JP2021173990A - Polarizing plate, image display device, and method of manufacturing polarizing plate - Google Patents
Polarizing plate, image display device, and method of manufacturing polarizing plate Download PDFInfo
- Publication number
- JP2021173990A JP2021173990A JP2020183486A JP2020183486A JP2021173990A JP 2021173990 A JP2021173990 A JP 2021173990A JP 2020183486 A JP2020183486 A JP 2020183486A JP 2020183486 A JP2020183486 A JP 2020183486A JP 2021173990 A JP2021173990 A JP 2021173990A
- Authority
- JP
- Japan
- Prior art keywords
- polarizing plate
- image display
- antioxidant
- water content
- adhesive 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 132
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 85
- 239000010410 layer Substances 0.000 claims abstract description 81
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 69
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 67
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 67
- 229920005989 resin Polymers 0.000 claims abstract description 62
- 239000011347 resin Substances 0.000 claims abstract description 62
- 239000012790 adhesive layer Substances 0.000 claims abstract description 48
- 230000001681 protective effect Effects 0.000 claims abstract description 37
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 8
- 239000011630 iodine Substances 0.000 claims abstract description 8
- 239000000853 adhesive Substances 0.000 claims description 73
- 230000001070 adhesive effect Effects 0.000 claims description 73
- 238000000034 method Methods 0.000 claims description 52
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 31
- 238000010030 laminating Methods 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 3
- 238000002834 transmittance Methods 0.000 abstract description 28
- 239000011229 interlayer Substances 0.000 abstract description 16
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 63
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 38
- 210000004027 cell Anatomy 0.000 description 24
- 230000007423 decrease Effects 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 235000013877 carbamide Nutrition 0.000 description 21
- 239000004202 carbamide Substances 0.000 description 20
- 239000004973 liquid crystal related substance Substances 0.000 description 19
- -1 carboxyvinyl Chemical group 0.000 description 17
- 230000003287 optical effect Effects 0.000 description 14
- 150000003672 ureas Chemical class 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 210000002858 crystal cell Anatomy 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 9
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000002530 phenolic antioxidant Substances 0.000 description 7
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 6
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002346 layers by function Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 150000003585 thioureas Chemical class 0.000 description 6
- 238000004043 dyeing Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 150000004291 polyenes Polymers 0.000 description 5
- 238000007127 saponification reaction Methods 0.000 description 5
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229940015043 glyoxal Drugs 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- MBAUOPQYSQVYJV-UHFFFAOYSA-N octyl 3-[4-hydroxy-3,5-di(propan-2-yl)phenyl]propanoate Chemical compound OC1=C(C=C(C=C1C(C)C)CCC(=O)OCCCCCCCC)C(C)C MBAUOPQYSQVYJV-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- NQPJDJVGBDHCAD-UHFFFAOYSA-N 1,3-diazinan-2-one Chemical compound OC1=NCCCN1 NQPJDJVGBDHCAD-UHFFFAOYSA-N 0.000 description 2
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 2
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 2
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- GMEGXJPUFRVCPX-UHFFFAOYSA-N butylthiourea Chemical compound CCCCNC(N)=S GMEGXJPUFRVCPX-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- POXAIQSXNOEQGM-UHFFFAOYSA-N propan-2-ylthiourea Chemical compound CC(C)NC(N)=S POXAIQSXNOEQGM-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HXCHZMHFZXNFIX-UHFFFAOYSA-N (2-methoxyphenyl)thiourea Chemical compound COC1=CC=CC=C1NC(N)=S HXCHZMHFZXNFIX-UHFFFAOYSA-N 0.000 description 1
- BLSVCHHBHKGCSQ-UHFFFAOYSA-N (2-methylphenyl)urea Chemical compound CC1=CC=CC=C1NC(N)=O BLSVCHHBHKGCSQ-UHFFFAOYSA-N 0.000 description 1
- IPRCBIWIPMJXIK-UHFFFAOYSA-N (3-hydroxyphenyl)urea Chemical compound NC(=O)NC1=CC=CC(O)=C1 IPRCBIWIPMJXIK-UHFFFAOYSA-N 0.000 description 1
- SRYLJBWDZZMDSK-UHFFFAOYSA-N (4-methoxyphenyl)thiourea Chemical compound COC1=CC=C(NC(N)=S)C=C1 SRYLJBWDZZMDSK-UHFFFAOYSA-N 0.000 description 1
- PGUKYDVWVXRPKK-UHFFFAOYSA-N (4-methoxyphenyl)urea Chemical compound COC1=CC=C(NC(N)=O)C=C1 PGUKYDVWVXRPKK-UHFFFAOYSA-N 0.000 description 1
- VXLFMCZPFIKKDZ-UHFFFAOYSA-N (4-methylphenyl)thiourea Chemical compound CC1=CC=C(NC(N)=S)C=C1 VXLFMCZPFIKKDZ-UHFFFAOYSA-N 0.000 description 1
- DMSHKWHLXNDUST-UHFFFAOYSA-N (4-methylphenyl)urea Chemical compound CC1=CC=C(NC(N)=O)C=C1 DMSHKWHLXNDUST-UHFFFAOYSA-N 0.000 description 1
- SNDGLCYYBKJSOT-UHFFFAOYSA-N 1,1,3,3-tetrabutylurea Chemical class CCCCN(CCCC)C(=O)N(CCCC)CCCC SNDGLCYYBKJSOT-UHFFFAOYSA-N 0.000 description 1
- ZSPQVOFATJEJMT-UHFFFAOYSA-N 1,1,3,3-tetraethylthiourea Chemical compound CCN(CC)C(=S)N(CC)CC ZSPQVOFATJEJMT-UHFFFAOYSA-N 0.000 description 1
- UWHSPZZUAYSGTB-UHFFFAOYSA-N 1,1,3,3-tetraethylurea Chemical class CCN(CC)C(=O)N(CC)CC UWHSPZZUAYSGTB-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical class CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 description 1
- CNLHIRFQKMVKPX-UHFFFAOYSA-N 1,1-diethylthiourea Chemical compound CCN(CC)C(N)=S CNLHIRFQKMVKPX-UHFFFAOYSA-N 0.000 description 1
- TUMNHQRORINJKE-UHFFFAOYSA-N 1,1-diethylurea Chemical compound CCN(CC)C(N)=O TUMNHQRORINJKE-UHFFFAOYSA-N 0.000 description 1
- ZQGWBPQBZHMUFG-UHFFFAOYSA-N 1,1-dimethylthiourea Chemical compound CN(C)C(N)=S ZQGWBPQBZHMUFG-UHFFFAOYSA-N 0.000 description 1
- YBBLOADPFWKNGS-UHFFFAOYSA-N 1,1-dimethylurea Chemical compound CN(C)C(N)=O YBBLOADPFWKNGS-UHFFFAOYSA-N 0.000 description 1
- FPZXQVCYHDMIIA-UHFFFAOYSA-N 1,1-diphenylthiourea Chemical compound C=1C=CC=CC=1N(C(=S)N)C1=CC=CC=C1 FPZXQVCYHDMIIA-UHFFFAOYSA-N 0.000 description 1
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- KWPNNZKRAQDVPZ-UHFFFAOYSA-N 1,3-bis(2-methylphenyl)thiourea Chemical compound CC1=CC=CC=C1NC(=S)NC1=CC=CC=C1C KWPNNZKRAQDVPZ-UHFFFAOYSA-N 0.000 description 1
- CPSIMDUNVYMPAH-UHFFFAOYSA-N 1,3-bis(4-methoxyphenyl)urea Chemical compound C1=CC(OC)=CC=C1NC(=O)NC1=CC=C(OC)C=C1 CPSIMDUNVYMPAH-UHFFFAOYSA-N 0.000 description 1
- ULNVBRUIKLYGDF-UHFFFAOYSA-N 1,3-bis(4-methylphenyl)thiourea Chemical compound C1=CC(C)=CC=C1NC(=S)NC1=CC=C(C)C=C1 ULNVBRUIKLYGDF-UHFFFAOYSA-N 0.000 description 1
- KREOCUNMMFZOOS-UHFFFAOYSA-N 1,3-di(propan-2-yl)thiourea Chemical compound CC(C)NC(S)=NC(C)C KREOCUNMMFZOOS-UHFFFAOYSA-N 0.000 description 1
- KAJICSGLHKRDLN-UHFFFAOYSA-N 1,3-dicyclohexylthiourea Chemical compound C1CCCCC1NC(=S)NC1CCCCC1 KAJICSGLHKRDLN-UHFFFAOYSA-N 0.000 description 1
- ADFXKUOMJKEIND-UHFFFAOYSA-N 1,3-dicyclohexylurea Chemical compound C1CCCCC1NC(=O)NC1CCCCC1 ADFXKUOMJKEIND-UHFFFAOYSA-N 0.000 description 1
- ZWAVGZYKJNOTPX-UHFFFAOYSA-N 1,3-diethylurea Chemical compound CCNC(=O)NCC ZWAVGZYKJNOTPX-UHFFFAOYSA-N 0.000 description 1
- BXBKNWRSAAAPKG-UHFFFAOYSA-N 1,3-dimethoxy-1,3-dimethylurea Chemical class CON(C)C(=O)N(C)OC BXBKNWRSAAAPKG-UHFFFAOYSA-N 0.000 description 1
- 229940057054 1,3-dimethylurea Drugs 0.000 description 1
- VUVPNTYTOUGMDG-UHFFFAOYSA-N 1-(2-hydroxyethyl)-3-prop-2-enylthiourea Chemical compound OCCNC(=S)NCC=C VUVPNTYTOUGMDG-UHFFFAOYSA-N 0.000 description 1
- NXCBDDGSOXJEFZ-UHFFFAOYSA-N 1-benzyl-3-phenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NCC1=CC=CC=C1 NXCBDDGSOXJEFZ-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- IGEQFPWPMCIYDF-UHFFFAOYSA-N 1-methyl-3-phenylthiourea Chemical compound CNC(=S)NC1=CC=CC=C1 IGEQFPWPMCIYDF-UHFFFAOYSA-N 0.000 description 1
- VSNHCAURESNICA-NJFSPNSNSA-N 1-oxidanylurea Chemical compound N[14C](=O)NO VSNHCAURESNICA-NJFSPNSNSA-N 0.000 description 1
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 1
- CLAHOZSYMRNIPY-UHFFFAOYSA-N 2-hydroxyethylurea Chemical compound NC(=O)NCCO CLAHOZSYMRNIPY-UHFFFAOYSA-N 0.000 description 1
- MQBITTBZTXUIPN-UHFFFAOYSA-N 2-methylpropylurea Chemical compound CC(C)CNC(N)=O MQBITTBZTXUIPN-UHFFFAOYSA-N 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 1
- QRLSTWVLSWCGBT-UHFFFAOYSA-N 4-((4,6-bis(octylthio)-1,3,5-triazin-2-yl)amino)-2,6-di-tert-butylphenol Chemical compound CCCCCCCCSC1=NC(SCCCCCCCC)=NC(NC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=N1 QRLSTWVLSWCGBT-UHFFFAOYSA-N 0.000 description 1
- PIVQQUNOTICCSA-UHFFFAOYSA-N ANTU Chemical compound C1=CC=C2C(NC(=S)N)=CC=CC2=C1 PIVQQUNOTICCSA-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 101100433727 Caenorhabditis elegans got-1.2 gene Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- RYECOJGRJDOGPP-UHFFFAOYSA-N Ethylurea Chemical compound CCNC(N)=O RYECOJGRJDOGPP-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VLCDUOXHFNUCKK-UHFFFAOYSA-N N,N'-Dimethylthiourea Chemical compound CNC(=S)NC VLCDUOXHFNUCKK-UHFFFAOYSA-N 0.000 description 1
- KFFQABQEJATQAT-UHFFFAOYSA-N N,N'-dibutylthiourea Chemical compound CCCCNC(=S)NCCCC KFFQABQEJATQAT-UHFFFAOYSA-N 0.000 description 1
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- KQJQICVXLJTWQD-UHFFFAOYSA-N N-Methylthiourea Chemical compound CNC(N)=S KQJQICVXLJTWQD-UHFFFAOYSA-N 0.000 description 1
- IPCRBOOJBPETMF-UHFFFAOYSA-N N-acetylthiourea Chemical compound CC(=O)NC(N)=S IPCRBOOJBPETMF-UHFFFAOYSA-N 0.000 description 1
- HRYILSDLIGTCOP-UHFFFAOYSA-N N-benzoylurea Chemical compound NC(=O)NC(=O)C1=CC=CC=C1 HRYILSDLIGTCOP-UHFFFAOYSA-N 0.000 description 1
- GMEHFXXZSWDEDB-UHFFFAOYSA-N N-ethylthiourea Chemical compound CCNC(N)=S GMEHFXXZSWDEDB-UHFFFAOYSA-N 0.000 description 1
- FULZLIGZKMKICU-UHFFFAOYSA-N N-phenylthiourea Chemical compound NC(=S)NC1=CC=CC=C1 FULZLIGZKMKICU-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- UHGKYJXJYJWDAM-UHFFFAOYSA-N Propylthiourea Chemical compound CCCNC(N)=S UHGKYJXJYJWDAM-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- MNOILHPDHOHILI-UHFFFAOYSA-N Tetramethylthiourea Chemical compound CN(C)C(=S)N(C)C MNOILHPDHOHILI-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001299 aldehydes Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- RJNJWHFSKNJCTB-UHFFFAOYSA-N benzylurea Chemical compound NC(=O)NCC1=CC=CC=C1 RJNJWHFSKNJCTB-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- CNWSQCLBDWYLAN-UHFFFAOYSA-N butylurea Chemical compound CCCCNC(N)=O CNWSQCLBDWYLAN-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- LEEHHPPLIOFGSC-UHFFFAOYSA-N cyclohexylthiourea Chemical compound NC(=S)NC1CCCCC1 LEEHHPPLIOFGSC-UHFFFAOYSA-N 0.000 description 1
- WUESWDIHTKHGQA-UHFFFAOYSA-N cyclohexylurea Chemical compound NC(=O)NC1CCCCC1 WUESWDIHTKHGQA-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229940077844 iodine / potassium iodide Drugs 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- XGEGHDBEHXKFPX-NJFSPNSNSA-N methylurea Chemical compound [14CH3]NC(N)=O XGEGHDBEHXKFPX-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- XRVHSOXXNQTWAW-UHFFFAOYSA-N n-(methylcarbamoyl)acetamide Chemical compound CNC(=O)NC(C)=O XRVHSOXXNQTWAW-UHFFFAOYSA-N 0.000 description 1
- GKRZNOGGALENQJ-UHFFFAOYSA-N n-carbamoylacetamide Chemical compound CC(=O)NC(N)=O GKRZNOGGALENQJ-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- ACLZYRNSDLQOIA-UHFFFAOYSA-N o-tolylthiourea Chemical compound CC1=CC=CC=C1NC(N)=S ACLZYRNSDLQOIA-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- GJNDMSSZEBNLPU-UHFFFAOYSA-N octadecylurea Chemical compound CCCCCCCCCCCCCCCCCCNC(N)=O GJNDMSSZEBNLPU-UHFFFAOYSA-N 0.000 description 1
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- VPJDULFXCAQHRC-UHFFFAOYSA-N prop-2-enylurea Chemical compound NC(=O)NCC=C VPJDULFXCAQHRC-UHFFFAOYSA-N 0.000 description 1
- ZQZJKHIIQFPZCS-UHFFFAOYSA-N propylurea Chemical compound CCCNC(N)=O ZQZJKHIIQFPZCS-UHFFFAOYSA-N 0.000 description 1
- SLUHLANJIVXTRQ-UHFFFAOYSA-N pyridin-2-ylthiourea Chemical compound NC(=S)NC1=CC=CC=N1 SLUHLANJIVXTRQ-UHFFFAOYSA-N 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 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
- 239000010409 thin film Substances 0.000 description 1
- 125000006617 triphenylamine group Chemical group 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polarising Elements (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
Abstract
Description
本発明は、偏光板に関する。さらに、本発明は当該偏光板の一方の面が画像表示セルと貼り合せられ、他方の面がタッチパネルや前面板等の透明部材と貼り合せられた画像表示装置に関する。 The present invention relates to a polarizing plate. Further, the present invention relates to an image display device in which one surface of the polarizing plate is bonded to an image display cell and the other surface is bonded to a transparent member such as a touch panel or a front plate.
液晶表示装置（ＬＣＤ）は、液晶テレビだけでなく、パソコン、携帯電話等のモバイル、カーナビ等の車載用途などで広く用いられている。通常、液晶表示装置は、液晶セルの両側に粘着剤層を介して偏光板を貼合した液晶パネルを有し、バックライトからの光を液晶パネルで制御することにより表示が行われている。また、有機ＥＬ表示装置も近年、液晶表示装置と同様に、テレビ、携帯電話等のモバイル、カーナビ等の車載用途で広く用いられて来ている。有機ＥＬ表示装置では、外光が金属電極（陰極）で反射され鏡面のように視認されることを抑止するために、画像表示パネルの視認側表面に円偏光板（偏光素子とλ／４板を含む積層体、以下、単に偏光板ということがある。）が配置される場合がある。 Liquid crystal displays (LCDs) are widely used not only in liquid crystal televisions but also in mobile devices such as personal computers and mobile phones, and in-vehicle applications such as car navigation systems. Usually, a liquid crystal display device has a liquid crystal panel in which polarizing plates are bonded to both sides of a liquid crystal cell via an adhesive layer, and display is performed by controlling the light from the backlight with the liquid crystal panel. Further, in recent years, organic EL display devices, like liquid crystal display devices, have been widely used in mobile applications such as televisions and mobile phones, and in-vehicle applications such as car navigation systems. In an organic EL display device, in order to prevent external light from being reflected by a metal electrode (cathode) and visually recognized like a mirror surface, a circular polarizing plate (polarizing element and a λ / 4 plate) is formed on the visible side surface of the image display panel. (Hereinafter, it may be simply referred to as a polarizing plate) may be arranged.
偏光板は上記のように、液晶表示装置や有機ＥＬ表示装置の部材として、車に搭載される機会が増えて来ている。車載用の画像表示装置に用いられる偏光板は、それ以外のテレビや携帯電話等のモバイル用途に比較して、高温環境下に曝されることが多く、より高温での特性変化が小さいこと（高温耐久性）が求められる。
一方、外表面から衝撃による画像表示パネルの破損防止等を目的として、画像表示パネルの偏光板よりもさらに視認側に、透明樹脂板やガラス板等の前面板（「ウインドウ層」等とも称される。）を設ける構成が増えてきている。また、タッチパネルを備える表示装置では、画像表示パネルの偏光板よりも視認側にタッチパネルが設けられ、タッチパネルよりもさらに視認側に前面板を備える構成が広く採用されている。
As described above, polarizing plates are increasingly mounted on automobiles as members of liquid crystal display devices and organic EL display devices. Polarizing plates used in in-vehicle image display devices are often exposed to high-temperature environments and have less characteristic changes at higher temperatures than other mobile applications such as televisions and mobile phones. High temperature durability) is required.
On the other hand, for the purpose of preventing damage to the image display panel due to impact from the outer surface, a front plate such as a transparent resin plate or a glass plate (also referred to as a "window layer" or the like) is further visible side than the polarizing plate of the image display panel. The number of configurations that provide ()) is increasing. Further, in a display device provided with a touch panel, a configuration in which a touch panel is provided on the viewing side of the polarizing plate of the image display panel and a front plate is provided on the viewing side of the touch panel is widely adopted.
このような構成において、画像表示パネルと前面板やタッチパネル等の透明部材との間に空気層が存在すると、空気層界面での光の反射による外光の映り込みが生じ、画面の視認性が低下する傾向がある。そのため、画像表示パネルの視認側表面に配置される偏光板と透明部材との間の空間を、空気層以外の層（以下「層間充填剤」と称する場合がある）で充填する構成（以下「層間充填構成」と称する場合がある）、好ましくはこれらの材料と屈折率が近い材料で充填する構成を採用する動きが広まっている。層間充填剤としては、界面での反射による視認性の低下を抑止すると共に、各部材間を接着固定する目的で、粘着剤やＵＶ硬化型接着剤が用いられる（例えば特許文献１参照）。 In such a configuration, if an air layer exists between the image display panel and a transparent member such as a front plate or a touch panel, external light is reflected due to the reflection of light at the interface of the air layer, and the visibility of the screen is improved. Tends to decline. Therefore, the space between the polarizing plate and the transparent member arranged on the visible surface of the image display panel is filled with a layer other than the air layer (hereinafter, may be referred to as "interlayer filler") (hereinafter, "interlayer filler"). There is a widespread movement to adopt a structure in which a material having a refractive index close to that of these materials is preferably used. As the interlayer filler, an adhesive or a UV curable adhesive is used for the purpose of suppressing deterioration of visibility due to reflection at the interface and adhesively fixing the members to each other (see, for example, Patent Document 1).
上記の層間充填構成は、屋外で使用されることが多い携帯電話等のモバイル用途での採用が広がっている。また、近年の視認性に対する要求の高まりから、カーナビゲーション装置等の車載用途においても、画像表示パネル表面に前面板を配置し、パネルと前面板との間を粘着剤層等で充填した層間充填構成の採用が検討されている。
しかし、このような構成を採用する場合、加熱耐久試験（９５℃で２００時間等）の結果、偏光板面内中央部に、透過率の著しい低下が見られること、その一方、偏光板単独では９５℃で１０００時間でも著しい透過率の低下は見られないことが報告されており、これらの結果から、高温環境における偏光板の透過率の著しい低下は、偏光板の一方の面が画像表示セルと貼り合せられ、他方の面がタッチパネルや前面板等の透明部材と貼り合せられている層間充填構成を採用する画像表示装置が高温環境に暴露された場合に特有の問題であることも報告されている（特許文献２）。
The above-mentioned interlayer filling configuration is widely adopted in mobile applications such as mobile phones, which are often used outdoors. In addition, due to the increasing demand for visibility in recent years, even in in-vehicle applications such as car navigation devices, a front plate is arranged on the surface of an image display panel, and the space between the panel and the front plate is filled with an adhesive layer or the like. Adoption of the configuration is being considered.
However, when such a configuration is adopted, as a result of a heating durability test (200 hours at 95 ° C., etc.), a significant decrease in transmittance is observed in the central portion of the polarizing plate surface, while the polarizing plate alone alone shows a significant decrease in transmittance. It has been reported that no significant decrease in transmittance is observed even at 95 ° C. for 1000 hours, and from these results, a significant decrease in the transmittance of the polarizing plate in a high temperature environment is caused by one surface of the polarizing plate being an image display cell. It has also been reported that this is a problem peculiar to an image display device that employs an interlayer filling configuration in which the other surface is bonded to a transparent member such as a touch panel or a front plate when exposed to a high temperature environment. (Patent Document 2).
そして、上記特許文献２には層間充填構成で透過率が著しく低下した偏光板は、ラマン分光測定で１１００ｃｍ−１付近（＝Ｃ−Ｃ＝結合に由来）および１５００ｃｍ−１付近（−Ｃ＝Ｃ−結合に由来）にピークを有していることから、ポリエン構造（−Ｃ＝Ｃ）ｎ−を形成していると考え、偏光素子を構成するポリビニルアルコールが脱水によりポリエン化されて生じたものであると推定している（特許文献２、段落［００１２］）。 In Patent Document 2, the polarizing plate having a significantly reduced transmittance due to the interlayer filling configuration is measured by Raman spectroscopy at around 1100 cm -1 (= CC = derived from bonding) and around 1500 cm -1 (-C = C). Since it has a peak (derived from − bond), it is considered that a polyene structure (−C = C) n − is formed, and the polyvinyl alcohol constituting the polarizing element is polyene formed by dehydration. (Patent Document 2, paragraph [0012]).
特許文献２ではその問題の解決策として、偏光板の単位面積当たりの水分量を所定量以下とし、なおかつ偏光素子に隣接する透明保護フィルムの飽和吸水量を所定量以下とすることにより透過率の低下を抑制する方法を提案している。
しかしながら、
In Patent Document 2, as a solution to the problem, the amount of water per unit area of the polarizing plate is set to a predetermined amount or less, and the saturated water absorption amount of the transparent protective film adjacent to the polarizing element is set to a predetermined amount or less to increase the transmittance. We are proposing a method to suppress the decrease.
However,
上記手段を以ってしても、高温耐久試験における透過率低下の抑制効果は十分でないものであった。本発明は、層間充填構成の画像表示装置に用いられた場合においても、高温環境下での透過率の低下が小さく、高温耐久性に優れる偏光板、及び画像表示装置を提供することを目的とする。 Even with the above means, the effect of suppressing the decrease in transmittance in the high temperature durability test was not sufficient. An object of the present invention is to provide a polarizing plate having a small decrease in transmittance in a high temperature environment and excellent high temperature durability even when used in an image display device having an interlayer filling configuration, and an image display device. do.
本発明は、以下の偏光板、画像表示装置、及び偏光板の製造方法を提供する。
〔１〕 ポリビニルアルコール系樹脂層にヨウ素を吸着配向させてなる偏光素子と透明保護フィルムとが、水系接着剤層を介して積層された偏光板であって、
前記水系接着剤層は、酸化防止剤を含有し、
前記偏光素子の含水率が温度２０℃かつ相対湿度３０％の平衡含水率以上であり、温度２０℃相対湿度５０％の平衡含水率以下である、偏光板。
〔２〕 ポリビニルアルコール系樹脂層にヨウ素を吸着配向させてなる偏光素子と透明保護フィルムとが、水系接着剤層を介して積層された偏光板であって、
前記水系接着剤層は、酸化防止剤を含有し、
前記偏光板の含水率が温度２０℃かつ相対湿度３０％の平衡含水率以上であり、温度２０℃相対湿度５０％の平衡含水率以下である、偏光板。
〔３〕 前記酸化防止剤が、フェノール系酸化防止剤、リン系酸化防止剤、及び硫黄系酸化防止剤からなる群より選ばれる少なくとも１つの酸化防止剤である、〔１〕または〔２〕に記載の偏光板。
〔４〕 前記水系接着剤層がポリビニルアルコール系樹脂を含有する、〔１〕〜〔３〕のいずれかに記載の偏光板。
〔５〕 前記水系接着剤層の前記酸化防止剤の含有量が、ポリビニルアルコール系樹脂１００質量部に対し、０．３質量部以上１００質量部以下である、〔４〕に記載の偏光板。
〔６〕 画像表示セルと、
〔１〕〜〔５〕のいずれかに記載された偏光板とを備え、
前記偏光板の両面には空気層以外の層が接して設けられている画像表示装置。
〔７〕 画像表示セルと、前記画像表示セルの視認側表面に積層された第１粘着剤層と、前記第１粘着剤層の視認側表面に積層された〔１〕〜〔５〕のいずれか１項に記載の偏光板と、を有する画像表示装置。
〔８〕 前記偏光板の視認側表面に積層された第２粘着剤層と、前記第２粘着剤層の視認側表面に積層された透明部材と、をさらに有する〔７〕に記載の画像表示装置。
〔９〕 前記透明部材がガラス板または透明樹脂板である、〔８〕に記載の画像表示装置。
〔１０〕 前記透明部材がタッチパネルである、〔８〕に記載の画像表示装置。
〔１１〕 偏光素子と透明保護フィルムとを、酸化防止剤を含有する水系接着剤を用いて積層する積層工程と、
前記偏光素子の含水率が温度２０℃かつ相対湿度３０％の平衡含水率以上であり、温度２０℃相対湿度５０％の平衡含水率以下となるように調整する含水率調整工程と、を有する、偏光板の製造方法。
The present invention provides the following polarizing plate, an image display device, and a method for manufacturing the polarizing plate.
[1] A polarizing plate in which a polarizing element in which iodine is adsorbed and oriented on a polyvinyl alcohol-based resin layer and a transparent protective film are laminated via an aqueous adhesive layer.
The water-based adhesive layer contains an antioxidant and contains
A polarizing plate having a water content of the polarizing element having a temperature of 20 ° C. and a relative humidity of 30% or more and an equilibrium water content of a temperature of 20 ° C. and a relative humidity of 50% or less.
[2] A polarizing plate in which a polarizing element in which iodine is adsorbed and oriented on a polyvinyl alcohol-based resin layer and a transparent protective film are laminated via an aqueous adhesive layer.
The water-based adhesive layer contains an antioxidant and contains
A polarizing plate having a water content of the polarizing plate having a temperature of 20 ° C. and a relative humidity of 30% or more and an equilibrium water content of a temperature of 20 ° C. and a relative humidity of 50% or less.
[3] The antioxidant is at least one antioxidant selected from the group consisting of a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant, according to [1] or [2]. The polarizing plate according to the description.
[4] The polarizing plate according to any one of [1] to [3], wherein the water-based adhesive layer contains a polyvinyl alcohol-based resin.
[5] The polarizing plate according to [4], wherein the content of the antioxidant in the aqueous adhesive layer is 0.3 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the polyvinyl alcohol-based resin.
[6] Image display cell and
The polarizing plate according to any one of [1] to [5] is provided.
An image display device provided with layers other than the air layer in contact with both surfaces of the polarizing plate.
[7] Any of [1] to [5] laminated on the image display cell, the first pressure-sensitive adhesive layer laminated on the visible side surface of the image display cell, and the visible side surface of the first pressure-sensitive adhesive layer. An image display device comprising the polarizing plate according to item 1.
[8] The image display according to [7], further comprising a second pressure-sensitive adhesive layer laminated on the visible side surface of the polarizing plate and a transparent member laminated on the visible side surface of the second pressure-sensitive adhesive layer. Device.
[9] The image display device according to [8], wherein the transparent member is a glass plate or a transparent resin plate.
[10] The image display device according to [8], wherein the transparent member is a touch panel.
[11] A laminating step of laminating a polarizing element and a transparent protective film using an aqueous adhesive containing an antioxidant.
The polarizing element has a water content adjusting step of adjusting the water content so that the temperature is 20 ° C. and the relative humidity is 30% or more and the temperature is 20 ° C. and the relative humidity is 50% or less. Method for manufacturing a polarizing plate.
本発明により、層間充填構成の画像表示装置に用いられた場合においても、高温環境下での透過率の低下が小さく、高温耐久性に優れる偏光板を提供することが可能となり、さらに、本発明の偏光板を用いることで高温環境下での透過率低下が抑制された画像表示装置を提供することが可能となる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a polarizing plate having a small decrease in transmittance in a high temperature environment and excellent high temperature durability even when used in an image display device having an interlayer filling configuration. By using the polarizing plate of No. 1, it is possible to provide an image display device in which a decrease in transmittance is suppressed in a high temperature environment.
本発明の偏光板は、ポリビニルアルコール系樹脂層にヨウ素を吸着配向させてなる偏光素子と透明保護フィルムが、酸化防止剤を含有する水系接着剤層を介して積層されているという特徴を有する。さらに、本実施形態に係る偏光板は、下記の（ａ）及び（ｂ）の少なくとも一方の特徴を有する。
（ａ）偏光素子の含水率が、温度２０℃かつ相対湿度３０％の平衡含水率以上、かつ温度２０℃相対湿度５０％の平衡含水率以下である。
（ｂ）偏光板の含水率が、温度２０℃かつ相対湿度３０％の平衡含水率以上、かつ温度２０℃相対湿度５０％の平衡含水率以下である。
The polarizing plate of the present invention is characterized in that a polarizing element in which iodine is adsorbed and oriented on a polyvinyl alcohol-based resin layer and a transparent protective film are laminated via an aqueous adhesive layer containing an antioxidant. Further, the polarizing plate according to the present embodiment has at least one of the following features (a) and (b).
(A) The water content of the polarizing element is equal to or higher than the equilibrium water content at a temperature of 20 ° C. and a relative humidity of 30%, and equal to or lower than the equilibrium water content at a temperature of 20 ° C. and a relative humidity of 50%.
(B) The water content of the polarizing plate is equal to or higher than the equilibrium water content at a temperature of 20 ° C. and a relative humidity of 30%, and equal to or lower than the equilibrium water content at a temperature of 20 ° C. and a relative humidity of 50%.
本発明の偏光板は、上記の（ａ）及び（ｂ）の少なくとも一方の特徴を有し、さらに酸化防止剤を含有した水系接着剤層を介して偏光素子と保護フィルムとを積層した構成であることにより、層間充填構成の画像表示装置の構成要素として、高温環境下に長時間さらされた場合でも単体透過率の低下が抑制される。 The polarizing plate of the present invention has at least one of the above-mentioned characteristics (a) and (b), and has a structure in which a polarizing element and a protective film are laminated via an aqueous adhesive layer containing an antioxidant. As a component of the image display device having an interlayer filling configuration, the decrease in the single transmittance is suppressed even when exposed to a high temperature environment for a long time.
［偏光素子］
本発明のポリビニルアルコール（以降ＰＶＡとも称す）系樹脂層にヨウ素を吸着配向させてなる偏光素子としては、周知の偏光素子を用いることができる。このような偏光素子は、一般にＰＶＡ系樹脂フィルムを用い、このＰＶＡ系樹脂フィルムをヨウ素で染色し、一軸延伸することによって形成される。
[Polarizing element]
A well-known polarizing element can be used as the polarizing element formed by adsorbing and orienting iodine on the polyvinyl alcohol (hereinafter, also referred to as PVA) -based resin layer of the present invention. Such a polarizing element is generally formed by using a PVA-based resin film, dyeing the PVA-based resin film with iodine, and uniaxially stretching the film.
ＰＶＡ系樹脂は、前述のように、一般に、ポリ酢酸ビニル系樹脂を鹸化して得られるものを用いる。鹸化度は、約８５モル％以上、好ましくは約９０モル％以上、より好ましくは約９９モル％〜１００モル％である。ポリ酢酸ビニル系樹脂としては、酢酸ビニルの単独重合体であるポリ酢酸ビニルのほか、酢酸ビニルとこれに共重合可能な他の単量体との共重合体、例えば、エチレン−酢酸ビニル共重合体などが挙げられる。共重合可能な他の単量体としては、例えば不飽和カルボン酸類、オレフィン類、ビニルエーテル類、不飽和スルホン酸類などが挙げられる。ＰＶＡ系樹脂の重合度としては、１０００〜１００００、好ましくは１５００〜５０００である。このＰＶＡ系樹脂は変性されていてもよく、たとえば、アルデヒド類で変性されたポリビニルホルマール、ポリビニルアセタール、ポリビニルブチラールなどでもよい。 As the PVA-based resin, as described above, generally, a PVA-based resin obtained by saponifying a polyvinyl acetate-based resin is used. The degree of saponification is about 85 mol% or more, preferably about 90 mol% or more, and more preferably about 99 mol% to 100 mol%. Examples of the polyvinyl acetate-based resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and a copolymer of vinyl acetate and another monomer copolymerizable therewith, for example, ethylene-vinyl acetate copolymer weight. Coalescence etc. can be mentioned. Examples of other copolymerizable monomers include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids and the like. The degree of polymerization of the PVA-based resin is 1000 to 10000, preferably 1500 to 5000. This PVA-based resin may be modified, and may be, for example, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, etc. modified with aldehydes.
偏光素子の製造方法は特に限定されないが、予めロール状に巻かれたポリビニルアルコール系樹脂フィルムを送り出して延伸、染色、架橋などを行って作製する方法やポリビニルアルコール系樹脂と延伸用樹脂基材との積層体を作製し、積層体の状態で延伸を行う工程を含む方法が典型的である。本発明ではこれら、何れの方法も用いることができる。
これらの偏光素子の製造方法については特開２０１４−４８４９７号公報の段落［０１０９］〜［０１２８］に記載されており、本実施形態ではこれらの方法を用いることができる。また、本実施形態の偏光素子の厚みは３〜３５μｍが好ましく、４〜３０μｍがより好ましく、５〜２５μｍが更に好ましい。
The manufacturing method of the polarizing element is not particularly limited, but a method of feeding out a polyvinyl alcohol-based resin film wound in a roll shape in advance and performing stretching, dyeing, cross-linking, etc., or a polyvinyl alcohol-based resin and a resin base material for stretching. A typical method includes a step of producing a laminated body of the above and stretching the laminated body in the state of the laminated body. In the present invention, any of these methods can be used.
Methods for manufacturing these polarizing elements are described in paragraphs [0109] to [0128] of JP-A-2014-488497, and these methods can be used in the present embodiment. The thickness of the polarizing element of the present embodiment is preferably 3 to 35 μm, more preferably 4 to 30 μm, and even more preferably 5 to 25 μm.
偏光素子は、好ましくは酸化防止剤を含む。本実施形態において、偏光素子と透明保護フィルムとが酸化防止剤を含有する接着剤から形成される接着剤層によって貼合されていることから、接着剤層から移行した酸化防止剤の一部が偏光素子に含まれているものと推測される。偏光素子中の酸化防止剤は、偏光素子の製造過程で添加されたものを含んでいてもよい。酸化防止剤を含む接着剤層を備えることにより、偏光板を高温環境下に晒しても透過率が低下しにくくなる。偏光素子に含まれる酸化防止剤によりＰＶＡ系樹脂のポリエン化が抑制されるためと推定される。 The polarizing element preferably contains an antioxidant. In the present embodiment, since the polarizing element and the transparent protective film are bonded by an adhesive layer formed of an adhesive containing an antioxidant, a part of the antioxidant transferred from the adhesive layer is partially bonded. It is presumed that it is contained in the polarizing element. The antioxidant in the polarizing element may include those added in the process of manufacturing the polarizing element. By providing an adhesive layer containing an antioxidant, the transmittance is less likely to decrease even when the polarizing plate is exposed to a high temperature environment. It is presumed that the antioxidant contained in the polarizing element suppresses the polyene formation of the PVA-based resin.
偏光素子に酸化防止剤を含有させる方法としては、酸化防止剤を含有する処理溶媒に、ＰＶＡ系樹脂層を浸漬する方法、又は処理溶媒をＰＶＡ系樹脂層に噴霧、流下もしくは滴下する方法が挙げられる。この中でも、酸化防止剤を含有する処理溶媒にＰＶＡ系樹脂層を浸漬させる方法が好ましく用いられる。酸化防止剤の具体的な例は、後述する接着剤に含有させるものとして例示されているものが挙げられる。 Examples of the method of incorporating the antioxidant into the polarizing element include a method of immersing the PVA-based resin layer in the treatment solvent containing the antioxidant, or a method of spraying, flowing down or dropping the treatment solvent on the PVA-based resin layer. Be done. Among these, a method of immersing the PVA-based resin layer in a treatment solvent containing an antioxidant is preferably used. Specific examples of the antioxidant include those exemplified as those contained in the adhesive described later.
酸化防止剤を含む処理溶媒にＰＶＡ系樹脂層を浸漬させる工程は、後述の偏光素子の製造方法における膨潤、延伸、染色、架橋、洗浄等の工程と同時に行ってもよいし、これらの工程とは別に設けてもよい。ＰＶＡ系樹脂層に酸化防止剤を含有させる工程は、ＰＶＡ系樹脂層をヨウ素で染色した後に行なうことが好ましく、染色後の架橋工程と同時に行うことがより好ましい。このような方法によれば、色相変化が小さく、偏光素子の光学特性への影響を小さくすることができる。 The step of immersing the PVA-based resin layer in the treatment solvent containing the antioxidant may be performed at the same time as the steps of swelling, stretching, dyeing, cross-linking, washing, etc. in the method for manufacturing a polarizing element described later, or these steps and May be provided separately. The step of incorporating the antioxidant into the PVA-based resin layer is preferably performed after dyeing the PVA-based resin layer with iodine, and more preferably performed at the same time as the cross-linking step after dyeing. According to such a method, the hue change is small, and the influence on the optical characteristics of the polarizing element can be reduced.
偏光素子に酸化防止剤を含有させるために、偏光素子の製造時における添加と接着剤への添加との両方を行ってもよい。 In order to contain the antioxidant in the polarizing element, both the addition at the time of manufacturing the polarizing element and the addition to the adhesive may be performed.
（特徴（ａ））
特徴（ａ）を有する場合、偏光素子の含水率は、温度２０℃相対湿度３０％の平衡含水率以上であり、温度２０℃相対湿度５０％の平衡含水率以下である。より好ましくは、温度２０℃相対湿度４５％の平衡含水率以下であり、さらに好ましくは、温度２０℃相対湿度４２％の平衡含水率以下であり、最も好ましくは、温度２０℃相対湿度３８％の平衡含水率以下である。このような範囲とすることで、偏光板の高温耐久性を高めることができる。温度２０℃相対湿度３０％の平衡含水率を下回ると、偏光素子のハンドリング性が低下し、割れやすくなる。偏光素子の含水率が、温度２０℃相対湿度５０％の平衡含水率を上回ると、偏光素子の透過率が低下しやすくなる。偏光素子の含水率が高いと、ＰＶＡ系樹脂のポリエン化が進みやすくなるためと推測される。偏光素子の上記含水率は、偏光板中における偏光素子の含水率である。
(Feature (a))
When it has the feature (a), the water content of the polarizing element is equal to or more than the equilibrium water content of a temperature of 20 ° C. and a relative humidity of 30%, and is equal to or less than the equilibrium water content of a temperature of 20 ° C. and a relative humidity of 50%. More preferably, the temperature is 20 ° C. and the relative humidity is 45% or less, more preferably, the temperature is 20 ° C. and the relative humidity is 42% or less, and most preferably the temperature is 20 ° C. and the relative humidity is 38%. It is less than or equal to the equilibrium moisture content. Within such a range, the high temperature durability of the polarizing plate can be improved. If the temperature is lower than the equilibrium water content of 20 ° C. and the relative humidity of 30%, the handleability of the polarizing element is lowered and the polarizing element is easily cracked. When the water content of the polarizing element exceeds the equilibrium water content of a temperature of 20 ° C. and a relative humidity of 50%, the transmittance of the polarizing element tends to decrease. It is presumed that when the water content of the polarizing element is high, polyene formation of the PVA-based resin is likely to proceed. The water content of the polarizing element is the water content of the polarizing element in the polarizing plate.
偏光素子の含水率が温度２０℃相対湿度３０％の平衡含水率以上、かつ温度２０℃相対湿度５０％の平衡含水率以下の範囲内であるかを確認する方法として、上記温度と上記相対湿度の範囲に調整された環境で保管し、一定時間質量の変化がなかった場合には環境と平衡に達しているとみなすことができ、又は上記温度と上記相対湿度の範囲に調整された環境の偏光素子の平衡含水率を予め計算し、偏光素子の含水率と予め計算した平衡含水率とを対比することにより確認することができる。 As a method of confirming whether the water content of the polarizing element is within the range of the equilibrium water content of the temperature of 20 ° C. and the relative humidity of 30% and the equilibrium water content of the temperature of 20 ° C. and the relative humidity of 50% or less, the above temperature and the above relative humidity If it is stored in an environment adjusted to the range of, and if there is no change in mass for a certain period of time, it can be considered that it has reached equilibrium with the environment, or the environment adjusted to the above temperature and the above relative humidity range. It can be confirmed by calculating the equilibrium water content of the polarizing element in advance and comparing the water content of the polarizing element with the pre-calculated equilibrium water content.
含水率が温度２０℃相対湿度３０％の平衡含水率以上、かつ温度２０℃相対湿度５０％の平衡含水率以下である偏光素子を製造する方法としては、特に限定されないが、例えば上記温度と上記相対湿度の範囲に調整された環境に偏光素子を１０分以上３時間以下保管する方法、又は３０℃以上９０℃以下で加熱処理する方法が挙げられる。 The method for manufacturing a polarizing element having a water content of 20 ° C. and a relative humidity of 30% or more and an equilibrium water content of a temperature of 20 ° C. and a relative humidity of 50% or less is not particularly limited. Examples thereof include a method of storing the polarizing element in an environment adjusted to a relative humidity range of 10 minutes or more and 3 hours or less, or a method of heat-treating at 30 ° C. or higher and 90 ° C. or lower.
上記含水率である偏光素子を製造する別の好ましい方法としては、偏光素子の少なくとも片面に保護フィルムを積層した積層体を、又は偏光素子を用いて構成した偏光板を、上記温度と上記相対湿度の範囲に調整された環境に、１０分以上１２０時間以下保管する方法、又は３０℃以上９０℃以下で加熱処理する方法が挙げられる。層間充填構成を採用する画像表示装置の作製時において、偏光板を画像表示セルに積層した画像表示パネルを、上記温度と上記相対湿度の範囲に調整された環境に１０分以上３時間以下保管又は３０℃以上９０℃以下で加熱した後に、前面板を貼合してもよい。 As another preferable method for producing a polarizing element having the water content, a laminated body in which a protective film is laminated on at least one surface of the polarizing element, or a polarizing plate formed by using the polarizing element is provided with the temperature and the relative humidity. Examples thereof include a method of storing in an environment adjusted to the above range for 10 minutes or more and 120 hours or less, or a method of heat treatment at 30 ° C. or more and 90 ° C. or less. At the time of manufacturing an image display device adopting an interlayer filling configuration, an image display panel in which a polarizing plate is laminated on an image display cell is stored in an environment adjusted to the above temperature and the above relative humidity range for 10 minutes or more and 3 hours or less. The front plate may be attached after heating at 30 ° C. or higher and 90 ° C. or lower.
偏光素子の含水率は、偏光素子単独又は偏光素子と保護フィルムとの積層体であって偏光板を構成するために用いられる材料段階で含水率が上記数値範囲となるように調整されていることが好ましい。偏光板を構成した後に含水率を調整した場合には、カールが大きくなりすぎ、画像表示セルへの貼合時に不具合が生じやすくなることがある。偏光板を構成する前の材料段階で上記含水率となるように調整されている偏光素子を用いて偏光板を構成することにより、含水率が上記数値範囲を満たす偏光素子を備える偏光板を容易に構成することができる。偏光板を画像表示セルに貼合した状態で、偏光板中における偏光素子の含水率が上記数値範囲となるように調整してもよい。この場合、偏光板は、画像表示セルに貼合されているのでカールが生じにくい。 The water content of the polarizing element shall be adjusted so that the water content is within the above numerical range at the material stage of the polarizing element alone or a laminate of the polarizing element and the protective film and used to form the polarizing plate. Is preferable. If the water content is adjusted after the polarizing plate is formed, the curl becomes too large, and problems may easily occur when the polarizing plate is attached to the image display cell. By constructing a polarizing plate using a polarizing element adjusted to have the above water content at the material stage before forming the polarizing plate, it is easy to obtain a polarizing plate having a polarizing element whose water content satisfies the above numerical range. Can be configured in. With the polarizing plate attached to the image display cell, the water content of the polarizing element in the polarizing plate may be adjusted to be within the above numerical range. In this case, since the polarizing plate is attached to the image display cell, curling is unlikely to occur.
（特徴（ｂ））
特徴（ｂ）を有する場合、偏光板の含水率は、温度２０℃相対湿度３０％の平衡含水率以上、かつ温度２０℃相対湿度５０％の平衡含水率以下である。偏光板の含水率は、好ましくは温度２０℃相対湿度４５％の平衡含水率以下であり、より好ましくは温度２０℃相対湿度４２％の平衡含水率以下であり、さらに好ましくは、温度２０℃相対湿度３８％の平衡含水率以下である。偏光板の含水率が温度２０℃相対湿度３０％の平衡含水率を下回ると、偏光板のハンドリング性が低下し、割れやすくなる。偏光板の含水率が、温度２０℃相対湿度５０％の平衡含水率を上回ると、偏光素子の透過率が低下しやすくなる。偏光板の含水率が高いと、ＰＶＡ系樹脂のポリエン化が進みやすくなるためと推定される。
(Feature (b))
When it has the feature (b), the water content of the polarizing plate is equal to or more than the equilibrium water content at a temperature of 20 ° C. and a relative humidity of 30%, and is equal to or less than the equilibrium water content at a temperature of 20 ° C. and a relative humidity of 50%. The water content of the polarizing plate is preferably equal to or less than the equilibrium water content of a temperature of 20 ° C. and a relative humidity of 45%, more preferably not more than the equilibrium water content of a temperature of 20 ° C. and a relative humidity of 42%, and further preferably relative to the temperature of 20 ° C. The humidity is 38% or less and is equal to or less than the equilibrium moisture content. When the water content of the polarizing plate is lower than the equilibrium water content of a temperature of 20 ° C. and a relative humidity of 30%, the handleability of the polarizing plate is lowered and the polarizing plate is easily cracked. When the water content of the polarizing plate exceeds the equilibrium water content of a temperature of 20 ° C. and a relative humidity of 50%, the transmittance of the polarizing element tends to decrease. It is presumed that when the water content of the polarizing plate is high, polyene formation of the PVA-based resin is likely to proceed.
偏光板の含水率が温度２０℃相対湿度３０％の平衡含水率以上、かつ温度２０℃相対湿度５０％の平衡含水率以下の範囲内であるかを確認する方法として、上記温度と上記相対湿度の範囲に調整された環境で保管し、一定時間質量の変化がなかった場合には環境と平衡に達しているとみなすことができ、又は上記温度と上記相対湿度の範囲に調整された環境の偏光板の平衡含水率を予め計算し、偏光板の含水率と予め計算した平衡含水率とを対比することにより確認することができる。 As a method of confirming whether the water content of the polarizing plate is within the range of the equilibrium water content of the temperature of 20 ° C. and the relative humidity of 30% and the equilibrium water content of the temperature of 20 ° C. and the relative humidity of 50% or less, the above temperature and the above relative humidity If it is stored in an environment adjusted to the range of, and if there is no change in mass for a certain period of time, it can be considered that it has reached equilibrium with the environment, or the environment adjusted to the above temperature and the above relative humidity range. It can be confirmed by calculating the equilibrium water content of the polarizing plate in advance and comparing the water content of the polarizing plate with the pre-calculated equilibrium water content.
含水率が温度２０℃相対湿度３０％の平衡含水率以上、かつ温度２０℃相対湿度５０％の平衡含水率以下である偏光板を製造する方法としては、特に限定されないが、例えば上記温度と上記相対湿度の範囲に調整された環境に偏光板を１０分以上３時間以下保管する方法、又は３０℃以上９０℃以下で加熱処理する方法が挙げられる。 The method for producing a polarizing plate having a water content of 20 ° C. and a relative humidity of 30% or more and an equilibrium water content of a temperature of 20 ° C. and a relative humidity of 50% or less is not particularly limited. Examples thereof include a method of storing the polarizing plate in an environment adjusted to a relative humidity range of 10 minutes or more and 3 hours or less, or a method of heat-treating at 30 ° C. or higher and 90 ° C. or lower.
層間充填構成を採用する画像表示装置の作製時において、偏光板を画像表示セルに積層した画像表示パネルを、上記温度と上記相対湿度の範囲に調整された環境に１０分以上３時間以下保管又は３０℃以上９０℃以下で加熱した後に、前面板を貼合してもよい。 At the time of manufacturing an image display device adopting an interlayer filling configuration, an image display panel in which a polarizing plate is laminated on an image display cell is stored in an environment adjusted to the above temperature and the above relative humidity range for 10 minutes or more and 3 hours or less. The front plate may be attached after heating at 30 ° C. or higher and 90 ° C. or lower.
＜接着剤層＞
偏光素子に保護フィルムを貼合するための接着剤層を形成する接着剤は、任意の適切な接着剤を用いることができる。本発明では、具体的には、接着剤として水系接着剤を用いる。
本発明で用いる水系接着剤には、酸化防止剤を含有していることが特徴であり、接着剤にフェノール系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤より選ばれる少なくとも一種の酸化防止剤を含有する。
上記接着剤の塗布時の厚みは、任意の適切な値に設定され得る。例えば、硬化後または加熱（乾燥）後に、所望の厚みを有する接着剤層が得られるように設定する。接着剤層の厚みは、好ましくは０．０１μｍ〜７μｍであり、より好ましくは０．０１μｍ〜５μｍであり、さらに好ましくは０．０１μｍ〜２μｍであり、最も好ましくは０．０１μｍ〜１μｍである。
<Adhesive layer>
Any suitable adhesive can be used as the adhesive for forming the adhesive layer for adhering the protective film to the polarizing element. Specifically, in the present invention, a water-based adhesive is used as the adhesive.
The water-based adhesive used in the present invention is characterized by containing an antioxidant, and the adhesive is at least one selected from a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant. Contains antioxidants.
The thickness of the adhesive at the time of application can be set to an arbitrary appropriate value. For example, after curing or heating (drying), an adhesive layer having a desired thickness is set so as to be obtained. The thickness of the adhesive layer is preferably 0.01 μm to 7 μm, more preferably 0.01 μm to 5 μm, still more preferably 0.01 μm to 2 μm, and most preferably 0.01 μm to 1 μm.
（酸化防止剤を含有する水系接着剤）
上記水系接着剤としては、任意の適切な水系接着剤が採用され得る。水系接着剤は、ポリアクリルアミド系樹脂；ポリビニルアルコール（ＰＶＡ）、およびエチレン−ビニルアルコール共重合体、（メタ）アクリル酸またはその無水物−ビニルアルコール共重合体等のビニルアルコール系樹脂；カルボキシビニル系樹脂；ポリビニルピロリドン；デンプン類；アルギン酸ナトリウム；またはポリエチレンオキシド系樹脂等の水溶性樹脂を含む。
中でも、ＰＶＡ系樹脂を含む水系接着剤（ＰＶＡ系接着剤）が好ましく用いられる。水系接着剤に含まれるＰＶＡ系樹脂の平均重合度は、接着性の点から、好ましくは１００〜５５００程度、さらに好ましくは１０００〜４５００である。平均鹸化度は、接着性の点から、好ましくは８５モル％〜１００モル％程度であり、さらに好ましくは９０モル％〜１００モル％である。
(Water-based adhesive containing antioxidant)
As the water-based adhesive, any suitable water-based adhesive can be adopted. Water-based adhesives are polyacrylamide-based resins; polyvinyl alcohol-based resins such as polyvinyl alcohol (PVA) and ethylene-vinyl alcohol copolymers, (meth) acrylic acid or its anhydride-vinyl alcohol copolymers; carboxyvinyl-based resins. Resins; polyvinylpyrrolidone; starches; sodium alginate; or water-soluble resins such as polyethylene oxide-based resins.
Of these, a water-based adhesive containing a PVA-based resin (PVA-based adhesive) is preferably used. The average degree of polymerization of the PVA-based resin contained in the water-based adhesive is preferably about 100 to 5500, more preferably 1000 to 4500, from the viewpoint of adhesiveness. The average saponification degree is preferably about 85 mol% to 100 mol%, and more preferably 90 mol% to 100 mol% from the viewpoint of adhesiveness.
上記水系接着剤に含まれるＰＶＡ系樹脂としては、アセトアセチル基を含有するものが好ましく、その理由は、ＰＶＡ系樹脂層と保護フィルムとの密着性に優れ、耐久性に優れているからである。アセトアセチル基含有ＰＶＡ系樹脂は、例えば、ＰＶＡ系樹脂とジケテンとを任意の方法で反応させることにより得られる。アセトアセチル基含有ＰＶＡ系樹脂のアセトアセチル基変性度は、代表的には０．１モル％以上であり、好ましくは０．１モル％〜２０モル％程度である。
上記水系接着剤の樹脂濃度は、好ましくは０．１重量％〜１５重量％であり、さらに好ましくは０．５重量％〜１０重量％である。
The PVA-based resin contained in the water-based adhesive preferably contains an acetoacetyl group, because the PVA-based resin layer and the protective film have excellent adhesion and durability. .. The acetoacetyl group-containing PVA-based resin can be obtained, for example, by reacting the PVA-based resin with diketene by an arbitrary method. The degree of acetoacetyl group modification of the acetoacetyl group-containing PVA resin is typically 0.1 mol% or more, preferably about 0.1 mol% to 20 mol%.
The resin concentration of the water-based adhesive is preferably 0.1% by weight to 15% by weight, more preferably 0.5% by weight to 10% by weight.
（架橋剤、溶剤）
本発明で好ましく用いることが出来る水溶性ＰＶＡ系接着剤は上記のＰＶＡ系樹脂の他に必要に応じて架橋剤を含有させることもできる。架橋剤としては公知の架橋剤を用いることができる。例えば、水溶性エポキシ化合物、ジアルデヒド化合物、イソシアネート化合物などが挙げられる。
(Crosslinking agent, solvent)
The water-soluble PVA-based adhesive that can be preferably used in the present invention may contain a cross-linking agent in addition to the above-mentioned PVA-based resin, if necessary. As the cross-linking agent, a known cross-linking agent can be used. For example, a water-soluble epoxy compound, a dialdehyde compound, an isocyanate compound and the like can be mentioned.
ＰＶＡ系樹脂がアセトアセチル基含有ＰＶＡ系樹脂である場合は、架橋剤としてグリオキサール、グリオキシル酸塩、メチロールメラミンのうちの何れかであることが好ましく、グリオキサール、グリオキシル酸塩の何れかであることが好ましく、グリオキサールであることが特に好ましい。接着剤および接着剤層における架橋剤の含有量は、ＰＶＡ系樹脂１００質量部に対し、０．１〜１００質量部であることが好ましく、０．５〜６０質量部であることがより好ましい。 When the PVA-based resin is an acetoacetyl group-containing PVA-based resin, the cross-linking agent is preferably any one of glyoxal, glyoxyphosphate, and methylolmelamine, and may be glyoxal or glyoxalate. Glyoxal is preferable, and glyoxal is particularly preferable. The content of the cross-linking agent in the adhesive and the adhesive layer is preferably 0.1 to 100 parts by mass, and more preferably 0.5 to 60 parts by mass with respect to 100 parts by mass of the PVA-based resin.
また、本発明の水溶性ＰＶＡ系接着剤は有機溶剤を含有していても構わない。その場合、水と混和性を有する点でアルコール類が好ましく、アルコール類の中でもメタノールまたはエタノールであることがより好ましい。
また、本発明では、酸化防止剤の一部は水に対する溶解度が低い反面、アルコールに対する溶解度は十分なものがある。その場合は、アルコールに溶解し、酸化防止剤のアルコール溶液を調製した後、酸化防止剤のアルコール溶液をＰＶＡ水溶液に添加し、接着剤を調製することも好ましい態様の一つである。
Further, the water-soluble PVA-based adhesive of the present invention may contain an organic solvent. In that case, alcohols are preferable because they are miscible with water, and methanol or ethanol is more preferable among the alcohols.
Further, in the present invention, some of the antioxidants have low solubility in water, but have sufficient solubility in alcohol. In that case, one of the preferred embodiments is to dissolve in alcohol to prepare an alcohol solution of the antioxidant, and then add the alcohol solution of the antioxidant to the PVA aqueous solution to prepare an adhesive.
（酸化防止剤）
本発明で用いる水系接着剤およびかかる水系接着剤から形成される水系接着剤層は、フェノール系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤からなる群より選ばれる少なくとも１種の酸化防止剤を含有する。
尚、水系接着剤から乾燥工程などを経て偏光素子と透明保護フィルムを積層する過程で、酸化防止剤の一部が水系接着剤から偏光素子などに移動していても構わない。すなわち、偏光素子は、酸化防止剤を含んでいてもよく、接着剤層に含まれる酸化防止剤と同じ種類の酸化防止剤を含んでいてもよい。
酸化防止剤には水溶性のものと難水溶性のものがあるが、どちらの酸化防止剤も本発明では使用することができる。難水溶性酸化防止剤を用いる場合は、偏光素子と透明保護フィルムを積層後に、ヘイズ上昇などが起きないように分散方法を工夫することが好ましい。
(Antioxidant)
The water-based adhesive used in the present invention and the water-based adhesive layer formed from such water-based adhesive are at least one type of oxidation selected from the group consisting of phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Contains an inhibitor.
In the process of laminating the polarizing element and the transparent protective film from the water-based adhesive through a drying step or the like, a part of the antioxidant may be transferred from the water-based adhesive to the polarizing element or the like. That is, the polarizing element may contain an antioxidant, or may contain the same type of antioxidant as the antioxidant contained in the adhesive layer.
There are water-soluble and poorly water-soluble antioxidants, and both antioxidants can be used in the present invention. When a poorly water-soluble antioxidant is used, it is preferable to devise a dispersion method so that haze does not increase after laminating the polarizing element and the transparent protective film.
酸化防止剤としては、特に限定されず、合成樹脂に配合されるような従来公知の酸化防止剤が好適なものとして挙げられる。例えば、ヒンダードフェノール系酸化防止剤、アミン系酸化防止剤、ラクトン系酸化防止剤、ヒドロキシルアミン系酸化防止剤等の一次酸化防止剤、および硫黄系酸化剤やリン系酸化剤等の二次酸化防止剤等が使用できる。 The antioxidant is not particularly limited, and conventionally known antioxidants such as those blended in synthetic resins can be mentioned as suitable ones. For example, primary antioxidants such as hindered phenolic antioxidants, amine-based antioxidants, lactone-based antioxidants, hydroxylamine-based antioxidants, and secondary oxidation of sulfur-based antioxidants and phosphorus-based antioxidants. Preventive agents etc. can be used.
ヒンダードフェノール系酸化防止剤としては、ヨシノックスＢＢ、ヨシノックス４２５（以上、三菱ケミカル株式会社製）、Ｉｒｇａｎｏｘ １０１０、Ｉｒｇａｎｏｘ １０３５、Ｉｒｇａｎｏｘ １０７６、Ｉｒｇａｎｏｘ １０９８、Ｉｒｇａｎｏｘ １１３５、Ｉｒｇａｎｏｘ １３３０、Ｉｒｇａｎｏｘ １５２０Ｌ、Ｉｒｇａｎｏｘ ２４５、Ｉｒｇａｎｏｘ ２５９、Ｉｒｇａｎｏｘ ３１１４、Ｉｒｇａｎｏｘ ５６５（以上、ＢＡＳＦジャパン株式会社製）、ＡＯ−２０、ＡＯ−３０、ＡＯ−４０、ＡＯ−５０、ＡＯ−５０Ｆ、ＡＯ−６０、ＡＯ−６０Ｇ、ＡＯ−７０、ＡＯ−８０、ＡＯ−３３０（以上、株式会社ＡＤＥＫＡ製）が挙げられる。ヒンダードフェノール系酸化防止剤としては、フェノール性水酸基の両側のオルト位にｔ−ブチル基を有するものが好ましい。 Examples of hindered phenolic antioxidants include Yoshinox BB, Yoshinox 425 (manufactured by Mitsubishi Chemical Corporation), Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1098, Irganox 1135, Irganox 1135, Irganox 1330, Irganox 1330, Irganox 1330, 259, Irganox 3114, Irganox 565 (above, manufactured by BASF Japan Ltd.), AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-70, AO -80 and AO-330 (all manufactured by ADEKA CORPORATION) can be mentioned. As the hindered phenolic antioxidant, those having t-butyl groups at the ortho positions on both sides of the phenolic hydroxyl group are preferable.
リン系酸化防止剤としては、ＰＥＰ−４Ｃ、ＰＥＰ−８、ＰＥＰ−８Ｗ、ＰＥＰ−２４Ｇ、ＰＥＰ−３６、ＰＥＰ−３６Ｚ、ＨＰ−１０、ＨＰ−２１１２、ＨＰ−２１１２ＲＧ（以上、株式会社ＡＤＥＫＡ製）が挙げられる。 Phosphorus-based antioxidants include PEP-4C, PEP-8, PEP-8W, PEP-24G, PEP-36, PEP-36Z, HP-10, HP-2112, HP-2112RG (all manufactured by ADEKA CORPORATION). ).
硫黄系酸化防止剤としては、ＡＯ−４１２Ｓ、ＡＯ−５０３（以上、株式会社ＡＤＥＫＡ製）が挙げられる。 Examples of the sulfur-based antioxidant include AO-412S and AO-503 (all manufactured by ADEKA Corporation).
これらの酸化防止剤は単独で使用してもよく、２種以上併用しても構わない。特に一次酸化防止剤であるヒンダードフェノール系酸化防止剤と、硫黄系酸化剤やリン系酸化剤等の二次酸化防止剤を組み合わせることで優れた耐候性や耐熱性が発揮される。 These antioxidants may be used alone or in combination of two or more. In particular, excellent weather resistance and heat resistance can be exhibited by combining a hindered phenol-based antioxidant, which is a primary antioxidant, with a secondary antioxidant such as a sulfur-based oxidant or a phosphorus-based oxidant.
接着剤がＰＶＡ系樹脂を含有する水系接着剤の場合、酸化防止剤の添加量は、ポリビニルアルコール系樹脂１００質量部に対し、０．３質量部以上１００質量部以下であることが好ましく、０．５〜５０質量部であることがより好ましく、１．０〜１０質量部であることが更に好ましい。 When the adhesive is a water-based adhesive containing a PVA-based resin, the amount of the antioxidant added is preferably 0.3 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the polyvinyl alcohol-based resin, and is 0. .5 to 50 parts by mass is more preferable, and 1.0 to 10 parts by mass is further preferable.
（その他の添加剤）
本発明で用いる接着剤には、その特性を損なわない範囲でその他の添加剤を含有していてもよい。耐熱性を向上させる観点から、例えば、尿素、尿素誘導体、チオ尿素及びチオ尿素誘導体から選ばれる少なくとも１種の尿素系化合物を含有させることも好ましい形態である。尿素系化合物には水溶性のものと難水溶性のものがあるが、どちらの尿素系化合物も本発明では使用することができる。難水溶性尿素系化合物を水溶性接着剤に用いる場合は、接着剤層を形成後、ヘイズ上昇などが起きないように分散方法を工夫することが好ましい。
(Other additives)
The adhesive used in the present invention may contain other additives as long as its properties are not impaired. From the viewpoint of improving heat resistance, it is also a preferable form to contain at least one urea compound selected from, for example, urea, a urea derivative, thiourea and a thiourea derivative. There are water-soluble and poorly water-soluble urea-based compounds, and both urea-based compounds can be used in the present invention. When a poorly water-soluble urea compound is used as a water-soluble adhesive, it is preferable to devise a dispersion method so that haze does not increase after the adhesive layer is formed.
接着剤がＰＶＡ系樹脂を含有する水系接着剤の場合、接着剤、および接着剤層における尿素系化合物の添加量は、ＰＶＡ１００質量部に対し、０．１〜４００質量部であることが好ましく、１〜２００質量部であることがより好ましく、３〜１００質量部であることが更に好ましい。 When the adhesive is a water-based adhesive containing a PVA-based resin, the amount of the adhesive and the urea-based compound added to the adhesive layer is preferably 0.1 to 400 parts by mass with respect to 100 parts by mass of PVA. It is more preferably 1 to 200 parts by mass, and further preferably 3 to 100 parts by mass.
（尿素誘導体）
尿素誘導体は、尿素分子の４つの水素原子の少なくとも１つが、置換基に置換された化合物である。この場合、置換基に特に制限はないが、炭素原子、水素原子および酸素原子よりなる置換基であることが好ましい。
(Urea derivative)
A urea derivative is a compound in which at least one of the four hydrogen atoms of a urea molecule is substituted with a substituent. In this case, the substituent is not particularly limited, but is preferably a substituent composed of a carbon atom, a hydrogen atom and an oxygen atom.
尿素誘導体の具体例として、１置換尿素として、メチル尿素、エチル尿素、プロピル尿素、ブチル尿素、イソブチル尿素、Ｎ−オクタデシル尿素、２−ヒドロキシエチル尿素、ヒドロキシ尿素、アセチル尿素、アリル尿素、２−プロピニル尿素、シクロヘキシル尿素、フェニル尿素、３−ヒドロキシフェニル尿素、（４−メトキシフェニル）尿素、ベンジル尿素、ベンゾイル尿素、ｏ−トリル尿素、ｐ−トリル尿素が挙げられる。
２置換尿素として、１，１−ジメチル尿素、１，３−ジメチル尿素、１，１−ジエチル尿素、１，３−ジエチル尿素、１，３−ビス（ヒドロキシメチル）尿素、１，３−ｔｅｒｔ−ブチル尿素、１，３−ジシクロヘキシル尿素、１，３−ジフェニル尿素、１，３−ビス（４−メトキシフェニル）尿素、１−アセチル−３−メチル尿素、２−イミダゾリジノン（エチレン尿素）、テトラヒドロ−２−ピリミジノン（プロピレン尿素）が挙げられる。
４置換尿素として、テトラメチル尿素、１，１，３，３−テトラエチル尿素、１，１，３，３−テトラブチル尿素、１，３−ジメトキシ−１，３−ジメチル尿素、１，３−ジメチル−２−イミダゾリジノン、１，３−ジメチル−３，４，５，６−テトラヒドロ−２（１Ｈ）−ピリミジノンが挙げられる。
Specific examples of urea derivatives include methyl urea, ethyl urea, propyl urea, butyl urea, isobutyl urea, N-octadecyl urea, 2-hydroxyethyl urea, hydroxyurea, acetylurea, allylurea, and 2-propynyl as monosubstituted ureas. Examples thereof include urea, cyclohexyl urea, phenyl urea, 3-hydroxyphenyl urea, (4-methoxyphenyl) urea, benzyl urea, benzoyl urea, o-tolyl urea and p-tolyl urea.
As the disubstituted urea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1-diethylurea, 1,3-diethylurea, 1,3-bis (hydroxymethyl) urea, 1,3-tert- Butylurea, 1,3-dicyclohexylurea, 1,3-diphenylurea, 1,3-bis (4-methoxyphenyl) urea, 1-acetyl-3-methylurea, 2-imidazolidinone (ethyleneurea), tetrahydro -2-Pyrimidinone (propylene urea) can be mentioned.
As tetra-substituted urea, tetramethylurea, 1,1,3,3-tetraethylurea, 1,1,3,3-tetrabutylurea, 1,3-dimethoxy-1,3-dimethylurea, 1,3-dimethyl- Examples thereof include 2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone.
（チオ尿素誘導体）
チオ尿素誘導体は、チオ尿素分子の４つの水素原子の少なくとも１つが、置換基に置換された化合物である。この場合、置換基に特に制限はないが、炭素原子、水素原子および酸素原子よりなる置換基であることが好ましい。
(Thiourea derivative)
A thiourea derivative is a compound in which at least one of the four hydrogen atoms of a thiourea molecule is substituted with a substituent. In this case, the substituent is not particularly limited, but is preferably a substituent composed of a carbon atom, a hydrogen atom and an oxygen atom.
チオ尿素誘導体の具体例として、１置換チオ尿素として、Ｎ−メチルチオ尿素、エチルチオ尿素、プロピルチオ尿素、イソプロピルチオ尿素、１−ブチルチオ尿素、シクロヘキシルチオ尿素、Ｎ−アセチルチオ尿素、Ｎ−アリルチオ尿素、（２−メトキシエチル）チオ尿素、Ｎ−フェニルチオ尿素、（４−メトキシフェニル）チオ尿素、Ｎ−（２−メトキシフェニル）チオ尿素、Ｎ−（１−ナフチル）チオ尿素、（２−ピリジル）チオ尿素、ｏ−トリルチオ尿素、ｐ−トリルチオ尿素が挙げられる。
２置換チオ尿素として、１，１−ジメチルチオ尿素、１，３−ジメチルチオ尿素、１，１−ジエチルチオ尿素、１，３−ジエチルチオ尿素、１，３−ジブチルチオ尿素、１，３−ジイソプロピルチオ尿素、１，３−ジシクロヘキシルチオ尿素、Ｎ，Ｎ−ジフェニルチオ尿素、Ｎ，Ｎ’−ジフェニルチオ尿素、１，３−ジ（ｏ−トリル）チオ尿素、１，３−ジ（ｐ−トリル）チオ尿素、１−ベンジル−３−フェニルチオ尿素、１−メチル−３−フェニルチオ尿素、Ｎ−アリル−Ｎ’−（２−ヒドロキシエチル）チオ尿素、エチレンチオ尿素が挙げられる。
３置換チオ尿素として、トリメチルチオ尿素が挙げられ、４置換チオ尿素として、テトラメチルチオ尿素、１，１，３，３−テトラエチルチオ尿素が挙げられる。
As a specific example of the thiourea derivative, as monosubstituted thiourea, N-methylthiourea, ethylthiourea, propylthiourea, isopropylthiourea, 1-butylthiourea, cyclohexylthiourea, N-acetylthiourea, N-allylthiourea, (2). -Methoxyethyl) thiourea, N-phenylthiourea, (4-methoxyphenyl) thiourea, N- (2-methoxyphenyl) thiourea, N- (1-naphthyl) thiourea, (2-pyridyl) thiourea, Examples thereof include o-tolylthiourea and p-tolylthiourea.
As the disubstituted thiourea, 1,1-dimethylthiourea, 1,3-dimethylthiourea, 1,1-diethylthiourea, 1,3-diethylthiourea, 1,3-dibutylthiourea, 1,3-diisopropylthiourea, 1 , 3-Dicyclohexylthiourea, N, N-diphenylthiourea, N, N'-diphenylthiourea, 1,3-di (o-tolyl) thiourea, 1,3-di (p-tolyl) thiourea, Examples thereof include 1-benzyl-3-phenylthiourea, 1-methyl-3-phenylthiourea, N-allyl-N'-(2-hydroxyethyl) thiourea and ethylenethiourea.
Examples of the 3-substituted thiourea include trimethylthiourea, and examples of the 4-substituted thiourea include tetramethylthiourea and 1,1,3,3-tetraethylthiourea.
尿素系化合物の中では、層間充填構成の画像表示装置に用いた時に、高温環境下での透過率の低下が抑制されて、且つ偏光度の低下が少ない点（偏光板をクロスニコル配置したときの光抜けが抑制される点）で、尿素誘導体またはチオ尿素誘導体が好ましく、尿素誘導体がより好ましい。尿素誘導体の中でも、１置換尿素または２置換尿素であることが好ましく、１置換体であることがより好ましい。２置換尿素には１，１−置換尿素と１，３−置換尿素があるが、１，３−置換尿素がより好ましい。 Among the urea compounds, when used in an image display device having an interlayer filling configuration, the decrease in transmittance in a high temperature environment is suppressed and the decrease in degree of polarization is small (when the polarizing plate is arranged in cross Nicol). A urea derivative or a thiourea derivative is preferable, and a urea derivative is more preferable. Among the urea derivatives, mono-substituted urea or di-substituted urea is preferable, and mono-substituted urea is more preferable. The di-substituted urea includes 1,1-substituted urea and 1,3-substituted urea, but 1,3-substituted urea is more preferable.
［透明保護フィルム］
本発明において用いられる透明保護フィルム（以降、単に「保護フィルム」とも称す。
）は、偏光素子の少なくとも片面側に水系接着剤層を介して貼り合わされる。この透明保護フィルムは偏光素子の片面又は両面に貼り合わされるが、両面に貼り合わされていることがより好ましい。一形態において、保護フィルムは酸化防止剤を含有する水系接着剤層を介して偏光素子に貼り合わされている。本発明でいう透明は、可視光の透過率が６０％以上であることを意味し、好ましくは８０％以上であることを意味し、特に好ましくは９０％以上であることを意味する。
また、偏光素子の両面に接着剤層を介して保護フィルムが貼り合わされている構成において、偏光素子両面の接着剤層の内、片面の接着剤層のみが酸化防止剤を含有する上記水系接着剤層であっても構わないが、両面の接着剤層が共に酸化防止剤を含有する上記水系接着剤層であることがより好ましい。
[Transparent protective film]
The transparent protective film used in the present invention (hereinafter, also simply referred to as "protective film".
) Is bonded to at least one side of the polarizing element via an aqueous adhesive layer. This transparent protective film is attached to one side or both sides of the polarizing element, but it is more preferable that the transparent protective film is attached to both sides. In one form, the protective film is attached to the polarizing element via a water-based adhesive layer containing an antioxidant. Transparency as used in the present invention means that the transmittance of visible light is 60% or more, preferably 80% or more, and particularly preferably 90% or more.
Further, in a configuration in which a protective film is bonded to both sides of the polarizing element via an adhesive layer, the above-mentioned water-based adhesive in which only one of the adhesive layers on both sides of the polarizing element contains an antioxidant. Although it may be a layer, it is more preferable that the adhesive layers on both sides are both water-based adhesive layers containing an antioxidant.
偏光素子の両面に接着剤層を介して保護フィルムが貼り合わされている構成において、偏光素子両面の接着剤層の内、片面の接着剤層のみが酸化防止剤を含有する上記水系接着剤層である場合には、もう片方の接着剤層として用いる接着剤は、任意の適切な接着剤を用いることができ、具体的には、水系接着剤、溶剤系接着剤、活性エネルギー線硬化型などを用いることができる。 In a configuration in which a protective film is bonded to both sides of the polarizing element via an adhesive layer, only one of the adhesive layers on both sides of the polarizing element is the water-based adhesive layer containing an antioxidant. In some cases, the adhesive used as the other adhesive layer can be any suitable adhesive, specifically, a water-based adhesive, a solvent-based adhesive, an active energy ray-curable type, or the like. Can be used.
保護フィルムは、同時に他の光学的機能を有していてもよく、更に他の層が積層された積層構造に形成されていてもよい。
この時の保護フィルムの膜厚は光学特性の観点から薄いものが好ましいが、薄すぎると強度が低下し加工性に劣るものとなる。適切な膜厚としては、５〜１００μｍであり、好ましくは１０〜８０μｍ、より好ましくは１５〜７０μｍである。
The protective film may have other optical functions at the same time, and may be formed in a laminated structure in which other layers are laminated.
The film thickness of the protective film at this time is preferably thin from the viewpoint of optical characteristics, but if it is too thin, the strength is lowered and the workability is inferior. The appropriate film thickness is 5 to 100 μm, preferably 10 to 80 μm, and more preferably 15 to 70 μm.
保護フィルムは、セルロースアシレート系樹脂フィルム、ポリカーボネート系樹脂からなるフィルム、ノルボルネンなどシクロオレフィン系樹脂からなるフィルム、（メタ）アクリル系重合体フィルム、ポリエチレンテレフタレートなどのポリエステル系樹脂フィルムなどのフィルムを用いることができる。
偏光素子の両面に保護フィルムを有する構成の場合、ＰＶＡ接着剤などの水系接着剤を用いて貼合する場合は透湿度の点で少なくとも片側の保護フィルムはセルロースアシレート系フィルムまたは（メタ）アクリル系重合体フィルムの何れかであることが好ましく、中でもセルロースアシレートフィルムが好ましい。
As the protective film, a film such as a cellulose acylate resin film, a polycarbonate resin film, a cycloolefin resin film such as norbornene, a (meth) acrylic polymer film, or a polyester resin film such as polyethylene terephthalate is used. be able to.
In the case of a configuration having protective films on both sides of the polarizing element, when bonding using a water-based adhesive such as PVA adhesive, the protective film on at least one side is a cellulose acylate film or (meth) acrylic in terms of moisture permeability. Any of the polymer films is preferable, and a cellulose acylate film is particularly preferable.
少なくとも一方の保護フィルムとしては、視野角補償などの目的で位相差機能を備えていてもよく、その場合、フィルム自身が位相差機能を有していてもよく、位相差層を別に有していてもよく、両者の組み合わせであってもよい。
なお、位相差機能を備えるフィルムは接着剤を介して、直接偏光素子に貼合される構成について説明したが、偏光素子に貼合された別の保護フィルムを介して粘着剤または接着剤を介して貼合された構成であっても構わない。
At least one protective film may have a retardation function for the purpose of compensating the viewing angle, and in that case, the film itself may have a retardation function and has a separate retardation layer. It may be a combination of both.
Although the configuration in which the film having the retardation function is directly bonded to the polarizing element via an adhesive has been described, the film is directly bonded to the polarizing element via an adhesive or an adhesive via another protective film bonded to the polarizing element. It may be a structure in which they are pasted together.
（その他の機能層）
先に記載したように、近年、偏光板の薄型化の要請に応えるために、偏光素子の片面にのみ保護フィルムを有する偏光板（以降、「片面保護フィルム付き偏光板」とも称す。）が開発されている。
このような構成において物理強度を上げることなどを目的として、偏光素子の保護フィルムを有さない面に硬化層（機能層）を積層する試みがなされている。（例えば特開２０１１−２２１１８５号公報）
(Other functional layers)
As described above, in recent years, in order to meet the demand for thinner polarizing plates, a polarizing plate having a protective film on only one side of the polarizing element (hereinafter, also referred to as "polarizing plate with a single-sided protective film") has been developed. Has been done.
Attempts have been made to laminate a cured layer (functional layer) on a surface of a polarizing element that does not have a protective film, for the purpose of increasing the physical strength in such a configuration. (For example, Japanese Patent Application Laid-Open No. 2011-221185)
本発明ではこのような硬化層（機能層）に酸化防止剤を含有させて酸化防止剤含有層を形成することも好ましい態様の一つである。通常このような硬化層は有機溶剤を含む硬化性組成物から形成されるが、特開２０１７−０７５９８６号公報の段落［００２０］〜［００４２］には活性エネルギー線硬化性樹脂組成物の水性溶液から、このような硬化層を形成する方法が記載されている。酸化防止剤として、水溶性、難水溶性のものがあり、適宜選択することで酸化防止剤含有層を形成することが可能である。 In the present invention, it is also one of the preferred embodiments that the hardened layer (functional layer) contains an antioxidant to form an antioxidant-containing layer. Normally, such a cured layer is formed from a curable composition containing an organic solvent, but paragraphs [0020] to [0042] of JP-A-2017-075986 describe an aqueous solution of the active energy ray-curable resin composition. Therefore, a method for forming such a cured layer is described. As the antioxidant, there are water-soluble and poorly water-soluble ones, and it is possible to form an antioxidant-containing layer by appropriately selecting them.
また、本発明ではこのような硬化層に尿素系化合物を含有させて尿素系化合物含有層として構成することも好ましい態様の一つである。通常このような硬化層は有機溶剤を含む硬化性組成物から形成されるが、特開２０１７−０７５９８６号公報の段落［００２０］〜［００４２］には活性エネルギー線硬化性高分子組成物の水性溶液から、このような硬化層を形成する方法が記載されている。尿素系化合物は水溶性のものが多いので、このような組成物に水溶性の尿素系化合物を含有させ、尿素系化合物含有層を形成するのも本実施形態の好ましい態様の一つである。 Further, in the present invention, it is also one of the preferable embodiments that such a cured layer contains a urea-based compound to form a urea-based compound-containing layer. Normally, such a cured layer is formed from a curable composition containing an organic solvent, but paragraphs [0020] to [0042] of JP-A-2017-075986 describe the aqueous active energy ray-curable polymer composition. A method of forming such a cured layer from a solution is described. Since many urea-based compounds are water-soluble, it is one of the preferred embodiments of the present embodiment to include a water-soluble urea-based compound in such a composition to form a urea-based compound-containing layer.
なお、酸化防止剤と尿素系化合物とを併用して、その他の機能層を形成することも有用な技術である。 It is also a useful technique to form other functional layers by using an antioxidant and a urea compound in combination.
［偏光板の製造方法］
本実施形態の偏光板の製造方法は、偏光素子と、透明保護フィルムとを、酸化防止剤を含有する水系接着剤を用いて積層する積層工程と、含水率調整工程と、を有する。含水率調整工程では、特徴（ａ）を有する偏光板を製造する場合は、偏光素子の含水率が温度２０℃相対湿度３０％の平衡含水率以上、かつ温度２０℃相対湿度５０％の平衡含水率以下となるように偏光素子の含水率を調整する。偏光素子の含水率は、上述の偏光素子の含水率の記載に従って調整することができる。含水率調整工程では、特徴（ｂ）を有する偏光板を製造する場合は、偏光板の含水率が温度２０℃相対湿度３０％の平衡含水率以上、かつ温度２０℃相対湿度５０％の平衡含水率以下となるように偏光板の含水率を調整する。偏光板の含水率は、上述の偏光板の含水率の記載に従って調整することができる。積層工程及び含水率調整工程の順番は限定されることはなく、また積層工程と含水率調整工程とが並行して行われてもよい。
[Manufacturing method of polarizing plate]
The method for manufacturing a polarizing plate of the present embodiment includes a laminating step of laminating a polarizing element and a transparent protective film using an aqueous adhesive containing an antioxidant, and a water content adjusting step. In the water content adjusting step, when producing a polarizing plate having the characteristic (a), the water content of the polarizing element is equal to or higher than the equilibrium water content of a temperature of 20 ° C. and a relative humidity of 30%, and the equilibrium water content of the temperature of 20 ° C. and a relative humidity of 50%. Adjust the water content of the polarizing element so that it is less than or equal to the rate. The water content of the polarizing element can be adjusted according to the above description of the water content of the polarizing element. In the water content adjusting step, when producing a polarizing plate having the characteristic (b), the water content of the polarizing plate is equal to or higher than the equilibrium water content of a temperature of 20 ° C. and a relative humidity of 30%, and the equilibrium water content of a temperature of 20 ° C. and a relative humidity of 50%. Adjust the water content of the polarizing plate so that it is less than or equal to the rate. The water content of the polarizing plate can be adjusted according to the above description of the water content of the polarizing plate. The order of the laminating step and the water content adjusting step is not limited, and the laminating step and the water content adjusting step may be performed in parallel.
前述したその他の機能層は、例えば、偏光素子と保護フィルムとを酸化防止剤を含有する水系接着剤で積層したのち、さらに偏光素子の他方の面に酸化防止剤含有溶液を塗布、乾燥もしくは活性エネルギー線による硬化工程を経て偏光素子の片面に酸化防止剤層を形成することにより、含水率調整前の偏光素子を得ることができる。なお、これらの工程は、並行して行われてもよい。さらに含水率調整工程においても、並行して行われてもよく、これらの一連の工程の順番は限定されない。これらの方法は、尿素系化合物を含有する層を形成する方法にも、同様に適用される。 In the other functional layer described above, for example, a polarizing element and a protective film are laminated with an aqueous adhesive containing an antioxidant, and then an antioxidant-containing solution is further applied to the other surface of the polarizing element, dried or activated. By forming an antioxidant layer on one side of the polarizing element through a curing step using energy rays, it is possible to obtain a polarizing element before adjusting the water content. In addition, these steps may be performed in parallel. Further, the water content adjusting step may be performed in parallel, and the order of these series of steps is not limited. These methods are similarly applied to the method of forming a layer containing a urea-based compound.
［画像表示装置の構成］
本発明の偏光板は、液晶表示装置や有機ＥＬ表示装置等の各種画像表示装置に用いられる。画像表示装置について、偏光板の両面が空気層以外の層が接するように構成されている層間充填構成である場合には、高温環境下で透過率が低下しやすい。本発明の偏光板を用いた画像表示装置においては、層間充填構成であっても、高温環境下での偏光板の透過率の低下を抑制することができる。画像表示装置としては、画像表示セルと、画像表示セルの視認側表面に積層された第１粘着剤層と、第１粘着剤層の視認側表面に積層された偏光板とを有する構成が例示される。かかる画像表示装置は、偏光板の視認側表面に積層された第２粘着剤層と、第２粘着剤層の表面に積層された透明部材とをさらに有してもよい。特に、本発明の偏光板は、画像表示装置の視認側に透明部材が配置され、偏光板と画像表示セルとが第１粘着剤層により貼り合わされ、偏光板と透明部材とが第２粘着剤層により貼り合わせられた層間充填構成を有する画像表示装置に好適に用いられる。本明細書においては、第１粘着剤層及び第２粘着剤層のいずれか一方又は両者を、単に「粘着剤層」と称する場合がある。なお、偏光板と画像表示セルとの貼り合わせや、偏光板と透明部材との貼り合わせに用いられる部材としては、粘着剤層に限定されることはなく接着剤層であってもよい。
[Configuration of image display device]
The polarizing plate of the present invention is used in various image display devices such as a liquid crystal display device and an organic EL display device. When the image display device has an interlayer filling structure in which both sides of the polarizing plate are in contact with layers other than the air layer, the transmittance tends to decrease in a high temperature environment. In the image display device using the polarizing plate of the present invention, it is possible to suppress a decrease in the transmittance of the polarizing plate in a high temperature environment even with an interlayer filling configuration. An example of the image display device is a configuration having an image display cell, a first pressure-sensitive adhesive layer laminated on the visible side surface of the image display cell, and a polarizing plate laminated on the visible side surface of the first pressure-sensitive adhesive layer. Will be done. Such an image display device may further include a second pressure-sensitive adhesive layer laminated on the visible side surface of the polarizing plate, and a transparent member laminated on the surface of the second pressure-sensitive adhesive layer. In particular, in the polarizing plate of the present invention, a transparent member is arranged on the visual side of the image display device, the polarizing plate and the image display cell are bonded by the first pressure-sensitive adhesive layer, and the polarizing plate and the transparent member are bonded together by the second pressure-sensitive adhesive. It is suitably used for an image display device having an interlayer filling structure in which layers are bonded together. In the present specification, either one or both of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer may be simply referred to as a "sticky agent layer". The member used for bonding the polarizing plate and the image display cell and for bonding the polarizing plate and the transparent member is not limited to the pressure-sensitive adhesive layer, and may be an adhesive layer.
＜画像表示セル＞
画像表示セルとしては、液晶セルや有機ＥＬセルが挙げられる。液晶セルとしては、外光を利用する反射型液晶セル、バックライト等の光源からの光を利用する透過型液晶セル、外部からの光と光源からの光の両者を利用する半透過半反射型液晶セルのいずれを用いてもよい。液晶セルが光源からの光を利用するものである場合、画像表示装置（液晶表示装置）は、画像表示セル（液晶セル）の視認側と反対側にも偏光板が配置され、さらに光源が配置される。光源側の偏光板と液晶セルとは、適宜の粘着剤層を介して貼り合せられていることが好ましい。液晶セルの駆動方式としては、例えばＶＡモード、ＩＰＳモード、ＴＮモード、ＳＴＮモードやベンド配向（π型）等の任意なタイプのものを用いうる。
<Image display cell>
Examples of the image display cell include a liquid crystal cell and an organic EL cell. The liquid crystal cell includes a reflective liquid crystal cell that uses external light, a transmissive liquid crystal cell that uses light from a light source such as a backlight, and a semi-transmissive semi-reflective type that uses both external light and light from the light source. Any liquid crystal cell may be used. When the liquid crystal cell uses the light from the light source, the image display device (liquid crystal display device) has a polarizing plate arranged on the side opposite to the viewing side of the image display cell (liquid crystal cell), and further arranges the light source. Will be done. It is preferable that the polarizing plate on the light source side and the liquid crystal cell are bonded to each other via an appropriate adhesive layer. As the driving method of the liquid crystal cell, for example, any type such as VA mode, IPS mode, TN mode, STN mode and bend orientation (π type) can be used.
有機ＥＬセルとしては、透明基板上に透明電極と有機発光層と金属電極とを順に積層して発光体（有機エレクトロルミネセンス発光体）を形成したもの等が好適に用いられる。
有機発光層は、種々の有機薄膜の積層体であり、例えば、トリフェニルアミン誘導体等からなる正孔注入層と、アントラセン等の蛍光性の有機固体からなる発光層との積層体や、これらの発光層とペリレン誘導体等からなる電子注入層の積層体、あるいは正孔注入層、発光層、および電子注入層の積層体等、種々の層構成が採用され得る。
As the organic EL cell, a cell in which a transparent electrode, an organic light emitting layer, and a metal electrode are sequentially laminated on a transparent substrate to form a light emitting body (organic electroluminescence light emitting body) or the like is preferably used.
The organic light emitting layer is a laminate of various organic thin films, for example, a laminate of a hole injection layer made of a triphenylamine derivative or the like and a light emitting layer made of a fluorescent organic solid such as anthracene, or a laminate of these. Various layer configurations can be adopted, such as a laminate of an electron-injected layer composed of a light-emitting layer and a perylene derivative, or a laminate of a hole-injected layer, a light-emitting layer, and an electron-injected layer.
＜画像表示セルと偏光板の貼り合せ＞
画像表示セルと偏光板との貼り合せには、粘着剤層（粘着シート）が好適に用いられる。中でも、偏光板の一方の面に粘着剤層が付設された粘着剤層付き偏光板を画像表示セルと貼り合わせる方法が、作業性等の観点から好ましい。偏光板への粘着剤層の付設は、適宜な方式で行いうる。その例としては、例えば、トルエンや酢酸エチル等の適宜な溶剤の単独物または混合物からなる溶剤にベースポリマーまたはその組成物を溶解あるいは分散させた１０〜４０重量％程度の粘着剤溶液を調製し、それを流延方式や塗工方式等の適宜な展開方式で偏光板上に直接付設する方式、あるいは前記に準じセパレータ上に粘着剤層を形成してそれを偏光板に移着する方式などが挙げられる。
<Attachment of image display cell and polarizing plate>
An adhesive layer (adhesive sheet) is preferably used for bonding the image display cell and the polarizing plate. Above all, a method in which a polarizing plate with an adhesive layer having an adhesive layer attached to one surface of the polarizing plate is attached to an image display cell is preferable from the viewpoint of workability and the like. The pressure-sensitive adhesive layer can be attached to the polarizing plate by an appropriate method. As an example, for example, a pressure-sensitive adhesive solution of about 10 to 40% by weight is prepared by dissolving or dispersing the base polymer or its composition in a solvent composed of a single substance or a mixture of appropriate solvents such as toluene and ethyl acetate. , A method of directly attaching it on a polarizing plate by an appropriate developing method such as a casting method or a coating method, or a method of forming an adhesive layer on a separator according to the above and transferring it to the polarizing plate, etc. Can be mentioned.
＜粘着剤層＞
粘着剤層については、特開２０１８−０２５７６５号公報の段落［０１０３］〜［０１４３］に記載されており、本発明ではこれらの粘着剤を用いることができる。
<Adhesive layer>
The pressure-sensitive adhesive layer is described in paragraphs [0103] to [0143] of JP-A-2018-025765, and these pressure-sensitive adhesives can be used in the present invention.
＜透明部材＞
画像表示装置の視認側に配置される透明部材としては、前面板（ウインドウ層）やタッチパネル等が挙げられる。前面板としては、適宜の機械強度および厚みを有する透明板が用いられる。このような前面板としては、例えばアクリル系樹脂やポリカーボネート系樹脂のような透明樹脂板、あるいはガラス板等が挙げられる。前面板の視認側には反射防止層などの機能層が積層されていても構わない。また、前面板が透明樹脂板の場合は、物理強度を上げるためにハードコート層や、透湿度を下げるために低透湿層が積層されていても構わない。
タッチパネルとしては、抵抗膜方式、静電容量方式、光学方式、超音波方式等の各種タッチパネルや、タッチセンサー機能を備えるガラス板や透明樹脂板等が用いられる。透明部材として静電容量方式のタッチパネルが用いられる場合、タッチパネルよりもさらに視認側に、ガラスや透明樹脂板からなる前面板が設けられることが好ましい。
<Transparent member>
Examples of the transparent member arranged on the visual side of the image display device include a front plate (window layer) and a touch panel. As the front plate, a transparent plate having appropriate mechanical strength and thickness is used. Examples of such a front plate include a transparent resin plate such as an acrylic resin or a polycarbonate resin, or a glass plate. A functional layer such as an antireflection layer may be laminated on the visible side of the front plate. When the front plate is a transparent resin plate, a hard coat layer may be laminated to increase the physical strength, or a low moisture permeability layer may be laminated to reduce the moisture permeability.
As the touch panel, various touch panels such as a resistive film method, a capacitance method, an optical method, and an ultrasonic method, a glass plate having a touch sensor function, a transparent resin plate, and the like are used. When a capacitive touch panel is used as the transparent member, it is preferable that a front plate made of glass or a transparent resin plate is provided on the visual side of the touch panel.
＜偏光板と透明部材の貼り合せ＞
偏光板と透明部材との貼り合せには、粘着剤またはＵＶ硬化型の接着剤が好適に用いられる。粘着剤が用いられる場合、粘着剤の付設は適宜な方式で行い得る。具体的な付設方法としては、例えば、前述の画像表示セルと偏光板の貼り合せで用いた粘着剤層の付設方法が挙げられる。
<Lasting of polarizing plate and transparent member>
A pressure-sensitive adhesive or a UV-curable adhesive is preferably used for bonding the polarizing plate and the transparent member. When a pressure-sensitive adhesive is used, the pressure-sensitive adhesive can be attached by an appropriate method. As a specific attachment method, for example, the attachment method of the pressure-sensitive adhesive layer used for bonding the image display cell and the polarizing plate described above can be mentioned.
ＵＶ硬化型の接着剤を用いる場合、硬化前の接着剤溶液の広がりを防止する目的で、画像表示パネル上の周縁部を囲むようにダム材が設けられ、ダム材上に透明部材を載置して、接着剤溶液を注入する方法が好適に用いられる。接着剤溶液の注入後は、必要に応じて位置合わせおよび脱泡が行われた後、ＵＶ光が照射されて硬化が行われる。 When a UV curable adhesive is used, a dam material is provided so as to surround the peripheral edge on the image display panel in order to prevent the adhesive solution from spreading before curing, and a transparent member is placed on the dam material. Then, the method of injecting the adhesive solution is preferably used. After the injection of the adhesive solution, alignment and defoaming are performed as necessary, and then UV light is irradiated to cure the adhesive solution.
以下、実施例に基づいて本発明を具体的に説明する。以下の実施例に示す材料、試薬、物質量とその割合、操作等は本発明の趣旨を逸脱しない限り適宜変更することができる。
従って、本発明は以下の実施例に限定され制限されるものではない。
Hereinafter, the present invention will be specifically described based on Examples. The materials, reagents, amounts of substances and their ratios, operations, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention.
Therefore, the present invention is not limited to the following examples.
（偏光素子１の作製）
平均重合度約２,４００、ケン化度９９．９モル％以上であるポリビニルアルコールからなる厚さ４０μｍのポリビニルアルコールフィルムを、乾式で約５倍に一軸延伸し、さらに緊張状態を保ったまま、６０℃の純水に１分間浸漬した後、ヨウ素／ヨウ化カリウム／水の重量比が０．０５／５／１００の水溶液に２８℃で６０秒間浸漬した。その後、ヨウ化カリウム／ホウ酸／水の重量比が８．５／８．５／１００の水溶液に７２℃で３００秒間浸漬した。引き続き２６℃の純水で２０秒間洗浄した後、６５℃で乾燥して、ポリビニルアルコールにヨウ素が吸着配向された厚み１５μｍの偏光素子を得た。
(Manufacturing of polarizing element 1)
A 40 μm-thick polyvinyl alcohol film composed of polyvinyl alcohol having an average degree of polymerization of about 2,400 and a saponification degree of 99.9 mol% or more was uniaxially stretched about 5 times by a dry method, and further maintained in a tense state. After immersing in pure water at 60 ° C. for 1 minute, it was immersed in an aqueous solution having a weight ratio of iodine / potassium iodide / water of 0.05 / 5/100 at 28 ° C. for 60 seconds. Then, it was immersed in an aqueous solution having a weight ratio of potassium iodide / boric acid / water of 8.5 / 8.5 / 100 at 72 ° C. for 300 seconds. Subsequently, the mixture was washed with pure water at 26 ° C. for 20 seconds and then dried at 65 ° C. to obtain a polarizing element having a thickness of 15 μm in which iodine was adsorbed and oriented on polyvinyl alcohol.
（接着剤用ＰＶＡ溶液の調製）
アセトアセチル基を含有する変性ＰＶＡ系樹脂（三菱ケミカル（株）製：ゴーセネックスＺ−４１０）５０ｇを９５０ｇの純水に溶解し、９０℃で２時間加熱後常温に冷却し、接着剤用ＰＶＡ溶液を得た。
(Preparation of PVA solution for adhesive)
50 g of a modified PVA resin containing an acetoacetyl group (manufactured by Mitsubishi Chemical Corporation: Gosenex Z-410) is dissolved in 950 g of pure water, heated at 90 ° C. for 2 hours, cooled to room temperature, and cooled to room temperature to provide a PVA solution for adhesives. Got
（酸化防止剤溶液の調製）
表１に従って、エタノール１００ｇにフェノール系酸化防止剤である、Ｉｒｇａｎｏｘ １０１０（ＢＡＳＦジャパン株式会社製）を０．２５ｇ添加し、フェノール系酸化防止剤のエタノール溶液（溶液１）を調製した。
(Preparation of antioxidant solution)
According to Table 1, 0.25 g of Irganox 1010 (manufactured by BASF Japan Ltd.), which is a phenolic antioxidant, was added to 100 g of ethanol to prepare an ethanol solution (solution 1) of the phenolic antioxidant.
表１に従って、エタノール１００ｇにフェノール系酸化防止剤である、Ｉｒｇａｎｏｘ１１３５（ＢＡＳＦジャパン株式会社製）を０．２５ｇ添加し、フェノール系酸化防止剤のエタノール溶液（溶液２）を調製した。 According to Table 1, 0.25 g of Irganox1135 (manufactured by BASF Japan Ltd.), which is a phenolic antioxidant, was added to 100 g of ethanol to prepare an ethanol solution (solution 2) of the phenolic antioxidant.
（偏光板用接着剤１の調製）
上記で調製した、接着剤用ＰＶＡ溶液、溶液１、および純水を、ＰＶＡ濃度３．０％、エタノール濃度３０％、Ｉｒｇａｎｏｘ １０１０濃度０．０７５％になるように配合し、偏光板用接着剤１を得た。偏光板用接着剤１中の酸化防止剤の含有量は、ＰＶＡ １００質量部に対し、２．５質量部であった。
(Preparation of Adhesive 1 for Polarizing Plate)
The PVA solution for adhesive, solution 1, and pure water prepared above are blended so as to have a PVA concentration of 3.0%, an ethanol concentration of 30%, and an Irganox 1010 concentration of 0.075%, and an adhesive for polarizing plates. I got 1. The content of the antioxidant in the polarizing plate adhesive 1 was 2.5 parts by mass with respect to 100 parts by mass of PVA.
（偏光板用接着剤２の調製）
同様に、上記で調製した、接着剤用ＰＶＡ溶液、溶液２、および純水を、ＰＶＡ濃度３．０％、エタノール濃度３０％、Ｉｒｇａｎｏｘ １１３５濃度０．０７５％になるように配合し、偏光板用接着剤２を得た。偏光板用接着剤２中の酸化防止剤の含有量は、ＰＶＡ １００質量部に対し、２．５質量部であった。
(Preparation of Adhesive 2 for Polarizing Plate)
Similarly, the PVA solution for adhesive, solution 2, and pure water prepared above are blended so as to have a PVA concentration of 3.0%, an ethanol concentration of 30%, and an Irganox 1135 concentration of 0.075%, and a polarizing plate is used. Adhesive 2 for use was obtained. The content of the antioxidant in the polarizing plate adhesive 2 was 2.5 parts by mass with respect to 100 parts by mass of PVA.
（偏光板用接着剤３の調製）
同様に、接着剤用ＰＶＡ溶液、純水およびエタノールを、ＰＶＡ濃度３．０％、エタノール濃度３０％になるように配合し、偏光板用接着剤３を得た。
(Preparation of Adhesive 3 for Polarizing Plate)
Similarly, a PVA solution for an adhesive, pure water and ethanol were blended so as to have a PVA concentration of 3.0% and an ethanol concentration of 30% to obtain an adhesive 3 for a polarizing plate.
（セルロースアシレートフィルムの鹸化）
市販のセルロースアシレートフィルムＴＤ４０（富士フイルム（株）製：膜厚４０μｍ）を、５５℃に保った１．５ｍｏｌ／ＬのＮａＯＨ水溶液（鹸化液）に２分間浸漬した後、フィルムを水洗し、その後、２５℃の０．０５ｍｏｌ／Ｌの硫酸水溶液に３０秒浸漬した後、更に水洗浴を３０秒流水下に通して、フィルムを中性の状態にした。そして、エアナイフによる水切りを３回繰り返し、水を落とした後に７０℃の乾燥ゾーンに１５秒間滞留させて乾燥し、鹸化処理したフィルムを作製した。
(Saponification of cellulose acylate film)
A commercially available cellulose acylate film TD40 (manufactured by FUJIFILM Corporation: film thickness 40 μm) was immersed in a 1.5 mol / L NaOH aqueous solution (saponification solution) maintained at 55 ° C. for 2 minutes, and then the film was washed with water. Then, after immersing the film in a 0.05 mol / L sulfuric acid aqueous solution at 25 ° C. for 30 seconds, the film was further passed through a water washing bath for 30 seconds under running water to neutralize the film. Then, draining with an air knife was repeated three times, and after the water was dropped, the film was allowed to stay in a drying zone at 70 ° C. for 15 seconds to be dried to prepare a saponified film.
（偏光板１の作製）
偏光素子１の両面に、上記で作製した鹸化処理したセルロースアシレートフィルムを、偏光板用接着剤１を介し、乾燥後の接着剤層の厚みが両面共、１００ｎｍになるように調整し、ロール貼合機を用いて貼合した後に６０℃で１０分間乾燥し、偏光板１を得た。
(Preparation of polarizing plate 1)
On both sides of the polarizing element 1, the saponified cellulose acylate film prepared above is passed through the polarizing plate adhesive 1 and adjusted so that the thickness of the adhesive layer after drying is 100 nm on both sides, and rolled. After bonding using a bonding machine, the film was dried at 60 ° C. for 10 minutes to obtain a polarizing plate 1.
（偏光板２〜３の作製）
偏光板用接着剤１を偏光板用接着剤２〜３に代えたこと以外は偏光板１と同様に偏光板２〜３を作製した。
(Preparation of polarizing plates 2 to 3)
Polarizing plates 2 and 3 were produced in the same manner as the polarizing plate 1 except that the polarizing plate adhesive 1 was replaced with the polarizing plate adhesives 2 and 3.
（光学積層体１の作製）
特開２０１８−０２５７６５号公報の実施例を参考に、上記で作製した偏光板１の両面にアクリル系粘着剤（製造元：リンテック（株）、品番：＃７）を塗布することにより、両面に、厚みが２５μｍの粘着剤層（第１粘着剤層と第２粘着剤層）を有する光学積層体１を作製した。
（光学積層体２〜３の作製）
偏光板１を偏光板２〜３に代えたこと以外は光学積層体１と同様に光学積層体２〜３を作製した。
(Preparation of Optical Laminated Body 1)
By applying an acrylic pressure-sensitive adhesive (manufacturer: Lintec Co., Ltd., product number: # 7) to both sides of the polarizing plate 1 produced above, referring to the examples of JP-A-2018-0275765, both sides can be subjected to. An optical laminate 1 having a pressure-sensitive adhesive layer (first pressure-sensitive adhesive layer and second pressure-sensitive adhesive layer) having a thickness of 25 μm was produced.
(Preparation of optical laminates 2 to 3)
Optical laminates 2 to 3 were produced in the same manner as the optical laminate 1 except that the polarizing plate 1 was replaced with the polarizing plates 2 to 3.
［高温耐久試験後の単体透過率評価（９５℃）］
上記で作製した光学積層体１〜３を、それぞれ、５０ｍｍ×１００ｍｍの大きさに裁断して、第１粘着剤層および第２粘着剤層それぞれの表面を無アルカリガラス〔商品名“ＥＡＧＬＥ ＸＧ”、コーニング社製〕に貼合することによって、評価サンプルを作製した。尚、これらのサンプルを作製する時、ガラス板貼合前に含水率を調整するために、表２に示す温度・湿度条件下で光学積層体を７２時間保管した。なお、すべてのサンプルで、保管６６時間、６９時間、７２時間経過時の重量を測定しても、変化がなかったことから、目的の平衡含水率に達しているとみなした。すなわち、光学積層体の含水率は、保管環境の含水率と平衡に達しているみなすことができ、また光学積層体中の偏光板及び偏光素子の含水率も、光学積層体の含水率と同じであるとみなすことができる。
この評価サンプルに、温度５０℃、圧力５ｋｇｆ／ｃｍ２（４９０．３ｋＰａ）で１時間オートクレーブ処理を施した後、温度２３℃、相対湿度５５％の環境下で２４時間放置した。その後、単体透過率を測定し（初期値）、温度９５℃の加熱環境下に保管し、１００〜２００時間まで５０時間おきに単体透過率を測定した。初期値に対し透過率低下が５％以上に達した時間を基に以下の基準で評価を行った。初期値に対し透過率低下が５％以上に達した時間を基に以下の基準で評価を行った。得られた結果を表２に示す。
２００時間後に透過率の低下が５％以下のもの ：Ａ
１５０〜２００時間で透過率の低下が５％以上に達したもの：Ｂ
１００〜１５０時間で透過率の低下が５％以上に達したもの：Ｃ
１００時間以内で透過率の低下が５％以上のもの ：Ｄ
[Evaluation of single transmittance after high temperature durability test (95 ° C)]
The optical laminates 1 to 3 produced above are each cut into a size of 50 mm × 100 mm, and the surfaces of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer are made of alkali-free glass [trade name “EAGLE XG”. , Made by Corning Inc.] to prepare an evaluation sample. When these samples were prepared, the optical laminate was stored for 72 hours under the temperature and humidity conditions shown in Table 2 in order to adjust the water content before bonding the glass plates. In addition, all the samples were considered to have reached the target equilibrium moisture content because there was no change even when the weights were measured after 66 hours, 69 hours, and 72 hours of storage. That is, the water content of the optical laminate can be regarded as reaching equilibrium with the water content of the storage environment, and the water content of the polarizing plate and the polarizing element in the optical laminate is also the same as the water content of the optical laminate. Can be considered to be.
This evaluation sample was autoclaved at a temperature of 50 ° C. and a pressure of 5 kgf / cm 2 (490.3 kPa) for 1 hour, and then left to stand in an environment of a temperature of 23 ° C. and a relative humidity of 55% for 24 hours. Then, the simple substance transmittance was measured (initial value), stored in a heating environment at a temperature of 95 ° C., and the simple substance transmittance was measured every 50 hours from 100 to 200 hours. The evaluation was performed according to the following criteria based on the time when the decrease in transmittance reached 5% or more with respect to the initial value. The evaluation was performed according to the following criteria based on the time when the decrease in transmittance reached 5% or more with respect to the initial value. The results obtained are shown in Table 2.
Those with a decrease in transmittance of 5% or less after 200 hours: A
When the decrease in transmittance reached 5% or more in 150 to 200 hours: B
When the decrease in transmittance reached 5% or more in 100 to 150 hours: C
Those with a decrease in transmittance of 5% or more within 100 hours: D
Claims (11)
前記水系接着剤層は、酸化防止剤を含有し、
前記偏光素子の含水率が温度２０℃かつ相対湿度３０％の平衡含水率以上であり、温度２０℃相対湿度５０％の平衡含水率以下である、偏光板。 A polarizing plate in which a polarizing element in which iodine is adsorbed and oriented on a polyvinyl alcohol-based resin layer and a transparent protective film are laminated via an aqueous adhesive layer.
The water-based adhesive layer contains an antioxidant and contains
A polarizing plate having a water content of the polarizing element having a temperature of 20 ° C. and a relative humidity of 30% or more and an equilibrium water content of a temperature of 20 ° C. and a relative humidity of 50% or less.
前記水系接着剤層は、酸化防止剤を含有し、
前記偏光板の含水率が温度２０℃かつ相対湿度３０％の平衡含水率以上であり、温度２０℃相対湿度５０％の平衡含水率以下である、偏光板。 A polarizing plate in which a polarizing element in which iodine is adsorbed and oriented on a polyvinyl alcohol-based resin layer and a transparent protective film are laminated via an aqueous adhesive layer.
The water-based adhesive layer contains an antioxidant and contains
A polarizing plate having a water content of the polarizing plate having a temperature of 20 ° C. and a relative humidity of 30% or more and an equilibrium water content of a temperature of 20 ° C. and a relative humidity of 50% or less.
請求項１〜５のいずれかに記載された偏光板とを備え、
前記偏光板の両面には空気層以外の層が接して設けられている画像表示装置。 Image display cell and
The polarizing plate according to any one of claims 1 to 5 is provided.
An image display device provided with layers other than the air layer in contact with both surfaces of the polarizing plate.
前記偏光素子の含水率が温度２０℃かつ相対湿度３０％の平衡含水率以上であり、温度２０℃相対湿度５０％の平衡含水率以下となるように調整する含水率調整工程と、を有する、偏光板の製造方法。 A laminating process in which a polarizing element and a transparent protective film are laminated using a water-based adhesive containing an antioxidant, and
The polarizing element has a water content adjusting step of adjusting the water content so that the temperature is 20 ° C. and the relative humidity is 30% or more and the temperature is 20 ° C. and the relative humidity is 50% or less. Method for manufacturing a polarizing plate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020073878 | 2020-04-17 | ||
| JP2020073878 | 2020-04-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2021173990A true JP2021173990A (en) | 2021-11-01 |
Family
ID=78281767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020183486A Pending JP2021173990A (en) | 2020-04-17 | 2020-11-02 | Polarizing plate, image display device, and method of manufacturing polarizing plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2021173990A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023228584A1 (en) * | 2022-05-26 | 2023-11-30 | 住友化学株式会社 | Method for producing polarizing plate |
-
2020
- 2020-11-02 JP JP2020183486A patent/JP2021173990A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023228584A1 (en) * | 2022-05-26 | 2023-11-30 | 住友化学株式会社 | Method for producing polarizing plate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2021095541A1 (en) | Polarization plate and image display device using said polarization plate | |
| JP2020190723A (en) | Polarizing plate, manufacturing method therefor, and image display device having the same | |
| WO2022075146A1 (en) | Polarizing plate and image display device | |
| WO2022075148A1 (en) | Polarizing plate and image display device | |
| JP2021173990A (en) | Polarizing plate, image display device, and method of manufacturing polarizing plate | |
| JP7499673B2 (en) | Polarizing plate and image display device | |
| WO2022085400A1 (en) | Polarizing plate and image display device | |
| WO2022075145A1 (en) | Polarizing plate and image display device | |
| WO2022102387A1 (en) | Polarizing plate and image display device including said polarizing plate | |
| WO2022102363A1 (en) | Polarizing plate and image display device | |
| WO2022102362A1 (en) | Polarizing plate and image display device | |
| JP2022135259A (en) | Polarizer and image display device | |
| WO2022075147A1 (en) | Polarizing plate, and image display device | |
| JP2024062155A (en) | Polarizer | |
| JP2023013221A (en) | Polarizing element, polarizing plate, and image display device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230925 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20240327 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240402 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240425 |