, N- vinyl-2-pyrrolidone. Among these, carboxyl group-containing monomers such as acrylic acid or acid anhydrides thereof are preferable. One or more of the above functional group-containing monomers can be used.
上記官能基含有単量体の使用量は、前記（メタ）アクリル酸アルキルエステル１００重量部に対して、例えば０．５〜１２重量部、好ましくは１〜８重量部程度である。 The usage-amount of the said functional group containing monomer is 0.5-12 weight part with respect to 100 weight part of said (meth) acrylic-acid alkylesters, Preferably it is about 1-8 weight part.
また、前記単量体混合物には、凝集力等の特性を高めるため、必要に応じて、その他の共重合性単量体が含まれていてもよい。このような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；シクロペンチルジ（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。 In addition, the monomer mixture may contain other copolymerizable monomers as necessary in order to enhance characteristics such as cohesive force. Examples of such copolymerizable monomers include methyl (meth) acrylate: vinyl esters such as vinyl acetate; aromatic vinyl compounds such as styrene and vinyl toluene; cyclopentyl di (meth) acrylate, isobornyl (meta ) (Meth) acrylic esters of cyclic alcohols such as acrylate; neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, And (meth) acrylic acid esters of polyhydric alcohols such as tetramethylol methane tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate. These copolymerizable monomers can also be used alone or in combination of two or more.
本発明において、前記（メタ）アクリル酸アルキルエステルと共重合されるシラン系単量体としては、ケイ素原子を有する重合性化合物であれば特に限定されないが、上記（メタ）アクリル酸アルキルエステルに対する共重合性に優れている点で（メタ）アクリロイルオキシアルキルシラン誘導体などの（メタ）アクリロイル基を有するシラン化合物が好ましい。シラン系単量体としては、例えば、３−メタクリロイルオキシプロピルトリメトキシシラン、３−アクリロイルオキシプロピルトリメトキシシラン、３−メタクリロイルオキシプロピルトリエトキシシラン、３−アクリロイルオキシプロピルトリエトキシシラン、３−メタクリロイルオキシプロピルメチルジメトキシシラン、３−アクリロイルオキシプロピルメチルジメトキシシラン、３−メタクリロイルオキシプロピルメチルジエトキシシラン、３−アクリロイルオキシプロピルメチルジエトキシシランなどが挙げられる。これらのシラン系単量体は単独で又は２種以上組み合わせて使用できる。 In the present invention, the silane monomer copolymerized with the (meth) acrylic acid alkyl ester is not particularly limited as long as it is a polymerizable compound having a silicon atom. A silane compound having a (meth) acryloyl group such as a (meth) acryloyloxyalkylsilane derivative is preferable in terms of excellent polymerizability. Examples of the silane monomer include 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, and 3-methacryloyloxy. Examples include propylmethyldimethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, and 3-acryloyloxypropylmethyldiethoxysilane. These silane monomers can be used alone or in combination of two or more.
また、上記以外に、共重合可能なシラン系単量体として、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、４−ビニルブチルトリメトキシシラン、４−ビニルブチルトリエトキシシラン、８−ビニルオクチルトリメトキシシラン、８−ビニルオクチルトリエトキシシラン、１０−メタクリロイルオキシデシルトリメトキシシラン、１０−アクリロイルオキシデシルトリメトキシシラン、１０−メタクリロイルオキシデシルトリエトキシシラン、１０−アクリロイルオキシデシルトリエトキシシランなども使用できる。 In addition to the above, as copolymerizable silane monomers, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, 8-vinyloctyltri Methoxysilane, 8-vinyloctyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltriethoxysilane, 10-acryloyloxydecyltriethoxysilane and the like can also be used. .
シラン系単量体の量は前記（メタ）アクリル酸アルキルエステルの種類や用途などに応じて適宜選択できるが、シラン系単量体の共重合量が、前記（メタ）アクリル酸アルキルエステルを主成分とする単量体混合物（シラン系単量体を除く）１００重量部に対して、１重量部を超えると接着できない程度まで粘着力が低下する場合があり、また０．００５重量部未満ではポリマー強度の不足で凝集力が低下しやすくなる。従って、本発明では、前記単量体混合物（シラン系単量体を除く）１００重量部に対するシラン系単量体の量は、０．００５〜１重量部が好ましく、さらに好ましくは０．０１〜０．５重量部の範囲である。 The amount of the silane monomer can be appropriately selected according to the type and use of the (meth) acrylic acid alkyl ester, but the copolymerization amount of the silane monomer is mainly the (meth) acrylic acid alkyl ester. For 100 parts by weight of the monomer mixture (excluding silane monomers) as the component, the adhesive strength may be reduced to the extent that it cannot be adhered if it exceeds 1 part by weight. Cohesive force tends to decrease due to insufficient polymer strength. Therefore, in the present invention, the amount of the silane monomer relative to 100 parts by weight of the monomer mixture (excluding the silane monomer) is preferably 0.005 to 1 part by weight, more preferably 0.01 to The range is 0.5 parts by weight.
本発明では、粘着剤の用途に応じて架橋剤を用いることができる。前記架橋剤としては、通常用いる架橋剤を使用することができ、例えば、イソシアネート系架橋剤、エポキシ系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、金属キレート系架橋剤などが挙げられる。架橋剤は、油溶性及び水溶性の何れであってもよい。 In this invention, a crosslinking agent can be used according to the use of an adhesive. As the crosslinking agent, a commonly used crosslinking agent can be used, and examples thereof include an isocyanate crosslinking agent, an epoxy crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent. The cross-linking agent may be either oil-soluble or water-soluble.
本発明の水分散型感圧性接着剤組成物は、例えば、前記（メタ）アクリル酸アルキルエステルを主成分とし且つシラン系単量体を含む単量体混合物を慣用の乳化重合に付して、（メタ）アクリル酸エステル共重合体の水分散液を得、これに必要に応じて前記架橋剤を添加することにより調製できる。 The water-dispersed pressure-sensitive adhesive composition of the present invention includes, for example, a conventional emulsion polymerization of a monomer mixture containing the (meth) acrylic acid alkyl ester as a main component and a silane monomer, It can be prepared by obtaining an aqueous dispersion of a (meth) acrylic acid ester copolymer and adding the cross-linking agent as necessary.
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。 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−メチルプロピオンアミジン）二硫酸塩、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、過酸化水素などの過酸化物系開始剤；フェニル置換エタンなどの置換エタン系開始剤；芳香族カルボニル化合物；過硫酸塩と亜硫酸水素ナトリウムとの組み合わせ、過酸化物とアスコルビン酸ナトリウムとの組み合わせなどのレドックス系開始剤などが挙げられるが、これらに限定されるものではない。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-methylpropionamidine) disulfate, 2,2′-azobis (2-amidino). Propane) dihydrochloride, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (N, N'-dimethyleneisobutylamidine), etc. Azo initiators; persulfates such as potassium persulfate and ammonium persulfate; peroxide initiators such as benzoyl peroxide, t-butyl hydroperoxide and hydrogen peroxide; substituted ethane initiators such as phenyl substituted ethane Agent; aromatic carbonyl compound; combination of persulfate and sodium bisulfite, peroxide and sodium ascorbate And redox initiators such as combinations with but are exemplified, but the invention is not limited thereto. 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、ポリオキシエチレンアルキルフェニルエーテル硫酸ナトリ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 dodecylbenzene sulfonate, sodium polyoxyethylene alkyl ether sulfate, ammonium polyoxyethylene alkyl phenyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate; polyoxy Nonionic emulsifiers such as ethylene alkyl ether and polyoxyethylene alkyl phenyl 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.
なお、水分散型感圧性接着剤組成物は、上記方法のほか、前記（メタ）アクリル酸エステル共重合体を乳化重合以外の方法で得た後、必要に応じて前記架橋剤を添加し、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 pressure-sensitive adhesive composition is obtained by obtaining the (meth) acrylic acid ester copolymer by a method other than emulsion polymerization, and then adding the crosslinking agent as necessary. It may be prepared by dispersing in water with an emulsifier.
水分散型感圧性接着剤組成物には、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。 The water-dispersed pressure-sensitive adhesive composition includes, in addition, a base for adjusting pH (such as aqueous ammonia), an acid, and additives usually used for pressure-sensitive adhesives, such as a tackifier resin, Surfactants, anti-aging agents, fillers, pigments, colorants and the like may be added.
本発明の水分散型感圧性接着剤組成物において、特に、（メタ）アクリル酸アルキルエステルを主成分とし且つシラン系単量体を含まない組成で重合した場合に溶剤不溶分が５％以下となる樹脂組成物が得られる単量体混合物と、該単量体混合物１００重量部に対して０．００５〜１重量部のシラン系単量体とを、前記シラン系単量体を含まない組成で重合した場合と同一条件下で重合して得られる共重合体を含有する水分散型感圧性接着剤組成物では、水分散型であるにもかかわらず、優れた端末剥がれ性と高い保持性とを両立させることが可能である。 In the water-dispersed pressure-sensitive adhesive composition of the present invention, in particular, when polymerized with a composition containing (meth) acrylic acid alkyl ester as a main component and no silane monomer, the solvent-insoluble content is 5% or less. A monomer mixture obtained from the resin composition, and 0.005 to 1 part by weight of a silane monomer with respect to 100 parts by weight of the monomer mixture, the composition not containing the silane monomer The water-dispersed pressure-sensitive adhesive composition containing a copolymer obtained by polymerizing under the same conditions as when polymerized in the case of water-dispersed, excellent terminal peelability and high retention It is possible to achieve both.
上記の「同一条件下」とは、シラン系単量体の有無を除く他の重合条件、例えば、反応温度、反応時間、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等が同一であることを意味する。 The above "same conditions" refers to other polymerization conditions excluding the presence or absence of silane monomers, such as reaction temperature, reaction time, type and amount of polymerization initiator, type and amount of chain transfer agent, etc. Means the same.
なお、シラン系単量体を含まない組成で重合した場合に溶剤不溶分が５％を超える樹脂組成物が得られる単量体混合物とシラン系単量体とを重合に付す場合には、端末剥がれ性が低下しやすい。 In addition, when polymerizing a monomer mixture and a silane monomer, which gives a resin composition having a solvent insoluble content exceeding 5% when polymerized with a composition not containing a silane monomer, a terminal is used. Peelability tends to decrease.
本発明の粘着シートは、シラン系単量体を含み且つ（メタ）アクリル酸アルキルエステルを主成分とする単量体混合物の共重合体からなる粘着剤層を備えている。 The pressure-sensitive adhesive sheet of the present invention is provided with a pressure-sensitive adhesive layer comprising a copolymer of a monomer mixture containing a silane monomer and having (meth) acrylic acid alkyl ester as a main component.
この粘着シートは、例えば、上記の水分散型感圧性接着剤組成物を基材上に塗布し、熱架橋して粘着剤層を形成することにより得られる。また、セパレータ上に上記粘着剤層を形成することにより基材を有しない粘着シートを得ることもできる。 This pressure-sensitive adhesive sheet is obtained, for example, by applying the above water-dispersed pressure-sensitive adhesive composition on a substrate and thermally cross-linking to form a pressure-sensitive adhesive layer. Moreover, the adhesive sheet which does not have a base material can also be obtained by forming the said adhesive layer on a separator.
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.
水分散型感圧性接着剤組成物の塗布は、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。前記水分散型感圧性接着剤組成物は、乾燥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 pressure-sensitive adhesive composition can be applied using a conventional coater such as a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray coater, etc. it can. The water-dispersed pressure-sensitive adhesive composition is applied so that the thickness of the pressure-sensitive adhesive layer after drying is, for example, about 10 to 100 μm.
熱架橋は、慣用の方法、例えば、シラン系単量体や架橋剤の種類に応じて架橋反応が進行する温度にまで加熱することにより行われる。架橋後の粘着剤層の溶剤不溶分は、例えば１５〜７０重量％程度である。また、架橋後の粘着剤層の溶剤可溶部の分子量（重量平均分子量；標準ポリスチレン換算）は、例えば１０万〜６０万程度、好ましくは２０万〜４５万程度である。架橋後の粘着剤層の溶剤不溶分や溶剤可溶部の分子量は、例えば、モノマー総量に対する前記シラン系単量体又は官能基含有単量体の割合、連鎖移動剤や架橋剤の種類や量、特にシラン系単量体と連鎖移動剤の量を適宜調整することにより任意に設定することができる。粘着シートは、ロール状に巻回した粘着テープであってもよい。 Thermal crosslinking is performed by a conventional method, for example, by heating to a temperature at which a crosslinking reaction proceeds according to the type of silane monomer or crosslinking agent. The solvent insoluble content of the pressure-sensitive adhesive layer after crosslinking is, for example, about 15 to 70% by weight. Moreover, the molecular weight (weight average molecular weight; standard polystyrene conversion) of the solvent soluble part of the pressure-sensitive adhesive layer after crosslinking is, for example, about 100,000 to 600,000, preferably about 200,000 to 450,000. The molecular weight of the solvent-insoluble part and solvent-soluble part of the pressure-sensitive adhesive layer after crosslinking is, for example, the ratio of the silane-based monomer or functional group-containing monomer to the total amount of monomers, the type and amount of chain transfer agent and crosslinking agent. In particular, it can be arbitrarily set by appropriately adjusting the amounts of the silane monomer and the chain transfer agent. The pressure-sensitive adhesive sheet may be a pressure-sensitive adhesive tape wound in a roll shape.
本発明の粘着シートは、水分散型のアクリル系粘着剤を用いるにもかかわらず、粘着シートの粘着剤層を構成する粘着剤の溶剤不溶分、溶剤可溶部の分子量、及び被着体に貼付したときの端末剥がれ性の経時安定性に優れている。すなわち、粘着シートを長時間保存しても、前記溶剤不溶分、溶剤可溶部の分子量及び端末剥がれ性の変動が極めて小さい。そのため、高い信頼性が得られる。 Although the pressure-sensitive adhesive sheet of the present invention uses a water-dispersed acrylic pressure-sensitive adhesive, the solvent-insoluble content of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet, the molecular weight of the solvent-soluble part, and the adherend It has excellent terminal peelability over time when applied. That is, even when the pressure-sensitive adhesive sheet is stored for a long period of time, fluctuations in the solvent-insoluble content, the molecular weight of the solvent-soluble portion, and the terminal peelability are extremely small. Therefore, high reliability can be obtained.
このような優れた効果が奏される理由は必ずしも明確ではないが、シラン系単量体が有する珪素原子含有基の縮合反応が、（メタ）アクリル酸アルキルエステルを主成分とする単量体混合物との共重合時（乳化重合時）よりもむしろ感圧性接着剤組成物を基材等に塗布した後の乾燥工程で主に起こるため、共重合工程では溶剤不溶分が過剰に生成することがなく、それ故優れた保持性が発現するとともに、乾燥後には水が介在しないため加水分解が起こらず、縮合反応が進行しないことから、構造及び物性が変化しにくく、よって良好な経時安定性が得られるものと推察される。 The reason why such an excellent effect is exhibited is not necessarily clear, but the condensation reaction of the silicon atom-containing group of the silane monomer is a monomer mixture mainly composed of (meth) acrylic acid alkyl ester. This occurs mainly in the drying process after the pressure-sensitive adhesive composition is applied to the substrate or the like, rather than during the copolymerization (at the time of emulsion polymerization). Therefore, excellent retention is exhibited, and water does not intervene after drying, so that hydrolysis does not occur and the condensation reaction does not proceed. It is assumed that it will be obtained.
また、特に、シラン系単量体を含まない組成で重合した場合の重合終了時の溶剤不溶分が５％以下となるような単量体混合物にシラン系単量体を共重合する場合には、熱架橋時において、水分散型感圧性接着剤の粒子の内部と外側が均一に架橋されるため、端末剥がれ性と保持性能とを高いレベルで両立できるものと推測される。 In particular, when the silane monomer is copolymerized with a monomer mixture in which the solvent-insoluble content at the end of the polymerization is 5% or less when polymerized with a composition not containing the silane monomer. During the thermal cross-linking, the inside and the outside of the water-dispersed pressure-sensitive adhesive particles are uniformly cross-linked, so that it is presumed that both the terminal peelability and the holding performance can be achieved at a high level.
以下の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」及び「％」は、特に断りがない限り重量基準である。 The following examples further illustrate the present invention in detail but are not to be construed to limit the scope thereof. “Parts” and “%” are based on weight unless otherwise specified.
実施例１
冷却管、窒素導入管、温度計および攪拌機を備えた反応容器を用い、アクリル酸ブチル７０部、アクリル酸２−エチルヘキシル３０部、アクリル酸３部、３−メタクリロイルオキシプロピルトリエトキシシラン０．０５部、ドデカンチオール（連鎖移動剤）０．０７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部を、ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウム（乳化剤）１．５部を添加した水１００部に加えて乳化重合したのち、１０％アンモニウム水を添加してｐＨ８に調整することにより、アクリル系共重合体の水分散液を得た。これを厚さ４０μｍのＰＥＴ（ポリエチレンテレフタレート）フィルムに塗布し、１２０℃で３分乾燥し、厚さ５０μｍの粘着剤層を付設して粘着シートを作製した。
Example 1
Using a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer and a stirrer, 70 parts of butyl acrylate, 30 parts of 2-ethylhexyl acrylate, 3 parts of acrylic acid, 0.05 part of 3-methacryloyloxypropyltriethoxysilane 0.07 part of dodecanethiol (chain transfer agent), 0.1 part of 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane)] dihydrochloride (initiator), Emulsion polymerization was carried out by adding 100 parts of water to which 1.5 parts of sodium polyoxyethylene nonylphenyl ether sulfate (emulsifier) was added, and then the pH of the acrylic copolymer was adjusted to 8 by adding 10% ammonium water. An aqueous dispersion was obtained. This was applied to a PET (polyethylene terephthalate) film having a thickness of 40 μm, dried at 120 ° C. for 3 minutes, and a pressure-sensitive adhesive layer having a thickness of 50 μm was provided to prepare a pressure-sensitive adhesive sheet.
実施例２
アクリル酸ブチル９０部、アクリル酸２−エチルヘキシル１０部、アクリル酸４部、３−メタクリロイルオキシプロピルトリエトキシシラン０．０６部、ドデカンチオール（連鎖移動剤）０．０５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部を、ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウム（乳化剤）１．５部を添加した水１００部に加えて乳化重合したのち、１０％アンモニウム水を添加してｐＨ８に調整することにより、アクリル系共重合体の水分散液を得た。これを厚さ４０μｍのＰＥＴフィルムに塗布し、１２０℃で３分乾燥し、厚さ５０μｍの粘着剤層を付設して粘着シートを作製した。
Example 2
90 parts of butyl acrylate, 10 parts of 2-ethylhexyl acrylate, 4 parts of acrylic acid, 0.06 part of 3-methacryloyloxypropyltriethoxysilane, 0.05 part of dodecanethiol (chain transfer agent), 2,2′-azobis Water to which 0.1 part of [2- (5-methyl-2-imidazolin-2-yl) propane)] dihydrochloride (initiator) was added and 1.5 parts of sodium polyoxyethylene nonylphenyl ether sulfate (emulsifier) was added. After emulsion polymerization in addition to 100 parts, an aqueous dispersion of an acrylic copolymer was obtained by adding 10% ammonium water and adjusting the pH to 8. This was applied to a PET film having a thickness of 40 μm, dried at 120 ° C. for 3 minutes, and a pressure-sensitive adhesive layer having a thickness of 50 μm was provided to prepare a pressure-sensitive adhesive sheet.
比較例１
アクリル酸ブチル７０部、アクリル酸２−エチルヘキシル３０部、アクリル酸３部、ドデカンチオール（連鎖移動剤）０．０７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部を、ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウム（乳化剤）１．５部を添加した水１００部に加えて乳化重合したのち、１０％アンモニウム水を添加してｐＨ８に調整することにより、アクリル系共重合体の水分散液を得た。これにトルエンに溶解した油溶性のエポキシ型架橋剤（テトラッド−Ｃ：三菱瓦斯化学株式会社製）を０．０５部添加して、これを厚さ４０μｍのＰＥＴフィルムに塗布し、１２０℃で３分乾燥し、厚さ５０μｍの粘着剤層を付設して粘着シートを作製した。
Comparative Example 1
70 parts of butyl acrylate, 30 parts of 2-ethylhexyl acrylate, 3 parts of acrylic acid, 0.07 part of dodecanethiol (chain transfer agent), 2,2′-azobis [2- (5-methyl-2-imidazoline-2 -Yl) propane)] dihydrochloride (initiator) 0.1 part was added to 100 parts of water to which 1.5 parts of polyoxyethylene nonylphenyl ether sodium sulfate (emulsifier) was added, and after emulsion polymerization, 10% ammonium was added. An aqueous dispersion of an acrylic copolymer was obtained by adjusting the pH to 8 by adding water. To this was added 0.05 part of an oil-soluble epoxy type crosslinking agent (Tetrad-C: manufactured by Mitsubishi Gas Chemical Co., Ltd.) dissolved in toluene, and this was applied to a PET film having a thickness of 40 μm. The mixture was dried, and a pressure-sensitive adhesive layer having a thickness of 50 μm was attached to prepare a pressure-sensitive adhesive sheet.
比較例２
アクリル酸ブチル９０部、アクリル酸２−エチルヘキシル１０部、アクリル酸４部、ドデカンチオール（連鎖移動剤）０．０５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部を、ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウム（乳化剤）１．５部を添加した水１００部に加えて乳化重合したのち、１０％アンモニウム水を添加してｐＨ８に調整することにより、アクリル系共重合体の水分散液を得た。これにトルエンに溶解した油溶性のエポキシ型架橋剤（テトラッド−Ｃ：三菱瓦斯化学株式会社製）を０．０６部添加して、これを厚さ４０μｍのＰＥＴフィルムに塗布し、１２０℃で３分乾燥し、厚さ５０μｍの粘着剤層を付設して粘着シートを作製した。
Comparative Example 2
90 parts of butyl acrylate, 10 parts of 2-ethylhexyl acrylate, 4 parts of acrylic acid, 0.05 parts of dodecanethiol (chain transfer agent), 2,2′-azobis [2- (5-methyl-2-imidazoline-2 -Yl) propane)] dihydrochloride (initiator) 0.1 part was added to 100 parts of water to which 1.5 parts of polyoxyethylene nonylphenyl ether sodium sulfate (emulsifier) was added, and after emulsion polymerization, 10% ammonium was added. An aqueous dispersion of an acrylic copolymer was obtained by adjusting the pH to 8 by adding water. To this was added 0.06 part of an oil-soluble epoxy type crosslinking agent (Tetrad-C: manufactured by Mitsubishi Gas Chemical Co., Ltd.) dissolved in toluene, and this was applied to a PET film having a thickness of 40 μm. The mixture was dried, and a pressure-sensitive adhesive layer having a thickness of 50 μm was attached to prepare a pressure-sensitive adhesive sheet.
評価試験１
以上の実施例１、２、比較例１、２で得た粘着剤及び粘着シートについて次の特性を調べた。結果を表１に示す。
Evaluation test 1
The following characteristics of the pressure-sensitive adhesives and pressure-sensitive adhesive sheets obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were examined. The results are shown in Table 1.
（溶剤不溶分）
作製直後（初期）の粘着シートと、作製して５０℃の雰囲気下に１４日間放置した粘着シートの粘着剤層から試料を採取し、前記の方法により溶剤不溶分を測定した。
(Solvent insoluble matter)
Samples were taken from the pressure-sensitive adhesive sheet immediately after production (initial stage) and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet that was prepared and allowed to stand for 14 days in an atmosphere at 50 ° C., and the solvent-insoluble content was measured by the method described above.
（分子量）
作製直後（初期）の粘着シートと、作製して５０℃の雰囲気下に１４日間放置した粘着シートの粘着剤層から試料を採取した。この試料を酢酸エチルに一定時間浸漬し、不溶分を濾過後、濾液を乾燥し、残留物（酢酸エチル溶出物）にテトラヒドロフラン（ＴＨＦ）を加え、０．１％のＴＨＦ溶液を調製した。これを孔径０．４５μｍのフィルターで濾過し、この濾液を用いてＧＰＣ（ゲル浸透クロマトグラフィ）により分子量（溶剤可溶部の分子量；Ｍｗ）を測定した。測定条件は以下の通りである。
測定条件：溶出液ＴＨＦ、液送量１．０ｍｌ／ｍｉｎ、
カラム温度３８℃、標準ポリスチレン換算
(Molecular weight)
A sample was collected from the pressure-sensitive adhesive sheet immediately after production (initial stage) and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet that was prepared and left in an atmosphere at 50 ° C. for 14 days. This sample was immersed in ethyl acetate for a certain period of time, insoluble matter was filtered off, the filtrate was dried, and tetrahydrofuran (THF) was added to the residue (ethyl acetate eluate) to prepare a 0.1% THF solution. This was filtered with a filter having a pore size of 0.45 μm, and the molecular weight (molecular weight of solvent-soluble part; Mw) was measured by GPC (gel permeation chromatography) using this filtrate. The measurement conditions are as follows.
Measurement conditions: eluent THF, liquid feed rate 1.0 ml / min,
Column temperature 38 ° C, standard polystyrene conversion
（端末剥がれ性試験）
粘着剤層をＰＥＴフィルム上に付設する代わりに、セパレーター基材上に付設した点以外は同様にして、各実施例及び比較例に対応するテープサンプルを得た。作製直後（初期）のテープサンプルと、作製して５０℃の雰囲気下に１４日間放置したテープサンプルを、それぞれ厚さ０．５ｍｍのアルミニウム板（面積：１０ｍｍ×１００ｍｍ）に貼り付けた後、前記セパレーター基材を剥がし、露出した粘着剤層面を直径５０ｍｍの円筒状のアクリルの丸棒の側面に貼り合わせた。これを、７０℃の雰囲気下に２時間置き、その時のアルミニウム板の端部の剥がれた高さを測定した。
(Terminal peelability test)
Instead of attaching the pressure-sensitive adhesive layer on the PET film, tape samples corresponding to the examples and comparative examples were obtained in the same manner except that the adhesive layer was attached on the separator substrate. The tape sample immediately after production (initial stage) and the tape sample produced and left in an atmosphere of 50 ° C. for 14 days were attached to an aluminum plate (area: 10 mm × 100 mm) having a thickness of 0.5 mm, respectively. The separator base material was peeled off, and the exposed pressure-sensitive adhesive layer surface was bonded to the side surface of a cylindrical acrylic round bar having a diameter of 50 mm. This was placed in an atmosphere of 70 ° C. for 2 hours, and the height at which the end of the aluminum plate was peeled was measured.
表１より明らかなように、比較例１及び２では、溶剤不溶分は経時的に増大し、溶剤可溶部の分子量は経時的に減少し、端末剥がれ性は経時的に悪化するのに対し、実施例１及び２では、溶剤不溶分、溶剤可溶部の分子量はほとんど変化せず、端末剥がれ性も悪化しなかった。 As is clear from Table 1, in Comparative Examples 1 and 2, the solvent-insoluble content increases with time, the molecular weight of the solvent-soluble part decreases with time, and the terminal peelability deteriorates with time. In Examples 1 and 2, the molecular weight of the solvent-insoluble part and the solvent-soluble part hardly changed, and the terminal peeling property did not deteriorate.
実施例３
冷却管、窒素導入管、温度計および攪拌機を備えた反応容器を用い、アクリル酸ブチル８０部、アクリル酸２−エチルヘキシル２０部、アクリル酸３部、３−メタクリロイルオキシプロピルトリエトキシシラン０．０５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）０．０５部を、ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウム（乳化剤）３部を添加した水１００部に加えて乳化重合したのち、１０％アンモニウム水を添加してｐＨ８に調整し、アクリル系共重合体の水分散液を得た。なお、シラン系単量体を混合しない組成で同様にして重合した場合の重合終了時の重合体の溶剤不溶分は０％であった。
上記で得られたアクリル系共重合体の水分散液を厚さ４０μｍのＰＥＴ（ポリエチレンテレフタレート）フィルムに塗布し、１２０℃で３分乾燥し、厚さ５０μｍの粘着剤層を付設して粘着シートを作製した。この粘着剤層の溶剤不溶分は５０％であった。
Example 3
Using a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer and a stirrer, 80 parts of butyl acrylate, 20 parts of 2-ethylhexyl acrylate, 3 parts of acrylic acid, 0.05 part of 3-methacryloyloxypropyltriethoxysilane , 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane)] dihydrochloride (initiator) 0.1 part, dodecanethiol (chain transfer agent) 0.05 part, Emulsion polymerization was carried out by adding 100 parts of water to which 3 parts of sodium polyoxyethylene nonylphenyl ether sulfate (emulsifier) was added, and then 10% ammonium water was added to adjust the pH to 8 to prepare an aqueous dispersion of acrylic copolymer. Obtained. In addition, the solvent insoluble content of the polymer at the time of completion | finish of superposition | polymerization at the time of superposing | polymerizing similarly with the composition which does not mix a silane type monomer was 0%.
The acrylic copolymer aqueous dispersion obtained above was applied to a 40 μm thick PET (polyethylene terephthalate) film, dried at 120 ° C. for 3 minutes, and a 50 μm thick adhesive layer was attached to the adhesive sheet. Was made. The solvent insoluble content of this pressure-sensitive adhesive layer was 50%.
実施例４
アクリル酸ブチル８０部、アクリル酸２−エチルヘキシル２０部、アクリル酸３部、３−メタクリロイルオキシプロピルトリメトキシシラン０．０５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）０．０５部を、ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウム（乳化剤）３部を添加した水１００部に加えて乳化重合したのち、１０％アンモニウム水を添加してｐＨ８に調整し、アクリル系共重合体の水分散液を得た。なお、シラン系単量体を混合しない組成で同様にして重合した場合の重合終了時の重合体の溶剤不溶分は０％であった。
上記で得られたアクリル系共重合体の水分散液を厚さ４０μｍのＰＥＴフィルムに塗布し、１２０℃で３分乾燥し、厚さ５０μｍの粘着剤層を付設して粘着シートを作製した。この粘着剤層の溶剤不溶分は５０％であった。
Example 4
80 parts of butyl acrylate, 20 parts of 2-ethylhexyl acrylate, 3 parts of acrylic acid, 0.05 part of 3-methacryloyloxypropyltrimethoxysilane, 2,2′-azobis [2- (5-methyl-2-imidazoline- 2-yl) propane)] dihydrochloride (initiator) 0.1 part, dodecanethiol (chain transfer agent) 0.05 part, polyoxyethylene nonylphenyl ether sodium sulfate (emulsifier) 3 parts added water 100 parts In addition to the emulsion polymerization, 10% aqueous ammonium was added to adjust the pH to 8 to obtain an aqueous dispersion of an acrylic copolymer. In addition, the solvent insoluble content of the polymer at the time of completion | finish of superposition | polymerization at the time of superposing | polymerizing similarly with the composition which does not mix a silane type monomer was 0%.
The acrylic copolymer aqueous dispersion obtained above was applied to a PET film having a thickness of 40 μm, dried at 120 ° C. for 3 minutes, and a pressure-sensitive adhesive layer having a thickness of 50 μm was provided to prepare a pressure-sensitive adhesive sheet. The solvent insoluble content of this pressure-sensitive adhesive layer was 50%.
実施例５
アクリル酸ブチル８０部、アクリル酸２−エチルヘキシル２０部、アクリル酸３部、３−メタクリロイルオキシプロピルトリエトキシシラン０．０１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）０．０５部を、ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウム（乳化剤）３部を添加した水１００部に加えて乳化重合したのち、１０％アンモニウム水を添加してｐＨ８に調整し、アクリル系共重合体の水分散液を得た。なお、シラン系単量体を混合しない組成で同様にして重合した場合の重合終了時の重合体の溶剤不溶分は０％であった。
上記で得られたアクリル系共重合体の水分散液を厚さ４０μｍのＰＥＴフィルムに塗布し、１２０℃で３分乾燥し、厚さ５０μｍの粘着剤層を付設して粘着シートを作製した。この粘着剤層の溶剤不溶分は２０％であった。
Example 5
80 parts of butyl acrylate, 20 parts of 2-ethylhexyl acrylate, 3 parts of acrylic acid, 0.01 part of 3-methacryloyloxypropyltriethoxysilane, 2,2′-azobis [2- (5-methyl-2-imidazoline- 2-yl) propane)] dihydrochloride (initiator) 0.1 part, dodecanethiol (chain transfer agent) 0.05 part, polyoxyethylene nonylphenyl ether sodium sulfate (emulsifier) 3 parts added water 100 parts In addition to the emulsion polymerization, 10% aqueous ammonium was added to adjust the pH to 8 to obtain an aqueous dispersion of an acrylic copolymer. In addition, the solvent insoluble content of the polymer at the time of completion | finish of superposition | polymerization at the time of superposing | polymerizing similarly with the composition which does not mix a silane type monomer was 0%.
The acrylic copolymer aqueous dispersion obtained above was applied to a PET film having a thickness of 40 μm, dried at 120 ° C. for 3 minutes, and a pressure-sensitive adhesive layer having a thickness of 50 μm was provided to prepare a pressure-sensitive adhesive sheet. The solvent insoluble content of this pressure-sensitive adhesive layer was 20%.
実施例６
アクリル酸ブチル９５部、アクリル酸５部、３−メタクリロイルオキシプロピルトリエトキシシラン０．０５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）０．０５部を、ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウム（乳化剤）３部を添加した水１００部に加えて乳化重合したのち、１０％アンモニウム水を添加してｐＨ８に調整し、アクリル系共重合体の水分散液を得た。なお、シラン系単量体を混合しない組成で同様にして重合した場合の重合終了時の重合体の溶剤不溶分は０％であった。
上記で得られたアクリル系共重合体の水分散液を厚さ４０μｍのＰＥＴフィルムに塗布し、１２０℃で３分乾燥し、厚さ５０μｍの粘着剤層を付設して粘着シートを作製した。この粘着剤層の溶剤不溶分は５０％であった。
Example 6
95 parts of butyl acrylate, 5 parts of acrylic acid, 0.05 part of 3-methacryloyloxypropyltriethoxysilane, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane)] dihydro After adding 0.1 part of chloride (initiator) and 0.05 part of dodecanethiol (chain transfer agent) to 100 parts of water to which 3 parts of polyoxyethylene nonylphenyl ether sodium sulfate (emulsifier) is added, emulsion polymerization is performed. 10% aqueous ammonium was added to adjust the pH to 8 to obtain an aqueous dispersion of an acrylic copolymer. In addition, the solvent insoluble content of the polymer at the time of completion | finish of superposition | polymerization at the time of superposing | polymerizing similarly with the composition which does not mix a silane type monomer was 0%.
The acrylic copolymer aqueous dispersion obtained above was applied to a PET film having a thickness of 40 μm, dried at 120 ° C. for 3 minutes, and a pressure-sensitive adhesive layer having a thickness of 50 μm was provided to prepare a pressure-sensitive adhesive sheet. The solvent insoluble content of this pressure-sensitive adhesive layer was 50%.
実施例７
アクリル酸ブチル８０部、アクリル酸２−エチルヘキシル２０部、アクリル酸３部、３−メタクリロイルオキシプロピルトリエトキシシラン０．０４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）０．０５部を、ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウム（乳化剤）３部を添加した水１００部に加えて乳化重合したのち、１０％アンモニウム水を添加してｐＨ８に調整し、アクリル系共重合体の水分散液を得た。なお、シラン系単量体を混合しない組成で同様にして重合した場合の重合終了時の重合体の溶剤不溶分は０％、シラン系単量体を混合した組成で重合した場合の重合終了時の重合体の溶剤不溶分は４０％であった。
上記で得られたアクリル系共重合体の水分散液に、トルエンに溶解した油溶性のエポキシ型架橋剤（テトラッド−Ｃ：三菱瓦斯化学株式会社製）を０．０２部添加して、これを厚さ４０μｍのＰＥＴフィルムに塗布し、１２０℃で３分乾燥し、厚さ５０μｍの粘着剤層を付設して粘着シートを作製した。この粘着剤層の溶剤不溶分は５０％であった。
Example 7
80 parts of butyl acrylate, 20 parts of 2-ethylhexyl acrylate, 3 parts of acrylic acid, 0.04 part of 3-methacryloyloxypropyltriethoxysilane, 2,2′-azobis [2- (5-methyl-2-imidazoline- 2-yl) propane)] dihydrochloride (initiator) 0.1 part, dodecanethiol (chain transfer agent) 0.05 part, polyoxyethylene nonylphenyl ether sodium sulfate (emulsifier) 3 parts added water 100 parts In addition to the emulsion polymerization, 10% aqueous ammonium was added to adjust the pH to 8 to obtain an aqueous dispersion of an acrylic copolymer. In addition, the solvent-insoluble content of the polymer at the end of polymerization when polymerizing in the same manner with a composition in which no silane monomer is mixed is 0%, and at the end of polymerization when polymerizing with a composition in which the silane monomer is mixed The solvent insoluble content of the polymer was 40%.
0.02 part of an oil-soluble epoxy-type cross-linking agent (Tetrad-C: manufactured by Mitsubishi Gas Chemical Co., Ltd.) dissolved in toluene was added to the aqueous dispersion of the acrylic copolymer obtained above. It was applied to a PET film having a thickness of 40 μm, dried at 120 ° C. for 3 minutes, and a pressure-sensitive adhesive layer having a thickness of 50 μm was provided to prepare a pressure-sensitive adhesive sheet. The solvent insoluble content of this pressure-sensitive adhesive layer was 50%.
比較例３
アクリル酸ブチル８０部、アクリル酸２−エチルヘキシル２０部、アクリル酸３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）０．０５部を、ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウム（乳化剤）３部を添加した水１００部に加えて乳化重合したのち、１０％アンモニウム水を添加してｐＨ８に調整し、アクリル系共重合体の水分散液を得た。なお、この時のアクリル系共重合体の溶剤不溶分は０％であった。
上記で得られたアクリル系共重合体の水分散液に、水に溶解した水溶性のオキサゾリン型架橋剤（エポクロスＷＳ−５００：日本触媒化学工業株式会社製）を０．１部添加して、これを厚さ４０μｍのＰＥＴフィルムに塗布し、１２０℃で３分乾燥し、厚さ５０μｍの粘着剤層を付設して粘着シートを作製した。この粘着剤層の溶剤不溶分は５０％であった。
Comparative Example 3
80 parts of butyl acrylate, 20 parts of 2-ethylhexyl acrylate, 3 parts of acrylic acid, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane)] dihydrochloride (initiator) 0.1 part, 0.05 part of dodecanethiol (chain transfer agent) was added to 100 parts of water to which 3 parts of polyoxyethylene nonylphenyl ether sodium sulfate (emulsifier) was added, and after emulsion polymerization, 10% ammonium water was added. The pH was adjusted to 8 and an aqueous dispersion of an acrylic copolymer was obtained. In addition, the solvent insoluble content of the acrylic copolymer at this time was 0%.
To the aqueous dispersion of the acrylic copolymer obtained above, 0.1 part of a water-soluble oxazoline-type crosslinking agent dissolved in water (Epocross WS-500: manufactured by Nippon Shokubai Chemical Industry Co., Ltd.) was added, This was applied to a PET film having a thickness of 40 μm, dried at 120 ° C. for 3 minutes, and a pressure-sensitive adhesive layer having a thickness of 50 μm was provided to prepare a pressure-sensitive adhesive sheet. The solvent insoluble content of this pressure-sensitive adhesive layer was 50%.
評価試験２
実施例３〜７及び比較例３で得た粘着剤（アクリル系共重合体の水分散液）及び粘着シートについて次の特性を調べた。結果を表２に示す。
Evaluation test 2
The following characteristics were investigated for the pressure-sensitive adhesives (acrylic copolymer aqueous dispersion) and pressure-sensitive adhesive sheets obtained in Examples 3 to 7 and Comparative Example 3. The results are shown in Table 2.
（端末剥がれ性試験）
各実施例及び比較例の方法に準じて粘着剤層をセパレーター基材に付設したテープサンプルを、厚さ０．５ｍｍのアルミニウム板（面積：１０ｍｍ×１００ｍｍ）に貼り付けた後、前記セパレーター基材を剥がし、露出した粘着剤層面を直径５０ｍｍの円筒状のアクリルの丸棒の側面に貼り合わせた。これを、（１）２３℃の雰囲気下に２４時間、又は（２）７０℃の雰囲気下に２時間置いた後、アルミニウム板の端部の剥がれた高さを測定した。
(Terminal peelability test)
A tape sample in which a pressure-sensitive adhesive layer is attached to a separator base material in accordance with the method of each example and comparative example was attached to an aluminum plate (area: 10 mm × 100 mm) having a thickness of 0.5 mm, and then the separator base material. Was peeled off, and the exposed adhesive layer surface was bonded to the side surface of a cylindrical acrylic round bar having a diameter of 50 mm. This was placed in (1) an atmosphere of 23 ° C. for 24 hours, or (2) in an atmosphere of 70 ° C. for 2 hours, and then the height at which the end of the aluminum plate was peeled was measured.
（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の接触面積で貼り付け、２０分経過後８０℃に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を測定した。
(Retention force test)
A 10 mm wide adhesive sheet with a 10 mm x 20 mm contact area is attached to the phenolic resin plate and left for 20 minutes at 80 ° C. after 20 minutes. Then, the phenolic resin plate is suspended, and 600 g is uniformly applied to the free end of the adhesive tape. A load was applied, and the drop time of the adhesive sheet at 80 ° C. was measured.
表２より、比較例３では端末剥がれ性が劣るのに対し、実施例３〜７では、優れた端末剥がれ性と高い保持力とを両立できることが分かる。 From Table 2, it can be seen that in Comparative Example 3, the terminal peelability is inferior, while in Examples 3 to 7, both excellent terminal peelability and high holding power can be achieved.
Claims (5)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009057490A (en) * | 2007-08-31 | 2009-03-19 | Saiden Chemical Industry Co Ltd | Water-based emulsion adhesive |
| JP2014504306A (en) * | 2010-11-12 | 2014-02-20 | テーザ・ソシエタス・ヨーロピア | Especially pressure sensitive adhesive tape for pasting windows of mobile devices |
| CN105670537A (en) * | 2016-01-18 | 2016-06-15 | 常州大学 | Adhesive for buildings and preparation method of adhesive for buildings |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3757185A4 (en) | 2018-02-21 | 2022-02-23 | Nitto Denko Corporation | Pressure-sensitive adhesive article |
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| JPH05230428A (en) * | 1992-02-21 | 1993-09-07 | Nitto Denko Corp | Pressure-sensitive adhesive composition dispersed in water |
| JPH06322338A (en) * | 1993-05-07 | 1994-11-22 | Nitto Denko Corp | Releasable adhesive and adhesive member using the same |
| JPH0735405B2 (en) * | 1988-02-29 | 1995-04-19 | 株式会社日本触媒 | Adhesive |
| JPH10183083A (en) * | 1996-12-26 | 1998-07-07 | Kao Corp | Emulsion-type self-adhesive for repeating peeling and surface protection film prepared by using the same |
| JPH11158453A (en) * | 1997-11-27 | 1999-06-15 | Sekisui Chem Co Ltd | Pressure-sensitive acrylic adhesive composition and pressure-sensitive processed article |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0735405B2 (en) * | 1988-02-29 | 1995-04-19 | 株式会社日本触媒 | Adhesive |
| JPH05230428A (en) * | 1992-02-21 | 1993-09-07 | Nitto Denko Corp | Pressure-sensitive adhesive composition dispersed in water |
| JPH06322338A (en) * | 1993-05-07 | 1994-11-22 | Nitto Denko Corp | Releasable adhesive and adhesive member using the same |
| JPH10183083A (en) * | 1996-12-26 | 1998-07-07 | Kao Corp | Emulsion-type self-adhesive for repeating peeling and surface protection film prepared by using the same |
| JPH11158453A (en) * | 1997-11-27 | 1999-06-15 | Sekisui Chem Co Ltd | Pressure-sensitive acrylic adhesive composition and pressure-sensitive processed article |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009057490A (en) * | 2007-08-31 | 2009-03-19 | Saiden Chemical Industry Co Ltd | Water-based emulsion adhesive |
| JP2014504306A (en) * | 2010-11-12 | 2014-02-20 | テーザ・ソシエタス・ヨーロピア | Especially pressure sensitive adhesive tape for pasting windows of mobile devices |
| US9260631B2 (en) | 2010-11-12 | 2016-02-16 | Tesa Se | Pressure-sensitive adhesive tapes for gluing windows, in particular in mobile devices |
| CN105670537A (en) * | 2016-01-18 | 2016-06-15 | 常州大学 | Adhesive for buildings and preparation method of adhesive for buildings |
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