JP6125789B2 - Adhesive composition, adhesive sheet and optical laminated sheet - Google Patents
Adhesive composition, adhesive sheet and optical laminated sheet Download PDFInfo
- Publication number
- JP6125789B2 JP6125789B2 JP2012222464A JP2012222464A JP6125789B2 JP 6125789 B2 JP6125789 B2 JP 6125789B2 JP 2012222464 A JP2012222464 A JP 2012222464A JP 2012222464 A JP2012222464 A JP 2012222464A JP 6125789 B2 JP6125789 B2 JP 6125789B2
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- sensitive adhesive
- meth
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- 239000000203 mixture Substances 0.000 title claims description 51
- 230000003287 optical effect Effects 0.000 title claims description 33
- 239000000853 adhesive Substances 0.000 title claims description 28
- 230000001070 adhesive effect Effects 0.000 title claims description 28
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 131
- 239000010410 layer Substances 0.000 claims description 90
- 239000000178 monomer Substances 0.000 claims description 55
- 125000000217 alkyl group Chemical group 0.000 claims description 48
- 229920000058 polyacrylate Polymers 0.000 claims description 47
- -1 alkyl acrylate ester Chemical class 0.000 claims description 43
- 125000004432 carbon atom Chemical group C* 0.000 claims description 40
- 230000009477 glass transition Effects 0.000 claims description 38
- 239000012790 adhesive layer Substances 0.000 claims description 24
- 229920001519 homopolymer Polymers 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 42
- 229920000642 polymer Polymers 0.000 description 36
- 239000010408 film Substances 0.000 description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 229920002799 BoPET Polymers 0.000 description 26
- 239000000243 solution Substances 0.000 description 17
- 230000002087 whitening effect Effects 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 9
- 239000004332 silver Substances 0.000 description 9
- 206010040844 Skin exfoliation Diseases 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000012788 optical film Substances 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- 239000002390 adhesive tape Substances 0.000 description 7
- 230000006866 deterioration Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 239000006260 foam Substances 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 230000000873 masking effect Effects 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000002834 transmittance Methods 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
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 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 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Chemical class 0.000 description 2
- 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 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003136 n-heptyl 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])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001196 nonadecyl 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])[H] 0.000 description 2
- 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 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 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 2
- 239000000126 substance Substances 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000002889 tridecyl 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])[H] 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- DKJBREHOVWISMR-UHFFFAOYSA-N 1-chloro-2,3-diisocyanatobenzene Chemical compound ClC1=CC=CC(N=C=O)=C1N=C=O DKJBREHOVWISMR-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-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
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000004420 Iupilon Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 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
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- 125000002511 behenyl 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])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000000755 henicosyl 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])C([H])([H])[H] 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010030 laminating Methods 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
- 150000007974 melamines Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000001451 organic peroxides Chemical class 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
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Chemical class 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 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
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/005—Diaphragms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
Description
本発明は、粘着剤組成物、粘着シート及び光学用積層シートに関する。 The present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet, and an optical laminated sheet.
モバイル端末のタッチパネルや、画像表示装置の液晶ディスプレイパネル及びプラズマディスプレイパネルにおいては、光学フィルム等のシート状部材の貼り合せにＯＣＡ（Optical Clear Adhesive）テープが使用されており、ＯＣＡテープを構成する粘着剤組成物には、タッチパネルやディスプレイパネルの機能に対応した特性が要求される。 In touch panels of mobile terminals and liquid crystal display panels and plasma display panels of image display devices, OCA (Optical Clear Adhesive) tape is used for bonding sheet-like members such as optical films, and the adhesive constituting the OCA tape. The agent composition is required to have characteristics corresponding to the functions of the touch panel and the display panel.
例えば、タッチパネルに適用する粘着剤組成物および粘着剤層には、まず、被接着部材であるＩＴＯ層の劣化を引き起こしにくいこと（低ＩＴＯ劣化性）が求められる。
また、タッチパネルが高温高湿の環境に曝された場合、水分が粘着剤層に入り込んで粘着剤層が白化する現象が知られているが、この白化現象が起こりにくいこと（耐湿熱白化性）が求められる。
さらには、タッチパネルが高温環境に曝されて被接着部材である樹脂製フィルムからガスが発生した場合でも、粘着剤層の発泡や膨れが起こりにくいこと（耐ガス浮き性）が求められる。
For example, a pressure-sensitive adhesive composition and a pressure-sensitive adhesive layer applied to a touch panel are required to first hardly cause deterioration of an ITO layer that is an adherend (low ITO deterioration property).
Also, when the touch panel is exposed to a high temperature and high humidity environment, it is known that moisture enters the pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer is whitened. This whitening phenomenon is unlikely to occur (moisture and heat whitening resistance). Is required.
Furthermore, even when the touch panel is exposed to a high temperature environment and gas is generated from the resin film as the adherend member, it is required that the pressure-sensitive adhesive layer is less likely to foam or swell (gas floating resistance).
ＯＣＡテープ用の粘着剤組成物として、従来、（メタ）アクリル系ポリマーを含む粘着剤組成物が広く用いられている。（メタ）アクリル系ポリマーを含む粘着剤組成物としては、例えば、特許文献１〜４に開示の粘着剤組成物が知られている。 Conventionally, pressure-sensitive adhesive compositions containing (meth) acrylic polymers have been widely used as pressure-sensitive adhesive compositions for OCA tapes. As the pressure-sensitive adhesive composition containing a (meth) acrylic polymer, for example, the pressure-sensitive adhesive compositions disclosed in Patent Documents 1 to 4 are known.
しかしながら、従来の粘着剤組成物および粘着剤層は、低ＩＴＯ劣化性に優れ、さらに、耐湿熱白化性および耐ガス浮き性に優れるとは言い難い。 However, it is difficult to say that conventional pressure-sensitive adhesive compositions and pressure-sensitive adhesive layers are excellent in low ITO deterioration, and are also excellent in resistance to moist heat whitening and gas resistance.
本発明は、上記状況のもとになされた。
本発明は、高温高湿環境に曝されても白化しにくく且つ高温環境に曝されても発泡や膨れが起こりにくい粘着剤層を形成し得る粘着剤組成物を提供することを課題とする。
The present invention has been made under the above circumstances.
An object of the present invention is to provide a pressure-sensitive adhesive composition that can form a pressure-sensitive adhesive layer that does not easily whiten even when exposed to a high-temperature and high-humidity environment, and that does not easily foam or bulge even when exposed to a high-temperature environment.
本開示には、下記の実施形態が含まれる。本開示は、課題を解決するためのより具体的な手段として、下記＜３＞及び下記＜３＞を直接に又は間接に引用する下記＜４＞〜＜８＞を提供する。
＜１＞ 炭素数１２以上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に由来の構成単位（Ａ）を５質量％以上、炭素数１以上８以下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に由来の構成単位（Ｂ）を５質量％以上、及び、水酸基を有する単量体に由来の構成単位（Ｃ）を２質量％以上３０質量％以下含み、前記構成単位（Ａ）、前記構成単位（Ｂ）及び前記構成単位（Ｃ）の総含有量が８０質量％以上である（メタ）アクリル系ポリマーを含有する粘着剤組成物。
＜２＞ 前記（メタ）アクリル系ポリマーは、前記構成単位（Ａ）に対する前記構成単位（Ｃ）の含有比率〔構成単位（Ｃ）の含有量（質量％）／構成単位（Ａ）の含有量（質量％）〕が０．０５以上４．００以下である、前記＜１＞に記載の粘着剤組成物。
＜３＞ 炭素数１２以上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に由来の構成単位（Ａ）を５質量％以上、炭素数１以上８以下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に由来の構成単位（Ｂ）を５質量％以上７０質量％以下、及び、水酸基を有する単量体に由来の構成単位（Ｃ）を１４質量％以上３０質量％以下含み、前記構成単位（Ａ）、前記構成単位（Ｂ）及び前記構成単位（Ｃ）の総含有量が８０質量％以上であり、前記構成単位（Ａ）に対する前記構成単位（Ｃ）の含有比率〔構成単位（Ｃ）の含有量（質量％）／構成単位（Ａ）の含有量（質量％）〕が０．１０以上４．００以下である（メタ）アクリル系ポリマーを含有する粘着剤組成物。
＜４＞ 前記炭素数１２以上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は、ホモポリマーとしたときのガラス転移温度が−１０℃以上である（メタ）アクリル酸アルキルエステルを含む、前記＜１＞〜＜３＞のいずれか１項に記載の粘着剤組成物。
＜５＞ 前記構成単位（Ａ）が炭素数１２以上のアルキル基を有するアクリル酸アルキルエステルに由来する、前記＜１＞〜＜４＞のいずれか１項に記載の粘着剤組成物。
＜６＞ 更に架橋剤を含有する、前記＜１＞〜＜５＞のいずれか１項に記載の粘着剤組成物。
＜７＞ 前記＜１＞〜＜６＞のいずれか１項に記載の粘着剤組成物が架橋反応して形成された架橋構造を含む粘着剤層を有する粘着シート。
＜８＞ シート状の光学部材と、前記光学部材の少なくとも片面に設けられ、前記＜１＞〜＜６＞のいずれか１項に記載の粘着剤組成物が架橋反応して形成された架橋構造を含む粘着剤層と、を有する光学用積層シート。
The present disclosure includes the following embodiments. The present disclosure provides the following <4> to <8> that directly or indirectly cite the following <3> and the following <3> as more specific means for solving the problems.
<1> 5% by mass or more of a structural unit (A) derived from an alkyl (meth) acrylate having an alkyl group having 12 or more carbon atoms and an alkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms 5% by mass or more of the structural unit (B) derived from the ester and 2% by mass or more and 30% by mass or less of the structural unit (C) derived from the monomer having a hydroxyl group, the structural unit (A), The adhesive composition containing the (meth) acrylic-type polymer whose total content of a structural unit (B) and the said structural unit (C) is 80 mass% or more.
<2> The (meth) acrylic polymer is a content ratio of the structural unit (C) to the structural unit (A) [content of structural unit (C) (% by mass) / content of structural unit (A). (Mass%)] is 0.05 or more and 4.00 or less, The adhesive composition as described in said <1>.
<3> 5% by mass or more of a structural unit (A) derived from a (meth) acrylic acid alkyl ester having an alkyl group having 12 or more carbon atoms, an alkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms 5 to 70% by mass of the structural unit (B) derived from the ester, and 14 to 30% by mass of the structural unit (C) derived from the monomer having a hydroxyl group, A), the total content of the structural unit (B) and the structural unit (C) is 80% by mass or more, and the content ratio of the structural unit (C) to the structural unit (A) [structural unit (C) Content (mass%) / content of structural unit (A) (mass%)] is a pressure-sensitive adhesive composition containing a (meth) acrylic polymer that is 0.10 or more and 4.00 or less.
< 4 > The (meth) acrylic acid alkyl ester having an alkyl group having 12 or more carbon atoms includes a (meth) acrylic acid alkyl ester having a glass transition temperature of −10 ° C. or higher when a homopolymer is used. The pressure-sensitive adhesive composition according to any one of 1> to <3> .
< 5 > The pressure-sensitive adhesive composition according to any one of <1> to < 4 >, wherein the structural unit (A) is derived from an alkyl acrylate ester having an alkyl group having 12 or more carbon atoms.
< 6 > The pressure-sensitive adhesive composition according to any one of <1> to < 5 >, further including a crosslinking agent.
< 7 > A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer including a crosslinked structure formed by crosslinking reaction of the pressure-sensitive adhesive composition according to any one of <1> to < 6 >.
< 8 > A cross-linked structure formed by a cross-linking reaction of the sheet-like optical member and the pressure-sensitive adhesive composition according to any one of <1> to < 6 >, provided on at least one side of the optical member. An optical laminated sheet comprising: an adhesive layer comprising:
本発明によれば、高温高湿環境に曝されても白化しにくく且つ高温環境に曝されても発泡や膨れが起こりにくい粘着剤層を形成し得る粘着剤組成物が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the adhesive composition which can form the adhesive layer which cannot be easily whitened even if exposed to a high temperature / humidity environment, and is hard to foam and swell even if exposed to a high temperature environment is provided.
以下に、本発明の実施の形態について説明する。なお、これらの説明及び実施例は本発明を例示するものであり、本発明の範囲を制限するものではない。 Embodiments of the present invention will be described below. In addition, these description and Examples illustrate this invention, and do not restrict | limit the scope of the present invention.
本明細書において「〜」は、その前後に記載される数値をそれぞれ最小値および最大値として含む範囲を示すものとする。 In the present specification, “to” indicates a range including numerical values described before and after that as a minimum value and a maximum value, respectively.
本明細書中において、（メタ）アクリレートは、アクリレート及びメタクリレートを意味し、（メタ）アクリルは、アクリル及びメタクリルを意味する。 In this specification, (meth) acrylate means acrylate and methacrylate, and (meth) acryl means acrylic and methacryl.
＜粘着剤組成物＞
本発明の粘着剤組成物は、構成単位（Ａ）を５質量％以上、構成単位（Ｂ）を５質量％以上、及び構成単位（Ｃ）を２質量％以上３０質量％以下含み、構成単位（Ａ）、構成単位（Ｂ）及び構成単位（Ｃ）の総含有量が８０質量％以上である（メタ）アクリル系ポリマー（以下「特定（メタ）アクリル系ポリマー」と称する。）を含有する。ここで、構成単位（Ａ）は、炭素数１２以上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に由来する構成単位であり、構成単位（Ｂ）は、炭素数１以上８以下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に由来する構成単位であり、構成単位（Ｃ）は、水酸基を有する単量体に由来する構成単位である。
本発明の粘着剤組成物は、かかる構成により、高温高湿環境に曝されても白化しにくく且つ高温環境に曝されても発泡や膨れが起こりにくい粘着剤層を形成し得る。
また、本発明の粘着剤組成物は、かかる構成により、ＩＴＯ層に接着する粘着剤層を形成した際に該ＩＴＯ層の劣化を引き起こしにくい。
<Adhesive composition>
The pressure-sensitive adhesive composition of the present invention comprises 5% by mass or more of the structural unit (A), 5% by mass or more of the structural unit (B), and 2% by mass or more and 30% by mass or less of the structural unit (C). (A), (meth) acrylic polymer (hereinafter referred to as “specific (meth) acrylic polymer”) having a total content of the structural unit (B) and the structural unit (C) of 80% by mass or more is contained. . Here, the structural unit (A) is a structural unit derived from a (meth) acrylic acid alkyl ester having an alkyl group having 12 or more carbon atoms, and the structural unit (B) is an alkyl group having 1 to 8 carbon atoms. Is a structural unit derived from a (meth) acrylic acid alkyl ester, and the structural unit (C) is a structural unit derived from a monomer having a hydroxyl group.
With such a configuration, the pressure-sensitive adhesive composition of the present invention can form a pressure-sensitive adhesive layer that does not easily whiten even when exposed to a high-temperature and high-humidity environment, and that does not easily foam or bulge even when exposed to a high-temperature environment.
Moreover, the pressure-sensitive adhesive composition of the present invention is less likely to cause deterioration of the ITO layer when the pressure-sensitive adhesive layer that adheres to the ITO layer is formed.
特定（メタ）アクリル系ポリマーは、ポリマー分子中に、構成単位（Ａ）を５質量％以上、構成単位（Ｂ）を５質量％以上、及び構成単位（Ｃ）を２質量％以上３０質量％以下含み、且つ、これら３種の構成単位をその総含有量が８０質量％以上となるように含む。
特定（メタ）アクリル系ポリマーが、かかる割合で構成単位（Ａ）、構成単位（Ｂ）及び構成単位（Ｃ）を含むことにより、本発明の粘着剤組成物が形成する粘着剤層は疎水性と親水性とのバランスがよく、したがって、粘着剤層への水分の浸入を抑制しつつ、水分が浸入した場合でも浸入した水分を粘着剤層に相溶させ得るので、高温高湿環境に曝されても白化現象が起こりにくい。
The specific (meth) acrylic polymer contains 5% by mass or more of the structural unit (A), 5% by mass or more of the structural unit (B), and 2% by mass or more and 30% by mass of the structural unit (C) in the polymer molecule. In addition, these three types of structural units are included so that the total content is 80% by mass or more.
When the specific (meth) acrylic polymer contains the structural unit (A), the structural unit (B) and the structural unit (C) in such a ratio, the pressure-sensitive adhesive layer formed by the pressure-sensitive adhesive composition of the present invention is hydrophobic. Therefore, it is possible to make the intruded water compatible with the adhesive layer even when the water has infiltrated while suppressing the intrusion of water into the adhesive layer. Even if it is done, the whitening phenomenon hardly occurs.
特定（メタ）アクリル系ポリマー中、構成単位（Ａ）の含有量は５質量％以上である。炭素数１２以上という長鎖のアルキル基を有する構成単位（Ａ）を５質量％以上含むことにより、特定（メタ）アクリル系ポリマーは、粘着剤層を適度に疎水化する。構成単位（Ａ）の含有量が５質量％未満であると、粘着剤層が親水性に傾き、水分の浸入を抑制できず、粘着剤層の白化現象が起きやすい。構成単位（Ａ）の含有量は、好ましくは１０質量％以上であり、より好ましくは２０質量％以上である。
構成単位（Ａ）の含有量の上限としては、６５質量％以下が好ましい。６５質量％以下であると、接着剤層の疎水性が高くなり過ぎず、水分が浸入した場合でも該水分が粘着剤層に相溶し得、粘着剤層の白化現象が起こりにくい。構成単位（Ａ）の含有量は、より好ましくは６０質量％以下であり、更に好ましくは４０質量％以下である。
In the specific (meth) acrylic polymer, the content of the structural unit (A) is 5% by mass or more. By containing 5% by mass or more of the structural unit (A) having a long-chain alkyl group having 12 or more carbon atoms, the specific (meth) acrylic polymer moderately hydrophobizes the pressure-sensitive adhesive layer. When the content of the structural unit (A) is less than 5% by mass, the pressure-sensitive adhesive layer is inclined to be hydrophilic, moisture entry cannot be suppressed, and the whitening phenomenon of the pressure-sensitive adhesive layer easily occurs. Content of a structural unit (A) becomes like this. Preferably it is 10 mass% or more, More preferably, it is 20 mass% or more.
As an upper limit of content of a structural unit (A), 65 mass% or less is preferable. When it is 65% by mass or less, the hydrophobicity of the adhesive layer does not become too high, and even when moisture enters, the moisture can be compatible with the pressure-sensitive adhesive layer, and the whitening phenomenon of the pressure-sensitive adhesive layer hardly occurs. Content of a structural unit (A) becomes like this. More preferably, it is 60 mass% or less, More preferably, it is 40 mass% or less.
特定（メタ）アクリル系ポリマー中、構成単位（Ｂ）の含有量は５質量％以上である。構成単位（Ｂ）の含有量が５質量％未満であると、その代わりに、比較的炭素数の多いアルキル基を有する（メタ）アクリル酸アルキルエステル又はその他の（メタ）アクリル酸エステル類を（メタ）アクリル系ポリマーの重合成分とすることになり、特定（メタ）アクリル系ポリマーのガラス転移温度を適度な範囲に制御することが難しく、粘着剤層の凝集力不足や密着性の低下により、粘着剤層の発泡や膨れが起きやすくなる。構成単位（Ｂ）の含有量は、好ましくは３０質量％以上であり、より好ましくは４０質量％以上であり、更に好ましくは５０質量％以上である。
構成単位（Ｂ）の含有量の上限としては、７５質量％以下が好ましい。７５質量％以下であると、特定（メタ）アクリル系ポリマーのガラス転移温度が低すぎず、接着剤層の耐ガス浮き性が良好である。構成単位（Ｂ）の含有量は、より好ましくは７０質量％以下であり、更に好ましくは６５質量％以下である。
In the specific (meth) acrylic polymer, the content of the structural unit (B) is 5% by mass or more. When the content of the structural unit (B) is less than 5% by mass, a (meth) acrylic acid alkyl ester or other (meth) acrylic acid ester having an alkyl group having a relatively large number of carbon atoms is used instead. It becomes the polymerization component of the (meth) acrylic polymer, it is difficult to control the glass transition temperature of the specific (meth) acrylic polymer to an appropriate range, due to insufficient cohesive force of the adhesive layer and a decrease in adhesion, Foaming and swelling of the pressure-sensitive adhesive layer easily occur. Content of a structural unit (B) becomes like this. Preferably it is 30 mass% or more, More preferably, it is 40 mass% or more, More preferably, it is 50 mass% or more.
As an upper limit of content of a structural unit (B), 75 mass% or less is preferable. When it is 75% by mass or less, the glass transition temperature of the specific (meth) acrylic polymer is not too low, and the gas float resistance of the adhesive layer is good. Content of a structural unit (B) becomes like this. More preferably, it is 70 mass% or less, More preferably, it is 65 mass% or less.
特定（メタ）アクリル系ポリマー中、構成単位（Ｃ）の含有量は２質量％以上３０質量％以下である。
構成単位（Ｃ）の含有量が２質量％未満であると、接着剤層に水分が浸入した場合に該水分が粘着剤層に相溶しにくく、粘着剤層の白化現象が起きやすい。構成単位（Ｃ）の含有量は、好ましくは５質量％以上であり、より好ましくは１０質量％以上である。
他方、構成単位（Ｃ）の含有量が３０質量％超であると、粘着剤層への水分の浸入を抑制できず、ＩＴＯ層が被接着部材である場合にＩＴＯ層を劣化させやすい。構成単位（Ｃ）の含有量は、好ましくは２５質量％以下である。
In the specific (meth) acrylic polymer, the content of the structural unit (C) is 2% by mass or more and 30% by mass or less.
When the content of the structural unit (C) is less than 2% by mass, when moisture enters the adhesive layer, the moisture hardly dissolves in the pressure-sensitive adhesive layer, and the whitening phenomenon of the pressure-sensitive adhesive layer easily occurs. Content of a structural unit (C) becomes like this. Preferably it is 5 mass% or more, More preferably, it is 10 mass% or more.
On the other hand, when the content of the structural unit (C) is more than 30% by mass, it is not possible to suppress the intrusion of moisture into the pressure-sensitive adhesive layer, and the ITO layer is likely to be deteriorated when the ITO layer is an adherend. The content of the structural unit (C) is preferably 25% by mass or less.
特定（メタ）アクリル系ポリマー中、構成単位（Ａ）、構成単位（Ｂ）及び構成単位（Ｃ）の総含有量は８０質量％以上である。該総含有量が８０質量％未満であると、これら以外のその他の構成単位が２０質量％超含まれるのでその影響が大きく、粘着剤層の疎水性と親水性とのバランスがくずれて疎水性又は親水性に傾き、粘着剤層の白化現象やＩＴＯ層の劣化が起きやすい。さらに、粘着剤の凝集力不足や密着性の低下により、粘着剤層の発泡や膨れも起きやすくなる。
構成単位（Ａ）、構成単位（Ｂ）及び構成単位（Ｃ）の総含有量は、好ましくは９０質量％以上であり、より好ましくは９５質量％以上であり、更に好ましくは１００質量％である。
In the specific (meth) acrylic polymer, the total content of the structural unit (A), the structural unit (B), and the structural unit (C) is 80% by mass or more. If the total content is less than 80% by mass, other structural units other than these are included in excess of 20% by mass, so that the influence is great, and the balance between the hydrophobicity and the hydrophilicity of the pressure-sensitive adhesive layer is lost and hydrophobicity is caused. Or, it tends to be hydrophilic and the whitening phenomenon of the pressure-sensitive adhesive layer and the deterioration of the ITO layer are likely to occur. Furthermore, foaming and swelling of the pressure-sensitive adhesive layer easily occur due to insufficient cohesive force of the pressure-sensitive adhesive and a decrease in adhesion.
The total content of the structural unit (A), the structural unit (B) and the structural unit (C) is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 100% by mass. .
以下に、本発明の粘着剤組成物に含まれる各成分について詳述する。 Below, each component contained in the adhesive composition of this invention is explained in full detail.
〔特定（メタ）アクリル系ポリマー〕
特定（メタ）アクリル系ポリマーは、少なくとも、構成単位（Ａ）、構成単位（Ｂ）及び構成単位（Ｃ）を含むポリマーである。
即ち、特定（メタ）アクリル系ポリマーは、少なくとも、炭素数１２以上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（「単量体（Ａ）」とも称する。）と、炭素数１以上８以下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（「単量体（Ｂ）」とも称する。）と、水酸基を有する単量体（「単量体（Ｃ）」とも称する。）とを共重合させて得られるポリマーである。
[Specific (meth) acrylic polymer]
The specific (meth) acrylic polymer is a polymer including at least the structural unit (A), the structural unit (B), and the structural unit (C).
That is, the specific (meth) acrylic polymer includes at least a (meth) acrylic acid alkyl ester having an alkyl group having 12 or more carbon atoms (also referred to as “monomer (A)”) and 1 to 8 carbon atoms. (Meth) acrylic acid alkyl ester (also referred to as “monomer (B)”) having an alkyl group and a hydroxyl group-containing monomer (also referred to as “monomer (C)”). It is the polymer obtained by making it.
［構成単位（Ａ）、単量体（Ａ）］
構成単位（Ａ）は、炭素数１２以上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（単量体（Ａ））に由来する。単量体（Ａ）は、好ましくは、下記一般式（１）で表される化合物である。
[Structural Unit (A), Monomer (A)]
The structural unit (A) is derived from a (meth) acrylic acid alkyl ester (monomer (A)) having an alkyl group having 12 or more carbon atoms. The monomer (A) is preferably a compound represented by the following general formula (1).
Ｈ２Ｃ＝Ｃ（Ｒ２）ＣＯＯＲ１ ・・・一般式（１）
一般式（１）において、Ｒ１は、直鎖状又は分岐状の炭素数１２以上のアルキル基を表し、Ｒ２は、水素原子又はメチル基を表す。
H 2 C═C (R 2 ) COOR 1 ... General formula (1)
In the general formula (1), R 1 represents a linear or branched alkyl group having 12 or more carbon atoms, and R 2 represents a hydrogen atom or a methyl group.
一般式（１）中、Ｒ１で表されるアルキル基は、特定（メタ）アクリル系ポリマーを適度に疎水化するために炭素数１２以上であり、ポリマーの合成の容易さ及びポリマーの取扱いの容易さの点で、炭素数２０以下が好ましい。
Ｒ１で表されるアルキル基としては、例えば、ラウリル基、イソラウリル基、トリデシル基、ミリスチル基、イソミリスチル基、ペンタデシル基、パルミチル基、イソパルミチル基、マルガリル基、ステアリル基、イソステアリル基、ノナデシル基、イコシル基、ヘンイコシル基、ドコシル基等が挙げられる。
In general formula (1), the alkyl group represented by R 1 has 12 or more carbon atoms in order to appropriately hydrophobize the specific (meth) acrylic polymer, and the ease of polymer synthesis and the handling of the polymer In terms of ease, carbon number of 20 or less is preferable.
Examples of the alkyl group represented by R 1 include lauryl group, isolauryl group, tridecyl group, myristyl group, isomyristyl group, pentadecyl group, palmityl group, isopalmityl group, margaryl group, stearyl group, isostearyl group, and nonadecyl group. , Icosyl group, henicosyl group, docosyl group and the like.
一般式（１）中、Ｒ２は、特定（メタ）アクリル系ポリマーのガラス転移温度を高める点で、水素原子が好ましい。即ち、一般式（１）で表される単量体は、炭素数１２以上のアルキル基を有するアクリル酸アルキルエステルであることが好ましい。 In general formula (1), R 2 is preferably a hydrogen atom in terms of increasing the glass transition temperature of the specific (meth) acrylic polymer. That is, the monomer represented by the general formula (1) is preferably an acrylic acid alkyl ester having an alkyl group having 12 or more carbon atoms.
単量体（Ａ）の具体例としては、例えば、ラウリル（メタ）アクリレート、イソラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、ミリスチル（メタ）アクリレート、パルミチル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、ノナデシル（メタ）アクリレート、イコシル（メタ）アクリレート等が挙げられる。
中でも、炭素数１２〜２０のアルキル基を有するアクリル酸アルキルエステルが好ましく、炭素数１２〜１８のアルキル基を有するアクリル酸アルキルエステルがより好ましい。
単量体（Ａ）は、１種単独で使用してもよく、２種以上を組み合わせて使用してよい。
Specific examples of the monomer (A) include, for example, lauryl (meth) acrylate, isolauryl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, Examples include isostearyl (meth) acrylate, nonadecyl (meth) acrylate, and icosyl (meth) acrylate.
Especially, the acrylic acid alkyl ester which has a C12-C20 alkyl group is preferable, and the acrylic acid alkylester which has a C12-C18 alkyl group is more preferable.
A monomer (A) may be used individually by 1 type, and may be used in combination of 2 or more type.
単量体（Ａ）は、ホモポリマーとしたときのガラス転移温度が−１０℃以上であることが好ましい。このような単量体（Ａ）を重合成分とすることで、特定（メタ）アクリル系ポリマーのガラス転移温度が高くなり、その結果、粘着剤層の凝集力が向上し、耐ガス浮き性が向上する。単量体（Ａ）は、ホモポリマーとしたときのガラス転移温度が０℃以上であることがより好ましく、１０℃以上であることが更に好ましい。
ここでいう「ホモポリマーとしたときのガラス転移温度」とは、Ｌ．Ｅ．ニールセン著、小野木重治訳「高分子の力学的性質」（化学同人刊）第１１〜３５頁に記載されているホモポリマーのガラス転移温度である。
The monomer (A) preferably has a glass transition temperature of −10 ° C. or higher when it is a homopolymer. By using such a monomer (A) as a polymerization component, the glass transition temperature of the specific (meth) acrylic polymer is increased. As a result, the cohesive force of the pressure-sensitive adhesive layer is improved, and the gas floating resistance is improved. improves. The monomer (A) preferably has a glass transition temperature of 0 ° C. or higher, more preferably 10 ° C. or higher when it is a homopolymer.
“Glass transition temperature when homopolymer” is used herein as “L. E. This is a glass transition temperature of a homopolymer described in Nielsen, translated by Shigeharu Onoki, “Mechanical Properties of Polymer” (Chemical Doujinshi), pages 11-35.
ホモポリマーとしたときのガラス転移温度が−１０℃以上である単量体（Ａ）としては、炭素数１２以上のアルキル基を有するアクリル酸アルキルエステル（「単量体（Ａ−１）」と称する。）が挙げられる。
炭素数１２以上のアルキル基を有するアクリル酸アルキルエステルは、同じアルキル基を有するメタクリル酸アルキルエステルに比べて、ホモポリマーとしたときのガラス転移温度が高く、ホモポリマーとしたときのガラス転移温度が−１０℃以上である。
したがって、特定（メタ）アクリル系ポリマーのガラス転移温度を高め、粘着剤層の凝集力を向上させ、耐ガス浮き性を向上させる観点で、構成単位（Ａ）は、その総質量の８０質量％以上が、単量体（Ａ−１）に由来の構成単位（「構成単位（Ａ−１）」と称する。）であることが好ましい。即ち、特定（メタ）アクリル系ポリマーの合成に供する単量体（Ａ）の総質量の８０質量％以上が、単量体（Ａ−１）であることが好ましい。
構成単位（Ａ）の総質量に占める構成単位（Ａ−１）の総質量は、９０質量％以上がより好ましく、１００質量％が更に好ましい。
As the monomer (A) having a glass transition temperature of −10 ° C. or higher when a homopolymer is used, an alkyl acrylate ester having an alkyl group having 12 or more carbon atoms (“monomer (A-1)”) For example).
Acrylic acid alkyl ester having an alkyl group having 12 or more carbon atoms has a higher glass transition temperature when it is a homopolymer than a methacrylic acid alkyl ester having the same alkyl group, and has a glass transition temperature when it is a homopolymer. It is −10 ° C. or higher.
Therefore, from the viewpoint of increasing the glass transition temperature of the specific (meth) acrylic polymer, improving the cohesive strength of the pressure-sensitive adhesive layer, and improving gas floating resistance, the structural unit (A) is 80% by mass of the total mass. The above is preferably a structural unit derived from the monomer (A-1) (referred to as “structural unit (A-1)”). That is, it is preferable that 80% by mass or more of the total mass of the monomer (A) used for the synthesis of the specific (meth) acrylic polymer is the monomer (A-1).
90 mass% or more is more preferable, and, as for the total mass of the structural unit (A-1) which occupies for the gross mass of a structural unit (A), 100 mass% is still more preferable.
［構成単位（Ｂ）、単量体（Ｂ）］
構成単位（Ｂ）は、炭素数１以上８以下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（単量体（Ｂ））に由来する。単量体（Ｂ）は、好ましくは、下記一般式（２）で表される化合物である。
[Structural Unit (B), Monomer (B)]
The structural unit (B) is derived from a (meth) acrylic acid alkyl ester (monomer (B)) having an alkyl group having 1 to 8 carbon atoms. The monomer (B) is preferably a compound represented by the following general formula (2).
Ｈ２Ｃ＝Ｃ（Ｒ４）ＣＯＯＲ３ ・・・一般式（２）
一般式（２）において、Ｒ３は、直鎖状又は分岐状の炭素数１以上８以下のアルキル基を表し、Ｒ４は、水素原子又はメチル基を表す。
H 2 C═C (R 4 ) COOR 3 ... General formula (2)
In the general formula (2), R 3 represents a linear or branched alkyl group having 1 to 8 carbon atoms, and R 4 represents a hydrogen atom or a methyl group.
一般式（２）中、Ｒ３で表されるアルキル基は、特定（メタ）アクリル系ポリマーのガラス転移温度を適度な範囲に制御しやすい点で、炭素数１以上８以下であり、炭素数１以上６以下が好ましく、炭素数２以上６以下がより好ましい。
Ｒ３で表される炭素数１以上８以下のアルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、ｎ−ヘキシル基、イソヘキシル基、ｓｅｃ−ヘキシル基、ｔｅｒｔ−ヘキシル基、ｎ−ヘプチル基、イソヘプチル基、ｓｅｃ−ヘプチル基、ｔｅｒｔ−ヘプチル基、ｎ−オクチル基、イソオクチル基、ｓｅｃ−オクチル基、ｔｅｒｔ−オクチル基等が挙げられる。
In general formula (2), the alkyl group represented by R 3 has 1 to 8 carbon atoms in that the glass transition temperature of the specific (meth) acrylic polymer can be easily controlled within an appropriate range. 1 or more and 6 or less are preferable, and 2 or more and 6 or less carbon atoms are more preferable.
Examples of the alkyl group having 1 to 8 carbon atoms represented by R 3 include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl. Group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, n-heptyl group, isoheptyl group, sec-heptyl group, tert -Heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group and the like.
一般式（２）中、Ｒ４は、特定（メタ）アクリル系ポリマーのガラス転移温度を適度な範囲に制御する点で、水素原子が好ましい。即ち、一般式（２）で表される単量体は、炭素数１以上８以下のアルキル基を有するアクリル酸アルキルエステルであることが好ましい。 In general formula (2), R 4 is preferably a hydrogen atom in that the glass transition temperature of the specific (meth) acrylic polymer is controlled within an appropriate range. That is, the monomer represented by the general formula (2) is preferably an acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms.
単量体（Ｂ）の具体例としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、t−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｎ−ペンチル（メタ）アクリレート、イソペンチル（メタ）アクリレート、ｔ−ペンチル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレート、ｎ−ヘプチル（メタ）アクリレート、イソヘプチル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２−エチルヘキシルアクリレート等が挙げられる。
中でも、炭素数１〜８のアルキル基を有するアクリル酸アルキルエステルが好ましく、炭素数１〜６のアルキル基を有するアクリル酸アルキルエステルがより好ましく、炭素数２〜６のアルキル基を有するアクリル酸アルキルエステルが更に好ましい。
単量体（Ｂ）は、１種単独で使用してもよく、２種以上を組み合わせて使用してよい。
Specific examples of the monomer (B) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t- Butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, t-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, Examples include isoheptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, and 2-ethylhexyl acrylate.
Among them, an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms is preferable, an alkyl acrylate having an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl acrylate having an alkyl group having 2 to 6 carbon atoms. Esters are more preferred.
A monomer (B) may be used individually by 1 type, and may be used in combination of 2 or more type.
構成単位（Ｂ）は、特定（メタ）アクリル系ポリマーのガラス転移温度を適度な範囲に制御する点で、その総質量の８０質量％以上が、炭素数１以上８以下のアルキル基を有するアクリル酸アルキルエステルに由来の構成単位（「構成単位（Ｂ−１）」と称する。）であることが好ましい。
即ち、特定（メタ）アクリル系ポリマーの合成に供する単量体（Ｂ）の総質量の８０質量％以上が、炭素数１以上８以下のアルキル基を有するアクリル酸アルキルエステル（「単量体（Ｂ−１）」と称する。）であることが好ましい。
構成単位（Ｂ）の総質量に占める構成単位（Ｂ−１）の総質量は、９０質量％以上がより好ましく、１００質量％が更に好ましい。
The structural unit (B) is an acrylic polymer in which 80% by mass or more of the total mass of the specific (meth) acrylic polymer has an alkyl group having 1 to 8 carbon atoms in terms of controlling the glass transition temperature to an appropriate range. A structural unit derived from an acid alkyl ester (referred to as “structural unit (B-1)”) is preferred.
That is, 80% by mass or more of the total mass of the monomer (B) used for the synthesis of the specific (meth) acrylic polymer is an alkyl acrylate ester having an alkyl group having 1 to 8 carbon atoms (“monomer” B-1) ”)).
90 mass% or more is more preferable, and, as for the total mass of the structural unit (B-1) which occupies for the gross mass of a structural unit (B), 100 mass% is still more preferable.
［構成単位（Ｃ）、単量体（Ｃ）］
構成単位（Ｃ）は、水酸基を有する単量体（単量体（Ｃ））に由来する。
単量体（Ｃ）の具体例としては、例えば、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、３−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート〔「（メタ）アクリル酸ヒドロキシアルキルエステル」とも称する。〕；アリルアルコール、メタリルアルコール；ポリエチレングリコールモノ（メタ）アクリレート：などのヒドロキシル基含有単量体が挙げられる。
中でも、炭素数１〜５のヒドロキシアルキル基を有するヒドロキシアルキル（メタ）アクリレートが好ましく、炭素数２〜４のヒドロキシアルキル基を有するヒドロキシアルキル（メタ）アクリレートがより好ましい。
単量体（Ｃ）は、１種単独で使用してもよく、２種以上を組み合わせて使用してよい。
[Structural Unit (C), Monomer (C)]
The structural unit (C) is derived from a monomer having a hydroxyl group (monomer (C)).
Specific examples of the monomer (C) include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Hydroxyalkyl (meth) acrylates such as 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate [also referred to as “(meth) acrylic acid hydroxyalkyl ester”. ]; Hydroxyl group-containing monomers such as allyl alcohol, methallyl alcohol; polyethylene glycol mono (meth) acrylate: and the like.
Especially, the hydroxyalkyl (meth) acrylate which has a C1-C5 hydroxyalkyl group is preferable, and the hydroxyalkyl (meth) acrylate which has a C2-C4 hydroxyalkyl group is more preferable.
A monomer (C) may be used individually by 1 type, and may be used in combination of 2 or more type.
構成単位（Ａ）に対する構成単位（Ｃ）の含有比率〔構成単位（Ｃ）の含有量（質量％）／構成単位（Ａ）の含有量（質量％）〕は、０．０５〜４．００が好ましい。前記含有比率がこの範囲にあると、粘着剤層の疎水性と親水性とのバランスがよく、高温高湿環境に曝されても粘着剤層の白化現象が起こりにくい。
前記含有比率は、０．１０〜３．５０がより好ましく、０．４０〜２．５０が更に好ましく、０．５０〜２．００が特に好ましい。
The content ratio of the structural unit (C) to the structural unit (A) [content of structural unit (C) (% by mass) / content of structural unit (A) (% by mass)] is 0.05 to 4.00. Is preferred. When the content ratio is within this range, the hydrophobicity and hydrophilicity of the pressure-sensitive adhesive layer are well balanced, and the whitening phenomenon of the pressure-sensitive adhesive layer hardly occurs even when exposed to a high temperature and high humidity environment.
The content ratio is more preferably 0.10 to 3.50, still more preferably 0.40 to 2.50, and particularly preferably 0.50 to 2.00.
［その他の構成単位、その他の単量体］
特定（メタ）アクリル系ポリマーは、構成単位（Ａ）、構成単位（Ｂ）及び構成単位（Ｃ）以外のその他の構成単位を、ポリマーの総質量に対し２０質量％以下の範囲で含んでいてもよい。
即ち、特定（メタ）アクリル系ポリマーは、単量体（Ａ）、単量体（Ｂ）及び単量体（Ｃ）以外のその他の単量体を、単量体の総質量に対し２０質量％以下の範囲で共重合させたポリマーであってよい。
[Other structural units and other monomers]
The specific (meth) acrylic polymer contains other structural units other than the structural unit (A), the structural unit (B), and the structural unit (C) in a range of 20% by mass or less based on the total mass of the polymer. Also good.
That is, the specific (meth) acrylic polymer is 20 masses of the monomer (A), the monomer (B), and other monomers other than the monomer (C) with respect to the total mass of the monomers. % Or less copolymer may be used.
その他の単量体は、疎水性の単量体が好ましく、例えば、炭素数９以上１１以下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が挙げられ、具体例としては、ｎ−ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、ｎ−デシル（メタ）アクリレート、ｎ−ウンデシル（メタ）アクリレートが挙げられる。 Other monomers are preferably hydrophobic monomers, and examples thereof include (meth) acrylic acid alkyl esters having an alkyl group having 9 to 11 carbon atoms. Specific examples include n-nonyl (meta ) Acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl (meth) acrylate.
特定（メタ）アクリル系ポリマーは、本発明の効果を損なわない限りにおいて、単量体（Ｃ）以外の、その他の親水性の単量体を重合成分として含んでいてもよいが、粘着剤層の低ＩＴＯ劣化性を確保する観点から、その他の親水性の単量体を含まないことが好ましい。 The specific (meth) acrylic polymer may contain other hydrophilic monomers other than the monomer (C) as a polymerization component as long as the effects of the present invention are not impaired. From the viewpoint of ensuring low ITO degradation, it is preferable not to contain other hydrophilic monomers.
その他の構成単位は、特定（メタ）アクリル系ポリマーの総質量に対し２０質量％以下であり、１０質量％以下が好ましく、５質量％以下がより好ましく、０質量％（含まれていないこと）が特に好ましい。 The other structural unit is 20% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, and 0% by mass (not included) with respect to the total mass of the specific (meth) acrylic polymer. Is particularly preferred.
［特定（メタ）アクリル系ポリマーの特性］
特定（メタ）アクリル系ポリマーの重量平均分子量（Ｍｗ）は、耐ガス浮き性及び凹凸や段差に対する追従性の観点から、３０万〜１００万が好ましく、４０万〜８０万がより好ましい。
特定（メタ）アクリル系ポリマーの重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）は、５〜１０が好ましい。
なお、特定（メタ）アクリル系ポリマーの重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）による分子量測定（ポリスチレン換算）で得られる値である。測定方法の詳細は、実施例に記載のとおりである。
[Characteristics of specific (meth) acrylic polymer]
The weight average molecular weight (Mw) of the specific (meth) acrylic polymer is preferably from 300,000 to 1,000,000, more preferably from 400,000 to 800,000, from the viewpoint of gas floating resistance and followability to unevenness and steps.
The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the specific (meth) acrylic polymer is preferably 5 to 10.
In addition, the weight average molecular weight (Mw) and number average molecular weight (Mn) of a specific (meth) acrylic-type polymer are the values obtained by the molecular weight measurement (polystyrene conversion) by gel permeation chromatography (GPC). Details of the measurement method are as described in the examples.
特定（メタ）アクリル系ポリマーのガラス転移温度は、粘着剤層の凝集力を向上させ、耐ガス浮き性を向上させる観点から、−５０℃以上が好ましく、−４０℃以上がより好ましく、−３５℃以上が更に好ましい。
特定（メタ）アクリル系ポリマーのガラス転移温度の上限としては、被接着部材との密着性を向上させ、耐ガス浮き性を向上させる観点から、−１０℃以下が好ましく、−２０℃以下がより好ましい。
本発明において、特定（メタ）アクリル系ポリマーのガラス転移温度（Ｔｇ）は、以下の式により求められるモル平均ガラス転移温度である。
１／Ｔｇ＝ｍ１／Ｔｇ１＋ｍ２／Ｔｇ２＋・・・・・・＋ｍｎ／Ｔｇｎ
上記式中のＴｇ１、Ｔｇ２、・・・・・・及びＴｇｎは、成分１、成分２、・・・・・・及び成分ｎそれぞれのホモポリマーのガラス転移温度であり、絶対温度（Ｋ）に換算して上記式に代入する。ｍ１、ｍ２、・・・・・・及びｍｎは、成分１、成分２、・・・・・・及び成分ｎそれぞれのモル分率である。ここでいう「ホモポリマーのガラス転移温度」には、Ｌ．Ｅ．ニールセン著、小野木重治訳「高分子の力学的性質」（化学同人刊）第１１〜３５頁に記載されているホモポリマーのガラス転移温度が適用される。上記式では、Ｔｇが絶対温度（Ｋ）の単位で算出されるので、式「摂氏温度＝絶対温度−２７３．１５」により摂氏温度（℃）に換算する。
The glass transition temperature of the specific (meth) acrylic polymer is preferably −50 ° C. or higher, more preferably −40 ° C. or higher, and −35 from the viewpoint of improving the cohesive force of the pressure-sensitive adhesive layer and improving gas resistance. More preferably, it is at least ° C.
The upper limit of the glass transition temperature of the specific (meth) acrylic polymer is preferably −10 ° C. or lower and more preferably −20 ° C. or lower from the viewpoint of improving the adhesion to the adherend and improving the gas floating resistance. preferable.
In the present invention, the glass transition temperature (Tg) of the specific (meth) acrylic polymer is a molar average glass transition temperature determined by the following formula.
1 / Tg = m 1 / Tg 1 + m 2 / Tg 2 +... + M n / Tg n
Tg 1, Tg 2 in the above formula, ...... and Tg n, the components 1, the glass transition temperature of the components 2, ...... and component n respectively homopolymers, absolute temperature ( Convert to K) and substitute into the above equation. m 1, m 2, ...... and m n, the components 1, component 2, the mole fraction of each ...... and component n. As used herein, “glass transition temperature of homopolymer” includes L.P. E. The homopolymer glass transition temperature described in Nielsen, translated by Shigeharu Onoki, "Mechanical Properties of Polymers" (published by Kagaku Dojin), pages 11 to 35 is applied. In the above equation, since Tg is calculated in units of absolute temperature (K), it is converted to Celsius temperature (° C.) by the equation “Celsius temperature = Absolute temperature−273.15”.
特定（メタ）アクリル系ポリマーの溶解性パラメーター（ＳＰ値、（Ｊ／ｃｍ３）１／２）は、１０〜３０が好ましく、１５〜２５がより好ましい。ＳＰ値は、例えば、Ｆｅｄｏｒの推算法により算出する。 10-30 are preferable and, as for the solubility parameter (SP value, (J / cm < 3 >) <1/2 >) of a specific (meth) acrylic-type polymer, 15-25 are more preferable. The SP value is calculated by, for example, Fedor's estimation method.
［特定（メタ）アクリル系ポリマーの合成方法］
特定（メタ）アクリル系ポリマーは、溶液重合、乳化重合、懸濁重合、塊状重合などの公知の重合方法で合成し得る。工程が比較的簡単で且つ短時間で行える点で、溶液重合が好ましい。
[Method of synthesizing specific (meth) acrylic polymer]
The specific (meth) acrylic polymer can be synthesized by a known polymerization method such as solution polymerization, emulsion polymerization, suspension polymerization or bulk polymerization. Solution polymerization is preferred because the process is relatively simple and can be performed in a short time.
溶液重合は、一般に、重合槽内に有機溶媒、単量体、重合開始剤を仕込み、窒素気流中で又は有機溶媒の還流下で、撹拌しながら数時間加熱反応させることにより行われる。
有機溶媒としては、芳香族炭化水素類、脂肪族炭化水素類、脂環族炭化水素類、エステル類、ケトン類、グリコールエーテル類、アルコール類などを使用してよい。
重合開始剤としては、有機過酸化物、アゾ化合物などを使用してよい。重合開始剤の使用量は、通常は、単量体の合計量１００質量部に対して０．０１〜２質量部、好ましくは０．１〜１質量部である。
重合温度としては、一般に３０℃〜１５０℃が好ましく、５０℃〜１２０℃がより好ましい。
In general, solution polymerization is performed by charging an organic solvent, a monomer, and a polymerization initiator in a polymerization tank, and heating and reacting for several hours with stirring in a nitrogen stream or under reflux of the organic solvent.
As the organic solvent, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, esters, ketones, glycol ethers, alcohols and the like may be used.
As the polymerization initiator, an organic peroxide, an azo compound or the like may be used. The usage-amount of a polymerization initiator is 0.01-2 mass parts normally with respect to 100 mass parts of total amounts of a monomer, Preferably it is 0.1-1 mass part.
Generally as polymerization temperature, 30 to 150 degreeC is preferable, and 50 to 120 degreeC is more preferable.
〔架橋剤〕
本発明の粘着剤組成物は、特定（メタ）アクリル系ポリマーと反応して架橋構造を形成し得る官能基を（好ましくは２個以上、より好ましくは２〜５個）有する架橋剤を含有していてもよい。
[Crosslinking agent]
The pressure-sensitive adhesive composition of the present invention contains a crosslinking agent having a functional group (preferably 2 or more, more preferably 2 to 5) that can react with a specific (meth) acrylic polymer to form a crosslinked structure. It may be.
架橋剤としては、例えば、イソシアネート化合物、エポキシ化合物、アジリジン化合物、メラミン化合物、金属塩、金属キレート化合物が挙げられる。これらの中でも、イソシアネート化合物が好ましい。架橋剤は、１種単独で使用してもよく、２種以上を組み合わせて使用してよい。 Examples of the crosslinking agent include isocyanate compounds, epoxy compounds, aziridine compounds, melamine compounds, metal salts, and metal chelate compounds. Among these, an isocyanate compound is preferable. A crosslinking agent may be used individually by 1 type, and may be used in combination of 2 or more type.
イソシアネート化合物は、分子中に２個以上のイソシアネート基を有する化合物が好ましく、例えば、トリレンジイソシアネート、クロルフェニレンジイソシアネート、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、テトラメチレンジイソシアネート、イソホロンジイソシアネート、ジフェニルメタンジイソシアネート、水添されたジフェニルメタンジイソシアネート等のジイソシアネート化合物；ジイソシアネート化合物の２量体若しくは３量体；ジイソシアネート化合物を各種の２価以上のアルコール化合物等に付加反応させたイソシアネート化合物若しくはイソシアヌレート化物；などが挙げられる。 The isocyanate compound is preferably a compound having two or more isocyanate groups in the molecule, such as tolylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hydrogenated. And diisocyanate compounds such as diphenylmethane diisocyanate; dimers or trimers of diisocyanate compounds; isocyanate compounds or isocyanurates obtained by addition reaction of diisocyanate compounds with various divalent or higher alcohol compounds; and the like.
粘着剤組成物中の架橋剤の含有量は、架橋剤の反応性官能基の種類にもより、特に限定されるものではない。例えば、架橋剤としてイソシアネート化合物を用いる場合、耐ガス浮き性及び凹凸や段差に対する追従性の観点から、特定（メタ）アクリル系ポリマー１００質量部に対して、０．０５〜１質量部が好ましく、０．１〜０．５質量部がより好ましい。 The content of the crosslinking agent in the pressure-sensitive adhesive composition is not particularly limited depending on the type of the reactive functional group of the crosslinking agent. For example, when an isocyanate compound is used as the crosslinking agent, 0.05 to 1 part by mass is preferable with respect to 100 parts by mass of the specific (meth) acrylic polymer from the viewpoint of gas floating resistance and followability to unevenness and steps. 0.1-0.5 mass part is more preferable.
〔その他の成分〕
本発明の粘着剤組成物は、さらに、光学用の粘着剤組成物に通常配合される成分、例えば、耐候性安定剤、タッキファイヤー、架橋促進剤、可塑剤、軟化剤、染料、顔料、無機充填剤などを含有していてもよい。
[Other ingredients]
The pressure-sensitive adhesive composition of the present invention further comprises components usually blended in an optical pressure-sensitive adhesive composition, such as a weather resistance stabilizer, tackifier, crosslinking accelerator, plasticizer, softener, dye, pigment, inorganic It may contain a filler or the like.
本発明の粘着剤組成物は、特定（メタ）アクリル系ポリマーを固形分換算で、３０〜６０質量％含むことが好ましい。
本発明の粘着剤組成物の粘度は、塗布性の観点から、２０００ｍＰａ・ｓ〜６０００ｍＰａ・ｓが好ましい。
It is preferable that the adhesive composition of this invention contains 30-60 mass% of specific (meth) acrylic-type polymers in conversion of solid content.
The viscosity of the pressure-sensitive adhesive composition of the present invention is preferably 2000 mPa · s to 6000 mPa · s from the viewpoint of applicability.
＜粘着シート＞
本発明の粘着シートは、粘着剤層を有し、該粘着剤層は、既述の本発明の粘着剤組成物が架橋反応して形成された架橋構造を含む。該粘着剤層は、高温高湿環境に曝されても白化現象が生じにくく、高温環境に曝されても発泡や膨れが起こりにくい。また、該粘着剤層は、ＩＴＯ層が被接着部材である場合にＩＴＯ層の劣化を引き起こしにくい。
<Adhesive sheet>
The pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer includes a crosslinked structure formed by a crosslinking reaction of the above-described pressure-sensitive adhesive composition of the present invention. When the pressure-sensitive adhesive layer is exposed to a high-temperature and high-humidity environment, the whitening phenomenon hardly occurs, and even when the pressure-sensitive adhesive layer is exposed to a high-temperature environment, foaming and swelling are unlikely to occur. Further, the pressure-sensitive adhesive layer hardly causes deterioration of the ITO layer when the ITO layer is an adherend.
本発明の粘着シートにおいて、粘着剤層の厚さは、例えば２０μｍ〜３００μｍの範囲で用途に応じて選択される。
従来、２０μｍ〜６０μｍ程度の厚さの粘着剤層は、それ以上の厚さの粘着剤層に比較して、高温高湿環境に曝された場合に白化現象が起こりやすいが、本発明の粘着シートは、粘着剤層が２０μｍ〜６０μｍ程度の厚さであっても、耐湿熱白化性が良好である。
In the pressure-sensitive adhesive sheet of the present invention, the thickness of the pressure-sensitive adhesive layer is selected in accordance with the use within a range of 20 μm to 300 μm, for example.
Conventionally, a pressure-sensitive adhesive layer having a thickness of about 20 μm to 60 μm is more susceptible to whitening when exposed to a high-temperature and high-humidity environment than a pressure-sensitive adhesive layer having a thickness larger than that. Even if the pressure-sensitive adhesive layer has a thickness of about 20 μm to 60 μm, the sheet has good moisture and heat whitening resistance.
粘着剤層のゲル分率は、４０〜９０質量％が好ましく、５０〜８０質量％がより好ましく、５５〜７５質量％が更に好ましい。粘着剤層のゲル分率が４０質量％以上であると、接着性と凹凸や段差に対する追従性が良好であり、９０質量％以下であると、耐ガス浮き性が良好である。
なお、粘着剤層のゲル分率は、酢酸エチルを抽出溶媒に用いて測定される、溶媒不溶分の割合である。測定方法の詳細は、実施例に記載のとおりである。
40-90 mass% is preferable, as for the gel fraction of an adhesive layer, 50-80 mass% is more preferable, and 55-75 mass% is still more preferable. When the gel fraction of the pressure-sensitive adhesive layer is 40% by mass or more, adhesiveness and followability to unevenness and steps are good, and when it is 90% by mass or less, gas floating resistance is good.
In addition, the gel fraction of an adhesive layer is a ratio of a solvent insoluble content measured using ethyl acetate as an extraction solvent. Details of the measurement method are as described in the examples.
粘着剤層は、透明であることが好ましく、例えば可視光波長領域における全光線透過率（ＪＩＳ Ｋ ７３６１）が８５％以上であることが好ましく、９０％以上であることがより好ましい。
粘着剤層のヘイズ（ＪＩＳ Ｋ ７１３６）は、１．０％以下が好ましく、０．５％以下がより好ましい。
The pressure-sensitive adhesive layer is preferably transparent. For example, the total light transmittance (JIS K 7361) in the visible light wavelength region is preferably 85% or more, and more preferably 90% or more.
The haze (JIS K 7136) of the pressure-sensitive adhesive layer is preferably 1.0% or less, and more preferably 0.5% or less.
本発明の粘着シートは、例えば、架橋剤を含有する本発明の粘着剤組成物を剥離シート等に塗布し、乾燥させ、架橋反応を起こすことによって粘着剤層を形成し作製する。 The pressure-sensitive adhesive sheet of the present invention is produced by, for example, forming a pressure-sensitive adhesive layer by applying the pressure-sensitive adhesive composition of the present invention containing a cross-linking agent to a release sheet and the like, and causing a cross-linking reaction.
本発明の粘着シートは、剥離シートによって粘着剤層が保護された両面粘着テープとして作製してよい。剥離シートは、粘着シートを実用に供するまでの間、粘着剤層の表面を保護する保護シートとして保持したままでよい。両面粘着テープは、基材を有しないタイプ（無基材タイプ）でも、基材（例えば透明基材）を有するタイプ（有基材タイプ）でもよい。 The pressure-sensitive adhesive sheet of the present invention may be produced as a double-sided pressure-sensitive adhesive tape whose pressure-sensitive adhesive layer is protected by a release sheet. The release sheet may be held as a protective sheet that protects the surface of the pressure-sensitive adhesive layer until the pressure-sensitive adhesive sheet is put to practical use. The double-sided pressure-sensitive adhesive tape may be a type having no base material (non-base material type) or a type having a base material (for example, a transparent base material) (base material type).
無基材タイプの両面粘着テープは、例えば、剥離シートの剥離処理面に粘着剤組成物を塗布し、この塗布層上に別の剥離シートを剥離処理面が接するように重ね、架橋反応を起こすことによって粘着剤層を形成する方法により作製し得る。
剥離シートとしては、粘着剤層からの剥離が容易に行なえるものであれば特に制限はなく、例えば、剥離処理剤を用いて少なくとも片面に剥離処理が施された樹脂フィルム（例えばポリエチレンテレフタレート（ＰＥＴ）等のポリエステルフィルム）が挙げられる。剥離処理剤としては、フッ素化合物、シリコーン化合物、長鎖アルキル化合物などが挙げられる。
The base-free double-sided pressure-sensitive adhesive tape, for example, applies a pressure-sensitive adhesive composition to the release-treated surface of a release sheet, and stacks another release sheet on this coating layer so that the release-treated surface comes into contact, thereby causing a crosslinking reaction. It can produce by the method of forming an adhesive layer by this.
The release sheet is not particularly limited as long as it can be easily peeled off from the pressure-sensitive adhesive layer. For example, a resin film (for example, polyethylene terephthalate (PET) having a release treatment applied to at least one side using a release treatment agent is used. And the like). Examples of the release treatment agent include fluorine compounds, silicone compounds, and long-chain alkyl compounds.
有基材タイプの両面粘着テープは、例えば、基材の両面に粘着剤組成物を塗布し、この両塗布層上にそれぞれ剥離シートを剥離処理面が接するように重ね、架橋反応を起こすことによって作製することができる。ほかに、剥離シートの剥離処理面に粘着剤層を形成し、この剥離シート付きの粘着剤層を基材の両面に接着させる方法により作製することができる。
基材としては、樹脂フィルム（例えば、ＰＥＴ等のポリエステルフィルム）が挙げられる。基材の厚さは、特に限定されないが、耐久性の観点から５μｍ〜１００μｍが好ましい。
A double-sided adhesive tape with a base material type is, for example, by applying a pressure-sensitive adhesive composition on both surfaces of a base material, and stacking a release sheet on both coating layers so that the release-treated surfaces are in contact with each other, thereby causing a crosslinking reaction. Can be produced. In addition, it can be produced by a method in which a pressure-sensitive adhesive layer is formed on the release-treated surface of the release sheet, and the pressure-sensitive adhesive layer with the release sheet is adhered to both surfaces of the substrate.
Examples of the substrate include a resin film (for example, a polyester film such as PET). Although the thickness of a base material is not specifically limited, 5 micrometers-100 micrometers are preferable from a durable viewpoint.
剥離シートや基材に粘着剤組成物を塗布する方法としては、グラビヤロールコーター、リバースロールコーター、キスロールコーター、ディップロールコーター、バーコーター、ナイフコーター、スプレーコーター等を用いた公知の方法が挙げられる。 Examples of the method for applying the pressure-sensitive adhesive composition to the release sheet or the base material include known methods using a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray coater, etc. It is done.
本発明の粘着シートの実施形態の一例を図１に示す。
図１は、本発明の粘着シートを備えた両面粘着テープの構成を示す概略断面図である。
図１に示す両面粘着テープ１０は、粘着剤層１１（粘着シート）を備え、粘着剤層１１の一方の面にＰＥＴフィルム１３（剥離シートの一例）を、他方の面にＰＥＴフィルム１５（剥離シートの一例）を備える。
ＰＥＴフィルム１３及びＰＥＴフィルム１５の粘着剤層１１に接する側の面には剥離処理が施されて剥離層１７が設けられており、粘着剤層１１は、剥離層１７を介してＰＥＴフィルム１３及びＰＥＴフィルム１５と接着している。
両面粘着テープ１０は、ＰＥＴフィルム１３及びＰＥＴフィルム１５を剥離層１７で剥離することができ、２枚のＰＥＴフィルムを剥がすことで、粘着剤層１１からなる粘着シートとなる。
An example of an embodiment of the pressure-sensitive adhesive sheet of the present invention is shown in FIG.
FIG. 1 is a schematic cross-sectional view showing the configuration of a double-sided pressure-sensitive adhesive tape provided with the pressure-sensitive adhesive sheet of the present invention.
A double-sided pressure-sensitive adhesive tape 10 shown in FIG. 1 includes a pressure-sensitive adhesive layer 11 (pressure-sensitive adhesive sheet), a PET film 13 (an example of a release sheet) on one surface of the pressure-sensitive adhesive layer 11, and a PET film 15 (peeling) on the other surface. An example of a sheet).
The surface of the PET film 13 and the PET film 15 on the side in contact with the pressure-sensitive adhesive layer 11 is subjected to a peeling treatment to provide a peeling layer 17, and the pressure-sensitive adhesive layer 11 is formed through the peeling layer 17 with the PET film 13 and It is adhered to the PET film 15.
The double-sided pressure-sensitive adhesive tape 10 can peel the PET film 13 and the PET film 15 with the release layer 17, and becomes a pressure-sensitive adhesive sheet composed of the pressure-sensitive adhesive layer 11 by peeling the two PET films.
本発明の粘着シートは、タッチパネルやディスプレイパネル等における光学フィルムの実装に用いるＯＣＡ用粘着剤として好適である。即ち、本発明の粘着シートは、例えば、偏光板、位相差板、反射防止フィルム、視野角拡大フィルム、輝度上昇フィルム、透明導電性フィルム（ＩＴＯフィルム等）等の光学フィルムと、電極、液晶セル、ガラス基板、保護フィルム等との貼り合わせに好適に用い得る。また、本発明の粘着シートは、例えば、上記の光学フィルム間の貼り合わせに好適に用い得る。 The pressure-sensitive adhesive sheet of the present invention is suitable as a pressure-sensitive adhesive for OCA used for mounting an optical film on a touch panel, a display panel or the like. That is, the pressure-sensitive adhesive sheet of the present invention includes, for example, an optical film such as a polarizing plate, a retardation plate, an antireflection film, a viewing angle widening film, a brightness enhancement film, a transparent conductive film (ITO film, etc.), an electrode, and a liquid crystal cell. , And can be suitably used for bonding with a glass substrate, a protective film or the like. Moreover, the adhesive sheet of this invention can be used suitably for bonding between said optical films, for example.
本発明の粘着シートは、下記の光学用積層シートに適用することができる。 The pressure-sensitive adhesive sheet of the present invention can be applied to the following optical laminated sheet.
＜光学用積層シート＞
本発明の光学用積層シートは、シート状の光学部材と、前記光学部材の少なくとも片面に設けられた粘着剤層とを有し、該粘着剤層は、既述の本発明の粘着剤組成物が架橋反応して形成された架橋構造を含む。該粘着剤層は、高温高湿環境に曝されても白化現象が生じにくく、高温環境に曝されても発泡や膨れが起こりにくい。したがって、本発明の光学用積層シートは、白化現象が生じにくく、発泡や膨れが起こりにくい。
<Laminated optical sheet>
The optical laminated sheet of the present invention has a sheet-like optical member and a pressure-sensitive adhesive layer provided on at least one surface of the optical member, and the pressure-sensitive adhesive layer is the pressure-sensitive adhesive composition of the present invention described above. Includes a crosslinked structure formed by a crosslinking reaction. When the pressure-sensitive adhesive layer is exposed to a high-temperature and high-humidity environment, the whitening phenomenon hardly occurs, and even when the pressure-sensitive adhesive layer is exposed to a high-temperature environment, foaming and swelling are unlikely to occur. Therefore, the optical laminated sheet of the present invention is less prone to whitening and less likely to foam or swell.
本発明の光学用積層シートにおいて、粘着剤層の厚さは、例えば２０μｍ〜３００μｍの範囲で用途に応じて選択される。
本発明の光学用積層シートにおける粘着剤層のゲル分率、全光線透過率、ヘイズは、既述の粘着シートの粘着剤層におけるゲル分率、全光線透過率、ヘイズと同様の範囲が好ましい。
In the optical laminated sheet of the present invention, the thickness of the pressure-sensitive adhesive layer is selected in accordance with the use within a range of 20 μm to 300 μm, for example.
The gel fraction, total light transmittance, and haze of the pressure-sensitive adhesive layer in the optical laminated sheet of the present invention are preferably in the same ranges as the gel fraction, total light transmittance, and haze in the pressure-sensitive adhesive layer of the aforementioned pressure-sensitive adhesive sheet. .
シート状の光学部材としては、例えば、偏光板、位相差板、反射防止フィルム、視野角拡大フィルム、輝度上昇フィルム、透明導電性フィルム（ＩＴＯフィルム等）等の光学フィルム；光学フィルム等の保護に用いる保護フィルム；これらを含む積層シート；などが挙げられる。
シート状の光学部材の素材としては、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等のポリエステル樹脂；ポリプロピレン、ポリメチルペンテン等のポリオレフィン樹脂；ポリスチレン樹脂；アクリル樹脂；ポリカーボネート樹脂；酢酸セルロース；などが挙げられる。
シート状の光学部材の厚さは、特に制限されないが、通常２０μｍ〜１５０μｍであり、用途に応じて選択される。
Examples of the sheet-like optical member include optical films such as a polarizing plate, a retardation plate, an antireflection film, a viewing angle widening film, a brightness enhancement film, a transparent conductive film (ITO film, etc.); Protective film to be used; laminated sheet containing these;
Examples of the material of the sheet-like optical member include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin resins such as polypropylene and polymethylpentene; polystyrene resins; acrylic resins; polycarbonate resins; It is done.
The thickness of the sheet-like optical member is not particularly limited, but is usually 20 μm to 150 μm, and is selected according to the application.
本発明の光学用積層シートは、例えば、剥離シート上に形成した粘着剤層をシート状の光学部材の片面又は両面に貼り合わせることで作製される。剥離シートは、光学用積層シートを実用に供するまでの間、粘着剤層の表面を保護する保護シートとして保持したままでもよい。
また、本発明の光学用積層シートは、シート状の光学部材の片面又は両面に直接、粘着剤層を形成することによっても作製される。この場合、粘着剤層の表面に剥離シートを貼り合わせ、光学用積層シートを実用に供するまでの間、保護シートとしてもよい。
The optical laminated sheet of the present invention is produced, for example, by laminating an adhesive layer formed on a release sheet to one or both sides of a sheet-like optical member. The release sheet may be retained as a protective sheet for protecting the surface of the pressure-sensitive adhesive layer until the optical laminated sheet is put to practical use.
The optical laminated sheet of the present invention can also be produced by directly forming an adhesive layer on one side or both sides of a sheet-like optical member. In this case, it is good also as a protective sheet until it sticks a peeling sheet on the surface of an adhesive layer, and uses an optical laminated sheet for practical use.
本発明の光学用積層シートの具体例としては、偏光板、位相差板、反射防止フィルム、視野角拡大フィルム、輝度上昇フィルム、透明導電性フィルム（ＩＴＯフィルム等）等の光学フィルムの片面又は両面に粘着剤層を備えた積層体；光学フィルム等の保護に用いる保護フィルムの片面又は両面に粘着剤層を備えた積層体；等が挙げられる。 Specific examples of the optical laminated sheet of the present invention include one or both sides of an optical film such as a polarizing plate, a retardation plate, an antireflection film, a viewing angle widening film, a brightness enhancement film, and a transparent conductive film (ITO film, etc.). And a laminate having a pressure-sensitive adhesive layer on one or both sides of a protective film used for protecting an optical film or the like.
以下、実施例により本発明を具体的に説明するが、本発明はこれら実施例に限定されるものではない。
以下において、特に断りがない限り、「部」は質量基準である。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples .
In the following, “part” is based on mass unless otherwise specified.
＜（メタ）アクリル系ポリマーの製造＞
〔ポリマー（１）の製造〕
（単量体混合物）
・ラウリルアクリレート １５０部
・ｎ−ブチルアクリレ−ト １０５０部
・２−ヒドロキシエチルアクリレート ３００部
攪拌機、還流冷却器、逐次滴下装置、及び温度計を備えた反応装置に、上記単量体混合物３００部（単量体混合物の２０質量％）と、酢酸エチル３５０部（重合用有機溶媒）とを入れて加熱し、還流温度で１０分間還流を行った。
次いで、還流温度条件下で、上記単量体混合物の残り１２００部（単量体混合物の８０質量％）と酢酸エチル３２部と２，２’−アゾビス（２，４−ジメチルバレロニトリル）０．１２部とを、１２０分間にわたって逐次滴下し、更に３０分間重合反応を行った。
その後、酢酸エチル１５部とｔ−ブチルパーオキシピバレート０．１３部の混合液を、４０分間にわたって逐次滴下し、更に１５０分間重合反応を行った。
反応終了後、酢酸エチルにて固形分４２％に希釈し、ポリマー（１）を含むポリマー溶液（１）を得た。
ポリマー（１）の重量平均分子量（Ｍｗ）、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比、及びガラス転移温度（Ｔｇ）を表１に示す。
<Manufacture of (meth) acrylic polymer>
[Production of polymer (1)]
(Monomer mixture)
150 parts of lauryl acrylate 1050 parts of n-butyl acrylate 300 parts of 2-hydroxyethyl acrylate 300 parts of the above monomer mixture (single unit) were added to a reactor equipped with a stirrer, reflux condenser, sequential dropping device, and thermometer. 20 mass% of the monomer mixture) and 350 parts of ethyl acetate (organic solvent for polymerization) were added and heated, and refluxed at reflux temperature for 10 minutes.
Subsequently, under the reflux temperature condition, the remaining 1200 parts of the monomer mixture (80% by mass of the monomer mixture), 32 parts of ethyl acetate, and 2,2′-azobis (2,4-dimethylvaleronitrile) 0. 12 parts were successively added dropwise over 120 minutes, and the polymerization reaction was further carried out for 30 minutes.
Thereafter, a mixed solution of 15 parts of ethyl acetate and 0.13 part of t-butyl peroxypivalate was successively added dropwise over 40 minutes, and a polymerization reaction was further performed for 150 minutes.
After completion of the reaction, it was diluted with ethyl acetate to a solid content of 42% to obtain a polymer solution (1) containing the polymer (1).
Table 1 shows the weight average molecular weight (Mw) of the polymer (1), the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), and the glass transition temperature (Tg).
〔ポリマー（２）〜（１２）の製造〕
組成を表１に示すとおりに変更し、ポリマー（１）の重合反応と同様にして、ポリマー（２）〜（１２）を合成した。そして、酢酸エチルにて固形分４２質量％に希釈し、ポリマー（２）〜（１２）をそれぞれ含むポリマー溶液（２）〜（１２）を得た。
ポリマー（２）〜（１２）の重量平均分子量（Ｍｗ）、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比、及びガラス転移温度（Ｔｇ）を表１に示す。
[Production of polymers (2) to (12)]
The composition was changed as shown in Table 1, and polymers (2) to (12) were synthesized in the same manner as in the polymerization reaction of polymer (1). And it diluted with ethyl acetate to 42 mass% of solid content, and obtained polymer solution (2)-(12) which respectively contains polymer (2)-(12).
Table 1 shows the weight average molecular weight (Mw), the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), and the glass transition temperature (Tg) of the polymers (2) to (12).
〔ポリマー（Ｃ１）〜（Ｃ１０）の製造〕
組成を表２に示すとおりに変更し、ポリマー（１）の重合反応と同様にして、ポリマー（Ｃ１）〜（Ｃ１０）を合成した。そして、酢酸エチルにて固形分４２質量％に希釈し、ポリマー（Ｃ１）〜（Ｃ１０）をそれぞれ含むポリマー溶液（Ｃ１）〜（Ｃ１０）を得た。
ポリマー（Ｃ１）〜（Ｃ１０）の重量平均分子量（Ｍｗ）、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比、及びガラス転移温度（Ｔｇ）を表２に示す。
[Production of polymers (C1) to (C10)]
The composition was changed as shown in Table 2, and the polymers (C1) to (C10) were synthesized in the same manner as the polymerization reaction of the polymer (1). And it diluted with ethyl acetate to 42 mass% of solid content, and obtained polymer solution (C1)-(C10) which respectively contains polymer (C1)-(C10).
Table 2 shows the weight average molecular weight (Mw), the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), and the glass transition temperature (Tg) of the polymers (C1) to (C10).
（メタ）アクリル系ポリマーの合成に供した単量体の詳細は、下記のとおりである。
・ＬＡ：ラウリルアクリレート、アルキル基の炭素数１２、ホモポリマーのガラス転移温度１５℃
・ＬＭ：ラウリルメタクリレート、アルキル基の炭素数１２、ホモポリマーのガラス転移温度−６５℃
・ＳＡ：ステアリルアクリレート、アルキル基の炭素数１８、ホモポリマーのガラス転移温度３０℃
・ＢＡ：ｎ−ブチルアクリレート、アルキル基の炭素数４、ホモポリマーのガラス転移温度−５７℃
・２−ＥＨＡ：２−エチルヘキシルアクリレート、アルキル基の炭素数８、ホモポリマーのガラス転移温度−７６℃
・ｉ−ＯＡ：イソオクチルアクリレート、アルキル基の炭素数８、ホモポリマーのガラス転移温度−５８℃
・ＭＡ：メチルアクリレート、アルキル基の炭素数１、ホモポリマーのガラス転移温度５℃
・２−ＨＥＡ：２−ヒドロキシエチルアクリレート、ホモポリマーのガラス転移温度−１５℃
・４−ＨＢＡ：４−ヒドロキシブチルアクリレート、ホモポリマーのガラス転移温度−３２℃
・ＩＮＡＡ：イソノニルアクリレート、アルキル基の炭素数９、ホモポリマーのガラス転移温度−５８℃
・２−ＭＥＡ：２−メトキシエチルアクリレート、ホモポリマーのガラス転移温度−５０℃
Details of the monomer used for the synthesis of the (meth) acrylic polymer are as follows.
LA: Lauryl acrylate, alkyl group 12 carbon atoms, homopolymer glass transition temperature 15 ° C.
LM: Lauryl methacrylate, alkyl group 12 carbon atoms, homopolymer glass transition temperature -65 ° C
SA: Stearyl acrylate, alkyl group having 18 carbon atoms, homopolymer glass transition temperature of 30 ° C.
BA: n-butyl acrylate, alkyl group having 4 carbon atoms, homopolymer glass transition temperature of −57 ° C.
2-EHA: 2-ethylhexyl acrylate, alkyl group having 8 carbon atoms, homopolymer glass transition temperature -76 ° C
I-OA: isooctyl acrylate, alkyl group having 8 carbon atoms, homopolymer glass transition temperature -58 ° C
MA: methyl acrylate, alkyl group carbon number 1, homopolymer glass transition temperature 5 ° C.
2-HEA: 2-hydroxyethyl acrylate, homopolymer glass transition temperature -15 ° C
4-HBA: 4-hydroxybutyl acrylate, homopolymer glass transition temperature -32 ° C
・ INAA: isononyl acrylate, carbon number of alkyl group 9, glass transition temperature of homopolymer −58 ° C.
2-MEA: 2-methoxyethyl acrylate, homopolymer glass transition temperature -50 ° C
（メタ）アクリル系ポリマーの重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、下記（１）〜（３）の手順で測定した。
（１）ポリマーの溶液を剥離紙に塗布し、１００℃で２分間乾燥させ、フィルム状のポリマーを得る。
（２）フィルム状のポリマーを、テトラヒドロフランに固形分０．２質量％になるように溶解する。
（３）ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用い、下記条件にて、分子量測定（ポリスチレン換算）を行う。
［条件］
・ＧＰＣ ：東ソー社製ＨＬＣ−８２２０
・カラム ：東ソー社製ＴＳＫ−ＧＥＬ ＧＭＨＸＬ、４本
・移動相溶媒：テトラヒドロフラン
・流速 ：０．６ｍｌ／ｍｉｎ
・カラム温度：４０℃
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the (meth) acrylic polymer were measured by the following procedures (1) to (3).
(1) A polymer solution is applied to release paper and dried at 100 ° C. for 2 minutes to obtain a film-like polymer.
(2) A film-like polymer is dissolved in tetrahydrofuran so that the solid content is 0.2% by mass.
(3) Using gel permeation chromatography (GPC), molecular weight measurement (polystyrene conversion) is performed under the following conditions.
[conditions]
-GPC: Tosoh HLC-8220
Column: Tosoh TSK-GEL GMHXL, 4 Mobile phase solvent: Tetrahydrofuran Flow rate: 0.6 ml / min
-Column temperature: 40 ° C
＜実施例１＞
〔粘着剤溶液の調製〕
以下の手順にしたがって、粘着剤溶液（粘着剤組成物）を調製した。
ポリマー溶液（１）１００部（固形分換算）と、架橋剤（イソシアネート化合物、三井化学社製タケネートＤ−１１０Ｎ）０．２部（固形分換算）とを混合し、粘着剤溶液を調製した。
<Example 1>
(Preparation of adhesive solution)
A pressure-sensitive adhesive solution (pressure-sensitive adhesive composition) was prepared according to the following procedure.
A polymer solution (1) 100 parts (solid content conversion) and a crosslinking agent (isocyanate compound, Takenate D-110N manufactured by Mitsui Chemicals, Inc.) 0.2 parts (solid content conversion) were mixed to prepare an adhesive solution.
〔両面粘着テープ及び試験用シートの作製〕
片面に剥離処理が施されたＰＥＴフィルムＰ（厚さ７５μｍ）の剥離処理面に、粘着剤溶液を、乾燥後の厚さが約５０μｍとなるように塗布し、１００℃で２分間加熱乾燥させて粘着剤層を形成した。
次いで、ＰＥＴフィルムＰ上の粘着剤層に、片面に剥離処理が施された軽剥離性のＰＥＴフィルムＱ（厚さ３８μｍ）をその剥離処理面が接触するように重ね、加圧ニップロールを通して圧着し、貼り合せた。
その後、温度２３℃／相対湿度５０％の環境下で４日間養生を行い、図１に示すように、粘着剤層の両面にそれぞれ剥離層を介してＰＥＴフィルムが設けられた両面粘着テープを得た。この両面粘着テープは、両面のＰＥＴフィルムを剥がすことで基材のない粘着剤層（粘着シート）となる。
この両面粘着テープのＰＥＴフィルムＱを剥離し、露出した粘着剤層に、剥離処理が施されていないＰＥＴフィルムＲ（厚さ１００μｍ）（東洋紡績社製Ａ４１００）を重ね、加圧ニップロールを通して圧着し、貼り合せることで試験用シートを得た。
[Production of double-sided adhesive tape and test sheet]
The adhesive solution is applied to the peel-treated surface of a PET film P (thickness 75 μm) that has been peeled on one side so that the thickness after drying is about 50 μm, and dried by heating at 100 ° C. for 2 minutes. Thus, an adhesive layer was formed.
Next, a light-peelable PET film Q (thickness: 38 μm) with a release treatment on one side is stacked on the pressure-sensitive adhesive layer on the PET film P so that the release treatment surface comes into contact with the pressure-sensitive adhesive layer, and is pressed through a pressure nip roll. , Pasted together.
Thereafter, curing is performed for 4 days in an environment of a temperature of 23 ° C./relative humidity of 50%, and as shown in FIG. 1, a double-sided pressure-sensitive adhesive tape in which a PET film is provided on each side of the pressure-sensitive adhesive layer via a release layer is obtained. It was. This double-sided pressure-sensitive adhesive tape becomes a pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet) having no substrate by peeling off the double-sided PET films.
The PET film Q of this double-sided pressure-sensitive adhesive tape is peeled off, and the exposed pressure-sensitive adhesive layer is overlaid with a PET film R (thickness: 100 μm) (A4100 manufactured by Toyobo Co., Ltd.) that has not been subjected to peeling treatment, and is pressed through a pressure nip roll. The test sheet was obtained by pasting.
＜実施例２〜７、参考例８及び実施例９〜１２＞
実施例１において、ポリマー溶液（１）を表３に示すとおり他のポリマー溶液に変更したこと以外は、実施例１と同様にして、実施例２〜７、参考例８及び実施例９〜１２の粘着剤溶液を調製した。
そして、各実施例又は参考例の粘着剤溶液を用いて、実施例１と同様にして、両面粘着テープ及び試験用シートを作製した。
<Examples 2 to 7, Reference Example 8 and Examples 9 to 12>
In Example 1, Examples 2-7 , Reference Example 8 and Examples 9-12 are the same as Example 1 except that the polymer solution (1) is changed to another polymer solution as shown in Table 3. A pressure-sensitive adhesive solution was prepared.
And the double-sided adhesive tape and the sheet for a test were produced like Example 1 using the adhesive solution of each example or a reference example .
＜比較例１〜１０＞
実施例１において、ポリマー溶液（１）を表４に示すとおり他のポリマー溶液に変更したこと以外は、実施例１と同様にして、比較例１〜１０の粘着剤溶液を調製した。
そして、各比較例の粘着剤溶液を用いて、実施例１と同様にして、両面粘着テープ及び試験用シートを作製した。
<Comparative Examples 1-10>
In Example 1, the adhesive solution of Comparative Examples 1-10 was prepared like Example 1 except having changed the polymer solution (1) into the other polymer solution as shown in Table 4.
And using the adhesive solution of each comparative example, it carried out similarly to Example 1, and produced the double-sided adhesive tape and the sheet | seat for a test.
＜評価＞
各実施例、参考例及び各比較例の両面粘着テープ及び試験用シートについて、下記の方法により物性の測定及び性能の評価を行なった。その結果を表３及び表４に示す。
<Evaluation>
With respect to the double-sided pressure-sensitive adhesive tapes and test sheets of each Example , Reference Example and each Comparative Example, the physical properties were measured and the performance was evaluated by the following methods. The results are shown in Tables 3 and 4.
〔ゲル分率〕
下記（１）〜（３）の操作を行ない、下記式からゲル分率（質量％）を算出した。
ゲル分率（質量％） ＝［（Ｚ−Ｘ）／（Ｙ−Ｘ）］×１００
ここに、Ｘ：金網の質量（ｇ）、Ｙ：抽出用試料の質量（粘着剤及び金網の総質量）（ｇ）、Ｚ：浸漬後、乾燥させた抽出用試料の質量（金網及び粘着剤の不溶分の総質量）（ｇ）。
[Gel fraction]
The following operations (1) to (3) were performed, and the gel fraction (% by mass) was calculated from the following formula.
Gel fraction (% by mass) = [(Z−X) / (Y−X)] × 100
Here, X: mass of wire mesh (g), Y: mass of sample for extraction (total mass of adhesive and wire mesh) (g), Z: mass of sample for extraction dried after immersion (wire mesh and adhesive) (Total mass of insoluble matter) (g).
［操作］
（１）精秤した２５０メッシュの金網（１００ｍｍ×１００ｍｍ）に、両面粘着テープの両面のＰＥＴフィルムを剥離して粘着剤層約０．５ｇを添付し、金網で包み、抽出用試料とした。この抽出用試料の質量（粘着剤及び金網の総質量）を精密天秤にて測定した。
（２）抽出溶媒として酢酸エチル８０ｇが入ったガラス瓶の中に、抽出用試料を入れて３日間浸漬した。
（３）浸漬終了後、抽出用試料を取り出して少量の酢酸エチルで洗浄し、１２０℃で２４時間乾燥させた。この乾燥後の抽出用試料の質量（金網及び粘着剤の不溶分の総質量）を精密天秤にて測定した。
[operation]
(1) A PET mesh on both sides of a double-sided adhesive tape was peeled off to a precisely weighed 250-mesh wire mesh (100 mm × 100 mm), and about 0.5 g of an adhesive layer was attached and wrapped with a wire mesh to obtain a sample for extraction. The mass of the sample for extraction (total mass of adhesive and wire mesh) was measured with a precision balance.
(2) An extraction sample was placed in a glass bottle containing 80 g of ethyl acetate as an extraction solvent and immersed for 3 days.
(3) After the immersion, the sample for extraction was taken out, washed with a small amount of ethyl acetate, and dried at 120 ° C. for 24 hours. The mass of the extraction sample after drying (the total mass of the insoluble content of the wire mesh and the adhesive) was measured with a precision balance.
〔耐湿熱白化性〕
試験用シートを８０ｍｍ×６０ｍｍに切り出し、ＰＥＴフィルムＰを剥離し、露出した粘着剤層を厚さ１．８ｍｍのガラス板（松浪硝子工業社製、光学ソーダガラス）に重ね、卓上ラミネート機を用いて圧着し、試験用試料とした。
この試験用試料のヘイズ（％）を、分光測色計（コニカミノルタ社製ＣＭ−３５００ｄ）にて、ＰＥＴフィルムＲ側から光束を入照して測定した。
次いで、試験用試料を温度８５℃／相対湿度９０％の環境下に１６８時間置き、この環境から取り出した直後、同様にしてヘイズ（％）を測定した。
試験環境への投入前後のヘイズ（％）の差（ΔＨ）を算出し、下記の評価基準にしたがって評価した。
［評価基準］
Ａ：ΔＨが１．００未満
Ｂ：ΔＨが１．００以上２．００未満
Ｃ：ΔＨが２．００以上
[Moisture and heat whitening resistance]
The test sheet was cut into 80 mm x 60 mm, the PET film P was peeled off, and the exposed adhesive layer was stacked on a 1.8 mm thick glass plate (manufactured by Matsunami Glass Industrial Co., Ltd., optical soda glass), and a table laminator was used. The test sample was pressed.
The haze (%) of the test sample was measured with a spectrocolorimeter (CM-3500d manufactured by Konica Minolta Co., Ltd.) by irradiating the light beam from the PET film R side.
Next, the test sample was placed in an environment at a temperature of 85 ° C./90% relative humidity for 168 hours, and immediately after removal from the environment, haze (%) was measured in the same manner.
A difference (ΔH) in haze (%) before and after introduction into the test environment was calculated and evaluated according to the following evaluation criteria.
[Evaluation criteria]
A: ΔH is less than 1.00 B: ΔH is 1.00 or more and less than 2.00 C: ΔH is 2.00 or more
〔耐ガス浮き性〕
試験用シートを８０ｍｍ×９０ｍｍに切り出し、ＰＥＴフィルムＰを剥離し、露出した粘着剤層を厚さ２．０ｍｍのポリカーボネート板（三菱ガス化学社製ユーピロンＭＲ５８）に重ね、卓上ラミネート機を用いて圧着し、試験用試料とした。
この試験用試料を温度８５℃の環境下に２４時間置いた後、ＰＥＴフィルムＲ側から目視にて観察し、粘着剤層に認められた気泡の個数を数え、下記の評価基準にしたがって評価した。
［評価基準］
Ａ：気泡が０個〜２個
Ｂ：気泡が３個〜５個
Ｃ：気泡が６個以上
(Gas resistance)
The test sheet is cut into 80 mm × 90 mm, the PET film P is peeled off, the exposed adhesive layer is layered on a 2.0 mm thick polycarbonate plate (Mitsubishi Gas Chemical Co., Ltd. Iupilon MR58), and crimped using a table laminator. And used as a test sample.
This test sample was placed in an environment at a temperature of 85 ° C. for 24 hours, then visually observed from the PET film R side, the number of bubbles observed in the adhesive layer was counted, and evaluated according to the following evaluation criteria. .
[Evaluation criteria]
A: 0 to 2 bubbles B: 3 to 5 bubbles C: 6 or more bubbles
〔低ＩＴＯ劣化性〕
下記（１）〜（５）の手順で、試験用試料を作製した。手順（１）〜（５）を図２を参照して説明する。
［手順］
（１）ＰＥＴフィルム上にＩＴＯ層を有するＩＴＯフィルム１０１（尾池工業社製テトライトＴＣＦ ＫＢ ３００Ｎ０３−１２５−Ｕ３／Ｐ。３００ｍｍ×１２５ｍｍ）を用意し、一方の１２５ｍｍ辺から５５ｍｍの幅を空けて該辺に平行にマスキングテープ１０２（幅６５ｍｍ）を貼り、同じく他方の１２５ｍｍ辺から５５ｍｍの幅を空けて該辺に平行にマスキングテープ１０２（幅６５ｍｍ）を貼った（図２（Ａ）参照）。
（２）マスキングしたＩＴＯフィルム１０１に銀ペースト１０３（藤倉化成社製ドータイトＦＡ−４０１ＣＡ）を薄く塗った（図２（Ｂ）参照）。次いで、２枚のマスキングテープ１０２を剥がし、温度１４０℃で１５分間乾燥させ銀ペースト層１０４を形成した。
（３）銀ペースト層１０４を形成したＩＴＯフィルム１０１を、銀ペースト層１０４の領域において、１２５ｍｍ辺に平行に切り（図２（Ｃ）参照）、９０ｍｍ×１２５ｍｍの大きさにした。
（４）試験用シートを７２ｍｍ×１００ｍｍに切り出して、ＰＥＴフィルムＰを剥離し、粘着剤層を露出させた光学用積層シート１０５を用意した。光学用積層シート１０５を、銀ペースト層１０４を形成したＩＴＯフィルム１０１に、銀ペースト層１０４の間（幅６５ｍｍ）を埋めるように重ね、オートクレーブ処理（０．５ＭＰａ／４０℃／３０分）を施して貼り合わせた（図２（Ｄ）参照）。
（５）光学用積層シート１０５を貼り合わせたＩＴＯフィルム１０１を、幅２０ｍｍの短冊状に切り、ＩＴＯフィルム１０１、銀ペースト層１０４、粘着剤層１０６、及びＰＥＴフィルムＲ（保護フィルム）がこの順に積層した試験用試料を得た（図２（Ｅ）参照）。
[Low ITO degradation]
Test samples were prepared by the following procedures (1) to (5). Procedures (1) to (5) will be described with reference to FIG.
[procedure]
(1) An ITO film 101 having an ITO layer on a PET film (Teitoite TCF KB 300N03-125-U3 / P manufactured by Oike Kogyo Co., Ltd., 300 mm × 125 mm) is prepared, with a width of 55 mm from one 125 mm side. A masking tape 102 (width 65 mm) was applied in parallel to the side, and a masking tape 102 (width 65 mm) was applied in parallel to the side with a width of 55 mm from the other 125 mm side (see FIG. 2A). .
(2) Silver paste 103 (Dotite FA-401CA manufactured by Fujikura Kasei Co., Ltd.) was thinly applied to the masked ITO film 101 (see FIG. 2B). Next, the two masking tapes 102 were peeled off and dried at a temperature of 140 ° C. for 15 minutes to form a silver paste layer 104.
(3) The ITO film 101 on which the silver paste layer 104 was formed was cut parallel to the 125 mm side in the region of the silver paste layer 104 (see FIG. 2C) to a size of 90 mm × 125 mm.
(4) The test sheet was cut out to 72 mm × 100 mm, the PET film P was peeled off, and an optical laminated sheet 105 with an adhesive layer exposed was prepared. The optical laminated sheet 105 is stacked on the ITO film 101 on which the silver paste layer 104 is formed so as to fill the space between the silver paste layers 104 (width: 65 mm), and subjected to autoclave treatment (0.5 MPa / 40 ° C./30 minutes). (See FIG. 2D).
(5) The ITO film 101 to which the optical laminated sheet 105 is bonded is cut into a strip shape having a width of 20 mm, and the ITO film 101, the silver paste layer 104, the adhesive layer 106, and the PET film R (protective film) are in this order. A laminated test sample was obtained (see FIG. 2E).
この試験用試料の抵抗値を、温度２３℃／相対湿度５０％の環境下で、試験用試料の両端に露出している銀ペースト層に抵抗値測定器の電極を当て測定した。
次いで、試験用試料を温度６０℃／相対湿度９０％の環境下に２５０時間置き、この環境から取り出した直後、温度２３℃／相対湿度５０％の環境下で、同様にして抵抗値を測定した。
試験環境への投入前後の抵抗値の変化率（％）、即ち［（投入後の抵抗値−投入前の抵抗値）／投入前の抵抗値］×１００（％）を算出し、下記の評価基準にしたがって評価した。
［評価基準］
Ａ：抵抗値の変化率１０％未満
Ｂ：抵抗値の変化率１０％以上２０％未満
Ｃ：抵抗値の変化率２０％以上
The resistance value of the test sample was measured by applying an electrode of a resistance value measuring instrument to the silver paste layer exposed at both ends of the test sample in an environment of a temperature of 23 ° C./relative humidity of 50%.
Next, the test sample was placed in an environment at a temperature of 60 ° C./90% relative humidity for 250 hours, and immediately after removal from the environment, the resistance value was measured in the same manner at an environment of 23 ° C./50% relative humidity. .
Change rate (%) of resistance value before and after introduction into test environment, that is, [(resistance value after introduction-resistance value before introduction) / resistance value before introduction] × 100 (%) was calculated and evaluated as follows. Evaluation was made according to criteria.
[Evaluation criteria]
A: Resistance value change rate of less than 10% B: Resistance value change rate of 10% or more and less than 20% C: Resistance value change rate of 20% or more
表３及び表４から明らかなとおり、実施例１〜７、参考例８及び実施例９〜１２は、ＩＴＯ層の劣化を引き起こしにくい上に、高温高湿環境に曝されても粘着剤層が白化しにくく、且つ、高温環境に曝されても粘着剤層の発泡が起こりにくかった。 As is apparent from Tables 3 and 4, Examples 1 to 7, Reference Example 8 and Examples 9 to 12 are less likely to cause deterioration of the ITO layer, and the pressure-sensitive adhesive layer is not exposed to a high temperature and high humidity environment. Whitening was difficult and foaming of the pressure-sensitive adhesive layer was difficult to occur even when exposed to a high temperature environment.
本発明は、タッチパネルやディスプレイパネル等における光学フィルムの実装に用いるＯＣＡ用粘着剤として好適である。 The present invention is suitable as an OCA pressure-sensitive adhesive used for mounting an optical film on a touch panel, a display panel, or the like.
１０ 両面粘着テープ
１１ 粘着剤層（粘着シート）
１３ ＰＥＴフィルム（剥離シート）
１５ ＰＥＴフィルム（剥離シート）
１７ 剥離層
10 Double-sided adhesive tape 11 Adhesive layer (adhesive sheet)
13 PET film (release sheet)
15 PET film (release sheet)
17 Release layer
１０１ ＩＴＯフィルム
１０４ 銀ペースト層
１０５ 光学用積層シート
１０６ 粘着剤層
Ｒ ＰＥＴフィルム（保護フィルム）
101 ITO film 104 Silver paste layer 105 Optical laminated sheet 106 Adhesive layer R PET film (protective film)
Claims (6)
炭素数１以上８以下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に由来の構成単位（Ｂ）を５質量％以上７０質量％以下、及び、
水酸基を有する単量体に由来の構成単位（Ｃ）を１４質量％以上３０質量％以下含み、
前記構成単位（Ａ）、前記構成単位（Ｂ）及び前記構成単位（Ｃ）の総含有量が８０質量％以上であり、
前記構成単位（Ａ）に対する前記構成単位（Ｃ）の含有比率〔構成単位（Ｃ）の含有量（質量％）／構成単位（Ａ）の含有量（質量％）〕が０．１０以上４．００以下である（メタ）アクリル系ポリマー
を含有する粘着剤組成物。 5% by mass or more of the structural unit (A) derived from (meth) acrylic acid alkyl ester having an alkyl group having 12 or more carbon atoms,
5% by mass to 70% by mass of the structural unit (B) derived from the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms, and
Containing 14 % by mass or more and 30% by mass or less of a structural unit (C) derived from a monomer having a hydroxyl group,
The structural unit (A), Ri der total content of more than 80 wt% of the structural unit (B) and the structural unit (C),
3. Content ratio of the structural unit (C) to the structural unit (A) [content of structural unit (C) (mass%) / content of structural unit (A) (mass%)] is 0.10 or more. A pressure-sensitive adhesive composition containing a (meth) acrylic polymer that is 00 or less .
前記光学部材の少なくとも片面に設けられ、請求項１〜請求項４のいずれか１項に記載の粘着剤組成物が架橋反応して形成された架橋構造を含む粘着剤層と、
を有する光学用積層シート。 A sheet-like optical member;
A pressure-sensitive adhesive layer that is provided on at least one surface of the optical member and includes a crosslinked structure formed by crosslinking reaction of the pressure-sensitive adhesive composition according to any one of claims 1 to 4 .
An optical laminated sheet having
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| KR1020130117474A KR102202879B1 (en) | 2012-10-04 | 2013-10-01 | Adhesive composition, adhesive sheet and laminated sheet for optical applications |
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| JP2012094877A (en) * | 2011-11-22 | 2012-05-17 | National Institute Of Advanced Industrial & Technology | Semiconductor device and heavy hydrogen processing apparatus for semiconductor substrate |
| JP5865064B2 (en) * | 2011-11-22 | 2016-02-17 | ニッタ株式会社 | Optical acrylic adhesive sheet and method for removing optical member using the same |
| JP2013129789A (en) * | 2011-12-22 | 2013-07-04 | Nitto Denko Corp | Adhesive, adhesive layer, and adhesive sheet |
| JP5732436B2 (en) * | 2012-06-11 | 2015-06-10 | 綜研化学株式会社 | Method for producing pressure-sensitive adhesive sheet and method for producing laminate for touch panel |
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| JP2014074122A (en) | 2014-04-24 |
| CN103709969B (en) | 2018-04-13 |
| KR102202879B1 (en) | 2021-01-14 |
| KR20140044269A (en) | 2014-04-14 |
| CN103709969A (en) | 2014-04-09 |
| TWI593766B (en) | 2017-08-01 |
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