JP5020521B2 - Adhesive sheet - Google Patents
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- JP5020521B2 JP5020521B2 JP2006048595A JP2006048595A JP5020521B2 JP 5020521 B2 JP5020521 B2 JP 5020521B2 JP 2006048595 A JP2006048595 A JP 2006048595A JP 2006048595 A JP2006048595 A JP 2006048595A JP 5020521 B2 JP5020521 B2 JP 5020521B2
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- sensitive adhesive
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- release
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- adhesive layer
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- 239000000853 adhesive Substances 0.000 title claims description 42
- 230000001070 adhesive effect Effects 0.000 title claims description 42
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 113
- 239000010410 layer Substances 0.000 claims description 40
- 239000011347 resin Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 229920001577 copolymer Polymers 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 15
- 229920001296 polysiloxane Polymers 0.000 claims description 15
- 239000012790 adhesive layer Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 12
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 11
- 229920006267 polyester film Polymers 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 235000007586 terpenes Nutrition 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 125000002298 terpene group Chemical group 0.000 claims description 2
- -1 Polyethylene Polymers 0.000 description 11
- 239000010408 film Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003431 cross linking reagent Substances 0.000 description 8
- 239000000123 paper Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 150000003505 terpenes Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 239000011086 glassine Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920006290 polyethylene naphthalate film Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 229920006271 aliphatic hydrocarbon resin Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
Description
本発明は、粘着シートに関する。本発明の粘着シートは、粘着シートから剥離シートを剥離するときの剥離力がある程度重く、且つ被着体に対して高粘着力を要求される粘着剤層を有する粘着シートに利用した場合において、前記剥離シートを前記粘着剤層から剥離した際に、ジッピングを有効に防止することができる。 The present invention relates to an adhesive sheet. In the case where the pressure-sensitive adhesive sheet of the present invention is used for a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer that requires a high degree of adhesive strength to the adherend, and the peeling force when peeling the release sheet from the pressure-sensitive adhesive sheet is somewhat heavy, When the release sheet is peeled from the pressure-sensitive adhesive layer, zipping can be effectively prevented.
粘着シートでは、通常、粘着剤層を保護するために粘着剤層に剥離シートが設けられている。粘着シートの粘着剤層の粘着力が強い場合や粘着剤層の厚みが薄い場合に剥離力の重い剥離シートを使用すると、粘着シートから剥離シートを剥がす際に、連続的かつ円滑に剥がれずに剥離音が生じたり、粘着剤層に剥離スジが形成する等、いわゆるジッピングが発生する。
また、両面粘着シートでは剥離操作が２回に分けて行われるので、最初の剥離操作の際にもう一方の剥離シートの剥離が起きないように、２つの剥離面の剥離力に差異を設けているが、重剥離面では、ジッピングが発生しやすくなる。
In the pressure-sensitive adhesive sheet, a release sheet is usually provided on the pressure-sensitive adhesive layer in order to protect the pressure-sensitive adhesive layer. If the adhesive layer of the adhesive sheet has a strong adhesive force or if the adhesive layer is thin, using a release sheet with a heavy release force will prevent the release sheet from peeling off continuously and smoothly when the release sheet is peeled off. So-called zipping occurs, for example, peeling sound is generated or peeling stripes are formed in the pressure-sensitive adhesive layer.
Moreover, since the peeling operation is performed in two steps in the double-sided pressure-sensitive adhesive sheet, a difference is provided in the peeling force between the two peeling surfaces so that the other peeling sheet does not peel off during the first peeling operation. However, zipping is likely to occur on the heavy release surface.
粘着シートを被着体から剥がす際のジッピングを防止する技術は種々提案されている。
例えば、ブチルアクリレートを主モノマーとするアクリル系共重合体に可塑剤を添加した粘着剤をウェットティシュ用粘着シートに用いると、粘着シートをウェットティシュの包装材から剥がす際に、剥離音が小さくなり、剥離感が良好になるとする技術が提案されている（特許文献１）。
Various techniques for preventing zipping when the pressure-sensitive adhesive sheet is peeled off from the adherend have been proposed.
For example, if an adhesive made by adding a plasticizer to an acrylic copolymer with butyl acrylate as the main monomer is used for an adhesive sheet for wet tissue, the peeling noise will be reduced when the adhesive sheet is removed from the wet tissue packaging material. A technique for improving the feeling of peeling has been proposed (Patent Document 1).
また、ガラス転移温度が−４０℃以下の（メタ）アクリル系ポリマーとガラス転移温度が８０℃以上の（メタ）アクリル系ポリマーとを架橋反応させて調製した感圧接着剤を支持体上に塗工してなる光学フィルム用表面保護シートによって、光学フィルムから表面保護シートを剥がす際に発生するジッピングを防止する技術が提案されている（特許文献２）。しかしながら、これらの技術は、粘着シートを被着体から剥がす際にジッピングを防止するものであり、粘着シートから剥離シートを剥がす際のジッピングに適用されるものではなかった。
また、両面粘着シートの重剥離面側剥離シートを剥離する際に発生するジッピングには触れていない。
Moreover, the zipping which generate | occur | produces when peeling the heavy peeling surface side peeling sheet of a double-sided adhesive sheet is not touched.
本発明の課題は、粘着力が高い粘着剤層を有し、かつ剥離力が重い粘着シートあるいは両面粘着シートの重剥離面の剥離の際のジッピングを有効に防止ないし軽減することが可能な、粘着剤層と剥離シートとの組み合わせを含む粘着シートを提供することにある。 The problem of the present invention is that it has an adhesive layer with high adhesive force, and can effectively prevent or reduce zipping at the time of peeling of the heavy release surface of the pressure-sensitive adhesive sheet or double-sided pressure-sensitive adhesive sheet, It is providing the adhesive sheet containing the combination of an adhesive layer and a peeling sheet.
前記の課題は、本発明により、基材の少なくとも片面に粘着剤層を有し、その粘着剤層の上に剥離シートが設けられた粘着シートにおいて、
前記粘着剤層を形成する粘着剤が、
（１）２−エチルヘキシルアクリレート８１〜９８重量％、カルボキシル基含有モノマー１〜１０重量％、及びその他の共重合可能なモノマー０〜１８重量％を共重合してなるアクリル酸エステル共重合体と、
（２）そのアクリル酸エステル共重合体１００重量部（固型分）に対して液状粘着付与樹脂１〜１５重量部と
を含むアクリル系粘着剤であり、前記剥離シートの剥離面に形成される剥離剤層の剥離剤がシリコーン系であることを特徴とする、前記粘着シートによって解決することができる。
In the pressure-sensitive adhesive sheet according to the present invention, the pressure-sensitive adhesive sheet has a pressure-sensitive adhesive layer on at least one side of the substrate, and a release sheet is provided on the pressure-sensitive adhesive layer.
The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is
(1) Acrylic ester copolymer obtained by copolymerizing 81 to 98% by weight of 2-ethylhexyl acrylate, 1 to 10% by weight of a carboxyl group-containing monomer, and 0 to 18% by weight of another copolymerizable monomer;
(2) An acrylic pressure-sensitive adhesive containing 1 to 15 parts by weight of a liquid tackifier resin with respect to 100 parts by weight (solid component) of the acrylate copolymer, and is formed on the release surface of the release sheet. It can be solved by the pressure-sensitive adhesive sheet, wherein the release agent of the release agent layer is a silicone type.
本発明の粘着シートの好ましい態様によれば、前記液状粘着付与樹脂がテルペン系である。
本発明の粘着シートの別の好ましい態様によれば、前記粘着剤層の塗布量が７〜２０ｇ／ｍ２である。
本発明の粘着シートの更に別の好ましい態様によれば、粘着シートの初期粘着力が１０Ｎ／２５ｍｍ以上であり、２４時間後の粘着力が１５Ｎ／２５ｍｍ以上である。
本発明の粘着シートの更に別の好ましい態様によれば、粘着シートから剥離シートを剥離するときの剥離力が２００〜７００ｍＮ／５０ｍｍである。
本発明の粘着シートの更に別の好ましい態様によれば、前記剥離シートの剥離基材がポリエステルフィルムである。
According to the preferable aspect of the adhesive sheet of this invention, the said liquid tackifying resin is a terpene type.
According to another preferable aspect of the pressure-sensitive adhesive sheet of the present invention, the coating amount of the pressure-sensitive adhesive layer is 7 to 20 g / m 2 .
According to still another preferred embodiment of the pressure-sensitive adhesive sheet of the present invention, the initial pressure-sensitive adhesive force of the pressure-sensitive adhesive sheet is 10 N / 25 mm or more, and the pressure-sensitive adhesive force after 24 hours is 15 N / 25 mm or more.
According to still another preferred embodiment of the pressure-sensitive adhesive sheet of the present invention, the peeling force when peeling the release sheet from the pressure-sensitive adhesive sheet is 200 to 700 mN / 50 mm.
According to still another preferred embodiment of the pressure-sensitive adhesive sheet of the present invention, the release substrate of the release sheet is a polyester film.
また、本発明は、両面粘着シートにおいて重剥離面側の粘着剤が、
（１）２−エチルヘキシルアクリレート８１〜９８重量％、カルボキシル基含有モノマー１〜１０重量％、及びその他の共重合可能なモノマー０〜１８重量％を共重合してなるアクリル酸エステル共重合体と、
（２）そのアクリル酸エステル共重合体１００重量部（固型分）に対して液状粘着付与樹脂１〜１５重量部と
を含むアクリル系粘着剤であり、重剥離面側の剥離剤がシリコーン系であること、
前記第２剥離シートの剥離力が２００〜７００ｍＮ／５０ｍｍであること、及び
前記軽剥離面の剥離力に対して、前記重剥離面が２〜３倍の剥離力を有することを特徴とする、前記両面粘着シートにも関する。
In the present invention, the double-sided pressure-sensitive adhesive sheet has a pressure-sensitive adhesive on the heavy release surface side.
(1) Acrylic ester copolymer obtained by copolymerizing 81 to 98% by weight of 2-ethylhexyl acrylate, 1 to 10% by weight of a carboxyl group-containing monomer, and 0 to 18% by weight of another copolymerizable monomer;
(2) An acrylic pressure-sensitive adhesive containing 1 to 15 parts by weight of a liquid tackifying resin with respect to 100 parts by weight (solid portion) of the acrylate copolymer, and the release agent on the heavy release surface side is a silicone-based release agent that is,
The peeling force of the second release sheet is 200 to 700 mN / 50 mm, and
The double- sided pressure-sensitive adhesive sheet also relates to the double-sided pressure-sensitive adhesive sheet , wherein the heavy peel surface has a peel force 2 to 3 times the peel force of the light release surface .
本発明の両面粘着シートの好ましい態様によれば、前記第２粘着剤層の液状粘着付与樹脂がテルペン系である。
本発明の両面粘着シートの別の好ましい態様によれば、前記第２粘着剤層の塗布量が７〜２０ｇ／ｍ２である。
本発明の両面粘着シートの更に別の好ましい態様によれば、前記第２粘着剤層の初期粘着力が１０Ｎ／２５ｍｍ以上であり、２４時間後の粘着力が１５Ｎ／２５ｍｍ以上である。
本発明の両面粘着シートの更に別の好ましい態様によれば、前記第２剥離シートの剥離基材がポリエステルフィルムである。
According to a preferred embodiment of the double-sided pressure-sensitive adhesive sheet of the present invention, the liquid tackifying resin of the second pressure-sensitive adhesive layer is a terpene system.
According to another preferable aspect of the double-sided pressure-sensitive adhesive sheet of the present invention, the coating amount of the second pressure-sensitive adhesive layer is 7 to 20 g / m 2 .
According to still another preferred embodiment of the double-sided pressure-sensitive adhesive sheet of the present invention, the initial pressure-sensitive adhesive strength of the second pressure-sensitive adhesive layer is 10 N / 25 mm or more, and the pressure-sensitive adhesive force after 24 hours is 15 N / 25 mm or more .
According to still another preferred aspect of the double-sided pressure-sensitive adhesive sheet of the present invention, the release substrate of the second release sheet is a polyester film.
本発明の粘着シートは、任意の用途において、粘着シートから剥離シートを剥離した場合に、ジッピングが起こりにくく、また、被着体に対して高粘着力を保証することができる。更に、ジッピングが発生して粘着剤層上に剥離スジが形成されて、粘着剤層表面が非平滑面になると、重大な欠陥が発生する用途において、優れたジッピング防止効果を示すことができる。 The pressure-sensitive adhesive sheet of the present invention is free from zipping when the release sheet is peeled from the pressure-sensitive adhesive sheet in any application, and can guarantee a high adhesive force to the adherend. Further, when zipping occurs and peeling stripes are formed on the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer surface becomes a non-smooth surface, an excellent anti-zipping effect can be exhibited in applications where serious defects occur.
本発明の粘着シートにおいて、前記基材としては、公知の粘着シートにおいて通常用いられている基材、例えば、紙類（例えば、上質紙又はグラシン紙）、合成樹脂フィルム又は合成紙〔例えば、ポリオレフィン（ポリエチレン又はポリプロピレン）、塩化ビニル、ポリスチレン、又はポリエステル（ポリエチレンテレフタレート、ポリブチレンテレフタレート、又はポリエチレンナフタレート）のフィルム又は合成紙〕、不織布類（例えば、レーヨン、ポリアミド、又はポリエステル製の不織布）、金属箔類（例えば、アルミニウム、又は銅の箔）など、更にこれらの積層体などを使用することができる。その中でも、寸法安定性等の面からポリエステルフィルムを使用するのが好ましい。 In the pressure-sensitive adhesive sheet of the present invention, as the base material, a base material usually used in known pressure-sensitive adhesive sheets, for example, papers (for example, fine paper or glassine paper), synthetic resin film or synthetic paper [for example, polyolefin (Polyethylene or polypropylene), vinyl chloride, polystyrene, or polyester (polyethylene terephthalate, polybutylene terephthalate, or polyethylene naphthalate) film or synthetic paper], non-woven fabric (eg, non-woven fabric made of rayon, polyamide, or polyester), metal Foil (for example, aluminum or copper foil) and the like, and a laminate of these can be used. Among these, it is preferable to use a polyester film from the viewpoint of dimensional stability.
ポリエステルフィルムとしては、東レ社製のポリエステルフィルム（商品名：ルミラー）、三菱化学ポリエステルフィルム社製のポリエステルフィルム（商品名：ダイヤホイル）、又は東洋紡績社製のポリエステルフィルム（商品名：クリスパー）を例示することができる。なお、必要に応じて、フィルム表面にコロナ処理を施したもの、又は表面に易接着処理を施したものを好適に使用することができる。基材の厚さは、通常１０〜１００μｍ、好ましくは２０〜８０μｍである。１０μｍ未満になると強度が弱く作業性が悪くなることがあり、１００μｍを超えるとフィルムのコシが強くなり、作業性が悪くなることがある。 Polyester film manufactured by Toray Industries, Inc. (trade name: Lumirror), polyester film manufactured by Mitsubishi Chemical Polyester Film Co., Ltd. (trade name: Diafoil), or polyester film manufactured by Toyobo Co., Ltd. (trade name: Crisper) It can be illustrated. In addition, the thing which gave the corona treatment to the film surface or the thing which gave the surface easy-adhesion processing can be used suitably as needed. The thickness of a base material is 10-100 micrometers normally, Preferably it is 20-80 micrometers. When the thickness is less than 10 μm, the strength is weak and workability may be deteriorated. When the thickness is more than 100 μm, the stiffness of the film becomes strong and workability may be deteriorated.
本発明の粘着シートにおいては、粘着剤層（両面粘着シートの場合は、重剥離面用の粘着剤層）を形成する粘着剤として、
（１）２−エチルヘキシルアクリレート８１〜９８重量％、カルボキシル基含有モノマー１〜１０重量％、及びその他の共重合可能なモノマー０〜１８重量％を共重合してなるアクリル酸エステル共重合体と、
（２）そのアクリル酸エステル共重合体１００重量部（固型分）に対して液状粘着付与樹脂１〜１５重量部と
を含むアクリル系粘着剤を用いる。
In the pressure-sensitive adhesive sheet of the present invention, as a pressure-sensitive adhesive that forms a pressure-sensitive adhesive layer (in the case of a double-sided pressure-sensitive adhesive sheet, a pressure-sensitive adhesive layer for a heavy release surface),
(1) Acrylic ester copolymer obtained by copolymerizing 81 to 98% by weight of 2-ethylhexyl acrylate, 1 to 10% by weight of a carboxyl group-containing monomer, and 0 to 18% by weight of another copolymerizable monomer;
(2) An acrylic pressure-sensitive adhesive containing 1 to 15 parts by weight of a liquid tackifying resin is used with respect to 100 parts by weight (solid content) of the acrylate copolymer.
カルボキシル基含有モノマーとしては、例えば、炭素−炭素二重結合１つを有し、炭素原子数３〜６のモノ若しくはジカルボン酸、例えば、メタクリル酸、アクリル酸、又はイタコン酸等を挙げることができる。その他の共重合可能なモノマーとしては、（メタ）アクリル酸誘導体（例えば、エステル、特には、低級アルキルエステル又はヒドロキシ低級アルキルエステルなど）、例えば、エチルアクリレート、ブチルアクリレート、アクリロニトリル、アクリルアミド、メチルメタクリレート、メチルアクリレート、グリシジルメタクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルメタクリレート、又はＮ−メチロールアクリルアミド、あるいはビニル化合物、例えば、酢酸ビニル、スチレン、又は無水マレイン酸等を用いて、粘着力を向上させることができる。 Examples of the carboxyl group-containing monomer include mono- or dicarboxylic acids having one carbon-carbon double bond and 3 to 6 carbon atoms, such as methacrylic acid, acrylic acid, or itaconic acid. . Other copolymerizable monomers include (meth) acrylic acid derivatives (eg, esters, particularly lower alkyl esters or hydroxy lower alkyl esters) such as ethyl acrylate, butyl acrylate, acrylonitrile, acrylamide, methyl methacrylate, Improve adhesive strength using methyl acrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, or N-methylol acrylamide, or a vinyl compound such as vinyl acetate, styrene, or maleic anhydride. Can do.
主モノマーとして用いる２−エチルヘキシルアクリレートは、ガラス転移温度が低く、柔らかい粘着剤を調製することができるため、ジッピングを起こしにくい。２−エチルヘキシルアクリレートの配合割合が８１重量％未満であると、ジッピング防止効果に乏しく、９８重量％を超えると、粘着力が乏しくなってしまう。２−エチルヘキシルアクリレートの配合量は、より好ましくは８５〜９５重量％である。カルボキシル基含有モノマーを配合することにより、粘着力の向上や粘着剤の凝集力が向上する効果がある。カルボキシル基含有モノマーの配合割合が１重量％未満であると、粘着力が乏しくなる。また、１０重量％を超えると、形成される粘着剤層が固くなりジッピングが発生しやすくなる。カルボキシル基含有モノマーの配合量は、より好ましくは２〜８重量％である。 Since 2-ethylhexyl acrylate used as a main monomer has a low glass transition temperature and can prepare a soft adhesive, it is difficult to cause zipping. When the blending ratio of 2-ethylhexyl acrylate is less than 81% by weight, the effect of preventing zipping is poor, and when it exceeds 98% by weight, the adhesive strength is poor. The blending amount of 2-ethylhexyl acrylate is more preferably 85 to 95% by weight. By blending the carboxyl group-containing monomer, there is an effect of improving the adhesive force and the cohesive force of the adhesive. When the blending ratio of the carboxyl group-containing monomer is less than 1% by weight, the adhesive strength becomes poor. On the other hand, if it exceeds 10% by weight, the formed pressure-sensitive adhesive layer becomes hard and zipping tends to occur. The blending amount of the carboxyl group-containing monomer is more preferably 2 to 8% by weight.
粘着剤層（両面粘着シートの場合は、重剥離面用の粘着剤層）を形成する粘着剤に、液状粘着付与樹脂を添加する。液状粘着付与樹脂としては、ロジン等の天然樹脂、テルペン系樹脂、脂肪族系炭化水素樹脂、シクロペンタジエン系樹脂、芳香族系石油樹脂、フェノール系樹脂、アルキル−フェノール−アセチレン系樹脂、クマロン−インデン系樹脂、又はビニルトルエン−α−メチルスチレン共重合体、あるいはこれらの変性体などを挙げることができる。これらの中で、タックと粘着力のバランスが優れているテルペン系樹脂が特に好ましい。なお、液状粘着付与樹脂を２種以上併用してもよい。 A liquid tackifying resin is added to the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer (in the case of a double-sided pressure-sensitive adhesive sheet, the pressure-sensitive adhesive layer for the heavy release surface). Examples of the liquid tackifying resin include natural resins such as rosin, terpene resins, aliphatic hydrocarbon resins, cyclopentadiene resins, aromatic petroleum resins, phenol resins, alkyl-phenol-acetylene resins, coumarone-indenes. Resin, vinyltoluene-α-methylstyrene copolymer, or modified products thereof. Of these, terpene resins having a good balance between tack and adhesive strength are particularly preferred. Two or more liquid tackifying resins may be used in combination.
液状粘着付与樹脂は、２−エチルヘキシルアクリレートを主成分とするアクリル酸エステル共重合体１００重量部（固型分）に対し、１〜１５重量部、好ましくは２〜１０重量部の範囲で配合する。配合量が１重量部に満たないと、ジッピング防止の向上等の効果が発揮されず、１５重量部を超えると粘着力が不充分になる。 The liquid tackifying resin is blended in an amount of 1 to 15 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight (solid component) of an acrylate copolymer mainly composed of 2-ethylhexyl acrylate. . When the blending amount is less than 1 part by weight, effects such as improvement of prevention of zipping cannot be exhibited, and when it exceeds 15 parts by weight, the adhesive strength becomes insufficient.
粘着剤層（両面粘着シートの場合は、重剥離面用の粘着剤層）には、粘着力及び凝集力を発現させるため、他に架橋剤を配合することが好ましい。架橋剤としては、イソシアナート系、エポキシ系、又は金属キレート系等の架橋剤を挙げることができる。架橋剤の配合量は、使用するアクリル酸エステル共重合体や架橋剤の種類によって変化するが、アクリル酸エステル共重合体１００重量部（固型分）に対し、０．３〜７．０重量部程度、好ましくは０．５〜５．０重量部程度である。 In the pressure-sensitive adhesive layer (in the case of a double-sided pressure-sensitive adhesive sheet, a pressure-sensitive adhesive layer for the heavy release surface), in order to express adhesive force and cohesive force, it is preferable to add a crosslinking agent. Examples of the crosslinking agent include isocyanate-based, epoxy-based, and metal chelate-based crosslinking agents. Although the compounding quantity of a crosslinking agent changes with kinds of acrylic ester copolymer and crosslinking agent to be used, it is 0.3-7.0 weight with respect to 100 weight part (solid part) of acrylic ester copolymer. Part, preferably 0.5 to 5.0 parts by weight.
前記粘着剤層（両面粘着シートの場合は、重剥離面用の粘着剤層）の塗布量は、通常７〜２０ｇ／ｍ２、好ましくは８〜１６ｇ／ｍ２である。前記粘着剤層は、前記粘着剤をナイフコーター、リバースコーター、ダイコーター、グラビアコーター、又はマイヤーバー等の公知の方法を用いて、基材に直接、前記粘着剤を塗布した後、乾燥させて粘着剤層を形成してもよい。あるいは、剥離シート（両面粘着シートの場合は、重剥離面用の剥離シート）の剥離剤層面に前記粘着剤を前述のような方法で塗布し、その後乾燥して前記剥離シートの表面に粘着剤層を形成した後、前記基材に粘着剤層を転写させてもよい。 The application amount of the pressure-sensitive adhesive layer (in the case of a double-sided pressure-sensitive adhesive sheet) is usually 7 to 20 g / m 2 , preferably 8 to 16 g / m 2 . The pressure-sensitive adhesive layer is formed by applying the pressure-sensitive adhesive directly to a substrate using a known method such as a knife coater, reverse coater, die coater, gravure coater, or Meyer bar, and then drying. An adhesive layer may be formed. Alternatively, the adhesive is applied to the release agent layer surface of a release sheet (in the case of a double-sided adhesive sheet, a release sheet for a heavy release surface) by the method described above, and then dried to provide an adhesive on the surface of the release sheet. After forming the layer, the pressure-sensitive adhesive layer may be transferred to the substrate.
剥離シート（両面粘着シートの場合は、重剥離面用の剥離シート）としては、剥離基材の片面上にシリコーン系の剥離剤層を有するシートを用いる。剥離シートの剥離基材としては、例えば、上質紙やグラシン紙等の紙類、ポリオレフィンやポリエステル等の合成樹脂フィルム類、紙類にポリオレフィンフィルムをラミネートしたラミネート紙類等が挙げられるが、平滑性、熱変形性及び寸法安定性の点から、ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム又はポリエチレンナフタレートフィルム等のポリエステルフィルムを用いるのが好ましい。剥離基材の厚さは、通常１０〜１００μｍ、好ましくは２０〜８０μｍである。１０μｍ未満になると強度が弱く作業性が悪くなることがあり、１００μｍを超えるとフィルムのコシが強くなり、作業性が悪くなることがある。剥離剤層は、剥離シートの剥離基材の片面に、シリコーン系の剥離剤を塗布することによって形成することができ、厚さは、例えば、０．０５〜１．０μｍであることができる。 As the release sheet (in the case of a double-sided PSA sheet, a release sheet for the heavy release surface), a sheet having a silicone release agent layer on one side of the release substrate is used. Examples of the release substrate of the release sheet include papers such as high-quality paper and glassine paper, synthetic resin films such as polyolefin and polyester, and laminate papers obtained by laminating a polyolefin film on paper. From the viewpoint of thermal deformability and dimensional stability, it is preferable to use a polyester film such as a polyethylene terephthalate film, a polybutylene terephthalate film, or a polyethylene naphthalate film. The thickness of a peeling base material is 10-100 micrometers normally, Preferably it is 20-80 micrometers. When the thickness is less than 10 μm, the strength is weak and workability may be deteriorated. When the thickness is more than 100 μm, the stiffness of the film becomes strong and workability may be deteriorated. The release agent layer can be formed by applying a silicone release agent to one side of the release substrate of the release sheet, and the thickness can be, for example, 0.05 to 1.0 μm.
前記シリコーン系の剥離剤としては、シリコーンに、シリコーン系剥離性調整剤を添加して調製されたものを用いるのが好ましい。シリコーンとしては、代表的にはジメチルポリシロキサンを用いることができる。本発明においては、剥離力を増加させる作用を有する化合物としては、シリコーン系剥離性調整剤を用いるのが好ましく、この種のシリコーン系剥離性調整剤は公知である。例えば、（ＣＨ３）３ＳｉＯ１／２単位及びＳｉＯ４／２単位からなる共重合体（特公昭４９−２７０３３号公報参照）、又は（ＣＨ３）３ＳｉＯ１／２単位、（ＣＨ３）２ＣＨ２＝ＣＨＳｉＯ１／２単位、及びＳｉＯ４／２単位からなる共重合体（特開昭５９−８４９５３号公報及び特公昭５３−２９６７８号公報参照）を、シリコーン系剥離性調整剤として用いることができる。更に、剥離力調整のために、前記剥離剤にはシリカ等の無機物を添加してもよい。 As the silicone release agent, it is preferable to use a silicone release agent prepared by adding a silicone release agent to silicone. As the silicone, dimethylpolysiloxane can be typically used. In the present invention, it is preferable to use a silicone-based peelability adjusting agent as the compound having an action of increasing the peeling force, and this type of silicone-based peelability adjusting agent is known. For example, a copolymer composed of (CH 3 ) 3 SiO 1/2 units and SiO 4/2 units (see Japanese Patent Publication No. 49-27033), or (CH 3 ) 3 SiO 1/2 units, (CH 3 ) A copolymer comprising 2 CH 2 ═CHSiO 1/2 units and SiO 4/2 units (see Japanese Patent Application Laid-Open No. 59-84953 and Japanese Patent Publication No. 53-29678) is used as a silicone-based release modifier. be able to. Furthermore, an inorganic substance such as silica may be added to the release agent in order to adjust the release force.
本発明による粘着シート（両面粘着シートの場合は、重剥離面側）の初期粘着力は、好ましくは１０Ｎ／２５ｍｍ以上、より好ましくは１０〜２０Ｎ／２５ｍｍである。また、２４時間後の粘着力は、好ましくは１５Ｎ／２５ｍｍ以上、より好ましくは１５〜２５Ｎ／２５ｍｍである。本明細書において「粘着力」は、ＪＩＳＺ０２３７に準拠して、ステンレス板を被着体として測定した値である。また、初期粘着力は、被着体への貼着から３０分経過後の測定値である。ここで、初期粘着力が１０Ｎ／２５ｍｍ未満になると、シートが最終的に剥がれることがある。同様に、２４時間後の粘着力が１５Ｎ／２５ｍｍ未満になると、シートが最終的に剥がれることがある。 The initial adhesive strength of the pressure-sensitive adhesive sheet according to the present invention (in the case of a double-sided pressure-sensitive adhesive sheet) is preferably 10 N / 25 mm or more, more preferably 10 to 20 N / 25 mm. The adhesive strength after 24 hours is preferably 15 N / 25 mm or more, more preferably 15 to 25 N / 25 mm. In this specification, “adhesive strength” is a value measured using a stainless steel plate as an adherend in accordance with JISZ0237. Moreover, initial adhesive force is a measured value after 30 minutes have passed since sticking to an adherend. Here, if the initial adhesive strength is less than 10 N / 25 mm, the sheet may eventually peel off. Similarly, if the adhesive strength after 24 hours is less than 15 N / 25 mm, the sheet may eventually peel off.
また、本発明による粘着シートから剥離シート（両面粘着シートの場合は、重剥離面用の剥離シート）を剥離するときの剥離力は、好ましくは２００〜７００ｍＮ／５０ｍｍ、より好ましくは３００〜６００ｍＮ／５０ｍｍである。本明細書において、前記剥離力は、ＪＩＳＺ０２３７に準拠して、剥離シートを粘着シートから、３００ｍｍ／ｍｉｎの速度で１８０度の角度で剥離して測定した値である。ここで、前記剥離力が、２００ｍＮ／５０ｍｍ未満になると、両面粘着シートの重剥離面に応用した際に軽剥離面との剥離力に差異を設けることが困難になる。一般的に、軽剥離面の剥離力に対して、重剥離面が２〜３倍の剥離力を有していないと、軽剥離面を剥離する際に重剥離面が同時に剥離されてしまう傾向が高くなる。一方、前記剥離力が７００ｍＮ／５０ｍｍを超えると、剥離が困難になる。 Moreover, the peeling force when peeling the release sheet (in the case of a double-sided pressure-sensitive adhesive sheet) is preferably 200 to 700 mN / 50 mm, more preferably 300 to 600 mN / 50 mm. In this specification, the said peeling force is the value measured by peeling a peeling sheet from an adhesive sheet at an angle of 180 degree | times at a speed | rate of 300 mm / min based on JISZ0237. Here, when the peeling force is less than 200 mN / 50 mm, it is difficult to provide a difference in the peeling force from the light peeling surface when applied to the heavy peeling surface of the double-sided PSA sheet. Generally, if the heavy peel surface does not have a peel force 2 to 3 times the peel force of the light peel surface, the heavy peel surface tends to peel at the same time when the light peel surface is peeled off. Becomes higher. On the other hand, when the peeling force exceeds 700 mN / 50 mm, peeling becomes difficult.
本発明による粘着シートが両面粘着シートである場合、軽剥離面における粘着剤層と剥離シートとの組み合わせに関しては、前記重剥離面に対して軽剥離面として作用する限り、任意の粘着剤層と任意の剥離シートとの組み合わせを用いることができる。 When the pressure-sensitive adhesive sheet according to the present invention is a double-sided pressure-sensitive adhesive sheet, with respect to the combination of the pressure-sensitive adhesive layer and the release sheet on the light release surface, as long as it acts as a light release surface with respect to the heavy release surface, Combinations with any release sheet can be used.
以下、実施例によって本発明を具体的に説明するが、これらは本発明の範囲を限定するものではない。なお、以下の実施例及び比較例において、特に断らない限り、部は重量部であり、％は重量％をそれぞれ表す。 EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but these do not limit the scope of the present invention. In the following examples and comparative examples, unless otherwise specified, parts are parts by weight and% represents% by weight.
《剥離シートの作製》
（１）厚さ５０μｍの透明ポリエチレンテレフタレートフィルム（東レ社製「ルミラー」）の片面に、ジメチルポリシロキサンにシリコーン系剥離性調整剤及びシリカが配合された市販剥離剤（東レ・ダウコーニング社製「ＳＲＸ−３７０」）をマイヤーバーで塗布して乾燥させ、厚さ０．２μｍの剥離剤層を設けて剥離シート（重剥離用）を作製した。
<Preparation of release sheet>
(1) A commercially available release agent (manufactured by Toray Dow Corning Co., Ltd.) in which a silicone-based release modifier and silica are blended with dimethylpolysiloxane on one side of a transparent polyethylene terephthalate film ("Lumirror" manufactured by Toray Industries Inc.) having a thickness of 50 μm SRX-370 ") was applied with a Meyer bar and dried, and a release agent layer having a thickness of 0.2 µm was provided to prepare a release sheet (for heavy release).
（２）厚さ５０μｍの白色ポリエチレンテレフタレートフィルムの片面にシリコーン系剥離剤層が設けられた剥離シート（東洋紡績社製「クリスパーＫ７２２４」）を軽剥離用シートとした。 (2) A release sheet (“Chrisper K7224” manufactured by Toyobo Co., Ltd.) provided with a silicone release agent layer on one side of a 50 μm thick white polyethylene terephthalate film was used as a light release sheet.
《実施例１》
（１）粘着剤の調製
２−エチルヘキシルアクリレート８６．８％とアクリル酸３％と酢酸ビニル１０％と２−ヒドロキシエチルメタクリレート０．２％とを共重合させて調製したアクリル酸エステル共重合体溶液（濃度４０％、酢酸エチル：トルエン＝４５：５５）の固型分１００部に対して、テルペン系液状粘着付与樹脂（ヤスハラケミカル社製「ＹＳレジンＬＰ」）５部、及びイソシアナート系架橋剤（東洋インキ製造社製「ＢＨＳ８５１５」）２．５部を配合し、充分攪拌して粘着剤を得た。
Example 1
(1) Preparation of pressure-sensitive adhesive Acrylic ester copolymer solution prepared by copolymerizing 86.8% 2-ethylhexyl acrylate, 3% acrylic acid, 10% vinyl acetate and 0.2% 2-hydroxyethyl methacrylate (100% solid content of 40% concentration, ethyl acetate: toluene = 45: 55), 5 parts of terpene-based liquid tackifier resin (“YS Resin LP” manufactured by Yashara Chemical Co., Ltd.) and isocyanate-based crosslinking agent ( 2.5 parts of “BHS8515” manufactured by Toyo Ink Manufacturing Co., Ltd. was blended and sufficiently stirred to obtain an adhesive.
（２）粘着シートの作製
前記「剥離シートの作製」（１）で作製した剥離シートの剥離面に、前記実施例１（１）で調製した粘着剤をナイフコーターにて塗布して乾燥させ、塗布量１０ｇ／ｍ２の粘着剤層を形成した。この粘着剤層の表面に、厚さ５０μｍの白色ポリエチレンテレフタレート基材（東洋紡績社製「クリスパーＫ２４１１」）を積層し、本発明の粘着シートを作製した。
(2) Preparation of pressure-sensitive adhesive sheet The pressure-sensitive adhesive prepared in Example 1 (1) was applied to the release surface of the release sheet prepared in "Preparation of release sheet" (1) with a knife coater and dried. An adhesive layer having a coating amount of 10 g / m 2 was formed. On the surface of this pressure-sensitive adhesive layer, a white polyethylene terephthalate base material (“Chrisper K2411” manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm was laminated to prepare a pressure-sensitive adhesive sheet of the present invention.
《実施例２》
実施例１において、粘着剤にテルペン系液状粘着付与樹脂（ヤスハラケミカル社製「ＹＳレジンＬＰ」）１０部を添加したこと以外は、前記実施例１と同様にして粘着シートを作製した。
Example 2
In Example 1, a pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that 10 parts of a terpene-based liquid tackifier resin (“YS Resin LP” manufactured by Yasuhara Chemical Co., Ltd.) was added to the pressure-sensitive adhesive.
《実施例３》
（１）軽剥離面側粘着剤の調製
２−エチルヘキシルアクリレート８５％とアクリル酸３％と酢酸ビニル１２％とを共重合させて調製したアクリル酸エステル共重合体溶液（濃度４０％、酢酸エチル：トルエン＝４５：５５）の固型分１００部に対して、イソシアナート系架橋剤（東洋インキ製造社製「ＢＨＳ８５１５」）２．５部を配合し、充分攪拌して軽剥離面側粘着剤を得た。
Example 3
(1) Preparation of light release surface side pressure-sensitive adhesive Acrylic ester copolymer solution prepared by copolymerizing 85% 2-ethylhexyl acrylate, 3% acrylic acid and 12% vinyl acetate (concentration 40%, ethyl acetate: Toluene = 45:55) To 100 parts of the solid component, 2.5 parts of an isocyanate-based cross-linking agent (“BHS8515” manufactured by Toyo Ink Co., Ltd.) is blended and stirred sufficiently to provide a light release surface side adhesive. Obtained.
（２）本発明の両面粘着シートの作製
前記「剥離シートの作製」（２）で作製した軽剥離用シートの剥離面に、前記実施例３（１）で調製した軽剥離面側粘着剤をナイフコーターにて塗布して乾燥させ、塗布量１４ｇ／ｍ２の粘着剤層を形成した。この粘着剤層の表面に、実施例１で作製した粘着シートの白色ポリエチレンテレフタレート基材面を積層し、両面粘着シートを作製した。
(2) Preparation of double-sided pressure-sensitive adhesive sheet of the present invention The light-release surface-side pressure-sensitive adhesive prepared in Example 3 (1) was applied to the release surface of the light-release sheet prepared in "Preparation of release sheet" (2). It was applied with a knife coater and dried to form an adhesive layer having a coating amount of 14 g / m 2 . On the surface of this pressure-sensitive adhesive layer, the white polyethylene terephthalate substrate surface of the pressure-sensitive adhesive sheet prepared in Example 1 was laminated to prepare a double-sided pressure-sensitive adhesive sheet.
《比較例１》
（１）粘着剤の調製
２−エチルヘキシルアクリレート３７％とブチルアクリレート４６％とアクリル酸７．５％と酢酸ビニル９．５％とを共重合させて調製したアクリル酸エステル共重合体溶液（濃度４３％、酢酸エチル：Ｎ−ヘキサン＝７９：２１）の固型分１００部に対して、イソシアナート系架橋剤（東洋インキ製造社製「ＢＨＳ８５１５」）２．５部を配合し、充分攪拌して粘着剤を得た。
<< Comparative Example 1 >>
(1) Preparation of pressure-sensitive adhesive Acrylic ester copolymer solution (concentration 43) prepared by copolymerizing 37% 2-ethylhexyl acrylate, 46% butyl acrylate, 7.5% acrylic acid and 9.5% vinyl acetate. %, Ethyl acetate: N-hexane = 79: 21) to 100 parts of a solid component, 2.5 parts of an isocyanate cross-linking agent (“BHS8515” manufactured by Toyo Ink Manufacturing Co., Ltd.) is blended and stirred thoroughly. An adhesive was obtained.
（２）粘着シートの作製
前記実施例１（２）の操作において、前記比較例１（１）で調製した粘着剤を使用したこと以外は、実施例１（２）と同じ操作を繰り返して粘着シートを作製した。
(2) Preparation of pressure-sensitive adhesive sheet In the operation of Example 1 (2), the same operation as in Example 1 (2) was repeated except that the pressure-sensitive adhesive prepared in Comparative Example 1 (1) was used. A sheet was produced.
《比較例２》
比較例１において、粘着剤にテルペン系液状粘着付与樹脂（ヤスハラケミカル社製「ＹＳレジンＬＰ」）５部を添加したこと以外は比較例１と同様にして粘着シートを作製した。
<< Comparative Example 2 >>
In Comparative Example 1, a pressure-sensitive adhesive sheet was prepared in the same manner as Comparative Example 1 except that 5 parts of a terpene-based liquid tackifier resin (“YS Resin LP” manufactured by Yasuhara Chemical Co., Ltd.) was added to the pressure-sensitive adhesive.
《物性評価》
（１）粘着力
粘着力は、ＪＩＳＺ０２３７に準拠し、被着体としてステンレス板を用い、初期粘着力及び２４時間後の粘着力を測定した。結果を表１に示す。
"Evaluation of the physical properties"
(1) Adhesive strength The adhesive strength was measured in accordance with JISZ0237, using a stainless steel plate as the adherend, and the initial adhesive strength and the adhesive strength after 24 hours. The results are shown in Table 1.
（２）剥離力
剥離力は、ＪＩＳＺ０２３７に準拠して、剥離シートを粘着シートから０．３ｍ／ｍｉｎの剥離速度で、１８０度の角度で剥離して剥離力を測定した。その際、引張試験機（テンシロン ＲＴＡ−Ｔ−２Ｍ；エー・アンド・デイ社製）によって、図１に模式的に示すように、剥離力の波形ａ，ｂが得られる。図１（ａ）は、ジッピングが発生しない場合の剥離力波形ａであり、図１（ｂ）は、ジッピングが発生する場合の剥離力波形ｂである。
測定結果を表１に示す。表１において、ジッピングが発生しなかった場合（実施例１〜３）については、図１（ａ）の剥離力値Ａを示し、ジッピングが発生した場合（比較例１〜２）については、谷型ボトム部Ｂ１、Ｂ２、Ｂ３、Ｂｎの平均値（Ｂ）と山型ピーク部Ｐ１、Ｐ２、Ｐ３、Ｐｎの平均値（Ｐ）とを「Ｂ〜Ｐ」として示した。
(2) Peeling force The peeling force was measured by peeling the release sheet from the adhesive sheet at a peeling speed of 0.3 m / min at an angle of 180 degrees in accordance with JISZ0237. At that time, peeling force waveforms a and b are obtained by a tensile tester (Tensilon RTA-T-2M; manufactured by A & D) as schematically shown in FIG. FIG. 1A shows a peeling force waveform a when zipping does not occur, and FIG. 1B shows a peeling force waveform b when zipping occurs.
The measurement results are shown in Table 1. In Table 1, when zipping did not occur (Examples 1 to 3), the peeling force value A of FIG. 1 (a) was shown, and when zipping occurred (Comparative Examples 1 and 2), trough The average value (B) of the mold bottom parts B1, B2, B3, and Bn and the average value (P) of the peak-shaped peak parts P1, P2, P3, and Pn are shown as “B to P”.
（３）ジッピングの評価
前項（２）の前記剥離力測定の際に、ジッピングの発生を３段階で評価した。ジッピングの評価基準は以下の通りである。結果を表１に示す。
○：極めて円滑に剥離し、剥離スジがなく、剥離音も発生しない。
△：わずかにジッピングが発生する。すなわち、剥離スジ及び剥離音が若干発生する。
×：ジッピングが発生する。すなわち、剥離スジが発生し、剥離音が大きい。
(3) Evaluation of zipping When the peel force was measured in (2) of the previous section, the occurrence of zipping was evaluated in three stages. The evaluation criteria for zipping are as follows. The results are shown in Table 1.
○: Peeling very smoothly, no peeling streaks, and no peeling noise.
Δ: Slight zipping occurs. That is, some peeling streaks and peeling noise are generated.
X: Zipping occurs. That is, peeling stripes are generated and peeling sound is loud.
（４）結果
前記実施例１〜３及び比較例１〜２で調製した粘着シートについて得られた物性評価の結果を表１に示す。
(4) Results Table 1 shows the results of physical property evaluations obtained for the pressure-sensitive adhesive sheets prepared in Examples 1 to 3 and Comparative Examples 1 and 2.
本発明の粘着シートは、剥離シートを剥離するときの剥離力がある程度重く、且つ被着体に対して高粘着力を要求される粘着剤層を有する粘着シートに利用した場合において、前記剥離シートを前記粘着剤層から剥離した際に、ジッピングを有効に防止することができる。 When the pressure-sensitive adhesive sheet of the present invention is used for a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer that has a somewhat heavy peeling force when peeling the release sheet and requires a high pressure-sensitive adhesive strength to the adherend, When peeling from the pressure-sensitive adhesive layer, zipping can be effectively prevented.
Claims (5)
前記第２粘着剤層を形成する粘着剤が、
（１）２−エチルヘキシルアクリレート８１〜９８重量％、カルボキシル基含有モノマー１〜１０重量％、及びその他の共重合可能なモノマー０〜１８重量％を共重合してなるアクリル酸エステル共重合体と、
（２）そのアクリル酸エステル共重合体１００重量部（固型分）に対して液状粘着付与樹脂１〜１５重量部と
を含むアクリル系粘着剤であり、前記第２剥離シートの剥離面に形成される第２剥離剤層の剥離剤がシリコーン系であること、
前記第２剥離シートの剥離力が２００〜７００ｍＮ／５０ｍｍであること、及び
前記軽剥離面の剥離力に対して、前記重剥離面が２〜３倍の剥離力を有することを特徴とする、前記両面粘着シート。 A first adhesive layer is provided on one surface of the substrate, a first release sheet is provided on the first adhesive layer, and a second adhesive layer is provided on the other surface of the substrate. The second release sheet is provided on the second adhesive layer, and the interface between the first adhesive layer and the first release sheet is a light release surface, and the second adhesive layer and the In the double-sided pressure-sensitive adhesive sheet whose interface with the second release sheet is a heavy release surface,
The pressure-sensitive adhesive forming the second pressure-sensitive adhesive layer is
(1) Acrylic ester copolymer obtained by copolymerizing 81 to 98% by weight of 2-ethylhexyl acrylate, 1 to 10% by weight of a carboxyl group-containing monomer, and 0 to 18% by weight of another copolymerizable monomer;
(2) An acrylic pressure-sensitive adhesive containing 1 to 15 parts by weight of a liquid tackifying resin with respect to 100 parts by weight (solid portion) of the acrylate copolymer and formed on the release surface of the second release sheet The release agent of the second release agent layer to be made is silicone-based ,
The peeling force of the second release sheet is 200 to 700 mN / 50 mm, and
The double-sided pressure-sensitive adhesive sheet , wherein the heavy peel surface has a peel force 2 to 3 times the peel force of the light release surface .
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