JP2007156066A - Optical functional film with adhesive composition layer for liquid crystal display and liquid crystal display including the same - Google Patents
Optical functional film with adhesive composition layer for liquid crystal display and liquid crystal display including the same Download PDFInfo
- Publication number
- JP2007156066A JP2007156066A JP2005350379A JP2005350379A JP2007156066A JP 2007156066 A JP2007156066 A JP 2007156066A JP 2005350379 A JP2005350379 A JP 2005350379A JP 2005350379 A JP2005350379 A JP 2005350379A JP 2007156066 A JP2007156066 A JP 2007156066A
- Authority
- JP
- Japan
- Prior art keywords
- film
- liquid crystal
- adhesive composition
- crystal display
- composition layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 114
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 77
- 239000000853 adhesive Substances 0.000 title claims abstract description 64
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 64
- 230000003287 optical effect Effects 0.000 title claims abstract description 55
- -1 acrylate compound Chemical class 0.000 claims abstract description 52
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003999 initiator Substances 0.000 claims abstract description 21
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 49
- 229960003424 phenylacetic acid Drugs 0.000 claims description 5
- 239000003279 phenylacetic acid Substances 0.000 claims description 5
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 230000035939 shock Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 182
- 239000010410 layer Substances 0.000 description 82
- 239000011521 glass Substances 0.000 description 35
- 238000000034 method Methods 0.000 description 26
- 229920005862 polyol Polymers 0.000 description 20
- 150000003077 polyols Chemical class 0.000 description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 19
- 238000012790 confirmation Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- 125000001931 aliphatic group Chemical group 0.000 description 9
- 238000010030 laminating Methods 0.000 description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000003085 diluting agent Substances 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 229920003232 aliphatic polyester Polymers 0.000 description 5
- 150000008064 anhydrides Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229920001228 polyisocyanate Polymers 0.000 description 5
- 239000005056 polyisocyanate Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- YWEJNVNVJGORIU-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl 2-hydroxy-2-phenylacetate Chemical compound OCCOCCOC(=O)C(O)C1=CC=CC=C1 YWEJNVNVJGORIU-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 description 3
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 206010052128 Glare Diseases 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
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- 125000004386 diacrylate group Chemical group 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000004313 glare Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- 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 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ROHUXHMNZLHBSF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCC(CN=C=O)CC1 ROHUXHMNZLHBSF-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-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
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
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- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
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- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
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- 238000004043 dyeing Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
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- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
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- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- CZMAXQOXGAWNDO-UHFFFAOYSA-N propane-1,1,2-triol Chemical compound CC(O)C(O)O CZMAXQOXGAWNDO-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
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- 230000002393 scratching effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
Description
本発明は粘着組成物層付き液晶ディスプレイ用光学機能フィルム及びそれを含む液晶ディスプレイに関する。 The present invention relates to an optical functional film for a liquid crystal display with an adhesive composition layer and a liquid crystal display including the same.
近年、液晶ディスプレイを搭載する携帯電話、デジタルスチルカメラ、ＰＤＡの軽量化、薄型化へのニーズが高まり、液晶ディスプレイについても軽量化、薄型化のニーズの高まりに従って、基材となるガラス基板についても薄肉化が求められており、従来その厚みが０．７ｍｍであるものを、０．４ｍｍや０．３ｍｍへと薄肉化する研究がなされている。しかし、ガラス基板を薄肉化するにつれ、携帯電話へ液晶ディスプレイを実装したときに外部衝撃により割れてしまう、液晶ディスプレイの組み立て時に工程の中で、ハンドリング時にガラスが割れてしまうといった実用耐久性の面で問題が発生した。 In recent years, there has been a growing need for weight reduction and thinning of mobile phones, digital still cameras, and PDAs equipped with liquid crystal displays. Thinning has been demanded, and studies have been made to reduce the thickness from 0.7 mm to 0.4 mm or 0.3 mm. However, as the glass substrate is made thinner, it breaks due to external impact when the liquid crystal display is mounted on a mobile phone, and the glass is broken during handling during assembly of the liquid crystal display. A problem occurred.
本発明者らは先に、プラズマディスプレイ用として、反射防止膜を有する光学フィルターを粘着剤層を介して貼り付けた構成（特許文献１）を提案しているが、小型化、軽量化の開発がすすむ液晶ディスプレイへ適用すると、ディスプレイ全体の厚みが厚くなってしまうため、薄型である特徴が相殺され好ましくなかった。 The inventors of the present invention have previously proposed a structure (Patent Document 1) in which an optical filter having an antireflection film is pasted via an adhesive layer for use in a plasma display. When applied to a liquid crystal display that is accelerated, the thickness of the entire display increases, which is not preferable because the thin feature is offset.
また、接着剤層と緩衝層を重畳してなる透明な樹脂シートを介して液晶表示パネルと透明保護板を密着配置する構成が提案されている（特許文献２）が、緩衝層へ接着剤層を設けため工程が増えることで、コストアップになり実用上好ましくなかった。 In addition, a configuration in which a liquid crystal display panel and a transparent protective plate are disposed in close contact via a transparent resin sheet in which an adhesive layer and a buffer layer are superimposed has been proposed (Patent Document 2). The increase in the number of processes for providing the cost increases the cost, which is not preferable in practice.
アクリル酸エステル化合物の重合組成物からなる２０℃における動的貯蔵弾性率が１ｘ１０７Ｐａ以下であるガラス割れ防止層と液晶表示用光学フィルムとを積層した構成（特許文献３）が提案されているが、薄型化を特徴とする液晶ディスプレイに対し、ガラス割れ防止層を薄肉化していくと耐衝撃性が不充分であり、光学フィルムを液晶パネル表面のガラス基板に貼り合せる際、貼りつけ位置がずれる、異物を噛みこむ、気泡が混入するなどの欠陥が生じ再剥離すると、粘着力が強すぎるためガラス基材が割れてしまう、粘着材がガラス基材に残ってしまうなどの問題が生じ、液晶ディスプレイ組立工程には適切に用いることはできなかった。 The structure (patent document 3) which laminated | stacked the glass crack prevention layer which consists of a polymerization composition of an acrylic ester compound and whose dynamic storage elastic modulus in 20 degreeC is 1x10 < 7 > Pa or less and the optical film for liquid crystal displays is proposed. However, when the glass crack prevention layer is made thinner, the impact resistance is insufficient for a liquid crystal display that is characterized by its thinness. When the optical film is attached to the glass substrate on the surface of the liquid crystal panel, the attachment position is Defects such as slipping, biting in foreign matter, mixing in bubbles and re-peeling cause problems such as the glass substrate cracking because the adhesive force is too strong, the adhesive material remains on the glass substrate, It could not be used properly in the liquid crystal display assembly process.
すなわち、薄肉化傾向にある液晶ディスプレイを対象とした粘着組成物層付き液晶ディスプレイ用光学機能フィルムとしては、薄型・軽量化を維持しつつ満足な耐衝撃性を保つことが困難であり、尚且つ再剥離性が良好となる適切な粘着力を有するものはなかった。 That is, as an optical functional film for a liquid crystal display with a pressure-sensitive adhesive composition layer for a liquid crystal display that tends to be thin, it is difficult to maintain satisfactory impact resistance while maintaining thinness and weight reduction, and None of them had adequate adhesive strength that would give good removability.
本発明が解決しようとする課題は、上記背景技術の問題点に鑑み、薄肉化する液晶ディスプレイに対し、優れた耐衝撃性能を発現することができ、再剥離性の優れる粘着組成物層付き液晶ディスプレイ用光学機能フィルムを提供することにある。 The problem to be solved by the present invention is a liquid crystal with a pressure-sensitive adhesive composition layer that can exhibit excellent impact resistance performance and has excellent removability with respect to a thinned liquid crystal display in view of the problems of the background art. The object is to provide an optical functional film for display.
本発明者らは、鋭意研究の結果、ウレタン系（メタ）アクリレート化合物と光重合開始剤とを含有する組成物を光重合によって硬化させた硬化物の層を、液晶ディスプレイ用光学機能フィルムから成る基層フィルムに積層することで、液晶ディスプレイに対し優れた耐衝撃性能を発現し、ディスプレイ製造工程において作業性の良好な再剥離性を伴った粘着組成物層付き液晶ディスプレイ用光学機能フィルムが得られることを見出し、本発明を完成した。 As a result of intensive studies, the inventors of the present invention comprise a layer of a cured product obtained by curing a composition containing a urethane-based (meth) acrylate compound and a photopolymerization initiator by photopolymerization, from an optical functional film for liquid crystal displays. By laminating on the base layer film, an optical functional film for a liquid crystal display with a pressure-sensitive adhesive composition layer that exhibits excellent impact resistance performance for liquid crystal displays and has good removability with good workability in the display manufacturing process can be obtained. As a result, the present invention has been completed.
すなわち、本発明は、液晶ディスプレイ用光学機能フィルムから成る基層フィルムの一面に、ウレタン系（メタ）アクリレート化合物と光重合開始剤とを含有する組成物を光重合によって硬化させた粘着組成物から成る、厚みが0.1mm以上の粘着組成物層を有する粘着組成物層付き液晶ディスプレイ用光学機能フィルムを提供する。また、本発明は、液晶ディスプレイの表面に、前記の粘着組成物層付き液晶ディスプレイ用光学機能フィルムを積層した液晶ディスプレイを提供する。 That is, this invention consists of the adhesion composition which hardened | cured the composition containing a urethane type (meth) acrylate compound and a photoinitiator on one surface of the base film which consists of an optical functional film for liquid crystal displays by photopolymerization. An optical functional film for a liquid crystal display with an adhesive composition layer having an adhesive composition layer having a thickness of 0.1 mm or more is provided. Moreover, this invention provides the liquid crystal display which laminated | stacked the said optical function film for liquid crystal displays with an adhesive composition layer on the surface of a liquid crystal display.
本発明により、薄くとも耐衝撃性能にすぐれ、再剥離時にディスプレイに損傷・汚染を与えることなく剥離できる粘着組成物層付き液晶ディスプレイ用光学機能フィルムが提供された。したがって、本発明のフィルムは、特に薄型化の開発の著しい液晶ディスプレイに対し優れた効果を発揮する。 According to the present invention, there is provided an optical functional film for a liquid crystal display with an adhesive composition layer that is excellent in impact resistance even when thin, and can be peeled off without damaging or contaminating the display during re-peeling. Therefore, the film of the present invention exhibits an excellent effect particularly on a liquid crystal display whose development of thinning is remarkable.
上記の通り、本発明の粘着組成物層付き液晶ディスプレイ用光学機能フィルムは、光学機能フィルムから成る基層フィルムの一面に、ウレタン系（メタ）アクリレート化合物と光重合開始剤とを含有する組成物を光重合によって硬化させた粘着組成物層を形成したことを特徴とする。本発明の粘着組成物層付き光学機能フィルム例の断面図を図１に示した。５１が光学機能フィルムから成る基層フィルムであり、５２が粘着組成物層である。 As described above, the optical functional film for a liquid crystal display with a pressure-sensitive adhesive composition layer according to the present invention comprises a composition containing a urethane (meth) acrylate compound and a photopolymerization initiator on one surface of a base film made of an optical functional film. A pressure-sensitive adhesive composition layer cured by photopolymerization is formed. A cross-sectional view of an example of the optical functional film with an adhesive composition layer of the present invention is shown in FIG. 51 is a base film made of an optical functional film, and 52 is an adhesive composition layer.
ここで言う「ウレタン系（メタ）アクリレート化合物」とは、ウレタン結合を介して、ポリオールの脱水素残基セグメントが連結し、１分子中に少なくとも１個の（メタ）アクリル酸残基を有する化合物を意味する。なお、「（メタ）アクリル酸」はアクリル酸又はメタアクリル酸を意味する。 The term “urethane-based (meth) acrylate compound” as used herein refers to a compound in which dehydrogenated residue segments of a polyol are linked via a urethane bond and have at least one (meth) acrylic acid residue in one molecule. Means. “(Meth) acrylic acid” means acrylic acid or methacrylic acid.
本発明に用いられるウレタン系（メタ）アクリレート化合物の好ましい例としては、ポリオキシアルキレンポリオール、脂肪族ポリエステルポリオール、脂肪族ポリカーボネートポリオールから選ばれる少なくとも１種のポリオールの脱水素残基と脂肪族イソシアネートの脱イソシアネート残基からなるウレタン系（メタ）アクリレート化合物を挙げることができ、特に、（１）下記の第１の方法により製造され、下記一般式［I］で表される化合物及び（２）下記の第２の方法により製造され、下記一般式［II］で表される化合物を挙げることができる。 Preferable examples of the urethane (meth) acrylate compound used in the present invention include a dehydrogenation residue of at least one polyol selected from polyoxyalkylene polyol, aliphatic polyester polyol, and aliphatic polycarbonate polyol, and aliphatic isocyanate. Mention may be made of urethane-based (meth) acrylate compounds consisting of deisocyanate residues, in particular (1) compounds produced by the following first method and represented by the following general formula [I] and (2) And the compound represented by the following general formula [II].
すなわち第１の方法は、ポリオキシアルキレンポリオール、脂肪族ポリエステルポリオール、脂肪族ポリカーボネートポリオールから選ばれる少なくとも１種のポリオール、好ましくは１分子当たり２個の水酸基を有するジオールと脂肪族ポリイソシアネート、好ましくは１分子当たり２個のイソシアネート基を有する脂肪族ジイソシアネートを公知のウレタン化反応によって反応させて、イソシアネート基末端のプレポリマーを合成した後、該末端イソシアネート基と水酸基含有アクリル化合物の水酸基とを反応させる２段階のウレタン化反応によって下記一般式［I］のウレタン系（メタ）アクリレートを得る方法である。
ＡＨ−Ｉ−Ｏ−Ｉ−ＡＨ ［I］
（式中、ＡＨは水酸基含有アクリル化合物の水酸基の脱水素残基。Ｉは脂肪族ポリイソシアネート残基。Ｏはポリオールの脱水素残基。）
That is, the first method comprises at least one polyol selected from polyoxyalkylene polyol, aliphatic polyester polyol, and aliphatic polycarbonate polyol, preferably a diol having two hydroxyl groups per molecule and an aliphatic polyisocyanate, preferably An aliphatic diisocyanate having two isocyanate groups per molecule is reacted by a known urethanation reaction to synthesize an isocyanate group-terminated prepolymer, and then the terminal isocyanate group is reacted with a hydroxyl group of a hydroxyl group-containing acrylic compound. In this method, a urethane-based (meth) acrylate represented by the following general formula [I] is obtained by a two-stage urethanization reaction.
AH-I-O-I-AH [I]
(In the formula, AH is a dehydrogenation residue of a hydroxyl group of a hydroxyl group-containing acrylic compound. I is an aliphatic polyisocyanate residue. O is a dehydrogenation residue of a polyol.)
第２の方法は、ポリオキシアルキレンポリオール、脂肪族ポリエステルポリオール、脂肪族ポリカーボネートポリオールから選ばれる少なくとも１種のポリオール、好ましくは１分子当たり２個の水酸基を有するジオールから選ばれる少なくとも１種のポリオールの片末端の水酸基とカルボキシル基含有（メタ）アクリル酸のカルボキシル基とを公知のエステル化反応によって重縮合することによって得た水酸基含有アクリル化合物と脂肪族ポリイソシアネート、好ましくは１分子当たり２個のイソシアネート基を有する脂肪族ジイソシアネートを反応させて下記一般式［II］のウレタン系（メタ）アクリレートを得る方法である。
ＡＣ−Ｏ−Ｉ−Ｏ−ＡＣ ［II］
（式中、ＡＣはカルボキシル基含有（メタ）アクリル酸の脱水酸残基。Ｏはポリオールの脱水素残基。Ｉは脂肪族イソシアネートのイソシアネート残基。）
The second method comprises at least one polyol selected from polyoxyalkylene polyols, aliphatic polyester polyols and aliphatic polycarbonate polyols, preferably at least one polyol selected from diols having two hydroxyl groups per molecule. Hydroxyl group-containing acrylic compound and aliphatic polyisocyanate obtained by polycondensation of one end hydroxyl group and carboxyl group of carboxyl group-containing (meth) acrylic acid by a known esterification reaction, preferably two isocyanates per molecule In this method, an aliphatic diisocyanate having a group is reacted to obtain a urethane (meth) acrylate of the following general formula [II].
AC-O-I-O-AC [II]
(In the formula, AC is a dehydration acid residue of carboxyl group-containing (meth) acrylic acid, O is a dehydrogenation residue of polyol, and I is an isocyanate residue of aliphatic isocyanate.)
本発明で使用するポリオキシアルキレングリコールはポリオキシエチレングリコール、ポリオキシプロピレングリコール、ポリオキシテトラメチレングリコール、ジオール例えば１，４−ブタンジオール、ネオペンチルグリコール、１，６−ヘキサンジオールまたはジオキサングリコールとエチレンオキシドまたはプロピレンオキシドとの反応により得られるポリオキシアルキレングリコール、およびそれらの２種またはそれ以上の混合物を包含する。ポリオキシエチレングリコール、ポリオキシプロピレングリコールおよびポリオキシテトラメチレングリコールが好ましく、その中でも分子量１，０００またはそれ以上のものが衝撃吸収性の点から特に好ましい。 The polyoxyalkylene glycol used in the present invention is polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, diol such as 1,4-butanediol, neopentyl glycol, 1,6-hexanediol or dioxane glycol and ethylene oxide. Or polyoxyalkylene glycols obtained by reaction with propylene oxide, and mixtures of two or more thereof. Polyoxyethylene glycol, polyoxypropylene glycol and polyoxytetramethylene glycol are preferable, and those having a molecular weight of 1,000 or more are particularly preferable from the viewpoint of impact absorption.
本発明で使用する脂肪族ポリエステルポリオールは２価アルコールと化学量論的に不足したジカルボン酸またはそれらの無水物もしくはハロゲン化物との反応生成物を包含する。そのようなポリエステルの製造に適当な２価アルコールはアルキレングリコール、例えばエチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、１，４−ブタンジオール、ネオペンチルグリコール、１，６−ヘキサンジオールおよびジオキサングリコール；オキシアルキレングリコール、例えば上記アルキレングリコールまたは２価フェノールとエチレンオキシドまたはプロピレンオキシドとの反応生成物、ジエチレングリコール、トリエチレングリコール、高級ポリオキシエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、高級ポリオキシプロピレングリコールおよびポリオキシテトラメチレングリコール（ポリテトラヒドロフラン）を包含する。上記ポリエステルの製造に適当なジカルボン酸および無水物は脂肪酸および無水物、例えばコハク酸、無水コハク酸、グルタル酸、グルタル酸無水物、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、マレイン酸、無水マレイン酸およびフマル酸；環状脂肪酸および無水物、例えばテトラヒドロフタル酸、ヘキサヒドロフタル酸およびそれらの無水物を含む。 The aliphatic polyester polyol used in the present invention includes a reaction product of a dihydric alcohol and a stoichiometrically short dicarboxylic acid or an anhydride or halide thereof. Suitable dihydric alcohols for the production of such polyesters are alkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexane. Diols and dioxane glycols; oxyalkylene glycols such as reaction products of the above alkylene glycols or dihydric phenols with ethylene oxide or propylene oxide, diethylene glycol, triethylene glycol, higher polyoxyethylene glycol, dipropylene glycol, tripropylene glycol, higher poly Includes oxypropylene glycol and polyoxytetramethylene glycol (polytetrahydrofuran). Dicarboxylic acids and anhydrides suitable for the preparation of the above polyesters are fatty acids and anhydrides such as succinic acid, succinic anhydride, glutaric acid, glutaric anhydride, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic Acids, maleic anhydride and fumaric acid; cyclic fatty acids and anhydrides such as tetrahydrophthalic acid, hexahydrophthalic acid and their anhydrides.
本発明で使用する脂肪族ポリカーボネート系ポリオールは、ポリオールとジアルキルカーボネート、アルキレンカーボネート、ジアリールカーボネートなどのカーボネート化合物との反応により得られる。脂肪族ポリカーボネートに用いられるポリオールとしては、脂肪族ポリエステルの構成成分として先に例示した２価アルコールを用いることができる。また、ジアルキルカーボネートとしてはジメチルカーボネート、ジエチルカーボネートなどを、アルキレンカーボネートとしてはエチレンカーボネートなどを、ジアリールカーボネートとしてはジフェニルカーボネートなどを挙げることができる。 The aliphatic polycarbonate polyol used in the present invention is obtained by a reaction between a polyol and a carbonate compound such as dialkyl carbonate, alkylene carbonate, or diaryl carbonate. As the polyol used for the aliphatic polycarbonate, the dihydric alcohol exemplified above as a constituent component of the aliphatic polyester can be used. Examples of the dialkyl carbonate include dimethyl carbonate and diethyl carbonate, examples of the alkylene carbonate include ethylene carbonate, and examples of the diaryl carbonate include diphenyl carbonate.
本発明で使用する脂肪族ポリイソシアネートは、環状脂肪族ポリイソシアネートを含み、例えば１，２−プロピレン−、１，３−プロピレン−、１，２−ブチレン−、１，４−ブチレン−、ペンタメチレン−、ヘキサメチレン−、２，４，４−トリメチルヘキサメチレン−、２，２，４−トリメチルヘキサメチレン−およびドデカメチレン−ジイソシアネート、１，３−シクロヘキシレン−および１，４−シクロヘキシレン−ジイソシアネート、メチル−２，４−シクロヘキシレンジイソシアネート、メチル−２，６−シクロヘキシレンジイソシアネート、１，３−ビス（イソシアナトメチル）シクロヘキサン、１，４−ビス（イソシアナトメチル）シクロヘキサン、３−イソシアナトメチル−３，５，５−トリメチルシクロヘキシルイソシアネート（イソホロンジイソシアネート）、および４，４'−メチレンビス（シクロヘキシルイソシアネート）を挙げることができる。上記ジイソシアネートの２種またはそれ以上の混合物が使用され得る。 The aliphatic polyisocyanates used in the present invention include cycloaliphatic polyisocyanates, such as 1,2-propylene-, 1,3-propylene-, 1,2-butylene-, 1,4-butylene-, pentamethylene. -, Hexamethylene-, 2,4,4-trimethylhexamethylene-, 2,2,4-trimethylhexamethylene- and dodecamethylene-diisocyanate, 1,3-cyclohexylene- and 1,4-cyclohexylene-diisocyanate, Methyl-2,4-cyclohexylene diisocyanate, methyl-2,6-cyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, 3-isocyanatomethyl- 3,5,5-trimethylcyclohexyl isocyanate It can be mentioned titanate (isophorone diisocyanate), and 4,4'-methylenebis (cyclohexyl isocyanate). Mixtures of two or more of the above diisocyanates can be used.
本発明でウレタン系（メタ）アクリレートを製造する第１の方法で使用する水酸基含有アクリル化合物は、例えば２−ヒドロキシエチルアクリレート、２−ヒドロキシプロピルアクリレート、３−ヒドロキシプロピルアクリレート、４−ヒドロキシブチルアクリレートおよび相当するメタクリレートである。特に好ましい化合物は２−ヒドロキシエチルアクリレートおよび２−ヒドロキシエチルメタクリレート等である。 Examples of the hydroxyl group-containing acrylic compound used in the first method for producing a urethane-based (meth) acrylate in the present invention include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate and The corresponding methacrylate. Particularly preferred compounds are 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.
ウレタン系（メタ）アクリレートを得るためのイソシアネート末端プレポリマーと水酸基含有アクリル化合物との反応、又は、脂肪族イソシアネート化合物と水酸基含有アルキレンアクリル化合物との反応は慣用の方法、例えば重合阻害剤例えばヒドロキノンの存在下で３０ないし１１０℃に加熱することにより行われ得る。 The reaction between an isocyanate-terminated prepolymer and a hydroxyl group-containing acrylic compound to obtain a urethane-based (meth) acrylate, or the reaction between an aliphatic isocyanate compound and a hydroxyl group-containing alkylene acrylic compound is performed by a conventional method such as a polymerization inhibitor such as hydroquinone. It can be carried out by heating to 30 to 110 ° C. in the presence.
なお、本発明で用いられる、上記したウレタン系（メタ）アクリレート化合物としては、市販品を使用することもできる。該市販品としては、ＵＮ−９２００Ａ（根上工業（株）製）、ＮＫオリゴＵＡ−３３４ＰＺ、ＮＫオリゴＵＡ−３４０Ｐ、ＮＫオリゴＵＡ−１６０ＴＭ、ＮＫオリゴＵＡ−１７０ＴＸ（新中村化学工業（株）製）等が挙げられる。 In addition, a commercial item can also be used as an above-mentioned urethane type (meth) acrylate compound used by this invention. As this commercial item, UN-9200A (manufactured by Negami Kogyo Co., Ltd.), NK oligo UA-334PZ, NK oligo UA-340P, NK oligo UA-160TM, NK oligo UA-170TX (manufactured by Shin-Nakamura Chemical Co., Ltd.) ) And the like.
本発明で使用する光反応開始剤は、アクリル物質の光重合のためのあらゆる公知開始剤であってよいが、硬化物の着色の点から、好ましくは、開裂型開始剤としてα置換アセトフェノン、水素引き抜き型開始剤としてチオキサントン、ベンゾフェノン、特に好ましい開始剤としては、分子内水素引き抜き型開始剤であり、該市販品としては、オキシ−フェニル−アセチックアシッド２−［２−オキソ−２−フェニル−アセトキシ−エトキシ］−エチルエステルとオキシ−フェニル−アセチックアシッド２−［２−ヒドロキシ−エトキシ］−エチルエステルの混合物であるＩＲＵＧＡＣＵＲＥ７５４（チバ・スペシャリティケミカルズ（株）製）等が挙げられる。上記開始剤は２種もしくはそれ以上の混合物であってもよい。また、上記開始剤の少なくとも１種を主開始剤として、４００ｎｍ以上の長波長領域に吸収を有する開始剤、例えばビスアシルフォスフィンオキサイド、モノアシルフォスフィンオキサイド等の光重合開始剤を併用すると、厚みを０．３ｍｍ以上とする場合の内部硬化性を向上させることができる。内部硬化性が不十分な場合、未反応成分が時間の経過とともに粘着材の表面に移行してベタつく場合がある。上記開始剤の添加量は、通常の量で、一般的には粘着材の全ウレタン系（メタ）アクリレート化合物含量の０．１〜２０重量％、好ましくは１〜１０重量％で使用され得る。上記４００ｎｍ以上の長波長領域に吸収を有する開始剤を併用する場合は、通常、開始剤総量の０．１〜５０重量％の範囲で使用され得る。 The photoinitiator used in the present invention may be any known initiator for the photopolymerization of an acrylic substance, but from the viewpoint of coloring of the cured product, preferably an α-substituted acetophenone, hydrogen as a cleavage type initiator. Thioxanthone and benzophenone as the pull-out type initiator, particularly preferable as the pull-in type initiator are intramolecular hydrogen pull-out type initiators, and as the commercial product, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl- IRUGACURE754 (manufactured by Ciba Specialty Chemicals Co., Ltd.), which is a mixture of acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester. The initiator may be a mixture of two or more. Further, when at least one of the above initiators is used as a main initiator, an initiator having absorption in a long wavelength region of 400 nm or longer, for example, a photopolymerization initiator such as bisacylphosphine oxide, monoacylphosphine oxide, The internal curability when the thickness is 0.3 mm or more can be improved. If the internal curability is insufficient, unreacted components may move to the surface of the adhesive material over time and become sticky. The addition amount of the initiator is a normal amount, generally 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the total urethane-based (meth) acrylate compound content of the adhesive. When using together the initiator which has absorption in the said 400 nm or more long wavelength area | region, it may be normally used in the range of 0.1 to 50 weight% of the initiator total amount.
粘着組成物層の粘着力調整、弾性率調整を目的として、透明性を阻害しない範囲で反応性希釈剤を添加しうる。該希釈剤としては、一般に粘度が１，０００ｍＰａ・ｓ／２５℃以下である低分子量モノ（メタ）アクリレート又はジ（メタ）アクリレート化合物が使用できる。該希釈剤として具体的には、アルキル（メタ）アクリレート；例えば、ｎ−ブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ポリオキシアルキレンモノ（メタ）アクリレート、ポリオキシアルキレンジ（メタ）アクリレート、アルカンジオールジ（メタ）アクリレート；例えば１，４−ブタンジオールジアクリレート、１，６−ヘキサンジオールジアクリレート、２，２’−ブチルエチルプロパンジオールジアクリレート等である。これらの反応性希釈物の添加量は、特に限定されないが、通常、ウレタン系（メタ）アクリレート化合物の含量の１〜１００重量％、好ましくは１０〜５０重量％である。 For the purpose of adjusting the adhesive strength of the adhesive composition layer and adjusting the elastic modulus, a reactive diluent can be added within a range that does not impair the transparency. As the diluent, a low molecular weight mono (meth) acrylate or di (meth) acrylate compound generally having a viscosity of 1,000 mPa · s / 25 ° C. or less can be used. Specific examples of the diluent include alkyl (meth) acrylates; for example, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, polyoxyalkylene mono (meth) acrylate, polyoxyalkylene di (meth) acrylate, and alkane. Diol di (meth) acrylate; for example, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 2,2′-butylethylpropanediol diacrylate, and the like. Although the addition amount of these reactive dilutions is not specifically limited, Usually, it is 1 to 100 weight% of the content of a urethane type (meth) acrylate compound, Preferably it is 10 to 50 weight%.
粘着組成物層の粘着力としては、プラスチックやガラスと貼り合わせる際に実用に耐えるものであれば良く、特に限定されないが、高温状態（３５〜１００℃）の使用によって貼り合わせ部分に気泡が発生しないものを用いることが望ましい。また、９０℃剥離粘着力として０．０５Ｎ／２５ｍｍ幅以上、１０Ｎ／２５ｍｍ幅以下、好ましくは０．１Ｎ／２５ｍｍ幅以上、５Ｎ／２５ｍｍ幅以下とすることで、被着対象であるプラスチックやガラスを変形させることなく、容易に剥がした後に繰り返し使用することができ、ディスプレイ表面への粘着組成物残りも防止することができる。粘着力の試験方法は以下の通りで行なうことができる。 The pressure-sensitive adhesive strength of the pressure-sensitive adhesive composition layer is not particularly limited as long as it can withstand practical use when bonded to plastic or glass, but bubbles are generated in the bonded portion by use of a high temperature state (35 to 100 ° C.). It is desirable to use those that do not. Further, the 90 ° C. peel adhesive strength is 0.05 N / 25 mm width or more and 10 N / 25 mm width or less, preferably 0.1 N / 25 mm width or more and 5 N / 25 mm width or less, so that the plastic or glass to be deposited Without being deformed, it can be used repeatedly after being easily peeled off, and the adhesive composition remaining on the display surface can be prevented. The test method of adhesive strength can be performed as follows.
基層フィルムに粘着組成物層の順で積層したフィルターを２５ｍｍ幅に切断し、顕微鏡用スライドガラス（７６mm（長さ）×２６mm（幅）×１．０mm（厚さ））に、粘着組成物層面を貼り合わせる。次に、２３℃環境下、引張試験機；オートグラフＡＧＳ５００Ａ（島津製作所製）を用いて、フィルターの端部をガラスに対して９０°方向へ、５０ｍｍ／分の速度で引っ張り粘着力を測定する。また、試験後にガラス面を観察し、引き剥がし後の粘着組成物残りの有無を目視により確認する。 The filter laminated on the base film in the order of the adhesive composition layer is cut to a width of 25 mm, and the adhesive composition layer surface is placed on a microscope slide glass (76 mm (length) × 26 mm (width) × 1.0 mm (thickness)). Paste together. Next, using a tensile tester; Autograph AGS500A (manufactured by Shimadzu Corporation) in an environment of 23 ° C., the tensile strength of the filter is measured at a speed of 50 mm / min in the 90 ° direction with respect to the glass. . Moreover, the glass surface is observed after a test, and the presence or absence of the adhesive composition remainder after peeling is confirmed visually.
粘着組成物層の弾性率は、１０５Ｐａ以上１０９Ｐａ以下であることが好ましい。粘着組成物層の弾性率が、１０９Ｐａを超えると、外部衝撃を受けた時に衝撃力が分散されず、直接ガラスに伝わりガラスが割れてしまう。一方で、粘着組成物層の弾性率が１０５Ｐａ以下である時は、外部衝撃を受けると形状を保持しきれず、衝撃力が貫通しガラスを破損し、所望の耐衝撃性が得られないばかりでなく、柔らかすぎて貼り合わせ時のハンドリングが困難、切断時にカッターの刃に巻きつく、貼合後の積層体の形状保持が難しい等の問題が生じる。さらに言えば耐衝撃性の点で弾性率が、１０５Ｐａ以上１０７Ｐａ以下であることがより好ましい。 The elastic modulus of the adhesive composition layer is preferably 10 5 Pa or more and 10 9 Pa or less. When the elastic modulus of the pressure-sensitive adhesive composition layer exceeds 10 9 Pa, the impact force is not dispersed when subjected to an external impact, and is directly transmitted to the glass and the glass is broken. On the other hand, when the elastic modulus of the pressure-sensitive adhesive composition layer is 10 5 Pa or less, the shape cannot be maintained when subjected to external impact, the impact force penetrates and breaks the glass, and the desired impact resistance cannot be obtained. In addition, the problem is that it is too soft and difficult to handle at the time of bonding, winds around the cutter blade at the time of cutting, and it is difficult to maintain the shape of the laminated body after bonding. Furthermore, the elastic modulus is more preferably from 10 5 Pa to 10 7 Pa in terms of impact resistance.
本発明において、基層フィルム上に粘着組成物層を積層する方法に特に制限はなく、基層フィルム上に直接ウレタン系（メタ）アクリレート化合物を塗工し光重合させる方法、先に離形フィルム上にウレタン系（メタ）アクリレート化合物を塗工し光重合させシート状の粘着組成物層を作成し、基層フィルムと貼り合わせる方法のいずれも採用することができる。貼合の際、積層時の気泡の混入を防ぐため、加熱および／または減圧環境で積層する方法が好ましく用いられ、さらに、積層後に気泡を拡散させるため加熱および／または加圧環境で処理することも好ましく用いられる。 In this invention, there is no restriction | limiting in particular in the method of laminating | stacking an adhesion composition layer on a base layer film, The method of apply | coating a urethane type (meth) acrylate compound directly on a base layer film, and carrying out photopolymerization, First on a release film Any method can be employed in which a urethane-based (meth) acrylate compound is applied and photopolymerized to form a sheet-like pressure-sensitive adhesive composition layer and bonded to the base film. In order to prevent air bubbles from being mixed during lamination during lamination, a method of laminating in a heated and / or reduced pressure environment is preferably used, and further, processing is performed in a heated and / or pressurized environment to diffuse the bubbles after lamination. Are also preferably used.
本発明における粘着組成物層の厚みは、耐衝撃性の点から、０．１ｍｍ以上の厚さを有する。これより小さいと耐衝撃効果が低いばかりではなく、貼りつけ作業時の取り扱いが困難になり、気泡が入りやすくなる。また、厚みの上限としては特に制限はないが、薄型ディスプレイの特徴を活かすという点で、２．０ｍｍ以下とすることが好ましい。粘着組成物層の厚みは、基層フィルムと粘着組成物層を積層した時のディスプレイの厚みと耐衝撃効果の点から、０．１〜１．０ｍｍの範囲とすることがより好ましい。 The thickness of the pressure-sensitive adhesive composition layer in the present invention has a thickness of 0.1 mm or more from the viewpoint of impact resistance. If it is smaller than this, not only the impact resistance effect is low, but also the handling at the time of sticking work becomes difficult, and bubbles tend to enter. Moreover, there is no restriction | limiting in particular as an upper limit of thickness, However, It is preferable to set it as 2.0 mm or less at the point of utilizing the characteristic of a thin display. The thickness of the pressure-sensitive adhesive composition layer is more preferably in the range of 0.1 to 1.0 mm from the viewpoint of the thickness of the display and the impact resistance effect when the base film and the pressure-sensitive adhesive composition layer are laminated.
本発明における基層フィルムは、液晶ディスプレイ用光学機能フィルムから成る。該基層フィルムは用途に応じ、例えば偏光フィルム、位相差フィルム、輝度向上フィルム、視野角拡大フィルム、反射防止フィルム、反射フィルム、半透過反射フィルム、光拡散フィルム等の光学機能フィルムのうち、１種類のフィルムまたは複数のフィルムを積層したものを使用しても良い。これらのフィルムの製造方法に制限は無く、公知のいずれの方法で作られても良い。中でも、基層フィルムとして、液晶ディスプレイの構成の簡略化・薄型化の点から、偏光フィルムであることが好ましく、さらに、画面のコントラストアップ、鮮明化の目的から偏光フィルムと位相差フィルム、輝度向上フィルムのいずれかまたは両方のフィルムの積層体も好ましく用いられる。すなわち、(1)偏光フィルム、(2)偏光フィルムと位相差フィルムの積層体、(3)偏光フィルムと輝度向上フィルムの積層体又は(4) 偏光フィルムと位相差フィルムと輝度向上フィルムの積層体も好ましく用いられる。基層フィルムとして積層体を用いる場合、各光学機能フィルムの積層の順番は任意に設定可能である。 The base layer film in this invention consists of an optical functional film for liquid crystal displays. The base layer film is one type of optical functional film such as a polarizing film, a retardation film, a brightness enhancement film, a viewing angle widening film, an antireflection film, a reflective film, a transflective film, and a light diffusion film, depending on the application. A film or a laminate of a plurality of films may be used. There is no restriction | limiting in the manufacturing method of these films, You may make by any well-known method. Among these, as the base film, a polarizing film is preferable from the viewpoint of simplification and thinning of the configuration of the liquid crystal display, and further, a polarizing film, a retardation film, and a brightness enhancement film for the purpose of increasing the contrast of the screen and sharpening. A laminate of either or both of these films is also preferably used. That is, (1) polarizing film, (2) laminate of polarizing film and retardation film, (3) laminate of polarizing film and brightness enhancement film, or (4) laminate of polarization film, retardation film and brightness enhancement film Are also preferably used. When using a laminated body as a base layer film, the order of lamination | stacking of each optical function film can be set arbitrarily.
偏光フィルムとしては、公知のいずれのものでもよく、ＰＶＡ系樹脂にヨウ素系、有機染料系を染色し配向させた偏光素子層の片面または両面に、機械的強度・耐熱性・耐湿性を付与するための保護層としてトリアセチルセルロースなどのセルロース系樹脂、シクロ系もしくはノボルネン構造のポリオレフィン、エチレン−プロピレン共重合体などのポリオレフィン系樹脂、ポリエチレンテレフタレートフィルムなどのポリエステル系樹脂などの光学的に等方なフィルムを積層したものが好ましく用いられる。 The polarizing film may be any known film, and imparts mechanical strength, heat resistance, and moisture resistance to one or both sides of a polarizing element layer obtained by dyeing and aligning an iodine-based or organic dye-based PVA resin. As a protective layer, optically isotropic such as cellulose resin such as triacetyl cellulose, polyolefin of cyclo or nobornene structure, polyolefin resin such as ethylene-propylene copolymer, polyester resin such as polyethylene terephthalate film, etc. What laminated | stacked the film is used preferably.
本発明で用いられ得る偏光フィルムには、目的に応じて、反射防止膜、ハードコート膜、反射膜、半透過反射膜等のうちの１種類または１種類以上の膜を設けてもよい。外光反射を抑制し表示画像の視認性を向上させるためには、偏光フィルム上に反射防止膜を設けることが好ましい。反射防止膜の形成方法・材料に特に制限はなく、偏光フィルムの片面に直接形成する方法、反射防止膜を形成したフィルムに粘着層を積層して偏光フィルムの片面に積層する方法といずれでもよい。反射防止膜は、通常、低屈折率と高屈折率のからなる２層以上の積層膜を用いるのが好ましいが、表面を乱反射させることによって眩しさを抑えるグレア処理であってもよい。これらは、液晶ディスプレイとしたときの使用環境、ディスプレイ性能により選択できるが、高コントラストを求めるには前者を用いることが好ましい。反射防止膜の形成は、公知のウエットコート法、ドライコート法といずれでもよいが、製造コストの点で、ウエットコート法で形成することが好ましい。また、表面の傷つき難さを向上するため偏光フィルムの片面もしくは両面にハードコート膜を形成することが好ましい。ハードコート膜としては、熱硬化型のオルガノポリシロキサン系のハードコートまたは、紫外線硬化型のアクリル系ハードコートなどを好ましく用いることができる。表面の耐擦傷性をさらに向上させるため、無機微粒子を含んだハードコート剤も好ましく用いられる。 Depending on the purpose, the polarizing film that can be used in the present invention may be provided with one kind or more kinds of films among an antireflection film, a hard coat film, a reflection film, a semi-transmissive reflection film, and the like. In order to suppress external light reflection and improve the visibility of the display image, it is preferable to provide an antireflection film on the polarizing film. There are no particular restrictions on the method and material for forming the antireflection film, and any of the method of forming directly on one side of the polarizing film or the method of laminating an adhesive layer on the film on which the antireflection film is formed and laminating on one side of the polarizing film may be used. . Usually, the antireflection film is preferably a laminated film of two or more layers having a low refractive index and a high refractive index, but may be a glare treatment for suppressing glare by irregularly reflecting the surface. These can be selected depending on the use environment and display performance when a liquid crystal display is used, but the former is preferably used to obtain high contrast. The antireflection film may be formed by either a known wet coating method or a dry coating method, but is preferably formed by a wet coating method from the viewpoint of manufacturing cost. Moreover, it is preferable to form a hard coat film on one side or both sides of the polarizing film in order to improve the difficulty of scratching the surface. As the hard coat film, a thermosetting organopolysiloxane hard coat or an ultraviolet curable acrylic hard coat can be preferably used. In order to further improve the scratch resistance of the surface, a hard coat agent containing inorganic fine particles is also preferably used.
本発明の粘着組成物層付き液晶ディスプレイ用光学機能フィルムを、入射光を反射させて表示する反射型液晶ディスプレイに用いる場合、基層フィルムとしては、外光を反射させるため反射膜を偏光フィルム上に形成したものを用いることができる。反射膜は偏光フィルムの片面に設けられ、例えば、金属酸化物または金属膜を１層または複数層積層する方法等、公知技術により反射膜を設けることができる。別のフィルムに反射膜を設けた反射シートを、粘着材を介して貼りつける方法も好ましく用いられる。また、半透過反射液晶ディスプレイ用途には、偏光フィルム上に半透過反射膜を形成することができる。半透過反射膜は、公知のいずれの方法で形成してもよく、例えば、金属または金属酸化物を１層または複数層積層する方法、半透過反射層を設けたフィルムを、粘着材を介して貼りつける方法と、いずれの方法で形成しても良い。 When the optical functional film for a liquid crystal display with the pressure-sensitive adhesive composition layer of the present invention is used in a reflective liquid crystal display that reflects incident light for display, the base film is a reflective film on the polarizing film for reflecting external light. What was formed can be used. The reflective film is provided on one surface of the polarizing film. For example, the reflective film can be provided by a known technique such as a method of laminating one or more metal oxides or metal films. A method of attaching a reflection sheet provided with a reflection film on another film via an adhesive is also preferably used. For transflective liquid crystal display applications, a transflective film can be formed on a polarizing film. The transflective film may be formed by any known method, for example, a method of laminating one or more layers of metal or metal oxide, or a film provided with a transflective layer via an adhesive. You may form by either the method of sticking and any method.
例えば、本発明における基層フィルムは、偏光フィルムに位相差フィルムを積層することで、楕円偏光フィルムまたは円偏光フィルムとすることができる。これら楕円偏光フィルムまたは円偏光フィルムを使用することで、複屈折により発生する楕円偏光が漏れることによるコントラストが低下を防止することができ、ＳＴＮ型液晶ディスプレイに対して好ましく用いることができる。また、円偏光フィルムは、画像の色調調整の目的でカラー表示の反射型液晶ディスプレイに好ましく用いられる。位相差フィルムとしては、公知の材料いずれでも良く、例えば、公知の高分子素材を１軸または２軸延伸処理した複屈折性フィルム、液晶ポリマーの配向フィルム、液晶ポリマーの配向層をフィルムで支持したものなどが用いられる。位相差フィルムの厚さについても特に限定はないが、２〜１５０μｍが好ましく用いられる。位相差フィルムは、波長板や液晶層の複屈折による着色の視覚などの補償を目的としており、これら使用目的に応じた適宜な位相差を有するものであればよく、２種以上の位相差板を積層してもよい。また、液晶パネルに対して２枚の偏光フィルムが設けられることがあるが、この場合は、両偏光フィルムとの間の任意位置に上記位相差フィルムを１枚または複数枚設けることができる。 For example, the base layer film in the present invention can be formed into an elliptically polarizing film or a circularly polarizing film by laminating a retardation film on the polarizing film. By using these elliptically polarizing films or circularly polarizing films, a decrease in contrast due to leakage of elliptically polarized light generated by birefringence can be prevented, and it can be preferably used for an STN type liquid crystal display. The circularly polarizing film is preferably used in a reflective liquid crystal display for color display for the purpose of adjusting the color tone of an image. The retardation film may be any known material. For example, a birefringent film obtained by uniaxially or biaxially stretching a known polymer material, a liquid crystal polymer alignment film, and a liquid crystal polymer alignment layer are supported by the film. Things are used. Although there is no limitation in particular also about the thickness of retardation film, 2-150 micrometers is used preferably. The retardation film is used for the purpose of compensating for vision of coloring due to birefringence of a wave plate or a liquid crystal layer, and may have an appropriate retardation according to the intended use. May be laminated. Moreover, although two polarizing films may be provided with respect to a liquid crystal panel, in this case, the said retardation film can be provided in the arbitrary positions between both polarizing films.
さらに、表示画像の輝度を向上させ、画像の鮮明化、省電力化するために偏光フィルム上に輝度向上フィルムを積層することができる。輝度向上フィルムとしては、とくに限定はなく、誘電体の多層薄膜や屈折率異方性が相違する薄膜フィルムの多層積層体のような所定偏光軸の直線偏光を透過して他の光は反射する特性を示すもの、コレスティック液晶ポリマーの配向フィルムやその配向液晶層をフィルム基材上に支持したもの、左回りまたは右回りのいずれか一方の円偏光を反射して他の光は透過する特性を示すものなど、目的に応じたものを使用することができる。偏光軸の直線偏光を透過するタイプの輝度向上フィルムでは、その透過光をそのまま偏光板に偏光軸を揃えて入射させることにより偏光板による吸収ロスを抑制しつつ効率良く透過させることができる。 Furthermore, a brightness enhancement film can be laminated on the polarizing film in order to improve the brightness of the display image and to clarify the image and save power. The brightness enhancement film is not particularly limited, and transmits linearly polarized light having a predetermined polarization axis and reflects other light, such as a dielectric multilayer thin film or a multilayer laminate of thin film films having different refractive index anisotropy. Characteristic, cholestic liquid crystal polymer alignment film and its alignment liquid crystal layer supported on a film substrate, reflection of either left-handed or right-handed circularly polarized light and other light transmission Anything that suits the purpose can be used. In a brightness enhancement film of a type that transmits linearly polarized light having a polarization axis, the transmitted light can be efficiently transmitted while suppressing absorption loss due to the polarizing plate by making the transmitted light enter the polarizing plate with the polarization axis aligned.
偏光フィルムに位相差フィルム及び輝度向上フィルムを積層する場合、適当な粘着材（接着剤）が用いられる。その材質や組成、厚さなどはとくに限定されないが、透明性や耐久性などの観点より、アクリル系粘着材が好ましく用いられ得る。あるいは、本発明における粘着組成物を使用してもよく、その場合には耐衝撃性をさらに付与することが期待できる。 When laminating a retardation film and a brightness enhancement film on a polarizing film, an appropriate pressure-sensitive adhesive material (adhesive) is used. The material, composition, thickness and the like are not particularly limited, but an acrylic pressure-sensitive adhesive material can be preferably used from the viewpoints of transparency and durability. Alternatively, the pressure-sensitive adhesive composition of the present invention may be used, and in that case, it can be expected to further impart impact resistance.
本発明の粘着組成物層付き液晶ディスプレイ用光学機能フィルムは、液晶ディスプレイに好適に使用できる。すなわち、液晶ディスプレイの表面に、本発明の粘着組成物層付き液晶ディスプレイ用光学機能フィルムを積層して用いることができる。また、本発明の液晶ディスプレイは耐衝撃性に優れており、携帯型電子端末に好ましく用いることができる。 The optical functional film for a liquid crystal display with an adhesive composition layer of the present invention can be suitably used for a liquid crystal display. That is, the optical functional film for liquid crystal displays with the pressure-sensitive adhesive composition layer of the present invention can be laminated on the surface of the liquid crystal display. The liquid crystal display of the present invention is excellent in impact resistance and can be preferably used for a portable electronic terminal.
以下実施例を用いて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES The present invention will be specifically described below using examples, but the present invention is not limited to these examples.
耐衝撃性の測定
本発明における耐衝撃性は次のように評価した（図２）。ゴムラバー１上にガラス２（１．１ｍｍ厚）を置き、その上にアクリルフォームテープ３（３Ｍ製、Ｊ−４９０５Ｊ、厚み0.5mm）で５ｍｍ巾、３ｃｍｘ４ｃｍの枠を作成した。粘着組成物付き光学機能フィルム５をゴムロールにて破損確認用ガラス４（０．７ｍｍ厚）に貼りあわせ、枠付きのガラス上に置いた。鋼球を任意の高さから光学機能フィルム上面に自由落下させ、耐衝撃試験用サンプルを貼合せた破損確認用ガラス４の破損状態を目視で確認した。すなわち、偏光フィルムの表面より２０ｃｍの高さから、質量３２．５ｇの鋼球を落下させ、破損確認用ガラス４の損傷の有無を調べた。破損確認用ガラス４に割れ、ヒビが生じたものを×、ヒビ、割れが観察されないものを○とし、さらに１５０ｃｍの高さから、鋼球を落下させ、破損確認用ガラス４にヒビ、割れが観察されないものを◎とした。
Measurement of impact resistance The impact resistance in the present invention was evaluated as follows (FIG. 2). A glass 2 (1.1 mm thickness) was placed on the
弾性率の測定
粘着組成物層を、幅が１５ｍｍ、長さ４０ｍｍの短冊状に切り抜き、弾性率測定用サンプルとした。長手方向の端から５ｍｍのところを、両端ともクリップで固定し、測定サンプルの長さＬを３０ｍｍとした。測定温度は室温、湿度は６５％±５％とした。クリップの一端を固定し、もう一方に、０．０５Ｋｇの荷重Ｍをかけ、試験片の伸び量ΔＬ（ｍ）を測定した。
Measurement of Elastic Modulus The adhesive composition layer was cut into a strip shape having a width of 15 mm and a length of 40 mm to obtain a sample for measuring elastic modulus. A
弾性率は、粘着組成物にＭ（ｋｇ）の荷重を掛けたときの、弾性率測定用サンプルの幅Ｓ（ｍ）、厚みＴ（ｍ）、測定サンプルの長さＬ（ｍ）、伸び量ΔＬ（ｍ）を用いて、次の式に従って求めた。
弾性率 ＝ （Ｍ／（Ｓ×Ｔ））／（ΔＬ／Ｌ） [Ｐａ]
The elastic modulus is the width S (m), the thickness T (m), the length L (m) of the measurement sample, and the elongation when the load of M (kg) is applied to the adhesive composition. It calculated | required according to the following formula | equation using (DELTA) L (m).
Elastic modulus = (M / (S × T)) / (ΔL / L) [Pa]
実施例１
（１） ウレタン系（メタ）アクリレート化合物として、ＮＫオリゴＵＡ−３３４ＰＺ（新中村化学（株）製、第１の方法により製造されジオール成分としてポリオキシプロピレングリコールを使用、分子量約１００００）を９０重量部、希釈剤として、ポリエチレングリコールジアクリレート（オキシエチレン繰り返し単位数９、分子量５０８、商品名「ＮＫエステルＡ−４００」、新中村化学（株）製）を１０重量部、光重合開始剤として、オキシ−フェニル−アセチックアシッド２−［２−オキソ−２−フェニル−アセトキシ−エトキシ］−エチルエステルとオキシ−フェニル−アセチックアシッド２−［２−ヒドロキシ−エトキシ］−エチルエステルの混合物（商品名ＩＲＵＧＡＣＵＲＥ７５４、チバ・スペシャリティケミカルズ（株）製）を１重量部混合した紫外線硬化性組成物を厚さ１００μｍのポリエステル系セパレータに塗布し、窒素雰囲気下、紫外線ランプにて１，０００ｍｊ／ｃｍ２の紫外線を照射して、光重合させ、厚さ０．４ｍｍの粘着組成物から成るフィルムを作製した。
Example 1
(1) 90 weights of NK oligo UA-334PZ (manufactured by Shin-Nakamura Chemical Co., Ltd., using polyoxypropylene glycol as a diol component, molecular weight of about 10,000) as a urethane-based (meth) acrylate compound Parts as a diluent, polyethylene glycol diacrylate (oxyethylene repeating unit number 9, molecular weight 508, trade name “NK Ester A-400”, manufactured by Shin-Nakamura Chemical Co., Ltd.) 10 parts by weight, as a photopolymerization initiator, Mixture of oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester (trade name) IRUGACURE 754, Ciba Specialty Chemicals Co., Ltd. )) Is mixed on a polyester separator having a thickness of 100 μm, and photopolymerization is performed by irradiating 1,000 mj / cm 2 of ultraviolet rays with an ultraviolet lamp in a nitrogen atmosphere. A film made of an adhesive composition having a thickness of 0.4 mm was prepared.
（２） 上記（１）で得た粘着組成物フィルムを偏光フィルム（住友化学製、ハイルミナンスＳＲ、４ｃｍｘ５ｃｍ）の片面にゴムロールを用いて貼り付け、粘着組成物層付き液晶ディスプレイ用光学機能フィルムとした。 (2) The adhesive composition film obtained in (1) above is attached to one side of a polarizing film (Sumitomo Chemical Co., Ltd., high luminance SR, 4 cm × 5 cm) using a rubber roll, and an optical functional film for liquid crystal displays with an adhesive composition layer did.
（３） 上記（２）の粘着組成物層付き液晶ディスプレイ用光学機能フィルムを、粘着組成物層を介して破損確認用ガラス（日本電気ガラス製、ＯＡ−１０、５ｃｍｘ５ｃｍ、０．７ｍｍ厚）にゴムロールで貼り合わせ、耐衝撃試験に供した。 (3) The optical functional film for a liquid crystal display with the pressure-sensitive adhesive composition layer of (2) above is applied to a glass for damage confirmation (made by Nippon Electric Glass, OA-10, 5 cm × 5 cm, 0.7 mm thickness) via the pressure-sensitive adhesive composition layer. Bonding with a rubber roll, it was subjected to an impact resistance test.
実施例２
（１） 偏光フィルム（住友化学製、ハイルミナンスＳＲ、４ｃｍｘ５ｃｍ）の一面に反射防止フィルム（東レフィルム加工（株）、ルミクリヤＳＦ、0.1ｍｍ）を２５μｍのアクリル系粘着材（綜研化学、ＳＫダイン）を介して積層し、さらに位相差フィルム（鐘淵化学工業、０．０５ｍｍ、ポリカーボネイトフィルム）を、反射防止フィルムとは反対の面に、２５μｍとした該粘着材を介し積層し、基層フィルムとした。
Example 2
(1) A polarizing film (Sumitomo Chemical Co., Ltd., high luminance SR, 4 cm x 5 cm) with an anti-reflection film (Toray Film Processing Co., Ltd., Lumicria SF, 0.1 mm) and a 25 μm acrylic adhesive (Soken Chemicals, SK Dyne) Further, a retardation film (Kanebuchi Chemical Industry, 0.05 mm, polycarbonate film) was laminated on the surface opposite to the antireflection film via the adhesive material having a thickness of 25 μm to obtain a base layer film. .
（２） 実施例１で得た粘着組成物フィルムを上記（１）で得た基層フィルムの位相差フィルム側にゴムロールを用いて貼り付け、粘着組成物層付き液晶ディスプレイ用光学機能フィルムとした。 (2) The pressure-sensitive adhesive composition film obtained in Example 1 was attached to the retardation film side of the base film obtained in (1) above using a rubber roll to obtain an optical functional film for a liquid crystal display with a pressure-sensitive adhesive composition layer.
（３） 上記（２）の粘着組成物層付き液晶ディスプレイ用光学機能フィルムを、粘着組成物層を介して破損確認用ガラス（日本電気ガラス製、ＯＡ−１０、５ｃｍｘ５ｃｍ、０．７ｍｍ厚）にゴムロールで貼り合わせ、耐衝撃試験に供した。 (3) The optical functional film for a liquid crystal display with the pressure-sensitive adhesive composition layer of (2) above is applied to a glass for damage confirmation (made by Nippon Electric Glass, OA-10, 5 cm × 5 cm, 0.7 mm thickness) via the pressure-sensitive adhesive composition layer. Bonding with a rubber roll, it was subjected to an impact resistance test.
実施例３
（１） ウレタン系（メタ）アクリレート化合物として、ＮＫオリゴＵＡ−３３４ＰＺを８０重量部、希釈剤として、ポリエチレングリコールジアクリレートを２０重量部とした以外は実施例１と同様にして厚さ０．２ｍｍの粘着組成物から成るフィルムを得た。
Example 3
(1) A thickness of 0.2 mm as in Example 1 except that 80 parts by weight of NK oligo UA-334PZ as a urethane-based (meth) acrylate compound and 20 parts by weight of polyethylene glycol diacrylate as a diluent. The film which consists of adhesive composition of this was obtained.
（２） 上記（１）で得た粘着組成物フィルムを実施例１で使用した偏光フィルムの片面にゴムロールを用いて貼り付け、粘着組成物層付き液晶ディスプレイ用光学機能フィルムとした。 (2) The pressure-sensitive adhesive composition film obtained in the above (1) was attached to one side of the polarizing film used in Example 1 using a rubber roll to obtain an optical functional film for a liquid crystal display with a pressure-sensitive adhesive composition layer.
（３） 上記（２）の粘着組成物層付き液晶ディスプレイ用光学機能フィルムを、粘着組成物層を介して破損確認用ガラス（日本電気ガラス製、ＯＡ−１０、５ｃｍｘ５ｃｍ、０．７ｍｍ厚）にゴムロールで貼り合わせ、耐衝撃試験に供した。 (3) The optical functional film for a liquid crystal display with the pressure-sensitive adhesive composition layer of (2) above is applied to a glass for damage confirmation (made by Nippon Electric Glass, OA-10, 5 cm × 5 cm, 0.7 mm thickness) via the pressure-sensitive adhesive composition layer. Bonding with a rubber roll, it was subjected to an impact resistance test.
実施例４
（１） ウレタン系（メタ）アクリレート化合物として、ＮＫオリゴＵＡ−３４０Ｐ（新中村化学（株）製、第１の方法により製造され、ジオール成分としてポリオキシプロピレングリコールを使用、分子量約１３０００）を９５重量部、希釈剤として、２−ヒドロキシエチルメタアクリレートを５重量部、光重合開始剤として、実施例１で用いたＩＲＵＧＡＣＵＲＥ７５４（チバ・スペシャリティケミカルズ（株）製）を１重量部混合した紫外線硬化性組成物を厚さ１００μｍのポリエステル系セパレータに塗布し、窒素雰囲気下、紫外線ランプにて１，０００ｍｊ／ｃｍ２の紫外線を照射して、光重合させ、厚さ０．２ｍｍの粘着組成物から成るフィルムを作製した。
Example 4
(1) NK Oligo UA-340P (manufactured by Shin-Nakamura Chemical Co., Ltd., manufactured by the first method using polyoxypropylene glycol as a diol component, molecular weight of about 13,000) as a urethane-based (meth) acrylate compound is 95 Ultraviolet curable mixed with 5 parts by weight of 2-hydroxyethyl methacrylate as a diluent and 1 part by weight of IRUGACURE 754 (manufactured by Ciba Specialty Chemicals) used in Example 1 as a photopolymerization initiator. The composition is applied to a polyester separator having a thickness of 100 μm, and is irradiated with 1,000 mj / cm 2 of ultraviolet rays with a UV lamp in a nitrogen atmosphere to cause photopolymerization, and is composed of an adhesive composition having a thickness of 0.2 mm. A film was prepared.
（２） 上記（１）で得た粘着組成物フィルムを、実施例２で得た基層フィルムの位相差フィルム側にゴムロールを用いて貼り付け、粘着組成物層付き液晶ディスプレイ用光学機能フィルムとした。 (2) The pressure-sensitive adhesive composition film obtained in the above (1) was attached to the retardation film side of the base layer film obtained in Example 2 using a rubber roll to obtain an optical functional film for a liquid crystal display with a pressure-sensitive adhesive composition layer. .
（３） 上記（２）の粘着組成物層付き液晶ディスプレイ用光学機能フィルムを、粘着組成物層を介して破損確認用ガラス（日本電気ガラス製、ＯＡ−１０、５ｃｍｘ５ｃｍ、０．７ｍｍ厚）にゴムロールで貼り合わせ、耐衝撃試験に供した。 (3) The optical functional film for a liquid crystal display with the pressure-sensitive adhesive composition layer of (2) above is applied to a glass for damage confirmation (made by Nippon Electric Glass, OA-10, 5 cm × 5 cm, 0.7 mm thickness) via the pressure-sensitive adhesive composition layer. Bonding with a rubber roll, it was subjected to an impact resistance test.
実施例５
（１） ウレタン系（メタ）アクリレート化合物として、ＮＫオリゴＵＡ−３４０Ｐを８５重量部、希釈剤として２−ヒドロキシエチルメタアクリレートを１５重量部とした以外は実施例４と同様にして厚さ０．２ｍｍの粘着組成物から成るフィルムを得た。
Example 5
(1) Thickness of 0.00 as in Example 4 except that 85 parts by weight of NK oligo UA-340P and 15 parts by weight of 2-hydroxyethyl methacrylate as a diluent were used as the urethane-based (meth) acrylate compound. A film made of a 2 mm adhesive composition was obtained.
（２） 上記（１）で得た粘着組成物フィルムを、実施例２で得た基層フィルムの位相差フィルム側にゴムロールを用いて貼り付け、粘着組成物層付き液晶ディスプレイ用光学機能フィルムとした。 (2) The pressure-sensitive adhesive composition film obtained in the above (1) was attached to the retardation film side of the base layer film obtained in Example 2 using a rubber roll to obtain an optical functional film for a liquid crystal display with a pressure-sensitive adhesive composition layer. .
（３） 上記（３）の粘着組成物層付き液晶ディスプレイ用光学機能フィルムを、粘着組成物層を介して破損確認用ガラス（日本電気ガラス製、ＯＡ−１０、５ｃｍｘ５ｃｍ、０．７ｍｍ厚）にゴムロールで貼り合わせ、耐衝撃試験に供した。 (3) The optical functional film for a liquid crystal display with the adhesive composition layer of (3) above is applied to a glass for damage confirmation (made by Nippon Electric Glass, OA-10, 5 cm × 5 cm, 0.7 mm thickness) through the adhesive composition layer. Bonding with a rubber roll, it was subjected to an impact resistance test.
実施例６
（１） ウレタン系（メタ）アクリレート化合物として、ＵＮ−９０００Ｈ（根上工業（株）製、分子量５０００）を９０重量部、光重合開始剤として、オキシ−フェニル−アセチックアシッド２−［２−オキソ−２−フェニル−アセトキシ−エトキシ］−エチルエステルとオキシ−フェニル−アセチックアシッド２−［２−ヒドロキシ−エトキシ］−エチルエステルの混合物（商品名ＩＲＵＧＡＣＵＲＥ７５４、チバ・スペシャリティケミカルズ（株）製）を１重量部混合した紫外線硬化性組成物を厚さ１００μｍのポリエステル系セパレータに塗布し、窒素雰囲気下、紫外線ランプにて１，０００ｍｊ／ｃｍ２の紫外線を照射して、光重合させ、厚さ０．４ｍｍの粘着組成物から成るフィルムを作製した。
Example 6
(1) 90 parts by weight of UN-9000H (manufactured by Negami Kogyo Co., Ltd., molecular weight 5000) as a urethane-based (meth) acrylate compound, and oxy-phenyl-acetic acid 2- [2-oxo as a photopolymerization initiator 2-Phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester (trade name IRUGACURE754, manufactured by Ciba Specialty Chemicals) An ultraviolet curable composition mixed with parts by weight was applied to a polyester separator having a thickness of 100 μm, and photopolymerization was performed by irradiating 1,000 mj / cm 2 of ultraviolet rays with an ultraviolet lamp in a nitrogen atmosphere. A film made of a 4 mm adhesive composition was prepared.
（２） 上記（１）で得た粘着組成物フィルムを、実施例１で用いた偏光フィルムの片面にゴムロールを用いて貼り付け、粘着組成物層付き液晶ディスプレイ用光学機能フィルムとした。 (2) The pressure-sensitive adhesive composition film obtained in the above (1) was attached to one side of the polarizing film used in Example 1 using a rubber roll to obtain an optical functional film for a liquid crystal display with a pressure-sensitive adhesive composition layer.
（３） 上記（２）の粘着組成物層付き液晶ディスプレイ用光学機能フィルムを、粘着組成物層を介して破損確認用ガラス（日本電気ガラス製、ＯＡ−１０、５ｃｍｘ５ｃｍ、０．７ｍｍ厚）にゴムロールで貼り合わせ、耐衝撃試験に供した。 (3) The optical functional film for a liquid crystal display with the pressure-sensitive adhesive composition layer of (2) above is applied to a glass for damage confirmation (made by Nippon Electric Glass, OA-10, 5 cm × 5 cm, 0.7 mm thickness) via the pressure-sensitive adhesive composition layer. Bonding with a rubber roll, it was subjected to an impact resistance test.
比較例１
（１） アクリル酸２−エチルヘキシル１００部、ＩＲＵＧＡＣＵＲＥ７５４（チバ・スペシャリティケミカルズ（株）製）０．２部を混合し、紫外線照射により部分重合体の粘ちょう液体を得た。この粘ちょう液体にトリメチロールプロパントリアクリレート（内部架橋剤）０．２部とＩＲＵＧＡＣＵＲＥ７５４（チバ・スペシャリティケミカルズ（株）製）０．２部を混合した紫外線硬化性組成物を厚さ１００μｍの偏光板上に塗布し、窒素雰囲気下、紫外線ランプにて２，０００ｍｊ／ｃｍ２の紫外線を照射して、光重合させ、厚さ０．４ｍｍの粘着組成物から成るフィルムを作製した。
Comparative Example 1
(1) 100 parts of 2-ethylhexyl acrylate and 0.2 part of IRUGACURE 754 (manufactured by Ciba Specialty Chemicals) were mixed, and a viscous liquid of a partial polymer was obtained by ultraviolet irradiation. A polarizing plate having a thickness of 100 μm is prepared by mixing an ultraviolet curable composition obtained by mixing 0.2 part of trimethylolpropane triacrylate (internal crosslinking agent) and 0.2 part of IRUGACURE754 (manufactured by Ciba Specialty Chemicals Co., Ltd.) with this viscous liquid. The film was coated on top and irradiated with ultraviolet rays of 2,000 mj / cm 2 with a UV lamp in a nitrogen atmosphere to cause photopolymerization, and a film made of an adhesive composition having a thickness of 0.4 mm was produced.
（２） 上記（１）で得た粘着組成物フィルムを、偏光板（住友化学製、ハイルミナンスＳＲ、４ｃｍｘ５ｃｍ）の片面にゴムロールを用いて貼り付け、粘着組成物層付き液晶ディスプレイ用光学機能フィルムとした。 (2) The adhesive composition film obtained in the above (1) is attached to one side of a polarizing plate (manufactured by Sumitomo Chemical Co., Ltd., high luminance SR, 4 cm × 5 cm) using a rubber roll, and an optical functional film for a liquid crystal display with an adhesive composition layer It was.
（３） 上記（２）の粘着組成物層付き液晶ディスプレイ用光学機能フィルムを、粘着組成物層を介して破損確認用ガラス（日本電気ガラス製、ＯＡ−１０、５ｃｍｘ５ｃｍ、０．７ｍｍ厚）にゴムロールで貼り合わせ、耐衝撃試験に供した。 (3) The optical functional film for a liquid crystal display with the pressure-sensitive adhesive composition layer of (2) above is applied to a glass for damage confirmation (made by Nippon Electric Glass, OA-10, 5 cm × 5 cm, 0.7 mm thickness) via the pressure-sensitive adhesive composition layer. Bonding with a rubber roll, it was subjected to an impact resistance test.
比較例２
（１） 実施例１の粘着組成物フィルムの厚さを０．０５mmとした以外は、同様の製法にて粘着組成物フィルムを得た。
Comparative Example 2
(1) An adhesive composition film was obtained by the same production method except that the thickness of the adhesive composition film of Example 1 was 0.05 mm.
（２） 上記（１）で得た粘着組成物フィルムを偏光フィルム（住友化学製、ハイルミナンスＳＲ、４ｃｍｘ５ｃｍ）の片面にゴムロールを用いて貼り付け、粘着組成物層付き液晶ディスプレイ用光学機能フィルムとした。 (2) The adhesive composition film obtained in (1) above is attached to one side of a polarizing film (Sumitomo Chemical Co., Ltd., high luminance SR, 4 cm × 5 cm) using a rubber roll, and an optical functional film for liquid crystal displays with an adhesive composition layer did.
（３） 上記（２）の粘着組成物層付き液晶ディスプレイ用光学機能フィルムを、粘着組成物層を介して破損確認用ガラス（日本電気ガラス製、ＯＡ−１０、５ｃｍｘ５ｃｍ、０．７ｍｍ厚）にゴムロールで貼り合わせ、耐衝撃試験に供した。 (3) The optical functional film for a liquid crystal display with the pressure-sensitive adhesive composition layer of (2) above is applied to a glass for damage confirmation (made by Nippon Electric Glass, OA-10, 5 cm × 5 cm, 0.7 mm thickness) via the pressure-sensitive adhesive composition layer. Bonding with a rubber roll, it was subjected to an impact resistance test.
上記実施例１〜６及び比較例１、２で得られた各フィルムについて、上記の方法により耐衝撃試験を行った。また、各例で作成した粘着組成物層付き液晶ディスプレイ用光学機能フィルムについて、上記方法により９０°剥離粘着力を測定し、剥離後のガラス基板上の粘着組成物残りを目視により観察した。 Each film obtained in Examples 1 to 6 and Comparative Examples 1 and 2 was subjected to an impact resistance test by the above method. Moreover, about the optical function film for liquid crystal displays with the adhesive composition layer produced in each case, 90 degree peeling adhesive force was measured by the said method, and the adhesive composition remainder on the glass substrate after peeling was observed visually.
結果を下記表１に示す。下記表１に示されるように、実施例１〜６の粘着組成物層付き液晶ディスプレイ用光学機能フィルムは、耐衝撃性が良好で、適度な粘着力を有し、剥離後に粘着組成物の残りがガラス面上に残留しなかった。これに対し、比較例１の粘着組成物層付き液晶ディスプレイ用光学機能フィルムは、粘着力が強く、剥離後に粘着組成物の残りがガラス面上に残留した。比較例１及び２の粘着組成物層付き液晶ディスプレイ用光学機能フィルムでは、耐衝撃性も不十分であった。 The results are shown in Table 1 below. As shown in Table 1 below, the optical functional films for liquid crystal displays with the adhesive composition layers of Examples 1 to 6 have good impact resistance, have an appropriate adhesive strength, and the remainder of the adhesive composition after peeling Did not remain on the glass surface. On the other hand, the optical function film for a liquid crystal display with a pressure-sensitive adhesive composition layer of Comparative Example 1 had high adhesive strength, and the remainder of the pressure-sensitive adhesive composition remained on the glass surface after peeling. In the optical functional film for liquid crystal displays with the adhesive composition layer of Comparative Examples 1 and 2, the impact resistance was also insufficient.
１ ゴムラバー
２ ガラス
３ アクリルフォームテープ
４ 破損確認用ガラス
５ 粘着組成物層付き光学機能フィルム
５１ 基層フィルム
５２ 粘着組成物層
５１１ 偏光素子層
５１２ 保護層
DESCRIPTION OF
Claims (6)
The liquid crystal display which laminated | stacked the optical function film for liquid crystal displays with the adhesion composition layer of any one of Claim 1 thru | or 5 on the surface of the liquid crystal display.
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