JP6884072B2 - Adhesive compositions, laminates, and display devices - Google Patents
Adhesive compositions, laminates, and display devices Download PDFInfo
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- JP6884072B2 JP6884072B2 JP2017169757A JP2017169757A JP6884072B2 JP 6884072 B2 JP6884072 B2 JP 6884072B2 JP 2017169757 A JP2017169757 A JP 2017169757A JP 2017169757 A JP2017169757 A JP 2017169757A JP 6884072 B2 JP6884072 B2 JP 6884072B2
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- adhesive composition
- pressure
- sensitive adhesive
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- 239000000203 mixture Substances 0.000 title claims description 162
- 239000000853 adhesive Substances 0.000 title claims description 23
- 230000001070 adhesive effect Effects 0.000 title claims description 23
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 145
- 229920000642 polymer Polymers 0.000 claims description 52
- 229920000058 polyacrylate Polymers 0.000 claims description 42
- 238000003860 storage Methods 0.000 claims description 40
- 150000001408 amides Chemical class 0.000 claims description 39
- 239000012788 optical film Substances 0.000 claims description 19
- 150000003950 cyclic amides Chemical group 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000010408 film Substances 0.000 description 32
- -1 acrylic ester Chemical class 0.000 description 29
- 239000000463 material Substances 0.000 description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 28
- 239000000178 monomer Substances 0.000 description 22
- 238000011156 evaluation Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 16
- 239000007788 liquid Substances 0.000 description 16
- 230000002087 whitening effect Effects 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 14
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 238000005259 measurement Methods 0.000 description 12
- 239000006260 foam Substances 0.000 description 11
- 238000005187 foaming Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000004417 polycarbonate Substances 0.000 description 10
- 229920000515 polycarbonate Polymers 0.000 description 10
- 239000011521 glass Substances 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000010030 laminating Methods 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 229920006243 acrylic copolymer Polymers 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229910052774 Proactinium Inorganic materials 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- PBGPBHYPCGDFEZ-UHFFFAOYSA-N 1-ethenylpiperidin-2-one Chemical compound C=CN1CCCCC1=O PBGPBHYPCGDFEZ-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- COORVRSSRBIIFJ-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]-1-methoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(O)COCCOCCO COORVRSSRBIIFJ-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical class NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 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
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Description
本発明は、粘着剤組成物、積層体、及び表示装置に関する。 The present invention relates to pressure-sensitive adhesive compositions, laminates, and display devices.
液晶ディスプレイに代表される表示装置では、一般に、表示素子上に複数の光学フィルムを貼り合わせて用いられており、光学フィルム間の貼り合わせに粘着シートが用いられている。
例えば、透明性が優れ、高温高湿下でも優れた密着性を維持できるアクリル系粘着剤組成物を得るために、アクリル系粘着剤組成物を、アクリル酸メチルと、アクリル酸メチル以外の（メタ）アクリル酸エステルと、これらと共重合可能なカルボキシル基含有モノマーおよびヒドロキシル基含有モノマーとを含むモノマー混合物（ａ）を共重合した重量平均分子量が５０万〜２００万のアクリル共重合体（Ａ）と、メタクリル酸メチルと環状構造を有するモノマーとを含むモノマー混合物（ｂ）を共重合した重量平均分子量が１０００〜１００００であるアクリル共重合体（Ｂ）と、架橋剤（Ｃ）とが配合され、前記アクリル共重合体（Ａ）１００質量部に対して、前記アクリル共重合体（Ｂ）を１０〜３５質量部含む構成とすることが開示されている（特許文献１参照）。
In a display device typified by a liquid crystal display, a plurality of optical films are generally used by laminating them on a display element, and an adhesive sheet is used for laminating between the optical films.
For example, in order to obtain an acrylic pressure-sensitive adhesive composition having excellent transparency and maintaining excellent adhesion even under high temperature and high humidity, the acrylic pressure-sensitive adhesive composition may be prepared with methyl acrylate and a copolymer other than methyl acrylate (meth). ) Acrylic copolymer (A) having a weight average molecular weight of 500,000 to 2 million obtained by copolymerizing a monomer mixture (a) containing an acrylic acid ester and a carboxyl group-containing monomer and a hydroxyl group-containing monomer copolymerizable therewith. Acrylic copolymer (B) having a weight average molecular weight of 1000 to 10,000 obtained by copolymerizing a monomer mixture (b) containing methyl methacrylate and a monomer having a cyclic structure, and a cross-linking agent (C) are blended. It is disclosed that the acrylic copolymer (B) is contained in an amount of 10 to 35 parts by mass with respect to 100 parts by mass of the acrylic copolymer (A) (see Patent Document 1).
また、タッチパネルやプラズマディスプレイパネルなどに使用する粘着剤組成物であって、厚塗り塗工乾燥した場合でも、高温高湿条件にさらされた後、室温に戻した際に、白化が発生しない光学用粘着剤組成物を得るために、光学用粘着剤組成物を、（メタ）アクリル酸の炭素数１〜１８のアルキルエステルモノマー（ａ）１００質量部、水酸基を含有する共重合可能なモノマー（ｂ）０．１〜１０質量部、及び、ジアルキル置換アクリルアミドモノマー（ｃ）５〜３０質量部を含むモノマーからなる、重量平均分子量が３０万〜２００万の共重合体であるアクリル樹脂（Ａ）を１００質量部と、架橋剤（Ｂ）を０．０１〜３．０質量部とを含有する構成とすることが開示されている（特許文献２参照）。 In addition, it is an adhesive composition used for touch panels, plasma display panels, etc., and even when it is thickly coated and dried, it does not cause whitening when it is returned to room temperature after being exposed to high temperature and high humidity conditions. In order to obtain a pressure-sensitive adhesive composition for use, the pressure-sensitive optical pressure-sensitive adhesive composition is a copolymerizable monomer containing 100 parts by mass of an alkyl ester monomer (a) having 1 to 18 carbon atoms of (meth) acrylic acid and a hydroxyl group. b) Acrylic resin (A), which is a copolymer having a weight average molecular weight of 300,000 to 2,000,000, consisting of a monomer containing 0.1 to 10 parts by mass and 5 to 30 parts by mass of a dialkyl-substituted acrylamide monomer (c). Is disclosed to contain 100 parts by mass and 0.01 to 3.0 parts by mass of the cross-linking agent (B) (see Patent Document 2).
しかしながら、特許文献１及び２の手法では、優れた耐発泡性と優れた耐白化性とを両立することができなかった。
本発明が解決しようとする課題は、耐発泡性と耐白化性に優れる粘着剤組成物、前記粘着剤組成物の作業性に優れる積層体及び表示素子の視認性に優れる表示装置を提供することにある。
However, the methods of Patent Documents 1 and 2 have not been able to achieve both excellent foaming resistance and excellent whitening resistance.
An object to be solved by the present invention is to provide a pressure-sensitive adhesive composition having excellent foaming resistance and whitening resistance, a laminate having excellent workability of the pressure-sensitive adhesive composition, and a display device having excellent visibility of a display element. It is in.
本発明は以下の＜１＞〜＜７＞のとおりである。
＜１＞ （メタ）アクリル系ポリマー及びアミド系ポリマーを含有し、
前記アミド系ポリマーの含有量が５．０質量％未満であり、かつ
２３℃における貯蔵弾性率が２．５×１０５Ｐａ以下であり、８５℃における貯蔵弾性率が３．８×１０４Ｐａ以上である粘着剤組成物。
＜２＞ 前記アミド系ポリマーの含有量が０．３質量％以上である＜１＞に記載の粘着剤組成物。
＜３＞ 前記アミド系ポリマーの含有量が０．５質量％以下である＜１＞又は＜２＞に記載の粘着剤組成物。
＜４＞ 前記アミド系ポリマーが、環状アミド基を有する＜１＞〜＜３＞のいずれか１つに記載の粘着剤組成物。
＜５＞ 前記２３℃における貯蔵弾性率が５．０×１０４Ｐａ以上であり、前記８５℃における貯蔵弾性率が２．３×１０５Ｐａ以下である＜１＞〜＜４＞のいずれか１つに記載の粘着剤組成物。
The present invention is as follows <1> to <7>.
<1> Contains (meth) acrylic polymer and amide polymer,
Wherein an amide less than the content of the polymer is 5.0 wt%, and is a storage elastic modulus at 23 ° C. is 2.5 × 10 5 Pa or less, a storage elastic modulus at 85 ° C. is 3.8 × 10 4 Pa The pressure-sensitive adhesive composition as described above.
<2> The pressure-sensitive adhesive composition according to <1>, wherein the content of the amide-based polymer is 0.3% by mass or more.
<3> The pressure-sensitive adhesive composition according to <1> or <2>, wherein the content of the amide-based polymer is 0.5% by mass or less.
<4> The pressure-sensitive adhesive composition according to any one of <1> to <3>, wherein the amide-based polymer has a cyclic amide group.
<5> Any of <1> to <4> in which the storage elastic modulus at 23 ° C. is 5.0 × 10 4 Pa or more and the storage elastic modulus at 85 ° C. is 2.3 × 10 5 Pa or less. The pressure-sensitive adhesive composition according to one.
＜６＞ 対峙する剥離基材間に、＜１＞〜＜５＞のいずれか１つに記載の粘着剤組成物が介在する積層体。
＜７＞ 表示素子上に複数の光学フィルムを備え、前記光学フィルム間を＜１＞〜＜５＞のいずれか１つに記載の粘着剤組成物で粘着した表示装置。
<6> A laminate in which the pressure-sensitive adhesive composition according to any one of <1> to <5> is interposed between the peeling substrates facing each other.
<7> A display device in which a plurality of optical films are provided on a display element, and the optical films are adhered to each other with the pressure-sensitive adhesive composition according to any one of <1> to <5>.
本発明によれば、耐発泡性と耐白化性に優れる粘着剤組成物、前記粘着剤組成物の作業性に優れる積層体及び表示素子の視認性に優れる表示装置を提供することができる。 According to the present invention, it is possible to provide a pressure-sensitive adhesive composition having excellent foaming resistance and whitening resistance, a laminate having excellent workability of the pressure-sensitive adhesive composition, and a display device having excellent visibility of a display element.
＜粘着剤組成物＞
本発明の粘着剤組成物は、（メタ）アクリル系ポリマー及びアミド系ポリマーを含有し、アミド系ポリマーの含有量が５．０質量％未満であり、かつ２３℃における貯蔵弾性率が２．５×１０５Ｐａ以下であり、８５℃における貯蔵弾性率が３．８×１０４Ｐａ以上である。
既述のように、液晶ディスプレイに代表される表示装置では、一般に、表示素子上に複数の光学フィルムを貼り合わせて用いられている。（メタ）アクリル系ポリマーのような粘着性成分は吸湿性を有する傾向にあるため、粘着組成物を熱湿環境下（例えば、８５℃／８５％ＲＨ環境下）に置いた後、室温に戻した際に、粘着剤組成物の吸湿水分が結露することにより白化して、表示素子が視認しにくくなる傾向にある。特に、特許文献１のように、アミド系ポリマーを含まない粘着剤組成物は、熱湿環境下に置いた後、室温に戻した際に、白化を生じ易かった。
また、光学フィルムを貼合する被粘着材料であるポリカーボネート、ポリ（メタ）アクリルエステル等は熱湿環境下で膨張し易いため、被粘着材料と粘着剤組成物との間に存在する微細気泡が膨らみ易かった。更に、熱湿環境下では、被粘着材料や粘着剤組成物中に残存する微量の揮発成分が蒸発し、微細な気泡が発生することがあり、粘着剤組成物も軟化し易く、内包する気泡が膨張し、視認性が低下することがあった。
これに対し、光学フィルムの貼り合せに本発明の粘着剤組成物を用いれば、白化を抑制し、粘着剤組成物の発泡を抑制することができる。かかる理由は定かではないが、次の理由によるものと推察される。
<Adhesive composition>
The pressure-sensitive adhesive composition of the present invention contains a (meth) acrylic polymer and an amide-based polymer, has an amide-based polymer content of less than 5.0% by mass, and has a storage elastic modulus of 2.5 at 23 ° C. It is × 10 5 Pa or less, and the storage elastic modulus at 85 ° C. is 3.8 × 10 4 Pa or more.
As described above, in a display device typified by a liquid crystal display, a plurality of optical films are generally used by sticking them on a display element. Since adhesive components such as (meth) acrylic polymers tend to have hygroscopicity, the adhesive composition is placed in a hot and humid environment (for example, 85 ° C./85% RH environment) and then returned to room temperature. At that time, the hygroscopic moisture of the pressure-sensitive adhesive composition tends to be whitened due to dew condensation, making it difficult for the display element to be visually recognized. In particular, as in Patent Document 1, the pressure-sensitive adhesive composition containing no amide-based polymer tends to cause whitening when it is returned to room temperature after being placed in a hot and humid environment.
Further, since polycarbonate, poly (meth) acrylic ester, etc., which are materials to be adhered to which an optical film is attached, easily expand in a hot and humid environment, fine bubbles existing between the material to be adhered and the pressure-sensitive adhesive composition are generated. It was easy to swell. Further, in a hot and humid environment, a small amount of volatile components remaining in the material to be adhered or the pressure-sensitive adhesive composition may evaporate to generate fine bubbles, and the pressure-sensitive adhesive composition is also easily softened, and the bubbles contained therein. May swell and visibility may decrease.
On the other hand, if the pressure-sensitive adhesive composition of the present invention is used for bonding the optical films, whitening can be suppressed and foaming of the pressure-sensitive adhesive composition can be suppressed. The reason for this is not clear, but it is presumed to be due to the following reasons.
粘着性を有する（メタ）アクリル系ポリマーと、粘着剤組成物中５．０質量％未満となる少量のアミド系ポリマーとを、共重合せずに含有することで（すなわち、粘着剤組成物中のアミド系ポリマーの含有量は０質量％を越える）、粘着剤組成物が水分を保持し易くなり、熱湿環境下でも、粘着剤組成物中の水分に起因する結露が生じにくいと考えられる。
更に、本発明では、アミド系ポリマーの粘着剤組成物中の含有量が５質量％未満であることで、透明性を維持することができ、発泡を抑制することができると考えられる。
By containing a (meth) acrylic polymer having adhesiveness and a small amount of amide-based polymer which is less than 5.0% by mass in the pressure-sensitive adhesive composition without copolymerization (that is, in the pressure-sensitive adhesive composition). The content of the amide-based polymer exceeds 0% by mass), and it is considered that the pressure-sensitive adhesive composition easily retains water, and dew condensation due to the water content in the pressure-sensitive adhesive composition is unlikely to occur even in a hot and humid environment. ..
Further, in the present invention, it is considered that transparency can be maintained and foaming can be suppressed when the content of the amide-based polymer in the pressure-sensitive adhesive composition is less than 5% by mass.
加えて、本発明の粘着剤組成物は、２３℃における貯蔵弾性率が２．５×１０５Ｐａ以下であり、８５℃における貯蔵弾性率が３．８×１０４Ｐａ以上である。これはつまり、粘着剤組成物が室温（２３℃）環境下に置かれている場合には、柔軟性を有し、高温（８５℃）環境下ではある程度の弾性力を有することを意味する。室温環境下において粘着剤組成物が柔軟性を有することで、粘着剤組成物を用いて被粘着材料（例えば、光学フィルム）を貼り合せるときは、粘着剤組成物が被粘着材料の形状に追随し、粘着剤組成物と被粘着材料との間に気泡が入りにくい。また、８５℃の貯蔵弾性率が３．８×１０４Ｐａ以上であることで、高温環境下で粘着剤組成物が柔らかくなりすぎず、その結果、界面接着強度が低下しにくくなり、発泡を抑制することができると考えられる。
以下、本発明の粘着剤組成物、これを用いた積層体及び表示装置について、詳細に説明する。
なお、粘着剤組成物について、２３℃における貯蔵弾性率を２．５×１０５Ｐａ以下とし、８５℃における貯蔵弾性率を３．８×１０４Ｐａ以上とすることを、「粘着剤組成物に特定の弾性力を与える」と記載することがある。
In addition, pressure sensitive adhesive composition of the present invention, the storage elastic modulus at 23 ° C. is not more than 2.5 × 10 5 Pa, at a storage modulus at 85 ° C. is 3.8 × 10 4 Pa or more. This means that the pressure-sensitive adhesive composition has flexibility when placed in a room temperature (23 ° C.) environment and has some elastic force in a high temperature (85 ° C.) environment. The flexibility of the pressure-sensitive adhesive composition in a room temperature environment allows the pressure-sensitive adhesive composition to follow the shape of the material to be adhered when the material to be adhered (for example, an optical film) is bonded using the pressure-sensitive adhesive composition. However, it is difficult for air bubbles to enter between the pressure-sensitive adhesive composition and the material to be adhered. Further, when the storage elastic modulus at 85 ° C. is 3.8 × 10 4 Pa or more, the pressure-sensitive adhesive composition does not become too soft in a high-temperature environment, and as a result, the interfacial adhesive strength is less likely to decrease, resulting in foaming. It is thought that it can be suppressed.
Hereinafter, the pressure-sensitive adhesive composition of the present invention, the laminate using the pressure-sensitive adhesive composition, and the display device will be described in detail.
Regarding the pressure-sensitive adhesive composition, the storage elastic modulus at 23 ° C. is 2.5 × 10 5 Pa or less, and the storage elastic modulus at 85 ° C. is 3.8 × 10 4 Pa or more. Gives a specific elastic force to. "
〔（メタ）アクリル系ポリマー〕
本発明の粘着剤組成物は、（メタ）アクリル系ポリマーを含有する。
（メタ）アクリル系ポリマーは、粘着剤組成物に粘着性をもたらし、本発明の粘着剤組成物は、例えば、ガラス、ポリカーボネート（ＰＣ）、ポリ（メタ）アクリルエステル等の被粘着材料に対して粘着性を有する。（メタ）アクリル系ポリマーは、また、粘着剤組成物に弾性をもたらすことから、熱湿環境下に粘着剤組成物が置かれたときに、粘着剤組成物の過度の柔軟化が抑制され、ある程度の弾性力（３．８×１０４Ｐａ以上）を保ち易くすることができる。
なお、（メタ）アクリル系ポリマーとは、メタクリル系ポリマー及びアクリル系ポリマーのいずれか一方又は両方を意味する。（メタ）アクリル系モノマー、（メタ）アクリル酸等も同様である。
[(Meta) acrylic polymer]
The pressure-sensitive adhesive composition of the present invention contains a (meth) acrylic polymer.
The (meth) acrylic polymer brings adhesiveness to the pressure-sensitive adhesive composition, and the pressure-sensitive adhesive composition of the present invention is used for a material to be adhered such as glass, polycarbonate (PC), poly (meth) acrylic ester and the like. It is sticky. Since the (meth) acrylic polymer also provides elasticity to the pressure-sensitive adhesive composition, excessive softening of the pressure-sensitive adhesive composition is suppressed when the pressure-sensitive adhesive composition is placed in a hot and humid environment. It is possible to easily maintain a certain level of elastic force (3.8 × 10 4 Pa or more).
The (meth) acrylic polymer means either one or both of the methacrylic polymer and the acrylic polymer. The same applies to (meth) acrylic monomers, (meth) acrylic acids and the like.
（メタ）アクリル系ポリマーとしては、（メタ）アクリル系モノマーを必須のモノマー成分（単量体成分）とする重合体であれば特に制限されない。例えば、直鎖又は分岐鎖状のアルキル基を有する（メタ）アクリル酸アルキルエステル及び（メタ）アクリル酸アルコキシアルキルエステルのいずれか一方又は両方をモノマー成分として構成された重合体を用いることができる。アクリル系ポリマーを構成するモノマー成分として、その他の共重合性モノマーを含んでいてもよい。 The (meth) acrylic polymer is not particularly limited as long as it is a polymer containing a (meth) acrylic monomer as an essential monomer component (monomer component). For example, a polymer composed of either or both of a (meth) acrylic acid alkyl ester and a (meth) acrylic acid alkoxyalkyl ester having a linear or branched alkyl group as a monomer component can be used. Other copolymerizable monomers may be contained as a monomer component constituting the acrylic polymer.
直鎖又は分岐鎖状のアルキル基を有する（メタ）アクリル酸アルキルエステル（以下、単に「（メタ）アクリル酸アルキルエステル」と称する場合がある）としては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓ−ブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸イソペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸オクチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、(メタ)アクリル酸イソデシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸トリデシル、（メタ）アクリル酸テトラデシル、（メタ）アクリル酸ペンタデシル、(メタ)アクリル酸ヘキサデシル、（メタ）アクリル酸ヘプタデシル、（メタ）アクリル酸オクタデシル、（メタ）アクリル酸ノナデシル、（メタ）アクリル酸エイコシルなどのアルキル基の炭素数が１〜２０の（メタ）アクリル酸アルキルエステルが挙げられる。なお、上記（メタ）アクリル酸アルキルエステルは単独で、又は２種以上を組み合わせて使用することができる。中でも、（メタ）アクリル酸アルキルエステルとしては、粘着剤組成物に特定の弾性力を与え易くし、また、粘着剤組成物の粘着性を上げる観点から、メタクリル酸メチル（ＭＭＡ）、アクリル酸ブチル（ＢＡ）、アクリル酸２−エチルヘキシル（２ＥＨＡ）が好ましい。 Examples of the (meth) acrylic acid alkyl ester having a linear or branched alkyl group (hereinafter, may be simply referred to as “(meth) acrylic acid alkyl ester”) include methyl (meth) acrylic acid, ( Ethyl acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, (meth) acrylate t-butyl, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) ) Isooctyl acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, (meth) Tridecyl acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecil (meth) acrylate, (meth) acrylic Examples thereof include (meth) acrylic acid alkyl esters having 1 to 20 carbon atoms in alkyl groups such as eicosyl acid. The above (meth) acrylic acid alkyl ester can be used alone or in combination of two or more. Among them, the (meth) acrylic acid alkyl ester includes methyl methacrylate (MMA) and butyl acrylate from the viewpoint of facilitating the application of a specific elastic force to the pressure-sensitive adhesive composition and increasing the stickiness of the pressure-sensitive adhesive composition. (BA), 2-ethylhexyl acrylate (2EHA) are preferred.
また、（メタ）アクリル酸アルコキシアルキルエステル［アルコキシアルキル（メタ）アクリレート］としては、特に限定されないが、例えば、（メタ）アクリル酸２−メトキシエチル、（メタ）アクリル酸２−エトキシエチル、（メタ）アクリル酸メトキシトリエチレングリコール、（メタ）アクリル酸３−メトキシプロピル、（メタ）アクリル酸３−エトキシプロピル、（メタ）アクリル酸４−メトキシブチル、（メタ）アクリル酸４−エトキシブチルなどが挙げられる。なお、（メタ）アクリル酸アルコキシアルキルエステルは単独で、又は２種以上を組み合わせて使用することができる。中でも、粘着剤組成物に特定の弾性力を与え易くし、また、粘着剤組成物の粘着性を上げる観点から、アクリル酸２−メトキシエチル（２ＭＥＡ）が好ましい。 The (meth) acrylic acid alkoxyalkyl ester [alkoxyalkyl (meth) acrylate] is not particularly limited, but for example, 2-methoxyethyl (meth) acrylic acid, 2-ethoxyethyl (meth) acrylic acid, (meth). ) Methoxytriethylene glycol acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 4-ethoxybutyl (meth) acrylate, etc. Be done. The (meth) acrylic acid alkoxyalkyl ester can be used alone or in combination of two or more. Of these, 2-methoxyethyl acrylate (2MEA) is preferable from the viewpoint of facilitating the application of a specific elastic force to the pressure-sensitive adhesive composition and increasing the stickiness of the pressure-sensitive adhesive composition.
（メタ）アクリル酸アルキルエステル及び（メタ）アクリル酸アルコキシアルキルエステルの含有量は、被粘着材料との接着性の観点から、（メタ）アクリル系ポリマーを構成するモノマー成分全量中、３０質量％以上（例えば、３０〜９９質量％）が好ましく、より好ましくは５０〜９９質量％である。なお、上記アクリル系ポリマーのモノマー成分として、（メタ）アクリル酸アルキルエステル及び（メタ）アクリル酸アルコキシアルキルエステルの両方が用いられている場合は、（メタ）アクリル酸アルキルエステルの含有量と（メタ）アクリル酸アルコキシアルキルエステルの含有量の合計量（合計含有量）が上記の範囲を満たせばよい。 The content of the (meth) acrylic acid alkyl ester and the (meth) acrylic acid alkoxyalkyl ester is 30% by mass or more in the total amount of the monomer components constituting the (meth) acrylic polymer from the viewpoint of adhesiveness to the material to be adhered. (For example, 30 to 99% by mass) is preferable, and 50 to 99% by mass is more preferable. When both (meth) acrylic acid alkyl ester and (meth) acrylic acid alkoxyalkyl ester are used as the monomer component of the acrylic polymer, the content of (meth) acrylic acid alkyl ester and (meth) acrylic acid alkyl ester are used. ) The total amount (total content) of the acrylic acid alkoxyalkyl ester content may satisfy the above range.
また、（メタ）アクリル系ポリマーを構成するモノマー成分として、（メタ）アクリル酸アルキルエステルと（メタ）アクリル酸アルコキシアルキルエステルの両方が用いられている場合、これらの合計含有量に対する（メタ）アクリル酸アルコキシアルキルエステルの含有量は、粘着剤組成物に特定の弾性力を与え易くし、また、粘着剤組成物の粘着性を上げる観点から、１〜７５質量％が好ましく、より好ましくは１〜５０質量％である。 When both (meth) acrylic acid alkyl ester and (meth) acrylic acid alkoxyalkyl ester are used as the monomer components constituting the (meth) acrylic polymer, (meth) acrylic with respect to the total content thereof. The content of the acid alkoxyalkyl ester is preferably 1 to 75% by mass, more preferably 1 to 75% by mass, from the viewpoint of facilitating the application of a specific elastic force to the pressure-sensitive adhesive composition and increasing the stickiness of the pressure-sensitive adhesive composition. It is 50% by mass.
（メタ）アクリル系ポリマーは、重量平均分子量（Ｍｗ）が、７００，０００〜２，０００，０００であることが好ましく、９００，０００〜１，４００，０００であることがより好ましく、９５０，０００〜１，３００，０００であることが更に好ましい。（メタ）アクリル系ポリマーの重量平均分子量を大きくすることで、粘着剤組成物の８５℃における貯蔵弾性率を大きくし易い。重量平均分子量を小さくすることで、粘着剤組成物の２３℃における貯蔵弾性率を小さくし易く、粘着剤組成物の被粘着材料への追随性を高め易い。
（メタ）アクリル系ポリマーは、粘着剤組成物に特定の弾性力を与えて耐発泡性を高める観点から、ガラス転移温度（Ｔｇ）が、−４５〜−１５℃であることが好ましく、−４５〜−２０℃であることがより好ましく、−４０〜−２５℃であることが更に好ましく、−４０〜−３１℃であることが更に好ましい。（メタ）アクリル系ポリマーのガラス転移温度を高くすることで、粘着剤組成物の８５℃における貯蔵弾性率を大きくし易く、また、ガラス転移温度を低くすることで、粘着剤組成物の２３℃における貯蔵弾性率を小さくし易い。
The weight average molecular weight (Mw) of the (meth) acrylic polymer is preferably 700,000 to 2,000,000, more preferably 900,000 to 1,400,000, and 950,000. It is more preferably ~ 1,300,000. By increasing the weight average molecular weight of the (meth) acrylic polymer, it is easy to increase the storage elastic modulus of the pressure-sensitive adhesive composition at 85 ° C. By reducing the weight average molecular weight, it is easy to reduce the storage elastic modulus of the pressure-sensitive adhesive composition at 23 ° C., and it is easy to improve the followability of the pressure-sensitive adhesive composition to the material to be adhered.
The glass transition temperature (Tg) of the (meth) acrylic polymer is preferably −45 to −45 ° C. from the viewpoint of imparting a specific elastic force to the pressure-sensitive adhesive composition to enhance foam resistance. It is more preferably ~ -20 ° C, further preferably -40 to -25 ° C, and even more preferably -40 to −31 ° C. By increasing the glass transition temperature of the (meth) acrylic polymer, it is easy to increase the storage elastic modulus of the pressure-sensitive adhesive composition at 85 ° C., and by lowering the glass transition temperature, the pressure-sensitive adhesive composition is 23 ° C. It is easy to reduce the storage elastic modulus in.
（メタ）アクリル系ポリマーは、粘着剤組成物の主成分であることが好ましく、具体的には、粘着剤組成物中の含有量が７０質量％以上であることが好ましく、８０質量％以上であることがより好ましく、９０質量％以上であることが更に好ましい。
なお、本発明において、粘着剤組成物中の各種成分の含有量は、特記する場合を除き、固形分濃度としての値を意味し、固形分濃度（質量％）を「ＮＶ（Non-Volatile）」と表すことがある。
The (meth) acrylic polymer is preferably the main component of the pressure-sensitive adhesive composition, and specifically, the content in the pressure-sensitive adhesive composition is preferably 70% by mass or more, and 80% by mass or more. It is more preferable that the amount is 90% by mass or more.
In the present invention, the content of various components in the pressure-sensitive adhesive composition means a value as a solid content concentration, and the solid content concentration (mass%) is defined as "NV (Non-Volatile)", unless otherwise specified. May be expressed.
〔アミド系ポリマー〕
本発明の粘着剤組成物は、アミド系ポリマーを含有し（含有量が０質量％超）、含有量が５．０質量％未満である。
本発明の粘着剤組成物が、５．０質量％未満の範囲でアミド系ポリマーを含有することで、粘着剤組成物に親水性を与え、熱湿環境下での光学フィルムの白化を抑制すると共に、透明性を維持することができ、高温環境下での発泡を抑制することができる。
アミド系ポリマーとしては、ポリマー分子中にアミド結合（−ＮＨ−ＣＯ−）を有するポリマーであれば特に制限されないが、粘着剤組成物の親水性を高める観点から、アミド系ポリマーを構成する単量単位中にアミド結合を有するポリマーであることが好ましい。
[Amide polymer]
The pressure-sensitive adhesive composition of the present invention contains an amide-based polymer (content is more than 0% by mass) and has a content of less than 5.0% by mass.
When the pressure-sensitive adhesive composition of the present invention contains an amide-based polymer in a range of less than 5.0% by mass, the pressure-sensitive adhesive composition is made hydrophilic and whitening of an optical film is suppressed in a hot and humid environment. At the same time, transparency can be maintained and foaming in a high temperature environment can be suppressed.
The amide-based polymer is not particularly limited as long as it is a polymer having an amide bond (-NH-CO-) in the polymer molecule, but from the viewpoint of increasing the hydrophilicity of the pressure-sensitive adhesive composition, a single amount constituting the amide-based polymer It is preferably a polymer having an amide bond in the unit.
また、アミド系ポリマーは、粘着剤組成物の親水性を高める観点から、環状アミド基を有するポリマーであることが好ましく、例えば、Ｎ−ビニルピロリドン、Ｎ−ビニルピペリドン、Ｎ−ビニルカプロラクタムなどの環状アミド基を有するモノマーを単独で重合あるいは他のモノマーと共重合させて得られるポリマーが挙げられる。その具体例としては、ポリビニルピロリドン（ＰＶＰ）、ポリビニルカプロラクタム、ポリビニルピロリドン／酢酸ビニル共重合物、ビニルピロリドン／ビニルカプロラクタム共重合物、ビニルピロリドン／ビニルイミダゾール共重合物、ビニルピロリドン／アクリル酸共重合物、ビニルピロリドン／メタクリル酸共重合物、ビニルピロリドン／３−メチル−１−ビニルイミダゾリウム塩共重合物などが挙げられる。 The amide-based polymer is preferably a polymer having a cyclic amide group from the viewpoint of increasing the hydrophilicity of the pressure-sensitive adhesive composition, and is, for example, a cyclic amide such as N-vinylpyrrolidone, N-vinylpiperidone, or N-vinylcaprolactam. Examples thereof include polymers obtained by polymerizing a monomer having a group alone or copolymerizing with another monomer. Specific examples thereof include polyvinylpyrrolidone (PVP), polyvinylcaprolactam, polyvinylpyrrolidone / vinyl acetate copolymer, vinylpyrrolidone / vinylcaprolactam copolymer, vinylpyrrolidone / vinylimidazole copolymer, and vinylpyrrolidone / acrylic acid copolymer. , Vinylpyrrolidone / methacrylic acid copolymer, vinylpyrrolidone / 3-methyl-1-vinylimidazolium salt copolymer and the like.
アミド系ポリマーの重量平均分子量（Ｍｗ）は、粘着剤組成物の親水性を高め、耐白化性を高める観点から、７，０００〜１５０，０００であることが好ましく、１０，０００〜１４０，０００であることがより好ましく、１５，０００〜１３０，０００であることが更に好ましい。
粘着剤組成物中のアミド系ポリマーの含有量は、耐白化性と耐発泡性をより向上する観点から、０．３質量％以上であることが好ましい。また、耐発泡性を高める観点から、粘着剤組成物中のアミド系ポリマーの含有量は、２．０質量％以下であることが好ましく、０．９質量％以下であることがより好ましく、０．５質量％以下であることが更に好ましい。粘着剤組成物の透明性を高める観点から、粘着剤組成物中のアミド系ポリマーの含有量は、０．４質量％以下であることがより更に好ましい。
The weight average molecular weight (Mw) of the amide-based polymer is preferably 7,000 to 150,000, preferably 10,000 to 140,000, from the viewpoint of increasing the hydrophilicity of the pressure-sensitive adhesive composition and enhancing the whitening resistance. Is more preferable, and 15,000 to 130,000 is even more preferable.
The content of the amide-based polymer in the pressure-sensitive adhesive composition is preferably 0.3% by mass or more from the viewpoint of further improving whitening resistance and foaming resistance. Further, from the viewpoint of enhancing foam resistance, the content of the amide polymer in the pressure-sensitive adhesive composition is preferably 2.0% by mass or less, more preferably 0.9% by mass or less, and is 0. It is more preferably 5.5% by mass or less. From the viewpoint of enhancing the transparency of the pressure-sensitive adhesive composition, the content of the amide-based polymer in the pressure-sensitive adhesive composition is more preferably 0.4% by mass or less.
（硬化剤）
本発明の粘着剤組成物は、更に、硬化剤を含有していることが好ましい。
粘着剤組成物が硬化剤を含有することで、粘着剤組成物の耐久性を高めることができる。
硬化剤は、（メタ）アクリル系ポリマー及びアミド系ポリマー、並びに必要に応じて含まれる各種ポリマーを架橋し得る化合物であれば、特に制限されず、例えば、金属キレート化合物、エポキシ化合物等が挙げられる。
(Hardener)
The pressure-sensitive adhesive composition of the present invention preferably further contains a curing agent.
When the pressure-sensitive adhesive composition contains a curing agent, the durability of the pressure-sensitive adhesive composition can be enhanced.
The curing agent is not particularly limited as long as it is a compound capable of cross-linking a (meth) acrylic polymer, an amide polymer, and various polymers contained as necessary, and examples thereof include a metal chelate compound and an epoxy compound. ..
金属キレート化合物としては、多価金属が有機化合物と共有結合または配位結合しているものが挙げられる。多価金属原子としては、Ａｌ、Ｚｒ、Ｃｏ、Ｃｕ、Ｆｅ、Ｎｉ、Ｖ、Ｚｎ、Ｉｎ、Ｃａ、Ｍｇ、Ｍｎ、Ｙ、Ｃｅ、Ｓｒ、Ｂａ、Ｍｏ、Ｌａ、Ｓｎ、Ｔｉなどが挙げられる。これらのなかでも、Ａｌ、Ｚｒ、Ｔｉが好ましい。特にＡｌが、着色が無く、透明性が良い点で好ましい。
また、共有結合または配位結合する有機化合物中の原子としては酸素原子などが挙げられ、有機化合物としては、アルキルエステル、アルコール化合物、カルボン酸化合物、エーテル化合物、ケトン化合物などが挙げられる。
具体的には、特に安定で取り扱いが容易なアルミニウムトリスアセチルアセトネートなどが好適に使用される。また、金属キレート化合物としては、単独で用いてもよいし、複数種を用いてもよい。
Examples of the metal chelate compound include those in which a polyvalent metal is covalently bonded or coordinated to an organic compound. Examples of the polyvalent metal atom include Al, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti and the like. .. Among these, Al, Zr, and Ti are preferable. In particular, Al is preferable because it is not colored and has good transparency.
Further, examples of the atom in the organic compound having a covalent bond or a coordination bond include an oxygen atom, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound.
Specifically, aluminum trisacetylacetoneate, which is particularly stable and easy to handle, is preferably used. Further, as the metal chelate compound, it may be used alone or a plurality of kinds may be used.
エポキシ化合物は、エポキシ基を１つ又は２つ以上有する化合物を用いることができる。具体的には、例えば、Ｎ，Ｎ，Ｎ，Ｎ’−テトラグリシジル−ｍ−キシレンジアミン、ビスフェノールＡ−エピクロルヒドリン型のエポキシ樹脂、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリジジルエーテル、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ジグリシジルアニリン、ジグリシジルアミン、１，３−ビス（Ｎ，Ｎ’−ジグリシジルアミノメチル）シクロヘキサン等を用いることができる。
以上の中でも、（メタ）アクリル系ポリマーの架橋を進め、粘着剤組成物に特定の弾性力を与え易くする観点から、エポキシ基を２つ以上有する多官能性エポキシ化合物が好ましく、１，３−ビス（Ｎ，Ｎ’−ジグリシジルアミノメチル）シクロヘキサン及びＮ，Ｎ，Ｎ，Ｎ’−テトラグリシジル−ｍ−キシレンジアミンがより好ましく、１，３−ビス（Ｎ，Ｎ’−ジグリシジルアミノメチル）シクロヘキサンが更に好ましい。
エポキシ化合物は、単独で用いてもよいし、複数種を用いてもよい。
As the epoxy compound, a compound having one or more epoxy groups can be used. Specifically, for example, N, N, N, N'-tetraglycidyl-m-xylene diamine, bisphenol A-epicrolhydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, Glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, diglycidyl amine, 1,3-bis (N, N'-diglycidyl aminomethyl) cyclohexane and the like are used. be able to.
Among the above, a polyfunctional epoxy compound having two or more epoxy groups is preferable, from the viewpoint of promoting cross-linking of the (meth) acrylic polymer and facilitating the application of a specific elastic force to the pressure-sensitive adhesive composition, 1,3-. Bis (N, N'-diglycidylaminomethyl) cyclohexane and N, N, N, N'-tetraglycidyl-m-xylenediamine are more preferred, 1,3-bis (N, N'-diglycidylaminomethyl). Cyclohexane is more preferred.
The epoxy compound may be used alone or in combination of two or more.
粘着剤組成物中の硬化剤の含有量は、粘着剤組成物の耐久性を高める観点から、（メタ）アクリル系ポリマー１００質量部に対して、０．０１〜２．０質量部であることが好ましい。特に、硬化剤が金属キレート化合物である場合は０．０５〜１．６質量部であることが好ましく、０．０５〜０．８質量部であることがより好ましい。また、硬化剤がエポキシ化合物である場合は０．０１〜０．４質量部であることが好ましく、０．０４〜０．２質量部であることがより好ましい。
粘着剤組成物は、（メタ）アクリル系ポリマー等の硬化を促進するために、更に、硬化促進剤、硬化助剤等として機能するヒドロキシ基を有するアミン系化合物等を含んでいてもよい。
The content of the curing agent in the pressure-sensitive adhesive composition is 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer from the viewpoint of enhancing the durability of the pressure-sensitive adhesive composition. Is preferable. In particular, when the curing agent is a metal chelate compound, it is preferably 0.05 to 1.6 parts by mass, and more preferably 0.05 to 0.8 parts by mass. When the curing agent is an epoxy compound, it is preferably 0.01 to 0.4 parts by mass, and more preferably 0.04 to 0.2 parts by mass.
The pressure-sensitive adhesive composition may further contain an amine-based compound having a hydroxy group that functions as a curing accelerator, a curing aid, or the like in order to promote curing of the (meth) acrylic polymer or the like.
（各種添加剤）
本発明の粘着剤組成物は、（メタ）アクリル系ポリマー及びアミド系ポリマー、並びに必要に応じて含み得る硬化剤のほかに、更に、紫外線吸収剤、酸化防止剤、防腐剤、防黴剤、可塑剤、消泡剤、濡れ性調製剤等の各種添加剤を含有していてもよい。また、本発明の効果を損なわない限度において、（メタ）アクリル系ポリマー及びアミド系ポリマー以外のポリマーを含有していてもよい。
被粘着材料として、ガラスを用いる場合は、粘着剤組成物とガラスとの粘着性及び密着性をより向上する観点から、粘着剤組成物は更にシランカップリング剤を含有していてもよい。シランカップリング剤としては、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−アミノプロピルトリメトキシシラン、Ｎ−フェニル−アミノプロピルトリメトキシシラン等が挙げられる。
(Various additives)
In addition to the (meth) acrylic polymer and the amide polymer, and the curing agent which may be contained if necessary, the pressure-sensitive adhesive composition of the present invention further comprises an ultraviolet absorber, an antioxidant, a preservative, a fungicide, and the like. It may contain various additives such as a plasticizer, a defoaming agent, and a wettability adjusting agent. Further, a polymer other than the (meth) acrylic polymer and the amide polymer may be contained as long as the effect of the present invention is not impaired.
When glass is used as the material to be adhered, the pressure-sensitive adhesive composition may further contain a silane coupling agent from the viewpoint of further improving the adhesiveness and adhesion between the pressure-sensitive adhesive composition and the glass. Examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-aminopropyltrimethoxysilane and the like.
〔粘着剤組成物の特性〕
（貯蔵弾性）
本発明の粘着剤組成物は、２３℃における貯蔵弾性率が２．５×１０５Ｐａ以下であり、８５℃における貯蔵弾性率が３．８×１０４Ｐａ以上である。
２３℃における粘着剤組成物の貯蔵弾性率が２．５×１０５Ｐａを超えると、粘着剤組成物を用いて被粘着材料（例えば、光学フィルム）を貼り合せるときに、粘着剤組成物が被粘着材料の形状に追随せず、粘着剤組成物と被粘着材料との間に気泡が入り易いため、耐発泡性を十分に発現することができない。
また、８５℃における粘着剤組成物の貯蔵弾性率が３．８×１０４Ｐａ未満であると、粘着剤組成物と被粘着材料の界面接着強度が低下し易く、また、粘着剤組成物と被粘着材料との間に存在する微細気泡が膨張し易いため、耐発泡性が得られない。
[Characteristics of adhesive composition]
(Storage elasticity)
The adhesive composition of the present invention, the storage elastic modulus at 23 ° C. is not more than 2.5 × 10 5 Pa, at a storage modulus at 85 ° C. is 3.8 × 10 4 Pa or more.
When the storage elastic modulus of the adhesive composition at 23 ° C. is more than 2.5 × 10 5 Pa, the pressure-sensitive material using an adhesive composition (e.g., an optical film) when laminating the pressure-sensitive adhesive composition Since it does not follow the shape of the material to be adhered and bubbles are likely to enter between the pressure-sensitive adhesive composition and the material to be adhered, it is not possible to sufficiently exhibit foam resistance.
Further, when the storage modulus of the pressure-sensitive adhesive composition in 85 ° C. is less than 3.8 × 10 4 Pa, easily interfacial adhesion strength of the adhesive composition and the adhesive material is reduced, also, the pressure-sensitive adhesive composition Since the fine bubbles existing between the material to be adhered and the material to be adhered easily expand, foam resistance cannot be obtained.
かかる観点から、本発明の粘着剤組成物は、２３℃における貯蔵弾性率が２．３×１０５Ｐａ以下であることが好ましく、８５℃における貯蔵弾性率が４．１×１０４Ｐａ以上であることが好ましい。
また、本発明の粘着剤組成物は、２３℃における貯蔵弾性率が、５．０×１０４Ｐａ以上であることが好ましい。室温環境下においてもある程度の弾性力を有することで、粘着剤組成物の加工性、作業性等に優れ、例えば、粘着剤組成物をフィルム状に加工したとき、裁断し易い。また、対峙する被粘着材料の粘着剤として粘着剤組成物を用いたときに、被粘着材料間から粘着剤組成物がはみ出しにくい。
８５℃における粘着剤組成物の貯蔵弾性率は、常温下での貼合性や段差吸収性、加工性などの性能バランスの観点から、２．３×１０５Ｐａ以下であることが好ましい。
From this point of view, the pressure-sensitive adhesive composition of the present invention preferably has a storage elastic modulus at 23 ° C. of 2.3 × 10 5 Pa or less, and a storage elastic modulus at 85 ° C. of 4.1 × 10 4 Pa or more. It is preferable to have.
Further, the pressure-sensitive adhesive composition of the present invention, the storage elastic modulus at 23 ° C. is preferably at 5.0 × 10 4 Pa or more. Having a certain degree of elastic force even in a room temperature environment, the pressure-sensitive adhesive composition is excellent in processability, workability, etc. For example, when the pressure-sensitive adhesive composition is processed into a film, it is easy to cut. Further, when the pressure-sensitive adhesive composition is used as the pressure-sensitive adhesive for the materials to be adhered to face each other, the pressure-sensitive adhesive composition does not easily protrude from the materials to be adhered.
Storage modulus of the pressure-sensitive adhesive composition in 85 ° C. is bonded compatibility and step absorbability at room temperature, from the viewpoint of the performance balance such as processability, it is preferably at most 2.3 × 10 5 Pa.
なお、８５℃における粘着剤組成物の貯蔵弾性率は、アクリル系ポリマーのモノマー組成、アクリル系ポリマーの重量平均分子量、硬化剤の含有量等により制御することができ、２３℃における粘着剤組成物の貯蔵弾性率は、アクリル系ポリマーの重量平均分子量、分子量分布、ガラス転移温度等により制御することができる。
粘着剤組成物の貯蔵弾性率は、動的粘弾性測定により、せん断貯蔵弾性率として測定することができる。具体的には、膜厚５０μｍの粘着剤組成物膜を積層して２ｍｍの測定サンプルを用意し、ＭＣＲ３０２（アントンパール社製）を用い、下記測定条件にて測定することで、貯蔵弾性率が求まる。
（測定条件）
変形モード：ずりモード
温度範囲：−６０℃〜２００℃
昇温速度：３℃／ｍｉｎ
周波数：１Ｈｚ
測定治具：パラレルプレート８ｍｍφ
環境：Ｎ２雰囲気下
The storage elastic modulus of the pressure-sensitive adhesive composition at 85 ° C. can be controlled by the monomer composition of the acrylic polymer, the weight average molecular weight of the acrylic polymer, the content of the curing agent, and the like, and the pressure-sensitive adhesive composition at 23 ° C. The storage elastic modulus of the acrylic polymer can be controlled by the weight average molecular weight, the molecular weight distribution, the glass transition temperature, and the like of the acrylic polymer.
The storage elastic modulus of the pressure-sensitive adhesive composition can be measured as a shear storage elastic modulus by dynamic viscoelasticity measurement. Specifically, a 2 mm measurement sample is prepared by laminating a pressure-sensitive adhesive composition film having a film thickness of 50 μm, and measurement is performed using MCR302 (manufactured by Anton Pearl Co., Ltd.) under the following measurement conditions to obtain a storage elastic modulus. I want it.
(Measurement condition)
Deformation mode: Slip mode Temperature range: -60 ° C to 200 ° C
Heating rate: 3 ° C / min
Frequency: 1Hz
Measuring jig: Parallel plate 8 mmφ
Environment: N 2 atmosphere
〔粘着剤組成物の製造方法〕
本発明の粘着剤組成物の製造方法は、アミド系ポリマーの含有量が０質量％超、５質量％未満となるように（メタ）アクリル系ポリマー及びアミド系ポリマーが含まれ、粘着剤組成物に特定の弾性力を与えることができる方法であれば、特に制限されない。
（メタ）アクリル系ポリマー、アミド系ポリマー、及び必要に応じて硬化剤並びに各種添加剤を溶剤に添加して混合し、乾燥することで、粘着剤組成物を製造することができる。既述のように、粘着剤組成物に特定の弾性力を与えるには、（メタ）アクリル系ポリマーのモノマー成分、重量平均分子量、ガラス転移温度等を制御し、また、粘着剤組成物の配合成分の固形分濃度を調整することが好ましい。
[Manufacturing method of adhesive composition]
The method for producing a pressure-sensitive adhesive composition of the present invention contains a (meth) acrylic polymer and an amide-based polymer so that the content of the amide-based polymer is more than 0% by mass and less than 5% by mass. The method is not particularly limited as long as it can give a specific elastic force to the polymer.
A pressure-sensitive adhesive composition can be produced by adding a (meth) acrylic polymer, an amide-based polymer, and if necessary, a curing agent and various additives to a solvent, mixing them, and drying them. As described above, in order to give a specific elastic force to the pressure-sensitive adhesive composition, the monomer component of the (meth) acrylic polymer, the weight average molecular weight, the glass transition temperature, etc. are controlled, and the pressure-sensitive adhesive composition is blended. It is preferable to adjust the solid content concentration of the component.
＜積層体＞
本発明の積層体は、対峙する剥離基材間に、本発明の粘着剤組成物が介在する。
対峙する剥離基材間に、本発明の粘着剤組成物を介在させることで、粘着剤組成物の加工性及び作業性に優れ、粘着剤組成物の特性を低下させずに使用し、保管することができる。
剥離基材としては、ポリエチレンラミネート紙、グラシン紙、クレーコート紙、水系樹脂コート紙、ポリエチレンテレフタレート（ＰＥＴ）、ポリプロピレン等のフィルムを剥離原紙に用い、粘着剤組成物が接する面に、シリコーン化合物、フッ素化合物等の離型剤を塗布した板状体を用いることができる。
本発明の積層体の層構成は特に制限されず、剥離基材／粘着剤組成物／剥離基材といった３層、剥離基材／粘着剤組成物／剥離基材／粘着剤組成物／剥離基材といった５層とすることができる。積層体に用いる２層以上の剥離機材の種類は、同じであってもよいし、異なっていてもよい。また、積層体に用いる２層以上の粘着剤組成物の種類は、同じであってもよいし、異なっていてもよい。
<Laminated body>
In the laminate of the present invention, the pressure-sensitive adhesive composition of the present invention is interposed between the peeling substrates facing each other.
By interposing the pressure-sensitive adhesive composition of the present invention between the peeling substrates facing each other, the pressure-sensitive adhesive composition is excellent in processability and workability, and is used and stored without deteriorating the characteristics of the pressure-sensitive adhesive composition. be able to.
As the release base material, a film such as polyethylene laminated paper, glassin paper, clay coated paper, water-based resin coated paper, polyethylene terephthalate (PET), or polypropylene is used as the release base paper, and a silicone compound is used on the surface in contact with the pressure-sensitive adhesive composition. A plate-like body coated with a release agent such as a fluorine compound can be used.
The layer structure of the laminate of the present invention is not particularly limited, and there are three layers such as a release base material / adhesive composition / release base material, and a release base material / pressure-sensitive adhesive composition / release base material / pressure-sensitive adhesive composition / release group. It can be made up of 5 layers such as wood. The types of the two or more layers of peeling equipment used for the laminated body may be the same or different. Further, the types of the two or more layers of the pressure-sensitive adhesive composition used for the laminate may be the same or different.
＜表示装置＞
本発明の表示装置は、表示素子上に複数の光学フィルムを備え、前記光学フィルム間を本発明の粘着剤組成物で粘着してなる。
本発明の粘着剤組成物は、熱湿環境下に置かれても、耐白化性及び耐発泡性に優れるため、光学フィルム間を本発明の粘着剤組成物で接着した光学フィルム積層体を表示素子上に備えた表示装置は、表示素子の視認性に優れる。
表示装置の種類は、特に制限されず、液晶表示装置、有機ＥＬ（エレクトロルミネッセンス）表示装置、ＰＤＰ（プラズマディスプレイパネル）、電子ペーパーなどの表示装置（画像表示装置）等の種々の表示装置に備えられる光学フィルムの貼り合せに本発明の粘着剤組成物を用いることができる。
光学フィルムは、特に制限されず、ポリカーボネート（ＰＣ）、ポリメチルメタクリレート（ＰＭＭＡ）、ポリエチレンテレフタレート（ＰＥＴ）等の樹脂フィルムが用いられる。粘着剤組成物は、ＩＴＯなどの金属薄膜が設けられた透明導電フィルム、ガラスレンズ、ハードコートフィルム等の各種板状体の貼り合せに用いてもよい。
<Display device>
The display device of the present invention includes a plurality of optical films on a display element, and the optical films are adhered to each other with the pressure-sensitive adhesive composition of the present invention.
Since the pressure-sensitive adhesive composition of the present invention is excellent in whitening resistance and foaming resistance even when placed in a hot and humid environment, an optical film laminate in which the optical films are bonded with the pressure-sensitive adhesive composition of the present invention is displayed. The display device provided on the element is excellent in visibility of the display element.
The type of display device is not particularly limited, and is provided for various display devices such as a liquid crystal display device, an organic EL (electroluminescence) display device, a PDP (plasma display panel), and a display device (image display device) such as electronic paper. The pressure-sensitive adhesive composition of the present invention can be used for laminating the optical films to be obtained.
The optical film is not particularly limited, and a resin film such as polycarbonate (PC), polymethylmethacrylate (PMMA), or polyethylene terephthalate (PET) is used. The pressure-sensitive adhesive composition may be used for bonding various plate-like bodies such as a transparent conductive film provided with a metal thin film such as ITO, a glass lens, and a hard coat film.
以下、本発明を実施例により具体的に説明するが、本発明は以下の例に限定されるものではない。
なお、「部」、「％」は、特に記載しない限り、質量基準である。
Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following examples.
Unless otherwise specified, "parts" and "%" are based on mass.
＜粘着剤組成物膜用塗工液の調製＞
粘着剤組成物膜用塗工液の調製に用いた成分は、下記のとおりである。
１．（メタ）アクリル系ポリマー
（１）藤倉化成株式会社製、商品名「ＬＫＧ−１００８Ａ」
〔重量平均分子量（Ｍｗ）＝１００万、ガラス転移温度＝−３５℃、ＮＶ：３５％〕
（２）日本カーバイド工業株式会社製、商品名「ＫＰ−２６１０」
〔重量平均分子量（Ｍｗ）＝５０万、ガラス転移温度＝−３０℃、ＮＶ：４５％〕
（３）サイデン化学株式会社製、商品名「ＴＰＯ−３２８１」
〔重量平均分子量（Ｍｗ）＝６０万、ガラス転移温度＝−２４℃、ＮＶ：３５％〕
<Preparation of coating liquid for adhesive composition film>
The components used to prepare the coating liquid for the pressure-sensitive adhesive composition film are as follows.
1. 1. (Meta) Acrylic polymer (1) Made by Fujikura Kasei Co., Ltd., Product name "LKG-1008A"
[Weight average molecular weight (Mw) = 1 million, glass transition temperature = -35 ° C, NV: 35%]
(2) Product name "KP-2610" manufactured by Nippon Carbide Industry Co., Ltd.
[Weight average molecular weight (Mw) = 500,000, glass transition temperature = -30 ° C, NV: 45%]
(3) Product name "TPO-3281" manufactured by Saiden Chemical Co., Ltd.
[Weight average molecular weight (Mw) = 600,000, glass transition temperature = -24 ° C, NV: 35%]
２．アミド系ポリマー
日本触媒株式会社製、商品名「ＰＶＰ Ｋ−３０」
〔ポリビニルピロリドン（ＰＶＰ）、重量平均分子量（Ｍｗ）＝１０万〕
2. Amide polymer Made by Nippon Shokubai Co., Ltd., trade name "PVP K-30"
[Polyvinylpyrrolidone (PVP), weight average molecular weight (Mw) = 100,000]
３．硬化剤
（１）三菱ガス化学株式会社製、商品名「ＴＥＴＲＡＤ−Ｃ」
〔１，３−ビス（Ｎ，Ｎ’−ジグリシジルアミノメチル）シクロヘキサン〕
（２）日本カーバイド工業株式会社製、商品名「ＣＫ−１２１」
〔イソシアネート系硬化剤；ＮＶ＝７５質量％〕
（３）サイデン化学株式会社製、商品名「Ｋ−３４１」
〔イソシアネート系硬化剤；ＮＶ＝７５質量％〕
3. 3. Hardener (1) Mitsubishi Gas Chemical Company, trade name "TETRAD-C"
[1,3-Bis (N, N'-diglycidylaminomethyl) cyclohexane]
(2) Product name "CK-121" manufactured by Nippon Carbide Industry Co., Ltd.
[Isocyanate-based curing agent; NV = 75% by mass]
(3) Product name "K-341" manufactured by Saiden Chemical Co., Ltd.
[Isocyanate-based curing agent; NV = 75% by mass]
〔実施例１〕
（メタ）アクリル系ポリマー（ＬＫＧ−１００８Ａ）と、（メタ）アクリル系ポリマー１００部に対して、０．０４５部の硬化剤（ＴＥＴＲＡＤ−Ｃ）と、アミド系ポリマー（ＰＶＰ Ｋ−３０）を混合し、全固形分中のＰＶＰ固形分濃度を０．３質量％として、実施例１の粘着剤組成物膜用塗工液を得た。
[Example 1]
0.045 parts of curing agent (TETRAD-C) and amide-based polymer (PVP K-30) are mixed with 100 parts of (meth) acrylic polymer (LKG-1008A) and (meth) acrylic polymer. Then, the PVP solid content concentration in the total solid content was set to 0.3% by mass, and the coating liquid for the pressure-sensitive adhesive composition film of Example 1 was obtained.
〔実施例２〜４〕
実施例１の粘着剤組成物膜用塗工液の調製において、全固形分中のＰＶＰ固形分濃度を、表２の「アミド系ポリマー」欄の「量」欄に示す濃度とした他は、同様にして、実施例２〜４の粘着剤組成物膜用塗工液を得た。
[Examples 2 to 4]
In the preparation of the coating liquid for the pressure-sensitive adhesive composition film of Example 1, the PVP solid content concentration in the total solid content was set to the concentration shown in the "Amount" column of the "Amid-based polymer" column of Table 2, except that the concentration was set. In the same manner, the coating liquid for the pressure-sensitive adhesive composition film of Examples 2 to 4 was obtained.
〔比較例１〕
（メタ）アクリル系ポリマー（ＫＰ−２６１０）と、（メタ）アクリル系ポリマー１００部に対して、０．２４部の硬化剤（ＣＫ−１２１）と、アミド系ポリマー（ＰＶＰ Ｋ−３０）を混合し、全固形分中のＰＶＰ固形分濃度を０．３質量％として、比較例１の粘着剤組成物膜用塗工液を得た。
[Comparative Example 1]
0.24 parts of curing agent (CK-121) and amide-based polymer (PVP K-30) are mixed with 100 parts of (meth) acrylic polymer (KP-2610) and (meth) acrylic polymer. Then, the PVP solid content concentration in the total solid content was set to 0.3% by mass, and the coating liquid for the pressure-sensitive adhesive composition film of Comparative Example 1 was obtained.
〔比較例２〕
（メタ）アクリル系ポリマー（ＴＰＯ−３２８１）と、（メタ）アクリル系ポリマー１００部に対して、０．４部の硬化剤（Ｋ−３４１）と、アミド系ポリマー（ＰＶＰ Ｋ−３０）を混合し、全固形分中のＰＶＰ固形分濃度を０．３質量％として、比較例２の粘着剤組成物膜用塗工液を得た。
[Comparative Example 2]
0.4 parts of curing agent (K-341) and amide-based polymer (PVP K-30) are mixed with 100 parts of (meth) acrylic polymer (TPO-3281) and (meth) acrylic polymer. Then, the PVP solid content concentration in the total solid content was set to 0.3% by mass, and the coating liquid for the pressure-sensitive adhesive composition film of Comparative Example 2 was obtained.
〔比較例３〕
実施例１の粘着剤組成物膜用塗工液の調製において、アミド系ポリマーを添加せずに混合液を作成した他は、同様にして、比較例３の粘着剤組成物膜用塗工液を得た。
[Comparative Example 3]
In the preparation of the coating liquid for the pressure-sensitive adhesive composition film of Example 1, the coating liquid for the pressure-sensitive adhesive composition film of Comparative Example 3 was prepared in the same manner except that the mixed liquid was prepared without adding the amide polymer. Got
〔比較例４、５〕
実施例１の粘着剤組成物膜用塗工液の調製において、全固形分中のＰＶＰ固形分濃度を、表２の「アミド系ポリマー」欄の「量」欄に示す濃度とした他は、同様にして、比較例４及び５の粘着剤組成物膜用塗工液を得た。
[Comparative Examples 4 and 5]
In the preparation of the coating liquid for the pressure-sensitive adhesive composition film of Example 1, the PVP solid content concentration in the total solid content was set to the concentration shown in the "Amount" column of the "Amid-based polymer" column of Table 2, except that the concentration was set. In the same manner, the coating liquids for the pressure-sensitive adhesive composition films of Comparative Examples 4 and 5 were obtained.
＜粘着剤組成物の物性測定＞
１．貯蔵弾性率
実施例１〜４及び比較例１〜５の粘着剤組成物膜用塗工液をシリコーン剥離材料上に塗布し、乾燥して、膜厚５０μｍの粘着剤組成物膜を作成し、粘着剤組成物膜を積層して、２ｍｍの測定サンプルを用意した。
用意した測定サンプルについて、ＭＣＲ３０２（アントンパール社製）を用い、下記測定条件にて測定することで、２３℃及び８５℃における貯蔵弾性率を求めた。
なお、実施例２〜４及び比較例３〜５の粘着剤組成物については、２３℃及び８５℃における貯蔵弾性率の詳細な測定結果は示さないが、いずれも、２３℃における貯蔵弾性率が２．５×１０５Ｐａ以下であり、８５℃における貯蔵弾性率が３．８×１０４Ｐａ以上であった。
（測定条件）
変形モード：ずりモード
温度範囲：−６０℃〜２００℃
昇温速度：３℃／ｍｉｎ
周波数：１Ｈｚ
測定治具：パラレルプレート８ｍｍφ
環境：Ｎ２雰囲気下
<Measurement of physical properties of adhesive composition>
1. 1. Storage Elastic Modulus The coating liquid for the pressure-sensitive adhesive composition film of Examples 1 to 4 and Comparative Examples 1 to 5 was applied onto the silicone release material and dried to prepare a pressure-sensitive adhesive composition film having a thickness of 50 μm. A 2 mm measurement sample was prepared by laminating the pressure-sensitive adhesive composition film.
The storage elastic modulus at 23 ° C. and 85 ° C. was determined by measuring the prepared measurement sample using MCR302 (manufactured by Anton Pearl Co., Ltd.) under the following measurement conditions.
Regarding the pressure-sensitive adhesive compositions of Examples 2 to 4 and Comparative Examples 3 to 5, detailed measurement results of the storage elastic modulus at 23 ° C. and 85 ° C. are not shown, but the storage elastic modulus at 23 ° C. is not shown. It was 2.5 × 10 5 Pa or less, and the storage elastic modulus at 85 ° C. was 3.8 × 10 4 Pa or more.
(Measurement condition)
Deformation mode: Slip mode Temperature range: -60 ° C to 200 ° C
Heating rate: 3 ° C / min
Frequency: 1Hz
Measuring jig: Parallel plate 8 mmφ
Environment: N 2 atmosphere
＜試料１〜４の作製＞
後述する耐発泡性評価、耐白化性評価及び光学特性測定に用いた試料１及び試料２は次のようにして作製した。
<Preparation of samples 1 to 4>
Samples 1 and 2 used for the evaluation of foam resistance, the evaluation of whitening resistance, and the measurement of optical characteristics, which will be described later, were prepared as follows.
（試料１）
粘着剤組成物膜用塗工液をシリコーン剥離基材に塗布し、乾燥して、表１又は２に示す膜厚の粘着剤組成物膜を得た後、粘着剤組成物膜を、東レ株式会社製のルミラー１００Ｔ６０（ＰＥＴ１００μｍ）に積層し、２３℃、５０％ＲＨの環境下で２４時間静置した。次いで、粘着剤組成物膜上に、被着体として、タキロン株式会社製のポリカーボネートシート「ＰＣ１６００」（厚さ２ｍｍ）を積層し、２３℃、５０％ＲＨの環境下で２４時間静置して、試料１とした。
(Sample 1)
The coating liquid for the pressure-sensitive adhesive composition film is applied to the silicone release base material and dried to obtain the pressure-sensitive adhesive composition film having the thickness shown in Table 1 or 2, and then the pressure-sensitive adhesive composition film is applied to Toray Co., Ltd. It was laminated on a company-made Lumirror 100T60 (PET 100 μm) and allowed to stand for 24 hours in an environment of 23 ° C. and 50% RH. Next, a polycarbonate sheet "PC1600" (thickness 2 mm) manufactured by Takiron Co., Ltd. was laminated on the pressure-sensitive adhesive composition film as an adherend, and allowed to stand in an environment of 23 ° C. and 50% RH for 24 hours. , Sample 1.
（試料２）
粘着剤組成物膜用塗工液をシリコーン剥離基材に塗布し、乾燥して、表２に示す膜厚の粘着剤組成物膜を得た後、粘着剤組成物膜を、１．１ｍｍのソーダガラス上に積層し、シリコーン剥離基材を剥離し、試料２とした。
(Sample 2)
The coating liquid for the pressure-sensitive adhesive composition film is applied to the silicone release base material and dried to obtain the pressure-sensitive adhesive composition film having the thickness shown in Table 2, and then the pressure-sensitive adhesive composition film is spread to 1.1 mm. It was laminated on soda glass and the silicone release base material was peeled off to obtain Sample 2.
（試料３、４）
試料１の作製において、被着体を、ポリカーボネートシートの代わりに、ガラスにした他は同様にして試料３を作製し、被着体を、ポリカーボネートシートの代わりに、ポリメチルメタクリルエステル（ＰＭＭＡ）シートにした他は同様にして試料４を作成した。
(Samples 3 and 4)
In the preparation of sample 1, sample 3 was prepared in the same manner except that the adherend was made of glass instead of the polycarbonate sheet, and the adherend was a polymethylmethacrylic ester (PMMA) sheet instead of the polycarbonate sheet. Sample 4 was prepared in the same manner except for the above.
＜評価＞
１．耐発泡性評価
実施例１〜４及び比較例１〜５において、試料１を評価用サンプルとして用い、８５℃、８５％ＲＨの環境下で２４時間静置した。静置後の試料１の粘着剤組成物膜の発泡の有無を目視観察し、下記評価基準に基づいて評価し、表１及び２に示した。
（評価基準）
Ａ：発泡は無い。
Ｂ：直径０．１ｍｍ程度の微細気泡が少量発生している。
Ｃ：貼合時に目視確認することができる気泡（異物）が増幅している。
Ｄ：少量の気泡が発生している。
Ｅ：多量の気泡が発生している。
<Evaluation>
1. 1. Evaluation of foam resistance In Examples 1 to 4 and Comparative Examples 1 to 5, Sample 1 was used as an evaluation sample and allowed to stand for 24 hours in an environment of 85 ° C. and 85% RH. The presence or absence of foaming of the pressure-sensitive adhesive composition film of Sample 1 after standing was visually observed and evaluated based on the following evaluation criteria, and is shown in Tables 1 and 2.
(Evaluation criteria)
A: There is no foaming.
B: A small amount of fine bubbles having a diameter of about 0.1 mm are generated.
C: Bubbles (foreign matter) that can be visually confirmed at the time of bonding are amplified.
D: A small amount of bubbles are generated.
E: A large amount of bubbles are generated.
２．耐白化性評価
（１）耐白化性評価１
実施例１、比較例１及び比較例２において、耐発泡性評価に用いた評価サンプル（試料１）について、スガ試験機株式会社製のヘイズメーター（型式：ＨＧＭ−２）を用い、８５℃×８５％ＲＨ×２４ｈの熱湿試験投入前（初期）と熱湿試験投入後（熱湿後）のヘイズを測定し、初期と熱湿後の両者の測定値の差（熱湿後のヘイズ値−初期のヘイズ値）をΔヘイズとした。
熱湿後のヘイズ値は、熱湿試験取出しから１０分後のヘイズ測定値を用いた。
下記基準にてΔヘイズを評価し、表１に示した。
（評価基準）
Ａ：５％未満
Ｂ：５％以上１１％未満
Ｃ：１１％以上１３％未満、
Ｄ：１３％以上
なお、実施例１は、以下に示す耐白化性評価２も行った。
2. Whitening resistance evaluation (1) Whitening resistance evaluation 1
In Example 1, Comparative Example 1 and Comparative Example 2, the evaluation sample (Sample 1) used for the foam resistance evaluation was 85 ° C. × using a haze meter (model: HGM-2) manufactured by Suga Test Instruments Co., Ltd. The haze of 85% RH × 24h before the hot / wet test was put in (initial) and after the hot / wet test was put in (after hot / wet) was measured, and the difference between the measured values at the initial stage and after the hot / wet test (haze value after hot / wet). − Initial haze value) was defined as Δ haze.
As the haze value after heat and humidity, the haze measured value 10 minutes after taking out the heat and humidity test was used.
The Δ haze was evaluated according to the following criteria and is shown in Table 1.
(Evaluation criteria)
A: Less than 5% B: 5% or more and less than 11% C: 11% or more and less than 13%,
D: 13% or more In Example 1, the whitening resistance evaluation 2 shown below was also performed.
（２）耐白化性評価２
実施例１〜４及び比較例３〜５において、耐発泡性評価に用いた評価サンプル（試料１）について、スガ試験機株式会社製のヘイズメーター（型式：ＨＧＭ−２）を用い、８５℃×８５％ＲＨ×２４ｈの熱湿試験投入前（初期）と熱湿試験投入後（熱湿後）のヘイズを測定し、表２に示した。また、初期と熱湿後の両者の測定値の差（熱湿後のヘイズ値−初期のヘイズ値）をΔヘイズとし、表２に示した。
なお、熱湿後のヘイズ値は、熱湿試験取出しから１０分後のヘイズ測定値である。
(2) Whitening resistance evaluation 2
In Examples 1 to 4 and Comparative Examples 3 to 5, the evaluation sample (sample 1) used for the foam resistance evaluation was 85 ° C. × using a haze meter (model: HGM-2) manufactured by Suga Test Instruments Co., Ltd. The haze of 85% RH × 24h before the hot / wet test was put in (initial stage) and after the hot / wet test was put in (after hot / wet) was measured and shown in Table 2. Further, the difference between the measured values after the initial stage and after heat and humidity (haze value after heat and humidity-initial haze value) was defined as Δ haze and is shown in Table 2.
The haze value after heat and humidity is a haze measured value 10 minutes after taking out the heat and humidity test.
３．粘着性評価
実施例１〜４及び比較例１〜５において、粘着剤組成物膜用塗工液をシリコーン剥離基材に塗布し、乾燥して、表１及び２に示す膜厚の粘着剤組成物膜を得た後、粘着剤組成物膜を、東洋紡株式会社製のコスモシャイン１００Ａ４３００（ＰＥＴ１００μｍ）に積層し、２３℃、５０％ＲＨの環境下で２４時間静置した。
得られた積層体を２５ｍｍ幅に裁断し、２ｋｇのゴムローラー１往復で、タキロン株式会社製のポリカーボネートシート「ＰＣ１６００」（厚さ２ｍｍ）を貼り合せ、２３℃、５０％ＲＨの環境下で２４時間静置して、評価サンプルを作製した。
得られた評価サンプルについて、２３℃、５０％ＲＨ雰囲気下、及び、８５℃雰囲気下で、それぞれ、３００ｍｍ／ｍｉｎ、１８０°ピールの条件でＰＥＴフィルムを引き剥がし、株式会社オリエンテック社製、テンシロン万能試験機（型式：ＲＴＣ−１２５０Ａ)により、２３℃及び８５℃における粘着力を測定した。２３℃及び８５℃における粘着力を表１及び２に示す。
3. 3. Adhesive Evaluation In Examples 1 to 4 and Comparative Examples 1 to 5, the coating liquid for a pressure-sensitive adhesive composition film was applied to a silicone release base material, dried, and the pressure-sensitive adhesive composition having the thickness shown in Tables 1 and 2 was obtained. After obtaining the material film, the pressure-sensitive adhesive composition film was laminated on Cosmoshine 100A4300 (PET 100 μm) manufactured by Toyo Boseki Co., Ltd., and allowed to stand in an environment of 23 ° C. and 50% RH for 24 hours.
The obtained laminate was cut into a width of 25 mm, and a polycarbonate sheet "PC1600" (thickness 2 mm) manufactured by Takiron Co., Ltd. was bonded with one reciprocation of a 2 kg rubber roller, and 24 at 23 ° C. and 50% RH. After allowing to stand for a while, an evaluation sample was prepared.
With respect to the obtained evaluation sample, the PET film was peeled off under the conditions of 300 mm / min and 180 ° peel under the conditions of 23 ° C., 50% RH atmosphere, and 85 ° C. atmosphere, respectively, and Tencilon manufactured by Orientec Co., Ltd. The adhesive strength at 23 ° C. and 85 ° C. was measured with a universal testing machine (model: RTC-1250A). The adhesive strength at 23 ° C. and 85 ° C. is shown in Tables 1 and 2.
４．実施例１〜４及び比較例３〜５の光学特性
実施例１〜４及び比較例３〜５において、評価サンプルとして試料２を用い、全光線透過率とヘイズを、スガ試験機株式会社製のヘイズメーター（型式：ＨＧＭ−２）にて測定した。なお、ガラス単体の全光線透過率は９２．７％であり、ヘイズは０．１％であった。結果を表２に示す。
4. Optical Characteristics of Examples 1 to 4 and Comparative Examples 3 to 5 In Examples 1 to 4 and Comparative Examples 3 to 5, sample 2 was used as an evaluation sample, and the total light transmittance and haze were determined by Suga Test Instruments Co., Ltd. It was measured with a haze meter (model: HGM-2). The total light transmittance of the glass alone was 92.7%, and the haze was 0.1%. The results are shown in Table 2.
表１及び２からわかるように、（メタ）アクリル系ポリマー及びアミド系ポリマーを含有し、アミド系ポリマーの含有量が５．０質量％未満であり、かつ２３℃における貯蔵弾性率が２．５×１０５Ｐａ以下であり、８５℃における貯蔵弾性率が３．８×１０４Ｐａ以上である実施例の粘着剤組成物は、ポリカーボネートのような被着体に対して優れた粘着性を有すると共に、優れた耐発泡性と優れた耐白化性とを両立することができることがわかる。 As can be seen from Tables 1 and 2, it contains a (meth) acrylic polymer and an amide polymer, the content of the amide polymer is less than 5.0% by mass, and the storage elastic modulus at 23 ° C. is 2.5. The pressure-sensitive adhesive composition of Examples having a storage elastic modulus of 3.8 × 10 4 Pa or more at × 10 5 Pa or less has excellent adhesiveness to an adherend such as polycarbonate. At the same time, it can be seen that both excellent foam resistance and excellent whitening resistance can be achieved at the same time.
なお、実施例１、３及び４において、試料１に代えて、試料３、４を用いて耐発泡性評価をしたところ、被着体として、ポリカーボネートよりも膨張率が低いガラスを用いた試料３のみならず、ポリカーボネートよりも膨張率が高いＰＭＭＡを用いた試料４においても、優れた耐発泡性（評価Ａ）が得られた。 In Examples 1, 3 and 4, when the foam resistance was evaluated using Samples 3 and 4 instead of Sample 1, Sample 3 using glass having a lower expansion coefficient than polycarbonate as the adherend. Not only that, in Sample 4 using PMMA, which has a higher expansion coefficient than polycarbonate, excellent foam resistance (evaluation A) was obtained.
このような粘着剤組成物を光学フィルム間の粘着剤として用いれば、視認性の高い表示装置が得られ、特に車載用ディスプレイ等に好適である。 When such an adhesive composition is used as an adhesive between optical films, a display device having high visibility can be obtained, which is particularly suitable for an in-vehicle display or the like.
Claims (7)
前記アミド系ポリマーの含有量が５．０質量％未満であり、かつ
２３℃における貯蔵弾性率が２．５×１０５Ｐａ以下であり、８５℃における貯蔵弾性率が３．８×１０４Ｐａ以上である粘着剤組成物。 Contains (meth) acrylic polymer and amide polymer,
Wherein an amide less than the content of the polymer is 5.0 wt%, and is a storage elastic modulus at 23 ° C. is 2.5 × 10 5 Pa or less, a storage elastic modulus at 85 ° C. is 3.8 × 10 4 Pa The pressure-sensitive adhesive composition as described above.
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