JP2002105420A - Re-releasable, water-dispersible, pressure-sensitive adhesive - Google Patents
Re-releasable, water-dispersible, pressure-sensitive adhesiveInfo
- Publication number
- JP2002105420A JP2002105420A JP2000298074A JP2000298074A JP2002105420A JP 2002105420 A JP2002105420 A JP 2002105420A JP 2000298074 A JP2000298074 A JP 2000298074A JP 2000298074 A JP2000298074 A JP 2000298074A JP 2002105420 A JP2002105420 A JP 2002105420A
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- pressure
- water
- copolymer
- dispersible
- 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.)
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- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、粘着ラベル、テー
プ、シート、表面保護フィルム等に使用でき、粘着性に
優れ、各種の被着体（金属板、ガラス、プラスチック板
等）に貼り付け後、長期間放置した後でも容易に剥離で
きる再剥離型水分散感圧接着剤に関するものである。The present invention can be used for adhesive labels, tapes, sheets, surface protective films, etc., has excellent adhesiveness, and can be used after being adhered to various adherends (metal plates, glass, plastic plates, etc.). And a removable water-dispersible pressure-sensitive adhesive which can be easily peeled off even after being left for a long time.
【０００２】[0002]
【従来の技術】プ ライスラベルや工程管理用ラベル、
宅配便の宛名ラベル等に粘着ラベルが使用されている
が、これらの用途で被着体に貼り付けた後、一定時間経
過後被着体から剥離される場合が少なくない。このと
き、感圧接着剤の一部が被着体に残ることがしばしば起
こる。また、基材が紙の場合、紙の強度が弱いため紙破
れを起こして被着体からの剥離が困難になる場合が多
い。このようなことがなく被着体から容易に剥離できる
ように、再剥離型感圧接着剤が従来から提案されてい
る。2. Description of the Related Art Rice labels and process control labels,
Adhesive labels are used as address labels for courier services, and in many cases, they are peeled off from the adherend after a certain period of time after being adhered to the adherend in these applications. At this time, a part of the pressure-sensitive adhesive often remains on the adherend. In addition, when the base material is paper, the strength of the paper is weak, so that the paper is often broken, making it difficult to peel off the adherend. Conventionally, a removable pressure-sensitive adhesive has been proposed so that it can be easily peeled off from an adherend without such a problem.
【０００３】特公平５−０７５０３４号公報には、特定
のモノマー組成、分子量、ガラス転移温度，粒子径の水
系共重合エマルジョンにポリグリシジル化合物を配合し
たことを特徴とする水系感圧接着剤が開示されている。
この感圧接着剤ではエマルジョンにポリグリシジル化合
物を配合すると、エマルジョンの粒子間架橋反応が進み
粘度増加やゲル化を起こすため、ポリグリシジル化合物
を配合後のポットライフの問題がある。[0003] Japanese Patent Publication No. 5-075034 discloses an aqueous pressure-sensitive adhesive characterized in that a polyglycidyl compound is blended in an aqueous copolymer emulsion having a specific monomer composition, molecular weight, glass transition temperature and particle size. Have been.
In this pressure-sensitive adhesive, when a polyglycidyl compound is blended with the emulsion, a cross-linking reaction between the emulsion particles proceeds to cause an increase in viscosity and gelation, so that there is a problem of pot life after blending the polyglycidyl compound.
【０００４】特開平７−２７８２３３号公報には、特定
のアクリル系エマルジョン型粘着剤に多官能アジリジン
化合物及び多官能カルボジイミド化合物から選ばれる１
種以上の架橋剤が添加されたアクリル系エマルジョン型
粘着剤が開示されている。この特許で挙げられている多
官能カルボジイミド化合物（商品名：ユーカリンクＸＬ
−２９ＳＥ、ユニオンカーバイド（株）製）を使用して
も良好な再剥離性は得られない。Japanese Patent Application Laid-Open No. 7-278233 discloses that a specific acrylic emulsion-type pressure-sensitive adhesive is selected from a polyfunctional aziridine compound and a polyfunctional carbodiimide compound.
An acrylic emulsion-type pressure-sensitive adhesive to which at least one kind of crosslinking agent is added is disclosed. The polyfunctional carbodiimide compound mentioned in this patent (trade name: Eukalink XL)
Even if -29SE (manufactured by Union Carbide Co., Ltd.) is used, good removability cannot be obtained.
【０００５】また、特開昭５５−１３７１７６号公報及
び特開平８−４１４３２号公報には、溶剤型のアクリル
酸エステル共重合体にカルボジイミド化合物を配合して
なる感圧接着剤組成物が開示されている。これらは溶剤
系であるため、環境衛生上望ましくなく、紙基材に対す
るしみこみが多過ぎるため使用上に問題点がある。Further, JP-A-55-137176 and JP-A-8-41432 disclose a pressure-sensitive adhesive composition obtained by blending a carbodiimide compound with a solvent-type acrylate copolymer. ing. Since these are solvent-based, they are not desirable in terms of environmental hygiene, and there is a problem in use because they excessively permeate the paper substrate.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、アク
リル系共重合体水分散液を用い、架橋剤添加による経時
安定性が良好であり、粘着性に優れ、各種の被着体（金
属板、ガラス、プラスチック板、段ボール等）に貼り付
け後、長期間放置した後でも容易に剥離できる再剥離型
水分散感圧接着剤を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to provide an aqueous dispersion of an acrylic copolymer, which has good stability over time due to the addition of a cross-linking agent, excellent tackiness, and various adherends (metals). It is an object of the present invention to provide a re-peelable water-dispersible pressure-sensitive adhesive which can be easily peeled off even after being attached to a plate, glass, plastic plate, corrugated cardboard, etc. and left for a long time.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、鋭意検討
した結果、保持力を特定範囲に設定したアクリル系共重
合体水分散液に特定のカルボジイミド化合物を添加して
も、感圧接着剤の経時安定性が良く、塗工後に架橋反応
が速やかに完結し、従って、再剥離性に優れた１液型の
再剥離型水分散感圧接着剤が得られることを知り、本発
明を完成するに至った。Means for Solving the Problems As a result of intensive studies, the present inventors have found that even when a specific carbodiimide compound is added to an aqueous dispersion of an acrylic copolymer in which the holding power is set within a specific range, pressure-sensitive adhesive bonding is performed. The present invention was found to have a good stability over time of the agent and a rapid completion of the cross-linking reaction after coating, thereby obtaining a one-part re-peelable water-dispersible pressure-sensitive adhesive excellent in re-peelability. It was completed.
【０００８】すなわち、本発明は、アルキル基の炭素数
が４〜１２の（メタ）アクリル酸アルキルエステルを主
成分とし、かつカルボキシル基含有不飽和単量体を０．
１〜５重量％含有する共重合体の水分散液に、カルボジ
イミド結合（−Ｎ＝Ｃ＝Ｎ−）とエチレンオキサイド部
位（−ＣＨ２−ＣＨ２−Ｏ−）を有するカルボジイミド
化合物を添加してなり、カルボジイミド化合物の添加量
が、カルボキシル基含有不飽和単量体のカルボキシル基
１当量当り、カルボジイミド結合が０．０１〜５当量か
らなる再剥離型水分散感圧接着剤であり、該共重合体の
４０℃おける保持力が１００秒〜１０，０００秒である
ことを特徴とする。That is, the present invention comprises an alkyl (meth) acrylate having 4 to 12 carbon atoms in the alkyl group as a main component and a carboxyl group-containing unsaturated monomer in an amount of 0.1 to 0.1%.
The aqueous dispersion of a copolymer containing 1 to 5 wt%, by adding a carbodiimide compound having a carbodiimide bond (-N = C = N-) with ethylene oxide moiety (-CH 2 -CH 2 -O-) The carbodiimide compound is a removable water-dispersible pressure-sensitive adhesive comprising 0.01 to 5 equivalents of a carbodiimide bond per equivalent of a carboxyl group of a carboxyl group-containing unsaturated monomer. The coalescence is characterized in that the holding power at 40 ° C. is 100 seconds to 10,000 seconds.
【０００９】本発明において、４０℃における保持力
は、アクリル系共重合体水分散液をシリコン系剥離紙に
塗膜厚が２５μｍになるように塗工し１００℃で１分間
乾燥後、２５μｍペットフィルムに転写して得られた粘
着シートをＪＩＳ Ｚ−０２３７「粘着テープ・粘着シ
ート試験法」に準じて測定する。幅２５ｍｍ×長さ５０
ｍｍ切断した試験片を接着面積が２５ｍｍ×２５ｍｍに
なるように、研磨し清浄にしたＳＵＳ３０４板に貼り付
け、重さ２Ｋｇの圧着ロールで１往復させ圧着し、２３
℃、６５％ＲＨ中に３０分放置後、４０℃の雰囲気中で
１Ｋｇの荷重をかけ落下するまでの時間（秒数）を測定
する。In the present invention, the holding power at 40.degree. C. is determined by applying an aqueous dispersion of an acrylic copolymer to a silicone release paper so that the coating thickness becomes 25 .mu.m, drying at 100.degree. The pressure-sensitive adhesive sheet obtained by transferring the film to a film is measured according to JIS Z-0237 "Testing method for pressure-sensitive adhesive tape / pressure-sensitive adhesive sheet". 25mm width x 50 length
The test piece cut in mm was adhered to a polished and cleaned SUS304 plate so that the adhesion area became 25 mm × 25 mm, and the test piece was reciprocated once with a pressure roll having a weight of 2 kg, and pressed.
After standing in a 65 ° C., 65% RH for 30 minutes, a load (1 kg) is applied in an atmosphere of 40 ° C. to measure the time (in seconds) until the device falls.
【００１０】[0010]
【発明の実施の形態】以下、本発明の構成を詳細に説明
する。本発明に用いる共重合体水分散液は、アルキル基
の炭素数が４〜１２の（メタ）アクリル酸アルキルエス
テルを主成分とし、かつカルボキシル基含有不飽和単量
体を０．１〜５重量％含む単量体混合物を公知の水を媒
体とする重合法、特に乳化重合法により得ることができ
る。本発明に使用するアルキル基の炭素数が４〜１２の
（メタ）アクリル酸アルキルエステル単量体としては、
アルキル基がブチル基、イソブチル基、イソアミル基、
ヘキシル基、ヘプチル基、２−エチルヘキシル基、イソ
オクチル基、イソノニル基、イソデシル基等からなるア
クリル酸ないしメタクリル酸のアルキルエステルであ
り、これらの群より選ばれた少なくとも１種以上使用す
ることができる。（メタ）アクリル酸アルキルエステル
単量体の使用量は、全単量体中５０〜９９．９重量％の
割合で用いられる。その使用量が５０重量％より少ない
場合には、初期粘着力の低下を招くため好ましくない。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration of the present invention will be described below in detail. The aqueous dispersion of the copolymer used in the present invention contains, as a main component, an alkyl (meth) acrylate having 4 to 12 carbon atoms in the alkyl group, and 0.1 to 5% by weight of a carboxyl group-containing unsaturated monomer. % Of the monomer mixture can be obtained by a known polymerization method using water as a medium, particularly an emulsion polymerization method. Examples of the alkyl (meth) acrylate monomer having 4 to 12 carbon atoms in the alkyl group used in the present invention include:
Alkyl group is butyl group, isobutyl group, isoamyl group,
It is an alkyl ester of acrylic acid or methacrylic acid comprising a hexyl group, a heptyl group, a 2-ethylhexyl group, an isooctyl group, an isononyl group, an isodecyl group and the like, and at least one selected from these groups can be used. The amount of the alkyl (meth) acrylate monomer used is 50 to 99.9% by weight based on the total amount of the monomers. If the amount is less than 50% by weight, the initial adhesive strength is undesirably reduced.
【００１１】本発明に使用するカルボキシル基含有不飽
和単量体は、架橋反応による凝集力を向上させるために
必要である。１分子中にカルボキシル基と炭素−炭素不
飽和結合を有する単量体、例えば、アクリル酸、メタク
リル酸、イタコン酸、マレイン酸、クロトン酸等が使用
することができ、これらの群より選ばれた少なくとも１
種以上使用することができる。カルボキシル基含有単量
体の使用量は、全単量体中０．１〜５重量％、好ましく
は０．２〜３重量％である。その使用量が０．１重量％
より少ない場合には、凝集力が低下し、また５重量％よ
り多い場合は、粘着力の経時上昇を招く。The unsaturated monomer having a carboxyl group used in the present invention is necessary for improving the cohesive force by a crosslinking reaction. Monomers having a carboxyl group and a carbon-carbon unsaturated bond in one molecule, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid and the like can be used, and are selected from these groups. At least one
More than one species can be used. The amount of the carboxyl group-containing monomer used is 0.1 to 5% by weight, preferably 0.2 to 3% by weight, based on all the monomers. 0.1% by weight
If the amount is less than the above, the cohesive strength is reduced, and if it is more than 5% by weight, the adhesive force is increased with time.
【００１２】上記の単量体のほか、メタクリル酸メチ
ル、アクリル酸エチル、アクリル酸イソプロピル、メタ
クリル酸トリデシル、（メタ）アクリル酸ステアリル、
（メタ）アクリル酸シクロヘキシル、（メタ）アクリル
酸ベンジル、（メタ）アクリル酸イソボルニル、（メ
タ）アクリル酸ｔ−ブチルシクロヘキシル等の（メタ）
アクリル酸エステル系単量体、さらに（メタ）アクリル
酸ヒドロキシアルキル、ジ（メタ）アクリル酸グリセリ
ンエステル等の水酸基含有単量体、及び、無水マレイン
酸、酢酸ビニル、スチレン、（メタ）アクリロニトリ
ル、Ｎ−ビニルピロリドン、（メタ）アクリロイルモル
ホリン、シクロヘキシルマレイミド、イソプロピルマレ
イミド、（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル
（メタ）アクリルアミド、（メタ）アクリル酸グリシジ
ル等も使用することができる。その使用量は、全単量体
体中０〜４３重量％であり、好ましくは０〜３０重量％
である。使用量が４３重量％より多い場合は、再剥離性
が低下する。In addition to the above monomers, methyl methacrylate, ethyl acrylate, isopropyl acrylate, tridecyl methacrylate, stearyl (meth) acrylate,
(Meth) such as cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, and t-butylcyclohexyl (meth) acrylate
Hydroxy group-containing monomers such as acrylic acid ester monomers, hydroxyalkyl (meth) acrylates and glycerin di (meth) acrylate, and maleic anhydride, vinyl acetate, styrene, (meth) acrylonitrile, N -Vinylpyrrolidone, (meth) acryloylmorpholine, cyclohexylmaleimide, isopropylmaleimide, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, glycidyl (meth) acrylate and the like can also be used. The amount used is from 0 to 43% by weight, preferably from 0 to 30% by weight, based on all the monomers.
It is. If the amount used is more than 43% by weight, the removability will decrease.
【００１３】なお、上記の単量体混合物のほかに、感圧
接着剤の凝集力をさらに向上させるため、内部架橋剤と
して、（ポリ）エチレングリコールジ（メタ）アクリレ
ート、メチレンビスアクリルアミド、１，６−ヘキサン
ジオ―ルジ（メタ）アクリレート、トリメチロ―ルプロ
パントリ（メタ）アクリレート等の多官能性アクリル系
単量体を使用してもよい。これらの多官能性アクリル系
単量体の使用量は、全単量体中０〜２重量％がよい。そ
の使用量が２重量％を超える場合には、再剥離性が低下
するために好ましくない。[0013] In addition to the above-mentioned monomer mixture, (poly) ethylene glycol di (meth) acrylate, methylenebisacrylamide, 1,2 Polyfunctional acrylic monomers such as 6-hexanediol di (meth) acrylate and trimethylolpropane tri (meth) acrylate may be used. The use amount of these polyfunctional acrylic monomers is preferably 0 to 2% by weight based on all the monomers. If the amount exceeds 2% by weight, the removability is undesirably reduced.
【００１４】本発明のアクリル系共重合体水分散液を得
るための乳化重合に際し、重合安定性を確保するため、
アニオン系やノニオン系の乳化剤が適量用いられる。ア
ニオン系乳化剤としては、ラウリル硫酸ナトリウム、ラ
ウリル硫酸アンモニウム、ドデシルベンゼンスルホン酸
ナトリウム、ポリオキシエチレンアルキルエーテル硫酸
ナトリウム、ポリオキシエチレンアルキルフエニルエ―
テル硫酸ナトリウム等が挙げられ、ノニオン系乳化剤と
しては、ポリオキシエチレンアルキルエ―テル、ポリオ
キシエチレンアルキルフエニルエーテル等が挙げられ
る。アニオン系乳化剤単独、あるいはノニオン系乳化剤
を併用して使用することができる。また、アニオン系及
びノニオン系のいずれにおいても、例えばプロペニル基
等を導入したラジカル重合性の乳化剤を用いてもよい。In the emulsion polymerization for obtaining the aqueous dispersion of the acrylic copolymer of the present invention, in order to secure polymerization stability,
An appropriate amount of an anionic or nonionic emulsifier is used. Examples of the anionic emulsifier include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium polyoxyethylene alkyl ether sulfate, and polyoxyethylene alkylphenyl ether.
Examples of the nonionic emulsifier include polyoxyethylene alkyl ether and polyoxyethylene alkyl phenyl ether. The anionic emulsifier can be used alone or in combination with a nonionic emulsifier. In both anionic and nonionic types, a radically polymerizable emulsifier into which, for example, a propenyl group or the like has been introduced may be used.
【００１５】本発明のアクリル系共重合体水分散液を得
るための乳化重合に際し、重合開始剤が用いられる。重
合開始剤として、具体的に２，２´−アゾビス（２−メ
チルプロピオンアミジン）二塩酸塩、２，２´−アゾビ
ス（２−アミジノプロパン）ジヒドロクロライド等のア
ゾ系、過硫酸カリウム、過硫酸アンモニウム等の過硫酸
塩、ベンゾイルパーオキサイド、ｔ−ブチルハイドロパ
ーオキサイド、過酸化水素等の過酸化物、過硫酸塩と亜
硫酸水素ナトリウムとの組み合わせや過酸化物とアスコ
ルビン酸ナトリウムとの組み合わせ等からなるレドツク
ス開始剤が用いられる。これらの重合開始剤は、通常
は、乳化重合の各段階に所定量を添加して、重合反応を
行わせるようにすればよい。In the emulsion polymerization for obtaining the aqueous dispersion of the acrylic copolymer of the present invention, a polymerization initiator is used. Specific examples of the polymerization initiator include azo compounds such as 2,2′-azobis (2-methylpropionamidine) dihydrochloride and 2,2′-azobis (2-amidinopropane) dihydrochloride, potassium persulfate, and ammonium persulfate. Persulfates such as benzoyl peroxide, t-butyl hydroperoxide, peroxides such as hydrogen peroxide, combinations of persulfates with sodium bisulfite, combinations of peroxides with sodium ascorbate, etc. Redox initiators are used. Usually, a predetermined amount of these polymerization initiators may be added to each stage of emulsion polymerization so as to cause a polymerization reaction.
【００１６】また、本発明のアクリル系共重合体水分散
液を得るための乳化重合に際し、重合度を調整するため
に連鎖移動剤を使用することができる。このような連鎖
移動剤として、ラウリルメルカプタン、ブチルメルカプ
タン、２−メルカプトエタノール、トリクロロブロモメ
タン等を挙げることができ、これらの群れより選ばれた
少なくとも１種以上使用することができる。In the emulsion polymerization for obtaining the aqueous dispersion of the acrylic copolymer of the present invention, a chain transfer agent can be used to adjust the degree of polymerization. Examples of such a chain transfer agent include lauryl mercaptan, butyl mercaptan, 2-mercaptoethanol, trichlorobromomethane, and the like, and at least one selected from these groups can be used.
【００１７】本発明のアクリル系共重合体水分散液を得
るための乳化重合に際し、乳化重合後、通常、アンモニ
ア等の中和剤を用いて中和処理し、所定のｐＨに調整す
ることにより、安定な水分散共重合体が得られる。In the emulsion polymerization for obtaining the aqueous dispersion of the acrylic copolymer of the present invention, the emulsion is usually neutralized with a neutralizing agent such as ammonia and adjusted to a predetermined pH. And a stable aqueous dispersion copolymer is obtained.
【００１８】本発明のアクリル系共重合体は、４０℃に
おける保持力が１００秒〜１０，０００秒であることが
必要である。好ましくは１００秒〜５，０００秒であ
る。保持力を１００秒〜１０，０００秒に調整すること
により基材へのしみこみ及び再剥離性のバランスの取れ
た再剥離型水分散感圧接着剤を得ることが出来る。４０
℃における保持力が１００秒より少ない場合は紙等基材
へのしみこみが多すぎて、外観上好ましくない。また１
０，０００秒を超える場合は、基材に対する密着性が悪
くなるため再剥離性が低下する。The acrylic copolymer of the present invention needs to have a holding power at 40 ° C. of 100 seconds to 10,000 seconds. Preferably, it is 100 seconds to 5,000 seconds. By adjusting the holding force to 100 seconds to 10,000 seconds, it is possible to obtain a re-peelable water-dispersible pressure-sensitive adhesive having a good balance between infiltration into the substrate and re-peelability. 40
If the holding power at 100 ° C. is less than 100 seconds, too much penetration into a substrate such as paper is unfavorable in appearance. Also one
If the time exceeds 000 seconds, the adhesion to the substrate becomes poor, so that the removability is reduced.
【００１９】本発明に用いるカルボジイミド化合物は、
分子内にカルボジイミド結合（−Ｎ＝Ｃ＝Ｎ−）とエチ
レンオキサイド部位（−ＣＨ２−ＣＨ２−Ｏ−）を有す
るものであれば、とくに制限することなく使用すること
ができる。該カルボジイミド化合物は、有機ジイソシア
ネートの脱二酸化炭素を伴う縮合反応を利用する公知の
方法により製造したカルボジイミド化合物にポリエチレ
ングリコールを反応させることで製造することができ、
市販品としては、日清紡（株）製の商品名カルボジライ
トＥ−０１、Ｅ−０２、Ｖ−０２、Ｖ−０４、Ｖ−０６
等を挙げることができる。これらの群れより選ばれた少
なくとも１種以上使用することができる。The carbodiimide compound used in the present invention is
As long as it has a molecular carbodiimide bond in the (-N = C = N-) with ethylene oxide moiety (-CH 2 -CH 2 -O-), it can be used without particular limitation. The carbodiimide compound can be produced by reacting polyethylene glycol with a carbodiimide compound produced by a known method utilizing a condensation reaction involving decarbonation of an organic diisocyanate,
As commercial products, Nisshinbo Co., Ltd. brand name Carbodilite E-01, E-02, V-02, V-04, V-06
And the like. At least one selected from these groups can be used.
【００２０】本発明に用いるカルボジイミド化合物の使
用量は、アクリル系共重合体に含まれるカルボキシル基
１当量当り、カルボジイミド基が０．０１〜５当量、好
ましくは０．０５〜３当量が使用できる。その使用量が
０．０１当量より少ない場合には、再剥離型感圧接着剤
の凝集性が劣り、またその使用量が５当量を超える場合
は、水分散共重合体との反応に関与しない未反応の架橋
剤が多く残存して、再剥離性が低下する。The carbodiimide compound used in the present invention can be used in an amount of 0.01 to 5 equivalents, preferably 0.05 to 3 equivalents of carbodiimide group per equivalent of carboxyl group contained in the acrylic copolymer. If the amount used is less than 0.01 equivalent, the cohesiveness of the removable pressure-sensitive adhesive is inferior. If the amount used exceeds 5 equivalents, it does not participate in the reaction with the water-dispersed copolymer. A large amount of unreacted crosslinking agent remains, and the removability is reduced.
【００２１】本発明の再剥離型水分散感圧接着剤は、必
要に応じ本発明の効果を損なわない範囲で、消泡剤、増
粘剤、粘着付与剤、可塑剤、濡れ剤、無機粉末や金属粉
末等の充填剤、顔料、着色剤の公知の添加剤を使用する
ことができる。The removable water-dispersible pressure-sensitive adhesive of the present invention may contain, if necessary, an antifoaming agent, a thickener, a tackifier, a plasticizer, a wetting agent, and an inorganic powder as long as the effects of the present invention are not impaired. Known additives such as fillers, pigments, and coloring agents such as metal powders and metal powders can be used.
【００２２】本発明の再剥離型水分散感圧接着剤は、水
分散液状態では共重合体とカルボジイミド化合物との反
応が起こらず、取り扱い上支障をきたすことのない経時
安定性を示す。一方、基材に塗布して、加熱乾燥後はカ
ルボキシル基とカルボジイミド基との架橋反応が速やか
に進行する。したがって、従来の架橋剤にみられたよう
な架橋が未反応の状態である心配がなく、所期の目的と
する良好な架橋効果を期待できるのである。The removable water-dispersible pressure-sensitive adhesive of the present invention does not cause a reaction between the copolymer and the carbodiimide compound in an aqueous dispersion state, and exhibits stability over time without any trouble in handling. On the other hand, after coating on a substrate and drying by heating, a crosslinking reaction between a carboxyl group and a carbodiimide group proceeds rapidly. Therefore, there is no concern that the crosslinking is unreacted as in the conventional crosslinking agent, and the desired desired crosslinking effect can be expected.
【００２３】本発明の再剥離型水分散感圧接着剤は、通
常の感圧接着シ―ト類の製造方法にしたがって、プラス
チツクフイルム、紙、金属箔等の適宜の支持体上に直接
塗工し乾燥することにより、あるいはセパレータ上に塗
工し乾燥したのち、適宜の支持体上に転写することによ
り、シート状やテープ状等の形態の再剥離型感圧接着シ
―ト類を得ることができる。The removable water-dispersible pressure-sensitive adhesive of the present invention is applied directly to a suitable support such as plastic film, paper, metal foil or the like in accordance with a usual method for producing pressure-sensitive adhesive sheets. To obtain a re-peelable pressure-sensitive adhesive sheet in the form of a sheet, tape, or the like, by drying, or by coating on a separator and drying, and then transferring it to an appropriate support. Can be.
【００２４】本発明の再剥離型水分散感圧接着剤は、通
常使用されている塗布装置、例えばロール塗布装置等で
塗工することができる。塗布量は、通常塗膜厚で５〜３
００μｍである。用途により塗膜厚を変えて使用するこ
とができる。The removable water-dispersible pressure-sensitive adhesive of the present invention can be applied by a commonly used coating device such as a roll coating device. The coating amount is usually 5 to 3
00 μm. The film thickness can be changed depending on the application.
【００２５】[0025]
【実施例】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、本発明は以下の実施例により限定
されるものではない。また、以下において、部もしくは
％とあるのはすべて重量部又は重量％を意味するもので
ある。Next, an embodiment of the present invention will be described in more detail. The present invention is not limited by the following examples. In the following, parts and% all mean parts by weight or% by weight.
【００２６】実施例１ 温度計、攪拌機、滴下装置、窒素導入管及び還流冷却管
を備えた反応器に、イオン交換水３８部及び窒素を封入
し、反応器の内温を８０℃に保ちながら、５％濃度の過
硫酸カリウム２部を添加し、予め別途に準備したアクリ
ル酸２−エチルヘキシル９９部、アクリル酸１部、ポリ
オキシエチレンノニルフェニルエーテル硫酸ナトリウム
（日本油脂（株）製 商品名トラックスＨ−４５）１．
５部及びイオン交換水５６部で乳化した単量体乳化物
を、２時間かけて滴下し乳化重合させた。並行して５％
濃度の過硫酸カリウム４部滴下した。滴下終了後８０℃
で２時間保ちその後室温まで冷却する。アンモニア水で
中和調製し、固形分５０％、粘度２００ｍＰａ・ｓ、ｐ
Ｈ８．０の水分散液を得た。該水分散液に、ポリアクリ
ル酸系増粘剤（ローム アンド ハース（株）製 商品
名ＡＳＥ−６０）を添加して増粘した。さらに、その固
形分１００部に対して５部のカルボジイミド化合物（日
清紡製 商品名カルボジライトＶ−０４）を添加してよ
く混合して、再剥離型水分散感圧接着剤を調製した。該
再剥離型水分散感圧接着剤を剥離紙に塗膜厚が２５μｍ
になるように塗布し、１００℃で１分間乾燥後、上質紙
（６４ｇ／ｍ２）に転写して、２３℃、６５％ＲＨの雰
囲気で７日間放置後、再剥離用粘着ラベルを得た。上記
架橋剤を配合する前の共重合体水分散液を、同様に剥離
紙に塗膜厚が２５μｍになるように塗布し、１００℃で
１分間乾燥後、２５μｍのペットフィルムに転写して、
保持力測定用試料とした。各項目を評価した結果、保持
力、初期及び経時粘着力、再剥離性、基材へのしみこみ
及び経時安定性全て良好であった。結果を表１に示す。Example 1 In a reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet pipe and a reflux condenser, 38 parts of ion-exchanged water and nitrogen were sealed, and the internal temperature of the reactor was kept at 80 ° C. 2 parts of 5% potassium persulfate were added, and 99 parts of 2-ethylhexyl acrylate, 1 part of acrylic acid, sodium polyoxyethylene nonylphenyl ether sulfate (trade name, manufactured by NOF CORPORATION) H-45) 1.
A monomer emulsion emulsified with 5 parts and 56 parts of ion-exchanged water was added dropwise over 2 hours to carry out emulsion polymerization. 5% in parallel
4 parts of potassium persulfate having a concentration were dropped. 80 ° C after dropping
And then cool to room temperature. Neutralized with ammonia water, solid content 50%, viscosity 200 mPa · s, p
An aqueous dispersion of H8.0 was obtained. A polyacrylic acid-based thickening agent (trade name: ASE-60, manufactured by Rohm and Haas Co., Ltd.) was added to the aqueous dispersion to increase the viscosity. Further, 5 parts of a carbodiimide compound (trade name: Carbodilite V-04, manufactured by Nisshinbo Co., Ltd.) was added to 100 parts of the solid content and mixed well to prepare a removable water-dispersible pressure-sensitive adhesive. The peelable water-dispersed pressure-sensitive adhesive is coated on a release paper with a coating thickness of 25 μm.
And dried at 100 ° C. for 1 minute, transferred to a high-quality paper (64 g / m 2 ), left for 7 days in an atmosphere of 23 ° C. and 65% RH to obtain an adhesive label for re-peeling. . The copolymer aqueous dispersion before blending the crosslinking agent was similarly applied to release paper so that the coating thickness became 25 μm, dried at 100 ° C. for 1 minute, and transferred to a 25 μm pet film.
A sample for holding force measurement was used. As a result of evaluating each item, all of the holding power, the initial and temporal adhesive strength, the removability, the penetration into the substrate and the temporal stability were all good. Table 1 shows the results.
【００２７】実施例２及び３ 実施例２は、実施例１の架橋剤の量を変える以外は全く
実施例と同様にして再剥離型水分散感圧接着剤を調製
し、再剥離用粘着ラベル及び保持力測定用試料を得た。
実施例３は、実施例１の単量体組成を変える以外は実施
例と全く同様にして再剥離型水分散感圧接着剤を調製
し、再剥離用粘着ラベル及び保持力測定用試料を得た。
共に保持力、初期及び経時粘着力、再剥離性、基材への
しみこみ及び経時安定性全て良好であった。結果を表１
に示す。Examples 2 and 3 In Example 2, a removable water-dispersible pressure-sensitive adhesive was prepared in exactly the same manner as in Example 1 except that the amount of the cross-linking agent was changed. And a sample for holding force measurement were obtained.
In Example 3, a re-peelable water-dispersible pressure-sensitive adhesive was prepared in exactly the same manner as in Example 1 except that the monomer composition of Example 1 was changed to obtain a re-peelable pressure-sensitive adhesive label and a holding force measurement sample. Was.
In both cases, the holding power, the initial and temporal adhesive strength, the removability, the penetration into the substrate and the temporal stability were all good. Table 1 shows the results
Shown in
【００２８】比較例１及び２ 比較例１及び２は、実施例１の架橋剤を変える以外は全
く実施例１と同様にして再剥離型水分散感圧接着剤を調
製し、再剥離用粘着ラベル及び保持力測定用試料を得
た。比較例１は、再剥離性のステンレス板及び段ボール
が悪かった。また経時安定性も悪かった。比較例２は、
経時安定性が悪かった。結果を表１及び表２に示す。Comparative Examples 1 and 2 In Comparative Examples 1 and 2, a removable water-dispersible pressure-sensitive adhesive was prepared in the same manner as in Example 1 except that the crosslinking agent in Example 1 was changed. A label and a sample for holding force measurement were obtained. In Comparative Example 1, the removable stainless steel plate and the corrugated cardboard were poor. The stability with time was also poor. Comparative Example 2
Stability over time was poor. The results are shown in Tables 1 and 2.
【００２９】比較例３及び４ 比較例３は、実施例１の単量体組成を変える以外は実施
例と全く同様にして再剥離型水分散感圧接着剤を調製
し、再剥離用粘着ラベル及び保持力測定用試料を得た。
４０℃における保持力が本発明の範囲外にあり、ステン
レス板の再剥離性が悪かった。比較例４は、実施例１に
連鎖移動剤を使用する以外は全く実施例１と同様にして
再剥離型水分散感圧接着剤を調製し、再剥離用粘着ラベ
ル及び保持力測定用試料を得た。４０℃における保持力
が本発明の範囲外にあり、ステンレス板の再剥離性及び
基材へのしみこみが悪かった。結果を表２に示す。Comparative Examples 3 and 4 In Comparative Example 3, a peelable water-dispersible pressure-sensitive adhesive was prepared in exactly the same manner as in Example 1 except that the monomer composition in Example 1 was changed, and the peelable adhesive label was used. And a sample for holding force measurement were obtained.
The holding power at 40 ° C. was out of the range of the present invention, and the removability of the stainless steel plate was poor. Comparative Example 4 prepared a re-peelable water-dispersed pressure-sensitive adhesive in exactly the same manner as in Example 1 except that a chain transfer agent was used in Example 1, and prepared a re-peelable pressure-sensitive adhesive label and a holding force measurement sample. Obtained. The holding power at 40 ° C. was out of the range of the present invention, and the removability of the stainless steel plate and the penetration into the substrate were poor. Table 2 shows the results.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【表２】 [Table 2]
【００３２】表１及び２中に、単量体及び架橋剤を下記
の略号で示す。 単量体； ２ＥＨＡ ：アクリル酸２−エチルヘキシル ＭＭＡ ：メタクリル酸メチル ＡＡｃ ：アクリル酸 架橋剤； Ｖ−０４ ：カルボジイミド化合物（日清紡（株）
製 商品名カルボジライトＶ−０４） ＸＬ−２９ＳＥ：多官能カルボジイミド化合物（ユニオ
ンカーバイド（株）製 商品名ユーカリンクＸＬ−２９
ＳＥ） ＥＸ−８１０ ：水溶性エポキシ化合物（ナガセ化成
（株）製 商品名デナコールＥＸ−８１０）In Tables 1 and 2, the monomers and crosslinking agents are indicated by the following abbreviations. Monomer; 2EHA: 2-ethylhexyl acrylate MMA: Methyl methacrylate AAc: Acrylic acid Crosslinker; V-04: Carbodiimide compound (Nisshinbo Co., Ltd.)
Manufactured by Carbodilite V-04) XL-29SE: polyfunctional carbodiimide compound (manufactured by Union Carbide Co., Ltd .; trade name: Eukalink XL-29)
SE) EX-810: Water-soluble epoxy compound (Denacol EX-810, trade name, manufactured by Nagase Kasei Co., Ltd.)
【００３３】試験方法 １.保持力 ４０℃保持力は、架橋剤を配合する前の共重合体水分散
液を、剥離紙に塗膜厚が２５μｍになるように塗布し、
１００℃で１分間乾燥後、２５μｍのペットフィルムに
転写して、保持力測定用試料とした。保持力測定用試料
ＪＩＳ Ｚ−０２７３に準じて、幅２５ｍｍ長さ５０ｍ
ｍに切断した試験片を接着面積が２５ｍｍ×２５ｍｍに
なるように、研磨し清浄にしたＳＵＳ３０４板に貼り付
け、２Ｋｇの圧着ロールで１往復させ圧着後、２３℃、
６５％ＲＨ中に３０分間放置して４０℃の雰囲気中で１
Ｋｇの荷重をかけ落下するまでの時間（秒数）を測定す
る。 ２.粘着力 再剥離型水分散感圧接着剤を剥離紙に塗膜厚が２５μｍ
になるように塗布し、１００℃で１分間乾燥後、上質紙
（６４ｇ／ｍ２）に転写して、２３℃、６５％ＲＨの雰
囲気で７日間放置後、再剥離用粘着ラベルを得た。該再
剥離用粘着ラベルをＪＩＳ Ｚ−０２３７の１８０°引
き剥がし粘着力測定に準じて測定した。再剥離用粘着ラ
ベルを幅２５ｍｍに切断し、ステンレス板、ポリプロピ
レン板及び段ボールに貼り付け、２Ｋｇのロ―ラで１往
復圧着したのち、直後に測定する初期粘着力と２３℃、
６５％ＲＨで２４時間放置した後に測定する経時粘着力
を引っ張り試験機にて、引き剥がし速度３００ｍｍ／分
で測定する。測定値はＮ／２５ｍｍである。 ３.再剥離性 粘着力試験と同様に得た再剥離用粘着ラベルを幅２５ｍ
ｍに切断し、ステンレス板、ポリプロピレン板及び段ボ
ールに貼り合わせ、２３℃、６５％ＲＨの雰囲気に３０
日放置後、引っ張り試験機にて引き剥がし速度３００ｍ
ｍ／分で剥離して剥離状態を、目視にて観察する。 ○：糊残りや紙破れなくきれいに剥離できる。 △：糊残りや紙破れが部分的にある。 ×：全面に糊残りや紙破れがある。 ４.基材へのしみこみ 粘着力試験と同様に得た再剥離用粘着ラベルを４０℃の
恒温槽に３０日間放置後、上質紙表面への感圧接着剤の
しみこみ状態を観察する。 ○：しみこみ無し。 △：上質紙の表面に少ししみこみがある。 ×：上質紙の表面にかなりしみこみがある。 ５. 経時安定性 架橋剤を配合した再剥離型水分散感圧接着剤を２５℃で
７日間放置後の液状態を観察する。 ○：初期と変化なし。 △：粘度が少し高い。 ×：ゲル化している。Test Method 1. Retention Force The retention power at 40 ° C. was determined by applying an aqueous dispersion of the copolymer before blending the crosslinking agent to release paper so that the coating thickness became 25 μm.
After drying at 100 ° C. for 1 minute, the sample was transferred to a 25 μm pet film to obtain a holding force measurement sample. According to JIS Z-0273 for holding force measurement sample, width 25 mm, length 50 m
The test piece cut into m was adhered to a polished and cleaned SUS304 plate so that the adhesion area became 25 mm x 25 mm, and the mixture was reciprocated once with a 2 kg pressure roll.
Leave in 65% RH for 30 minutes in an atmosphere of 40 ° C.
A time (number of seconds) required to fall by applying a load of Kg is measured. 2. Adhesive strength Recoatable water-dispersible pressure-sensitive adhesive is applied to release paper with a coating thickness of 25 μm
And dried at 100 ° C. for 1 minute, transferred to a high-quality paper (64 g / m 2 ), left for 7 days in an atmosphere of 23 ° C. and 65% RH to obtain an adhesive label for re-peeling. . The re-peelable pressure-sensitive adhesive label was measured according to JIS Z-0237 180 ° peeling strength measurement. The adhesive label for re-peeling was cut to a width of 25 mm, attached to a stainless steel plate, a polypropylene plate, and a cardboard, and pressed back and forth with a 2 kg roller once, and immediately after the initial adhesive force measured at 23 ° C.
After standing at 65% RH for 24 hours, the adhesive force with time is measured by a tensile tester at a peeling speed of 300 mm / min. The measured value is N / 25 mm. 3. Removability The re-peelable adhesive label obtained in the same manner as in the adhesive strength test was 25 m wide.
m, and bonded to a stainless steel plate, a polypropylene plate, and a corrugated cardboard.
After standing for a day, peeling speed 300m with a tensile tester
After peeling at m / min, the peeling state is visually observed. ：: Peeling can be performed neatly without glue residue or paper breakage. Δ: Adhesive residue and paper tear are partially present. ×: Adhesive residue or paper tear on the entire surface. 4. Infiltration into base material After leaving the re-peelable adhesive label obtained in the same manner as in the adhesive strength test in a constant temperature bath at 40 ° C. for 30 days, the state of infiltration of the pressure-sensitive adhesive onto the surface of high quality paper is observed. ：: No penetration. Δ: Slight infiltration on the surface of high quality paper. X: The surface of the high-quality paper is considerably impregnated. 5. Stability over time The state of the liquid after leaving the removable water-dispersible pressure-sensitive adhesive containing a crosslinking agent at 25 ° C. for 7 days is observed. ：: No change from initial stage. Δ: The viscosity is slightly high. ×: Gelled.
【００３４】上記の表１及び表２の結果から明らかなよ
うに、本発明の実施例１〜３の各再剥離用粘着ラベル
は、被着体への粘着力の経時上昇性が少なくて。再剥離
性及び基材へのしみこみ性能を満足し、しかも、経時安
定性が良いことがわかる。As is evident from the results of Tables 1 and 2, each of the removable adhesive labels of Examples 1 to 3 of the present invention has a small increase in adhesive force to an adherend with time. It can be seen that the removability and the ability to penetrate the substrate are satisfied, and the stability over time is good.
【００３５】[0035]
【発明の効果】以上のように、本発明は、架橋剤配合前
の保持力を特定範囲に設定した、アクリル系の共重合体
水分散液に特定のカルボジイミド化合物を特定量配合す
ることにより、経時安定性が良く、塗工後に架橋反応が
速やかに完結し、被着体への粘着力の経時上昇性が少な
くて、再剥離性に非常に優れ、基材へのしみこみも良好
な１液再剥離型水分散感圧接着剤を提供でき、粘着ラベ
ル、テープ、シート、表面保護フィルム、塗装用マスキ
ングテープ、粘着メモ等として幅広く利用することがで
きる。As described above, according to the present invention, a specific amount of a specific carbodiimide compound is blended with an aqueous acrylic copolymer dispersion in which the holding power before blending a crosslinking agent is set to a specific range. One-pack with good stability over time, rapid completion of the crosslinking reaction after coating, little increase in adhesive strength to adherend over time, excellent removability, and good penetration into substrates A removable water-dispersible pressure-sensitive adhesive can be provided, and can be widely used as an adhesive label, tape, sheet, surface protective film, masking tape for coating, adhesive memo, and the like.
Claims (3)
タ）アクリル酸アルキルエステルを主成分とし、かつカ
ルボキシル基含有不飽和単量体を０．１〜５重量％含有
する共重合体の水分散液に、カルボジイミド結合（−Ｎ
＝Ｃ＝Ｎ−）とエチレンオキサイド部位（−ＣＨ２−Ｃ
Ｈ２−Ｏ−）を有するカルボジイミド化合物を添加して
なる再剥離型水分散感圧接着剤。1. A copolymer comprising, as a main component, an alkyl (meth) acrylate having an alkyl group of 4 to 12 carbon atoms and containing 0.1 to 5% by weight of a carboxyl group-containing unsaturated monomer. A carbodiimide bond (-N
= C = N-) with ethylene oxide moiety (-CH 2 -C
A removable water-dispersible pressure-sensitive adhesive obtained by adding a carbodiimide compound having H 2 —O—).
ボキシル基１当量当り、カルボジイミド結合が０．０１
〜５当量となるようにカルボジイミド結合とエチレンオ
キサイド部位を有するカルボジイミド化合物を添加して
なる請求項１に記載の再剥離型水分散感圧接着剤。2. A carbodiimide bond is present in an amount of 0.01 per equivalent of the carboxyl group of the carboxyl group-containing unsaturated monomer.
2. The removable water-dispersible pressure-sensitive adhesive according to claim 1, wherein a carbodiimide compound having a carbodiimide bond and an ethylene oxide site is added so as to be in an amount of 5 to 5 equivalents.
主成分とする共重合体の４０℃における保持力が１００
秒〜１０，０００秒である共重合体水分散液に、カルボ
ジイミド結合とエチレンオキサイド部位を有するカルボ
ジイミド化合物を添加してなる請求項１に記載の再剥離
型水分散感圧接着剤。3. A copolymer containing a (meth) acrylic acid alkyl ester as a main component has a holding power at 40 ° C. of 100.
The removable water-dispersible pressure-sensitive adhesive according to claim 1, wherein a carbodiimide compound having a carbodiimide bond and an ethylene oxide site is added to an aqueous dispersion of the copolymer for 10 seconds to 10,000 seconds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000298074A JP2002105420A (en) | 2000-09-29 | 2000-09-29 | Re-releasable, water-dispersible, pressure-sensitive adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000298074A JP2002105420A (en) | 2000-09-29 | 2000-09-29 | Re-releasable, water-dispersible, pressure-sensitive adhesive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002105420A true JP2002105420A (en) | 2002-04-10 |
Family
ID=18780085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000298074A Pending JP2002105420A (en) | 2000-09-29 | 2000-09-29 | Re-releasable, water-dispersible, pressure-sensitive adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002105420A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005036153A (en) * | 2003-07-18 | 2005-02-10 | Toyo Ink Mfg Co Ltd | Method for manufacturing pressure sensitive adhesive sheet and pressure sensitive adhesive sheet |
| JP2006348058A (en) * | 2005-05-19 | 2006-12-28 | Nippon Carbide Ind Co Inc | Aqueous pressure-sensitive adhesive composition and method for manufacturing pressure-sensitive adhesive sheet using the same |
| JP2007177003A (en) * | 2005-12-27 | 2007-07-12 | Nitto Denko Corp | Water dispersion type acrylic adhesive composition for re-exfoliation and adhesive sheet |
| JP2009073920A (en) * | 2007-09-20 | 2009-04-09 | Lintec Corp | Removable adhesive sheet |
| JP2011140216A (en) * | 2009-12-07 | 2011-07-21 | Toyobo Co Ltd | Easy-to-adhere thermoplastic resin film |
| JP2020055924A (en) * | 2018-09-28 | 2020-04-09 | 三菱ケミカル株式会社 | Adhesive composition, and adhesive and adhesive sheet including the same |
| JP2020143211A (en) * | 2019-03-06 | 2020-09-10 | 三菱ケミカル株式会社 | Pressure-sensitive adhesive composition, pressure-sensitive adhesive and pressure-sensitive adhesive sheet each obtained using the same |
| JP7358722B1 (en) | 2022-12-23 | 2023-10-11 | 東洋インキＳｃホールディングス株式会社 | Coating agent for forming hydrogel sheet and hydrogel sheet |
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|---|---|---|---|---|
| JPH07278233A (en) * | 1994-04-13 | 1995-10-24 | Sekisui Chem Co Ltd | Production of acrylic emulsion self-adhesive, acrylic emulsion self-adhesive, self-adhesive tape, or sheet and surface protective material |
| JPH1060272A (en) * | 1996-08-16 | 1998-03-03 | Nippon Polyurethane Ind Co Ltd | Polycarbodiimide curing agent composition for carboxyl group-containing resin and adhesive and coating material using the same |
| JP2001131512A (en) * | 1999-11-02 | 2001-05-15 | Nitto Denko Corp | Water dispersion type removable pressure-sensitive adhesive and adhesive sheets thereof |
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2000
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07278233A (en) * | 1994-04-13 | 1995-10-24 | Sekisui Chem Co Ltd | Production of acrylic emulsion self-adhesive, acrylic emulsion self-adhesive, self-adhesive tape, or sheet and surface protective material |
| JPH1060272A (en) * | 1996-08-16 | 1998-03-03 | Nippon Polyurethane Ind Co Ltd | Polycarbodiimide curing agent composition for carboxyl group-containing resin and adhesive and coating material using the same |
| JP2001131512A (en) * | 1999-11-02 | 2001-05-15 | Nitto Denko Corp | Water dispersion type removable pressure-sensitive adhesive and adhesive sheets thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005036153A (en) * | 2003-07-18 | 2005-02-10 | Toyo Ink Mfg Co Ltd | Method for manufacturing pressure sensitive adhesive sheet and pressure sensitive adhesive sheet |
| JP4561057B2 (en) * | 2003-07-18 | 2010-10-13 | 東洋インキ製造株式会社 | Method for producing pressure-sensitive adhesive sheet and pressure-sensitive adhesive sheet |
| JP2006348058A (en) * | 2005-05-19 | 2006-12-28 | Nippon Carbide Ind Co Inc | Aqueous pressure-sensitive adhesive composition and method for manufacturing pressure-sensitive adhesive sheet using the same |
| JP2007177003A (en) * | 2005-12-27 | 2007-07-12 | Nitto Denko Corp | Water dispersion type acrylic adhesive composition for re-exfoliation and adhesive sheet |
| JP2009073920A (en) * | 2007-09-20 | 2009-04-09 | Lintec Corp | Removable adhesive sheet |
| JP2011140216A (en) * | 2009-12-07 | 2011-07-21 | Toyobo Co Ltd | Easy-to-adhere thermoplastic resin film |
| JP2020055924A (en) * | 2018-09-28 | 2020-04-09 | 三菱ケミカル株式会社 | Adhesive composition, and adhesive and adhesive sheet including the same |
| JP7205144B2 (en) | 2018-09-28 | 2023-01-17 | 三菱ケミカル株式会社 | Adhesive composition, and adhesive and adhesive sheet using the same |
| JP2020143211A (en) * | 2019-03-06 | 2020-09-10 | 三菱ケミカル株式会社 | Pressure-sensitive adhesive composition, pressure-sensitive adhesive and pressure-sensitive adhesive sheet each obtained using the same |
| JP7259420B2 (en) | 2019-03-06 | 2023-04-18 | 三菱ケミカル株式会社 | Adhesive composition, adhesive and adhesive sheet using the same |
| JP7358722B1 (en) | 2022-12-23 | 2023-10-11 | 東洋インキＳｃホールディングス株式会社 | Coating agent for forming hydrogel sheet and hydrogel sheet |
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