JP5545515B2 - Double-sided adhesive sheet for metal surface sticking, transparent conductive film laminate, touch panel device - Google Patents
Double-sided adhesive sheet for metal surface sticking, transparent conductive film laminate, touch panel device Download PDFInfo
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- JP5545515B2 JP5545515B2 JP2009081884A JP2009081884A JP5545515B2 JP 5545515 B2 JP5545515 B2 JP 5545515B2 JP 2009081884 A JP2009081884 A JP 2009081884A JP 2009081884 A JP2009081884 A JP 2009081884A JP 5545515 B2 JP5545515 B2 JP 5545515B2
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- Prior art keywords
- meth
- sensitive adhesive
- pressure
- adhesive sheet
- acrylic acid
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- 229910052751 metal Inorganic materials 0.000 title claims description 76
- 239000002184 metal Substances 0.000 title claims description 76
- 239000000853 adhesive Substances 0.000 title claims description 58
- 230000001070 adhesive effect Effects 0.000 title claims description 58
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 131
- 239000000178 monomer Substances 0.000 claims description 86
- 239000010410 layer Substances 0.000 claims description 59
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 claims description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims description 34
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 24
- -1 acrylic ester Chemical class 0.000 claims description 24
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 11
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 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
- 238000002834 transmittance Methods 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 5
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 125000005462 imide group Chemical group 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 54
- 229920006243 acrylic copolymer Polymers 0.000 description 41
- 230000007797 corrosion Effects 0.000 description 20
- 238000005260 corrosion Methods 0.000 description 20
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 229920001577 copolymer Polymers 0.000 description 17
- 239000003431 cross linking reagent Substances 0.000 description 17
- 239000012790 adhesive layer Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- 239000002253 acid Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
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- 229920002799 BoPET Polymers 0.000 description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 5
- 238000004080 punching Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 229920006267 polyester film Polymers 0.000 description 4
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- 238000006467 substitution reaction Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
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- 125000000524 functional group Chemical group 0.000 description 3
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- LMAUULKNZLEMGN-UHFFFAOYSA-N 1-ethyl-3,5-dimethylbenzene Chemical compound CCC1=CC(C)=CC(C)=C1 LMAUULKNZLEMGN-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
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- 125000004103 aminoalkyl group Chemical group 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- 229920005994 diacetyl cellulose Polymers 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- FKIRSCKRJJUCNI-UHFFFAOYSA-N ethyl 7-bromo-1h-indole-2-carboxylate Chemical compound C1=CC(Br)=C2NC(C(=O)OCC)=CC2=C1 FKIRSCKRJJUCNI-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 2
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920006284 nylon film Polymers 0.000 description 2
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 2
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
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- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
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- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
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- ZHKJHQBOAJQXQR-UHFFFAOYSA-N 1H-azirine Chemical compound N1C=C1 ZHKJHQBOAJQXQR-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- XFZOHDFQOOTHRH-UHFFFAOYSA-N 7-methyloctyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C(C)=C XFZOHDFQOOTHRH-UHFFFAOYSA-N 0.000 description 1
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
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- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
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Images
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、金属面に貼り付ける両面粘着シートおよび該両面粘着シートを使用した透明導電膜積層体、該透明導電膜積層体を使用したタッチパネル装置に関する。 The present invention relates to a double-sided pressure-sensitive adhesive sheet to be attached to a metal surface, a transparent conductive film laminate using the double-sided pressure-sensitive adhesive sheet, and a touch panel device using the transparent conductive film laminate.
近年、直感的に電子機器を操作するために、タッチセンサが搭載され始めている。タッチセンサには、主に入力時の圧力で検知する抵抗膜方式のタッチパネルと、入力時の人体からの静電気で入力箇所を検知する静電容量方式のタッチパネルが主に搭載されており、入力方法の多機能性から静電容量方式が主流となりつつある。静電容量方式のタッチパネルには、透明な樹脂フィルムやガラスに導電層が設けられた透明導電膜を積層した構成が使用されている。 In recent years, touch sensors have begun to be installed in order to intuitively operate electronic devices. The touch sensor is mainly equipped with a resistive touch panel that detects pressure based on the input pressure and a capacitive touch panel that detects the input location with static electricity from the human body during input. Capacitance method is becoming mainstream because of its multi-functionality. The capacitive touch panel uses a configuration in which a transparent conductive film in which a conductive layer is provided on a transparent resin film or glass is laminated.
透明導電膜フィルムは、透明導電膜の導電層の全面に両面粘着シートを貼り付けて積層され、透明導電膜積層体が形成される。透明導電膜フィルムの導電層は、例えば酸化インジウムスズなど高い透明性と導電性を有する金属を蒸着することで形成されており、両面粘着シートによる金属の酸化反応が起こり、導電機能の低下が起こる問題がある。このため、両面粘着シートには高い金属腐食防止性が要請されている。 The transparent conductive film is laminated by attaching a double-sided pressure-sensitive adhesive sheet to the entire surface of the conductive layer of the transparent conductive film to form a transparent conductive film laminate. The conductive layer of the transparent conductive film is formed by depositing a metal having high transparency and conductivity, such as indium tin oxide, and the metal oxidation reaction by the double-sided pressure-sensitive adhesive sheet occurs and the conductive function is lowered. There's a problem. For this reason, the double-sided pressure-sensitive adhesive sheet is required to have high metal corrosion prevention properties.
金属腐食防止性を有する両面粘着シートとしては、粘着剤層に含有する酸成分が金属の腐食の原因であることから、酸成分を含有しない両面粘着シート（例えば、特許文献１参照）が提案されている。当該両面粘着シートは、金属を腐食させる要因となる酸成分を含有しない粘着剤層により金属腐食防止性を有するものである。しかし、酸成分を含有しない粘着シートは、粘着剤層の凝集力が低く、高温下で剥がれが生じる問題があった。 As a double-sided pressure-sensitive adhesive sheet having metal corrosion prevention properties, a double-sided pressure-sensitive adhesive sheet that does not contain an acid component (see, for example, Patent Document 1) has been proposed because the acid component contained in the pressure-sensitive adhesive layer is a cause of metal corrosion. ing. The double-sided pressure-sensitive adhesive sheet has metal corrosion prevention properties due to a pressure-sensitive adhesive layer that does not contain an acid component that causes corrosion of the metal. However, the pressure-sensitive adhesive sheet containing no acid component has a problem that the cohesive force of the pressure-sensitive adhesive layer is low and peeling occurs at a high temperature.
また、酸成分を含有しつつ、当該酸成分による腐食を防止するために金属腐食防止剤を含有する両面粘着シートが開示されている（例えば特許文献２参照）。しかし、金属腐食防止剤は、それ自身が高温環境下で変質や変色を生じる場合があり、このような変質や変色により、両面粘着シートが着色し、視認性が悪化する問題があった。 Further, a double-sided pressure-sensitive adhesive sheet containing a metal corrosion inhibitor in order to prevent corrosion due to the acid component while containing an acid component has been disclosed (for example, see Patent Document 2). However, the metal corrosion inhibitor itself may be altered or discolored in a high temperature environment, and such a change or discoloration causes a problem that the double-sided PSA sheet is colored and visibility is deteriorated.
本発明が解決しようとする課題は、金属面に対して直接貼り合わせても金属面を腐食させず、また、粘着剤層の凝集力に優れ、高温環境下での剥がれや着色による視認性の低下が生じ難く、耐剥がれ性に優れる両面粘着シートを提供することにある。 The problem to be solved by the present invention is that the metal surface is not corroded even when directly bonded to the metal surface, and the cohesive strength of the pressure-sensitive adhesive layer is excellent, and the visibility due to peeling or coloring in a high-temperature environment is excellent. It is an object of the present invention to provide a double-sided pressure-sensitive adhesive sheet that hardly deteriorates and has excellent peeling resistance.
本発明においては、窒素原子を含有する単量体を使用したアクリル酸エステル共重合体を、他のアクリル酸エステル共重合体と併用した粘着剤層を使用することで、酸成分を含有しなくとも粘着剤の凝集力を好適に確保でき、金属面に対する腐食性が低く、高温下での剥がれや、着色による視認性の低下が生じ難い両面粘着シートを実現した。 In the present invention, an acrylic acid ester copolymer using a nitrogen atom-containing monomer is used together with another acrylic acid ester copolymer so that no acid component is contained. In both cases, a double-sided pressure-sensitive adhesive sheet that can suitably secure the cohesive strength of the pressure-sensitive adhesive, has low corrosiveness to the metal surface, and does not easily peel off at high temperatures or deteriorate visibility due to coloring is realized.
すなわち本発明は、金属面に貼り付ける粘着シートであって、（メタ）アクリル酸エステル単量体を主たる単量体成分として含有し、カルボキシル基含有単量体を含有しない（メタ）アクリル酸エステル共重合体（Ａ）と、（メタ）アクリル酸エステル単量体及び窒素原子含有共重合性単量体を単量体成分として含有し、カルボキシル基含有単量体を含有しない（メタ）アクリル酸エステル共重合体（Ｂ）とを含有するアクリル系粘着剤組成物からなる粘着剤層を有することを特徴とする金属面貼付用粘着シートを提供する。 That is, the present invention is a pressure-sensitive adhesive sheet to be attached to a metal surface, and contains a (meth) acrylate monomer as a main monomer component and does not contain a carboxyl group-containing monomer. Copolymer (A), (meth) acrylic acid ester monomer and nitrogen atom-containing copolymerizable monomer as monomer components, and (meth) acrylic acid not containing a carboxyl group-containing monomer There is provided a pressure-sensitive adhesive sheet for sticking a metal surface, which has a pressure-sensitive adhesive layer made of an acrylic pressure-sensitive adhesive composition containing an ester copolymer (B).
本発明の金属面貼付用両面粘着シートは、粘着剤層中に酸成分を含有しない（メタ）アクリル酸エステル共重合体と、特定の窒素含有（メタ）アクリル酸エステル共重合体が配合されているため、変色や変質を生じる金属腐食防止剤を含有しなくとも金属面の腐食を抑制でき、また好適な凝集力により高温環境下でも金属面からの剥がれが生じ難いため、好適な視認性と接着性を有する。 The double-sided pressure-sensitive adhesive sheet for sticking metal surfaces of the present invention comprises a (meth) acrylic acid ester copolymer containing no acid component and a specific nitrogen-containing (meth) acrylic acid ester copolymer in the pressure-sensitive adhesive layer. Therefore, even if it does not contain a metal corrosion inhibitor that causes discoloration or alteration, corrosion of the metal surface can be suppressed, and it is difficult to peel off from the metal surface even in a high temperature environment due to suitable cohesive force. Adhesive.
このため、本発明の金属面貼付用両面粘着シートは、好適な視認性や耐腐食性が求められる導電層を有する携帯電子機器や画像表示装置の部品固定用、特に静電容量方式のタッチパネル用途に好適に使用できる。 For this reason, the double-sided pressure-sensitive adhesive sheet for metal surface sticking of the present invention is used for fixing parts of portable electronic devices and image display devices having a conductive layer that requires suitable visibility and corrosion resistance, particularly for capacitive touch panels. Can be suitably used.
また、本発明の金属面貼付用両面粘着シートは、粘着剤層が好適な凝集力を有し、良好な打ち抜き加工性を有することから、各種部品形態に応じて精密な打ち抜き加工が求められる携帯電子機器や画像表示装置の部品固定用に好適に使用できる。 Moreover, the double-sided pressure-sensitive adhesive sheet for sticking a metal surface of the present invention has a cohesive force suitable for the pressure-sensitive adhesive layer and has a good punching processability. It can be suitably used for fixing components of electronic devices and image display devices.
本発明の金属面貼付用粘着シートは、（メタ）アクリル酸エステル単量体を主たる単量体成分として含有し、カルボキシル基含有単量体を含有しない（メタ）アクリル酸エステル共重合体（Ａ）と、（メタ）アクリル酸エステル単量体及び窒素原子含有共重合性単量体を単量体成分として含有し、カルボキシル基含有単量体を含有しない（メタ）アクリル酸エステル共重合体（Ｂ）とを含有するアクリル系粘着剤組成物からなる粘着剤層を有する粘着シートである。 The pressure-sensitive adhesive sheet for sticking a metal surface of the present invention contains a (meth) acrylic acid ester monomer as a main monomer component and does not contain a carboxyl group-containing monomer (meth) acrylic acid ester copolymer (A ), A (meth) acrylic acid ester monomer and a nitrogen atom-containing copolymerizable monomer as monomer components, and a (meth) acrylic acid ester copolymer containing no carboxyl group-containing monomer ( B) and a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer made of an acrylic pressure-sensitive adhesive composition.
［（メタ）アクリル酸エステル共重合体（Ａ）］
本発明に用いられる（メタ）アクリル酸エステル共重合体（Ａ）は、単量体成分として金属を腐食させやすいカルボキシル基含有単量体を含有せず、主たる単量体成分として（メタ）アクリル酸エステル単量体を使用した重合体である。また、（メタ）アクリル酸エステル共重合体（Ａ）は、窒素原子含有単量体を実質的に含有しない。（メタ）アクリル酸エステル単量体は、カルボキシル基を含有しないものであれば良いが、炭素数１〜１４の（メタ）アクリル酸エステル単量体を好ましく使用できる。当該炭素数１〜１４の（メタ）アクリル酸エステルを主成分とすることで、金属面を固定する際に必要な接着力、および光学特性を粘着剤層に好適に付与できる。
[(Meth) acrylic acid ester copolymer (A)]
The (meth) acrylic acid ester copolymer (A) used in the present invention does not contain a carboxyl group-containing monomer that easily corrodes metals as a monomer component, and (meth) acrylic as a main monomer component. It is a polymer using an acid ester monomer. The (meth) acrylic acid ester copolymer (A) does not substantially contain a nitrogen atom-containing monomer. Although the (meth) acrylic acid ester monomer should just be a thing which does not contain a carboxyl group, a C1-C14 (meth) acrylic acid ester monomer can be used preferably. By using the (meth) acrylic acid ester having 1 to 14 carbon atoms as a main component, the adhesive force and optical characteristics necessary for fixing the metal surface can be suitably imparted to the pressure-sensitive adhesive layer.
炭素数１〜１４の（メタ）アクリル酸エステル単量体としては、具体的には、メチルアクリレート、エチルアクリレート、ｎ−プロピルアクリレート、イソプロピルアクリレート、ｎ−ブチルアクリレート、ｓｅｃ−ブチルアクリレート、ｔ−ブチルアクリレート、ｎ−ヘキシルアクリレート、シクロヘキシルアクリレート、ｎ−オクチルアクリレート、イソオクチルアクリレート、２−エチルヘキシルアクリレート、イソノニルアクリレート、イソデシルアクリレート、ラウリルアクリレート、メチルメタクリレート、エチルメタクリレート、ｎ−プロピルメタクリレート、イソプロピルメタクリレート、ｎ−ブチルメタクリレート、ｓｅｃ−ブチルメタクリレート、ｔ−ブチルメタクリレート、ｎ−ヘキシルメタクリレート、シクロヘキシルメタクリレート、ｎ−オクチルメタクリレート、イソオクチルメタクリレート、２−エチルヘキシルメタクリレート、イソノニルメタクリレート、イソデシルメタクリレート、ラウリルメタクリレート等が挙げられる。 Specific examples of the (meth) acrylic acid ester monomer having 1 to 14 carbon atoms include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, and t-butyl. Acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, isodecyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n -Butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, cyclohex Methacrylate, n- octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, isononyl methacrylate, isodecyl methacrylate, lauryl methacrylate and the like.
そのなかでも、炭素数が１〜９のアルキル側鎖を有するアクリル酸アルキルエステル単量体又は炭素数が２〜９のアルキル側鎖を有するアクリル酸アルキルエステル単量体が好ましく、炭素数が４〜９のアルキル側鎖を有するアクリル酸アルキルエステル単量体がより好ましい。なかでもｎ−ブチルアクリレート、２−エチルヘキシルアクリレートが特に好ましい。当該範囲の炭素数のアルキル側鎖を有するアクリル酸アルキルエステルを使用することで、金属面に対して高い接着性を好適に付与できる。 Among them, an acrylic acid alkyl ester monomer having an alkyl side chain having 1 to 9 carbon atoms or an acrylic acid alkyl ester monomer having an alkyl side chain having 2 to 9 carbon atoms is preferable, and the number of carbon atoms is 4 More preferred are acrylic acid alkyl ester monomers having ˜9 alkyl side chains. Of these, n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferable. By using an alkyl acrylate ester having an alkyl side chain having a carbon number within the above range, high adhesiveness can be suitably imparted to the metal surface.
（メタ）アクリル酸エステル共重合体（Ａ）中の炭素数１〜１４の（メタ）アクリル酸エステル単量体の含有量は、９０〜９９質量％とすることが好ましく、９０〜９６質量％にすることがより好ましい。当該範囲のカルボキシル基含有（メタ）アクリル酸エステル共重合体（Ａ）中の上記炭素数１〜１４の（メタ）アクリル酸エステル単量体の含有量にすることで、粘着剤層に金属面を固定するために必要な接着性を好適に付与できる。 The content of the (meth) acrylic acid ester monomer having 1 to 14 carbon atoms in the (meth) acrylic acid ester copolymer (A) is preferably 90 to 99% by mass, and 90 to 96% by mass. More preferably. By making content of the said C1-C14 (meth) acrylic acid ester monomer in the carboxyl group-containing (meth) acrylic acid ester copolymer (A) of the said range, it is a metal surface to an adhesive layer. Adhesiveness necessary for fixing the film can be suitably imparted.
また、架橋剤と好適に架橋反応させることにより粘着剤層の凝集力を高くするために、架橋剤と反応する官能基を有するビニルモノマーを使用することも好ましい。架橋剤と反応する官能基を有するビニルモノマーとしては、特に限定されないが、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、４−ヒドロキシブチルアクリレート等の水酸基含有ビニルモノマーが挙げられる。中でも、４−ヒドロキシブチルアクリレートが好ましい。官能基を有するビニルモノマーの使用量はアクリル共重合体を構成するモノマー成分中の０．１質量％〜１０質量％であることが好ましく、１．０〜３．０質量％であることが特に好ましい。 It is also preferable to use a vinyl monomer having a functional group that reacts with the crosslinking agent in order to increase the cohesive force of the pressure-sensitive adhesive layer by suitably crosslinking with the crosslinking agent. Although it does not specifically limit as a vinyl monomer which has a functional group which reacts with a crosslinking agent, Hydroxyl group-containing vinyl monomers, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, are mentioned. Of these, 4-hydroxybutyl acrylate is preferable. It is preferable that the usage-amount of the vinyl monomer which has a functional group is 0.1 mass%-10 mass% in the monomer component which comprises an acrylic copolymer, and it is especially 1.0-3.0 mass%. preferable.
当該（メタ）アクリル酸エステル共重合体（Ａ）の重量平均分子量Ｍｗは７０万〜１５０万であることが好ましく、８０万〜１４５万がより好ましく、８５万〜１４０万がさらに好ましい。当該（メタ）アクリル酸エステル共重合体（Ａ）の重量平均分子量Ｍｗが上記範囲内だと、透明導電膜を固定するために必要な凝集力を好適に付与できる。 The weight average molecular weight Mw of the (meth) acrylic acid ester copolymer (A) is preferably 700,000 to 1,500,000, more preferably 800,000 to 1,450,000, and further preferably 850,000 to 1,400,000. When the weight average molecular weight Mw of the (meth) acrylic acid ester copolymer (A) is within the above range, a cohesive force necessary for fixing the transparent conductive film can be suitably imparted.
なお、本発明では、当該（メタ）アクリル酸エステル共重合体（Ａ）の重量平均分子量Ｍｗは、ゲルパーミエーションクロマトグラフ（ＧＰＣ）により測定することができる。より具体的には、ＧＰＣ測定装置として、東ソー株式会社製「ＳＣ８０２０」を用いて、ポリスチレン換算値により、次のＧＰＣ測定条件で測定して求めることができる。
（ＧＰＣの測定条件）
・サンプル濃度：０．５重量％（テトラヒドロフラン溶液）
・サンプル注入量：１００μＬ
・溶離液：テトラヒドロフラン（ＴＨＦ）
・流速：１．０ｍＬ／ｍｉｎ
・カラム温度（測定温度）：４０℃
・カラム：東ソー株式会社製「ＴＳＫｇｅｌ ＧＭＨＨＲ−Ｈ」
・検出器：示差屈折
In the present invention, the weight average molecular weight Mw of the (meth) acrylic acid ester copolymer (A) can be measured by gel permeation chromatography (GPC). More specifically, as a GPC measurement device, “SC8020” manufactured by Tosoh Corporation can be used to measure and obtain the following GPC measurement conditions based on polystyrene conversion values.
(GPC measurement conditions)
Sample concentration: 0.5% by weight (tetrahydrofuran solution)
Sample injection volume: 100 μL
・ Eluent: Tetrahydrofuran (THF)
・ Flow rate: 1.0 mL / min
Column temperature (measurement temperature): 40 ° C
Column: “TSKgel GMHHR-H” manufactured by Tosoh Corporation
・ Detector: Differential refraction
［窒素原子含有（メタ）アクリル酸エステル共重合体（Ｂ）］
本発明に用いられる窒素原子含有（メタ）アクリル酸エステル共重合体（Ｂ）は、単量体成分として金属を腐食させやすいカルボキシル基含有単量体を含有せず、単量体成分として（メタ）アクリル酸エステル単量体と窒素原子含有共重合性単量体を使用した重合体である。（メタ）アクリル酸エステル単量体は、カルボキシル基を含有しないものであれば良いが、炭素数１〜９の（メタ）アクリル酸エステル単量体であることが好ましい。当該炭素数１〜９の（メタ）アクリル酸エステルを主成分とすることで、金属面を固定するために必要な凝集力と接着性を付与できる。また、窒素原子含有共重合性単量体を共重合することで、金属面に対する接着性を高めると共に、（メタ）アクリル酸エステル共重合体（Ａ）と架橋剤との反応を促進させることができ、粘着剤組成物に金属面を固定するために必要な凝集力を好適に付与できる。
[Nitrogen atom-containing (meth) acrylic acid ester copolymer (B)]
The nitrogen atom-containing (meth) acrylic acid ester copolymer (B) used in the present invention does not contain a carboxyl group-containing monomer that easily corrodes metals as a monomer component. ) A polymer using an acrylate monomer and a nitrogen atom-containing copolymerizable monomer. Although the (meth) acrylic acid ester monomer should just be a thing which does not contain a carboxyl group, it is preferable that it is a C1-C9 (meth) acrylic acid ester monomer. By using the (meth) acrylic acid ester having 1 to 9 carbon atoms as a main component, cohesive force and adhesiveness necessary for fixing the metal surface can be imparted. In addition, by copolymerizing the nitrogen atom-containing copolymerizable monomer, it is possible to enhance the adhesion to the metal surface and promote the reaction between the (meth) acrylic acid ester copolymer (A) and the crosslinking agent. The cohesive force necessary for fixing the metal surface to the pressure-sensitive adhesive composition can be suitably imparted.
炭素数１〜９の（メタ）アクリル酸エステル単量体としては、具体的には、メチルアクリレート、エチルアクリレート、ｎ−プロピルアクリレート、イソプロピルアクリレート、ｎ−ブチルアクリレート、ｓｅｃ−ブチルアクリレート、ｔ−ブチルアクリレート、ｎ−ヘキシルアクリレート、シクロヘキシルアクリレート、ｎ−オクチルアクリレート、イソオクチルアクリレート、２−エチルヘキシルアクリレート、メチルメタクリレート、エチルメタクリレート、ｎ−プロピルメタクリレート、イソプロピルメタクリレート、ｎ−ブチルメタクリレート、ｓｅｃ−ブチルメタクリレート、ｔ−ブチルメタクリレート、ｎ−ヘキシルメタクリレート、シクロヘキシルメタクリレート、ｎ−オクチルメタクリレート、イソオクチルメタクリレート、２−エチルヘキシルメタクリレート等が挙げられる。 Specific examples of the (meth) acrylic acid ester monomer having 1 to 9 carbon atoms include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, and t-butyl. Acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t- Butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate , 2-ethylhexyl methacrylate and the like.
その中でも、炭素数が１〜６のアルキル側鎖を有する（メタ）アクリル酸アルキルエステル単量体が好ましい。なかでもメチルメタクリレート、シクロヘキシルアクリレート、シクロヘキシルメタクリレートが特に好ましい。当該範囲の炭素数のアルキル側鎖を有する（メタ）アクリル酸アルキルエステル単量体を使用することで、金属面を固定するために必要な凝集力を好適に付与できる。 Among these, a (meth) acrylic acid alkyl ester monomer having an alkyl side chain having 1 to 6 carbon atoms is preferable. Of these, methyl methacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate are particularly preferable. By using a (meth) acrylic acid alkyl ester monomer having an alkyl side chain with a carbon number within the range, the cohesive force necessary for fixing the metal surface can be suitably imparted.
窒素原子含有（メタ）アクリル酸エステル共重合体（Ｂ）を構成する単量体成分中の炭素数１〜８の（メタ）アクリル酸エステル単量体の含有量は、７０〜９９質量％とすることが好ましく、９０〜９８質量％とすることがより好ましい。当該範囲内の窒素原子含有（メタ）アクリル酸エステル共重合体（Ｂ）中の上記炭素数１〜８の（メタ）アクリル酸エステル単量体の含有量にすることで、粘着剤層に金属面を固定するために必要な接着性および凝集力を好適に付与できる。 The content of the (meth) acrylic acid ester monomer having 1 to 8 carbon atoms in the monomer component constituting the nitrogen atom-containing (meth) acrylic acid ester copolymer (B) is 70 to 99% by mass. It is preferable to make it 90 to 98% by mass. By setting the content of the (meth) acrylic acid ester monomer having 1 to 8 carbon atoms in the nitrogen atom-containing (meth) acrylic acid ester copolymer (B) within the range, the pressure-sensitive adhesive layer is made of metal. Adhesiveness and cohesive force necessary for fixing the surface can be suitably imparted.
窒素原子含有共重合性単量体としては、窒素原子を含有し、上記炭素数１〜８の（メタ）アクリル酸エステル単量体との共重合が可能であればよいが、例えば、アミノ基含有単量体、アミド基含有単量体、窒素系複素環含有単量体、シアノ基含有単量体、イミド基含有単量体等が挙げられる。これら単量体としては、例えば、アミノ基含有単量体としては、（メタ）アクリル酸アミノメチル、（メタ）アクリル酸アミノエチル、（メタ）アクリル酸アミノプロピル、（メタ）アクリル酸アミノイソプロピル等の（メタ）アクリル酸アミノアルキルや、（メタ）アクリル酸（Ｎ−置換）アミノアルキルなどが挙げられる。前記（メタ）アクリル酸（Ｎ−置換）アミノアルキルとしては、例えば、（メタ）アクリル酸Ｎ−（ｔ−ブチル）アミノエチル等の（メタ）アクリル酸Ｎ−アルキルアミノアルキル；（メタ）アクリル酸Ｎ，Ｎ−ジメチルアミノエチル、（メタ）アクリル酸Ｎ，Ｎ−ジメチルアミノプロピル等の（メタ）アクリル酸Ｎ，Ｎ−ジアルキルアミノアルキルなどが挙げられる。 The nitrogen atom-containing copolymerizable monomer may contain a nitrogen atom and can be copolymerized with the (meth) acrylic acid ester monomer having 1 to 8 carbon atoms. For example, an amino group Examples thereof include a monomer containing monomer, an amide group-containing monomer, a nitrogen-based heterocyclic ring-containing monomer, a cyano group-containing monomer, and an imide group-containing monomer. Examples of these monomers include amino group-containing monomers such as aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, and aminoisopropyl (meth) acrylate. (Meth) acrylic acid aminoalkyl and (meth) acrylic acid (N-substituted) aminoalkyl. Examples of the (meth) acrylic acid (N-substituted) aminoalkyl include (meth) acrylic acid N-alkylaminoalkyl such as N- (t-butyl) aminoethyl (meth) acrylate; (meth) acrylic acid Examples include N, N-dialkylaminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl and N, N-dimethylaminopropyl (meth) acrylate.
その中でも、アミノ基含有単量体、アミド基含有単量体が好ましい。なかでもアミノ基含有単量体が特に好ましい。当該窒素含有共重合性単量体を使用することで、金属面に対する接着性を高めると共に、上記共重合体（Ａ）と架橋剤との反応を促進させることで、粘着剤組成物に金属面を固定するために必要な凝集力が好適に付与できる。 Of these, amino group-containing monomers and amide group-containing monomers are preferred. Of these, amino group-containing monomers are particularly preferred. By using the nitrogen-containing copolymerizable monomer, the adhesion to the metal surface is enhanced, and by promoting the reaction between the copolymer (A) and the crosslinking agent, the pressure-sensitive adhesive composition has a metal surface. The cohesive force required to fix the can be suitably imparted.
窒素原子含有（メタ）アクリル酸エステル共重合体（Ｂ）を構成する単量体成分中の窒素原子含有共重合性単量体の含有量は、当該共重合体の総量に対し、１〜３０重量％とすることが好ましく、１〜２０質量％にすることがより好ましい。当該範囲の窒素原子含有（メタ）アクリル酸エステル共重合体（Ｂ）中の上記窒素原子含有共重合性単量体の含有量にすることで、金属面に対する接着性を高めると共に、（メタ）アクリル酸エステル共重合体（Ａ）と架橋剤との反応を促進させることで、粘着剤組成物に金属面を固定するために必要な凝集力を好適に付与できる。 Content of the nitrogen atom containing copolymerizable monomer in the monomer component which comprises a nitrogen atom containing (meth) acrylic acid ester copolymer (B) is 1-30 with respect to the total amount of the said copolymer. It is preferable to set it as weight%, and it is more preferable to set it as 1-20 mass%. By making the content of the nitrogen atom-containing copolymerizable monomer in the nitrogen atom-containing (meth) acrylic acid ester copolymer (B) in the above range, the adhesion to the metal surface is improved, and (meth) By promoting the reaction between the acrylic ester copolymer (A) and the crosslinking agent, the cohesive force necessary to fix the metal surface to the pressure-sensitive adhesive composition can be suitably imparted.
当該窒素原子含有（メタ）アクリル酸エステル共重合体（Ｂ）の重量平均分子量Ｍｗは５０００〜１０万であることが好ましく、５０００〜８万がより好ましく、５０００〜５万がさらに好ましい。当該窒素原子含有（メタ）アクリル酸エステル共重合体（Ｂ）の重量平均分子量Ｍｗが上記範囲内だと、金属面を固定するために必要な接着力を好適に付与できる。 The weight average molecular weight Mw of the nitrogen atom-containing (meth) acrylic acid ester copolymer (B) is preferably 5,000 to 100,000, more preferably 5,000 to 80,000, and further preferably 5,000 to 50,000. When the weight average molecular weight Mw of the nitrogen atom-containing (meth) acrylic acid ester copolymer (B) is within the above range, an adhesive force necessary for fixing the metal surface can be suitably imparted.
［粘着剤組成物］
本発明の金属面貼付用両面粘着シートの粘着剤層を形成する粘着剤組成物は、カルボキシル基を含有しない（メタ）アクリル酸エステル共重合体（Ａ）と、カルボキシル基を含有しない窒素原子含有（メタ）アクリル酸エステル共重合体（Ｂ）とが配合されることで、金属面の腐食を防止でき、さらに酸成分を含有しなくとも粘着剤層の凝集力を好適にでき、金属面に対して優れた接着性能を当該両面粘着シートの粘着剤層に付与できる。また、高温下での変色の懸念がある金属腐食防止剤を使用する必要がないため高温環境下でも着色による視認性の低下が生じない。
[Adhesive composition]
The pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer of the double-sided pressure-sensitive adhesive sheet for metal surface application of the present invention contains a (meth) acrylic acid ester copolymer (A) that does not contain a carboxyl group and a nitrogen atom that does not contain a carboxyl group. By blending with the (meth) acrylic acid ester copolymer (B), the corrosion of the metal surface can be prevented, and the cohesive force of the pressure-sensitive adhesive layer can be suitably adjusted without containing an acid component. On the other hand, the outstanding adhesive performance can be provided to the adhesive layer of the said double-sided adhesive sheet. Further, since it is not necessary to use a metal corrosion inhibitor that may cause discoloration at a high temperature, the visibility due to coloring does not deteriorate even in a high temperature environment.
また、上記（メタ）アクリル酸エステル共重合体（Ａ）１００質量％に対して、窒素原子含有（メタ）アクリル酸エステル共重合体（Ｂ）は１〜５０質量％が好ましく、５〜３０質量％がより好ましく、５〜２０質量％がさらに好ましい。上記範囲内で共重合体（Ａ）と（Ｂ）とが配合されることで、当該両面粘着シートに優れた凝集力と光学特性を好適に付与できる。 Moreover, 1-50 mass% is preferable with respect to 100 mass% of said (meth) acrylic acid ester copolymers (A), and nitrogen atom containing (meth) acrylic acid ester copolymer (B), 5-30 masses. % Is more preferable, and 5 to 20% by mass is more preferable. By blending the copolymers (A) and (B) within the above range, excellent cohesive force and optical properties can be suitably imparted to the double-sided PSA sheet.
また、上記（メタ）アクリル酸エステル共重合体（Ａ）と窒素原子含有（メタ）アクリル酸エステル共重合体共重合体（Ｂ）の配合に際しては、各々の共重合体に使用する（メタ）アクリル酸エステル単量体の一種以上を同一とした共重合体を配合することが好ましい。配合する両共重合体の単量体成分として一種以上の同一の単量体を使用することで、両共重合体の相溶性を向上させることができ、粘着剤層中での光の拡散を大きく抑制できヘイズが低く高い光学特性を有する粘着剤層とすることができる。 In addition, when the (meth) acrylic acid ester copolymer (A) and the nitrogen atom-containing (meth) acrylic acid ester copolymer (B) are blended, they are used for each copolymer (meth). It is preferable to blend a copolymer in which one or more acrylate monomers are the same. By using one or more identical monomers as monomer components of both copolymers to be blended, the compatibility of both copolymers can be improved, and light diffusion in the adhesive layer can be improved. The pressure-sensitive adhesive layer can be largely suppressed and has low haze and high optical properties.
上記粘着剤組成物中には、上記共重合体（Ａ）及び（Ｂ）以外の成分として、粘着剤層の凝集力を上げるために、架橋剤を含有することが好ましい。 In the said adhesive composition, in order to raise the cohesion force of an adhesive layer as components other than the said copolymer (A) and (B), it is preferable to contain a crosslinking agent.
使用する架橋剤としては、イソシアネート系架橋剤、エポキシ系架橋剤、キレート系架橋剤、アジリン系架橋剤、多官能アクリレート系等が挙げられる。その中でも、（メタ）アクリル系共重合体の（Ａ）成分との反応性に富むイソシアネート系架橋剤が好ましい。 Examples of the crosslinking agent used include isocyanate crosslinking agents, epoxy crosslinking agents, chelating crosslinking agents, azirine crosslinking agents, and polyfunctional acrylates. Among these, an isocyanate-based crosslinking agent rich in reactivity with the component (A) of the (meth) acrylic copolymer is preferable.
当該両面粘着シートの粘着剤層に添加する架橋剤の配合量は、０．１〜５質量部が好ましく、０．１〜３質量部がより好ましく、０．１〜１．５質量部がさらに好ましい。当該範囲の架橋剤の含有量にすることで、粘着剤層のゲル分率を好適な範囲に調整しやすい。 0.1-5 mass parts is preferable, as for the compounding quantity of the crosslinking agent added to the adhesive layer of the said double-sided adhesive sheet, 0.1-3 mass parts is more preferable, and 0.1-1.5 mass parts is further preferable. By setting the content of the crosslinking agent in this range, it is easy to adjust the gel fraction of the pressure-sensitive adhesive layer to a suitable range.
［金属面貼付用両面粘着シート］
本発明の金属面貼付用両面粘着シートは、上記粘着剤組成物からなる粘着剤層を有することで、金属面と好適に接着でき、かつ金属面の腐食が生じ難い。
[Double-sided pressure-sensitive adhesive sheet for metal surfaces]
The double-sided pressure-sensitive adhesive sheet for sticking a metal surface of the present invention has a pressure-sensitive adhesive layer made of the above-mentioned pressure-sensitive adhesive composition, so that it can be suitably bonded to the metal surface, and corrosion of the metal surface hardly occurs.
本発明の金属面貼付用両面粘着シートは、基材を有するものであっても、基材を有さず粘着剤層のみからなる両面粘着シートであってもよい。また、粘着剤層は単一層からなるものであっても複数層が積層されていてもよい。なかでも、透明性の確保や、形状追従性の観点からは、基材を有さず、粘着剤層のみからなる両面粘着シートであることが好ましい。 The double-sided pressure-sensitive adhesive sheet for sticking a metal surface of the present invention may be a double-sided pressure-sensitive adhesive sheet having only a pressure-sensitive adhesive layer without having a base material. Moreover, even if the adhesive layer consists of a single layer, multiple layers may be laminated | stacked. Especially, it is preferable that it is a double-sided adhesive sheet which does not have a base material but consists only of an adhesive layer from a viewpoint of ensuring transparency and shape followability.
本発明の金属面貼付用両面粘着シートが、基材を有する場合には、当該基材として透明基材を使用できる。当該透明基材としては、例えば、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、ポリエチレンナフタレート、ポリエチレンフィルム、ポリプロピレンフィルム、セロファン、ジアセチルセルロースフィルム、トリアセチルセルロースフィルム、アセチルセルロースブチレートフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム、ポリビニルアルコールフィルム、エチレン−酢酸ビニル共重合体フィルム、ポリスチレンフィルム、ポリカーボネートフィルム、ポリメチルペンテンフィルム、ポリスルホンフィルム、ポリエーテルエーテルケトンフィルム、ポリエーテルスルホンフィルム、ポリエーテルイミドフィルム、ポリイミドフィルム、フッソ樹脂フィルム、ナイロンフィルム、アクリル樹脂フィルム等を挙げることができる。なかでもアクリル樹脂フィルムが好ましい。上記基材を使用すると、例えば、アクリル樹脂フィルムの屈折率が１．４５〜１．４９に対して、粘着剤層の屈折率が１．４７程度であるため、基材と粘着剤層との間での屈折率の差が低く、粘着剤層と透明基材との間での反射ロスが抑制しやすい。 When the double-sided pressure-sensitive adhesive sheet for sticking a metal surface of the present invention has a substrate, a transparent substrate can be used as the substrate. As the transparent substrate, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, polyvinyl chloride Vinylidene film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyetherimide film, polyimide film, fluorine Resin film, nylon film, acrylic resin film, etc. Rukoto can. Of these, an acrylic resin film is preferable. When the base material is used, for example, the refractive index of the acrylic resin film is 1.45 to 1.49, and the refractive index of the pressure-sensitive adhesive layer is about 1.47. The difference in refractive index between the two is low, and reflection loss between the pressure-sensitive adhesive layer and the transparent substrate is easily suppressed.
また、フィルム基材には、粘着剤層との密着性を向上させる目的で、サンドブラスト法や溶剤処理法などによる表面の凹凸化処理、あるいはコロナ放電処理、クロム酸処理、火炎処理、熱風処理、オゾン・紫外線照射処理などの表面の酸化処理などの表面処理を施すことができる。 In addition, for the purpose of improving the adhesiveness with the pressure-sensitive adhesive layer, the film substrate is subjected to surface unevenness treatment by sandblasting method or solvent treatment method, or corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, Surface treatment such as surface oxidation treatment such as ozone / ultraviolet irradiation treatment can be performed.
本発明の金属面貼付用両面粘着シートの粘着剤層は、トルエン中に２４時間浸漬した際の下記式で表されるゲル分率が、３０〜９０％であることが好ましく、４０〜８０％であるのがより好ましく、５０〜８０％が最も好ましい。粘着剤層のゲル分率が上記の範囲内だと、透明導電膜を固定において経時での剥がれを抑制しやすく、また、打ち抜き加工時に加工端面からの糸引きなどを抑制しやすい。
ゲル分率（％）＝［（両面粘着シートのトルエン浸漬後質量）／（両面粘着シートのトルエン浸漬前質量）］×１００
The pressure-sensitive adhesive layer of the double-sided pressure-sensitive adhesive sheet for sticking metal surfaces of the present invention preferably has a gel fraction represented by the following formula of 30 to 90% when immersed in toluene for 24 hours, and 40 to 80%. Is more preferable, and 50 to 80% is most preferable. When the gel fraction of the pressure-sensitive adhesive layer is within the above range, it is easy to suppress peeling over time in fixing the transparent conductive film, and it is easy to suppress stringing from the processed end face during punching.
Gel fraction (%) = [(mass after immersion of toluene in double-sided PSA sheet) / (mass before immersion of toluene in double-sided PSA sheet)] × 100
本発明の金属面貼付用両面粘着シートは、透明導電膜の透明性を阻害しないよう、６０℃、９０％ＲＨ条件下に１００時間静置直後の全光線透過率が９０％以上、ヘイズが２．０％以下であることが好ましい。上記範囲内だと、当該両面粘着シートを使用されたタッチパネル装置搭載ディスプレイが高温高湿条件でも高鮮明が保たれやすい。全光線透過率及びヘイズを上記範囲内にするためには、上記共重合体（Ａ）１００質量％に対する上記共重合体（Ｂ）の配合量を１〜５０質量％にすることで達成しやすい。 The double-sided pressure-sensitive adhesive sheet for sticking a metal surface of the present invention has a total light transmittance of 90% or more immediately after standing for 100 hours at 60 ° C. and 90% RH so that the transparency of the transparent conductive film is not impaired, and a haze of 2 It is preferably 0.0% or less. If it is within the above range, the display equipped with the touch panel device using the double-sided pressure-sensitive adhesive sheet can easily maintain high definition even under high temperature and high humidity conditions. In order to make the total light transmittance and haze within the above ranges, it is easy to achieve by setting the amount of the copolymer (B) to 1 to 50% by mass relative to 100% by mass of the copolymer (A). .
本発明の金属面貼付用両面粘着シートの温度２３℃、相対湿度５０％ＲＨの環境下で、酸化インジウムスズ膜に対し、２ｋｇローラーを使用して圧着回数一往復で圧着し、１時間静置した後の３００ｍｍ／ｍｉｎでの１８０°剥離接着力は、酸化インジウムスズ膜に対してそれぞれ５〜１５Ｎ／２０ｍｍであることが好ましい。上記範囲内だと、透明導電膜の固定において端面からの剥がれを抑制しやすく、また、製造工程での貼り合わせ不良品において両面粘着シートの剥離が可能となる。 The pressure-sensitive adhesive double-sided pressure-sensitive adhesive sheet of the present invention is bonded to an indium tin oxide film with a 2 kg roller in a temperature of 23 ° C. and a relative humidity of 50% RH with one reciprocation for one hour. The 180 ° peel adhesion at 300 mm / min after placement is preferably 5 to 15 N / 20 mm for the indium tin oxide film. Within the above range, it is easy to suppress peeling from the end face in fixing the transparent conductive film, and the double-sided pressure-sensitive adhesive sheet can be peeled off in a poorly bonded product in the manufacturing process.
本発明の金属面貼付用両面粘着シートの粘着剤層のガラス転移温度（Ｔｇ）が−４０〜１０℃が好ましく、−３０〜５℃がより好ましく、−２５〜０℃がさらに好ましい。粘着剤層のＴｇが上記範囲内だと、常温下で優れた接着性を付与しやすく、また、打ち抜き加工時に粘着剤層からの糸引きが発生しづらく、歩留まり向上に貢献しやすい。 The glass transition temperature (Tg) of the pressure-sensitive adhesive layer of the double-sided pressure-sensitive adhesive sheet for metal surface sticking of the present invention is preferably −40 to 10 ° C., more preferably −30 to 5 ° C., and further preferably −25 to 0 ° C. When the Tg of the pressure-sensitive adhesive layer is within the above range, excellent adhesiveness is easily imparted at room temperature, and stringing from the pressure-sensitive adhesive layer is difficult to occur at the time of punching, which easily contributes to yield improvement.
本発明の金属面貼付用両面粘着シートの厚みは、使用する態様により適宜選択すればよいが、５〜２００μｍであることが好ましい。なかでも、平滑面に接着する場合には、１０〜１００μｍに調整することで、タッチパネル装置を薄型化しやすい。また、段差や凹凸を有する面に貼り付ける場合には、粘着剤層の厚さを２０μｍ以上とすることが好ましく、２５〜１５０μｍとすることが特に好ましい。 The thickness of the double-sided pressure-sensitive adhesive sheet for sticking a metal surface of the present invention may be appropriately selected depending on the mode of use, but is preferably 5 to 200 μm. Especially, when adhering to a smooth surface, it is easy to make a touch panel apparatus thin by adjusting to 10-100 micrometers. Moreover, when sticking on the surface which has a level | step difference or an unevenness | corrugation, it is preferable that the thickness of an adhesive layer shall be 20 micrometers or more, and it is especially preferable to set it as 25-150 micrometers.
本発明の金属面貼付用粘着シートは、一般的に使用されている方法で作成できる。例えば、フィルム基材または離型シート上に粘着剤層を形成して製造することができる。具体的には、粘着剤の組成物を基材フィルムに直接塗布し乾燥または硬化・重合するか、或いは、いったん離型シート上に塗布し、乾燥または硬化・重合し、粘着剤層を形成後、同様にして離型シート上に作成した粘着剤層又は基材フィルムに貼り合わせる方法などにより製造できる。 The pressure-sensitive adhesive sheet for attaching a metal surface of the present invention can be prepared by a generally used method. For example, it can be produced by forming an adhesive layer on a film substrate or a release sheet. Specifically, the adhesive composition is directly applied to the base film and dried or cured / polymerized, or once applied on the release sheet and dried / cured / polymerized to form an adhesive layer. Similarly, it can be produced by a method of bonding to an adhesive layer or a base film prepared on a release sheet.
本発明の金属面貼付用粘着シートの打ちぬき加工後において、剥離フィルムの端面への粘着剤層の付着がないことが好ましい。粘着剤層が剥離フィルム端面に付着しないと、加工時での歩留まりが向上しやすい。 It is preferable that the pressure-sensitive adhesive layer does not adhere to the end face of the release film after the punching process of the pressure-sensitive adhesive sheet for attaching a metal surface of the present invention. If the pressure-sensitive adhesive layer does not adhere to the end face of the release film, the yield during processing tends to be improved.
両面粘着シートの粘着剤層の剥離フィルム端面への付着を防ぐためには、粘着剤層の凝集力、接着性等を最適な範囲に調整することで達成しやすい。具体的な方法としては、粘着剤層へカルボキシル基含有単量体の使用、粘着剤層のゲル分率の上記範囲内への調整等が挙げられる。なかでも、打ち抜き加工に必要な凝集力の付与と透明導電膜を固定するために必要な接着性の付与の両立がしやすい粘着剤層へカルボキシル基含有単量体の使用が好ましい。 In order to prevent adhesion of the pressure-sensitive adhesive layer of the double-sided pressure-sensitive adhesive sheet to the end face of the release film, it is easy to achieve by adjusting the cohesive force, adhesiveness and the like of the pressure-sensitive adhesive layer to the optimum ranges. Specific examples of the method include use of a carboxyl group-containing monomer in the pressure-sensitive adhesive layer, adjustment of the gel fraction of the pressure-sensitive adhesive layer to the above range, and the like. Especially, it is preferable to use a carboxyl group-containing monomer for the pressure-sensitive adhesive layer that can easily provide cohesive force necessary for punching and adhesion necessary for fixing the transparent conductive film.
［透明導電膜積層体］
本発明の透明導電膜積層体は、透明導電膜の導電層に対して上記金属面貼付用両面粘着シートの粘着剤層が直接貼り合わされて少なくとも２層以上の積層体が形成されている積層体であり、例えば、基材上に導電層が設けられた透明導電膜と上記金属面貼付用両面粘着シートからなる積層体（図１）が挙げられる。また、導電層の反対面にハードコート層が設けられた積層体（図２）や、上記金属面貼付用両面粘着シートの両面にハードコート層を有する透明導電膜が設けられた積層体（図３）も挙げられる。積層体の傷つき防止のため、ハードコート層が設けられた積層体（図２、３）が好ましい。
[Transparent conductive film laminate]
The transparent conductive film laminate of the present invention is a laminate in which the adhesive layer of the double-sided pressure-sensitive adhesive sheet for metal surface bonding is directly bonded to the conductive layer of the transparent conductive film to form a laminate of at least two layers. For example, a laminate (FIG. 1) composed of a transparent conductive film provided with a conductive layer on a base material and the above double-sided pressure-sensitive adhesive sheet for attaching a metal surface can be mentioned. Moreover, the laminated body (FIG. 2) in which the hard-coat layer was provided in the opposite surface of the conductive layer, and the laminated body (FIG. 2) in which the transparent conductive film which has a hard-coat layer was provided in both surfaces of the said double-sided adhesive sheet for metal surface sticking. 3) is also included. In order to prevent damage to the laminate, a laminate (FIGS. 2 and 3) provided with a hard coat layer is preferable.
本発明に使用する透明導電膜は、少なくとも片面の表層に導電層を有するものであればよく、透明基材の表層に導電物質が蒸着やコーティングにより設けられた透明導電膜を好適に使用できる。なかでも導電物質が蒸着により形成された導電層を有する透明導電膜が、製造が容易であるため好ましい。 The transparent conductive film used for this invention should just have a conductive layer in the surface layer of at least one side, and can use the transparent conductive film by which the electrically conductive substance was provided in the surface layer of the transparent base material by vapor deposition or coating. Among these, a transparent conductive film having a conductive layer in which a conductive material is formed by vapor deposition is preferable because it is easy to manufacture.
透明導電膜の導電層において蒸着やコーティングされる導電物質は、特に限定されないが、具体的には、酸化インジウムスズ、酸化インジウム、酸化スズ、酸化亜鉛、酸化カドミウム、酸化ガリウム、酸化チタンなどが挙げられる。なかでも特に、透明性、導電性に優れる酸化インジウムスズが好ましい。 The conductive material deposited or coated in the conductive layer of the transparent conductive film is not particularly limited, and specific examples include indium tin oxide, indium oxide, tin oxide, zinc oxide, cadmium oxide, gallium oxide, and titanium oxide. It is done. In particular, indium tin oxide having excellent transparency and conductivity is preferable.
透明導電膜において、導電物質が蒸着またはコーティングされる基材としては、特に限定されるものではないが、ガラス、樹脂フィルムなどが挙げられる。 In the transparent conductive film, the substrate on which the conductive material is deposited or coated is not particularly limited, and examples thereof include glass and resin films.
透明導電物質が蒸着される樹脂フィルムとしては、例えば、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、ポリエチレンナフタレート、ポリエチレンフィルム、ポリプロピレンフィルム、セロファン、ジアセチルセルロースフィルム、トリアセチルセルロースフィルム、アセチルセルロースブチレートフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム、ポリビニルアルコールフィルム、エチレン−酢酸ビニル共重合体フィルム、ポリスチレンフィルム、ポリカーボネートフィルム、ポリメチルペンテンフィルム、ポリスルホンフィルム、ポリエーテルエーテルケトンフィルム、ポリエーテルスルホンフィルム、ポリエーテルイミドフィルム、ポリイミドフィルム、フッソ樹脂フィルム、ナイロンフィルム、アクリル樹脂フィルム等を挙げることができる。なかでも、透明性、耐久性に優れたポリエチレンテレフタレートが好ましい。 Examples of the resin film on which the transparent conductive material is deposited include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polychlorinated Vinyl film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether ether ketone film, polyether sulfone film, polyetherimide film , Polyimide film, fluorine resin film, nylon film, It can be exemplified Lil resin film. Of these, polyethylene terephthalate having excellent transparency and durability is preferable.
透明導電膜の透明性は、全光線透過率が８０％以上、ヘイズが２．０％以下であることが好ましく、全光線透過率が９０％以上、ヘイズが１．０％以下であることがより好ましい。透明導電膜の透明性が上記範囲内だと、当該透明導電膜を使用されたタッチパネル装置搭載ディスプレイの透明性が保たれやすい。 The transparency of the transparent conductive film is preferably such that the total light transmittance is 80% or more and the haze is 2.0% or less, the total light transmittance is 90% or more, and the haze is 1.0% or less. More preferred. When the transparency of the transparent conductive film is within the above range, the transparency of the display equipped with the touch panel device using the transparent conductive film is easily maintained.
当該透明導電膜積層体の厚さは、０．１ｍｍ〜２．０ｍｍであることが好ましい。上記範囲内だと、タッチパネル装置を薄型にしやすい。 The thickness of the transparent conductive film laminate is preferably 0.1 mm to 2.0 mm. Within the above range, it is easy to make the touch panel device thin.
当該透明導電膜積層体において、下記の式で表される導電膜層の電気抵抗値の上昇率が、６０℃、９０％ＲＨ条件下に５００時間放置後で５％以下であることが好ましい。上記範囲内だと、当該透明導電膜積層体を用いて製造されたタッチパネル装置が正常に作動する。
導電膜層の電気抵抗値の上昇率（％）＝［（６０℃、９０％ＲＨに５００時間放置後の電気抵抗値）−（初期の電気抵抗値）］／（初期の電気抵抗値）×１００
In the transparent conductive film laminate, the rate of increase in the electrical resistance value of the conductive film layer represented by the following formula is preferably 5% or less after being left for 500 hours under the conditions of 60 ° C. and 90% RH. Within the above range, the touch panel device manufactured using the transparent conductive film laminate operates normally.
Rate of increase in electric resistance value of conductive film layer (%) = [(electric resistance value after standing at 60 ° C., 90% RH for 500 hours) − (initial electric resistance value)] / (initial electric resistance value) × 100
［タッチパネル装置］
本発明のタッチパネル装置は、上記両面粘着シートが透明導電膜に貼り合わせて形成された透明導電膜積層体を有することを特徴とする。本発明のタッチパネル装置の構成は特に制限されないが、静電容量方式のタッチパネルの構成であることが好ましい。
[Touch panel device]
The touch panel device of the present invention is characterized by having a transparent conductive film laminate formed by bonding the double-sided pressure-sensitive adhesive sheet to a transparent conductive film. The configuration of the touch panel device of the present invention is not particularly limited, but is preferably a configuration of a capacitive touch panel.
本発明のタッチパネル装置の好適な構成例としては、両面粘着シートの片面に透明導電膜が設けられた透明導電膜積層体が、表示パネル（透明パネル）と画像表示モジュールとの間に二層設けられた静電容量方式のタッチパネル装置（図４）を例示できる。二層設けられた粘着剤層付き透明導電膜のうち、少なくとも一層が上記本発明の透明導電膜積層体であればよく、画像表示モジュール側の粘着剤層付き透明導電膜が上記本発明の透明導電膜積層体である構成、または、二層の粘着剤層付き透明導電膜がいずれも上記本発明の透明導電膜積層体である構成を好ましい構成として使用できる。また、他の好適な構成例として、両面粘着シートの両面に透明導電膜が設けられた透明導電膜積層体が、固定用テープや固定用接着剤により表示パネルと画像表示モジュールの間に固定された静電容量方式のタッチパネル装置（図５）を例示できる。当該構成においては、表示パネル、透明導電膜積層体及び画像表示モジュールを、固定用テープや固定用接着剤を使用して固定することでタッチパネル装置を製造できるため組み立て工程が容易となる。 As a preferred configuration example of the touch panel device of the present invention, a transparent conductive film laminate in which a transparent conductive film is provided on one side of a double-sided pressure-sensitive adhesive sheet is provided in two layers between a display panel (transparent panel) and an image display module. The capacitive type touch panel device (FIG. 4) can be exemplified. Of the two transparent conductive films with pressure-sensitive adhesive layers, at least one layer may be the transparent conductive film laminate of the present invention, and the transparent conductive film with pressure-sensitive adhesive layer on the image display module side is transparent of the present invention. The structure which is an electrically conductive film laminated body, or the structure where all the two transparent conductive films with an adhesive layer are the transparent electrically conductive film laminated body of the said invention can be used as a preferable structure. As another preferred configuration example, a transparent conductive film laminate in which a transparent conductive film is provided on both sides of a double-sided pressure-sensitive adhesive sheet is fixed between a display panel and an image display module with a fixing tape or a fixing adhesive. A capacitive touch panel device (FIG. 5) can be exemplified. In the said structure, since a touch panel apparatus can be manufactured by fixing a display panel, a transparent conductive film laminated body, and an image display module using a fixing tape or a fixing adhesive, an assembly process becomes easy.
本発明のタッチパネル装置の保護パネルは、特に制限されないが、（メタ）アクリル樹脂、ポリカーボネート樹脂、ガラス、ポリエチレンテレフタレート樹脂等が挙げられる。なかでも、透明性と軽量性で優れた（メタ）アクリル樹脂が好ましい。 The protective panel of the touch panel device of the present invention is not particularly limited, and examples thereof include (meth) acrylic resin, polycarbonate resin, glass, and polyethylene terephthalate resin. Of these, a (meth) acrylic resin excellent in transparency and lightness is preferable.
本発明のタッチパネル装置の表示パネルには、装飾部があってもよい。具体的な装飾部としては、例えば、携帯電子端末の画像表示部の周囲に視認される文字や図形、あるいは、これらの背面に設けられる黒色や白色の下地などが挙げられる。これら装飾部は、携帯電子端末へ意匠性を付与するため、設けられることが好ましい。 The display panel of the touch panel device of the present invention may have a decorative portion. Specific examples of the decorative part include characters and figures visually recognized around the image display part of the portable electronic terminal, or a black or white background provided on the back face thereof. These decorative portions are preferably provided in order to impart designability to the portable electronic terminal.
当該タッチパネル装置の画像表示モジュールを除いた厚さは、０．３ｍｍ〜３．０ｍｍであることが好ましい。上記範囲内だと当該タッチパネル装置が組み込まれた電子機器を薄型にしやすい。 The thickness of the touch panel device excluding the image display module is preferably 0.3 mm to 3.0 mm. Within the above range, the electronic device in which the touch panel device is incorporated can be easily made thin.
なお、画像表示モジュール側の粘着剤層付き透明導電膜を上記本発明の透明導電膜積層体とする場合には、当該透明導電膜積層体の両面粘着シートの厚さを５〜２００μｍとすることが好ましく、１０〜１００μｍとすることが特に好ましい。また、表示パネルと貼り合わせる側の粘着剤層付き透明導電膜を上記本発明の透明導電膜積層体とする際に、表示パネルに装飾部が設けられている場合には、両面粘着シートの厚みは、２５〜２００μｍが好ましく、２５〜１５０μｍがより好ましい。上記範囲内だと、表示パネルの装飾部に両面粘着シートが追従しやすい。 In addition, when making the transparent conductive film with an adhesive layer by the side of an image display module into the transparent conductive film laminated body of the said invention, the thickness of the double-sided adhesive sheet of the said transparent conductive film laminated body shall be 5-200 micrometers. Is preferable, and 10 to 100 μm is particularly preferable. In addition, when the transparent conductive film with the pressure-sensitive adhesive layer on the side to be bonded to the display panel is used as the transparent conductive film laminate of the present invention, the thickness of the double-sided pressure-sensitive adhesive sheet is provided when a decorative part is provided on the display panel. Is preferably 25 to 200 μm, and more preferably 25 to 150 μm. Within the above range, the double-sided PSA sheet easily follows the decorative part of the display panel.
タッチパネル装置に使用する画像表示モジュールは、特に制限されず、小型電子端末に通常使用されるＬＣＤモジュールや、有機ＥＬモジュールなどが使用できる。 The image display module used for the touch panel device is not particularly limited, and an LCD module or an organic EL module usually used for a small electronic terminal can be used.
以下に実施例および比較例により本発明をより具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
［アクリル共重合体の調製］
＜アクリル共重合体（Ａ１）＞
アクリル共重合体の調製攪拌機、寒流冷却器、温度計、滴下漏斗及び窒素ガス導入口を備えた反応容器に、ｎ−ブチルアクリレート８７．０重量部、シクロヘキシルアクリレート１０．０重量部、２−ヒドロキシエチルアクリレート３．０重量部と重合開始剤として２，２’−アゾビスイソブチルニトリル０．２部とを酢酸エチル１００重量部に溶解し、窒素置換後、８０℃で８時間重合して重量平均分子量９０万のアクリル共重合体（Ａ１）を得た。
＜アクリル共重合体（Ａ２）＞
アクリル共重合体の調製攪拌機、寒流冷却器、温度計、滴下漏斗及び窒素ガス導入口を備えた反応容器に、ｎ−ブチルアクリレート８７．０重量部、メチルアクリレート１０．０重量部、２−ヒドロキシエチルアクリレート３．０重量部と重合開始剤として２，２’−アゾビスイソブチルニトリル０．２部とを酢酸エチル１００重量部に溶解し、窒素置換後、８０℃で８時間重合して重量平均分子量８８万のアクリル共重合体（Ａ２）を得た。
[Preparation of acrylic copolymer]
<Acrylic copolymer (A1)>
Preparation of acrylic copolymer In a reaction vessel equipped with a stirrer, cold flow condenser, thermometer, dropping funnel and nitrogen gas inlet, 87.0 parts by weight of n-butyl acrylate, 10.0 parts by weight of cyclohexyl acrylate, 2-hydroxy 3.0 parts by weight of ethyl acrylate and 0.2 parts of 2,2′-azobisisobutylnitrile as a polymerization initiator are dissolved in 100 parts by weight of ethyl acetate, and after nitrogen substitution, polymerized at 80 ° C. for 8 hours to obtain a weight average. An acrylic copolymer (A1) having a molecular weight of 900,000 was obtained.
<Acrylic copolymer (A2)>
Preparation of acrylic copolymer In a reaction vessel equipped with a stirrer, cold flow cooler, thermometer, dropping funnel and nitrogen gas inlet, 87.0 parts by weight of n-butyl acrylate, 10.0 parts by weight of methyl acrylate, 2-hydroxy 3.0 parts by weight of ethyl acrylate and 0.2 parts of 2,2′-azobisisobutylnitrile as a polymerization initiator are dissolved in 100 parts by weight of ethyl acetate, and after nitrogen substitution, polymerized at 80 ° C. for 8 hours to obtain a weight average. An acrylic copolymer (A2) having a molecular weight of 880,000 was obtained.
＜アクリル共重合体（Ａ３）＞
アクリル共重合体の調製攪拌機、寒流冷却器、温度計、滴下漏斗及び窒素ガス導入口を備えた反応容器に、ｎ−ブチルアクリレート９７．０重量部、２−ヒドロキシエチルアクリレート３．０重量部と重合開始剤として２，２’−アゾビスイソブチルニトリル０．２部とを酢酸エチル１００重量部に溶解し、窒素置換後、８０℃で８時間重合して重量平均分子量９０万のアクリル共重合体（Ａ３）を得た。
<Acrylic copolymer (A3)>
Preparation of acrylic copolymer In a reaction vessel equipped with a stirrer, cold flow cooler, thermometer, dropping funnel and nitrogen gas inlet, 97.0 parts by weight of n-butyl acrylate, 3.0 parts by weight of 2-hydroxyethyl acrylate, An acrylic copolymer having a weight average molecular weight of 900,000 is obtained by dissolving 0.2 part of 2,2′-azobisisobutylnitrile as a polymerization initiator in 100 parts by weight of ethyl acetate, purging with nitrogen and polymerizing at 80 ° C. for 8 hours. (A3) was obtained.
＜アクリル共重合体（Ｂ１）＞
アクリル共重合体の調製攪拌機、寒流冷却器、温度計、滴下漏斗及び窒素ガス導入口を備えた反応容器に、シクロヘキシルメチルメタクリレート９５．０重量部、ジメチルアミノエチルメタクリレート５．０重量部と重合開始剤として２，２’−アゾビスイソブチルニトリル１．０重量部とを酢酸エチル１００重量部に溶解し、窒素置換後、８０℃で８時間重合して重量平均分子量２万のメタクリル共重合体（Ｂ１）を得た。
<Acrylic copolymer (B1)>
Preparation of acrylic copolymer Polymerization started with 95.0 parts by weight of cyclohexylmethyl methacrylate and 5.0 parts by weight of dimethylaminoethyl methacrylate in a reaction vessel equipped with a stirrer, cold flow cooler, thermometer, dropping funnel and nitrogen gas inlet. As an agent, 1.0 part by weight of 2,2′-azobisisobutylnitrile is dissolved in 100 parts by weight of ethyl acetate, and after substitution with nitrogen, polymerization is carried out at 80 ° C. for 8 hours to give a methacrylic copolymer having a weight average molecular weight of 20,000 ( B1) was obtained.
＜アクリル共重合体（Ｂ２）＞
アクリル共重合体の調製攪拌機、寒流冷却器、温度計、滴下漏斗及び窒素ガス導入口を備えた反応容器に、メチルメタクリレート９５．０重量部、ジメチルアミノエチルメタクリレート５．０重量部と重合開始剤として２，２’−アゾビスイソブチルニトリル１．０重量部とを酢酸エチル１００重量部に溶解し、窒素置換後、８０℃で８時間重合して重量平均分子量２万のメタクリル共重合体（Ｂ２）を得た。
<Acrylic copolymer (B2)>
Preparation of acrylic copolymer In a reaction vessel equipped with a stirrer, cold flow cooler, thermometer, dropping funnel and nitrogen gas inlet, 95.0 parts by weight of methyl methacrylate, 5.0 parts by weight of dimethylaminoethyl methacrylate and a polymerization initiator As a methacrylic copolymer having a weight average molecular weight of 20,000 (B2), 1.0 part by weight of 2,2′-azobisisobutylnitrile is dissolved in 100 parts by weight of ethyl acetate, purged with nitrogen and polymerized at 80 ° C. for 8 hours. )
＜アクリル共重合体（Ｂ３）＞
アクリル共重合体の調製攪拌機、寒流冷却器、温度計、滴下漏斗及び窒素ガス導入口を備えた反応容器に、ｎ−ブチルアクリレート９６．５重量部、２−ヒドロキシエチルアクリレート０．５重量部、ジメチルアミノエチルメタクリレート３．０重量部と重合開始剤として２，２’−アゾビスイソブチルニトリル０．２部とを酢酸エチル１００重量部に溶解し、窒素置換後、８０℃で８時間重合して重量平均分子量４０万のアクリル共重合体（Ｂ３）を得た。
<Acrylic copolymer (B3)>
Preparation of acrylic copolymer In a reaction vessel equipped with a stirrer, cold flow cooler, thermometer, dropping funnel and nitrogen gas inlet, 96.5 parts by weight of n-butyl acrylate, 0.5 parts by weight of 2-hydroxyethyl acrylate, Dissolve 3.0 parts by weight of dimethylaminoethyl methacrylate and 0.2 part of 2,2′-azobisisobutylnitrile as a polymerization initiator in 100 parts by weight of ethyl acetate, and after purging with nitrogen, polymerize at 80 ° C. for 8 hours. An acrylic copolymer (B3) having a weight average molecular weight of 400,000 was obtained.
＜アクリル共重合体（Ｈ１）＞
アクリル共重合体の調製攪拌機、寒流冷却器、温度計、滴下漏斗及び窒素ガス導入口を備えた反応容器に、ｎ−ブチルアクリレート９５．５重量部、アクリル酸４．０重量部、２−ヒドロキシエチルアクリレート０．５重量部と重合開始剤として２，２’−アゾビスイソブチルニトリル０．２部とを酢酸エチル１００重量部に溶解し、窒素置換後、８０℃で８時間重合して重量平均分子量９０万のアクリル共重合体（Ｈ１）を得た。
<Acrylic copolymer (H1)>
Preparation of acrylic copolymer In a reaction vessel equipped with a stirrer, cold flow cooler, thermometer, dropping funnel and nitrogen gas inlet, 95.5 parts by weight of n-butyl acrylate, 4.0 parts by weight of acrylic acid, 2-hydroxy 0.5 parts by weight of ethyl acrylate and 0.2 parts of 2,2′-azobisisobutylnitrile as a polymerization initiator are dissolved in 100 parts by weight of ethyl acetate, and after nitrogen substitution, polymerized at 80 ° C. for 8 hours to obtain a weight average. An acrylic copolymer (H1) having a molecular weight of 900,000 was obtained.
＜粘着剤（Ｐ１）＞
上記アクリル共重合体（Ａ１）１００重量部に、上記アクリル共重合体（Ｂ１）を２．５重量部添加し、酢酸エチルで希釈し樹脂固形分３０％の粘着剤（Ｐ１）を得た。
<Adhesive (P1)>
2.5 parts by weight of the acrylic copolymer (B1) was added to 100 parts by weight of the acrylic copolymer (A1), and diluted with ethyl acetate to obtain a pressure-sensitive adhesive (P1) having a resin solid content of 30%.
＜粘着剤（Ｐ２）＞
上記アクリル共重合体（Ａ１）１００重量部に、上記アクリル共重合体（Ｂ１）を１０重量部添加し、酢酸エチルで希釈し樹脂固形分３０％の粘着剤（Ｐ２）を得た。
<Adhesive (P2)>
10 parts by weight of the acrylic copolymer (B1) was added to 100 parts by weight of the acrylic copolymer (A1), and diluted with ethyl acetate to obtain an adhesive (P2) having a resin solid content of 30%.
＜粘着剤（Ｐ３）＞
上記アクリル共重合体（Ａ１）１００重量部に、上記アクリル共重合体（Ｂ１）を１２．５重量部添加し、酢酸エチルで希釈し樹脂固形分３０％の粘着剤（Ｐ３）を得た。
<Adhesive (P3)>
12.5 parts by weight of the acrylic copolymer (B1) was added to 100 parts by weight of the acrylic copolymer (A1), and diluted with ethyl acetate to obtain an adhesive (P3) having a resin solid content of 30%.
＜粘着剤（Ｐ４）＞
上記アクリル共重合体（Ａ２）１００重量部に、上記アクリル共重合体（Ｂ２）を２．５重量部添加し、酢酸エチルで希釈し樹脂固形分３０％の粘着剤（Ｐ４）を得た。
<Adhesive (P4)>
2.5 parts by weight of the acrylic copolymer (B2) was added to 100 parts by weight of the acrylic copolymer (A2), and diluted with ethyl acetate to obtain a pressure-sensitive adhesive (P4) having a resin solid content of 30%.
＜粘着剤（Ｐ５）＞
上記アクリル共重合体（Ａ２）１００重量部に、上記アクリル共重合体（Ｂ２）を５．０重量部添加し、酢酸エチルで希釈し樹脂固形分３０％の粘着剤（Ｐ５）を得た。
<Adhesive (P5)>
5.0 parts by weight of the acrylic copolymer (B2) was added to 100 parts by weight of the acrylic copolymer (A2), and diluted with ethyl acetate to obtain an adhesive (P5) having a resin solid content of 30%.
＜粘着剤（Ｐ６）＞
上記アクリル共重合体（Ａ３）１００重量部に、上記アクリル共重合体（Ｂ２）を１０重量部添加し、酢酸エチルで希釈し樹脂固形分３０％の粘着剤（Ｐ６）を得た。
<Adhesive (P6)>
10 parts by weight of the acrylic copolymer (B2) was added to 100 parts by weight of the acrylic copolymer (A3), and diluted with ethyl acetate to obtain an adhesive (P6) having a resin solid content of 30%.
＜粘着剤（Ｐ７）＞
上記アクリル共重合体（Ｂ３）１００重量部を酢酸エチルで希釈し樹脂固形分３０％の粘着剤（Ｐ７）を得た。
<Adhesive (P7)>
100 parts by weight of the acrylic copolymer (B3) was diluted with ethyl acetate to obtain an adhesive (P7) having a resin solid content of 30%.
＜粘着剤（Ｐ８）＞
上記アクリル共重合体（Ｂ３）１００重量部に、上記アクリル共重合体（Ｂ１）を１０重量部添加し、酢酸エチルで希釈し樹脂固形分３０％の粘着剤（Ｐ８）を得た。
<Adhesive (P8)>
10 parts by weight of the acrylic copolymer (B1) was added to 100 parts by weight of the acrylic copolymer (B3), and diluted with ethyl acetate to obtain a pressure-sensitive adhesive (P8) having a resin solid content of 30%.
＜粘着剤（Ｐ９）＞
上記アクリル共重合体（Ｈ１）１００重量部に、上記アクリル共重合体（Ｂ１）を１０重量部添加し、酢酸エチルで希釈し樹脂固形分３０％の粘着剤（Ｐ９）を得た。
<Adhesive (P9)>
10 parts by weight of the acrylic copolymer (B1) was added to 100 parts by weight of the acrylic copolymer (H1), and diluted with ethyl acetate to obtain an adhesive (P9) having a resin solid content of 30%.
＜粘着剤（Ｐ１０）＞
上記アクリル共重合体（Ｈ１）１００重量部を酢酸エチルで希釈し樹脂固形分３０％の粘着剤（Ｐ１０）を得た。
<Adhesive (P10)>
100 parts by weight of the acrylic copolymer (H1) was diluted with ethyl acetate to obtain an adhesive (P10) having a resin solid content of 30%.
＜粘着剤（Ｐ１１）＞
上記アクリル共重合体（Ｈ１）１００重量部に、金属不活性剤ＢＴＺＭ（共同薬品（株）製）を５重量部添加し、酢酸エチルで希釈し樹脂固形分３０％の粘着剤（Ｐ１１）を得た。
<Adhesive (P11)>
5 parts by weight of a metal deactivator BTZM (manufactured by Kyodo Chemical Co., Ltd.) is added to 100 parts by weight of the acrylic copolymer (H1), diluted with ethyl acetate, and an adhesive (P11) having a resin solid content of 30% is added. Obtained.
（実施例１）
上記粘着剤（Ｐ１）１００重量部にイソシアネート系架橋剤（三井化学ポリウレタン社製Ｄ−１６０Ｎ、固形分７５％）を０．１重量部添加し１５分攪拌後、シリコーン化合物で片面を剥離処理した厚さ５０μｍのポリエステルフィルム（以下＃７５剥離フィルム）上に乾燥後の厚さが２５μｍになるように塗工して、７５℃で５分間乾燥した。得られた粘着シートと、シリコーン化合物で片面を剥離処理した厚さ３８μｍのポリエステルフィルム（以下＃３８剥離フィルム）を貼り合わせた。その後２３℃で７日間熟成し厚さ２５μｍの、ゲル分率７５％の基材レス粘着シートを得た。
Example 1
0.1 part by weight of an isocyanate-based crosslinking agent (D-160N, Mitsui Chemicals Polyurethanes Co., Ltd., 75% solids) was added to 100 parts by weight of the pressure-sensitive adhesive (P1) and stirred for 15 minutes, and then one side was peeled with a silicone compound. It was coated on a 50 μm thick polyester film (hereinafter referred to as # 75 release film) so that the thickness after drying was 25 μm, and dried at 75 ° C. for 5 minutes. The obtained pressure-sensitive adhesive sheet and a 38 μm-thick polyester film (hereinafter referred to as # 38 release film) having one surface peel-treated with a silicone compound were bonded together. Thereafter, it was aged at 23 ° C. for 7 days to obtain a substrate-less pressure-sensitive adhesive sheet having a thickness of 25 μm and a gel fraction of 75%.
（実施例２）
粘着剤（Ｐ１）１００重量部を粘着剤（Ｐ２）１００重量部にする以外は、実施例１と同様にして、ゲル分率７２％の粘着シートを得た。
(Example 2)
A pressure-sensitive adhesive sheet having a gel fraction of 72% was obtained in the same manner as in Example 1 except that 100 parts by weight of the pressure-sensitive adhesive (P1) was changed to 100 parts by weight of the pressure-sensitive adhesive (P2).
（実施例３）
粘着剤（Ｐ１）１００重量部を粘着剤（Ｐ３）１００重量部にする以外は、実施例１と同様にして、ゲル分率６８％の粘着シートを得た。
(Example 3)
A pressure-sensitive adhesive sheet having a gel fraction of 68% was obtained in the same manner as in Example 1 except that 100 parts by weight of the pressure-sensitive adhesive (P1) was changed to 100 parts by weight of the pressure-sensitive adhesive (P3).
（実施例４）
粘着剤（Ｐ１）１００重量部を粘着剤（Ｐ４）１００重量部にする以外は、実施例１と同様にして、ゲル分率７４％の粘着シートを得た。
Example 4
A pressure-sensitive adhesive sheet having a gel fraction of 74% was obtained in the same manner as in Example 1 except that 100 parts by weight of the pressure-sensitive adhesive (P1) was changed to 100 parts by weight of the pressure-sensitive adhesive (P4).
（実施例５）
粘着剤（Ｐ１）１００重量部を粘着剤（Ｐ５）１００重量部にする以外は、実施例１と同様にして、ゲル分率６９％の粘着シートを得た。
(Example 5)
A pressure-sensitive adhesive sheet having a gel fraction of 69% was obtained in the same manner as in Example 1 except that 100 parts by weight of the pressure-sensitive adhesive (P1) was changed to 100 parts by weight of the pressure-sensitive adhesive (P5).
（実施例６）
粘着剤（Ｐ１）１００重量部を粘着剤（Ｐ６）１００重量部にする以外は、実施例１と同様にして、ゲル分率６８％の粘着シートを得た。
(Example 6)
An adhesive sheet having a gel fraction of 68% was obtained in the same manner as in Example 1 except that 100 parts by weight of the adhesive (P1) was changed to 100 parts by weight of the adhesive (P6).
（比較例１）
粘着剤（Ｐ１）１００重量部を粘着剤（Ｐ７）１００重量部にする以外は、実施例１と同様にして、ゲル分率８０％の粘着シートを得た。
(Comparative Example 1)
An adhesive sheet having a gel fraction of 80% was obtained in the same manner as in Example 1 except that 100 parts by weight of the adhesive (P1) was changed to 100 parts by weight of the adhesive (P7).
（比較例２）
粘着剤（Ｐ１）１００重量部を粘着剤（Ｐ８）１００重量部にする以外は、実施例１と同様にして、ゲル分率７０％の粘着シートを得た。
(Comparative Example 2)
A pressure-sensitive adhesive sheet having a gel fraction of 70% was obtained in the same manner as in Example 1 except that 100 parts by weight of the pressure-sensitive adhesive (P1) was changed to 100 parts by weight of the pressure-sensitive adhesive (P8).
（比較例３）
上記粘着剤（Ｐ９）１００重量部にイソシアネート系架橋剤（日本ポリウレタン社製Ｌ−４５、固形分４５％）を０．７重量部添加し１５分攪拌後、シリコーン化合物で片面を剥離処理した厚さ５０μｍのポリエステルフィルム（以下＃７５剥離フィルム）上に乾燥後の厚さが２５μｍになるように塗工して、７５℃で５分間乾燥した。得られた粘着シートと、シリコーン化合物で片面を剥離処理した厚さ３８μｍのポリエステルフィルム（以下＃３８剥離フィルム）を貼り合わせた。その後２３℃で７日間熟成し厚さ２５μｍの、ゲル分率７５％の基材レス粘着シートを得た。
(Comparative Example 3)
A thickness obtained by adding 0.7 parts by weight of an isocyanate-based crosslinking agent (L-45 manufactured by Nippon Polyurethane Co., Ltd., solid content: 45%) to 100 parts by weight of the above-mentioned pressure-sensitive adhesive (P9), stirring for 15 minutes, and then removing one surface with a silicone compound The film was coated on a 50 μm thick polyester film (hereinafter referred to as # 75 release film) so that the thickness after drying was 25 μm, and dried at 75 ° C. for 5 minutes. The obtained pressure-sensitive adhesive sheet and a 38 μm-thick polyester film (hereinafter referred to as # 38 release film) having one surface peel-treated with a silicone compound were bonded together. Thereafter, it was aged at 23 ° C. for 7 days to obtain a substrate-less pressure-sensitive adhesive sheet having a thickness of 25 μm and a gel fraction of 75%.
（比較例４）
粘着剤（Ｐ９）１００重量部を粘着剤（Ｐ１０）１００重量部にする以外は、比較例４と同様にして、ゲル分率８３％の粘着シートを得た。
(Comparative Example 4)
A pressure-sensitive adhesive sheet having a gel fraction of 83% was obtained in the same manner as in Comparative Example 4 except that 100 parts by weight of the pressure-sensitive adhesive (P9) was changed to 100 parts by weight of the pressure-sensitive adhesive (P10).
（比較例５）
粘着剤（Ｐ９）１００重量部を粘着剤（Ｐ１１）１００重量部にする以外は、比較例４と同様にして、ゲル分率７０％の粘着シートを得た。
(Comparative Example 5)
A pressure-sensitive adhesive sheet having a gel fraction of 70% was obtained in the same manner as in Comparative Example 4 except that 100 parts by weight of the pressure-sensitive adhesive (P9) was changed to 100 parts by weight of the pressure-sensitive adhesive (P11).
（接着力測定）
粘着シートの一方の側の剥離ライナーを剥がして、ポリエチレンテレフタレート製フィルム（厚さ：２５μｍ）に貼り合わせ、幅２０ｍｍ、長さ１００ｍｍに切断した後、他方の側の剥離ライナーを剥がして、銅箔（ 厚さ：８０μｍ）貼り合わせた。銅箔に貼付してから１時間放置後、１８０°ピール粘着力を測定した。なお、１８０°ピール粘着力の測定条件は、剥離角度：１８０°、引張速度：３００ｍｍ／ｍｉｎ、温度：２３℃ 、湿度：５０％ＲＨであり、銅箔より、ポリエチレンテレフタレート製フィルムに貼り合わせられた粘着シートを剥離することにより、１８０°ピール粘着力を測定した。
(Adhesive strength measurement)
The release liner on one side of the pressure-sensitive adhesive sheet is peeled off, bonded to a polyethylene terephthalate film (thickness: 25 μm), cut into a width of 20 mm and a length of 100 mm, and then the release liner on the other side is peeled off to obtain a copper foil. (Thickness: 80 μm) Bonded together. After being attached to the copper foil, the plate was allowed to stand for 1 hour, and then 180 ° peel adhesive strength was measured. In addition, the measurement conditions for 180 ° peel adhesive strength are peeling angle: 180 °, tensile speed: 300 mm / min, temperature: 23 ° C., humidity: 50% RH, and bonded to a polyethylene terephthalate film from copper foil. The 180 ° peel adhesive strength was measured by peeling off the adhesive sheet.
（金属腐食試験）
粘着シートの一方の側の剥離ライナーを剥がして、透明なポリエチレンテレフタレート製フィルム（厚さ：１００μｍ）に貼り合わせ、さらに、他方の側の剥離ライナーを剥がして、銅箔（厚さ：８０μｍ）に貼り合わせた後、６０℃×９０％ＲＨの雰囲気下に２５０時間保存した。その後、目視で、ポリエチレンテレフタレート製フィルム側から銅箔の表面を観察して、粘着シートが貼り合わせられている銅箔の表面の腐食の有無を確認した。
○：腐食無し
×：腐食有り
(Metal corrosion test)
The release liner on one side of the pressure-sensitive adhesive sheet is peeled off and bonded to a transparent polyethylene terephthalate film (thickness: 100 μm). Further, the release liner on the other side is peeled off to form a copper foil (thickness: 80 μm). After pasting, it was stored for 250 hours in an atmosphere of 60 ° C. × 90% RH. Thereafter, the surface of the copper foil was visually observed from the polyethylene terephthalate film side to confirm the presence or absence of corrosion on the surface of the copper foil to which the adhesive sheet was bonded.
○: No corrosion ×: Corrosion
（全光線透過率およびヘイズ測定）
粘着シートを６０℃、９０％ＲＨ条件下に１００時間放置した後、ＰＥＴフィルム、ガラスの順で貼り合わせて試験サンプルを調整した。（株）村上色彩技術研究所製「ＨＲ−１００型」を使用し、調整サンプルの全光線透過率およびヘイズ（％）を測定した。
(Total light transmittance and haze measurement)
After the pressure-sensitive adhesive sheet was allowed to stand for 100 hours under conditions of 60 ° C. and 90% RH, a test sample was prepared by laminating in the order of PET film and glass. Using the “HR-100 Model” manufactured by Murakami Color Research Laboratory Co., Ltd., the total light transmittance and haze (%) of the adjusted sample were measured.
（色差測定）
粘着シートをＰＥＴフィルム、ガラスの順で貼り合わせて試験サンプルを調整した。コニカミノルタセンシング（株）製「分光測色計ＣＭ３５００ｄ」を使用し、調整サンプルのＬ１＊、ａ１＊、ｂ１＊を測定した。その後、調整サンプルを８５℃、１００時間放置し、Ｌ２＊、ａ２＊、ｂ２＊を測定した。色差ΔＥ＊ａｂは下記の式から算出し、粘着シートの変色を評価した。
色差ΔＥ＊ａｂ＝［（Ｌ２＊−Ｌ１＊）２＋（ａ２＊−ａ１＊）２＋（ｂ２＊−ｂ１＊）２］１／２
○：ΔＥ＊ａｂ ０〜０．５
△：ΔＥ＊ａｂ ０．５〜１．５
×：ΔＥ＊ａｂ １．５以上
(Color difference measurement)
The pressure-sensitive adhesive sheet was bonded in the order of PET film and glass to prepare a test sample. Using a “spectral colorimeter CM3500d” manufactured by Konica Minolta Sensing Co., Ltd., L1 * , a1 * , and b1 * of the adjusted sample were measured. Thereafter, the adjusted sample was left at 85 ° C. for 100 hours, and L2 * , a2 * , and b2 * were measured. The color difference ΔE * ab was calculated from the following formula, and the discoloration of the pressure-sensitive adhesive sheet was evaluated.
Color difference ΔE * ab = [(L2 * −L1 * ) 2 + (a2 * −a1 * ) 2 + (b2 * −b1 * ) 2 ] 1/2
○: ΔE * ab 0-0.5
Δ: ΔE * ab 0.5 to 1.5
×: ΔE * ab 1.5 or more
（耐剥がれ性の評価）
４５ｍｍ×３５ｍｍのハードコート層付きＰＥＴフィルムのＰＥＴフィルム面と、５０ｍｍ×４０ｍｍのガラスとを粘着シートで貼り合せた後、８５℃条件に５００時間放置し、目視でハードコート付きＰＥＴフィルムの剥がれを評価した。
○：剥がれ無し
×：剥がれ有り
(Evaluation of peeling resistance)
After adhering the PET film surface of a 45 mm x 35 mm PET film with a hard coat layer and 50 mm x 40 mm glass with an adhesive sheet, leave it at 85 ° C for 500 hours and visually peel off the PET film with a hard coat. evaluated.
○: No peeling ×: There is peeling
上記のとおり、実施例１〜６の本発明の金属貼付用両面粘着シートは、腐食試験においても金属面に腐食を生じさせず、高温環境下で好適な耐剥がれ性を示し、かつ、粘着剤層の着色による視認性の低下が生じず優れた光透過性を有するものであった。一方、窒素含有共重合性単量体を含有させた（メタ）アクリル酸エステル共重合体のみを使用した比較例１〜２の両面粘着テープは、高温環境下での耐剥がれ性試験によって剥がれが生じるものであった。また、酸成分を含有する（メタ）アクリル酸エステル共重合体を使用した比較例３〜４の両面粘着テープにおいては、金属の腐食を抑制できなかった。また、金属腐食防止剤を含有させた比較例５の両面粘着テープにおいては、金属の腐食を抑制できたが高温下で着色が生じ、視認性の悪化が生じた。 As described above, the double-sided pressure-sensitive adhesive sheet for metal sticking of the present invention of Examples 1 to 6 does not cause corrosion on the metal surface even in a corrosion test, exhibits suitable peeling resistance in a high temperature environment, and is a pressure-sensitive adhesive. The visibility was not deteriorated due to the coloring of the layer, and the light transmittance was excellent. On the other hand, the double-sided pressure-sensitive adhesive tapes of Comparative Examples 1 and 2 using only a (meth) acrylic acid ester copolymer containing a nitrogen-containing copolymerizable monomer are peeled off by a peel resistance test in a high temperature environment. It occurred. Moreover, in the double-sided adhesive tapes of Comparative Examples 3 to 4 using the (meth) acrylic acid ester copolymer containing an acid component, metal corrosion could not be suppressed. Moreover, in the double-sided pressure-sensitive adhesive tape of Comparative Example 5 containing a metal corrosion inhibitor, although corrosion of the metal could be suppressed, coloring occurred at a high temperature, and visibility deteriorated.
１ 透明導電膜積層体
２ 金属面貼付用両面粘着シート
３ 導電層
４ 透明基材
５ ハードコート層
６ 保護パネル
７ 装飾層
８ 粘着剤層付き透明導電膜
９ 固定用テープ
１０ 画像表示モジュール
DESCRIPTION OF
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| Application Number | Priority Date | Filing Date | Title |
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| JP2009081884A JP5545515B2 (en) | 2009-03-30 | 2009-03-30 | Double-sided adhesive sheet for metal surface sticking, transparent conductive film laminate, touch panel device |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2009081884A JP5545515B2 (en) | 2009-03-30 | 2009-03-30 | Double-sided adhesive sheet for metal surface sticking, transparent conductive film laminate, touch panel device |
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| JP2010235646A JP2010235646A (en) | 2010-10-21 |
| JP5545515B2 true JP5545515B2 (en) | 2014-07-09 |
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| JP5540383B2 (en) * | 2010-10-25 | 2014-07-02 | 王子ホールディングス株式会社 | Tin-doped indium oxide film adhesive and double-sided adhesive sheet |
| KR101738645B1 (en) * | 2010-11-08 | 2017-05-23 | 삼성디스플레이 주식회사 | touch screen panel and fabrication method the same |
| JP6033543B2 (en) * | 2010-12-15 | 2016-11-30 | 日東電工株式会社 | Optical adhesive sheet |
| JP5193377B2 (en) * | 2011-04-11 | 2013-05-08 | 王子ホールディングス株式会社 | Double-sided pressure-sensitive adhesive sheet, double-sided pressure-sensitive adhesive sheet with release sheet, and optical laminate |
| KR101890790B1 (en) * | 2012-03-30 | 2018-08-22 | 어플라이드 머티어리얼스, 인코포레이티드 | Transparent body for use in a touch screen panel manufacturing method and system |
| KR101542643B1 (en) | 2012-04-19 | 2015-08-07 | (주)엘지하우시스 | Transparent plastic film comprising optically clear adhesive layer and method for producing it |
| EP4230664A1 (en) | 2020-10-15 | 2023-08-23 | KJ Chemicals Corporation | Polymerizable composition, product of polymerization of same, and molded article obtained using these |
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| JPH0551567A (en) * | 1991-08-24 | 1993-03-02 | Sony Chem Corp | Self-crosslinking pressure-sensitive adhesive composition |
| JP4420389B2 (en) * | 2004-04-19 | 2010-02-24 | 日東電工株式会社 | Adhesive composition and adhesive sheet |
| JP5191080B2 (en) * | 2004-05-14 | 2013-04-24 | 日東電工株式会社 | Pressure-sensitive adhesive sheets for application to metal surfaces and articles having metal surfaces |
| JP5258178B2 (en) * | 2005-08-18 | 2013-08-07 | 日東電工株式会社 | Pressure sensitive adhesive sheets for metal surfaces |
| JP4863779B2 (en) * | 2006-06-07 | 2012-01-25 | 日東電工株式会社 | Pressure sensitive adhesive sheets for metal surfaces |
| JP4914309B2 (en) * | 2007-08-24 | 2012-04-11 | グンゼ株式会社 | Substrate manufacturing method and capacitive touch panel using substrate |
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