JP4676748B2 - Water-dispersed acrylic pressure-sensitive adhesive composition and method for producing the same - Google Patents
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本発明は、水分散型アクリル系粘着剤組成物に関し、さらに詳しくは、被着体に対して必要な粘着力を示すと共に、高凝集力で耐熱性や耐水性に優れた接着特性を発揮する水分散型アクリル系粘着剤組成物に関するものである。
The present invention relates to a water-dispersed acrylic pressure-sensitive adhesive composition. More specifically, the present invention shows a necessary adhesive force to an adherend and exhibits adhesive properties excellent in heat resistance and water resistance with high cohesive force. The present invention relates to a water-dispersed acrylic pressure-sensitive adhesive composition.
これまで、有機溶剤溶液型のアクリル系粘着剤組成物を使用した様々な粘着テープや粘着シート等が開発されてきたが、最近では、環境問題の点より、有機溶剤を用いない水分散型のアクリル系粘着剤組成物が注目されている。また、粘着剤の用途が多岐にわたり、構造用や自動車用等、大きな応力が加わる用途に使用する場合、粘着剤には、高凝集力で耐熱性に優れるものが要求されるようになってきたが、これまでの粘着剤では、一般に、凝集力が不足し耐熱性に劣るいう問題があった。
Up to now, various adhesive tapes and adhesive sheets using an organic solvent solution type acrylic adhesive composition have been developed, but recently, from the viewpoint of environmental problems, water-dispersed type that does not use organic solvents. Acrylic adhesive compositions are attracting attention. In addition, pressure sensitive adhesives have a wide range of applications, and when used in applications where large stress is applied, such as for structures and automobiles, pressure sensitive adhesives with high cohesive force and excellent heat resistance have been required. However, conventional pressure-sensitive adhesives generally have a problem that the cohesive force is insufficient and the heat resistance is poor.
この問題を克服するため、粘着剤組成物中に層状粘土鉱物を分散させる方法が知られている（特許文献１参照）。この方法は光重合タイプの粘着剤組成物に関するものであり、この方法を水分散型粘着剤組成物に適用しても、層状粘土鉱物が核となる疑集物が発生しやすいという問題があった。また、水分散型粘着剤ポリマーの合成時に層状粘土鉱物を添加する方法が知られている（特許文献２参照）。しかし、この方法は、粘着剤ポリマーの製造工程が複雑になり、凝集物の発生も免れなかった。
本発明は、このような事情に照らし、水分散型粘着剤組成物中に層状粘土鉱物を疑集物を発生することなく簡単に分散させることができ、これにより被着体に対して必要な粘着力を示すと共に、高凝集力で耐熱性や耐水性に優れた接着特性を発揮する水分散型アクリル系粘着剤組成物を得ることを課題としている。
In light of such circumstances, the present invention can easily disperse a layered clay mineral in a water-dispersed pressure-sensitive adhesive composition without generating any suspicious matter, and is thus necessary for an adherend. An object is to obtain a water-dispersed acrylic pressure-sensitive adhesive composition that exhibits adhesive strength and exhibits adhesive properties with high cohesive strength and excellent heat resistance and water resistance.
本発明者らは、上記の課題に対して、鋭意検討を重ねた結果、特定の有機化処理剤にて親油化処理された層状粘土鉱物を、特定の界面活性剤を添加して水に分散させた状態で、特定モノマー組成のアクリル系共重合体の水分散体中に添加することにより、層状粘土鉱物を凝集物を発生することなく簡単に分散でき、これにより被着体に対して必要な粘着力を示すと共に、高凝集力で耐熱性や耐水性に優れた接着特性を発揮する水分散型アクリル系粘着剤組成物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 investigations on the above problems, the present inventors have added a specific surfactant to the layered clay mineral that has been oleophilicized with a specific organic treatment agent and added to water. In a dispersed state, the layered clay mineral can be easily dispersed without generating aggregates by adding it to an aqueous dispersion of an acrylic copolymer having a specific monomer composition. The inventors have found that a water-dispersed acrylic pressure-sensitive adhesive composition exhibiting necessary adhesive strength and exhibiting adhesive properties with high cohesive strength and excellent heat resistance and water resistance can be obtained, and the present invention has been completed.
すなわち、本発明は、（ａ）炭素数４〜１４個のアルキルアルコールの（メタ）アクリル酸アルキルエステルを主成分とするビニル系モノマー９０〜９９重量％と極性基含有モノマー１０〜１重量％とのアクリル系共重合体の水分散体中に、上記アクリル系共重合体１００重量部あたり、（ｂ）親油性の層状粘土鉱物２〜２０重量部が、（ｃ）酸性かつ疎水性である界面活性剤１〜１０重量部の存在下、分散されている水分散型アクリル系粘着剤組成物の製造方法において、（ｂ）成分の親油性の層状粘土鉱物を水に膨潤させ、これに（ｃ）成分の酸性かつ疎水性である界面活性剤を加えて分散させ、これを（ａ）成分の水分散体中に加えて混合分散させることを特徴とする水分散型アクリル系粘着剤組成物の製造方法に係るものである。
特に、本発明は、（ｂ）成分の親油性の層状粘土鉱物がスメクタイト系である上記構成の水分散型アクリル系粘着剤組成物の製造方法、（ｂ）成分の親油性の層状粘土鉱物が水酸基含有の４級アンモニウム塩を含む上記構成の水分散型アクリル系粘着剤組成物の製造方法、（ｃ）成分の酸性かつ疎水性である界面活性剤がスチレン−マレイン酸共重合体の部分エステル化物である上記構成の水分散型アクリル系粘着剤組成物の製造方法を提供できるものである。
That is, the present invention includes (a) 90 to 99% by weight of a vinyl-based monomer having a main component of a (meth) acrylic acid alkyl ester of an alkyl alcohol having 4 to 14 carbon atoms and 10 to 1% by weight of a polar group-containing monomer. In an aqueous dispersion of the acrylic copolymer, (b) 2-20 parts by weight of a lipophilic layered clay mineral per 100 parts by weight of the acrylic copolymer, (c) an interface that is acidic and hydrophobic In the method for producing a water-dispersed acrylic pressure-sensitive adhesive composition dispersed in the presence of 1 to 10 parts by weight of an activator, the lipophilic layered clay mineral (b) is swollen in water, and (c A water-dispersible acrylic pressure-sensitive adhesive composition comprising: (1) an acidic and hydrophobic surfactant as a component and dispersing; and (3) adding and dispersing the component in an aqueous dispersion of component (a). It relates to a manufacturing method .
In particular, the present invention relates to a method for producing a water-dispersed acrylic pressure-sensitive adhesive composition having the above structure, wherein the lipophilic layered clay mineral of component (b) is a smectite system, and the lipophilic layered clay mineral of component (b) A method for producing a water-dispersed acrylic pressure-sensitive adhesive composition having the above-described structure containing a hydroxyl group-containing quaternary ammonium salt, and (c) component acidic and hydrophobic surfactant is a partial ester of a styrene-maleic acid copolymer It is possible to provide a method for producing a water-dispersed acrylic pressure-sensitive adhesive composition having the above structure, which is a chemical compound.
このように、本発明は、水分散型粘着剤組成物中に層状粘土鉱物を凝集物を発生することなく簡単に分散させることができ、これにより被着体に対して必要な粘着力を示すと共に、高凝集力で耐熱性や耐水性に優れた接着特性を発揮する粘着テープや粘着シート等を作製できる水分散型アクリル系粘着剤組成物を得ることができる。
As described above, the present invention can easily disperse the layered clay mineral in the water-dispersed pressure-sensitive adhesive composition without generating aggregates, thereby exhibiting the necessary adhesive force to the adherend. At the same time, it is possible to obtain a water-dispersed acrylic pressure-sensitive adhesive composition capable of producing a pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet that exhibits high cohesive strength and excellent heat resistance and water resistance.
本発明において、（ａ）成分のアクリル系共重合体の水分散体は、炭素数４〜１４個のアルキルアルコールの（メタ）アクリル酸アルキルエステルを主成分とするビニル系モノマーと極性基含有モノマーとのモノマー混合物を、通常の水分散重合法、例えば、乳化重合法、懸濁重合法等により共重合させることにより、得られるものである。
この水分散体におけるアクリル系共重合体の平均粒径は、特に限定されないが、テープ化した際に良好な特性を得るため、適宜の範囲に設定されているのが望ましい。例えば、乳化重合法では０．１〜５０μｍ、好適には０．２〜１μｍ、懸濁重合法では１〜１００μｍ、好適には１０〜８０μｍであるのがよい。
In the present invention, the aqueous dispersion of the acrylic copolymer of the component (a) is composed of a vinyl monomer and a polar group-containing monomer, the main component of which is a (meth) acrylic acid alkyl ester of an alkyl alcohol having 4 to 14 carbon atoms. Is obtained by copolymerizing the monomer mixture with a conventional water dispersion polymerization method such as an emulsion polymerization method or a suspension polymerization method.
The average particle size of the acrylic copolymer in the aqueous dispersion is not particularly limited, but is desirably set within an appropriate range in order to obtain good characteristics when taped. For example, the emulsion polymerization method may be 0.1 to 50 μm, preferably 0.2 to 1 μm, and the suspension polymerization method may be 1 to 100 μm, preferably 10 to 80 μm.
モノマー混合物において、ビニル系モノマーの主成分である炭素数４〜１４個のアルキルアルコールの（メタ）アクリル酸アルキルエステルには、ブチル基、イソブチル基、ペンチル基、イソペンチル基、ヘキシル基、ヘプチル基、オクチル基、イソオクチル基、ノニル基、イソノニル基、デシル基、イソデシル基等のアルキル基を有するアクリル酸またはメタクリル酸のアルキルエステルが挙げられる。
これらのモノマーのほかに、モノマー全体の３０重量％以下の割合で、共重合可能な他のビニル系モノマーを併用してもよい。具体的には、上記炭素数以外のアルキルアルコールの（メタ）アクリル酸アルキルエステルや、酢酸ビニル、スチレンやその誘導体、（メタ）アクリロニトリル、（メタ）アクリルアミド等が挙げられる。
上記のビニル系モノマーと共に、必須成分として用いられる極性基含有モノマーには、（メタ）アクリル酸、イタコン酸、２−アクリルアミドプロパンスルホン酸等のカルボキシル基含有モノマー、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート等の水酸基含有モノマー等が挙げられる。
In the monomer mixture, the alkyl methacrylate (meth) acrylic acid alkyl ester having 4 to 14 carbon atoms, which is the main component of the vinyl monomer, includes a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, Examples thereof include alkyl esters of acrylic acid or methacrylic acid having an alkyl group such as an octyl group, an isooctyl group, a nonyl group, an isononyl group, a decyl group, and an isodecyl group.
In addition to these monomers, other copolymerizable vinyl monomers may be used in combination at a ratio of 30% by weight or less of the total monomers. Specific examples include (meth) acrylic acid alkyl esters of alkyl alcohols other than the above carbon number, vinyl acetate, styrene and its derivatives, (meth) acrylonitrile, (meth) acrylamide, and the like.
Along with the above vinyl monomers, polar group-containing monomers used as essential components include (meth) acrylic acid, itaconic acid, carboxyl group-containing monomers such as 2-acrylamidopropanesulfonic acid, 2-hydroxyethyl (meth) acrylate, Examples thereof include hydroxyl group-containing monomers such as 2-hydroxypropyl (meth) acrylate.
モノマー混合物において、炭素数４〜１４個のアルキルアルコールの（メタ）アクリル酸アルキルエステルを主成分とするビニル系モノマーと極性基含有モノマーとの使用割合は、前者のビニル系モノマーが９０〜９９重量％、特に好ましくは９４〜９８重量％で、後者の極性基含有モノマーが１０〜１重量％、特に好ましくは６〜２重量％であるのがよい。後者の極性基含有モノマーが１重量％未満となると層状粘土鉱物との十分な相互作用が得られず、高凝集力で耐熱性等に優れる接着特性を発現させにくく、また１０重量％を超えると増粘し、やはり好ましい特性が得られにくい。
In the monomer mixture, the proportion of the vinyl monomer having the main component of the alkyl alcohol (meth) acrylic acid alkyl ester having 4 to 14 carbon atoms and the polar group-containing monomer is 90 to 99 wt. %, Particularly preferably 94 to 98% by weight, the latter polar group-containing monomer being 10 to 1% by weight, particularly preferably 6 to 2% by weight. When the latter polar group-containing monomer is less than 1% by weight, sufficient interaction with the layered clay mineral cannot be obtained, and it is difficult to exhibit adhesive properties such as high cohesive force and excellent heat resistance, and when it exceeds 10% by weight. It thickens and it is difficult to obtain desirable characteristics.
本発明において、（ｂ）成分の親油性の層状粘土鉱物は、結晶構造中に交換性陽イオンを有する層状珪酸塩鉱物を親油化処理したものが好ましく用いられる。
層状珪酸塩鉱物には、モンモリロナイト、サポナイト、ヘクトライト スチーブンサイト等のスメクタイト系粘土鉱物、フッ素四ケイ素雲母等のマイカ系粘土鉱物が挙げられ、１種または２種以上を併用することができる。これらの中でも、スメクタイト系粘土鉱物が特に好ましく用いられる。
層状珪酸塩の形状は、厚さが約１ｎｍ、幅（縦横）がそれぞれ１０〜１，０００ｎｍの板状である。その平均長は、幅の長さの平均長を意味し、この平均長は、粘着剤組成物の電子顕微鏡（ＴＥＭ）写真により、実測して求めることができる。
In the present invention, as the lipophilic layered clay mineral of component (b), a layered silicate mineral having an exchangeable cation in the crystal structure is preferably used.
Examples of layered silicate minerals include smectite clay minerals such as montmorillonite, saponite, and hectorite stevensite, and mica clay minerals such as fluorite tetrasilicon mica, and one or more of them can be used in combination. Among these, smectite clay minerals are particularly preferably used.
The shape of the layered silicate is a plate shape having a thickness of about 1 nm and a width (length and width) of 10 to 1,000 nm, respectively. The average length means the average length of the width, and this average length can be obtained by actual measurement from an electron microscope (TEM) photograph of the pressure-sensitive adhesive composition.
結晶構造中に交換性陽イオンを有する層状珪酸塩鉱物は、層間の交換性陽イオンを有機カチオン等でイオン交換処理し、層間を親油化する必要がある。
上記の交換性陽イオンとは、層状珪酸塩鉱物の結晶層の表面に存在するナトリウムやカリウム等の金属イオンのことである。これらのイオンは親水性であるため、親油性の粘着剤ポリマーは層状珪酸塩鉱物の層間に侵入することができず、良好な分散物を得ることが難しい。粘着剤ポリマーを層間に侵入させるためには、交換性陽イオンを親油性のカチオン性界面活性剤等でイオン交換することが必要である。
The layered silicate mineral having an exchangeable cation in the crystal structure needs to exchange the exchangeable cation between layers with an organic cation or the like to make the interlayer lipophilic.
The exchangeable cation is a metal ion such as sodium or potassium existing on the surface of the crystal layer of the layered silicate mineral. Since these ions are hydrophilic, the lipophilic pressure-sensitive adhesive polymer cannot penetrate between the layers of the layered silicate mineral, and it is difficult to obtain a good dispersion. In order for the pressure-sensitive adhesive polymer to enter between the layers, it is necessary to ion-exchange the exchangeable cation with a lipophilic cationic surfactant or the like.
このような目的で用いられるカチオン性界面活性剤には、例えば、４級アンモニウム塩や４級ホスニウム塩等があり、その１種または２種以上が用いられる。特に好ましくは、水酸基含有の４級アンモニウム塩が用いられる。
水酸基含有の４級アンモニウム塩には、例えば、プロピレンオキサイド骨格を有する４級アンモニウム塩が挙げられる。有機化処理剤に水酸基を含有することにより、水に分散させることが可能であり、またアクリル系共重合体を構成する極性基含有モノマーと相互作用して、分散性を改善したり、耐熱性を付与することができる。
Cationic surfactants used for such purposes include, for example, quaternary ammonium salts and quaternary phosnium salts, and one or more of them are used. Particularly preferably, a hydroxyl group-containing quaternary ammonium salt is used.
Examples of the hydroxyl group-containing quaternary ammonium salt include a quaternary ammonium salt having a propylene oxide skeleton. By containing a hydroxyl group in the organic treatment agent, it can be dispersed in water, and it interacts with the polar group-containing monomer constituting the acrylic copolymer to improve dispersibility and heat resistance. Can be granted.
このように構成される（ｂ）成分の親油性の層状粘土鉱物は、塩基性で疎水性の性質を有するが、両性質は、以下の方法で確認することができる。
疎水性の性質については、層状粘土鉱物の表面エネルギーを指標として評価することで確認できる。すなわち、この評価方法は、種々の濃度の水／アセトン混合溶液を準備し、それらの溶液上に層状粘土鉱物の粉体を落として、この粉体が濡れて分散沈降し始める溶液の表面張力を粉体の表面エネルギーとし、水の表面張力７３ｍＮ／ｍ以上のものを親水性、未満のものを疎水性と、評価するものである。
The (b) component lipophilic layered clay mineral constituted as described above has basic and hydrophobic properties, and both properties can be confirmed by the following methods.
The hydrophobic property can be confirmed by evaluating the surface energy of the layered clay mineral as an index. That is, in this evaluation method, water / acetone mixed solutions having various concentrations are prepared, and a layered clay mineral powder is dropped on these solutions, and the surface tension of the solution that begins to wet and disperse and settle. The surface energy of the powder is evaluated as water having a surface tension of 73 mN / m or more as hydrophilic and less than water as hydrophobic.
塩基性の性質については、以下のように評価することにより、確認できる。
まず、層状粘土鉱物の粉体（０．１〜１０ｇから異なる重量３点）と、０．０１Ｎの過塩素酸のメチルイソブチルケトン（ＭＩＢＫ）溶液３０ｍｌを、５０ｍｌスクリュー缶瓶に測りとり、超音波洗浄器（ＢＲＡＮＳＯＮ ２２１０）で１時間超音波分散させる。この分散液から粉体を遠心分離して得た上澄み液１０ｍｌを、ＭＩＢＫ１００ｍｌで希釈したのち、０．０１Ｎのテトラブチルアンモニウムヒドロキシド（ＴＢＨＡ）のＭＩＢＫ溶液で滴定（逆滴定）して、粉体表面の塩基で消費された過塩素酸の量を求め、測定した粉体量とその過塩素酸消費量をプロットした傾きから、粉体単位重量あたりの塩基量を決定する。
The basic property can be confirmed by evaluating as follows.
First, a layered clay mineral powder (3 weights different from 0.1 to 10 g) and 30 ml of 0.01N methyl isobutyl ketone (MIBK) solution of perchloric acid were weighed into a 50 ml screw can bottle. Disperse ultrasonically with a scrubber (BRANSON 2210) for 1 hour. 10 ml of the supernatant obtained by centrifuging the powder from this dispersion is diluted with 100 ml of MIBK and then titrated (back titration) with a MIBK solution of 0.01 N tetrabutylammonium hydroxide (TBHA) to obtain a powder. The amount of perchloric acid consumed by the surface base is determined, and the amount of base per unit weight of the powder is determined from the measured powder amount and the slope of the perchloric acid consumption plotted.
つぎに、層状粘土鉱物の粉体（０．１〜１０ｇから異なる重量３点）と、０．０１ＮのＴＢＨＡのＭＩＢＫ溶液３０ｍｌを、５０ｍｌスクリュー缶瓶に測りとり、上記の塩基量測定と同様の操作を行って得た上澄み液１０ｍｌを、０．０１Ｎの過塩素酸のＭＩＢＫ溶液で滴定して、粉体表面の酸で消費されたＴＢＨＡの量を求め、測定した粉体量とそのＴＢＨＡ消費量をプロットした傾きから、粉体単位重量あたりの酸量を決定する。
このように決定した塩基量と酸量とを比較し、酸量が多ければ酸性、塩基量が多ければ塩基性と、評価するものである。なお、上記の塩基量と酸量の決定において、滴定は、自動滴定装置（平沼ＣＯＭＴＩＴＥ−５５０）にてガラス電極（指示電極ＲＥ−２０１／参照電極ＧＥ−１０１）を用いて行うことができる。
Next, a layered clay mineral powder (3 weights different from 0.1 to 10 g) and 30 ml of 0.01N TBHA MIBK solution were weighed into a 50 ml screw can bottle, and the same amount of base as above was measured. 10 ml of the supernatant obtained by the operation was titrated with a MIBK solution of 0.01 N perchloric acid to determine the amount of TBHA consumed by the acid on the powder surface, and the measured powder amount and its TBHA consumption The acid amount per unit weight of the powder is determined from the slope of the plotted amount.
The base amount determined in this way and the acid amount are compared, and the acidity is evaluated when the acid amount is large, and the basicity is evaluated when the base amount is large. In the determination of the amount of base and the amount of acid, titration can be performed using a glass electrode (indicating electrode RE-201 / reference electrode GE-101) with an automatic titration apparatus (Hiranuma COMMITE-550).
本発明において、（ｂ）成分の親油性の層状粘土鉱物の使用量は、（ａ）成分の水分散体を構成するアクリル系共重合体１００重量部あたり、２〜２０重量部、好ましくは３〜１５重量部、さらに好ましくは４〜１０重量部するのがよい。（ｂ）成分の層状粘土鉱物が２重量部未満となると、この層状粘土鉱物に基づく効果、つまり、高凝集力で耐熱性や耐水性などに優れる接着特性を発揮させにくくなり、また２０重量部を超えると、粘着剤組成物が増粘して、塗布外観が低下する等の不具合が生じやすい。
In the present invention, the amount of the (b) component lipophilic layered clay mineral used is 2 to 20 parts by weight, preferably 3 parts per 100 parts by weight of the acrylic copolymer constituting the aqueous dispersion of the component (a). -15 parts by weight, more preferably 4-10 parts by weight. When the amount of the layered clay mineral (b) is less than 2 parts by weight, it becomes difficult to exhibit the effects based on the layered clay mineral, that is, high cohesive force and excellent adhesive properties such as heat resistance and water resistance, and 20 parts by weight. Exceeding the viscosity tends to increase the viscosity of the pressure-sensitive adhesive composition and cause problems such as deterioration in coating appearance.
本発明において、（ｃ）成分の酸性で疎水性である界面活性剤は、上記した（ｂ）成分の層状粘土鉱物が塩基性で疎水性の性質を示すことから、この（ｂ）成分の層状粘土鉱物との相互作用により、この層状粘土鉱物をアクリル系共重合体の水分散体中に凝集物を発生させることなく良好に分散させる働きを有している。
これに対し、酸性で親水性である界面活性剤、塩基性で疎水性である界面活性剤、塩基性で親水性である界面活性剤等を用いると、上記のような（ｂ）成分の層状粘土鉱物との相互作用を期待できず、この層状粘土鉱物をアクリル系共重合体の水分散体中に分散させるのが難しくなり、凝集物を多く発生させやすい。
In the present invention, the acidic and hydrophobic surfactant of component (c) is a layered layer of component (b) because the layered clay mineral of component (b) described above exhibits basic and hydrophobic properties. Due to the interaction with the clay mineral, the layered clay mineral has a function of satisfactorily dispersing the layered clay mineral in the aqueous dispersion of the acrylic copolymer without generating aggregates.
On the other hand, when an acidic and hydrophilic surfactant, a basic and hydrophobic surfactant, a basic and hydrophilic surfactant, and the like are used, the layered state of the component (b) is as described above. The interaction with the clay mineral cannot be expected, and it becomes difficult to disperse the layered clay mineral in the aqueous dispersion of the acrylic copolymer, so that many aggregates are likely to be generated.
（ｃ）成分の界面活性剤としては、酸性で疎水性である限り、公知の種々の界面活性剤を使用することができるが、特に、スチレン−マレイン酸共重合体の部分エステル化物が好ましく用いられる。このような部分エステル化物の市販品としては、例えば、荒川化学工業（株）製の「アラスター７０３Ｓ」等が挙げられる。
このような（ｃ）成分の界面活性剤の使用量は、（ａ）成分の水分散体を構成するアクリル系共重合体１００重量部あたり、１〜１０重量部、好適には２〜５重量部であるのがよい。（ｃ）成分の界面活性剤が１重量部未満となると、分散性の改善効果が十分に得られず、凝集物が発生しやすくなり、１０重量部を超えると、初期の粘着力が低下したり、高凝集力で耐熱性や耐水性に優れた接着特性を発現させにくい。
As the surfactant of component (c), various known surfactants can be used as long as they are acidic and hydrophobic, and in particular, a partially esterified product of a styrene-maleic acid copolymer is preferably used. It is done. As a commercially available product of such a partially esterified product, for example, “Alastor 703S” manufactured by Arakawa Chemical Industries, Ltd. may be mentioned.
The amount of the component (c) surfactant used is 1 to 10 parts by weight, preferably 2 to 5 parts by weight per 100 parts by weight of the acrylic copolymer constituting the aqueous dispersion of the component (a). Good part. When the surfactant of component (c) is less than 1 part by weight, the effect of improving dispersibility cannot be sufficiently obtained, and aggregates tend to be generated. It is difficult to develop adhesive properties with high cohesion and excellent heat resistance and water resistance.
本発明においては、（ａ）成分のアクリル系共重合体の水分散体中に、（ｂ）成分の親油性の層状粘土鉱物が、（ｃ）成分の酸性で疎水性である界面活性剤の存在下、凝集物を発生することなく分散されてなる水分散型アクリル系粘着剤組成物を得る。
このような水分散型アクリル系粘着剤組成物は、（ａ）成分のアクリル系共重合体の水分散体中に（ｂ）成分の親油性の層状粘土鉱物と（ｃ）成分の酸性で疎水性である界面活性剤とをただ単に添加混合するだけでは、得られない。すなわち、このような方法では、層状粘土鉱物を良好に分散できず、凝集物の発生をさけられない。
In the present invention, the lipophilic layered clay mineral of component (b) is an acidic and hydrophobic surfactant of component (c) in the aqueous dispersion of the acrylic copolymer of component (a). In the presence, a water-dispersed acrylic pressure-sensitive adhesive composition that is dispersed without generating aggregates is obtained.
Such a water-dispersed acrylic pressure-sensitive adhesive composition comprises (b) a lipophilic layered clay mineral (c) and an acidic and hydrophobic component (c) in an aqueous dispersion of the acrylic copolymer (a). It cannot be obtained simply by adding and mixing with a surfactant which is a functional substance. That is, in such a method, the layered clay mineral cannot be dispersed well and the generation of aggregates cannot be avoided.
本発明者らは、この問題を克服するために、鋭意検討した結果、最初に、（ｂ）成分の親油性の層状粘土鉱物の前記所定量を水に膨潤させ、これに（ｃ）成分の酸性で疎水性である界面活性剤の前記所定量を加えて分散させ、つぎに、この分散液を（ａ）成分のアクリル系共重合体の水分散体中に加えて混合分散させると、上記（ｂ）成分の親油性の層状粘土鉱物の均一分散化がはかられ、凝集物の発生がみられない水分散型アクリル系粘着剤組成物の製造が可能となることを見出したものである。
As a result of intensive studies to overcome this problem, the present inventors first swollen the predetermined amount of the lipophilic layered clay mineral of component (b) in water, When the predetermined amount of the surfactant that is acidic and hydrophobic is added and dispersed, then this dispersion is added to the aqueous dispersion of the acrylic copolymer of component (a) and mixed and dispersed. It has been found that the water-dispersible acrylic pressure-sensitive adhesive composition in which the lipophilic layered clay mineral (b) is uniformly dispersed and no agglomerates are produced can be produced. .
具体的には、最初に、水１００重量部あたり、（ｂ）成分の親油性の層状粘土鉱物１〜２０重量部を加えて、十分に膨潤させ、層状粘土鉱物の層間距離を広げて分散しやすくする。この膨潤後、（ｃ）成分の酸性で疎水性である界面活性剤を加えて、超音波分散機等のハイパワー分散機により、層状粘土鉱物の層間を剥離する。層状粘土鉱物のシリケート層の平均重なりが６層以下になるまで分散するのが好ましい。６層を超えると層状粘土鉱物の総表面積が低下し、有機成分との相互作用が低下して、粘着剤の強靭性が低下する。平均重なりの分析は、電子顕微鏡（ＴＥＭ）にて行うことができる。
つぎに、このように層状粘土鉱物を分散させた分散液を、（ａ）成分のアクリル系共重合体の水分散体中に加えて混合分散するが、その際、超音波分散機等のハイパワー分散機で分散すると、機械的安定性の悪い上記水分散体の場合、凝集物が発生するおそれがあるため、上記のような強力な分散機は使用しない方が好ましい。
Specifically, first, 1 to 20 parts by weight of the lipophilic layered clay mineral (b) component is added per 100 parts by weight of water, and the mixture is sufficiently swollen to disperse the layered clay mineral by increasing the interlayer distance. Make it easier. After this swelling, an acidic and hydrophobic surfactant of component (c) is added, and the layers of the layered clay mineral are peeled off by a high power disperser such as an ultrasonic disperser. It is preferable to disperse until the average overlap of the silicate layers of the layered clay mineral is 6 layers or less. When it exceeds six layers, the total surface area of the layered clay mineral is reduced, the interaction with the organic component is reduced, and the toughness of the pressure-sensitive adhesive is reduced. The average overlap analysis can be performed with an electron microscope (TEM).
Next, the dispersion liquid in which the layered clay mineral is dispersed in this way is added to the aqueous dispersion of the acrylic copolymer of the component (a) and mixed and dispersed. When dispersed with a power disperser, in the case of the above-mentioned aqueous dispersion having poor mechanical stability, aggregates may be generated. Therefore, it is preferable not to use a powerful disperser as described above.
このように製造される水分散型アクリル系粘着剤組成物において、（ａ）成分のアクリル系共重合体を構成するモノマー組成中、極性基含有モノマーの割合が低いと、破断伸びが低下する傾向がある。この場合、カップリング剤を添加すると、上記破断伸びを向上できるので、望ましい。この理由は、カップリング剤が層状粘土鉱物と有機成分との分子レベルの相互反応を手助けする役割を果たすためと思われる。
カップリング剤は、特に限定されないが、分子中に２個以上の異なった反応基を持つ有機珪素単量体が好ましく用いられる。２個の反応基の一つは無機質と化学結合する反応基であり、もう一つは有機材料と化学結合する反応基である。
上記の無機質と化学結合する反応基としては、メトキシ基、エトキシ基、シラノール基等があり、また有機材料と化学結合する反応基としては、ビニル基、エポキシ基、メタクリル基、アミノ基、メルカプト基等がある。
In the water-dispersed acrylic pressure-sensitive adhesive composition produced in this manner, the elongation at break tends to decrease when the proportion of the polar group-containing monomer is low in the monomer composition constituting the acrylic copolymer of component (a). There is. In this case, it is desirable to add a coupling agent because the elongation at break can be improved. The reason seems to be that the coupling agent plays a role in assisting the molecular level interaction between the layered clay mineral and the organic component.
The coupling agent is not particularly limited, but an organosilicon monomer having two or more different reactive groups in the molecule is preferably used. One of the two reactive groups is a reactive group that chemically bonds to an inorganic substance, and the other is a reactive group that chemically bonds to an organic material.
Examples of reactive groups that chemically bond with the above inorganic materials include methoxy groups, ethoxy groups, and silanol groups, and reactive groups that chemically bond with organic materials include vinyl groups, epoxy groups, methacryl groups, amino groups, and mercapto groups. Etc.
このようなシランカップリング剤としては、ビニルトリクロルシラン、ビニルトリス（β−メトキシエトキシ）シラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリメトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−クロロプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−メタクリロキシプロピルメチルジエトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリメトキシシラン等が挙げられる。
Examples of such silane coupling agents include vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxy (Cyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- ( Aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ- Glycid Xylpropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, etc. Is mentioned.
本発明においては、これらのカップリング剤の中から、その１種または２種以上を選択して使用できるが、その選択は、（ａ）成分のアクリル系共重合体との相溶性、増粘性、ゲル化の有無等を考慮して、適宜決定すればよい。
このようなカップリング剤は、（ａ）成分のアクリル系共重合体１００重量部あたり、０〜３重量部、好ましくは０．０５〜０．８重量部、より好ましくは０．１〜０．５重量部とするのがよい。過多になると、粘着力が低下する傾向がある。
In the present invention, one or two or more of these coupling agents can be selected and used. The selection is based on compatibility with the acrylic copolymer of the component (a) and viscosity increase. It may be appropriately determined in consideration of the presence or absence of gelation.
Such a coupling agent is used in an amount of 0 to 3 parts by weight, preferably 0.05 to 0.8 parts by weight, and more preferably 0.1 to 0.00 parts by weight per 100 parts by weight of the acrylic copolymer of component (a). The amount is preferably 5 parts by weight. When it is excessive, the adhesive strength tends to decrease.
本発明の水分散型アクリル系粘着剤組成物は、これを紙、織布、不織布、プラスチックフィルム、金属箔、発泡シートなどの支持体、あるいはこれらに剥離処理を施した支持体の片面または両面に塗布し、乾燥して、所望厚さの粘着剤層を形成することにより、粘着テープや粘着シート等の各種の粘着製品とすることができる。
The water-dispersed acrylic pressure-sensitive adhesive composition of the present invention comprises a support such as paper, woven fabric, non-woven fabric, plastic film, metal foil, foamed sheet, or one or both sides of a support subjected to a release treatment. It can be set as various adhesive products, such as an adhesive tape and an adhesive sheet, by apply | coating and drying and forming the adhesive layer of desired thickness.
つぎに、本発明の実施例を記載して、より具体的に説明する。なお、以下において、部とあるのは重量部を意味するものとする。なおまた、以下において、％とあるのは特に断らない限り重量％を意味するものとする。
Next, examples of the present invention will be described in more detail. In the following, “parts” means parts by weight. In the following, “%” means “% by weight” unless otherwise specified.
冷却管、窒素導入管、温度計および撹拌機を備えた反応容器を用い、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メトキシシラン（架橋剤）（信越シリコーン社製「ＫＢＭ−５０３」）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（重合開始剤）０．１部を、ポリオキシエチレンラウリル硫酸ナトリウム（乳化剤）１．５部を添加した水１００部に加えて、乳化重合した。これに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体を得た。
また、親水性のスメクタイト系層状粘土鉱物をプロピレンオキサイド骨格を有する４級アンモニュウム塩で有機化処理して層間を親油化した層状粘土鉱物（コープケミカル社製の「ルーセンタイトＳＰＮ」）３部を２７部のイオン交換水に２４時間浸漬して膨潤させたのち、これにスチレン−マレイン酸共重合体の部分エステル化物からなる酸性で疎水性である界面活性剤（荒川化学工業社製「アラスター７０３Ｓ」）１部を添加し、超音波分散機（ホモジナイザー）にて１０分間分散を行い、層状粘土鉱物の分散液を得た。
上記のアクリル系共重合体の水分散体２００部に対して、上記の層状粘土鉱物の分散液３１部を加えて、ホモミキサーにより撹拌混合して、水分散型アクリル系粘着剤組成物を調製した。つぎに、この水分散型アクリル系粘着剤組成物を、シリコーン系剥離剤を塗布した剥離ライナー上に塗工し、１２０℃で３分乾燥して、厚さが５０μｍの粘着剤層を形成することにより、粘着シートを作製した。
Using a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer and a stirrer, 95 parts of butyl acrylate, 5 parts of acrylic acid, 3-methacryloyloxypropyltrimethoxysilane (crosslinking agent) (“KBM” manufactured by Shin-Etsu Silicone Co., Ltd.) -503 ") 0.05 part, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride (polymerization initiator) 0.1 part, polyoxyethylene lauryl In addition to 100 parts of water to which 1.5 parts of sodium sulfate (emulsifier) was added, emulsion polymerization was performed. 10% ammonium water was added thereto to adjust the pH to 8 to obtain an aqueous dispersion of an acrylic copolymer.
In addition, 3 parts of a layered clay mineral (“Lucentite SPN” manufactured by Coop Chemical Co., Ltd.) obtained by organically treating a hydrophilic smectite-based layered clay mineral with a quaternary ammonium salt having a propylene oxide skeleton to make the layer lipophilic After being immersed in 27 parts of ion-exchanged water for 24 hours and then swollen, an acidic and hydrophobic surfactant made of a partially esterified product of a styrene-maleic acid copolymer ("Alaster 703S" manufactured by Arakawa Chemical Industries, Ltd.). ") 1 part was added and dispersed for 10 minutes with an ultrasonic disperser (homogenizer) to obtain a dispersion of layered clay mineral.
The aqueous dispersion acrylic pressure-sensitive adhesive composition is prepared by adding 31 parts of the layered clay mineral dispersion to 200 parts of the acrylic copolymer aqueous dispersion and stirring and mixing with a homomixer. did. Next, this water-dispersed acrylic pressure-sensitive adhesive composition is applied onto a release liner coated with a silicone-based release agent and dried at 120 ° C. for 3 minutes to form a pressure-sensitive adhesive layer having a thickness of 50 μm. Thus, an adhesive sheet was produced.
層間を親油化した層状粘土鉱物（実施例１と同じもの）１０部を９０部のイオン交換水に２４時間浸漬して膨潤させたのち、これにスチレン−マレイン酸共重合体の部分エステル化物からなる酸性で疎水性である界面活性剤（実施例１と同じもの）３部を添加し、実施例１と同様に分散を行い、層状粘土鉱物の分散液を得た。
実施例１で得たアクリル系共重合体の水分散体２００部に対して、上記の層状粘土鉱物の分散液１０３部を加えて、ホモミキサーにより撹拌混合して、水分散型アクリル系粘着剤組成物を調製した。つぎに、この水分散型アクリル系粘着剤組成物を用いて、実施例１と同様にして、粘着シートを作製した。
After 10 parts of a layered clay mineral (same as in Example 1) with lipophilic layers were immersed in 90 parts of ion-exchanged water for 24 hours to swell, this was partially esterified with a styrene-maleic acid copolymer. 3 parts of an acidic and hydrophobic surfactant (same as in Example 1) was added and dispersed in the same manner as in Example 1 to obtain a layered clay mineral dispersion.
To 200 parts of the acrylic copolymer aqueous dispersion obtained in Example 1, 103 parts of the above-mentioned layered clay mineral dispersion was added and stirred and mixed with a homomixer to obtain a water-dispersed acrylic pressure-sensitive adhesive. A composition was prepared. Next, a pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 using this water-dispersed acrylic pressure-sensitive adhesive composition.
層間を親油化した層状粘土鉱物（実施例１と同じもの）１５部を１００部のイオン交換水に２４時間浸漬して膨潤させたのち、これにスチレン−マレイン酸共重合体の部分エステル化物からなる酸性で疎水性である界面活性剤（実施例１と同じもの）５部を添加し、実施例１と同様に分散を行い、層状粘土鉱物の分散液を得た。
実施例１で得たアクリル系共重合体の水分散体２００部に対して、上記の層状粘土鉱物の分散液１２０部を加えて、ホモミキサーにより撹拌混合して、水分散型アクリル系粘着剤組成物を調製した。つぎに、この水分散型アクリル系粘着剤組成物を用いて、実施例１と同様にして、粘着シートを作製した。
After 15 parts of layered clay mineral (same as in Example 1) having lipophilic layers were immersed in 100 parts of ion exchange water for 24 hours to swell, this was partially esterified with a styrene-maleic acid copolymer. 5 parts of an acidic and hydrophobic surfactant (same as in Example 1) was added and dispersed in the same manner as in Example 1 to obtain a layered clay mineral dispersion.
To 200 parts of the acrylic copolymer aqueous dispersion obtained in Example 1, 120 parts of the above-mentioned layered clay mineral dispersion was added and stirred and mixed with a homomixer to obtain a water-dispersed acrylic pressure-sensitive adhesive. A composition was prepared. Next, a pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 using this water-dispersed acrylic pressure-sensitive adhesive composition.
比較例１
アクリル酸ブチル９５部およびアクリル酸５部を、アクリル酸ブチル１００部に変更した以外は、実施例１と同様にして、アクリル系共重合体の水分散体を得た。
このアクリル系共重合体の水分散体２００部に対して、実施例２で得た層状粘土鉱物の分散液１０３部を加えて、ホモミキサーにより撹拌混合して、水分散型アクリル系粘着剤組成物を調製した。つぎに、この水分散型アクリル系粘着剤組成物を用いて、実施例１と同様にして、粘着シートを作製した。
Comparative Example 1
An aqueous dispersion of an acrylic copolymer was obtained in the same manner as in Example 1 except that 95 parts of butyl acrylate and 5 parts of acrylic acid were changed to 100 parts of butyl acrylate.
To 200 parts of this acrylic copolymer aqueous dispersion, 103 parts of the layered clay mineral dispersion obtained in Example 2 was added and stirred and mixed with a homomixer to obtain a water-dispersed acrylic pressure-sensitive adhesive composition. A product was prepared. Next, a pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 using this water-dispersed acrylic pressure-sensitive adhesive composition.
比較例２
層間を親油化した層状粘土鉱物（実施例１と同じもの）１０部を９０部のイオン交換水に２４時間浸漬して膨潤させ、これにスチレン−マレイン酸共重合体の部分エステル化物からなる酸性で疎水性である界面活性剤を添加することなく、超音波分散機（ホモジナイザー）にて１０分間分散を行い、層状粘土鉱物の分散液を得た。
実施例１で得たアクリル系共重合体の水分散体２００部に対して、上記の層状粘土鉱物の分散液１００部を加えて、ホモミキサーにより撹拌混合して、水分散型アクリル系粘着剤組成物を調製した。つぎに、この水分散型アクリル系粘着剤組成物を用いて、実施例１と同様にして、粘着シートを作製した。
Comparative Example 2
10 parts of a layered clay mineral (same as in Example 1) with lipophilic layers were immersed in 90 parts of ion-exchanged water for 24 hours to swell, and this consisted of a partially esterified product of a styrene-maleic acid copolymer. Without adding an acidic and hydrophobic surfactant, dispersion was performed for 10 minutes with an ultrasonic disperser (homogenizer) to obtain a dispersion of a layered clay mineral.
To 200 parts of the acrylic copolymer aqueous dispersion obtained in Example 1, 100 parts of the above-mentioned layered clay mineral dispersion was added and stirred and mixed with a homomixer to obtain a water-dispersed acrylic pressure-sensitive adhesive. A composition was prepared. Next, a pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 using this water-dispersed acrylic pressure-sensitive adhesive composition.
比較例３
層間を親油化した層状粘土鉱物（実施例１と同じもの）１５部を１００部のイオン交換水に２４時間浸漬して膨潤させたのち、これにスチレン−マレイン酸共重合体の部分エステル化物からなる酸性で疎水性である界面活性剤（実施例１と同じもの）２０部を添加し、実施例１と同様に分散を行い、層状粘土鉱物の分散液を得た。
実施例１で得たアクリル系共重合体の水分散体２００部に対して、上記の層状粘土鉱物の分散液１３５部を加えて、ホモミキサーにより撹拌混合して、水分散型アクリル系粘着剤組成物を調製した。つぎに、この水分散型アクリル系粘着剤組成物を用いて、実施例１と同様にして、粘着シートを作製した。
Comparative Example 3
After 15 parts of layered clay mineral (same as in Example 1) having lipophilic layers were immersed in 100 parts of ion exchange water for 24 hours to swell, this was partially esterified with a styrene-maleic acid copolymer. 20 parts of an acidic and hydrophobic surfactant (same as in Example 1) was added and dispersed in the same manner as in Example 1 to obtain a layered clay mineral dispersion.
To 200 parts of the acrylic copolymer aqueous dispersion obtained in Example 1, 135 parts of the above layered clay mineral dispersion was added and stirred and mixed with a homomixer to obtain a water-dispersed acrylic pressure-sensitive adhesive. A composition was prepared. Next, a pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 using this water-dispersed acrylic pressure-sensitive adhesive composition.
比較例４
実施例１で得たアクル系共重合体の水分散体２００部に、層問を親油化した層状粘土鉱物（実施例１と同じもの）３部、イオン交換水２７部、ステレン−マレイン酸共重合体の部分エステル化物からなる酸性で疎水性である界面活性剤（実施例１と同じもの）１部を添加し、超音波分散機（ホモジナイザー）にて１０分間分散を行い、水分散型アクリル系粘着剤組成物を調製した。つぎに、この水分散型アクリル系粘着剤組成物を用いて、実施例１と同様にして、粘着シートを作製した。
Comparative Example 4
200 parts of an aqueous dispersion of an acryl copolymer obtained in Example 1, 3 parts of a layered clay mineral (same as in Example 1), 27 parts of ion-exchanged water, and stearene-maleic acid 1 part of an acidic and hydrophobic surfactant composed of a partially esterified copolymer (the same as in Example 1) was added, and dispersed for 10 minutes with an ultrasonic disperser (homogenizer). An acrylic pressure-sensitive adhesive composition was prepared. Next, a pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 using this water-dispersed acrylic pressure-sensitive adhesive composition.
比較例５
酸性で疎水性である界面活性剤（荒川化学工業社製「アラスター７０３Ｓ」）３部を、酸性で親水性である界面活性剤（花王社製「ポイズ５２１」）３部に変更した以外は、実施例２と同様にして、層状粘土鉱物の分散液を得た。
この層状粘土鉱物の分散液を使用した以外は、実施例２と同様にして、水分散型アクリル系粘着剤組成物を調製した。つぎに、この水分散型アクリル系粘着剤組成物を用いて、実施例１と同様にして、粘着シートを作製した。
Comparative Example 5
Except for changing 3 parts of an acidic and hydrophobic surfactant ("Alastor 703S" manufactured by Arakawa Chemical Industries) to 3 parts of an acidic and hydrophilic surfactant ("Poise 521" manufactured by Kao), In the same manner as in Example 2, a layered clay mineral dispersion was obtained.
A water-dispersed acrylic pressure-sensitive adhesive composition was prepared in the same manner as in Example 2 except that this layered clay mineral dispersion was used. Next, a pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 using this water-dispersed acrylic pressure-sensitive adhesive composition.
比較例６
酸性で疎水性である界面活性剤（荒川化学工業社製「アラスター７０３Ｓ」）３部を、塩基性で疎水性である界面活性剤（ウイルバーエリス社製「ＥＦＫＡ４５５」）３部に変更した以外は、実施例２と同様にして、層状粘土鉱物の分散液を得た。
この層状粘土鉱物の分散液を使用した以外は、実施例２と同様にして、水分散型アクリル系粘着剤組成物を調製した。つぎに、この水分散型アクリル系粘着剤組成物を用いて、実施例１と同様にして、粘着シートを作製した。
Comparative Example 6
Except for changing 3 parts of acidic and hydrophobic surfactant ("Alastor 703S" manufactured by Arakawa Chemical Industries) to 3 parts of basic surfactant ("EFKA455" manufactured by Wilber Ellis). In the same manner as in Example 2, a dispersion of layered clay mineral was obtained.
A water-dispersed acrylic pressure-sensitive adhesive composition was prepared in the same manner as in Example 2 except that this layered clay mineral dispersion was used. Next, a pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 using this water-dispersed acrylic pressure-sensitive adhesive composition.
比較例７
酸性で疎水性である界面活性剤（荒川化学工業社製「アラスター７０３Ｓ」）３部を、塩基性で親水性である界面活性剤（ライオン社製「ポリティＰＳ−１９００」）３部に変更した以外は、実施例２と同様にして、層状粘土鉱物の分散液を得た。
この層状粘土鉱物の分散液を使用した以外は、実施例２と同様にして、水分散型アクリル系粘着剤組成物を調製した。つぎに、この水分散型アクリル系粘着剤組成物を用いて、実施例１と同様にして、粘着シートを作製した。
Comparative Example 7
3 parts of acidic and hydrophobic surfactant (“Alastor 703S” manufactured by Arakawa Chemical Industries) was changed to 3 parts of basic surfactant (“POLYTY PS-1900” manufactured by Lion). A layered clay mineral dispersion was obtained in the same manner as Example 2 except for the above.
A water-dispersed acrylic pressure-sensitive adhesive composition was prepared in the same manner as in Example 2 except that this layered clay mineral dispersion was used. Next, a pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 using this water-dispersed acrylic pressure-sensitive adhesive composition.
比較例８
実施例１で得たアクリル系共重合体の水分散体を、これに層状粘土鉱物の分散液を添加することなく、水分散型アクリル系粘着剤組成物とした。つぎに、この水分散型アクリル系粘着剤組成物を用いて、実施例１と同様にして、粘着シートを作製した。
Comparative Example 8
The aqueous dispersion of the acrylic copolymer obtained in Example 1 was used as a water-dispersed acrylic pressure-sensitive adhesive composition without adding a layered clay mineral dispersion. Next, a pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 using this water-dispersed acrylic pressure-sensitive adhesive composition.
上記の実施例１〜３および比較例１〜８の各水分散型アクリル系粘着剤組成物につき、以下の方法で、凝集物の発生割合を調べた。また、上記の実施例１〜３および比較例１〜８の各粘着シートについて、以下の方法で、耐熱保持性、初期粘着力および耐水粘着力を調べた。これらの結果は、表１に示されるとおりであった。
About each water dispersion type acrylic adhesive composition of said Examples 1-3 and Comparative Examples 1-8, the generation | occurrence | production ratio of the aggregate was investigated with the following method. Moreover, about each adhesive sheet of said Examples 1-3 and Comparative Examples 1-8, the heat resistant retention property, initial stage adhesive force, and water-resistant adhesive force were investigated with the following method. These results were as shown in Table 1.
＜凝集物の発生割合＞
水分散型アクリル系粘着剤組成物を、＃８０ナイロンメッシュでフィルタリングを行い、メッシュ上に残った固形分を秤量し、凝集物の発生割合を下記の式より求めた。
（凝集物の発生割合）％＝〔（メッシュ上の固形分）ｇ／（理論固形分総量）ｇ〕
×１００
<Occurrence rate of aggregate>
The water-dispersed acrylic pressure-sensitive adhesive composition was filtered with a # 80 nylon mesh, the solid content remaining on the mesh was weighed, and the generation rate of aggregates was determined from the following formula.
(Generation rate of aggregates)% = [(solid content on mesh) g / (total theoretical solid content) g]
× 100
＜耐熱保持性試験＞
厚さ０．４mm、７０mm×２５mmの大きさのアルミ板に、１５mm×１５mmに切り出した粘着シートを貼り合わせる。同サイズのアルミ板を５kgロールで、１往復して圧着して貼り合わせたのち、２３℃の雰囲気で２４時間放置後、各雰囲気温度で２kgの荷重を加えて、２時間保持可能な最高温度を調べた。
<Heat resistance retention test>
An adhesive sheet cut out to 15 mm × 15 mm is bonded to an aluminum plate having a thickness of 0.4 mm and a size of 70 mm × 25 mm. After the aluminum plate of the same size is reciprocated once with a 5kg roll and bonded together, it is left for 24 hours in an atmosphere at 23 ° C, then a 2kg load is applied at each ambient temperature, and the maximum temperature that can be maintained for 2 hours I investigated.
＜初期粘着力試験＞
ＪＩＳ Ｃ ２１０７の粘着力試験（１８０度引き剥がし法）に準じて、粘着力の測定を行った。ただし、圧着は２kgのローラーを１往復して行い、試験板はステンレス板を使用し、試験片は幅２０mmにした。その他は、上記試験と同様に測定した。
<Initial adhesion test>
The adhesive strength was measured according to the adhesive strength test of JIS C 2107 (180 degree peeling method). However, crimping was performed by reciprocating a 2 kg roller once, a stainless steel plate was used as a test plate, and a test piece was 20 mm wide. Others were measured in the same manner as in the above test.
＜耐水粘着力試験＞
初期粘着力試験と同様に作製した試験片を、４０℃で９２％ＲＨの雰囲気に１０日保存したのち、初期粘着力試験と同様に粘着力を測定した。
<Waterproof adhesion test>
A test piece prepared in the same manner as in the initial adhesive strength test was stored in an atmosphere of 92% RH at 40 ° C. for 10 days, and then the adhesive strength was measured in the same manner as in the initial adhesive strength test.
表１
┌────┬──────┬─────┬────────┬────────┐
│ │凝集物の発生│耐熱保持性│ 初期粘着力 │ 耐水粘着力 │
│ │ │ │ │ │
│ │ （％） │ （℃） │（Ｎ／２０mm幅）│（Ｎ／２０mm幅）│
│ │ │ │ │ │
├────┼──────┼─────┼────────┼────────┤
│ │ │ │ │ │
│実施例１│ ０ │ １８０ │ ４ │ ５ │
│ │ │ │ │ │
│実施例２│ ０ │ ２００ │ ４ │ ５ │
│ │ │ │ │ │
│実施例３│ ０ │ １８０ │ ４ │ ５ │
│ │ │ │ │ │
├────┼──────┼─────┼────────┼────────┤
│ │ │ │ │ │
│比較例１│ ０ │ ９０ │ １ │ １ │
│ │ │ │ │ │
│比較例２│ １０ │ １００ │ ３ │ ２ │
│ │ │ │ │ │
│比較例３│ ０ │ １２０ │ ２ │ １ │
│ │ │ │ │ │
│比較例４│ １０ │ １００ │ ３ │ ２ │
│ │ │ │ │ │
│比較例５│ ６ │ １５０ │ ３ │ ２ │
│ │ │ │ │ │
│比較例６│ ５ │ １５０ │ ３ │ ３ │
│ │ │ │ │ │
│比較例７│ １０ │ １２０ │ ２ │ ２ │
│ │ │ │ │ │
│比較例８│ ０ │ ８０ │ ４ │ １ │
│ │ │ │ │ │
└────┴──────┴─────┴────────┴────────┘
Table 1
┌────┬──────┬─────┬────────┬────────┐
│ │ Aggregate generation │ Heat resistance │ Initial adhesion │ Water adhesion │
│ │ │ │ │ │
│ │ (%) │ (℃) │ (N / 20mm width) │ (N / 20mm width) │
│ │ │ │ │ │
├────┼──────┼─────┼────────┼────────┤
│ │ │ │ │ │
│Example 1 │ 0 │ 180 │ 4 │ 5 │
│ │ │ │ │ │
│Example 2│ 0 │ 200 │ 4 │ 5 │
│ │ │ │ │ │
│Example 3│ 0 │ 180 │ 4 │ 5 │
│ │ │ │ │ │
├────┼──────┼─────┼────────┼────────┤
│ │ │ │ │ │
│Comparative Example 1│ 0 │ 90 │ 1 │ 1 │
│ │ │ │ │ │
│Comparative Example 2│ 10 │ 100 │ 3 │ 2 │
│ │ │ │ │ │
│Comparative Example 3│ 0 │ 120 │ 2 │ 1 │
│ │ │ │ │ │
│Comparative Example 4│ 10 │ 100 │ 3 │ 2 │
│ │ │ │ │ │
│Comparative Example 5│ 6 │ 150 │ 3 │ 2 │
│ │ │ │ │ │
│Comparative Example 6│ 5 │ 150 │ 3 │ 3 │
│ │ │ │ │ │
│Comparative Example 7│ 10 │ 120 │ 2 │ 2 │
│ │ │ │ │ │
│Comparative Example 8│ 0 │ 80 │ 4 │ 1 │
│ │ │ │ │ │
└────┴──────┴─────┴────────┴────────┘
上記の表１の結果から明らかなように、本発明の実施例１〜３の各水分散型アクリル系粘着剤組成物は、凝集物の発生が全くみられず、これらの水分散型アクリル系粘着剤組成物から作製した各粘着シートは、良好な初期粘着力を示すと共に、高凝集力で耐熱保持性や耐水粘着力に非常にすぐれていることがわかる。
これに対して、本発明の構成を採用しない比較例１〜８の各水分散型アクリル系粘着剤組成物は、凝集物の発生がみられて、初期粘着力や凝集力が不足するか、あるいは、凝集物の発生がみられないものでも、初期粘着力か凝集力を満足できず、耐熱保持性や耐水粘着力に劣っていることがわかる。
As is clear from the results in Table 1 above, each of the water-dispersed acrylic pressure-sensitive adhesive compositions of Examples 1 to 3 of the present invention shows no occurrence of aggregates, and these water-dispersed acrylic pressure-sensitive adhesive compositions are not observed. It can be seen that each pressure-sensitive adhesive sheet prepared from the pressure-sensitive adhesive composition exhibits a good initial pressure-sensitive adhesive force, and also has a high cohesive force and excellent heat resistance and water-resistant pressure-sensitive adhesive strength.
On the other hand, in each of the water-dispersed acrylic pressure-sensitive adhesive compositions of Comparative Examples 1 to 8 that do not employ the configuration of the present invention, generation of aggregates is observed, and initial adhesive force and cohesive force are insufficient, Or even if it does not generate | occur | produce agglomerate, it turns out that initial stage adhesive force or cohesion force is not satisfied, but it is inferior to heat-resistant retention and water-resistant adhesive force.
Claims (4)
(A) an acrylic copolymer of 90 to 99% by weight of a vinyl monomer and 10 to 1% by weight of a polar group-containing monomer, the main component of which is a (meth) acrylic acid alkyl ester of an alkyl alcohol having 4 to 14 carbon atoms. (B) 2 to 20 parts by weight of an oleophilic layered clay mineral is (c) 1 to 10 parts by weight of a surfactant that is acidic and hydrophobic per 100 parts by weight of the acrylic copolymer. In the process for producing a water-dispersed acrylic pressure-sensitive adhesive composition dispersed in the presence of a part, the lipophilic layered clay mineral (b) is swollen in water, and the acidic and hydrophobic component (c) A method for producing a water-dispersed acrylic pressure-sensitive adhesive composition, which comprises adding a surfactant that is water-soluble and dispersing it in an aqueous dispersion of component (a) and mixing and dispersing it.
The method for producing a water-dispersed acrylic pressure-sensitive adhesive composition according to claim 1, wherein the lipophilic layered clay mineral (b) is a smectite type.
The method for producing a water-dispersed acrylic pressure-sensitive adhesive composition according to claim 1 or 2, wherein the lipophilic layered clay mineral (b) contains a hydroxyl group-containing quaternary ammonium salt.
The water-dispersed acrylic pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein the acidic and hydrophobic surfactant (c) is a partially esterified product of a styrene-maleic acid copolymer . Manufacturing method .
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| LAPS | Cancellation because of no payment of annual fees |