JPH07173445A - Water-swellable pressure-sensitive adhesive composition - Google Patents
Water-swellable pressure-sensitive adhesive compositionInfo
- Publication number
- JPH07173445A JPH07173445A JP6457194A JP6457194A JPH07173445A JP H07173445 A JPH07173445 A JP H07173445A JP 6457194 A JP6457194 A JP 6457194A JP 6457194 A JP6457194 A JP 6457194A JP H07173445 A JPH07173445 A JP H07173445A
- Authority
- JP
- Japan
- Prior art keywords
- water
- weight
- sensitive adhesive
- parts
- acrylate
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】この発明は、水膨潤性の感圧接着
剤組成物、つまり常時感圧接着性を有するとともに、水
により膨潤して容易に剥離できる接着剤組成物に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-swellable pressure-sensitive adhesive composition, that is, an adhesive composition which has a constant pressure-sensitive adhesive property and is swollen by water and easily peeled off.
【0002】[0002]
【従来の技術】水により剥離できる感圧接着剤には、水
溶性のもの、水分散性のもの、水膨潤性のものがある。
しかし、前二者のものは、完全に溶解ないし分散するの
に時間がかかり、通常その途中で剥がれてくるが、凝集
破壊により接着剤の一部が被着体に残るため、被着体を
汚染し、剥離後の水洗いが不可欠となる。しかも、とく
に水分散性のものでは、接着特性自体にも不安がある。2. Description of the Related Art Pressure-sensitive adhesives which can be peeled off with water include water-soluble adhesives, water-dispersible adhesives and water-swellable adhesives.
However, in the former two, it takes time to completely dissolve or disperse, and although it usually peels off in the middle, a part of the adhesive remains on the adherend due to cohesive failure, so the adherend is Contamination and washing with water after peeling are indispensable. Moreover, especially with water-dispersible substances, there is concern about the adhesive properties themselves.
【0003】これに対し、水膨潤性のものは、水を吸う
ことにより界面での接着力がなくなつて、比較的速やか
に剥離できるし、その際に接着剤層は破壊しないので、
被着体を汚染する心配もない。このため、水により剥離
できる感圧接着剤としては、水膨潤性のものが最も好ま
しいものといえる。On the other hand, a water-swelling material loses its adhesive force at the interface by absorbing water and can be peeled off relatively quickly, and the adhesive layer is not destroyed at that time,
There is no need to worry about contaminating the adherend. Therefore, it can be said that the water-swellable pressure-sensitive adhesive is most preferable as the pressure-sensitive adhesive that can be peeled off with water.
【0004】従来の水膨潤性の感圧接着剤は、米国特許
2,838,421号明細書、特公昭50−84578
号公報、特公昭52−22768号公報、特公昭49−
23813号公報などに示されているように、ポリアク
リル酸などの分子内にカルボキシル基を含有するポリマ
―をベ―スポリマ―とし、これに多官能の架橋剤を配合
して、水膨潤性の感圧接着剤としていた。A conventional water-swellable pressure-sensitive adhesive is disclosed in US Pat. No. 2,838,421, JP-B-50-84578.
JP-B, JP-B-52-22768, JP-B-49-
As disclosed in Japanese Patent No. 23813, a polymer containing a carboxyl group in the molecule such as polyacrylic acid is used as a base polymer, and a polyfunctional cross-linking agent is added to the polymer to make it water-swellable. It was used as a pressure sensitive adhesive.
【0005】しかし、分子内に極性の強い官能基である
カルボキシル基を含有するモノマ―を重合させて得たポ
リマ―は、ガラス転移温度が高く、このポリマ―だけで
は室温にて十分な感圧接着性を得にくく、そのうえ多官
能の架橋剤による架橋で硬さが増すため、感圧接着性に
どうしても劣りやすい。そこで、この感圧接着性を上げ
るために、上記ポリマ―に可塑剤を多量に配合させてい
る。However, a polymer obtained by polymerizing a monomer containing a carboxyl group which is a highly polar functional group in the molecule has a high glass transition temperature, and this polymer alone has a sufficient pressure-sensitive property at room temperature. Since it is difficult to obtain adhesiveness and the hardness is increased by crosslinking with a polyfunctional crosslinking agent, the pressure-sensitive adhesiveness is apt to deteriorate. Therefore, in order to improve the pressure-sensitive adhesiveness, a large amount of a plasticizer is blended with the polymer.
【0006】[0006]
【発明が解決しようとする課題】しかるに、上記従来の
水膨潤性の感圧接着剤は、多量の可塑剤の使用により低
温下での接着力が低くなりやすく、また可塑剤は通常水
溶性のものであるため、多量配合は接着剤全体を水溶性
に近いものとし、被着体を汚染させる。さらに、多官能
の架橋剤で架橋しているため、ポリマ―分子間の距離が
短くなり、水分子の入り込むスペ―スが小さく、それだ
け水膨潤性に劣る問題もあつた。However, the above conventional water-swellable pressure-sensitive adhesives tend to have low adhesive strength at low temperatures due to the use of a large amount of plasticizer, and the plasticizer is usually water-soluble. Therefore, a large amount of the compound makes the entire adhesive almost water-soluble and contaminates the adherend. Further, since the polyfunctional cross-linking agent is used for the cross-linking, the distance between the polymer molecules is shortened, the space where water molecules enter is small, and the water swelling property is poor.
【0007】この発明は、上記従来の事情に鑑み、常時
感圧接着性を有して、とくに常温はもちろん低温下でも
大きな接着力を示すとともに、水膨潤性にもすぐれて、
水により容易にかつ比較的速やかに剥離でき、しかもそ
の際に被着体を汚染させることのない感圧接着剤組成物
を提供することを目的としている。In view of the above conventional circumstances, the present invention has a pressure-sensitive adhesive property at all times, exhibits a large adhesive force at room temperature as well as at a low temperature, and is excellent in water swelling property.
It is an object of the present invention to provide a pressure-sensitive adhesive composition that can be easily and relatively quickly peeled off with water and does not contaminate an adherend at that time.
【0008】[0008]
【課題を解決するための手段】この発明者らは、上記の
目的を達成するために、鋭意検討した結果、特定のモノ
マ―を重合させて得られるガラス転移温度の低い共重合
ポリマ―がこれ単独でも良好な感圧接着性を示し、これ
に架橋剤を配合して、架橋後のゲル分率および膨潤度が
特定の値となるように設定したときには、すぐれた水膨
潤性も発揮し、常温および低温での接着特性にすぐれ
て、しかも水により容易にかつ比較的速やかに剥離で
き、その際に被着体を汚染させることのない感圧接着剤
が得られることを知り、この発明を完成するに至つた。Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to achieve the above object, and as a result, found that a copolymerized polymer having a low glass transition temperature obtained by polymerizing a specific monomer is Shows good pressure-sensitive adhesiveness alone, and when a crosslinking agent is added to this and the gel fraction and the degree of swelling after crosslinking are set to specific values, excellent water swellability is also exhibited, It was found that a pressure-sensitive adhesive having excellent adhesive properties at room temperature and low temperature, which can be easily and relatively quickly peeled off with water, and which does not contaminate an adherend at that time, is obtained, It was completed.
【0009】すなわち、この発明は、a)メトキシエチ
ルアクリレ―トおよび/またはカプロラクトンアクリレ
―ト15〜100重量%(ただし、カプロラクトンアク
リレ―トは50重量%以下)と、b)カプロラクトンア
クリレ―ト以外のカルボキシル基含有モノマ―10〜0
重量%と、c)これらと共重合可能な他のモノマ―85
〜0重量%との共重合ポリマ―に、架橋剤および必要に
より可塑剤その他の配合剤を配合してなり、架橋後のゲ
ル分率が20〜70%、膨潤度が20以上であることを
特徴とする水膨潤性の感圧接着剤組成物に係るものであ
る。That is, the present invention comprises: a) 15 to 100% by weight of methoxyethyl acrylate and / or caprolactone acrylate (however, caprolactone acrylate is 50% by weight or less); and b) caprolactone acrylate. Carboxyl group-containing monomer other than rate 10-0
% By weight, c) another monomer 85 copolymerizable with them
To 0% by weight of a copolymerized polymer with a crosslinking agent and, if necessary, a plasticizer and other compounding agents, the gel fraction after crosslinking is 20 to 70%, and the swelling degree is 20 or more. The present invention relates to a characteristic water-swellable pressure-sensitive adhesive composition.
【0010】なお、この明細書において、ゲル分率およ
び膨潤度は、以下の方法で測定,算出される値である。
まず、接着剤組成物を0.5g程度秤量し、その重さを
Aとする。つぎに、これを水500ml中に48時間浸
漬したのち、ナイロンメツシユでろ過し、水を含んだ接
着剤組成物の重さ(B)を測定する。その後、130℃
で5時間乾燥したのち、不揮発分の重さ(C)を測定す
る。これらの測定値A〜Cより、ゲル分率および膨潤度
は、それぞれ、ゲル分率(%)=〔C/A〕×100と
して、また膨潤度=B/Cとして、求められる。In this specification, the gel fraction and the swelling degree are values measured and calculated by the following methods.
First, about 0.5 g of the adhesive composition is weighed and its weight is set to A. Next, this is immersed in 500 ml of water for 48 hours and then filtered through a nylon mesh to measure the weight (B) of the adhesive composition containing water. After that, 130 ℃
After drying for 5 hours, the weight (C) of the non-volatile matter is measured. From these measured values A to C, the gel fraction and the degree of swelling can be determined as gel fraction (%) = [C / A] × 100 and degree of swelling = B / C, respectively.
【0011】[0011]
【発明の構成・作用】この発明において使用するa成分
のモノマ―のひとつは、つぎの式; で表わされるメトキシエチルアクリレ―トであり、この
モノマ―はそのホモポリマ―のガラス転移温度が−20
℃以下となるものであつて、感圧接着性を付与するモノ
マ―として有効に機能するものである。One of the monomers of the component a used in the present invention has the following formula: This monomer is a methoxyethyl acrylate represented by and the homopolymer has a glass transition temperature of -20.
It has a temperature of not higher than 0 ° C and effectively functions as a monomer that imparts pressure-sensitive adhesiveness.
【0012】この発明において使用するa成分のモノマ
―の他のひとつは、つぎの式; で表わされるカプロラクトンアクリレ―トであつて、式
中mの数が1〜10の範囲でありかつmの平均値が1〜
5の範囲にあるモノマ―混合物である。この種のモノマ
―は、重合性炭素−炭素二重結合とカルボキシル基との
間の距離が離れており、これを付加重合させたとき重合
主鎖に対して側鎖として結合するカルボキシル基が上記
主鎖から遠ざかつた位置に存在するというような分子構
造をとるため、ガラス転移温度の低いポリマ―を与え、
しかも架橋後の水膨潤性の向上にも好ましい結果を与え
るものである。Another one of the a-component monomers used in the present invention has the following formula: A caprolactone acrylate represented by the formula wherein the number of m is in the range of 1 to 10 and the average value of m is 1 to
It is a monomer mixture in the range of 5. In this type of monomer, the distance between the polymerizable carbon-carbon double bond and the carboxyl group is large, and when this is subjected to addition polymerization, the carboxyl group bonded as a side chain to the polymerization main chain is the above-mentioned. Since it has a molecular structure such that it exists at a position away from the main chain, it gives a polymer with a low glass transition temperature,
Moreover, it also gives favorable results in improving the water swelling property after crosslinking.
【0013】この発明において使用するb成分のモノマ
―は、上記のカプロラクトンアクリレ―ト以外のカルボ
キシル基含有モノマ―であつて、具体的には、アクリル
酸、メタクリル酸、イタコン酸、マレイン酸、アクリル
酸2−カルボキシルエチルなどを挙げることができる。
これらのカルボキシル基含有モノマ―は、主に接着力調
整用として必要により用いられるものであり、とくにa
成分のモノマ―としてメトキシエチルアクリレ―トをこ
れ単独で用いるときには、このb成分のモノマ―を使用
することが望ましい。The monomer of component b used in the present invention is a carboxyl group-containing monomer other than the above-mentioned caprolactone acrylate, and specifically, acrylic acid, methacrylic acid, itaconic acid, maleic acid, 2-carboxyethyl acrylate etc. can be mentioned.
These carboxyl group-containing monomers are mainly used as needed for adjusting the adhesive strength, and particularly a
When methoxyethyl acrylate is used alone as the component monomer, it is desirable to use the component b monomer.
【0014】この発明において使用するc成分のモノマ
―は、上記のa,b成分のモノマ―と共重合可能なもの
であつて、このモノマ―もやはり接着力や凝集力などの
接着特性調整用として必要により用いられるものであ
る。具体的には、アルキル基の炭素数が1〜12である
(メタ)アクリル酸アルキルエステル、(メタ)アクリ
ル酸2−ヒドロキシエチル、(メタ)アクリル酸2−ヒ
ドロキシプロピルなどの水酸基含有モノマ―、酢酸ビニ
ル、プロピオン酸ビニル、スチレンまたはその誘導体
(たとえばスチレンスルホン酸ナトリウム)、アクリロ
ニトリル、メタクリロニトリルなどを挙げることができ
る。The monomer of the component c used in the present invention is a copolymer which can be copolymerized with the monomer of the components a and b, and this monomer is also used for adjusting the adhesive properties such as the adhesive force and the cohesive force. Is used as necessary. Specifically, a hydroxyl group-containing monomer such as an alkyl ester of (meth) acrylic acid having an alkyl group having 1 to 12 carbon atoms, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate, Examples thereof include vinyl acetate, vinyl propionate, styrene or a derivative thereof (eg sodium styrenesulfonate), acrylonitrile, methacrylonitrile and the like.
【0015】この発明において、上記a,b,c成分の
モノマ―の使用割合は、全モノマ―中、a成分のモノマ
―が15〜100重量%(好ましくは40〜95重量
%)、b成分のモノマ―が10〜0重量%(好ましくは
5〜0重量%)、c成分のモノマ―が85〜0重量%
(好ましくは55〜5重量%)となるように、接着剤組
成物の個々の用途目的に応じて適宜決められる。また、
a成分のモノマ―は、メトキシエチルアクリレ―ト単
独、カプロラクトンアクリレ―ト単独、両者の併用系の
いずれでもよいが、併用系の場合はその合計量が上記割
合となるようにする。また、カプロラクトンアクリレ―
ト単独または上記併用系の場合、カプロラクトンアクリ
レ―トの使用量は、全モノマ―中、50重量%以下(好
ましくは40重量%以下)となるようにすべきである。In the present invention, the proportions of the monomers of the a, b, and c components used are such that the monomer of the a component is 15 to 100% by weight (preferably 40 to 95% by weight), and the b component is all monomers. 10 to 0% by weight (preferably 5 to 0% by weight), and the component c monomer is 85 to 0% by weight.
(Preferably 55 to 5% by weight) is appropriately determined according to the individual purpose of use of the adhesive composition. Also,
The monomer of component a may be either methoxyethyl acrylate alone, caprolactone acrylate alone, or a combination of both, but in the case of a combination, the total amount thereof should be the above ratio. Also, caprolactone acrylate
When used alone or in the combination system described above, the amount of caprolactone acrylate used should be 50% by weight or less (preferably 40% by weight or less) based on the total monomers.
【0016】a成分のモノマ―が15重量%未満となつ
たり、カプロラクトンアクリレ―トが50重量%を超え
たり、またb成分のモノマ―が10重量%を超えたり、
さらにc成分のモノマ―が85重量%を超えたりする
と、感圧接着性とくに低温接着力や水膨潤性などの特性
に好結果が得られない。なお、a成分のモノマ―がメト
キシエチルアクリレ―ト単独の場合は、b成分のモノマ
―を、全モノマ―中、1〜10重量%、好ましくは3〜
5重量%の割合で用いて、接着力の向上を図るのが望ま
しいが、a成分のモノマ―にカプロラクトンアクリレ―
トが含まれる場合は、b成分のモノマ―はあえて使用し
なくてもよい。The component a monomer is less than 15% by weight, the caprolactone acrylate is more than 50% by weight, and the component b monomer is more than 10% by weight.
Further, when the amount of the component c monomer exceeds 85% by weight, favorable results cannot be obtained in properties such as pressure-sensitive adhesiveness, particularly low temperature adhesiveness and water swelling property. When the monomer of the component a is methoxyethyl acrylate alone, the monomer of the component b is 1 to 10% by weight, preferably 3 to 10% by weight based on the total amount of the monomers.
It is desirable to use 5% by weight to improve the adhesive strength, but the caprolactone acrylate is added to the monomer of the component a.
When the component b is included, the component b monomer may not be used.
【0017】この発明において、これらのモノマ―から
共重合ポリマ―を生成するには、塊状重合法、溶液重合
法、エマルジヨン重合法、懸濁重合法などの適宜のラジ
カル重合手法により、上記モノマ―を共重合させればよ
い。重合開始剤としては、アゾビスイソブチロニトリ
ル、アゾビスバレロニトリルなどのアゾ系化合物、ベン
ゾイルペルオキシド、ラウロイルペルオキシドなどの過
酸化物、過硫酸アンモニウム、過硫酸カリウムなどの過
硫酸塩、これらと亜硫酸水素ナトリウム、アスコルビン
酸ナトリウム、金属塩などとのレドツクス系触媒が用い
られる。In the present invention, in order to form a copolymerized polymer from these monomers, the above-mentioned monomers are prepared by a suitable radical polymerization technique such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization. May be copolymerized. Examples of the polymerization initiator include azo compounds such as azobisisobutyronitrile and azobisvaleronitrile, peroxides such as benzoyl peroxide and lauroyl peroxide, persulfates such as ammonium persulfate and potassium persulfate, and hydrogen sulfite. Redox catalysts with sodium, sodium ascorbate, metal salts and the like are used.
【0018】このようにして得られる共重合ポリマ―
は、ガラス転移温度が通常0℃以下、好ましくは−10
℃〜−70℃程度であつて、これ単独でも良好な感圧接
着性を発揮する。接着特性の調整のために、この共重合
ポリマ―にポリエ―テルポリオ―ル、多価アルコ―ル、
酸化ロジンのアルカノ―ルアミン塩などの水溶性の可塑
剤を配合してもよいが、その量は、低温接着力や非汚染
性を損なわないように、共重合ポリマ―100重量部に
対し、100重量部以下、好ましくは50重量部以下、
さらに好ましくは20重量部以下の少なめとする。The copolymerized polymer thus obtained
Has a glass transition temperature of usually 0 ° C. or lower, preferably −10.
C. to -70.degree. C., and even by itself, it exhibits good pressure-sensitive adhesiveness. In order to adjust the adhesive properties, this copolymer is added with polyether polyol, polyhydric alcohol,
A water-soluble plasticizer such as an alkanolamine salt of rosin oxide may be added, but the amount thereof should be 100 parts by weight based on 100 parts by weight of the copolymerized polymer so as not to impair the low temperature adhesive strength and the non-staining property. Parts by weight or less, preferably 50 parts by weight or less,
More preferably, the amount is 20 parts by weight or less.
【0019】この発明において、上記の共重合ポリマ―
に配合する架橋剤としては、エポキシ系架橋剤、金属
塩、水溶性フエノ―ルなどが挙げられる。これらの中で
も、とくに好ましい架橋剤は、つぎの式; で表されるポリエチレングリコ―ル(重合度nが9以
上、通常22程度まで)のジグリシジルエ―テルであつ
て、この架橋剤は、2官能でかつ長いポリエチレングリ
コ―ル鎖を有することから、架橋間分子量を大きくし
て、架橋後の接着剤組成物に非常にすぐれた水膨潤性を
付与する機能を有している。In the present invention, the above copolymerized polymer
Examples of the cross-linking agent to be blended in include epoxy cross-linking agents, metal salts, water-soluble phenols and the like. Among these, a particularly preferable crosslinking agent has the following formula; A diglycidyl ether having a polyethylene glycol (polymerization degree n of 9 or more, usually up to about 22) represented by the formula (1), which has a bifunctional and long polyethylene glycol chain, It has a function of increasing the intermolecular weight to give the adhesive composition after crosslinking excellent water swellability.
【0020】このような架橋剤は、共重合ポリマ―10
0重量部に対し、通常0.01〜5重量部、好ましくは
0.05〜3重量部、さらに好ましくは0.1〜1重量
部の割合で配合するのがよい。0.01重量部より少な
いと、十分な水膨潤性が得られない。また、5重量部を
超えて用いてもそれ以上の効果はなく、経済的に不利で
あるとともに、接着力などの低下を引き起こしやすい。Such a cross-linking agent is a copolymerized polymer-10.
It is usually 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, and more preferably 0.1 to 1 part by weight, relative to 0 parts by weight. If the amount is less than 0.01 part by weight, sufficient water swellability cannot be obtained. Further, even if it is used in an amount of more than 5 parts by weight, there is no further effect, which is economically disadvantageous and tends to cause a decrease in adhesive strength and the like.
【0021】この発明の水膨潤性の感圧接着剤組成物
は、上記の共重合ポリマ―に上記の架橋剤および必要に
より前記の可塑剤を配合してなり、さらに必要により着
色剤、充てん剤、老化防止剤などの公知の各種の配合剤
を配合できるが、その際、架橋後のゲル分率が20〜7
0%、膨潤度が20以上となるようにすべきであり、好
ましくは架橋後のゲル分率が35〜60%、膨潤度が5
0以上200程度までとなるようにするのがよい。架橋
後のゲル分率が20%未満では、水溶性の性質が強くな
つて被着体を汚染するおそれがあり、また同ゲル分率が
70%を超えたり膨潤度が20未満となると、水の吸収
が遅く、膨潤剥離までに時間がかかつたり剥がれなくな
るといつた問題を生じてくる。The water-swellable pressure-sensitive adhesive composition of the present invention comprises the above-mentioned copolymerized polymer and the above-mentioned crosslinking agent and, if necessary, the above-mentioned plasticizer, and if necessary, a coloring agent and a filler. Various known compounding agents such as antiaging agents can be added, but the gel fraction after crosslinking is 20 to 7
0%, the degree of swelling should be 20 or more, preferably the gel fraction after crosslinking is 35 to 60%, and the degree of swelling is 5
It is preferable to set it to 0 or more and about 200. If the gel fraction after cross-linking is less than 20%, the water-soluble property may be strengthened to contaminate the adherend, and if the gel fraction exceeds 70% or the swelling degree is less than 20, When the absorption of swelling is slow, and it takes time before swelling and peeling off or the peeling does not occur, some problems occur.
【0022】この発明の水膨潤性の感圧接着剤組成物
は、使用に際し、不織布、ポリ塩化ビニル、ポリエチレ
ン、ポリプロピレン、ポリエチレンラミネ―ト紙などの
各種基材の片面または両面に塗工し、乾燥工程と同時ま
たはその後に適宜架橋処理して、シ―ト状やテ―プ状な
どの接着シ―ト類としてもよい。この接着シ―ト類は、
これを被着体に貼着後剥離する際に、水を付与して膨潤
させると、接着力が大きく低下して、容易にかつ短時間
に剥離できることから、被着体のリサイクルなどに有効
に寄与させることができる。The water-swellable pressure-sensitive adhesive composition of the present invention, when used, is coated on one or both sides of various substrates such as non-woven fabric, polyvinyl chloride, polyethylene, polypropylene, polyethylene laminated paper, Adhesive sheets in the form of sheets, tapes, etc. may be obtained by appropriately performing crosslinking treatment at the same time as or after the drying step. This adhesive sheet
When it is peeled off after being adhered to an adherend, if water is applied to cause it to swell, the adhesive strength is greatly reduced, and peeling can be performed easily and in a short time, which is effective for recycling the adherend. Can be contributed.
【0023】[0023]
【実施例】つぎに、この発明の実施例を記載して、より
具体的に説明する。なお、以下、部とあるのは重量部
を、粘度とあるのはB型粘度計による30℃での粘度
を、それぞれ意味する。EXAMPLES Next, examples of the present invention will be described to explain more specifically. In the following, “parts” means “parts by weight” and “viscosity” means the viscosity at 30 ° C. measured by a B-type viscometer.
【0024】実施例1 1リツトルの三つ口フラスコに、カプロラクトンアクリ
レ―ト〔東亜合成(株)の商品名「アロニツクスM−5
300」;前記の式中、m=1〜5(平均値=約1.
8)である〕45部、アクリル酸ブチル50部、スチレ
ンスルホン酸ナトリウム5部、水酸化カリウム8.8
部、水96部、メタノ―ル144部、アゾビスイソブチ
ロニトリル0.175部を投入して混合し、フラスコ内
を窒素置換しながら、60℃で5時間重合した。Example 1 A 1-liter three-necked flask was charged with caprolactone acrylate [trade name "Aronix M-5 manufactured by Toagosei Co., Ltd.].
300 "; m = 1-5 in the above formula (mean value = about 1.
8)] 45 parts, butyl acrylate 50 parts, sodium styrenesulfonate 5 parts, potassium hydroxide 8.8
Parts, 96 parts of water, 144 parts of methanol, and 0.175 parts of azobisisobutyronitrile were added and mixed, and the contents of the flask were replaced with nitrogen, and polymerization was carried out at 60 ° C. for 5 hours.
【0025】このようにして得た共重合ポリマ―のガラ
ス転移温度は−36℃、このポリマ―を含む溶液の粘度
は30ポイズであつた。このポリマ―溶液に、共重合ポ
リマ―100部に対し、水溶性の可塑剤(三洋化成社製
の商品名「サンニツクスSP750」20部と、架橋剤
〔ナガセ化学社製の商品名「EX−830」;重合度
(n)≒9のポリエチレングリコ―ルのジグリシジルエ
―テル〕0.2部とを配合し、均一に混合して、水膨潤
性の感圧接着剤組成物とした。The glass transition temperature of the copolymer thus obtained was -36 ° C., and the viscosity of the solution containing this polymer was 30 poises. In this polymer solution, with respect to 100 parts of the copolymer polymer, 20 parts of a water-soluble plasticizer (trade name "Sannix SP750" manufactured by Sanyo Kasei Co., Ltd. and a crosslinking agent [trade name "EX-830 manufactured by Nagase Chemical Co., Ltd." 0.2 parts of polyethylene glycol diglycidyl ether having a degree of polymerization (n) ≈9] was mixed and uniformly mixed to obtain a water-swellable pressure-sensitive adhesive composition.
【0026】実施例2 架橋剤を、ナガセ化学社製の商品名「EX−512」
(直鎖状、4官能性のエポキシ化合物)0.1部に変更
した以外は、実施例1と同様にして、水膨潤性の感圧接
着剤組成物を調製した。Example 2 The cross-linking agent was trade name "EX-512" manufactured by Nagase Chemical Co., Ltd.
(Linear, tetrafunctional epoxy compound) A water-swellable pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that the content was changed to 0.1 part.
【0027】実施例3 重合原料を、メトキシエチルアクリレ―ト55部、カプ
ロラクトンアクリレ―ト(実施例1と同じもの)40
部、スチレンスルホン酸ナトリウム5部、水酸化カリウ
ム8.8部、水96部、メタノ―ル144部、アゾビス
イソブチロニトリル0.175部とした以外は、実施例
1と同様に重合して、共重合ポリマ―のガラス転移温度
が−33℃、溶液粘度が70ポイズであるポリマ―溶液
を得た。この溶液に、実施例1と同じ水溶性の可塑剤2
0部と、架橋剤として酢酸クロム・1水和物〔Cr(C
H3 COO)3 ・H2 O〕1部とを、配合して、水膨潤
性の感圧接着剤組成物とした。Example 3 Polymerization raw materials were mixed with 55 parts of methoxyethyl acrylate and 40 parts of caprolactone acrylate (the same as in Example 1).
Parts, sodium styrenesulfonate 5 parts, potassium hydroxide 8.8 parts, water 96 parts, methanol 144 parts, and azobisisobutyronitrile 0.175 parts except that the polymerization was carried out in the same manner as in Example 1. As a result, a polymer solution having a glass transition temperature of the copolymerized polymer of -33 ° C and a solution viscosity of 70 poise was obtained. The same water-soluble plasticizer 2 as in Example 1 was added to this solution.
0 parts and chromium acetate monohydrate [Cr (C
H 3 COO) 3 · H 2 O] 1 part was blended to give a water-swellable pressure-sensitive adhesive composition.
【0028】実施例4 重合原料を、メトキシエチルアクリレ―ト75部、アク
リル酸5部、アクリル酸2−エチルヘキシル20部、水
96部、メタノ―ル144部、アゾビスイソブチロニト
リル0.175部とした以外は、実施例1と同様に重合
して、共重合ポリマ―のガラス転移温度が−30℃、溶
液粘度が80ポイズであるポリマ―溶液を得た。この溶
液に、実施例1と同じ水溶性の可塑剤および架橋剤を、
実施例1と同量配合して、水膨潤性の感圧接着剤組成物
とした。Example 4 Polymerization raw materials were mixed with 75 parts of methoxyethyl acrylate, 5 parts of acrylic acid, 20 parts of 2-ethylhexyl acrylate, 96 parts of water, 144 parts of methanol, 0.1 part of azobisisobutyronitrile. Polymerization was carried out in the same manner as in Example 1 except that the amount was 175 parts to obtain a polymer solution having a glass transition temperature of -30 ° C and a solution viscosity of 80 poise. To this solution, the same water-soluble plasticizer and crosslinking agent as in Example 1 were added,
The same amount as in Example 1 was blended to give a water-swellable pressure-sensitive adhesive composition.
【0029】実施例5 架橋剤の配合量を1部に変更した以外は、実施例4と同
様にして、水膨潤性の感圧接着剤組成物を調製した。Example 5 A water-swellable pressure-sensitive adhesive composition was prepared in the same manner as in Example 4 except that the amount of the crosslinking agent was changed to 1 part.
【0030】比較例1 和光純薬工業(株)製のポリアクリル酸水溶液(固型分
濃度が25重量%で、溶液粘度が約100ポイズ)10
0部に、実施例1と同じ水溶性の可塑剤400部と、実
施例1と同じ架橋剤0.2部とを添加混合して、水膨潤
性の感圧接着剤組成物とした。Comparative Example 1 Aqueous polyacrylic acid solution manufactured by Wako Pure Chemical Industries, Ltd. (concentration of solid content is 25% by weight, solution viscosity is about 100 poise) 10
400 parts of the same water-soluble plasticizer as in Example 1 and 0.2 part of the same cross-linking agent as in Example 1 were added to 0 parts and mixed to give a water-swellable pressure-sensitive adhesive composition.
【0031】比較例2 実施例3で得たポリマ―溶液に、実施例1と同じ水溶性
の可塑剤20部と、架橋剤〔日産化学(株)製の商品名
「TEPIC」;トリグリシジルイソシアヌレ―ト〕1
部とを添加混合して、水膨潤性の感圧接着剤組成物とし
た。Comparative Example 2 20 parts of the same water-soluble plasticizer as in Example 1 was added to the polymer solution obtained in Example 3 and a crosslinking agent [trade name "TEPIC" manufactured by Nissan Kagaku KK; triglycidyl isocyanate]. Nuret] 1
And a part thereof were added and mixed to obtain a water-swellable pressure-sensitive adhesive composition.
【0032】以上の実施例1〜5および比較例1,2の
各感圧接着剤組成物について、架橋後のゲル分率および
膨潤度を測定するとともに、以下の要領で、剥離性試
験、常温接着力試験および低温接着力試験を行つた。こ
れらの結果は、後記の表1に示されるとおりであつた。With respect to each of the pressure-sensitive adhesive compositions of Examples 1 to 5 and Comparative Examples 1 and 2 described above, the gel fraction and the degree of swelling after crosslinking were measured, and the peelability test and the room temperature were conducted as follows. An adhesion test and a low temperature adhesion test were performed. The results are shown in Table 1 below.
【0033】<剥離性試験>剥離紙上に感圧接着剤組成
物を乾燥後の厚さが80μmとなるように塗布,乾燥
し、これをポリエステル不織布からなる基材の両面に貼
り合わせて、両面接着シ―トを作製した。このシ―トよ
り幅20mm,長さ100mmの試験片をつくり、これを被
着体としてのポリスチレン板に貼り、糊面をさらした状
態で水中に浸漬して、剥離性を確認した。剥離性が良好
を○、不良を×、と判定した。<Peelability Test> The pressure-sensitive adhesive composition was applied onto release paper so that the thickness after drying was 80 μm, and dried, and this was adhered to both sides of a substrate made of polyester nonwoven fabric, An adhesive sheet was prepared. A test piece having a width of 20 mm and a length of 100 mm was prepared from this sheet, adhered to a polystyrene plate as an adherend, and immersed in water with the adhesive surface exposed to confirm the releasability. The peelability was judged to be good, and the bad was judged to be bad.
【0034】<常温接着力試験>剥離性試験の場合と同
様にして作製した両面接着シ―トより、幅20mm,長さ
150mmの試験片をつくつた。この試験片を、ポリスチ
レン板からなる被着体の表面に、2kgゴムロ―ラ1往復
にて貼り合わせ、約30分間の放置後、引張速度300
mm/分、剥離角180度にて、シヨツパ―式引張試験機
により、剥離接着力を測定した。なお、貼り合わせおよ
び測定は、いずれも、温度23℃,相対湿度65%の雰
囲気中で行つた。<Normal temperature adhesive strength test> A test piece having a width of 20 mm and a length of 150 mm was prepared from a double-sided adhesive sheet prepared in the same manner as in the peelability test. This test piece was attached to the surface of an adherend made of a polystyrene plate with one reciprocation of a 2 kg rubber roller, left for about 30 minutes, and then pulled at a pulling speed of 300.
The peel adhesion strength was measured by a shocker type tensile tester at mm / min and a peel angle of 180 degrees. In addition, both the bonding and the measurement were performed in an atmosphere of a temperature of 23 ° C. and a relative humidity of 65%.
【0035】<低温接着力試験>常温接着力試験の場合
と同様にしてつくつた試験片と、ポリスチレン板からな
る被着体とを、ともに10℃の雰囲気中に30分間保存
したのち、同温度下で上記試験片を上記被着体の表面に
2kgゴムロ―ラ1往復にて貼り合わせ、同温度下に30
分保存後、取り出して、同温度下で引張速度300mm/
分、剥離角180度にて、シヨツパ―式引張試験機によ
り、剥離接着力を測定した。<Low Temperature Adhesion Test> A test piece prepared in the same manner as in the room temperature adhesion test and an adherend made of a polystyrene plate were both stored in an atmosphere of 10 ° C. for 30 minutes and then kept at the same temperature. Then, the above test piece was attached to the surface of the adherend by one round trip of a 2 kg rubber roller, and the same temperature was applied for 30 seconds.
After storing for 1 minute, take out and pull at the same temperature 300mm /
At a peeling angle of 180 degrees, the peeling adhesive force was measured by a shocker type tensile tester.
【0036】[0036]
【表1】 (※)×中、比較例1は被着体汚染、比較例2は短時間
で剥離できない[Table 1] (*) × Medium, Comparative Example 1 stains the adherend, Comparative Example 2 cannot be peeled off in a short time
【0037】[0037]
【発明の効果】以上のように、この発明の水膨潤性の感
圧接着剤組成物は、常時感圧接着性を有して、常温はも
ちろん低温下でも大きな感圧接着力を示すとともに、水
により膨潤する性質を備えており、水により容易にかつ
短時間に剥離できて、しかもその際に被着体を汚染する
おそれがないため、各種の産業分野において、剥離容易
な接着シ―ト類などとして幅広く利用することができ
る。INDUSTRIAL APPLICABILITY As described above, the water-swellable pressure-sensitive adhesive composition of the present invention has a constant pressure-sensitive adhesive property and exhibits a large pressure-sensitive adhesive force at room temperature as well as at low temperature. Adhesive sheets that can be easily peeled off in various industrial fields because they have the property of swelling with water, can be easily peeled off with water in a short time, and there is no risk of contaminating the adherend at that time. It can be widely used as such.
Claims (2)
/またはカプロラクトンアクリレ―ト15〜100重量
%(ただし、カプロラクトンアクリレ―トは50重量%
以下)と、b)カプロラクトンアクリレ―ト以外のカル
ボキシル基含有モノマ―10〜0重量%と、c)これら
と共重合可能な他のモノマ―85〜0重量%との共重合
ポリマ―に、架橋剤および必要により可塑剤その他の配
合剤を配合してなり、架橋後のゲル分率が20〜70
%、膨潤度が20以上であることを特徴とする水膨潤性
の感圧接着剤組成物。1. A) 15 to 100% by weight of methoxyethyl acrylate and / or caprolactone acrylate (provided that caprolactone acrylate is 50% by weight)
The following), b) 10 to 0% by weight of a carboxyl group-containing monomer other than caprolactone acrylate, and c) a copolymerized polymer of 85 to 0% by weight of another monomer copolymerizable therewith, A cross-linking agent and, if necessary, a plasticizer and other compounding agents are added, and the gel fraction after cross-linking is 20 to 70.
%, The degree of swelling is 20 or more, a water-swellable pressure-sensitive adhesive composition.
度9以上)のジグリシジルエ―テルである請求項1に記
載の水膨潤性の感圧接着剤組成物。2. The water-swellable pressure-sensitive adhesive composition according to claim 1, wherein the cross-linking agent is polyethylene glycol (polymerization degree: 9 or more) diglycidyl ether.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6457194A JPH07173445A (en) | 1993-10-29 | 1994-03-07 | Water-swellable pressure-sensitive adhesive composition |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP29431293 | 1993-10-29 | ||
JP5-294312 | 1993-10-29 | ||
JP6457194A JPH07173445A (en) | 1993-10-29 | 1994-03-07 | Water-swellable pressure-sensitive adhesive composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH07173445A true JPH07173445A (en) | 1995-07-11 |
Family
ID=26405660
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6457194A Pending JPH07173445A (en) | 1993-10-29 | 1994-03-07 | Water-swellable pressure-sensitive adhesive composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH07173445A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0859403A1 (en) * | 1997-02-14 | 1998-08-19 | Lintec Corporation | Pressure sensitive adhesive composition for the polishing of the back of a wafer |
JP2001123136A (en) * | 1999-10-28 | 2001-05-08 | Soken Chem & Eng Co Ltd | Moisture-resistant adhesive sheet and its use |
WO2002055626A1 (en) * | 2001-01-10 | 2002-07-18 | Kaken Tech C0., Ltd. | Removable adhesive compositions and process for producing the same |
JP2007051271A (en) * | 2005-07-21 | 2007-03-01 | Nitto Denko Corp | Adhesive composition, pressure sensitive adhesive double coated tape, adhesion method and portable electronic device |
WO2010047041A1 (en) * | 2008-10-22 | 2010-04-29 | 株式会社ニトムズ | Pressure-sensitive adhesive tape |
WO2021024863A1 (en) * | 2019-08-02 | 2021-02-11 | 日東電工株式会社 | Adhesive sheet and use thereof |
-
1994
- 1994-03-07 JP JP6457194A patent/JPH07173445A/en active Pending
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0859403A1 (en) * | 1997-02-14 | 1998-08-19 | Lintec Corporation | Pressure sensitive adhesive composition for the polishing of the back of a wafer |
US6255423B1 (en) | 1997-02-14 | 2001-07-03 | Lintec Corporation | Pressure sensitive adhesive sheet and use thereof |
CN1098902C (en) * | 1997-02-14 | 2003-01-15 | 琳得科株式会社 | Pressure sensitive adhesive composition and use thereof |
KR100568039B1 (en) * | 1997-02-14 | 2006-06-23 | 린텍 가부시키가이샤 | Adhesive composition and its use method |
JP2001123136A (en) * | 1999-10-28 | 2001-05-08 | Soken Chem & Eng Co Ltd | Moisture-resistant adhesive sheet and its use |
WO2002055626A1 (en) * | 2001-01-10 | 2002-07-18 | Kaken Tech C0., Ltd. | Removable adhesive compositions and process for producing the same |
JP2007051271A (en) * | 2005-07-21 | 2007-03-01 | Nitto Denko Corp | Adhesive composition, pressure sensitive adhesive double coated tape, adhesion method and portable electronic device |
WO2010047041A1 (en) * | 2008-10-22 | 2010-04-29 | 株式会社ニトムズ | Pressure-sensitive adhesive tape |
JP2010100688A (en) * | 2008-10-22 | 2010-05-06 | Nitomuzu:Kk | Adhesive tape |
WO2021024863A1 (en) * | 2019-08-02 | 2021-02-11 | 日東電工株式会社 | Adhesive sheet and use thereof |
JP2021024938A (en) * | 2019-08-02 | 2021-02-22 | 日東電工株式会社 | Adhesive sheet and use thereof |
CN114127216A (en) * | 2019-08-02 | 2022-03-01 | 日东电工株式会社 | Adhesive sheet and use thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5047983B2 (en) | Acrylic adhesive composition | |
JP6243440B2 (en) | Crosslinkable and crosslinked compositions | |
JPH06166857A (en) | Pressure-sensitive adhesive and adhesive sheet or the like containing the same | |
KR20080003858A (en) | Wet and dry stick adhesive, articles, and methods | |
JP2624917B2 (en) | Water-soluble or water-dispersible pressure-sensitive adhesive composition | |
JP3411065B2 (en) | Acrylic pressure-sensitive adhesive composition and double-sided tape | |
JPH06207151A (en) | Acrylic pressure-sensitive adhesive composition an double-coated tape | |
JPH10168407A (en) | Acrylic self-adhesive composition | |
JPH08325544A (en) | Removable pressure-sensitive adhesive and its adhesive sheets | |
JPH03243679A (en) | Acrylic adhesive composition and adhesive tape, lavel, sheet | |
JPH07173445A (en) | Water-swellable pressure-sensitive adhesive composition | |
JP4763379B2 (en) | Pressure-sensitive adhesive resin composition | |
JP3849889B2 (en) | Acrylic adhesive composition | |
JP2686324B2 (en) | Pressure sensitive adhesive composition | |
US20190352544A1 (en) | Phase separated pressure-sensitive adhesive compositions | |
JP2000303045A (en) | Pressure-sensitive acrylic adhesive composition, and adhesive tape, or the like, coated therewith | |
JP4518450B2 (en) | Photopolymerizable adhesive composition and adhesive sheet thereof | |
JPS59122566A (en) | Pressure-sensitive adhesive composition | |
JPH0819392B2 (en) | Pressure-sensitive adhesives and their adhesive sheets | |
JP3475451B2 (en) | Resin for adhesive | |
JP3154739B2 (en) | Photopolymerizable adhesive composition, pressure-sensitive adhesive using the same, and adhesive sheets thereof | |
JPH02120381A (en) | Water-soluble or water-dispersible pressure-sensitive adhesive composition | |
JPH0885779A (en) | Rereleasable pressure-sensitive adhesive and sheet or the like coated therewith | |
JP2536703B2 (en) | Pressure sensitive adhesive composition | |
JP3346636B2 (en) | Dustproof mat |