JP2001107007A - Pressure-sensitive adhesive composition and its utilization - Google Patents
Pressure-sensitive adhesive composition and its utilizationInfo
- Publication number
- JP2001107007A JP2001107007A JP28893799A JP28893799A JP2001107007A JP 2001107007 A JP2001107007 A JP 2001107007A JP 28893799 A JP28893799 A JP 28893799A JP 28893799 A JP28893799 A JP 28893799A JP 2001107007 A JP2001107007 A JP 2001107007A
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- adhesive sheet
- adherend
- adhesive composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、常温では指触粘着
性を示さず、加圧下に被着体と接触せしめることにより
積層体を提供し得る剥離紙不要の感圧性接着シート、及
び該感圧性接着シートの感圧性接着層を提供し得る感圧
性接着剤組成物に関し、並びに該感圧性接着シートと被
着体とを高圧下に接触せしめ、貼り合わせてなる積層体
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pressure-sensitive adhesive sheet which does not exhibit finger-tackiness at room temperature and which can provide a laminate by being brought into contact with an adherend under pressure, without the need for release paper. The present invention relates to a pressure-sensitive adhesive composition capable of providing a pressure-sensitive adhesive layer of a pressure-sensitive adhesive sheet, and to a laminate obtained by bringing the pressure-sensitive adhesive sheet and an adherend into contact with each other under high pressure and bonding them.
【０００２】[0002]
【従来の技術】各種の輸送手段により配送される荷物の
取り扱い量が増大するに従い、コストの削減、効率化が
強く要求されている。配送時に荷物に貼り付けられる配
送伝票についても同様であり、従来より、種々の作成方
法、構成、形状にして、コストの削減、効率化が進めら
れてきた。近年、このような目的に対し、常温では指触
粘着性を示さない感圧性接着剤組成物を塗布してなる感
圧性接着シートと被着体とを圧着シーラー等を用いて高
い圧力で圧着し、必要に応じて感圧性接着シートと被着
体とを再剥離し得る配送伝票が使用されてきている。こ
のような用途に使用される剥離可能な感圧性接着剤組成
物は、一般に天然ゴムラテックス、又は天然ゴムラテッ
クスをスチレンやアクリル単量体で変成した変性ゴムラ
テックス等を主剤成分とし、これに必要に応じアクリル
ラテックスや合成ゴムラテックス等を配合し、さらにシ
リカ、カオリン、炭酸カルシウム等の微粒子の充填剤を
配合している。2. Description of the Related Art As the handling volume of packages delivered by various transportation means increases, there is a strong demand for cost reduction and efficiency improvement. The same applies to a delivery slip attached to a package at the time of delivery. Conventionally, various creation methods, configurations, and shapes have been used to reduce costs and increase efficiency. In recent years, for such purposes, a pressure-sensitive adhesive sheet formed by applying a pressure-sensitive adhesive composition that does not exhibit finger tackiness at room temperature and an adherend are pressed with a high pressure using a pressure sealer or the like. In addition, a delivery slip capable of re-peeling the pressure-sensitive adhesive sheet and the adherend as necessary has been used. The peelable pressure-sensitive adhesive composition used in such applications generally comprises natural rubber latex or a modified rubber latex obtained by modifying natural rubber latex with styrene or an acrylic monomer as a main component, and is required for this. Acrylic latex, synthetic rubber latex, and the like are added according to the above, and a filler of fine particles such as silica, kaolin, and calcium carbonate is further added.
【０００３】しかしながら、上記のような天然ゴムラテ
ックスを主剤成分とした接着剤組成物は、種々の課題を
有している。即ち、天然ゴムラテックスの原料である天
然ゴムは、生産地、季節により、その樹脂の特性が大き
く変動するため、粘度等の溶液性状、接着強度等の物理
的性能にバラツキが大きく、安定した品質を保持する事
は困難である。又、天然ゴムは、基材に対する初期接着
強度が低く、且つ、その構造中に、反応性の不飽和二重
結合を多量に含有しているため、酸素や紫外線により酸
化、分解され易く、劣化し易い。その結果、接着強度
が、経時的に急激に低下する等の問題がある。[0003] However, the adhesive composition containing the above natural rubber latex as a main component has various problems. In other words, natural rubber, which is a raw material of natural rubber latex, has large fluctuations in solution properties such as viscosity, physical properties such as adhesive strength and the like, since the properties of the resin greatly vary depending on the place of production and season, and stable quality. Is difficult to hold. Also, natural rubber has low initial adhesive strength to a substrate and contains a large amount of reactive unsaturated double bonds in its structure, so it is easily oxidized and decomposed by oxygen and ultraviolet rays, and deteriorates. Easy to do. As a result, there is a problem that the adhesive strength rapidly decreases over time.
【０００４】天然ゴムラテックスのこのような欠点を補
うことを目的として、天然ゴムラテックスに非架橋型の
アクリル系ラテックスや変成天然ゴムラテックスを配合
してなる感圧性接着剤組成物が提案されている。しか
し、天然ゴムラテックスに由来する上記の問題点を根本
的に解決するには至っていない。さらに、上質紙等の浸
透性を有する被着体に感圧性接着シートを貼着した場合
には、非架橋型のアクリル系ラテックスや変成天然ゴム
ラテックスが圧着後の初期段階に上記浸透性の被着体に
浸透するため、接着強度が上昇してしまうので、剥離す
る際に感圧性接着シートの基材を破壊したり、被着体を
破壊したりする等の問題が発生する。For the purpose of compensating for such disadvantages of the natural rubber latex, a pressure-sensitive adhesive composition comprising a non-crosslinked acrylic latex or a modified natural rubber latex mixed with the natural rubber latex has been proposed. . However, the above-mentioned problems derived from natural rubber latex have not been fundamentally solved. Furthermore, when a pressure-sensitive adhesive sheet is adhered to a permeable adherend such as high-quality paper, the non-crosslinkable acrylic latex or modified natural rubber latex is applied to the permeable adherend at an initial stage after pressure bonding. Since it penetrates into the adherend, the adhesive strength is increased, so that when peeling, problems such as destruction of the base material of the pressure-sensitive adhesive sheet and destruction of the adherend occur.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、従来の感圧
性接着剤組成物等の上記の課題を解決することを目的と
したものである。即ち、本発明は、必要十分な初期接着
強度を示し、且つ、接着強度が経時で変化することのな
い積層体であって、しかも基材及び被着体を損傷するこ
となく必要に応じて剥離可能な積層体を提供し得る、５
０℃では指触粘着性を示さない剥離紙不要の感圧性接着
シートを提供することを目的とし、該感圧性接着シート
の感圧性接着層を提供し得る感圧性接着剤組成物を提供
し得る一液型であって使用可能な時間に制限のない感圧
性接着剤組成物を得ることを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of conventional pressure-sensitive adhesive compositions and the like. That is, the present invention is a laminate showing a necessary and sufficient initial adhesive strength, and the adhesive strength does not change with time, and is peeled off as necessary without damaging the base material and the adherend. 5 that can provide a possible laminate
It is an object of the present invention to provide a pressure-sensitive adhesive sheet that does not exhibit finger tackiness at 0 ° C. and does not require release paper, and can provide a pressure-sensitive adhesive composition that can provide a pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet. An object of the present invention is to obtain a pressure-sensitive adhesive composition which is a one-part type and has no limitation on the usable time.
【０００６】[0006]
【課題を解決するための手段】上記の目的を達成するた
めに鋭意研究した結果、本発明者は、ラジカル重合性不
飽和基を２個以上有する多官能性単量体を含有するラジ
カル重合性単量体混合物を共重合して得られる内部を３
次元架橋させた既架橋型共重合体であって、特定のガラ
ス転移温度を呈するものと平均粒径が１〜３０μｍの微
粒子とを含有する再剥離可能な感圧性接着剤組成物が必
要充分な初期接着強度を示し、且つ、接着強度の経時的
変化が少ない等の本目的を達成することを見いだし、本
発明に至った。As a result of intensive studies to achieve the above object, the present inventor has found that a radical polymerizable monomer containing a polyfunctional monomer having two or more radical polymerizable unsaturated groups has been obtained. The interior obtained by copolymerizing the monomer mixture is 3
It is necessary and sufficient to provide a removable pressure-sensitive adhesive composition which is a cross-linked copolymer which has been cross-dimensionally crosslinked and which has a specific glass transition temperature and fine particles having an average particle diameter of 1 to 30 μm. The present inventors have found that the present invention achieves the object of the present invention, such as exhibiting an initial adhesive strength and having little change over time in the adhesive strength, leading to the present invention.
【０００７】即ち、第１の発明は、ラジカル重合性不飽
和基を２個以上有する多官能性単量体１〜２０重量％含
有するラジカル重合性単量体混合物を共重合してなるガ
ラス転移温度が−６０〜０℃の皮膜形成能を有する既架
橋型共重合体（Ａ）１００重量部に対して、平均粒径が
１〜３０μｍの微粒子（Ｂ）２０〜１５０重量部を含有
することを特徴とする再剥離可能な感圧性接着剤組成物
であり、That is, a first invention is a glass transition obtained by copolymerizing a radical polymerizable monomer mixture containing 1 to 20% by weight of a polyfunctional monomer having two or more radical polymerizable unsaturated groups. 20 to 150 parts by weight of fine particles (B) having an average particle size of 1 to 30 μm with respect to 100 parts by weight of the cross-linked copolymer (A) having a film forming ability at a temperature of −60 to 0 ° C. A removable pressure-sensitive adhesive composition characterized by the fact that
【０００８】第２の発明は、既架橋型共重合体（Ａ）を
水性媒体に分散せしめてなる水性分散体を含有すること
を特徴とする第１の発明記載の感圧性接着剤組成物であ
る。A second invention provides a pressure-sensitive adhesive composition according to the first invention, which comprises an aqueous dispersion obtained by dispersing the crosslinked copolymer (A) in an aqueous medium. is there.
【０００９】第３の発明は、第２の発明記載の感圧性接
着剤組成物をシート状基材に塗工、乾燥してなる感圧性
接着シートである。A third aspect of the present invention is a pressure-sensitive adhesive sheet obtained by applying the pressure-sensitive adhesive composition according to the second aspect to a sheet-like substrate and drying.
【００１０】第４の発明は、感圧性接着剤組成物の塗工
層が、５０℃において指触粘着性を有しないことを特徴
とする第３の発明記載の感圧性接着シートである。A fourth invention is the pressure-sensitive adhesive sheet according to the third invention, wherein the coating layer of the pressure-sensitive adhesive composition has no tackiness at 50 ° C.
【００１１】第５の発明は、第４の発明記載の感圧性接
着シートの感圧性接着剤組成物の層を被着体に接触せし
め、３０ｋｇ／ｃｍ2 以上に加圧して、感圧性接着シー
トと被着体とを再剥離可能に貼り合わせて得られる積層
体である。A fifth invention provides a pressure-sensitive adhesive sheet according to the fourth invention, wherein a layer of the pressure-sensitive adhesive composition of the pressure-sensitive adhesive sheet is brought into contact with an adherend and pressurized to 30 kg / cm 2 or more. And an adherend are releasably attached to each other.
【００１２】第６の発明は、第４の発明に記載の感圧性
接着シートと被着体の総厚の３０〜８０％にロール隙間
を調整した２本のロールの間を、感圧性接着シートの感
圧性接着剤層と被着体とを接触させつつ、通過させるこ
とを特徴とする感圧性接着シートと被着体とを貼り合わ
せる方法である。A sixth invention provides a pressure-sensitive adhesive sheet between the pressure-sensitive adhesive sheet according to the fourth invention and two rolls having a roll gap adjusted to 30 to 80% of the total thickness of the adherend. A pressure-sensitive adhesive sheet and an adherend, characterized in that the pressure-sensitive adhesive layer and the adherend are passed through while being in contact with each other.
【００１３】[0013]
【発明の実施の形態】既架橋型共重合体（Ａ）を得るた
めに使用されるラジカル重合性不飽和基を２個以上有す
る多官能性単量体としては、例えば、エチレングリコー
ルジ（メタ）アクリレート、ジエチレングリコールジ
（メタ）アクリレート、ポリエチレングリコールジ（メ
タ）アクリレート、ポリプロピレングリコールジ（メ
タ）アクリレート、１，３−ブチレングリコールジ（メ
タ）アクリレート、ネオペンチルグリコールジ（メタ）
アクリレート、１，６−ヘキサンジオールジ（メタ）ア
クリレート、グリセリントリ（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テトラ（メタ）アクリレート、ジビ
ニルベンゼン等をあげることができる。これらの多官能
性単量体を１種又は２種以上を使用する事ができる。BEST MODE FOR CARRYING OUT THE INVENTION The polyfunctional monomer having two or more radically polymerizable unsaturated groups used for obtaining the crosslinked copolymer (A) includes, for example, ethylene glycol di (meth) A) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth)
Acrylate, 1,6-hexanediol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, divinylbenzene and the like can be mentioned. One or more of these polyfunctional monomers can be used.
【００１４】上記多官能性単量体と共重合し得るラジカ
ル重合性不飽和基を有する単官能性単量体としては、例
えば、（メタ）アクリル酸、メチル（メタ）アクリレー
ト、エチル（メタ）アクリレート、ブチル（メ タ）ア
クリレート、２−エチルヘキシル（メタ）アクリレー
ト、オクチル（メ タ） アクリレート、ドデシル（メ
タ）アクリレト、フェニール（メタ）アクリレート、ス
テアリル（メタ）アクリレート、ノニルフェニル（メ
タ）アクリレート、スチレン、ｔ−ブチルスチレン等を
あげることができる。これらの単官能性単量体を１種又
は２種以上を 使用する事ができる。Examples of the monofunctional monomer having a radically polymerizable unsaturated group copolymerizable with the polyfunctional monomer include (meth) acrylic acid, methyl (meth) acrylate, and ethyl (meth) acrylate. Acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, stearyl (meth) acrylate, nonylphenyl (meth) acrylate, styrene , T-butylstyrene and the like. One or more of these monofunctional monomers can be used.
【００１５】既架橋型共重合体（Ａ）を製造する際に使
用されるラジカル重合性不飽和基を２個以上有する多官
能性単量体は、全単量体１００重量％中、１〜２０重量
％であることが重要であり、５〜１５重量％であること
が好ましい。多官能性単量体が１重量％未満では、得ら
れる積層体の接着強度が経時的に変化してしまうので好
ましくない。一方、多官能性単量体が２０重量％よりも
多いと、既架橋型共重合体（Ａ）の架橋密度が高くなり
すぎ、該既架橋型共重合体のガラス転移温度（以下、Ｔ
ｇという）が、−６０〜０℃の範囲にあっても、必要な
初期接着強度の積層体を得ることができない。The polyfunctional monomer having two or more radically polymerizable unsaturated groups used for producing the crosslinked copolymer (A) is 1 to 100% by weight of the total monomers. It is important that the content is 20% by weight, and preferably 5 to 15% by weight. When the amount of the polyfunctional monomer is less than 1% by weight, the adhesive strength of the obtained laminate changes with time, which is not preferable. On the other hand, if the amount of the polyfunctional monomer is more than 20% by weight, the cross-linking density of the cross-linked copolymer (A) becomes too high, and the glass transition temperature of the cross-linked copolymer (hereinafter referred to as T
g) is in the range of −60 to 0 ° C., it is not possible to obtain a laminate having a necessary initial adhesive strength.
【００１６】本発明の感圧性接着剤組成物に使用する既
架橋型共重合体（Ａ）のＴｇは、−６０〜０℃であるこ
とが重要であり、−４０〜−１０℃であることが好まし
い。Ｔｇが−６０℃未満では、感圧性接着シートの塗工
面が指触粘着性を呈し易く、被着体又は基材を損傷する
ことなく、被着体から感圧性接着シートを剥離すること
が困難である。一方、Ｔｇが０℃を越えると、感圧性接
着シートの塗工面は指触粘着性を呈しないが、その反面
積層体としての必要な接着強度を得ることができない。It is important that the Tg of the cross-linked copolymer (A) used in the pressure-sensitive adhesive composition of the present invention is from -60 to 0 ° C, and from -40 to -10 ° C. Is preferred. When the Tg is lower than -60 ° C, the coated surface of the pressure-sensitive adhesive sheet tends to exhibit finger tackiness, and it is difficult to peel the pressure-sensitive adhesive sheet from the adherend without damaging the adherend or the base material. It is. On the other hand, when the Tg exceeds 0 ° C., the coated surface of the pressure-sensitive adhesive sheet does not exhibit finger-tackiness, but the required adhesive strength as an anti-area layer body cannot be obtained.
【００１７】本発明の感圧性接着剤組成物に使用する既
架橋型共重合体（Ａ）は、公知の方法、即ち、乳化重
合、懸濁重合又は、非水系分散重合から選ばれる重合方
法により容易に製造することができ、何れの方法も好適
に使用することができるが、乳化重合によって得られる
水性分散体の状態で供されることが好ましい。The crosslinked copolymer (A) used in the pressure-sensitive adhesive composition of the present invention can be prepared by a known method, that is, a polymerization method selected from emulsion polymerization, suspension polymerization and non-aqueous dispersion polymerization. Although it can be easily produced and any method can be suitably used, it is preferably provided in a state of an aqueous dispersion obtained by emulsion polymerization.
【００１８】乳化重合は、アニオン系、ノニオン系、カ
チオン系、両性イオン系もしくはこれらを混合してなる
界面滑性剤とラジカル重合性単量体混合物とを、過硫酸
アンモニウム、過硫酸カリウム等の水溶性の過硫酸塩と
必要に応じＬ−アスコルビン酸等の還元剤、ＰＨ調節剤
等を存在下、水中に攪拌、混合して、乳化状態にし、こ
れを５０〜９５℃に加熱した水中に滴下することによ
り、重合を行う方法である。このような乳化重合の場
合、通常、単量体混合物濃度約３０〜５０重量％の条件
で約３〜７時間反応させる。また、乳化重合は、上記の
ような界面活性剤の不存在下に重合するソープフリー重
合でも良い。In the emulsion polymerization, an anionic, nonionic, cationic, amphoteric or a mixture of these surfactants and a radical polymerizable monomer mixture are mixed with an aqueous solution of ammonium persulfate, potassium persulfate or the like. In the presence of an acidic persulfate and, if necessary, a reducing agent such as L-ascorbic acid, a pH regulator, etc., the mixture is stirred and mixed in water to form an emulsified state, and this is dropped into water heated to 50 to 95 ° C. This is a method for carrying out polymerization. In the case of such emulsion polymerization, usually, the reaction is carried out for about 3 to 7 hours under the condition of a monomer mixture concentration of about 30 to 50% by weight. Emulsion polymerization may be soap-free polymerization in which polymerization is carried out in the absence of a surfactant as described above.
【００１９】懸濁重合は、上記界面滑性剤とメチルセル
ロース、デンプン、ゼラチン、ポリビニールアルコール
等の保護コロイド剤の水溶液を５０〜９５℃に加熱し、
この中に、単量体混合物とベンゾイルパーオキサイド、
２、２’アゾビスイソブチロニトリル等の油溶性の重合
開始剤とを混合して滴下し、共重合体を水中に懸濁させ
ることにより重合を行う方法である。懸濁重合の場合の
単量体混合物濃度、反応時間等は上記乳化重合の場合と
同様である。In the suspension polymerization, an aqueous solution of the above-mentioned surfactant and a protective colloid agent such as methylcellulose, starch, gelatin and polyvinyl alcohol is heated to 50 to 95 ° C.
In this, the monomer mixture and benzoyl peroxide,
This is a method in which an oil-soluble polymerization initiator such as 2,2'azobisisobutyronitrile is mixed and dropped, and the copolymer is suspended in water to carry out polymerization. The concentration of the monomer mixture, the reaction time and the like in the case of suspension polymerization are the same as in the case of the emulsion polymerization.
【００２０】非水系分散重合は、ブチルエーテル化メラ
ミン樹脂等の分散安定剤を非極性有機溶媒に溶解した溶
液を６０〜１２０℃に加熱し、この中に、単量体混合物
とベンゾイルパーオキサイド、２、２’アゾビスイソブ
チロニトリル等の油溶性重合開始剤を混合して滴下し、
共重合体を有機溶媒に懸濁させることにより重合を行う
方法である。非水系分散重合の場合の単量体混合物濃
度、反応時間等も上記乳化重合、懸濁重合の場合と同様
である。In the non-aqueous dispersion polymerization, a solution in which a dispersion stabilizer such as a butyl etherified melamine resin is dissolved in a non-polar organic solvent is heated to 60 to 120 ° C., and the monomer mixture and benzoyl peroxide, 2, 2 'azobisisobutyronitrile and other oil-soluble polymerization initiators are mixed and added dropwise,
In this method, polymerization is carried out by suspending a copolymer in an organic solvent. The monomer mixture concentration, reaction time and the like in the case of non-aqueous dispersion polymerization are the same as those in the case of the emulsion polymerization and suspension polymerization.
【００２１】本発明の感圧性接着剤組成物に使用される
平均粒径が１〜３０μｍの微粒子（Ｂ）は、感圧性接着
シートの感圧性接着剤組成物塗工面が指触粘着性を呈し
ないようにし、該シートの保管及び輸送時の粘着（ブロ
ッキング）を防止するために必要である。平均粒径が１
μよりも小さい微粒子を用いた場合には、感圧性接着剤
組成物塗工面の静摩擦係数若しくは動摩擦係数が大き
く、滑性に劣るため作業性が悪くなる。一方、平均粒径
が３０μよりも大きい微粒子を用いた場合には、感圧性
接着剤組成物塗工面の表面状態が不良となる。従って、
微粒子（Ｂ）の平均粒径は１〜３０μｍであることが重
要である。ここで使用される微粒子（Ｂ）は、シリカ、
酸化チタン、カオリン、タルク、炭酸カルシウム、シリ
カ／アルミナ結晶体、珪酸マグネシウム、マイカ等の無
機系微粒子、米澱粉、小麦澱粉、コーン澱粉、ポテト澱
粉、セルロース、カルボキシメチルセルロース、アスパ
ラギン酸等の有機系微粒子等であり、これらの微粒子
（Ｂ）は、単独で使用することもできるが、感圧性接着
シートとしては指触粘着性を呈さず、積層体としては十
分な接着強度を確保するためには、無機系微粒子と有機
系微粒子を併用することが特に好ましい。The fine particles (B) having an average particle size of 1 to 30 μm used in the pressure-sensitive adhesive composition of the present invention show that the pressure-sensitive adhesive composition coated surface of the pressure-sensitive adhesive sheet has finger-tackiness. It is necessary to prevent the sheet from sticking (blocking) during storage and transportation of the sheet. Average particle size is 1
When the fine particles smaller than μ are used, the static friction coefficient or the kinetic friction coefficient of the pressure-sensitive adhesive composition coated surface is large, and the workability is deteriorated due to poor lubricity. On the other hand, when fine particles having an average particle size of more than 30 μm are used, the surface state of the coated surface of the pressure-sensitive adhesive composition becomes poor. Therefore,
It is important that the average particle size of the fine particles (B) is 1 to 30 μm. The fine particles (B) used here are silica,
Inorganic fine particles such as titanium oxide, kaolin, talc, calcium carbonate, silica / alumina crystal, magnesium silicate, mica, etc., organic fine particles such as rice starch, wheat starch, corn starch, potato starch, cellulose, carboxymethyl cellulose, aspartic acid, etc. These fine particles (B) can be used alone, but as a pressure-sensitive adhesive sheet, it does not exhibit finger-tackiness, and in order to ensure sufficient adhesive strength as a laminate, It is particularly preferable to use inorganic fine particles and organic fine particles in combination.
【００２２】本発明の感圧性接着剤組成物は、架橋構造
を有する特定のＴｇの共重合体（Ａ）１００重量部に対
して、平均粒径１〜３０μｍの微粒子（Ｂ）を２０〜１
５０重量部配合することが重要である。比較的高Ｔｇの
共重合体（Ａ）を用いた場合であっても、微粒子（Ｂ）
が２０重量部未満では、積層体の接着強度が強くなりす
ぎ再剥離が不可能となり、一方、比較的低Ｔｇの共重合
体（Ａ）を用いた場合であっても、微粒子（Ｂ）が１５
０重量部よりも多いと、十分な接着強度の積層体を得る
ことができない。The pressure-sensitive adhesive composition of the present invention contains 20 to 1 fine particles (B) having an average particle size of 1 to 30 μm per 100 parts by weight of a specific Tg copolymer (A) having a crosslinked structure.
It is important to add 50 parts by weight. Even when the copolymer (A) having a relatively high Tg is used, the fine particles (B)
Is less than 20 parts by weight, the adhesive strength of the laminate becomes too strong to allow re-peeling. On the other hand, even when the copolymer (A) having a relatively low Tg is used, the fine particles (B) are Fifteen
If it is more than 0 parts by weight, a laminate having a sufficient adhesive strength cannot be obtained.
【００２３】本発明の感圧性接着剤組成物には、積層体
の接着強度の向上等の目的のため、必要に応じ、上記共
重合体（Ａ）以外の樹脂、可塑剤、架橋剤、その他の添
加剤等を添加することができる。例えば、粘着性を向上
することを目的として、ロジン樹脂、水素添加ロジン樹
脂、ロジンフエノール樹脂、テルペン樹脂、クマロンー
インデン樹脂や、ジメチルフタレート、ジブチルフタレ
ート等の可塑剤を、本発明の感圧性接着剤組成物にさら
に添加することができる。The pressure-sensitive adhesive composition of the present invention may contain, if necessary, a resin other than the copolymer (A), a plasticizer, a crosslinking agent, and the like for the purpose of improving the adhesive strength of the laminate. And the like can be added. For example, a plasticizer such as rosin resin, hydrogenated rosin resin, rosin phenol resin, terpene resin, coumarone-indene resin, dimethyl phthalate, dibutyl phthalate, etc. It can be further added to the agent composition.
【００２４】架橋度をさらに上げ、凝集力を高めるため
に、既架橋型共重合体（Ａ）が水酸基やアミノ基等の官
能基を有する場合には、かかる官能基と反応し得る官能
基を２個以上有する樹脂や化合物を架橋剤として、本発
明の感圧性接着剤組成物にさらに配合することができ
る。例えば、トルエンジイソシアネート、イソホロンジ
イソシアネート等のポリイソシアネート化合物、メラミ
ン−ホルムアルデヒド樹脂、エポキシ樹脂、多価金属
塩、金属キレート化合物ポリアミン化合物等を挙げるこ
とができる。When the crosslinked copolymer (A) has a functional group such as a hydroxyl group or an amino group in order to further increase the degree of crosslinking and enhance the cohesive strength, a functional group capable of reacting with such a functional group is used. As a crosslinking agent, a resin or compound having two or more resins can be further added to the pressure-sensitive adhesive composition of the present invention. Examples thereof include polyisocyanate compounds such as toluene diisocyanate and isophorone diisocyanate, melamine-formaldehyde resins, epoxy resins, polyvalent metal salts, metal chelate compounds and polyamine compounds.
【００２５】塗工適性、塗工液の保存安定性、塗工皮膜
の経時 安定性等の向上のために、例えば、酸化防止
剤、オゾン劣化防止剤、紫外線吸収剤、滑性剤、界面活
性剤、防腐剤、防黴剤、溶剤、消泡剤、増粘剤等を、本
発明の感圧性接着剤組成物にさらに添加することができ
る。上記種々の樹脂や、可塑剤、架橋剤、その他の添加
剤は、それぞれ必要に応じ、１種又は２種以上を混合し
て使用することができる。In order to improve the coating suitability, the storage stability of the coating solution, and the stability of the coating film over time, for example, an antioxidant, an antiozonant, an ultraviolet absorber, a lubricant, a surfactant Agents, preservatives, fungicides, solvents, defoamers, thickeners and the like can be further added to the pressure-sensitive adhesive composition of the present invention. The above various resins, plasticizers, crosslinking agents, and other additives can be used alone or as a mixture of two or more, if necessary.
【００２６】本発明の感圧性接着剤組成物をシート状の
基材に塗工し、水等の液状媒体を除去することにより感
圧性接着シートを得ることができる。ここで使用される
シート状基材とは、塗工面の大きさに比して基材の厚み
が薄く、平たい基材をいい、長尺ものをロール状に巻き
取ったものであっても、一定の長さに切ったものであっ
ても良い。シート状基材としては、例えば、上質紙、更
紙、ガラビア紙、ボンド紙、クラフト紙等の非塗工紙、
澱粉、カルボキシメチルセルロース、ポリビニルアルコ
ール等のバインダーに体質顔料を配合した目止め剤を上
記の上質紙等の非塗工紙に塗工したアート紙、コート
紙、キャストコート紙、エンボスコート紙、クレーコー
ト紙、艶消しアート紙等の塗工紙、クラフト紙にポリエ
ステル樹脂、天然ゴム、合成ゴム等の樹脂を塗工、含浸
させたコート紙等、ポリエチレン樹脂、ポリプロピレン
樹脂、ポリエチレンテレフタレート樹脂、ポリ塩化ビニ
ル樹脂、ポリ酢酸ビニル樹脂、ポリビニルアルコール樹
脂、ナイロン樹脂、ポリアミド樹脂、ポリカーボネート
樹脂、セルロース樹脂等の合成樹脂のフイルム、上記の
合成樹脂フイルムと上記の上質紙等とを積層してなるラ
ミネート紙、等を挙げることができる。A pressure-sensitive adhesive sheet can be obtained by applying the pressure-sensitive adhesive composition of the present invention to a sheet-like substrate and removing a liquid medium such as water. The sheet-shaped substrate used here, the thickness of the substrate is thin compared to the size of the coated surface, refers to a flat substrate, even if a long thing is wound into a roll, It may be cut into a certain length. Examples of the sheet-like base material include, for example, uncoated paper such as high-quality paper, paper-change, gravure paper, bond paper, and kraft paper;
Art paper, coated paper, cast-coated paper, embossed-coated paper, clay-coated, coated with unfilled paper such as the above-mentioned high-quality paper, with a filler containing a filler such as starch, carboxymethylcellulose, polyvinyl alcohol, etc. Polyester resin, polypropylene resin, polyethylene terephthalate resin, polyvinyl chloride, coated paper impregnated with polyester resin, natural rubber, synthetic rubber, etc. on coated paper such as paper and matte art paper, and kraft paper Resin, polyvinyl acetate resin, polyvinyl alcohol resin, nylon resin, polyamide resin, polycarbonate resin, synthetic resin film such as cellulose resin, laminated paper obtained by laminating the above synthetic resin film and the above high quality paper, etc. Can be mentioned.
【００２７】本発明の感圧性接着剤組成物は、インクジ
ェット記録紙、感熱記録紙等の裏面に塗工されても、イ
ンキの転移性、感熱性等の記録紙本来の性能を損なうこ
とがなく、インクジェットプリンター、感熱プリンタ
ー、レーザープリンター等を使用して、必要な情報を記
録紙表面に印字することができる。The pressure-sensitive adhesive composition of the present invention can be applied to the back surface of an ink jet recording paper, a heat-sensitive recording paper or the like without impairing the original performance of the recording paper such as ink transferability and heat sensitivity. The necessary information can be printed on the surface of the recording paper by using an inkjet printer, a thermal printer, a laser printer, or the like.
【００２８】本発明の感圧性接着シートは、一般にロー
ルコーター、エアナイフコーター、バーコーター、リッ
プコーター、グラビアコーター等の塗装機を用いて、上
述の感圧性接着剤組成物を乾燥重量が１〜２０ｇ／ｍ2
となるようにシート状基材に塗布することによって得る
ことができる。基材が浸透性を有する場合に感圧性接着
剤組成物の乾燥重量が１ｇ／ｍ2 未満だと、感圧性接着
剤組成物が基材中に浸透してしまい、得られる感圧性接
着シートと被着体とを貼り合わせても十分な接着強度が
得られない。一方、感圧性接着剤組成物の乾燥重量が２
０ｇ／ｍ2 よりも大きいと、感圧性接着シートと被着体
とを貼り合わせた際に接着剤のはみ出したりすることが
ある。The pressure-sensitive adhesive sheet of the present invention is prepared by using a coating machine such as a roll coater, an air knife coater, a bar coater, a lip coater or a gravure coater to dry the above-mentioned pressure-sensitive adhesive composition in a dry weight of 1 to 20 g. / M 2
It can be obtained by applying to a sheet-like substrate such that When the dry weight of the pressure-sensitive adhesive composition is less than 1 g / m 2 when the base material has permeability, the pressure-sensitive adhesive composition permeates into the base material, and the resulting pressure-sensitive adhesive sheet Sufficient adhesive strength cannot be obtained even when bonded to an adherend. On the other hand, when the dry weight of the pressure-sensitive adhesive composition is 2
If it is larger than 0 g / m 2 , the adhesive may protrude when the pressure-sensitive adhesive sheet is adhered to the adherend.
【００２９】本発明の感圧性接着シートは、常温、即
ち、日常の生活温度はもちろん、５０℃程度でも、感圧
性接着剤層面が指触粘着性を呈さない。従って、常温に
おいて指触粘着性を呈し、被着体と貼り合わせる際に剥
離し、廃棄しなければならない剥離材で感圧性接着剤層
面を被覆しなければならない一般的な感圧性接着シート
とは異なり、本発明の感圧性接着シートは、感圧性接着
剤層面を剥離材で被覆する必要がない。In the pressure-sensitive adhesive sheet of the present invention, the surface of the pressure-sensitive adhesive layer does not exhibit finger-tackiness even at room temperature, that is, about 50 ° C. as well as at ordinary daily living temperature. Therefore, a general pressure-sensitive adhesive sheet that exhibits finger-tackiness at room temperature, peels off when bonded to an adherend, and has to cover the pressure-sensitive adhesive layer surface with a release material that must be discarded is Unlike the pressure-sensitive adhesive sheet of the present invention, it is not necessary to cover the surface of the pressure-sensitive adhesive layer with a release material.
【００３０】本発明の感圧性接着シートは、常温におい
ては、感圧性接着剤層面が指触粘着性を呈さないが、以
下のようにして高圧下に被着体と感圧性接着剤層とを接
触せしめることによって、被着体と感圧性接着シートと
を貼り合わせ、剥離可能な積層体を提供できる。例え
ば、２本のロールのロール隙間を、感圧性接着シートと
被着体の総厚の３０〜８０％に調整し、その２本のロー
ルの間を、感圧性接着シートの感圧性接着剤層と被着体
とを接触させつつ通過させたり、被着体と感圧性接着シ
ートの感圧性接着剤層とを接触せしめた状態で、プレス
機でプレスしたりすることによって得ることができる。
本発明の積層体は、３０ｋｇ／ｃｍ2 以上の圧力下に被
着体と感圧性接着シートとを貼着してなるものであり、
３０〜３００ｋｇ／ｃｍ2 の圧力をかけて貼り合わせる
ことがより好ましい。３０ｋｇ／ｃｍ2 未満の圧力で
は、十分な接着強度を得ることができない。一方、３０
０ｋｇ／ｃｍ2 よりも大きな圧力を加えることは、機械
的にかなり困難である。このようにして得られる積層体
は、必要且つ充分な初期接着強度を有し、しかも経時的
接着強度の変化も少なく、長期間一定の接着強度を保持
することができる。本発明の積層体の初期及び経時後接
着強度は、５０〜１５０［ｇ／２．５ｃｍ］の範囲にあ
ることが重要である。即ち、接着強度が５０［ｇ／２．
５ｃｍ］未満では、取り扱い時に意図せずに剥離するこ
とあり、一方、接着強度が１５０［ｇ／２．５ｃｍ］を
越えると、剥離時に感圧性接着シート若しくは被着体を
破壊してしまうことがあり、好ましくない。本発明の積
層体に用いられる被着体としては、上記の感圧性接着シ
ートの基材として例示したものを同様に例示できる。In the pressure-sensitive adhesive sheet of the present invention, the surface of the pressure-sensitive adhesive layer does not exhibit finger-tackiness at room temperature, but the adherend and the pressure-sensitive adhesive layer are separated under high pressure as follows. By bringing them into contact with each other, the adherend and the pressure-sensitive adhesive sheet can be bonded to each other to provide a peelable laminate. For example, the gap between the two rolls is adjusted to 30 to 80% of the total thickness of the pressure-sensitive adhesive sheet and the adherend, and the gap between the two rolls is the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet. The pressure-sensitive adhesive layer can be obtained by passing the substrate and the adherend while making them contact with each other, or by pressing with a press in a state where the adherend and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet are in contact with each other.
The laminate of the present invention is obtained by adhering an adherend and a pressure-sensitive adhesive sheet under a pressure of 30 kg / cm 2 or more,
It is more preferable to apply the pressure by applying a pressure of 30 to 300 kg / cm 2 . If the pressure is less than 30 kg / cm 2 , sufficient adhesive strength cannot be obtained. On the other hand, 30
Applying pressures greater than 0 kg / cm 2 is quite difficult mechanically. The laminate obtained in this way has a necessary and sufficient initial adhesive strength, has little change in adhesive strength with time, and can maintain a constant adhesive strength for a long time. It is important that the adhesive strength of the laminate of the present invention at the initial stage and after aging is in the range of 50 to 150 [g / 2.5 cm]. That is, the adhesive strength is 50 [g / 2.
When the adhesive strength exceeds 150 [g / 2.5 cm], the pressure-sensitive adhesive sheet or the adherend may be broken at the time of peeling. Yes, not preferred. Examples of the adherend used in the laminate of the present invention include those exemplified as the base material of the pressure-sensitive adhesive sheet.
【００３１】[0031]
【実施例】以下に本発明の実施例を説明するが、本発明
は、これらに限定されるものでは無い。尚、以下の記載
において、特にことわらない限り、部は重量部を示す。EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. In addition, in the following description, a part shows a weight part unless there is particular notice.
【００３２】［製造例１］既架橋型共重合体の製造例 攪拌機、還流冷却器、滴下槽及び温度計を取り付けた反
応容器に、純水２１０部を仕込み、温度を８０℃に保持
した後、過硫酸アンモニウム ０．３部を添加した。次
に純水９０部、ポリオキシエチレンノニルフェニルエー
テルの２５％水溶液３６部、過硫酸アンモニウム０．９
部、及び単量体（Ａ）として、 エチレングリコールジメタクリレート（ＥＤＭＡ） １５部、 アクリル酸 （ＡＡ） ３部、 メチルメタクリレート （ＭＭＡ） ６０部、 ブチルアクリレート （ＢＡ） １３２部、 ２−エチルヘキシルアクリレート （２ＥＨＡ） ９０部 を 仕込み、混合、攪拌した。 得られた混合液を３時間をかけて反応容器に滴下した。
滴下終了後、８０℃に１時間保持し、反応を終了させ、
ガラス転移温度−３３．０℃の既架橋型共重合体（１）
の水性分散体（固形分 ５０％）を得た。[Production Example 1] Production Example of Pre-crosslinked Copolymer 210 parts of pure water was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer, and the temperature was maintained at 80 ° C. And 0.3 parts of ammonium persulfate. Next, 90 parts of pure water, 36 parts of a 25% aqueous solution of polyoxyethylene nonylphenyl ether, and 0.9 parts of ammonium persulfate were used.
And as the monomer (A), 15 parts of ethylene glycol dimethacrylate (EDMA), 3 parts of acrylic acid (AA), 60 parts of methyl methacrylate (MMA), 132 parts of butyl acrylate (BA), and 2-ethylhexyl acrylate ( 2EHA) 90 parts were charged, mixed and stirred. The obtained mixture was dropped into the reaction vessel over 3 hours.
After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 1 hour to terminate the reaction.
Pre-crosslinked copolymer having a glass transition temperature of -33.0 ° C (1)
An aqueous dispersion (solid content: 50%) was obtained.
【００３３】［製造例２］既架橋型共重合体の製造例 ［製造例１］に於いて用いたエチレングリコールジメタ
クリレートをジビニルベンゼン（ＤＢＶ）に代えた以外
は製造例１と同様にして、で反応し、ガラス転移温度−
３３．４℃の既架橋型共重合体（２）の水性分散体（固
形分 ５０％）を得た。[Production Example 2] Production Example of Cross-Linked Copolymer In the same manner as in Production Example 1, except that ethylene glycol dimethacrylate used in [Preparation Example 1] was replaced with divinylbenzene (DBV). And the glass transition temperature −
An aqueous dispersion (solid content: 50%) of the crosslinked copolymer (2) at 33.4 ° C was obtained.
【００３４】［製造例３〜６］［比較製造例１〜４］既
架橋型共重合体の製造例 表１、２に示す単量体混合物を用いて、製造例１と同様
にして既架橋型共重合体（３）〜（６）及び（イ）〜
（ニ）の水性分散体を得た。[Production Examples 3 to 6] [Comparative Production Examples 1 to 4] Production Examples of Cross-Linked Copolymers Using the monomer mixtures shown in Tables 1 and 2, cross-linking was carried out in the same manner as in Production Example 1. Type copolymers (3) to (6) and (a)
An aqueous dispersion of (d) was obtained.
【００３５】尚、既架橋型共重合体のガラス転移温度
は、以下の式に基づき、求めた。 １／Ｔｇ＝（Ｗ1 ／Ｔｇ1 ）＋ （Ｗ2 ／Ｔｇ2 ）＋・
・＋（Ｗn ／Ｔｇn ） Ｔｇ：既架橋型共重合体のガラス転移温度（Ｋ） Ｗn ：単量体の重量分率 Ｔｇn ：各単量体の単独重合体のＴｇ（Ｋ） 又、ガラス転移温度を求めるにあたっては、以下に示す
各単量体の単独重合体のガラス転移温度の値を使用し
た。 エチレングリコールジメタクリレート：４０５Ｋ ジビニールベンゼン ：３７９Ｋ アクリル酸 ：３７９Ｋ メチルメタクリレート ：３７８Ｋ ブチルアクリレート ：２１９Ｋ ２−エチルヘキシルアクリレート ：２０３ＫThe glass transition temperature of the crosslinked copolymer was determined based on the following equation. 1 / Tg = (W 1 / Tg 1) + (W 2 / Tg 2) + ·
· + (W n / Tg n ) Tg: Glass transition temperature of the already cross-linked copolymer (K) W n: weight fraction Tg n of monomers: Tg of a homopolymer of each monomer (K) In determining the glass transition temperature, the value of the glass transition temperature of the homopolymer of each monomer shown below was used. Ethylene glycol dimethacrylate: 405K Divinylbenzene: 379K Acrylic acid: 379K Methyl methacrylate: 378K Butyl acrylate: 219K 2-Ethylhexyl acrylate: 203K
【００３６】[0036]
【表１】 [Table 1]
【００３７】[0037]
【表２】 [Table 2]
【００３８】［実施例１〜６］及び［比較例１〜８］製
造例１〜６で得られた既架橋型共重合体（１）〜（６）
及び比較製造例１〜４で得られた既架橋型共重合体
（イ）〜（ニ）を使用し、表３に示す処方（固形分）に
従って、それぞれ感圧性接着剤組成物を得た。得られた
各感圧性接着剤組成物を用いて乾燥後の重量が５ｇ／ｍ
2 になるようにワイヤーバーコーターで上質紙に塗工
し、熱風循環式オーブンを使用して、８０℃−６０秒間
乾燥し、感圧性接着接着シートを作成した。次いで、２
本の鉄ロール間の隙間を感圧性接着シート及び上質紙の
総厚の４０％に調整し、得られた感圧性接着シートの感
圧性接着接着剤層と、被着体たる上質紙とを接触せしめ
つつ、その２本の鉄ロール間を通過させて、圧着・貼り
合わせて、積層体を得た。得られた感圧性接着シートの
指触粘着性を評価し、さらに得られた積層体について初
期、及び室温２３℃、相対湿度４３％、蛍光灯の点灯下
で１４日間及びに２１日間保存した後の接着強度を以下
のようにして求め、結果を表３に示す。[Examples 1 to 6] and [Comparative Examples 1 to 8] The crosslinked copolymers (1) to (6) obtained in Production Examples 1 to 6
Using the crosslinked copolymers (a) to (d) obtained in Comparative Production Examples 1 to 4, pressure-sensitive adhesive compositions were respectively obtained in accordance with the formulations (solid contents) shown in Table 3. The weight after drying using each of the obtained pressure-sensitive adhesive compositions is 5 g / m2.
The coated paper was coated on wood free paper with a wire bar coater so as to obtain No. 2, and dried at 80 ° C. for 60 seconds using a hot air circulation oven to prepare a pressure-sensitive adhesive sheet. Then 2
The gap between the iron rolls is adjusted to 40% of the total thickness of the pressure-sensitive adhesive sheet and the high-quality paper, and the pressure-sensitive adhesive layer of the obtained pressure-sensitive adhesive sheet is brought into contact with the high-quality paper as an adherend. While passing, the sheet was passed between the two iron rolls, pressed and bonded to obtain a laminate. The resulting pressure-sensitive adhesive sheet was evaluated for finger-tactility, and the resulting laminate was initially stored and kept at room temperature of 23 ° C. and relative humidity of 43% for 14 days and for 21 days under lighting of a fluorescent lamp. Was determined as follows, and the results are shown in Table 3.
【００３９】１．指触粘着性 ：感圧性接着剤組成物の
塗工面を指触し、タック（粘着によるベタツキ）の有無
を評価する。 〇：タックが全くなし。 △：タックがあるが弱い。 ×：タックが強くある。1. Finger touch adhesion: The coated surface of the pressure-sensitive adhesive composition is touched with a finger to evaluate the presence or absence of tack (stickiness due to adhesion). 〇: No tack at all. Δ: Tack is present but weak. X: The tack is strong.
【００４０】２．接着強度：積層体を２．５ｃｍ幅に切
断し、３０ｃｍ／分の速度でＴ型剥離を行った。接着強
度を求めた。［ｇ／２．５ｃｍ］の単位で表す。2. Adhesive strength: The laminate was cut into a width of 2.5 cm, and T-shaped peeling was performed at a speed of 30 cm / min. The adhesive strength was determined. Expressed in the unit of [g / 2.5 cm].
【００４１】[0041]
【表３】 [Table 3]
【００４２】[0042]
【発明の効果】以上に詳述したように、天然ゴムラテッ
クスを用いた場合には溶液性状の不安定さを呈するが、
本発明の感圧性接着剤組成物は、そのような溶液性状の
不安定さを呈することもなく、常温では指触粘着性を示
さない剥離紙不要の感圧性接着シートを提供することが
でき、該感圧性接着シートは、必要十分な初期接着強度
を示し、且つ、接着強度が経時で変化することのない積
層体であって、しかも基材及び被着体を損傷することな
く必要に応じて剥離可能な積層体を提供することができ
る。As described in detail above, when natural rubber latex is used, instability of solution properties is exhibited.
The pressure-sensitive adhesive composition of the present invention can provide a pressure-sensitive adhesive sheet which does not exhibit such solution property instability and does not require a release paper which does not exhibit finger tackiness at room temperature. The pressure-sensitive adhesive sheet has a necessary and sufficient initial adhesive strength, and is a laminate in which the adhesive strength does not change with time, and as necessary without damaging the base material and the adherend. A peelable laminate can be provided.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｊ 133/02 Ｃ０９Ｊ 133/02 133/06 133/06 Ｆターム(参考） 4J004 AA04 AA07 AA10 AA17 AA18 AB01 CA02 CA03 CA04 CA05 CA06 CC02 CC03 CD03 CD04 CD06 EA06 FA10 GA01 4J040 BA012 BA112 DB041 DB071 DF041 DF051 GA02 GA07 GA08 HA126 HA136 HA196 HA306 HA356 HC09 JA03 JA09 JB09 KA03 KA42 LA02 LA03 LA06 MA09 NA06 PA33 PA42 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C09J 133/02 C09J 133/02 133/06 133/06 F term (Reference) 4J004 AA04 AA07 AA10 AA17 AA18 AB01 CA02 CA03 CA04 CA05 CA06 CC02 CC03 CD03 CD04 CD06 EA06 FA10 GA01 4J040 BA012 BA112 DB041 DB071 DF041 DF051 GA02 GA07 GA08 HA126 HA136 HA196 HA306 HA356 HC09 JA03 JA09 JB09 KA03 KA42 LA02 LA03 LA06 MA09 NA06 PA33 PA42
Claims (6)
る多官能性単量体を１〜２０重量％含有するラジカル重
合性単量体混合物を共重合してなるガラス転移温度が−
６０〜０℃の皮膜形成能を有する既架橋型共重合体
（Ａ）１００重量部に対して、平均粒径が１〜３０μｍ
ｍの微粒子（Ｂ）２０〜１５０重量部を含有することを
特徴とする再剥離可能な感圧性接着剤組成物。A glass transition temperature obtained by copolymerizing a radical polymerizable monomer mixture containing 1 to 20% by weight of a polyfunctional monomer having two or more radical polymerizable unsaturated groups is-
The average particle size is 1 to 30 μm with respect to 100 parts by weight of the crosslinked copolymer (A) having a film-forming ability at 60 to 0 ° C.
A removable pressure-sensitive adhesive composition comprising 20 to 150 parts by weight of fine particles (B) having a particle size of m.
散せしめてなる水性分散体を含有することを特徴とする
請求項１記載の感圧性接着剤組成物。2. The pressure-sensitive adhesive composition according to claim 1, further comprising an aqueous dispersion obtained by dispersing the cross-linked copolymer (A) in an aqueous medium.
ート状基材に塗工、乾燥してなる感圧性接着シート。3. A pressure-sensitive adhesive sheet obtained by applying the pressure-sensitive adhesive composition according to claim 2 to a sheet-like substrate and drying.
において指触粘着性を有しないことを特徴とする請求項
３記載の感圧性接着シート。4. The coating layer of the pressure-sensitive adhesive composition has a temperature of 50 ° C.
The pressure-sensitive adhesive sheet according to claim 3, wherein the pressure-sensitive adhesive sheet has no finger touch adhesiveness.
性接着剤組成物の層を被着体に接触せしめ、３０ｋｇ／
ｃｍ2 以上に加圧して、感圧性接着シートと被着体とを
再剥離可能に貼り合わせて得られる積層体。5. A layer of the pressure-sensitive adhesive composition of the pressure-sensitive adhesive sheet according to claim 4, which is brought into contact with an adherend, to obtain 30 kg /
A laminate obtained by pressing the pressure-sensitive adhesive sheet and the adherend so that the pressure-sensitive adhesive sheet and the adherend can be removably peeled off by applying a pressure of at least 2 cm 2 .
体の総厚の３０〜８０％にロール隙間を調整した２本の
ロールの間を、感圧性接着シートの感圧性接着剤層と被
着体とを接触させつつ、通過させることを特徴とする感
圧性接着シートと被着体とを貼り合わせる方法。6. The pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet between the pressure-sensitive adhesive sheet according to claim 4 and two rolls whose roll gap is adjusted to 30 to 80% of the total thickness of the adherend. A method of bonding a pressure-sensitive adhesive sheet and an adherend, wherein the pressure-sensitive adhesive sheet and the adherend are passed through while making contact with the adherend.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28893799A JP2001107007A (en) | 1999-10-12 | 1999-10-12 | Pressure-sensitive adhesive composition and its utilization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28893799A JP2001107007A (en) | 1999-10-12 | 1999-10-12 | Pressure-sensitive adhesive composition and its utilization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001107007A true JP2001107007A (en) | 2001-04-17 |
Family
ID=17736750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28893799A Withdrawn JP2001107007A (en) | 1999-10-12 | 1999-10-12 | Pressure-sensitive adhesive composition and its utilization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001107007A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2177584A1 (en) | 2008-10-16 | 2010-04-21 | Nitto Denko Corporation | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| EP2177583A1 (en) | 2008-10-16 | 2010-04-21 | Nitto Denko Corporation | Pressure-sensitive adhesive composition and use thereof |
| JP2013166915A (en) * | 2012-01-16 | 2013-08-29 | Toyo Ink Sc Holdings Co Ltd | Pressure-sensitive adhesive composition using alcohol solvent and pressure sensitive adhesive sheet using the same |
| JP6149148B1 (en) * | 2016-12-07 | 2017-06-14 | 株式会社アートネイチャー | Wig pressure-sensitive adhesive and method of using the wig pressure-sensitive adhesive |
| JP2017149116A (en) * | 2016-02-26 | 2017-08-31 | 日東紡績株式会社 | Transparent composite sheet |
-
1999
- 1999-10-12 JP JP28893799A patent/JP2001107007A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2177584A1 (en) | 2008-10-16 | 2010-04-21 | Nitto Denko Corporation | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| EP2177583A1 (en) | 2008-10-16 | 2010-04-21 | Nitto Denko Corporation | Pressure-sensitive adhesive composition and use thereof |
| US8258240B2 (en) | 2008-10-16 | 2012-09-04 | Nitto Denko Corporation | Pressure-sensitive adhesive composition and use thereof |
| US8501640B2 (en) | 2008-10-16 | 2013-08-06 | Nitto Denko Corporation | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| JP2013166915A (en) * | 2012-01-16 | 2013-08-29 | Toyo Ink Sc Holdings Co Ltd | Pressure-sensitive adhesive composition using alcohol solvent and pressure sensitive adhesive sheet using the same |
| JP2017149116A (en) * | 2016-02-26 | 2017-08-31 | 日東紡績株式会社 | Transparent composite sheet |
| JP6149148B1 (en) * | 2016-12-07 | 2017-06-14 | 株式会社アートネイチャー | Wig pressure-sensitive adhesive and method of using the wig pressure-sensitive adhesive |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6734010B2 (en) | Temperature-sensitive adhesive sheet and temperature-sensitive adhesive tape | |
| JP5485864B2 (en) | Removable microsphere particle adhesive coated article | |
| JPH08218040A (en) | Tacky adhesive sheet | |
| JPH0649415A (en) | Tacky agent and double-sided tacky tape | |
| JP2002532609A (en) | Label adhesive and structure showing low adhesive residue in printer | |
| JP4047434B2 (en) | Adhesive sheets | |
| JP2001107007A (en) | Pressure-sensitive adhesive composition and its utilization | |
| KR101193705B1 (en) | Releasable adhesive sheet, method for manufacturing same, and releasable adhesive sheet laminate | |
| JP3495981B2 (en) | Cold seal adhesive | |
| JP2000192007A (en) | Acrylic pressure sensitive adhesive composition and its production | |
| JPH11116904A (en) | Adhesive sheet for oil surface | |
| JP4492981B2 (en) | Manufacturing method of adhesive sheet | |
| JP2001131503A (en) | Pressure-sensitive adhesive sheet | |
| JPH08183935A (en) | Re-releasable pressure-sensitive adhesive sheet | |
| JP3063762B2 (en) | Adhesive sheet | |
| JPH09111200A (en) | Pressure-sensitive adhesive sheet for sticking wafer | |
| JP3503855B2 (en) | Adhesive sheet and method for producing the same | |
| JP2000355680A (en) | Production of molded product | |
| JP2003246821A (en) | Vinylidene chloride copolymer latex | |
| JP2946796B2 (en) | Adhesive sheet | |
| JPH10292161A (en) | Adhesive tape for polyolefin | |
| JP4253171B2 (en) | Cold seal adhesive | |
| JP2000038554A (en) | Pressure-sensitive adhesive label | |
| JPH10237399A (en) | Re-releasable adhesive sheet | |
| JP2001311068A (en) | Composite-type ultraviolet curing adhesive mass composition, double-sided tacky tape and method for producing the same tape |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060706 |
|
| A761 | Written withdrawal of application |
Free format text: JAPANESE INTERMEDIATE CODE: A761 Effective date: 20080807 |