JPH10158617A - Repeatedly peelable pressure-sensitive adhesive composition of water dispersion type and repeatedly peelable pressure-sensitive adhesive sheet and the like using the same - Google Patents
Repeatedly peelable pressure-sensitive adhesive composition of water dispersion type and repeatedly peelable pressure-sensitive adhesive sheet and the like using the sameInfo
- Publication number
- JPH10158617A JPH10158617A JP8319435A JP31943596A JPH10158617A JP H10158617 A JPH10158617 A JP H10158617A JP 8319435 A JP8319435 A JP 8319435A JP 31943596 A JP31943596 A JP 31943596A JP H10158617 A JPH10158617 A JP H10158617A
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- pressure
- monomer
- water
- peeling
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、アクリル系の再剥
離用水分散型感圧性接着剤組成物と、これを用いたシ―
ト状、テ―プ状などの再剥離用感圧性接着シ―ト類に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-dispersible acrylic pressure-sensitive adhesive composition for re-peeling, and a sheet using the same.
The present invention relates to a pressure-sensitive adhesive sheet for re-peeling in the form of tape, tape or the like.
【０００２】[0002]
【従来の技術】再剥離用感圧性接着シ―ト類は、被着体
に貼り付けたのち、屋外での暴露や加熱などの厳しい条
件下に曝されることがあり、その間には十分に接着して
被着体の表面保護やマスキングなどの使用目的を果た
し、この目的達成後は被着体から容易に剥離できるとと
もに、被着体への糊残りやテ―プ跡などが生じないもの
であることが望まれる。このような接着性、再剥離性お
よび低汚染性の点では、ゴム系よりも、アクリル系の再
剥離用感圧性接着剤がすぐれている。2. Description of the Related Art A pressure-sensitive adhesive sheet for re-peeling may be exposed to severe conditions such as outdoor exposure and heating after being adhered to an adherend. Adhering to achieve the intended use such as surface protection and masking of the adherend, and after achieving this purpose, it can be easily peeled off from the adherend without leaving adhesive residue or tape marks on the adherend. It is desired that In terms of such adhesiveness, removability and low contamination, acrylic pressure-sensitive adhesives for removability are superior to rubber-based pressure-sensitive adhesives.
【０００３】また、再剥離用感圧性接着剤としては、一
般の感圧性接着剤の場合と同様に、環境保護、省資源、
安全衛生に対する社会的な要請と規制強化から、脱溶剤
が重要な課題となつているが、溶剤型の感圧性接着剤に
代わるものとして、汎用性や応用展開の可能性から、ホ
ツトメルト型や硬化型感圧性接着剤よりも、水系の感圧
性接着剤が優位であると考えられている。[0003] Further, as the pressure-sensitive adhesive for re-peeling, as in the case of a general pressure-sensitive adhesive, environmental protection, resource saving,
Solvent removal has become an important issue due to social demands for safety and health and stricter regulations.However, as a substitute for solvent-based pressure-sensitive adhesives, hot-melt and curing It is considered that a water-based pressure-sensitive adhesive is superior to a type pressure-sensitive adhesive.
【０００４】このような理由により、再剥離用感圧性接
着剤として、従来より、アクリル系の水分散型感圧性接
着剤が広く検討されてきた。とくに、アクリル系共重合
体からなる水分散粒子を適度に架橋処理することによつ
て、接着性、再剥離性および低汚染性を十分に満足させ
る検討がなされており、上記の架橋処理としては、一般
に、架橋剤水溶液を添加する方式が採用されている。[0004] For these reasons, acrylic water-dispersed pressure-sensitive adhesives have been widely studied as pressure-sensitive adhesives for re-peeling. In particular, studies have been made to adequately satisfy the adhesiveness, removability and low-stainability by appropriately crosslinking the water-dispersed particles made of an acrylic copolymer. In general, a method of adding an aqueous solution of a crosslinking agent is employed.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記の
架橋剤水溶液を添加する方式では、ポツトライフの関係
から、アクリル系共重合体を含む水分散液と上記架橋剤
水溶液との二液として、両液を接着シ―ト類などの作製
に際して支持体上に塗工する直前に混合する必要があ
り、この場合、接着シ―ト類などの製造作業性、二液混
合比率のばらつきなどに起因した前記特性の低下などの
問題を生じることが多かつた。However, in the method of adding the above-mentioned aqueous solution of the crosslinking agent, in view of the pot life, both of the aqueous solution containing the acrylic copolymer and the above-mentioned aqueous solution of the crosslinking agent are separated into two solutions. Must be mixed immediately before coating on a support in the production of adhesive sheets and the like. In this case, the workability of the adhesive sheets and the like, the dispersion of the two-component mixing ratio, etc. In many cases, problems such as deterioration of characteristics are caused.
【０００６】本発明は、このような事情に照らして、一
液型で十分なポツトライフを有するとともに、再剥離用
として望まれる良好な接着性、再剥離性および低汚染性
を示すアクリル系の再剥離用水分散型感圧性接着剤組成
物と、これを用いた再剥離用感圧性接着シ―ト類を提供
することを目的としている。In view of such circumstances, the present invention is directed to an acrylic resin which has a sufficient pot life as a one-pack type and has good adhesiveness, removability and low contamination desired for re-peeling. An object of the present invention is to provide a water-dispersible pressure-sensitive adhesive composition for peeling and a pressure-sensitive adhesive sheet for re-peeling using the same.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、上記の目
的を達成するために、鋭意検討した結果、アクリル系共
重合体の水分散液を乳化重合法により調製する際に、互
いに反応する二種の官能基含有モノマ―を共重合成分と
して用いたときに、一液型で十分なポツトライフを示す
水分散型感圧性接着剤組成物が得られ、これを支持体上
に塗工し加熱乾燥するとアクリル系共重合体からなる水
分散粒子に含まれる上記二種の官能基によつて粒子内部
とさらに粒子間で架橋反応を起こして、適度なゲル分率
を有するものとなり、再剥離用として望まれる良好な接
着性、再剥離性および低汚染性が得られることを知り、
本発明を完成するに至つた。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, when an aqueous dispersion of an acrylic copolymer is prepared by an emulsion polymerization method, they have reacted with each other. When two types of functional group-containing monomers are used as a copolymer component, a water-dispersed pressure-sensitive adhesive composition having a one-pot type and sufficient pot life is obtained, and this is coated on a support. When heated and dried, the above two types of functional groups contained in the water-dispersed particles made of the acrylic copolymer cause a cross-linking reaction between the inside of the particles and between the particles, resulting in an appropriate gel fraction and re-peeling. Knowing that good adhesiveness, removability and low contamination desired for use can be obtained,
The present invention has been 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５０
重量％以上、カルボキシル基含有モノマ―０．１〜１０
重量％およびエポキシ基含有モノマ―０．１〜１０重量
％を必須成分とした単量体混合物の共重合体を含む水分
散液であつて、加熱乾燥後のゲル分率が５０〜９５重量
％であることを特徴とする再剥離用水分散型感圧性接着
剤組成物（請求項１）、ならびに、支持体とこの支持体
上に上記の再剥離用水分散型感圧性接着剤組成物を加熱
乾燥してなる感圧性接着剤層とを有することを特徴とす
る再剥離用感圧性接着シ―ト類（請求項３）に係るもの
である。That is, the present invention provides an alkyl (meth) acrylate having 4 to 12 carbon atoms in the alkyl group.
Weight% or more, carboxyl group-containing monomer 0.1 to 10
An aqueous dispersion containing a copolymer of a monomer mixture containing, as an essential component, 0.1% by weight of an epoxy group-containing monomer and 0.1 to 10% by weight, and has a gel fraction after heating and drying of 50 to 95% by weight. A water-dispersible pressure-sensitive adhesive composition for re-peeling (Claim 1), and a support and the above-mentioned water-dispersible pressure-sensitive adhesive composition for re-peelable on a support, dried by heating. And a pressure-sensitive adhesive sheet for re-peeling (claim 3).
【０００９】なお、本発明において、ゲル分率は、以下
の方法により求められる。まず、剥離処理したフイルム
上に再剥離用水分散型感圧性接着剤組成物を塗布したの
ち、１３０℃で５分間乾燥し、得られたポリマ―を一定
量採取する（Ｗ1 ｇ）。つぎに、このポリマ―を口径
０．２μｍのテフロン膜で包み、たこ糸で口を縛り、酢
酸エチル中で７日間室温で放置して、ゾル分を溶出さ
せ、ゲル分の含まれたテフロン膜を１３０℃で２時間乾
燥して、ゲル分の重量を測定する（Ｗ2 ｇ）。上記のＷ
1 とＷ2 を下記の式に当てはめると、ゲル分率が求めら
れる。 ゲル分率（重量％）＝（Ｗ2 ／Ｗ1 ）×１００In the present invention, the gel fraction is determined by the following method. First, after applying the water-dispersible pressure-sensitive adhesive composition for re-peeling on the film subjected to the peeling treatment, the film is dried at 130 ° C. for 5 minutes, and a predetermined amount of the obtained polymer is collected (W 1 g). Next, the polymer was wrapped with a Teflon membrane having a diameter of 0.2 μm, the mouth was tied up with a octopus thread, and the mixture was allowed to stand in ethyl acetate at room temperature for 7 days to elute the sol component. Is dried at 130 ° C. for 2 hours, and the weight of the gel portion is measured (W 2 g). W above
Applying 1 and W 2 to the following equation gives the gel fraction. Gel fraction (% by weight) = (W 2 / W 1 ) × 100
【００１０】[0010]
【発明の実施の形態】本発明におけ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
は、アクリル酸またはメタクリル酸と炭素数が４〜１２
のアルコ―ルとのエステルであつて、具体的には、アク
リル酸ブチル、アクリル酸２−エチルヘキシル、アクリ
ル酸イソノニル、アクリル酸ラウリル、メタクリル酸ブ
チル、メタクリル酸ラウリルなどが挙げられ、これらの
アルキルエステルの中から、その１種または２種以上が
用いられる。これらのアルキルエステルは、単量体混合
物の主成分として、単量体混合物中、５０重量％以上の
割合で用いられる。これより少ないと、良好な再剥離性
を示す感圧性接着剤が得られにくい。BEST MODE FOR CARRYING OUT THE INVENTION The alkyl (meth) acrylate having 4 to 12 carbon atoms in the alkyl group according to the present invention is used in combination with acrylic acid or methacrylic acid in 4 to 12 carbon atoms.
And acrylates, specifically, butyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, lauryl acrylate, butyl methacrylate, lauryl methacrylate, and the like. Among them, one or more of them are used. These alkyl esters are used as a main component of the monomer mixture in a proportion of 50% by weight or more in the monomer mixture. If the amount is less than this, it is difficult to obtain a pressure-sensitive adhesive exhibiting good removability.
【００１１】本発明におけるカルボキシル基含有モノマ
―としては、アクリル酸、メタクリル酸、イタコン酸、
無水マレイン酸、クロトン酸、マレイン酸、フマル酸な
どがあり、これらの中から、１種または２種以上が用い
られる。使用量は、単量体混合物中、０．１〜１０重量
％、好ましくは０．５〜７重量％である。The carboxyl group-containing monomer in the present invention includes acrylic acid, methacrylic acid, itaconic acid,
There are maleic anhydride, crotonic acid, maleic acid, fumaric acid and the like, and one or more of these are used. The amount used is 0.1 to 10% by weight, preferably 0.5 to 7% by weight in the monomer mixture.
【００１２】本発明におけるエポキシ基含有モノマ―と
しては、アクリル酸グリシジル、メタクリル酸グリシジ
ル、メタクリル酸メチルグリシジル、脂環式エポキシ基
を有する（メタ）アクリル酸エステルなどを挙げること
ができ、これらの中から、１種または２種以上が用いら
れる。使用量は、単量体混合物中、０．１〜１０重量
％、好ましくは０．５〜７重量％である。Examples of the epoxy group-containing monomer in the present invention include glycidyl acrylate, glycidyl methacrylate, methyl glycidyl methacrylate, and (meth) acrylic esters having an alicyclic epoxy group. , One or more of them are used. The amount used is 0.1 to 10% by weight, preferably 0.5 to 7% by weight in the monomer mixture.
【００１３】本発明において、上記のカルボキシル基含
有モノマ―とエポキシ基含有モノマ―の使用量は、保存
安定性（一液型としてのポツトライフ）、再剥離用とし
ての接着性、再剥離性および低汚染性を満足させるうえ
で、非常に重要な因子となるものであり、両モノマ―の
使用量が前記範囲を逸脱すると、上記いずれかの特性に
劣るようになる。また、上記各特性に好結果を得るとと
もに、重合時の凝集物量を低減させるという観点から、
カルボキシル基含有モノマ―とエポキシ基含有モノマ―
の併用比率は、カルボキシル基のモル数がエポキシ基の
モル数よりも多くなるような使用割合とするのが望まし
い。In the present invention, the amount of the carboxyl group-containing monomer and the epoxy group-containing monomer used is determined for storage stability (pot life as a one-pack type), adhesion for re-peeling, re-peelability, This is a very important factor in satisfying the contamination property, and if the amount of the both monomers is out of the above range, any of the above characteristics will be inferior. Further, from the viewpoint of obtaining a good result in each of the above properties, and reducing the amount of aggregates during polymerization,
Carboxy group-containing monomer and epoxy group-containing monomer
Is preferably used such that the number of moles of carboxyl groups is larger than the number of moles of epoxy groups.
【００１４】本発明における単量体混合物は、上記のア
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、カルボキシル基含有モノマ―およびエポ
キシ基含有モノマ―を必須成分とするほか、必要に応じ
てこれらと共重合可能な他のモノマ―を併用したもので
あつてもよい。この他のモノマ―は、これと前記のアル
キル基の炭素数が４〜１２の（メタ）アクリル酸アルキ
ルエステルとの合計量が８０〜９９．８重量％、好まし
くは８６〜９９重量％となる範囲内で、モノマ―の種類
に応じて適宜使用量を決めることができるが、再剥離用
として良好な接着性などを発現させるためには、得られ
る共重合体のガラス転移点が通常−２０℃以下となるよ
うに、使用量を決めるのが望ましい。The monomer mixture of the present invention comprises the above-mentioned alkyl (meth) acrylate having 4 to 12 carbon atoms in the alkyl group, a carboxyl group-containing monomer and an epoxy group-containing monomer as essential components. If necessary, other monomers copolymerizable therewith may be used. The other monomer has a total amount of 80 to 99.8% by weight, preferably 86 to 99% by weight of the monomer and the alkyl (meth) acrylate having 4 to 12 carbon atoms in the alkyl group. Within the range, the amount to be used can be appropriately determined according to the type of the monomer. However, in order to exhibit good adhesiveness for re-peeling, the glass transition point of the obtained copolymer is usually -20. It is desirable to determine the amount to be used so as to be lower than or equal to ° C.
【００１５】この他のモノマ―としては、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な
どのアルキル基の炭素数が１〜３の（メタ）アクリル酸
アルキルエステル、メタクリル酸トリデシル、（メタ）
アクリル酸ステアリルなどのアルキル基の炭素数が１３
〜１８の（メタ）アクリル酸アルキルエステル、（メ
タ）アクリル酸ヒドロキシアルキル、グリセリンジメタ
クリレ―トなどの水酸基含有モノマ―、トリエチレング
リコ―ルジアクリレ―ト、エチレングリコ―ルジメタク
リレ―ト、トリメチロ―ルプロパントリ（メタ）アクリ
レ―トなどの多官能モノマ―、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ド、（メタ）アクリルアミ
ドなどが挙げられる。Other monomers include alkyl (meth) acrylates having 1 to 3 carbon atoms in the alkyl group, such as methyl methacrylate, ethyl acrylate, and isopropyl acrylate, tridecyl methacrylate, and (meth)
An alkyl group such as stearyl acrylate has 13 carbon atoms
To 18-hydroxyalkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, hydroxyl-containing monomers such as glycerin dimethacrylate, triethylene glycol diacrylate, ethylene glycol dimethacrylate, and trimethylolpropanetri. Polyfunctional monomers such as (meth) acrylate, vinyl acetate, styrene,
(Meth) acrylonitrile, n-vinylpyrrolidone,
(Meth) acryloylmorpholine, cyclohexylmaleimide, isopropylmaleide, (meth) acrylamide and the like can be mentioned.
【００１６】本発明においては、このような単量体混合
物を、適宜の重合開始剤と乳化剤を用いて、常法により
乳化重合させることにより、アクリル系共重合体の水分
散液を調製する。乳化重合は、一般的な一括重合、連続
滴下重合、分割滴下重合などにより、３０〜８０℃の温
度で行うことができる。In the present invention, an aqueous dispersion of an acrylic copolymer is prepared by subjecting such a monomer mixture to emulsion polymerization using a suitable polymerization initiator and an emulsifier in a conventional manner. Emulsion polymerization can be performed at a temperature of 30 to 80 ° C. by general batch polymerization, continuous drop polymerization, divided drop polymerization, or the like.
【００１７】重合開始剤としては、たとえば、２，２´
−アゾビスイソブチロニトリル、２，２´−アゾビス
（２−アミジノプロパン）ジヒドロクロライド、２，２
´−アゾビス（Ｎ，Ｎ´−ジメチレンイソブチルアミジ
ン）などのアゾ系、過硫酸カリウム、過硫酸アンモニウ
ムなどの過硫酸塩、ベンゾイルパ―オキサイド、ｔ−ブ
チルハイドロパ―オキサイドなどの過酸化物系や、過硫
酸塩と亜硫酸水素ナトリウムなどのレドツクス系開始剤
などが挙げられる。As the polymerization initiator, for example, 2,2 '
-Azobisisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2
Azo-based compounds such as' -azobis (N, N'-dimethyleneisobutylamidine), persulfates such as potassium persulfate and ammonium persulfate; Redox initiators such as persulfate and sodium bisulfite are included.
【００１８】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―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などのアニオン系、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―テルなどのノニオン系などが挙げら
れ、これらの中から、１種または２種以上が用いられ
る。アニオン系およびノニオン系のいずれの場合も、プ
ロペニル基などを導入したラジカル重合性の乳化剤を用
いてもよい。Examples of the emulsifier include anionic polyoxyethylene alkyl such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium polyoxyethylene alkyl ether sulfate, and sodium polyoxyethylene alkyl phenyl ether sulfate. Nonionics such as ethers and polyoxyethylene alkylphenyl ethers may be mentioned, and one or more of these may be used. In both the anionic and nonionic types, a radical polymerizable emulsifier into which a propenyl group or the like is introduced may be used.
【００１９】本発明においては、このように調製される
アクリル系共重合体の水分散液を、一液型の再剥離用水
分散型感圧性接着剤組成物としたものであり、このもの
は、上記共重合体からなる分散粒子の内部または粒子表
面に互いに反応するカルボキシル基およびエポキシ基を
併有しているものの、常態下では高い保存安定性を示
し、実用可能なポツトライフを有している。一方、この
組成物を支持体上などに塗工して加熱乾燥したときに
は、分散粒子の上記両官能基が粒子内部または粒子間で
有効に架橋反応して、適度なゲル分率を有するものとな
り、これが再剥離用として望まれる良好な接着性、再剥
離性および低汚染性を付与する。In the present invention, the aqueous dispersion of the acrylic copolymer prepared as described above is used as a one-part type water-dispersible pressure-sensitive adhesive composition for re-peeling. Although it has both a carboxyl group and an epoxy group that react with each other inside or on the surface of the dispersed particles made of the above copolymer, it shows high storage stability under normal conditions and has a practical pot life. On the other hand, when the composition is coated on a support or the like and dried by heating, the above-mentioned two functional groups of the dispersed particles are effectively cross-linked inside or between the particles, and have an appropriate gel fraction. This provides good adhesion, removability and low contamination desired for re-stripping.
【００２０】本発明における上記適度なゲル分率とは、
５０〜９５重量％、好ましくは７０〜９０重量％の範囲
にあることを指し、このときの初期接着力は、たとえ
ば、被着体がステンレス板であれば、２００〜６００ｇ
／２０mm幅となる程度であり、この接着後高温下に放置
したのち剥離したときに、接着力の著しい増大をみるこ
となく容易に剥離できる、良好な再剥離性を示し、また
その際に凝集破壊による糊残りなどに基づく被着体汚染
はほとんどみられない。In the present invention, the above-mentioned moderate gel fraction refers to:
The initial adhesive strength at this time is, for example, 200 to 600 g if the adherend is a stainless steel plate.
/ 20mm width, and when peeled after being left at high temperature after bonding, shows good re-peelability, which can be easily peeled without noticeable increase in adhesive strength. Substrate contamination due to adhesive residue due to destruction is hardly observed.
【００２１】このようなゲル分率の設定は、カルボキシ
ル基含有モノマ―およびエポキシ基含有モノマ―の使用
量を前記割合とし、これらのモノマ―および主モノマ―
であ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とさらにその他の共重合モノマ―
の種類に応じて、乳化重合時の反応温度、反応時間およ
び添加方式などを適宜選択して、適度な分子量構成など
とすることにより、容易に行えるものである。ゲル分率
が前記の範囲外となると、再剥離用としての前記いずれ
かの特性に劣り、とくに、５０重量％より低くなると、
再剥離時に凝集破壊による糊残りが発生しやすく、また
９５重量％より高いと、初期接着力が十分に得られなく
なるなどの不都合を生じやすい。The gel fraction is set such that the amount of the carboxyl group-containing monomer and the epoxy group-containing monomer is used as the ratio, and these monomers and the main monomer are used.
(Meth) acrylic acid alkyl esters having 4 to 12 carbon atoms in the alkyl group and other copolymerized monomers
The reaction can be easily carried out by appropriately selecting the reaction temperature, reaction time, addition method and the like at the time of emulsion polymerization depending on the kind of the above, and by setting an appropriate molecular weight structure and the like. When the gel fraction is out of the above range, any of the above properties for re-peeling is inferior, especially when the gel fraction is lower than 50% by weight,
Adhesive residue is likely to occur due to cohesive failure at the time of re-peeling, and if it is more than 95% by weight, problems such as insufficient initial adhesive strength are likely to occur.
【００２２】なお、特公平１−４５５０５号公報や特開
平５−１０５７９９号公報には、カルボキシル基とエポ
キシ基との反応性を利用した自己架橋性の一液型の水分
散型感圧性接着剤組成物が開示されている。しかし、こ
れらは、いずれも二段階の乳化重合法によつて共重合体
からなる分散粒子を二層構造とし、両層間で上記官能基
同士の反応を生起させて、自己架橋させるようにしたも
のである。このような自己架橋は、粒子内での架橋が主
体となり、粒子間での架橋は起こりにくい。このため、
一般の水分散型感圧性接着剤組成物として利用できて
も、本発明のような再剥離用としての用途には適さな
い。In addition, Japanese Patent Publication No. 1-45055 and Japanese Patent Application Laid-Open No. 5-105799 disclose a self-crosslinking, one-part, water-dispersible pressure-sensitive adhesive utilizing the reactivity between a carboxyl group and an epoxy group. A composition is disclosed. However, in each of these methods, the dispersed particles made of a copolymer are formed into a two-layer structure by a two-stage emulsion polymerization method, and a reaction between the functional groups is caused between the two layers to cause self-crosslinking. It is. Such self-crosslinking mainly involves crosslinking within particles, and crosslinking between particles is unlikely to occur. For this reason,
Even if it can be used as a general water-dispersed pressure-sensitive adhesive composition, it is not suitable for use for re-peeling as in the present invention.
【００２３】これに対して、本発明では、一段階の乳化
重合により、分散粒子の内部および粒子表面にカルボキ
シル基とエポキシ基とを特定比率で存在させることがで
き、これにより、粒子内での架橋とともに粒子間の架橋
も生起しやすく、その結果、前記高いゲル分率が容易に
達成されて、再剥離用として望まれる良好な接着性、再
剥離性および低汚染性を実現できるのである。また、本
発明では、上記のように一段階の乳化重合でよいため、
水分散型感圧性接着剤組成物およびその感圧性接着シ―
ト類の製造作業性にすぐれるという利点も得られる。On the other hand, according to the present invention, the carboxyl group and the epoxy group can be present at a specific ratio inside the dispersed particles and on the surface of the particles by one-stage emulsion polymerization. Crosslinking between particles is likely to occur together with crosslinking, and as a result, the high gel fraction is easily achieved, and good adhesion, removability and low contamination desired for removability can be realized. In addition, in the present invention, since one-stage emulsion polymerization may be used as described above,
Water-dispersed pressure-sensitive adhesive composition and its pressure-sensitive adhesive sheet
It also has the advantage of excellent workability in the production of products.
【００２４】本発明の再剥離用水分散型感圧性接着剤組
成物は、前記のように調製されるアクリル系共重合体の
水分散液に対し、必要に応じて、従来公知の各種の添加
剤、たとえば、粘着付与剤、架橋剤、可塑剤、軟化剤、
充填剤、顔料、染料、老化防止剤などを通常の添加量で
配合したものであつてもよい。The water-dispersible pressure-sensitive adhesive composition for re-peeling of the present invention may be added to the aqueous dispersion of the acrylic copolymer prepared as described above, if necessary, with various known additives. , For example, tackifiers, crosslinkers, plasticizers, softeners,
Fillers, pigments, dyes, antioxidants and the like may be blended in usual addition amounts.
【００２５】本発明の再剥離用感圧性接着シ―ト類は、
プラスチツクフイルム、紙、金属箔などの厚さが通常９
〜２００μｍの支持体と、この支持体上に上記の再剥離
用水分散型感圧性接着剤組成物を加熱乾燥してなる厚さ
が通常５〜５０μｍの感圧性接着剤層とを有するもので
ある。感圧性接着剤層の形成は、公知の方法に準じ、支
持体上に上記の再剥離用水分散型感圧性接着剤組成物を
直接塗工し、加熱乾燥する方法で行つてもよいし、セパ
レ―タ上に塗工し、加熱乾燥したのちに、支持体上に転
写するという方法で行つてもよい。The peelable pressure-sensitive adhesive sheets of the present invention include:
Normal thickness of plastic film, paper, metal foil etc. is 9
A support having a thickness of about 200 μm, and a pressure-sensitive adhesive layer having a thickness of usually 5 to 50 μm formed by heating and drying the water-dispersible pressure-sensitive adhesive composition for re-peeling on the support. . The pressure-sensitive adhesive layer may be formed by directly applying the water-dispersible pressure-sensitive adhesive composition for re-peeling on a support and heating and drying the same according to a known method. The method may be carried out in such a manner that the composition is coated on a substrate, dried by heating, and then transferred onto a support.
【００２６】[0026]
【実施例】つぎに、本発明をさらに具体的に説明するた
め、実施例および比較例を示す。本発明はこれらの実施
例によつてなんら限定されるものではない。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。EXAMPLES Next, examples and comparative examples will be described in order to more specifically explain the present invention. The present invention is not limited in any way by these examples. In the following, “parts” means “parts by weight”.
【００２７】実施例１ 温度計、撹拌機、窒素導入管および還流冷却管を備えた
反応器に、水５０部および過硫酸カリウム０．２部を仕
込み、撹拌下、１時間窒素置換した。ここに、アクリル
酸ブチル９４部、アクリル酸４部およびメタクリル酸グ
リシジル２部からなる単量体混合物、ラウリル硫酸ナト
リウム２部、ポリオキシエチレンラウリルエ―テル１部
を水１５０部で乳化したものを、７０℃で３時間かけて
滴下し、７０℃で２時間熟成を行つた。その後、室温ま
で冷却し、１０重量％のアンモニア水で中和して、再剥
離用水分散型感圧性接着剤組成物を調製した。Example 1 A reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with 50 parts of water and 0.2 parts of potassium persulfate, and the atmosphere was replaced with nitrogen for 1 hour with stirring. Here, a mixture of 94 parts of butyl acrylate, 4 parts of acrylic acid and 2 parts of glycidyl methacrylate, 2 parts of sodium lauryl sulfate and 1 part of polyoxyethylene lauryl ether emulsified with 150 parts of water were used. At 70 ° C. over 3 hours, and aged at 70 ° C. for 2 hours. Thereafter, the mixture was cooled to room temperature and neutralized with 10% by weight of aqueous ammonia to prepare a water-dispersible pressure-sensitive adhesive composition for re-peeling.
【００２８】つぎに、この再剥離用水分散型感圧性接着
剤組成物を、厚さが１２μｍのポリエステルフイルム上
に、乾燥後の厚さが２０μｍとなるように塗布したの
ち、１３０℃で５分間加熱乾燥し、再剥離用感圧性接着
テ―プを作製した。このテ―プの感圧性接着剤層（加熱
乾燥後）のゲル分率は８５重量％であつた。Next, this water-dispersible pressure-sensitive adhesive composition for re-peeling was applied on a polyester film having a thickness of 12 μm so that the thickness after drying became 20 μm, and then the coating was carried out at 130 ° C. for 5 minutes. After heating and drying, a pressure-sensitive adhesive tape for re-peeling was prepared. The gel fraction of the pressure-sensitive adhesive layer (after heating and drying) of this tape was 85% by weight.
【００２９】比較例１ 単量体混合物を、アクリル酸ブチル８７部、アクリル酸
１１部およびメタクリル酸グリシジル２部とした以外
は、実施例１と同様にして、再剥離用水分散型感圧性接
着剤組成物を調製し、また再剥離用感圧性接着テ―プを
作製した。このテ―プの感圧性接着剤層（加熱乾燥後）
のゲル分率は８７重量％であつた。Comparative Example 1 A water-dispersible pressure-sensitive adhesive for re-peeling was prepared in the same manner as in Example 1, except that the monomer mixture was changed to 87 parts of butyl acrylate, 11 parts of acrylic acid and 2 parts of glycidyl methacrylate. A composition was prepared and a removable pressure sensitive adhesive tape was prepared. Pressure-sensitive adhesive layer of this tape (after heating and drying)
Was 87% by weight.
【００３０】比較例２ 単量体混合物を、アクリル酸ブチル８５部、アクリル酸
４部およびメタクリル酸グリシジル１１部とした以外
は、実施例１と同様にして、再剥離用水分散型感圧性接
着剤組成物を調製し、また再剥離用感圧性接着テ―プを
作製した。このテ―プの感圧性接着剤層（加熱乾燥後）
のゲル分率は８８重量％であつた。Comparative Example 2 A water-dispersible pressure-sensitive adhesive for re-peeling was prepared in the same manner as in Example 1, except that the monomer mixture was changed to 85 parts of butyl acrylate, 4 parts of acrylic acid and 11 parts of glycidyl methacrylate. A composition was prepared and a removable pressure sensitive adhesive tape was prepared. Pressure-sensitive adhesive layer of this tape (after heating and drying)
Was 88% by weight.
【００３１】実施例２ 単量体混合物を、アクリル酸２−エチルヘキシル８１
部、メタクリル酸メチル１０部、メタクリル酸５部およ
びメタクリル酸グリシジル４部とし、かつ熟成時間を
２．５時間とした以外は、実施例１と同様にして、再剥
離用水分散型感圧性接着剤組成物を調製し、また再剥離
用感圧性接着テ―プを作製した。このテ―プの感圧性接
着剤層（加熱乾燥後）のゲル分率は８９重量％であつ
た。Example 2 A monomer mixture was prepared using 2-ethylhexyl acrylate 81
Parts, 10 parts of methyl methacrylate, 5 parts of methacrylic acid, and 4 parts of glycidyl methacrylate, and the aging time was 2.5 hours. A composition was prepared and a removable pressure sensitive adhesive tape was prepared. The gel fraction of the pressure-sensitive adhesive layer (after heat drying) of this tape was 89% by weight.
【００３２】比較例３ 単量体混合物を、アクリル酸２−エチルヘキシル８５
部、メタクリル酸メチル１０部およびメタクリル酸５部
とした以外は、実施例２と同様にして、再剥離用水分散
型感圧性接着剤組成物を調製し、また再剥離用感圧性接
着テ―プを作製した。この再剥離用感圧性接着テ―プの
感圧性接着剤層（加熱乾燥後）のゲル分率は５５重量％
であつた。COMPARATIVE EXAMPLE 3 A monomer mixture was prepared by using 2-ethylhexyl acrylate 85
, A water-dispersible pressure-sensitive adhesive composition for re-peeling, and a pressure-sensitive adhesive tape for re-peeling, in the same manner as in Example 2, except that 10 parts by weight, 10 parts of methyl methacrylate and 5 parts of methacrylic acid were used. Was prepared. The gel fraction of the pressure-sensitive adhesive layer (after heating and drying) of the pressure-sensitive adhesive tape for re-peeling was 55% by weight.
It was.
【００３３】比較例４ 単量体混合物を、アクリル酸２−エチルヘキシル８５
部、メタクリル酸メチル１０部およびメタクリル酸グリ
シジル５部とした以外は、実施例２と同様にして再剥離
用水分散型感圧性接着剤組成物を調製し、また再剥離用
感圧性接着テ―プを作製した。この再剥離用感圧性接着
テ―プの感圧性接着剤層（加熱乾燥後）のゲル分率は４
９重量％であつた。COMPARATIVE EXAMPLE 4 A monomer mixture was prepared using 2-ethylhexyl acrylate 85
, A water-dispersible pressure-sensitive adhesive composition for re-peeling was prepared in the same manner as in Example 2, except that 10 parts, 10 parts of methyl methacrylate and 5 parts of glycidyl methacrylate were used. Was prepared. The gel fraction of the pressure-sensitive adhesive layer (after heating and drying) of the pressure-sensitive adhesive tape for re-peeling was 4%.
It was 9% by weight.
【００３４】実施例３ 単量体混合物を、アクリル酸２−エチルヘキシル８４．
５部、アクリル酸ブチル１０部、アクリル酸３部および
メタクリル酸グリシジル２．５部とした以外は、実施例
１と同様にして、再剥離用水分散型感圧性接着剤組成物
を調製し、また再剥離用感圧性接着テ―プを作製した。
このテ―プの感圧性接着剤層（加熱乾燥後）のゲル分率
は８７重量％であつた。Example 3 A mixture of monomers was prepared using 2-ethylhexyl acrylate.
5 parts, 10 parts of butyl acrylate, 3 parts of acrylic acid, and 2.5 parts of glycidyl methacrylate were prepared in the same manner as in Example 1 to prepare a water-dispersible pressure-sensitive adhesive composition for re-peeling. A pressure-sensitive adhesive tape for re-peeling was prepared.
The gel fraction of the pressure-sensitive adhesive layer (after heating and drying) of this tape was 87% by weight.
【００３５】実施例４ 単量体混合物を、アクリル酸２−エチルヘキシル８６．
５部、アクリル酸ブチル１０部、メタクリル酸３部およ
びメタクリル酸グリシジル０．５部とした以外は、実施
例１と同様にして、再剥離用水分散型感圧性接着剤組成
物を調製し、また再剥離用感圧性接着テ―プを作製し
た。このテ―プの感圧性接着剤層（加熱乾燥後）のゲル
分率は７５重量％であつた。Example 4 A mixture of monomers was prepared using 2-ethylhexyl acrylate 86.
5 parts, 10 parts of butyl acrylate, 3 parts of methacrylic acid and 0.5 part of glycidyl methacrylate were prepared in the same manner as in Example 1 to prepare a water-dispersible pressure-sensitive adhesive composition for re-peeling, A pressure-sensitive adhesive tape for re-peeling was prepared. The gel fraction of the pressure-sensitive adhesive layer (after heating and drying) of this tape was 75% by weight.
【００３６】以上の実施例１〜４および比較例１〜４の
各再剥離用水分散型感圧性接着剤組成物について、下記
の方法により、保存安定性を調べた。また、各再剥離用
感圧性接着テ―プについて、下記の方法により、初期接
着力、再剥離性および汚染性を調べた。これらの結果
は、表１に示されるとおりであつた。The storage stability of each of the water-dispersible pressure-sensitive adhesive compositions for peeling in Examples 1 to 4 and Comparative Examples 1 to 4 was examined by the following method. In addition, the initial adhesive strength, removability and stainability of each pressure-sensitive adhesive tape for removability were examined by the following methods. These results were as shown in Table 1.
【００３７】＜保存安定性＞再剥離用水分散型感圧性接
着剤組成物を４０℃で３日間保存したのち、塗工性の良
否を調べた。塗工性の良好なものを○、やや良くないも
のを△、塗工困難なものを×、と評価した。なお、再剥
離用水分散型感圧性接着剤組成物の調製後、支持体上に
塗工するまでの時間は、通常２日間程度であるため、４
０℃で３日間の保存試験は、保存安定性の良否を調べる
うえで、十分な条件である。<Storage Stability> The water-dispersible pressure-sensitive adhesive composition for re-peeling was stored at 40 ° C. for 3 days, and the coatability was examined. Good coating properties were evaluated as ○, slightly poor ones as Δ, and ones that were difficult to apply as ×. The time from preparation of the water-dispersible pressure-sensitive adhesive composition for re-peeling until coating on the support is usually about 2 days,
The storage test at 0 ° C. for 3 days is a sufficient condition for examining the storage stability.
【００３８】＜初期接着力＞ＪＩＳ Ｚ−０２３７に準
じて、被着体（＃２８０のサンドペ―パでサンデイング
したステンレス板）に再剥離用感圧性接着テ―プを貼り
合わせ、１８０度ピ―リング試験を行い、剥離力（ｇ／
２０mm幅）を測定した。<Initial Adhesive Strength> According to JIS Z-0237, a pressure-sensitive adhesive tape for re-peeling is adhered to an adherend (a stainless steel plate sanded with a sandpaper of # 280), and a 180-degree peak is applied. A ring test was performed and the peel force (g /
20 mm width).
【００３９】＜再剥離性＞初期接着力の場合と同様にし
て、再剥離用感圧性接着テ―プを被着体（＃２８０のサ
ンドペ―パでサンデイングしたステンレス板）に貼り合
わせた試験片を、８０℃で１時間加熱し、放冷後、１８
０度ピ―リング試験を行い、剥離力（ｇ／２０mm幅）を
測定した。この剥離力が初期接着力に比べて極端に増大
していなければ、再剥離性が良好であることを示してい
る。なお、表１中、※は上記の測定時に凝集破壊したこ
とを示している。<Removability> A test piece in which a pressure-sensitive adhesive tape for removability was adhered to an adherend (a stainless steel plate sanded with # 280 sandpaper) in the same manner as in the case of the initial adhesive strength. Was heated at 80 ° C. for 1 hour, and allowed to cool.
A 0-degree peeling test was performed to measure the peeling force (g / 20 mm width). If this peeling force is not extremely increased as compared with the initial adhesive force, it indicates that the re-peelability is good. In Table 1, * indicates that cohesive failure occurred during the above measurement.
【００４０】＜汚染性＞初期接着力の場合と同様にし
て、再剥離用感圧性接着テ―プを被着体（＃２８０のサ
ンドペ―パでサンデイングしたステンレス板）に貼り合
わせた試験片を、１００℃で１時間加熱し、直後に剥離
した。このときの被着体表面の糊残りによる汚染状況を
調べ、下記のように評価した。 ○：被着体の汚染がみられない（接着剤の破壊形態が界
面破壊） △：被着体の汚染がややみられる（接着剤の破壊形態が
一部凝集破壊） ×：被着体の汚染が著しい（接着剤の破壊形態が凝集破
壊）<Stainability> In the same manner as in the case of the initial adhesive strength, a test piece in which a pressure-sensitive adhesive tape for re-peeling was adhered to an adherend (a stainless steel plate sanded with a # 280 sandpaper) was used. And heated at 100 ° C. for 1 hour, and immediately peeled off. At this time, the state of contamination due to adhesive residue on the surface of the adherend was examined and evaluated as follows. ○: no contamination of the adherend was observed (adhesive destruction mode was interface destruction) △: contamination of the adherend was slightly observed (adhesive destruction was partially cohesive failure) ×: adhesion of the adherend was observed Severe contamination (adhesive failure form cohesive failure)
【００４１】 [0041]
【００４２】上記の表１の結果から明らかなように、本
発明の実施例１〜４の各再剥離用水分散型感圧性接着剤
組成物は、いずれも、保存安定性が良好で一液型として
十分なポツトライフを示しており、またこれより作製さ
れる各再剥離用感圧性接着テ―プは、いずれも、良好な
初期接着力を有しているとともに、高温条件下に曝され
たのちでも接着力の極端な増大がみられず、再剥離性に
すぐれており、また、被着体の汚染性も低いものである
ことがわかる。As is clear from the results shown in Table 1 above, each of the water-dispersible pressure-sensitive adhesive compositions for removability of Examples 1 to 4 of the present invention has good storage stability and is a one-pack type. Each of the pressure-sensitive adhesive tapes for re-peeling has a good initial adhesive strength and has been exposed to high temperature conditions. However, it can be seen that no extreme increase in the adhesive force was observed, the removability was excellent, and the contamination of the adherend was low.
【００４３】[0043]
【発明の効果】以上のように、本発明によれば、一液型
で十分なポツトライフを有し、しかも良好な接着性、再
剥離性および低汚染性を示すアクリル系の再剥離用水分
散型感圧性接着剤組成物とその感圧性接着シ―ト類を提
供することができる。As described above, according to the present invention, an acrylic water-dispersible type for one-pack type which has a sufficient pot life and exhibits good adhesiveness, removability and low contamination. A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet thereof can be provided.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０８Ｆ 220:32） ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI C08F 220: 32)
Claims (3)
タ）アクリル酸アルキルエステル５０重量％以上、カル
ボキシル基含有モノマ―０．１〜１０重量％およびエポ
キシ基含有モノマ―０．１〜１０重量％を必須成分とし
た単量体混合物の共重合体を含む水分散液であつて、加
熱乾燥後のゲル分率が５０〜９５重量％であることを特
徴とする再剥離用水分散型感圧性接着剤組成物。1. An alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms in an amount of 50% by weight or more, a carboxyl group-containing monomer 0.1 to 10% by weight, and an epoxy group-containing monomer 0.1 to 10%. An aqueous dispersion containing a copolymer of a monomer mixture having a weight% of an essential component, wherein the gel fraction after heating and drying is 50 to 95% by weight. Pressure-sensitive adhesive composition.
キシ基含有モノマ―は、カルボキシル基のモル数がエポ
キシ基のモル数より多くなるような使用割合とされてい
る請求項１に記載の再剥離用水分散型感圧性接着剤組成
物。2. The aqueous dispersion for re-stripping according to claim 1, wherein the carboxyl group-containing monomer and the epoxy group-containing monomer are used in such a proportion that the number of moles of the carboxyl group is larger than the number of moles of the epoxy group. -Type pressure-sensitive adhesive composition.
２に記載の再剥離用水分散型感圧性接着剤組成物を加熱
乾燥してなる感圧性接着剤層とを有することを特徴とす
る再剥離用感圧性接着シ―ト類。3. A support comprising a support and a pressure-sensitive adhesive layer formed by heating and drying the water-dispersible pressure-sensitive adhesive composition for re-peeling according to claim 1 or 2 on the support. Pressure-sensitive adhesive sheets for re-peeling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8319435A JPH10158617A (en) | 1996-11-29 | 1996-11-29 | Repeatedly peelable pressure-sensitive adhesive composition of water dispersion type and repeatedly peelable pressure-sensitive adhesive sheet and the like using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8319435A JPH10158617A (en) | 1996-11-29 | 1996-11-29 | Repeatedly peelable pressure-sensitive adhesive composition of water dispersion type and repeatedly peelable pressure-sensitive adhesive sheet and the like using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10158617A true JPH10158617A (en) | 1998-06-16 |
Family
ID=18110173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8319435A Pending JPH10158617A (en) | 1996-11-29 | 1996-11-29 | Repeatedly peelable pressure-sensitive adhesive composition of water dispersion type and repeatedly peelable pressure-sensitive adhesive sheet and the like using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10158617A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001303007A (en) * | 2000-04-21 | 2001-10-31 | Chuo Rika Kogyo Corp | Acrylic resin emulsion for pressure sensitive peelable adhesive |
| KR100427407B1 (en) * | 2001-12-10 | 2004-04-14 | 태영화학공업 주식회사 | Removable pressure sensitive adhesive based on an acrylic emulsion |
| JP2005089666A (en) * | 2003-09-19 | 2005-04-07 | Chuo Rika Kogyo Corp | Aqueous adhesive composition |
| KR100933564B1 (en) | 2007-09-06 | 2009-12-23 | (주)건양 | Acrylic adhesive composition for concrete weighing |
| JP2010174260A (en) * | 2003-06-09 | 2010-08-12 | Nitto Denko Corp | Pressure-sensitive adhesive tape |
| JP2014116431A (en) * | 2012-12-07 | 2014-06-26 | Furukawa Electric Co Ltd:The | Semiconductor wafer surface protection adhesive tape |
| JP2014160852A (en) * | 2014-04-18 | 2014-09-04 | Furukawa Electric Co Ltd:The | Adhesive tape for semiconductor wafer surface protection |
| JP2021073366A (en) * | 2016-05-27 | 2021-05-13 | 住友化学株式会社 | Resin composition and cured film |
-
1996
- 1996-11-29 JP JP8319435A patent/JPH10158617A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001303007A (en) * | 2000-04-21 | 2001-10-31 | Chuo Rika Kogyo Corp | Acrylic resin emulsion for pressure sensitive peelable adhesive |
| KR100427407B1 (en) * | 2001-12-10 | 2004-04-14 | 태영화학공업 주식회사 | Removable pressure sensitive adhesive based on an acrylic emulsion |
| JP2010174260A (en) * | 2003-06-09 | 2010-08-12 | Nitto Denko Corp | Pressure-sensitive adhesive tape |
| JP2005089666A (en) * | 2003-09-19 | 2005-04-07 | Chuo Rika Kogyo Corp | Aqueous adhesive composition |
| KR100933564B1 (en) | 2007-09-06 | 2009-12-23 | (주)건양 | Acrylic adhesive composition for concrete weighing |
| JP2014116431A (en) * | 2012-12-07 | 2014-06-26 | Furukawa Electric Co Ltd:The | Semiconductor wafer surface protection adhesive tape |
| JP2014160852A (en) * | 2014-04-18 | 2014-09-04 | Furukawa Electric Co Ltd:The | Adhesive tape for semiconductor wafer surface protection |
| JP2021073366A (en) * | 2016-05-27 | 2021-05-13 | 住友化学株式会社 | Resin composition and cured film |
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