JPH0275679A - Pressure-sensitive adhesive member - Google Patents
Pressure-sensitive adhesive memberInfo
- Publication number
- JPH0275679A JPH0275679A JP22795488A JP22795488A JPH0275679A JP H0275679 A JPH0275679 A JP H0275679A JP 22795488 A JP22795488 A JP 22795488A JP 22795488 A JP22795488 A JP 22795488A JP H0275679 A JPH0275679 A JP H0275679A
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- pressure
- crosslinking
- adhesive layer
- adhesive
- 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.)
- Granted
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 65
- 238000004132 cross linking Methods 0.000 claims abstract description 37
- 239000010410 layer Substances 0.000 claims abstract description 31
- 239000000853 adhesive Substances 0.000 claims description 57
- 230000001070 adhesive effect Effects 0.000 claims description 57
- 239000000463 material Substances 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 abstract description 15
- 230000009477 glass transition Effects 0.000 abstract description 8
- 239000000178 monomer Substances 0.000 abstract description 7
- -1 polyethylene Polymers 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 5
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 abstract description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012965 benzophenone Substances 0.000 abstract description 4
- 239000004698 Polyethylene Substances 0.000 abstract description 3
- 229920000573 polyethylene Polymers 0.000 abstract description 3
- 229920001971 elastomer Polymers 0.000 abstract description 2
- 229920000058 polyacrylate Polymers 0.000 abstract description 2
- 239000012790 adhesive layer Substances 0.000 abstract 4
- 238000013329 compounding Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000001723 curing Methods 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 235000013405 beer Nutrition 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 229940024874 benzophenone Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、紫外線硬化により架橋度を部分的に相違させ
て接着力と凝集力とを両立させた粘着部材に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an adhesive member that achieves both adhesive strength and cohesive strength by partially varying the degree of crosslinking through ultraviolet curing.
従来の技術及び課題
感圧接着層にあっては、タック等の接着力と、保持性に
関係する凝集力とをバランスさせることが基本的重要事
項である。Prior Art and Problems In pressure-sensitive adhesive layers, it is fundamentally important to balance adhesive strength, such as tack, with cohesive strength, which is related to retention.
従来、かかるバランスを調節する手段としては過酸化物
、金属系化合物、多官能性化合物の如き架橋剤を用いた
り、紫外線や電子線等の放射線を照射して、感圧接着層
の全体を均一に架橋処理する方式が知られていた。Conventionally, methods for adjusting this balance include using crosslinking agents such as peroxides, metal compounds, and polyfunctional compounds, or irradiating radiation such as ultraviolet rays or electron beams to uniformly spread the entire pressure-sensitive adhesive layer. A method of crosslinking was known.
しかしながら、得られる感圧接着層の接着力と凝集力と
を高度にバランスさせることが困難な問題点があった。However, there is a problem in that it is difficult to achieve a high balance between adhesive force and cohesive force of the resulting pressure-sensitive adhesive layer.
すなわち、タック等の接着力を低下させずに凝集力を増
大させることができず、架橋度の上昇による凝集力の増
大には、接着力の低下が不可避であった。また、架橋度
の上昇に伴い耐反発性が低下する問題点もあった。従っ
て、従来の架橋方式では、いずれの場合も接着力と凝集
力を両立させることができなかった。That is, the cohesive force cannot be increased without reducing the adhesive force such as tack, and an increase in the cohesive force due to an increase in the degree of crosslinking inevitably involves a decrease in the adhesive force. There was also the problem that the rebound resistance decreased as the degree of crosslinking increased. Therefore, with conventional crosslinking methods, it has not been possible to achieve both adhesive strength and cohesive strength in any case.
一方、粘着部材の主要な用途に、金属板、樹脂板、塗装
板、化粧板等の表面に貼着して保存時、輸送時、加工時
等における保護を目的とした表面保護シートの如く、貼
着目的達成後に被着体より容易に剥離できるようにした
ものがある。かかる再剥離用途の粘着部材、特に表面保
護シートには、被着体への貼着が容易で切断やプレス等
の加工時に浮き等の剥がれを生じることがなり、シかも
目的達成後は簡単に剥離できること、という性能が要求
される。つまり経時上昇しに（い接着力と、糊残りを生
じにくい凝集力が要求される。On the other hand, the main uses of adhesive materials include surface protection sheets that are attached to the surfaces of metal plates, resin plates, painted plates, decorative boards, etc. for the purpose of protection during storage, transportation, processing, etc. Some adhesives are designed to be easily peeled off from the adherend after the purpose of attachment is achieved. Adhesive materials for such removable purposes, especially surface protection sheets, are easy to adhere to adherends and may peel off during cutting, pressing, etc., and may easily peel off after the purpose is achieved. The performance required is that it can be peeled off. In other words, adhesive strength that increases over time and cohesive strength that does not easily leave adhesive residue are required.
従来、かかる要求性能に応える粘着部材としては、ガラ
ス転移点の高いホモポリマを形成する単量体を共重合さ
せた感圧接着性ポリマを用いたもの、乳化剤を添加した
もの、上記した架橋方式を併用したものが提案されてい
るが、その調製に高度な技術を要する問題点のほか、被
着体や支持基材の種類によりその性能が大きく変化し、
要求性能をバランスよ（マツチングさせることが困難な
問題点があった。Conventionally, adhesive members that meet such performance requirements include those using pressure-sensitive adhesive polymers copolymerized with monomers that form a homopolymer with a high glass transition point, those with added emulsifiers, and those using the above-mentioned crosslinking method. Combination use has been proposed, but in addition to the problems that require advanced technology to prepare, the performance varies greatly depending on the type of adherend and supporting substrate.
There was a problem that it was difficult to balance the required performance.
課題を解決するための手段
本発明は、架橋度を部分的に相違させる方式により上記
の課題を克服したものである。Means for Solving the Problems The present invention overcomes the above problems by partially varying the degree of crosslinking.
すなわち、本発明は、支持基材に感圧接着層を設けてな
る粘着部材において、その感圧接着層を紫外線硬化型感
圧接着剤で形成し、かつ紫外線硬化により架橋度に部分
的な相違をもたせて接着力と凝集力とをバランスさせた
ことを特徴とする粘着部材を提供するものである。That is, the present invention provides an adhesive member in which a pressure-sensitive adhesive layer is provided on a supporting base material, in which the pressure-sensitive adhesive layer is formed of an ultraviolet-curable pressure-sensitive adhesive, and the degree of crosslinking is partially differentiated by ultraviolet curing. The present invention provides an adhesive member characterized by having a balance between adhesive force and cohesive force.
作用
紫外線硬化型感圧接着剤を用いることにより、パターン
マスク等を介して紫外線を照射するなどの簡単な処理操
作で、容易にかつ精度よく架橋度に部分的な相違を゛も
たせることができる。一方、架橋度に部分的な相違をも
たせることにより、高架橋域に基づ（高凝集力と、低架
橋域ないし未架橋域に基づ（高接着力を付与することが
できて、接着力を維持させたまま凝集力を高めることが
できる。その接着力と凝集力のバランスは、架橋度相違
領域の配置や占有面積割合、架橋度差等の制御で調節す
ることができる。その結果、被着体や支持基材の種類に
応じた性能バランスを容易に付与することができる。By using an ultraviolet-curable pressure-sensitive adhesive, it is possible to easily and precisely create local differences in the degree of crosslinking by a simple processing operation such as irradiating ultraviolet rays through a pattern mask or the like. On the other hand, by providing local differences in the degree of crosslinking, it is possible to impart high adhesive strength based on highly crosslinked areas (high cohesive force) and low crosslinked areas or non-crosslinked areas (high adhesive strength). The cohesive force can be increased while maintaining the cohesive force.The balance between the adhesive force and the cohesive force can be adjusted by controlling the arrangement of regions with different degrees of crosslinking, the occupied area ratio, the difference in the degree of crosslinking, etc. It is possible to easily provide a balance of performance depending on the type of wearer and supporting base material.
発明の構成要素の例示
本発明においては紫外線硬化型感圧接着剤が用いられる
。その種類につき特に限定はない。好ましく用いつるも
のは、ゴム系やアクリル系などの種々のポリマからなる
ガラス転移点が２５０に以下の感圧接着性ポリマに、重
合性二重結合を２個以上有する架橋性単量体と、光開始
剤を配合したものである。就中、紫外線による硬化処理
前後における感圧接着性ポリマの溶剤不溶分の差が５重
量％以上となるよう調製したものが好ましい。特に、再
剥離用途の場合には、紫外線による硬化処理後７ にお
ける感圧接着性ポリマの良溶媒に対する不溶分が６０重
量％以上となるよう調製したものが好ましい。Examples of Components of the Invention In the present invention, an ultraviolet curable pressure-sensitive adhesive is used. There are no particular limitations on the type. Preferably used materials include a pressure-sensitive adhesive polymer having a glass transition point of 250 or less, which is made of various polymers such as rubber-based and acrylic-based polymers, and a crosslinkable monomer having two or more polymerizable double bonds; Contains a photoinitiator. Particularly preferred is a pressure-sensitive adhesive polymer prepared such that the difference in solvent-insoluble content before and after curing treatment with ultraviolet rays is 5% by weight or more. In particular, in the case of removable applications, it is preferable to prepare the pressure-sensitive adhesive polymer so that the insoluble content in a good solvent after curing treatment with ultraviolet rays is 60% by weight or more.
なお、前記の感圧接着性ポリマとしては、ガラス転移点
の調節性、アクリル酸やアクリロニトリル等の共重合に
よる極性基の導入性、酢酸ビニルやスチレン等の共重合
による改質性などの点より、アクリル酸やメタクリル酸
のアルキルエステルを主成分とするアクリル系ポリマが
適当である。The above-mentioned pressure-sensitive adhesive polymers are selected from the viewpoints of adjustability of glass transition point, ability to introduce polar groups through copolymerization with acrylic acid, acrylonitrile, etc., and modification ability through copolymerization with vinyl acetate, styrene, etc. , an acrylic polymer whose main component is an alkyl ester of acrylic acid or methacrylic acid is suitable.
また、架橋性単量体としては通例、エチレングリコール
ジアクリレート、エチレングリコールジメタクリレート
、トリエチレングリコールジアクリレート、トリエチレ
ングリコールジメタクリレート、トリメチロールプロパ
ントリアクリレート、トリメチロールプロパントリメタ
クリレート、ジペンタエリスリトールへキサアクリレー
ト、ジペンタエリスリトールへキサメタクリレート、ジ
ビニルベンゼンなどが用いられる。架橋性単量体は、感
圧接着性ポリマが架橋性二重結合を有する場合には配合
されないときもあるなど、その配合量は他の併用成分の
種類や量、架橋性単量体そのものの種類などにより適宜
に決定される。架橋性単量体の配合量が過少では架橋に
よる凝集力の増大に乏しくて糊残りする場合があり、過
多では接着力の低下が大きい。一般には、感圧接着性ポ
リマＩ００重量部あたり００１〜２０重量部の配合量と
され、再剥離用途の場合には０．０５〜１０重量部の配
合量とされる。In addition, the crosslinkable monomers are usually ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, dipentaerythritol hexane. Acrylate, dipentaerythritol hexamethacrylate, divinylbenzene, etc. are used. The crosslinking monomer may not be added if the pressure-sensitive adhesive polymer has a crosslinking double bond, so its amount depends on the type and amount of other concomitant ingredients, and the amount of the crosslinking monomer itself. It is determined appropriately depending on the type, etc. If the amount of the crosslinkable monomer is too small, the increase in cohesive force due to crosslinking may be insufficient and adhesive residue may be left; if the amount is too large, the adhesive strength will be significantly reduced. In general, the amount is from 0.01 to 20 parts by weight per 00 parts by weight of the pressure-sensitive adhesive polymer, and for removable applications, the amount is from 0.05 to 10 parts by weight.
用いる光開始剤の一般的なものとしては、ベンゾフェノ
ン、ベンゾイン、ベンゾインアルキルエーテル、ベンジ
ルジメチルケタールの如き、光開裂型ないし水素引抜き
型のものなどがあげられる。Commonly used photoinitiators include those of the photocleavable type or hydrogen abstraction type, such as benzophenone, benzoin, benzoin alkyl ether, and benzyl dimethyl ketal.
光開始剤の配合量は、感圧接着性ポリマ１００重量部あ
たり０．０１〜５重量部が適当である。その配合量が過
多であると、残存物が耐候性の低下如黄変の原因となる
ので必要最少量の配合が望ましい。The appropriate amount of the photoinitiator is 0.01 to 5 parts by weight per 100 parts by weight of the pressure-sensitive adhesive polymer. If the amount is too large, the residual material may cause a decrease in weather resistance or yellowing, so it is desirable to use the minimum necessary amount.
なお、本発明において用いる紫外線硬化型感圧接着剤は
、溶液型、水分散型、バルク型等のいずれの形態に調製
されたものであってもよい。紫外線による硬化処理によ
り５％以上、再剥離用途の場合には２０％以上の架橋度
の差を形成できる範囲において、加熱型架橋剤など通例
の架橋剤を含有していてもよい。また、必要に応じ各種
の可塑剤や充填剤等の添加剤を含有していてもよい。通
例の架橋剤を含有する場合、その架橋剤はこれに基づき
予め全体を均一に架橋処理するなどして、感圧接着層の
ベースの形成などに利用される。The ultraviolet curable pressure-sensitive adhesive used in the present invention may be prepared in any form such as a solution type, water dispersion type, or bulk type. A conventional crosslinking agent such as a heating type crosslinking agent may be contained within a range that can form a difference in the degree of crosslinking of 5% or more by ultraviolet curing treatment, and 20% or more in the case of removable use. Moreover, additives such as various plasticizers and fillers may be contained as necessary. When a customary crosslinking agent is contained, the crosslinking agent is used for forming the base of the pressure-sensitive adhesive layer by uniformly crosslinking the entire surface in advance.
本発明の粘着部材は、紫外線硬化型感圧接着剤を架橋度
が部分的に相違するよう紫外線硬化させてなる感圧接着
層を、支持基材に設けたものである。The adhesive member of the present invention is provided with a pressure-sensitive adhesive layer formed by UV-curing an ultraviolet-curable pressure-sensitive adhesive so that the degree of crosslinking differs locally on a supporting base material.
その製造は例えば、紫外線硬化型感圧接着剤を支持基村
上に塗布乾燥後、パターンマスクを介するなどして紫外
線を照射し、架橋度が部分的に相違する感圧接着層が形
成されるよう硬化処理する方法などにより行うことがで
きる。形成する高架橋域の割合は１０〜８０％が適当で
ある。特に、再剥離用途の場合には４０〜７０％が適当
である。凝集力は高架橋域を増すことにより高めること
ができ、接着力は低架橋域ないし未架橋域を増すことに
より太き（することができる。接着力と凝集力のバラン
スは、前記した架橋度相違領域の占有面積割合の調節の
ほか、その配置パターンや、架橋度差などを制御するこ
とによっても調節することができる。なお、高架橋域の
割合が前記範囲における下限未満では満足できる凝集力
が発現しにくく、上限を超えると満足できる接着力が発
現し、に（い。For example, its production involves applying an ultraviolet-curable pressure-sensitive adhesive onto a supporting substrate, drying it, and then irradiating it with ultraviolet light through a pattern mask to form a pressure-sensitive adhesive layer with partially different degrees of crosslinking. This can be done by a hardening treatment method. The proportion of the hyperlinked region formed is suitably 10 to 80%. In particular, 40 to 70% is suitable for removable applications. The cohesive force can be increased by increasing the highly crosslinked area, and the adhesive force can be increased by increasing the low crosslinked or uncrosslinked area.The balance between adhesive force and cohesive force is determined by the difference in degree of crosslinking as described above. In addition to adjusting the area ratio occupied by the regions, it can also be adjusted by controlling the arrangement pattern, the difference in the degree of crosslinking, etc.If the ratio of the highly crosslinked regions is less than the lower limit of the above range, a satisfactory cohesive force is expressed. If the upper limit is exceeded, a satisfactory adhesion force will be developed.
感圧接着層にもたせる架橋度の相違パターンは適宜に決
定される。一般には、所定架橋度のベースに、その架橋
度とは相違する架橋度の部分が点在するか、モザイク状
に分布するパターンなどとされる。好ましいパターンは
、低架橋ないし未架橋のベースに、高架橋域を点在させ
るか、モザイク状に分布させたものである。なお、再剥
離用途にあっては、ベースの架橋度が比較的高めに設定
され、良溶媒に対する不溶分が６０重量％以上、就中７
０重量％以上の高架橋域と、４０重量％以下の低架橋域
の組合せとなるよう調節することが好ましい。The pattern of different degrees of crosslinking to be imparted to the pressure-sensitive adhesive layer is determined as appropriate. Generally, a base having a predetermined degree of crosslinking is dotted with portions having a degree of crosslinking different from the predetermined degree of crosslinking, or is distributed in a mosaic pattern. A preferred pattern is a low crosslinked or uncrosslinked base with highly crosslinked areas interspersed or distributed in a mosaic pattern. In addition, for re-peelable applications, the degree of crosslinking of the base is set to be relatively high, and the insoluble content in good solvents is 60% by weight or more, especially 7.
It is preferable to adjust to a combination of a highly crosslinked region of 0% by weight or more and a low crosslinked region of 40% by weight or less.
支持基材としては、紙、布、プラスチックフィルム、発
泡体、金属箔などの公知物のいずれも用いることができ
る。また、剥離剤で表面処理したものなどからなるセパ
レータなどを用いて、両面粘着テープの如き粘着部材と
することもできる。As the supporting base material, any known material such as paper, cloth, plastic film, foam, metal foil, etc. can be used. Furthermore, an adhesive member such as a double-sided adhesive tape can be made by using a separator made of a material whose surface has been treated with a release agent.
その場合、感圧接着層を紙や不織布等の繊維で補強して
もよい。再剥離用途の粘着部材の形成には作業性や加工
性等の点より、厚さが２０〜１５０ｕｍ、伸び６０〜７
００％の可とう性フィルムからなる支持基材が好ましく
用いられる。可とう性フィルムの材質としてはポリエチ
レン、エチレン・酢酸ビニル共重合体、軟質塩化ビニル
などが一般であるが、特に限定はない。In that case, the pressure-sensitive adhesive layer may be reinforced with fibers such as paper or nonwoven fabric. In order to form an adhesive member for removable use, from the viewpoint of workability and processability, the thickness should be 20 to 150 um and the elongation should be 60 to 7.
A support substrate consisting of 0.00% flexible film is preferably used. The material of the flexible film is generally polyethylene, ethylene/vinyl acetate copolymer, soft vinyl chloride, etc., but is not particularly limited.
なお、紫外線の照射による硬化処理は、高圧水銀灯、メ
タルハライドランプ、カーボンアーク灯、キセノン灯な
どの適宜な紫外線照射装置を用いて行ってよい。照射光
量は感圧接着剤の紫外線硬化特性に応じ決定される。例
示した装置を光源に用いた場合、通例０．３秒以上、就
中３秒以上の照射処理が施される。Note that the curing treatment by irradiation with ultraviolet rays may be performed using an appropriate ultraviolet irradiation device such as a high-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a xenon lamp, or the like. The amount of irradiation light is determined depending on the ultraviolet curing characteristics of the pressure sensitive adhesive. When the illustrated device is used as a light source, irradiation treatment is usually performed for 0.3 seconds or more, especially 3 seconds or more.
発明の効果
本発明によれば、感圧接着層を紫外線硬化型感圧接着剤
で形成し、これを架橋度が部分的に相違するよう架橋処
理したので、タック等の接着力を良好に維持させたまま
凝集力を向上させることができ、接着力と凝集力が良好
にバランスした感圧接着層を有する粘着部材を得ること
ができる。Effects of the Invention According to the present invention, the pressure-sensitive adhesive layer is formed with an ultraviolet-curable pressure-sensitive adhesive, and this is cross-linked so that the degree of cross-linking is partially different, so that adhesive strength such as tack is maintained well. The cohesive force can be improved while the adhesive force is maintained, and an adhesive member having a pressure-sensitive adhesive layer with a good balance between adhesive force and cohesive force can be obtained.
また、接着力と凝集力のバランスを、架橋度の部分的な
相違のパターンや割合等を変えることにより制御するこ
とができ、その制御をマスクパターンの変更など紫外線
照射条件の変更で容易に行うことができる。従って、使
用目的に応じた接着力と凝集力のバランスを有する幅広
い粘着部材を容易に形成できる利点を有している。その
場合、接着力が経時上昇しにくい特性も容易に付与でき
る。その結果、表面保護シートの如き再剥離用途に好適
な粘着部材も容易に得ることができる。In addition, the balance between adhesive force and cohesive force can be controlled by changing the pattern and ratio of local differences in the degree of crosslinking, and this can be easily controlled by changing the UV irradiation conditions such as changing the mask pattern. be able to. Therefore, it has the advantage that a wide range of adhesive members having a balance between adhesive force and cohesive force depending on the purpose of use can be easily formed. In that case, it is also possible to easily impart the property that the adhesive strength does not easily increase over time. As a result, adhesive members suitable for removable applications such as surface protection sheets can be easily obtained.
特に、再剥離用途の粘着部材の場合、剥離に際して紫外
線を再照射することにより被着体に対する接着力を低下
させることができ、剥離がより容易になる利点なども有
している。Particularly, in the case of an adhesive member for re-peeling purposes, the adhesion force to the adherend can be lowered by re-irradiating ultraviolet rays upon peeling, which also has the advantage of making peeling easier.
実施例
実施例１
アクリル酸ｎ−ブチル９５重量％とアクリル酸５重量％
からなるガラス転移点が２２４にの感圧接着性ポリマ１
００部（重量部、以下同じ）、テトラエチレングリコー
ルジメタクリレート５部、ベンゾフェノン１部をトルエ
ン２００部に溶解させてなる紫外線硬化型感圧接着剤を
、厚さ２５μｓのポリエステルフィルムに乾燥後の厚さ
が５０μｌとなるよう塗布し、乾燥させた。Examples Example 1 95% by weight n-butyl acrylate and 5% by weight acrylic acid
A pressure-sensitive adhesive polymer 1 having a glass transition point of 224 consisting of
A UV-curable pressure-sensitive adhesive prepared by dissolving 00 parts (by weight, same hereinafter), 5 parts of tetraethylene glycol dimethacrylate, and 1 part of benzophenone in 200 parts of toluene was applied to a polyester film with a thickness of 25 μs, and the thickness after drying was as follows: It was applied to a total volume of 50 μl and dried.
次に、形成された感圧接着層を、直径１畷の孔を多数有
する全孔面積の占有割合が５５％のマスクを介し、高圧
水銀灯にて１５００＋＋＋ｊ／ｃＪの紫外線を照射し、
架橋度が部分的に相違する感圧接着層を有する粘着シー
トを得た。その感圧接着層の溶剤不溶分は１５．５重量
％であった。Next, the formed pressure-sensitive adhesive layer was irradiated with ultraviolet rays of 1500+++j/cJ using a high-pressure mercury lamp through a mask having a large number of pores each having a diameter of 1 mm and having an occupation rate of 55% of the total pore area.
A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer with partially different degrees of crosslinking was obtained. The solvent-insoluble content of the pressure-sensitive adhesive layer was 15.5% by weight.
実施例２
アクリル酸２−エチルヘキシル９２重量％と酢酸ビニル
６重量％とアクリル酸２重量％からなるガラス転移点が
２１０ ｋの感圧接着性ポリマ１００部、トリメチロー
ルプロパントリアクリレート３部、ジフェニルメタン４
，４゛−ジイソシアネート２部、ヘンシルジメチルケタ
ール０．５部をトルエン２００部に溶解させてなる紫外
線硬化型感圧接着剤を、厚さ２５μｍのポリエステルフ
ィルムに乾燥後の厚さが５０μｍとなるよう塗布し、１
００℃で３分間乾燥硬化処理した。Example 2 100 parts of a pressure-sensitive adhesive polymer with a glass transition point of 210 k consisting of 92% by weight of 2-ethylhexyl acrylate, 6% by weight of vinyl acetate and 2% by weight of acrylic acid, 3 parts of trimethylolpropane triacrylate, 4 parts of diphenylmethane
, 2 parts of 4'-diisocyanate and 0.5 parts of hensyl dimethyl ketal dissolved in 200 parts of toluene were applied to a polyester film with a thickness of 25 μm, and the thickness after drying was 50 μm. Apply as shown, 1
Dry hardening treatment was performed at 00°C for 3 minutes.
次に、形成された感圧接着層を、１醜角の孔のモザイク
パターンを有する全孔面積の占有割合が５０％のマスク
を介し、メタルハライドランプにて１２００＋ａｊ／ｃ
ｊの紫外線を照射し、架橋度が部分的に相違する感圧接
着層を有する粘着シートを得た。Next, the formed pressure-sensitive adhesive layer was heated at 1200 + aj/c using a metal halide lamp through a mask having a mosaic pattern of 1-ugly-angled holes and having an occupation rate of 50% of the total hole area.
A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer with partially different degrees of crosslinking was obtained by irradiating the adhesive with ultraviolet rays.
その感圧接着層の溶剤不溶分は３１．７重量％であった
。The solvent-insoluble content of the pressure-sensitive adhesive layer was 31.7% by weight.
実施例３
アクリル酸ｎ−ブチル６６．６重量％とアクリロニトリ
ル３１重量％とアクリル酸２．４重量％からなるガラス
転移点が２３５にの感圧接着性ポリマ１００部、トリメ
チロールプロパントリアクリレート５部、ベンジルジメ
チルケタール０．３部をトルエンに溶解させてなる１０
重量％濃度の紫外線硬化型感圧接着剤を、厚さ６０μ−
のポリエチレンフィルムに乾燥後の厚さがｌｈ−となる
よう塗布し、乾燥させた。Example 3 100 parts of a pressure-sensitive adhesive polymer with a glass transition point of 235 consisting of 66.6% by weight of n-butyl acrylate, 31% by weight of acrylonitrile and 2.4% by weight of acrylic acid, and 5 parts of trimethylolpropane triacrylate. , 10 obtained by dissolving 0.3 part of benzyl dimethyl ketal in toluene.
UV-curable pressure-sensitive adhesive with a concentration of 60μ-
It was coated on a polyethylene film of 100% to have a dry thickness of lh-, and dried.
次に、形成された感圧接着層を、１１角の孔のモザイク
パターンを有する全孔面積の占有割合が５０％のマスク
を介し、高圧水銀灯にて１５００＋ａｊ／ｃｄの紫外線
を照射し、架橋度が部分的に相違する感圧接着層を有す
る表面保護シートを得た。その感圧接着層の溶剤不溶分
は７５重量％であった。Next, the formed pressure-sensitive adhesive layer was irradiated with ultraviolet rays of 1500+aj/cd using a high-pressure mercury lamp through a mask having a mosaic pattern of 11 square holes and an occupation ratio of 50% of the total pore area, to determine the degree of crosslinking. A surface protection sheet having a pressure-sensitive adhesive layer with partially different values was obtained. The solvent-insoluble content of the pressure-sensitive adhesive layer was 75% by weight.
実施例４
アクリル酸ｎ−ブチル６６．６重量％とアクリロニトリ
ル３１重量％とアクリル酸２．４重量％からなるガラス
転移点が２３５にの感圧接着性ポリマ１００部、ジペン
タエリスリトールへキサメタクリレート２部、ベンゾフ
ェノン２部、ジフェニルメタン４゜４′−ジイソシアネ
ート０．５部をトルエンに溶解させてなる１０重量％濃
度の紫外線硬化型感圧接着剤を、厚さ６部ｍのポリエチ
レンフィルムに乾燥後の厚さがｌＯｕｍとなるよう塗布
し、１００℃で５分間乾燥硬化処理した。Example 4 100 parts of a pressure-sensitive adhesive polymer with a glass transition point of 235 consisting of 66.6% by weight of n-butyl acrylate, 31% by weight of acrylonitrile and 2.4% by weight of acrylic acid, 2 parts of dipentaerythritol hexamethacrylate A 10% by weight ultraviolet curable pressure-sensitive adhesive prepared by dissolving 2 parts of benzophenone, 4°4'-diisocyanate of diphenylmethane and 0.5 parts of toluene was applied to a polyethylene film with a thickness of 6 parts m after drying. It was coated to a thickness of 1 Oum and dried and cured at 100° C. for 5 minutes.
次に、形成された感圧接着層を、直径１閣の孔を有する
全孔面積の占有割合が５５％のマスクを介し、高圧水銀
灯にて１５００ ｔａ ｊ ／ ｃｄの紫外線を照射し
、架橋度が部分的に相違する感圧接着層を有する表面保
護シートを得た。その感圧接着層における高架橋域の溶
剤不溶分は８９重量％であり、低架橋域のそれは２５重
量％であった。Next, the formed pressure-sensitive adhesive layer was irradiated with ultraviolet rays of 1500 taj/cd using a high-pressure mercury lamp through a mask having pores with a diameter of 55% to determine the degree of crosslinking. A surface protection sheet having a pressure-sensitive adhesive layer with partially different values was obtained. The solvent-insoluble content in the highly crosslinked area of the pressure sensitive adhesive layer was 89% by weight, and that in the low crosslinked area was 25% by weight.
比較例１
実施例１における紫外線硬化処理前の粘着シートをその
まま用いた。その感圧接着層の溶剤不溶分はＯＮ量％で
あった。Comparative Example 1 The adhesive sheet of Example 1 before ultraviolet curing treatment was used as it was. The solvent-insoluble content of the pressure-sensitive adhesive layer was ON amount %.
比較例２
マスクを用いずに紫外線を全面照射して硬化処理した以
外は実施例１に準じて粘着シートを得た。Comparative Example 2 A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1, except that the entire surface was irradiated with ultraviolet rays and cured without using a mask.
その感圧接着層の溶剤不溶分は３５．２重量％であった
。The solvent-insoluble content of the pressure-sensitive adhesive layer was 35.2% by weight.
比較例３
実施例２における紫外線硬化処理前の粘着シートをその
まま用いた。その感圧接着層の溶剤不溶分は２２．５重
量％であった。Comparative Example 3 The pressure-sensitive adhesive sheet of Example 2 before ultraviolet curing treatment was used as it was. The solvent-insoluble content of the pressure-sensitive adhesive layer was 22.5% by weight.
比較例４
マスクを用いずに紫外線を全面照射して硬化処理した以
外は実施例２に準じて粘着シートを得た。Comparative Example 4 A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 2, except that the entire surface was irradiated with ultraviolet rays for curing treatment without using a mask.
その感圧接着層の溶剤不溶分は５３．１重量％であった
。The solvent-insoluble content of the pressure-sensitive adhesive layer was 53.1% by weight.
評価試験
実施例１，２及び比較例１〜４で得た粘着シートにつき
下記の試験を行った。Evaluation Test The following tests were conducted on the pressure-sensitive adhesive sheets obtained in Examples 1 and 2 and Comparative Examples 1 to 4.
［接着力］
ＪＩＳ Ｚ １５２８に準じてステンレス板に対する
接着力（１８０度ビール）を測定した。[Adhesive Strength] Adhesive strength (180 degrees beer) to a stainless steel plate was measured according to JIS Z 1528.
［タック］
２０℃、６５％ｎ、ｌ（、下、傾斜角３０度の斜面で粘
着シートの粘着面上に直径の異なるステンレスボールを
助走距離１Ｏｃ１１１でころがし、粘着面のｌｏｃｍの
ところで停止する直径が最大のボールを調べた。なお表
にはポール嵐で示したが、その直径は次式で算出される
。[Tack] 20°C, 65% n, l (bottom) Stainless steel balls of different diameters are rolled on the adhesive surface of the adhesive sheet with a run-up distance of 1Oc111 on a slope with an inclination angle of 30 degrees, and the diameter is determined by rolling the stainless steel balls at a run-up distance of 1Oc111, stopping at locm of the adhesive surface. investigated the largest ball.It is shown in the table as a pole storm, and its diameter is calculated by the following formula.
直径（インチ）−ボールＮＧ／３６
［保持力１
粘着シートの試験片を１０醜幅×２０−長の接着面積で
ベークライト板に貼着し、その試験片の自由端に５００
ｇの荷重を吊り下げ、４０℃又は８０℃の恒温機中で
試験片が凝集破壊により落下するまでの時間を測定した
。Diameter (inch) - Ball NG/36 [Holding force 1] A test piece of the adhesive sheet is pasted on a Bakelite board with an adhesion area of 10 mm width x 20 mm long, and 500 mm is attached to the free end of the test piece.
The test piece was suspended under a load of 1.5 g, and the time required for the test piece to fall due to cohesive failure was measured in a thermostat at 40°C or 80°C.
上記の結果を第１表に示した。The above results are shown in Table 1.
第１表より、実施例の粘着シートにあっては、接着力、
タックを損なうことなく、凝集力が大幅に向上して、接
着力と凝集力が良好なバランスで両立していることがわ
かる。From Table 1, the adhesive strength of the adhesive sheet of the example,
It can be seen that the cohesive force is significantly improved without compromising the tack, and that both adhesion and cohesive force are in good balance.
［経時接着力１
実施例３．４で得た表面保護シートを厚さ０．６−のス
テンレス板に常温で貼着し、３０分経過後及び１ケ月経
過後の接着力（１８０度ビール、剥離速度３００ ｍ
７分）を調べた。また、剥離後のステンレス板における
糊残りの有無を調べた。[Adhesion strength over time 1] The surface protection sheet obtained in Example 3.4 was adhered to a 0.6-thick stainless steel plate at room temperature, and the adhesive strength after 30 minutes and 1 month (180 degrees beer, Peeling speed 300 m
7 minutes). In addition, the presence or absence of adhesive residue on the stainless steel plate after peeling was examined.
［加工性］
実施例３．４で得た表面保護シートを厚さ０．５−のス
テンレス板に常温で貼着し、深さ５鴫のエリクセン絞り
加工を施し、表面保護シートの浮きの有無調べた。また
、剥離後のステンレス板における糊残りの有無を調べた
。[Workability] The surface protection sheet obtained in Example 3.4 was adhered to a 0.5-thick stainless steel plate at room temperature, and Erichsen drawing processing was performed to a depth of 5 to determine whether or not the surface protection sheet was lifted. Examined. In addition, the presence or absence of adhesive residue on the stainless steel plate after peeling was examined.
°上記の結果を第２表に示した。°The above results are shown in Table 2.
第２表
第２表より、実施例の表面保護シートは、加工時に浮き
等の剥がれを生じない接着力を示し、接着力の経時上昇
が小さくて被着体よりの剥離が容易であることがわかる
。また、経時や加工によっても糊残りを生じず、充分な
凝集力も有していることがわかる。Table 2 From Table 2, it can be seen that the surface protection sheets of the examples exhibited adhesive strength that did not cause peeling such as lifting during processing, and that the increase in adhesive strength over time was small and that it was easy to peel off from the adherend. Recognize. It is also seen that no adhesive remains after aging or processing, and that it has sufficient cohesive strength.
なお、実施例４の表面保護シートを１ケ月放置後、再度
紫外線で照射処理するとそのステンレス板に対する接着
力は５０ｇ／２０ｍｍとなった。In addition, when the surface protection sheet of Example 4 was left for one month and then irradiated with ultraviolet rays again, its adhesive strength to the stainless steel plate was 50 g/20 mm.
特許出願人 日東電工株式会社Patent applicant: Nitto Denko Corporation
Claims (1)
て、その感圧接着層を紫外線硬化型感圧接着剤で形成し
、かつ紫外線硬化により架橋度に部分的な相違をもたせ
て接着力と凝集力とをバランスさせたことを特徴とする
粘着部材。 ２、支持基材に可とう性フィルムを用い、再剥離を容易
とした請求項１に記載の粘着部材。[Claims] 1. In an adhesive member having a pressure-sensitive adhesive layer provided on a supporting base material, the pressure-sensitive adhesive layer is formed of an ultraviolet-curable pressure-sensitive adhesive, and the degree of crosslinking is partially changed by ultraviolet curing. An adhesive member characterized by having a balance between adhesive force and cohesive force with different characteristics. 2. The adhesive member according to claim 1, wherein a flexible film is used as the supporting base material to facilitate re-peeling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63227954A JP2548970B2 (en) | 1988-09-12 | 1988-09-12 | Adhesive member |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63227954A JP2548970B2 (en) | 1988-09-12 | 1988-09-12 | Adhesive member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0275679A true JPH0275679A (en) | 1990-03-15 |
| JP2548970B2 JP2548970B2 (en) | 1996-10-30 |
Family
ID=16868867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63227954A Expired - Fee Related JP2548970B2 (en) | 1988-09-12 | 1988-09-12 | Adhesive member |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2548970B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11189664A (en) * | 1997-09-29 | 1999-07-13 | Basf Ag | Method for crosslinking radiation crosslinkable pressure-sensitive contact film |
| JP2003514746A (en) * | 1999-11-18 | 2003-04-22 | ガーディアン・インダストリーズ・コーポレーション | Hydrophobic coating containing DLC on substrate |
| JP2009046620A (en) * | 2007-08-22 | 2009-03-05 | Mitsubishi Plastics Inc | Adhesive sheet |
| JP2009227891A (en) * | 2008-03-25 | 2009-10-08 | Mitsubishi Plastics Inc | Self-adhesive sheet |
| JP2009292893A (en) * | 2008-06-03 | 2009-12-17 | Seiko Epson Corp | Joining method and joined body |
| US8570470B2 (en) | 2008-08-20 | 2013-10-29 | Lg Chem, Ltd. | Adhesive agent |
| US9085121B2 (en) | 1999-05-13 | 2015-07-21 | 3M Innovative Properties Company | Adhesive-backed articles |
-
1988
- 1988-09-12 JP JP63227954A patent/JP2548970B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11189664A (en) * | 1997-09-29 | 1999-07-13 | Basf Ag | Method for crosslinking radiation crosslinkable pressure-sensitive contact film |
| US9085121B2 (en) | 1999-05-13 | 2015-07-21 | 3M Innovative Properties Company | Adhesive-backed articles |
| JP2003514746A (en) * | 1999-11-18 | 2003-04-22 | ガーディアン・インダストリーズ・コーポレーション | Hydrophobic coating containing DLC on substrate |
| JP2009046620A (en) * | 2007-08-22 | 2009-03-05 | Mitsubishi Plastics Inc | Adhesive sheet |
| JP2009227891A (en) * | 2008-03-25 | 2009-10-08 | Mitsubishi Plastics Inc | Self-adhesive sheet |
| JP2009292893A (en) * | 2008-06-03 | 2009-12-17 | Seiko Epson Corp | Joining method and joined body |
| US8570470B2 (en) | 2008-08-20 | 2013-10-29 | Lg Chem, Ltd. | Adhesive agent |
| US8704982B2 (en) | 2008-08-20 | 2014-04-22 | Lg Chem, Ltd. | Adhesive agent |
| US9019463B2 (en) | 2008-08-20 | 2015-04-28 | Lg Chem, Ltd. | Adhesive agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2548970B2 (en) | 1996-10-30 |
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