WO2021149311A1 - Retardation layer–equipped polarizing plate and image display device using same - Google Patents
Retardation layer–equipped polarizing plate and image display device using same Download PDFInfo
- Publication number
- WO2021149311A1 WO2021149311A1 PCT/JP2020/039431 JP2020039431W WO2021149311A1 WO 2021149311 A1 WO2021149311 A1 WO 2021149311A1 JP 2020039431 W JP2020039431 W JP 2020039431W WO 2021149311 A1 WO2021149311 A1 WO 2021149311A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- retardation layer
- polarizing plate
- retardation
- group
- Prior art date
Links
- 239000010410 layer Substances 0.000 claims abstract description 577
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 124
- 239000011630 iodine Substances 0.000 claims abstract description 122
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 122
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 120
- 229920005989 resin Polymers 0.000 claims abstract description 84
- 239000011347 resin Substances 0.000 claims abstract description 84
- 150000001875 compounds Chemical class 0.000 claims abstract description 50
- 239000012790 adhesive layer Substances 0.000 claims abstract description 38
- 238000000576 coating method Methods 0.000 claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 230000001629 suppression Effects 0.000 claims abstract description 16
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 14
- 230000009477 glass transition Effects 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims description 69
- 239000000463 material Substances 0.000 claims description 52
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 39
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 21
- 238000010521 absorption reaction Methods 0.000 claims description 19
- 238000005401 electroluminescence Methods 0.000 claims description 17
- 125000001424 substituent group Chemical group 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 13
- 230000010287 polarization Effects 0.000 claims description 12
- 238000007711 solidification Methods 0.000 claims description 11
- 230000008023 solidification Effects 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 239000002356 single layer Substances 0.000 claims description 8
- 230000000007 visual effect Effects 0.000 claims description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 5
- 125000003172 aldehyde group Chemical group 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 125000003566 oxetanyl group Chemical group 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 125000005504 styryl group Chemical group 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 31
- 239000002184 metal Substances 0.000 abstract description 31
- 230000007797 corrosion Effects 0.000 abstract description 16
- 238000005260 corrosion Methods 0.000 abstract description 16
- 230000005540 biological transmission Effects 0.000 abstract 2
- 238000011282 treatment Methods 0.000 description 44
- 239000004925 Acrylic resin Substances 0.000 description 33
- 229920000178 Acrylic resin Polymers 0.000 description 33
- 239000000243 solution Substances 0.000 description 33
- 239000004372 Polyvinyl alcohol Substances 0.000 description 32
- 229920002451 polyvinyl alcohol Polymers 0.000 description 32
- 239000011241 protective layer Substances 0.000 description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 29
- 239000003822 epoxy resin Substances 0.000 description 29
- 229920000647 polyepoxide Polymers 0.000 description 29
- 238000000034 method Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 21
- 238000011156 evaluation Methods 0.000 description 18
- -1 methyl 2-ethylhexyl Chemical group 0.000 description 17
- 229910052796 boron Inorganic materials 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- 230000002401 inhibitory effect Effects 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 13
- 239000004327 boric acid Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 238000007334 copolymerization reaction Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229920005992 thermoplastic resin Polymers 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 125000000686 lactone group Chemical group 0.000 description 7
- KNCYXPMJDCCGSJ-UHFFFAOYSA-N piperidine-2,6-dione Chemical group O=C1CCCC(=O)N1 KNCYXPMJDCCGSJ-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000004043 dyeing Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229920000058 polyacrylate Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- 239000004416 thermosoftening plastic Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000002042 Silver nanowire Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- ZHRPSCAQBZTQHQ-UHFFFAOYSA-N 2-(2-phenylphenyl)ethyl prop-2-enoate Chemical group C(C=C)(=O)OCCC1=C(C=CC=C1)C1=CC=CC=C1 ZHRPSCAQBZTQHQ-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 description 3
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000004988 Nematic liquid crystal Substances 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 3
- 229940006461 iodide ion Drugs 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000000059 patterning Methods 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical group O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 229960002479 isosorbide Drugs 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- VAZQKPWSBFZARZ-UHFFFAOYSA-N 2-(2-phenylphenoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1C1=CC=CC=C1 VAZQKPWSBFZARZ-UHFFFAOYSA-N 0.000 description 1
- DNVXWIINBUTFEP-UHFFFAOYSA-N 2-[(2-phenylphenoxy)methyl]oxirane Chemical compound C1OC1COC1=CC=CC=C1C1=CC=CC=C1 DNVXWIINBUTFEP-UHFFFAOYSA-N 0.000 description 1
- CDFCBRMXZKAKKI-UHFFFAOYSA-N 2-hydroxybenzaldehyde;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1C=O CDFCBRMXZKAKKI-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- YTNUOGWCFLMGLF-UHFFFAOYSA-N 5-methylbenzene-1,2,3,4-tetrol Chemical compound CC1=CC(O)=C(O)C(O)=C1O YTNUOGWCFLMGLF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 206010052128 Glare Diseases 0.000 description 1
- DKNPRRRKHAEUMW-UHFFFAOYSA-N Iodine aqueous Chemical compound [K+].I[I-]I DKNPRRRKHAEUMW-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- XQKKWWCELHKGKB-UHFFFAOYSA-L calcium acetate monohydrate Chemical compound O.[Ca+2].CC([O-])=O.CC([O-])=O XQKKWWCELHKGKB-UHFFFAOYSA-L 0.000 description 1
- 229940067460 calcium acetate monohydrate Drugs 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 150000002496 iodine Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000002535 lyotropic effect Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- LUCXVPAZUDVVBT-UHFFFAOYSA-N methyl-[3-(2-methylphenoxy)-3-phenylpropyl]azanium;chloride Chemical compound Cl.C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1C LUCXVPAZUDVVBT-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 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
- 239000012860 organic pigment Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- LYKRPDCJKSXAHS-UHFFFAOYSA-N phenyl-(2,3,4,5-tetrahydroxyphenyl)methanone Chemical compound OC1=C(O)C(O)=CC(C(=O)C=2C=CC=CC=2)=C1O LYKRPDCJKSXAHS-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002335 surface treatment layer Substances 0.000 description 1
- 238000010345 tape casting Methods 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
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- WRTMQOHKMFDUKX-UHFFFAOYSA-N triiodide Chemical compound I[I-]I WRTMQOHKMFDUKX-UHFFFAOYSA-N 0.000 description 1
- 229940006158 triiodide ion Drugs 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8793—Arrangements for polarized light emission
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
Definitions
- the present invention relates to a polarizing plate with a retardation layer and an image display device using the same.
- image display devices represented by liquid crystal display devices and electroluminescence (EL) display devices for example, organic EL display devices and inorganic EL display devices
- EL electroluminescence
- a polarizing plate and a retardation plate are typically used in the image display device.
- a polarizing plate with a retardation layer in which a polarizing plate and a retardation plate are integrated is widely used (for example, Patent Document 1), and recently, there has been a strong demand for thinner image display devices. As a result, there is an increasing demand for thinner plates with retardation layers.
- the protective layer of the polarizer which greatly contributes to the thickness, is thinned (or omitted), and the retardation film is thinned.
- metal members for example, electrodes, sensors, wiring, metal layer
- Such corrosion of metal members is remarkable in a high temperature and high humidity environment.
- the present invention has been made to solve the above-mentioned conventional problems, and a main object thereof is to provide a thin polarizing plate with a retardation layer capable of suppressing corrosion of a metal member when applied to an image display device. There is.
- the polarizing plate with a retardation layer of the present invention has a polarizing plate containing a polarizer, a retardation layer, and an adhesive layer in this order from the visual side, and the retardation layer has a circular polarization function or an elliptical polarization function. It is an orientation solidification layer of a liquid crystal compound having.
- an iodine permeation suppressing layer which is a solidified or thermosetting film of a coating film of an organic solvent solution of a resin, is provided between the polarizing element and the pressure-sensitive adhesive layer.
- the glass transition temperature of the resin constituting the iodine permeation suppressing layer is 85 ° C.
- the iodine permeation inhibitory layer is provided between the polarizer and the retardation layer. In another embodiment, the iodine permeation suppressing layer is provided between the retardation layer and the pressure-sensitive adhesive layer. In one embodiment, the iodine permeation suppressing layer is provided with two or more layers between the polarizer and the pressure-sensitive adhesive layer. In one embodiment, the iodine permeation inhibitory layer has a thickness of 0.05 ⁇ m to 10 ⁇ m. In one embodiment, the glass transition temperature of the resin constituting the iodine permeation suppressing layer is 90 ° C. or higher.
- the resin constituting the iodine permeation suppressing layer is represented by the formula (1) of more than 50 parts by weight (meth) acrylic monomer and more than 0 parts by weight and less than 50 parts by weight.
- X is a group consisting of a vinyl group, a (meth) acrylic group, a styryl group, a (meth) acrylamide group, a vinyl ether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group.
- the retardation layer is a single layer
- the Re (550) of the retardation layer is 100 nm to 190 nm
- the slow axis of the retardation layer and the absorption axis of the polarizer The angle of formation is 40 ° to 50 °.
- the retardation layer has a laminated structure of an oriented solidified layer of a first liquid crystal compound and an oriented solidified layer of a second liquid crystal compound; an oriented solidified layer of the first liquid crystal compound.
- the Re (550) of the second liquid crystal compound is 200 nm to 300 nm, and the angle formed by the slow axis thereof and the absorption axis of the polarizer is 10 ° to 20 °; the Re (550) of the orientation solidification layer of the second liquid crystal compound is formed. ) Is 100 nm to 190 nm, and the angle formed by the slow axis thereof and the absorption axis of the polarizer is 70 ° to 80 °.
- the polarizing plate with a retardation layer further has a conductive layer or an isotropic base material with a conductive layer between the iodine permeation suppressing layer and the pressure-sensitive adhesive layer.
- the polarizing plate with a retardation layer has a total thickness of 60 ⁇ m or less.
- an image display device is provided. This image display device includes the above-mentioned polarizing plate with a retardation layer.
- the image display device is an organic electroluminescence display device or an inorganic electroluminescence display device.
- a metal when the polarizing plate with a retardation layer is applied to an image display device. Corrosion of members can be suppressed.
- the iodine permeation suppressing layer that can be used in the embodiment of the present invention is a solidified or thermosetting product of a coating film of an organic solvent solution of a resin, and the glass transition temperature of the resin constituting the iodine permeation suppressing layer is 85 ° C. or higher. And the weight average molecular weight Mw is 25,000 or more.
- Refractive index (nx, ny, nz) "Nx" is the refractive index in the direction in which the in-plane refractive index is maximized (that is, the slow-phase axis direction), and "ny” is the in-plane direction orthogonal to the slow-phase axis (that is, the phase-advance axis direction). Is the refractive index of, and "nz” is the refractive index in the thickness direction.
- In-plane phase difference (Re) “Re ( ⁇ )” is an in-plane phase difference measured with light having a wavelength of ⁇ nm at 23 ° C.
- Re (550) is an in-plane phase difference measured with light having a wavelength of 550 nm at 23 ° C.
- Phase difference in the thickness direction (Rth) is a phase difference in the thickness direction measured with light having a wavelength of ⁇ nm at 23 ° C.
- Rth (550) is a phase difference in the thickness direction measured with light having a wavelength of 550 nm at 23 ° C.
- FIG. 1A is a schematic cross-sectional view of a polarizing plate with a retardation layer according to one embodiment of the present invention
- FIG. 1B is a polarizing plate with a retardation layer according to another embodiment of the present invention. It is a schematic cross-sectional view of a polarizing plate.
- the polarizing plates 100 and 101 with a retardation layer of FIGS. 1A and 1B each have a polarizing plate 10, a retardation layer 20, and an adhesive layer 30 in this order from the visual side.
- the polarizing plate 10 typically includes a polarizing element 11 and a protective layer 12 arranged on the visual side of the polarizing element 11.
- the retardation layer 20 is an oriented solidified layer of a liquid crystal compound having a circular polarization function or an elliptically polarized function (hereinafter, may be simply referred to as a liquid crystal oriented solidified layer).
- the pressure-sensitive adhesive layer 30 is provided as the outermost layer, and the polarizing plate with a retardation layer can be attached to an image display device (substantially, an image display cell).
- the iodine permeation suppressing layer 40 is provided between the polarizer 11 and the pressure-sensitive adhesive layer 30.
- the iodine permeation suppressing layer 40 may be provided between the polarizer 11 and the retardation layer 20 (that is, adjacent to the polarizer 11) as shown in FIG. 1A, and the retardation difference as shown in FIG. 1B. It may be provided between the layer 20 and the pressure-sensitive adhesive layer 30.
- the iodine permeation suppressing layer is provided between the polarizer and the retardation layer (particularly when the iodine permeation suppressing layer is adjacent to the polarizer), it is possible to suppress iodine transfer from the polarizer in a high temperature and high humidity environment.
- the iodine permeation suppressing layer is provided between the retardation layer and the pressure-sensitive adhesive layer (particularly when the iodine permeation suppressing layer is adjacent to the pressure-sensitive adhesive layer), components that are considered to affect metal corrosion other than iodine (for example). , Residual monomer component in the ultraviolet curable adhesive, decomposition product of the photoinitiator) can also be prevented from migrating into the adhesive at the same time, and has the advantage of further enhancing the metal corrosion suppressing effect.
- two or more iodine permeation suppressing layers may be provided between the polarizer and the pressure-sensitive adhesive layer (for example, FIGS. 4 and 5).
- the polarizing plate with a retardation layer has two or more iodine permeation suppression layers, corrosion of the metal member can be remarkably suppressed when the polarizing plate with a retardation layer is applied to an image display device.
- two iodine permeation suppressing layers are provided between the polarizer and the pressure-sensitive adhesive layer.
- the iodine permeation suppressing layer is provided with two layers, one between the polarizer 11 and the retardation layer 20, and the other between the retardation layer 20 and the pressure-sensitive adhesive layer 30.
- the iodine permeation inhibitor layer is provided adjacent to the polarizer.
- the iodine permeation inhibitory layer is provided adjacent to the retardation layer. In the present specification, "adjacent" means that they are directly laminated without an adhesive layer or the like.
- the iodine permeation suppressing layer is provided with two layers between the polarizer 11 and the retardation layer 20, and one layer between the retardation layer 20 and the pressure-sensitive adhesive layer 30. ing.
- the two iodine permeation suppressing layers between the polarizer 11 and the retardation layer 20 are provided adjacent to the polarizer and the other adjacent to the retardation layer.
- the iodine permeation suppressing layer may be 4 or more layers (for example, 4 layers, 5 layers, 6 layers).
- the number of iodine permeation suppressing layers can be set in consideration of cost, manufacturing efficiency, total thickness of the polarizing plate with a retardation layer, and the like.
- the iodine permeation suppression layer is a solidified product or thermosetting product of a coating film of a resin organic solvent solution. Further, the glass transition temperature (Tg) of the resin constituting the iodine permeation suppressing layer is 85 ° C. or higher, and the weight average molecular weight Mw is 25000 or higher.
- the above-mentioned iodine permeation suppressing layer organic resin having specific Tg and Mw
- the solidified layer or thermosetting layer of the coating film of the solvent solution is useful, and have completed the present invention. That is, such an effect solves a new problem that has not been known in the past, and is an unexpectedly excellent effect.
- the iodine permeation suppressing layer can be formed very thinly, and by providing the iodine permeation suppressing layer, the protective layer on the side opposite to the viewing side can be omitted. This effect can contribute to further thinning of the polarizing plate with a retardation layer.
- another retardation layer 50 and / or a conductive layer or an isotropic base material 60 with a conductive layer may be provided.
- Another retardation layer 50 is typically provided between the retardation 20 and the pressure-sensitive adhesive layer 30 (ie, outside the retardation layer 20).
- the conductive layer or the isotropic base material 60 with the conductive layer is typically provided between the iodine permeation suppressing layer 40 and the pressure-sensitive adhesive layer 30 (that is, outside the iodine permeation suppressing layer 40).
- Another retardation layer 50 and the conductive layer or the isotropic base material 60 with the conductive layer are typically provided in this order from the retardation layer 20 side.
- the iodine permeation suppressing layer 40, the retardation layer 20, another retardation layer 50, and the conductive layer or the isotropic base material 60 with the conductive layer are provided in this order from the visual side, but different retardation. Any is provided as long as the layer 50 is provided between the phase difference 20 and the pressure-sensitive adhesive layer 30, and the conductive layer or the isotropic base material 60 with the conductive layer is provided between the iodine permeation suppressing layer 40 and the pressure-sensitive adhesive layer 30. Appropriate placement order can be adopted.
- the other retardation layer 50 and the conductive layer or the isotropic base material 60 with the conductive layer are typically arbitrary layers provided as needed, and one or both of them may be omitted.
- the retardation layer 20 may be referred to as a first retardation layer
- another retardation layer 50 may be referred to as a second retardation layer.
- the polarizing plate with a retardation layer is a so-called inner touch panel type in which a touch sensor is incorporated between an image display cell (for example, an organic EL cell) and the polarizing plate. Can be applied to input display devices.
- the conductive layer or the isotropic base material 60 with the conductive layer on the outside of the iodine permeation suppressing layer 40 the corrosion of the conductive layer can be remarkably suppressed.
- the first retardation layer 20 is a liquid crystal oriented solidifying layer.
- the first retardation layer 20 may be a single layer as shown in FIGS. 1A, 1B and 2, and the first liquid crystal oriented solidified layer 21 and the second liquid crystal oriented solidified layer as shown in FIG. It may have a laminated structure with 22.
- the polarizing plate with a retardation layer 101 of FIG. 1B may be provided with a second retardation layer 50 and / or an isotropic base material 60 with a conductive layer or a conductive layer; the polarizing plate with a retardation layer 101 of FIG. 1B.
- the retardation layer 20 of the above may have a two-layer structure as shown in FIG. 3; the polarizing plate 103 with the retardation layer of FIG. 3 has a second retardation layer 50 and / or a conductive layer or a conductive layer, etc.
- a square substrate 60 may be provided; the iodine permeation suppressing layer 40 of the polarizing plate 102 with a retardation layer of FIG. 2 may be provided between the retardation layer 20 and the conductive layer or the isotropic substrate 60 with a conductive layer. good.
- the polarizing plate with a retardation layer according to the embodiment of the present invention may further include other retardation layers.
- the optical characteristics for example, refractive index characteristics, in-plane retardation, Nz coefficient, photoelastic coefficient
- thickness, arrangement position, and the like of other retardation layers can be appropriately set according to the purpose.
- the polarizing plate with a retardation layer may be single-wafered or elongated.
- the term "long” means an elongated shape having a length sufficiently long with respect to the width, and for example, an elongated shape having a length of 10 times or more, preferably 20 times or more with respect to the width. include.
- the long-shaped polarizing plate with a retardation layer can be wound in a roll shape.
- the total thickness of the polarizing plate with a retardation layer is preferably 60 ⁇ m or less, more preferably 55 ⁇ m or less, further preferably 50 ⁇ m or less, and particularly preferably 40 ⁇ m or less.
- the lower limit of the total thickness can be, for example, 28 ⁇ m.
- a polarizing plate with a retardation layer can be particularly preferably applied to a curved image display device and / or a foldable or foldable image display device.
- the total thickness of the polarizing plate with a retardation layer is the polarizing plate, the retardation layer (the first retardation layer and the second retardation layer if present), the iodine permeation suppression layer, and the layers thereof.
- the total thickness of the adhesive layer or the pressure-sensitive adhesive layer for the purpose that is, the total thickness of the polarizing plate with the retardation layer is the conductive layer or the isotropic base material 60 with the conductive layer, and the pressure-sensitive adhesive layer 30 and its surface. Does not include the thickness of the release film that can be temporarily attached).
- a release film is temporarily attached to the surface of the pressure-sensitive adhesive layer 30 until a polarizing plate with a retardation layer is used.
- the pressure-sensitive adhesive layer can be protected and a roll of the polarizing plate with a retardation layer can be formed.
- the components of the polarizing plate with a retardation layer will be described in more detail. Since a structure well known in the industry can be adopted for the pressure-sensitive adhesive layer 30, the detailed structure of the pressure-sensitive adhesive layer will be omitted.
- Polarizing plate B-1 Polarizer
- the polarizer is typically composed of a polyvinyl alcohol (PVA) -based resin film containing a dichroic substance.
- the thickness of the polarizer is preferably 1 ⁇ m to 8 ⁇ m, more preferably 1 ⁇ m to 7 ⁇ m, and even more preferably 2 ⁇ m to 5 ⁇ m. If the thickness of the polarizer is in such a range, it can greatly contribute to the thinning of the polarizing plate with a retardation layer. Further, the effect of the present invention is remarkable in a thin polarizing plate with a retardation layer using such a polarizer.
- the boric acid content of the polarizer is preferably 10% by weight or more, more preferably 13% by weight to 25% by weight.
- the boric acid content can be calculated as, for example, the amount of boric acid contained in the polarizer per unit weight by using the following formula from the neutralization method.
- the iodine content of the polarizer is preferably 2% by weight or more, more preferably 2% by weight to 10% by weight.
- the iodine content of the polarizer is in such a range, the ease of curl adjustment at the time of bonding is well maintained due to the synergistic effect with the above boric acid content, and the curl at the time of heating is maintained. It is possible to improve the appearance durability at the time of heating while satisfactorily suppressing the above.
- the term "iodine content” means the amount of all iodine contained in the polarizer (PVA-based resin film).
- Iodine content means the amount of iodine that includes all of these forms.
- the iodine content can be calculated, for example, by the calibration curve method of fluorescent X-ray analysis.
- the polyiodine ion exists in a state in which a PVA-iodine complex is formed in the polarizer. By forming such a complex, absorption dichroism can be exhibited in the wavelength range of visible light.
- a complex of PVA and tri-iodide ion (PVA ⁇ I 3 -) has a light absorption peak around 470 nm
- a complex of PVA and five iodide ion (PVA ⁇ I 5 -) is 600nm near Has an absorptive peak.
- polyiodine ions can absorb light in a wide range of visible light, depending on their morphology.
- iodide ion (I ⁇ ) has an absorption peak near 230 nm and is not substantially involved in the absorption of visible light. Therefore, polyiodine ions present in the form of a complex with PVA may be mainly involved in the absorption performance of the polarizer.
- the polarizer preferably exhibits absorption dichroism at any wavelength of 380 nm to 780 nm.
- the simple substance transmittance Ts of the polarizer is preferably 40% to 48%, more preferably 41% to 46%.
- the degree of polarization P of the polarizer is preferably 97.0% or more, more preferably 99.0% or more, and further preferably 99.9% or more.
- the simple substance transmittance is typically a Y value measured using an ultraviolet-visible spectrophotometer and corrected for luminosity factor.
- the degree of polarization is typically obtained by the following formula based on the parallel transmittance Tp and the orthogonal transmittance Tc measured by using an ultraviolet-visible spectrophotometer and corrected for luminosity factor.
- Polarization degree (%) ⁇ (Tp-Tc) / (Tp + Tc) ⁇ 1/2 ⁇ 100
- the polarizer can typically be made using a laminate of two or more layers.
- Specific examples of the polarizer obtained by using the laminate include a polarizer obtained by using a laminate of a resin base material and a PVA-based resin layer coated and formed on the resin base material.
- the polarizer obtained by using the laminate of the resin base material and the PVA-based resin layer coated and formed on the resin base material is, for example, a resin base material obtained by applying a PVA-based resin solution to the resin base material and drying the resin base material.
- the obtained resin substrate / polarizer laminate may be used as it is (that is, the resin substrate may be used as a protective layer for the polarizer), and the resin substrate is peeled off from the resin substrate / polarizer laminate.
- an arbitrary appropriate protective layer according to the purpose may be laminated on the peeled surface. Details of the method for producing such a polarizer are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580 and Japanese Patent No. 6470455. The entire description of these publications is incorporated herein by reference.
- a typical method for producing a polarizer is to form a polyvinyl alcohol-based resin layer containing a halide and a polyvinyl alcohol-based resin on one side of a long thermoplastic resin base material to form a laminate. Then, the laminated body is subjected to an aerial auxiliary stretching treatment, a dyeing treatment, an underwater stretching treatment, and a drying shrinkage treatment in which the laminate is shrunk by 2% or more in the width direction by heating while being conveyed in the longitudinal direction. including.
- This makes it possible to provide a polarizer that is extremely thin, has excellent optical characteristics, and suppresses variations in optical characteristics.
- the crystallinity of PVA can be enhanced, and high optical characteristics can be achieved.
- by increasing the orientation of PVA in advance it is possible to prevent problems such as deterioration of PVA orientation and dissolution when immersed in water in a subsequent dyeing step or stretching step, resulting in high optical characteristics. Will be possible to achieve.
- the PVA-based resin layer is immersed in a liquid, the disorder of the orientation of the polyvinyl alcohol molecules and the decrease in the orientation can be suppressed as compared with the case where the PVA-based resin layer does not contain a halide.
- the protective layer 12 is formed of any suitable film that can be used as a protective layer for the polarizer.
- the material that is the main component of the film include cellulose-based resins such as triacetyl cellulose (TAC), polyester-based, polyvinyl alcohol-based, polycarbonate-based, polyamide-based, polyimide-based, polyethersulfone-based, and polysulfone-based.
- TAC triacetyl cellulose
- thermosetting resins such as (meth) acrylic, urethane, (meth) acrylic urethane, epoxy, and silicone, or ultraviolet curable resins can also be mentioned.
- glassy polymers such as siloxane-based polymers can also be mentioned.
- the polymer film described in JP-A-2001-343529 (WO01 / 37007) can also be used.
- a resin composition containing a thermoplastic resin having a substituted or unsubstituted imide group in the side chain and a thermoplastic resin having a substituted or unsubstituted phenyl group and a nitrile group in the side chain.
- the polymer film can be, for example, an extruded product of the above resin composition.
- the polarizing plate with a retardation layer is typically arranged on the visible side of the image display device, and the protective layer 12 is typically arranged on the visible side. Therefore, the protective layer 12 may be subjected to surface treatment such as hard coat treatment, antireflection treatment, anti-sticking treatment, and anti-glare treatment, if necessary. Further / or, if necessary, the protective layer 12 is provided with a process for improving visibility when visually recognizing through polarized sunglasses (typically, a (elliptical) circular polarization function is provided, and an ultra-high phase difference is provided. May be given). By performing such a process, excellent visibility can be realized even when the display screen is visually recognized through a polarized lens such as polarized sunglasses. Therefore, the polarizing plate with a retardation layer can be suitably applied to an image display device that can be used outdoors.
- polarized sunglasses typically, a (elliptical) circular polarization function is provided, and an ultra-high phase difference is provided. May be given.
- the thickness of the protective layer is preferably 10 ⁇ m to 50 ⁇ m, more preferably 10 ⁇ m to 30 ⁇ m.
- the thickness of the outer protective layer is the thickness including the thickness of the surface treatment layer.
- the first retardation layer 20 is a liquid crystal oriented solidifying layer as described above.
- the difference between nx and ny of the obtained retardation layer can be made much larger than that of the non-liquid crystal material, so that the thickness of the retardation layer for obtaining a desired in-plane retardation can be obtained. Can be made much smaller. As a result, it is possible to further reduce the thickness of the polarizing plate with a retardation layer.
- the term "liquid crystal oriented solidified layer” refers to a layer in which a liquid crystal compound is oriented in a predetermined direction within the layer and the oriented state is fixed.
- the "oriented solidified layer” is a concept including an oriented cured layer obtained by curing a liquid crystal monomer as described later.
- the rod-shaped liquid crystal compounds are typically oriented in a state of being aligned in the slow-phase axial direction of the first retardation layer (homogeneous orientation).
- the liquid crystal compound examples include a liquid crystal compound (nematic liquid crystal) in which the liquid crystal phase is a nematic phase.
- a liquid crystal compound for example, a liquid crystal polymer or a liquid crystal monomer can be used.
- the liquid crystal expression mechanism of the liquid crystal compound may be either lyotropic or thermotropic.
- the liquid crystal polymer and the liquid crystal monomer may be used alone or in combination.
- the liquid crystal monomer is preferably a polymerizable monomer and a crosslinkable monomer. This is because the orientation state of the liquid crystal monomer can be fixed by polymerizing or cross-linking (that is, curing) the liquid crystal monomer. After the liquid crystal monomers are oriented, for example, if the liquid crystal monomers are polymerized or crosslinked with each other, the oriented state can be fixed.
- the polymer is formed by polymerization, and the three-dimensional network structure is formed by cross-linking, but these are non-liquid crystal.
- the formed first retardation layer does not undergo a transition to a liquid crystal phase, a glass phase, or a crystal phase due to a temperature change peculiar to a liquid crystal compound, for example.
- the first retardation layer becomes an extremely stable retardation layer that is not affected by temperature changes.
- the temperature range in which the liquid crystal monomer exhibits liquid crystal properties differs depending on the type. Specifically, the temperature range is preferably 40 ° C. to 120 ° C., more preferably 50 ° C. to 100 ° C., and most preferably 60 ° C. to 90 ° C.
- any suitable liquid crystal monomer can be adopted as the liquid crystal monomer.
- the polymerizable mesogen compounds described in Special Tables 2002-533742 WO00 / 37585
- EP358208 US5211877
- EP666137 US4388453
- WO93 / 22397 EP02671712, DE19504224, DE4408171, GB2280445 and the like
- Specific examples of such a polymerizable mesogen compound include, for example, BASF's trade name LC242, Merck's trade name E7, and Wacker-Chem's trade name LC-Silicon-CC3767.
- the liquid crystal monomer for example, a nematic liquid crystal monomer is preferable.
- the liquid crystal alignment solidified layer is subjected to an orientation treatment on the surface of a predetermined base material, and a coating liquid containing a liquid crystal compound is applied to the surface to orient the liquid crystal compound in a direction corresponding to the orientation treatment. It can be formed by fixing the state.
- the substrate is any suitable resin film and the liquid crystal oriented solidified layer formed on the substrate is transferred to the surface of an adjacent layer (eg, a polarizer, an iodine permeation inhibitory layer). Can be done.
- any appropriate orientation treatment can be adopted.
- Specific examples thereof include mechanical orientation treatment, physical orientation treatment, and chemical orientation treatment.
- Specific examples of the mechanical orientation treatment include a rubbing treatment and a stretching treatment.
- Specific examples of the physical orientation treatment include magnetic field orientation treatment and electric field orientation treatment.
- Specific examples of the chemical alignment treatment include an orthorhombic deposition method and a photoalignment treatment.
- As the treatment conditions for various orientation treatments any appropriate conditions can be adopted depending on the purpose.
- the orientation of the liquid crystal compound is performed by treating at a temperature indicating the liquid crystal phase according to the type of the liquid crystal compound. By performing such temperature treatment, the liquid crystal compound takes a liquid crystal state, and the liquid crystal compound is oriented according to the orientation treatment direction of the surface of the base material.
- the orientation state is fixed by cooling the liquid crystal compound oriented as described above.
- the orientation state is fixed by subjecting the liquid crystal compound oriented as described above to a polymerization treatment or a crosslinking treatment.
- liquid crystal compound and details of the method for forming the oriented solidified layer are described in JP-A-2006-163343. The description of this publication is incorporated herein by reference.
- the first retardation layer 20 is a single layer as shown in FIGS. 1A, 1B and 2.
- its thickness is preferably 0.5 ⁇ m to 7 ⁇ m, and more preferably 1 ⁇ m to 5 ⁇ m.
- the first retardation layer has a circular polarization function or an elliptically polarization function as described above.
- the first retardation layer is typically provided to impart antireflection characteristics to the polarizing plate, and can function as a ⁇ / 4 plate when the first retardation layer is a single layer.
- the in-plane retardation Re (550) of the first retardation layer is preferably 100 nm to 190 nm, more preferably 110 nm to 170 nm, and even more preferably 130 nm to 160 nm.
- the Nz coefficient of the first retardation layer is preferably 0.9 to 1.5, and more preferably 0.9 to 1.3. By satisfying such a relationship, a very excellent reflected hue can be achieved when the obtained polarizing plate with a retardation layer is used in an image display device.
- the first retardation layer may exhibit a reverse dispersion wavelength characteristic in which the retardation value increases according to the wavelength of the measurement light, and a positive wavelength dispersion characteristic in which the retardation value decreases according to the wavelength of the measurement light. It may be shown, or may show a flat wavelength dispersion characteristic in which the phase difference value hardly changes with the wavelength of the measurement light.
- the first retardation layer exhibits inverse dispersion wavelength characteristics.
- the Re (450) / Re (550) of the retardation layer is preferably 0.8 or more and less than 1, and more preferably 0.8 or more and 0.95 or less. With such a configuration, very excellent antireflection characteristics can be realized.
- the angle ⁇ formed by the slow axis of the first retardation layer 20 and the absorption axis of the polarizer 11 is preferably 40 ° to 50 °, more preferably 42 ° to 48 °, and even more preferably about. It is 45 °. If the angle ⁇ is in such a range, by using the ⁇ / 4 plate as the first retardation layer as described above, very excellent circular polarization characteristics (as a result, very excellent antireflection characteristics). A polarizing plate with a retardation layer having the above can be obtained.
- the first retardation layer 20 may have a laminated structure of the first liquid crystal oriented solidified layer 21 and the second liquid crystal oriented solidified layer 22 as shown in FIG.
- either one of the first liquid crystal oriented solidified layer 21 and the second liquid crystal oriented solidified layer 22 may function as a ⁇ / 4 plate, and the other may function as a ⁇ / 2 plate. Therefore, the thicknesses of the first liquid crystal oriented solidified layer 21 and the second liquid crystal oriented solidified layer 22 can be adjusted so as to obtain a desired in-plane phase difference between the ⁇ / 4 plate or the ⁇ / 2 plate.
- the thickness of the first liquid crystal oriented solidified layer 21 is, for example, 2.
- the thickness is 0.0 ⁇ m to 3.0 ⁇ m
- the thickness of the second liquid crystal oriented solidifying layer 22 is, for example, 1.0 ⁇ m to 2.0 ⁇ m.
- the in-plane retardation Re (550) of the first liquid crystal oriented solidified layer is preferably 200 nm to 300 nm, more preferably 230 nm to 290 nm, and further preferably 250 nm to 280 nm.
- the in-plane retardation Re (550) of the second liquid crystal oriented solidified layer is as described above with respect to the single layer.
- the angle formed by the slow axis of the first liquid crystal oriented solidification layer and the absorption axis of the polarizer is preferably 10 ° to 20 °, more preferably 12 ° to 18 °, and even more preferably about 15 °. Is.
- the angle formed by the slow axis of the second liquid crystal oriented solidification layer and the absorption axis of the polarizer is preferably 70 ° to 80 °, more preferably 72 ° to 78 °, and even more preferably about 75 °. Is.
- liquid crystal compounds constituting the first liquid crystal oriented solidified layer and the second liquid crystal oriented solidified layer, the method for forming the first liquid crystal oriented solidified layer and the second liquid crystal oriented solidified layer, the optical characteristics, and the like are described above with respect to the single layer. As explained in.
- the iodine permeation suppression layer is, as described above, a solidified product or a thermosetting product of a coating film of an organic solvent solution of a resin. With such a configuration, the thickness can be made very thin (for example, 10 ⁇ m or less).
- the thickness of the iodine permeation inhibitory layer is preferably 0.05 ⁇ m to 10 ⁇ m, more preferably 0.08 ⁇ m to 5 ⁇ m, still more preferably 0.1 ⁇ m to 1 ⁇ m, and particularly preferably 0.2 ⁇ m to 0.7 ⁇ m. Is.
- the iodine permeation suppressing layer can be formed directly (that is, without an adhesive layer or an adhesive layer) directly on the adjacent layer (for example, a polarizer or a retardation layer).
- the polarizer, the retardation layer and the iodine permeation suppressing layer are very thin, and the adhesive layer or the pressure-sensitive adhesive layer for laminating the iodine permeation suppressing layer is omitted. Therefore, the total thickness of the polarizing plate with a retardation layer can be made extremely thin.
- such an iodine permeation suppressing layer has an advantage that it is excellent in humidification durability because it has a smaller hygroscopicity and moisture permeability than a solidified water-based coating film such as an aqueous solution or an aqueous dispersion. As a result, it is possible to realize a polarizing plate with a retardation layer having excellent durability, which can maintain optical characteristics even in a high temperature and high humidity environment. Further, such an iodine permeation suppressing layer can suppress an adverse effect on a polarizing plate (polarizer) due to ultraviolet irradiation as compared with a cured product of, for example, an ultraviolet curable resin.
- polarizing plate polarizer
- the iodine permeation inhibitory layer is preferably a solidified coating film of a resin organic solvent solution.
- the solidified product has a smaller shrinkage during film molding than the cured product, and since it does not contain residual monomers, deterioration of the film itself is suppressed, and the solidified product has a resistance to a polarizing plate (polarizer) caused by the residual monomers and the like. The adverse effect can be suppressed.
- the glass transition temperature (Tg) of the resin constituting the iodine permeation suppressing layer is 85 ° C. or higher, and the weight average molecular weight Mw is 25000 or higher.
- Tg and Mw of the resin are in such a range, the effect synergistically with the effect of forming the iodine permeation suppressing layer with a solidified product or a thermosetting material of a coating film of an organic solvent solution of the resin is extremely effective.
- the transfer of iodine in the polarizer to the image display cell can be significantly suppressed.
- corrosion of the metal member can be remarkably suppressed.
- the Tg of the resin is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, still more preferably 110 ° C. or higher, and particularly preferably 120 ° C. or higher.
- the upper limit of Tg can be, for example, 200 ° C.
- the Mw of the resin is preferably 30,000 or more, more preferably 35,000 or more, and further preferably 40,000 or more.
- the upper limit of Mw can be, for example, 150,000.
- any suitable thermoplastic resin can be formed as long as it can form a solidified product or a thermosetting product of a coating film of an organic solvent solution and has Tg and Mw as described above.
- a thermosetting resin can be used.
- a thermoplastic resin is preferable.
- the thermoplastic resin include acrylic resins and epoxy resins. Acrylic resin and epoxy resin may be used in combination.
- typical examples of the acrylic resin and the epoxy resin that can be used for the iodine permeation suppressing layer will be described.
- Acrylic resins typically contain a repeating unit derived from a (meth) acrylic acid ester-based monomer having a linear or branched structure as a main component.
- the term (meth) acrylic refers to acrylic and / or methacryl.
- the acrylic resin may contain repeating units derived from any suitable copolymerized monomer depending on the intended purpose.
- the copolymerization monomer include a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an amide group-containing monomer, an aromatic ring-containing (meth) acrylate, and a heterocyclic ring-containing vinyl-based monomer.
- the acrylic resin is a (meth) acrylic monomer having a weight of more than 50 parts by weight and a monomer having a weight of more than 0 parts by weight and less than 50 parts by weight (hereinafter, represented by the formula (1)). , May be referred to as a copolymerized monomer) and a copolymer obtained by polymerizing a monomer mixture (hereinafter, may be referred to as a boron-containing acrylic resin).
- X is a group consisting of a vinyl group, a (meth) acrylic group, a styryl group, a (meth) acrylamide group, a vinyl ether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group.
- R 1 and R 2 each independently have a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, and a substituent. It represents an aryl group which may be used, or a heterocyclic group which may have a substituent, and R 1 and R 2 may be linked to each other to form a ring).
- the boron-containing acrylic resin typically has a repeating unit represented by the following formula.
- the boron-containing acrylic resin By polymerizing a monomer mixture containing the copolymerization monomer represented by the formula (1) and the (meth) acrylic monomer, the boron-containing acrylic resin has a substituent containing boron in the side chain (for example,). It has a repeating unit of k in the following formula).
- the boron-containing substituent may be continuously (that is, in a block shape) contained in the boron-containing acrylic resin, or may be randomly contained.
- R 6 represents an arbitrary functional group, and j and k represent integers of 1 or more).
- Any suitable (meth) acrylic monomer can be used as the (meth) acrylic monomer.
- a (meth) acrylic acid ester-based monomer having a linear or branched structure and a (meth) acrylic acid ester-based monomer having a cyclic structure can be mentioned.
- Examples of the (meth) acrylic acid ester-based monomer having a linear or branched structure include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic acid. Examples thereof include isopropyl, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and the like. .. Preferably, methyl (meth) acrylate is used.
- the (meth) acrylic acid ester-based monomer only one type may be used, or two or more types may be used in combination.
- Examples of the (meth) acrylate-based monomer having a cyclic structure include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, and ( Dicyclopentenyl acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, biphenyl (meth) acrylate, o-biphenyloxyethyl (meth) acrylate, o-biphenyloxyethoxy Ethyl (meth) acrylate, m-biphenyloxyethyl acrylate, p-biphenyloxyethyl (meth) acrylate, o-biphenyloxy-2-hydroxypropyl (meth) acrylate, p-biphenyloxy-2-hydroxypropyl
- 1-adamantyl (meth) acrylate and dicyclopentanyl (meth) acrylate are used.
- these monomers a polymer having a high glass transition temperature can be obtained. Only one kind of these monomers may be used, or two or more kinds thereof may be used in combination.
- a silsesquioxane compound having a (meth) acryloyl group may be used instead of the above (meth) acrylic acid ester-based monomer.
- a silsesquioxane compound having a (meth) acryloyl group By using the silsesquioxane compound, an acrylic polymer having a high glass transition temperature can be obtained.
- the silsesquioxane compound is known to have various skeletal structures, for example, a basket-shaped structure, a ladder-shaped structure, and a random structure.
- the silsesquioxane compound may have only one of these structures, or may have two or more of these structures. Only one type of silsesquioxane compound may be used, or two or more types may be used in combination.
- silsesquioxane compound containing a (meth) acryloyl group for example, MAC grade and AC grade of Toagosei Co., Ltd. SQ series can be used.
- the MAC grade is a silsesquioxane compound containing a methacryloyl group, and specific examples thereof include MAC-SQ TM-100, MAC-SQ SI-20, and MAC-SQ HDM.
- the AC grade is a silsesquioxane compound containing an acryloyl group, and specific examples thereof include AC-SQ TA-100 and AC-SQ SI-20.
- the (meth) acrylic monomer is used in an amount of more than 50 parts by weight with respect to 100 parts by weight of the monomer mixture.
- ⁇ Copolymerization monomer> As the copolymerization monomer, a monomer represented by the above formula (1) is used. By using such a copolymerization monomer, a substituent containing boron is introduced into the side chain of the obtained polymer. Only one type of copolymerization monomer may be used, or two or more types may be used in combination.
- the aliphatic hydrocarbon group in the above formula (1) may have a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and 3 to 3 carbon atoms which may have a substituent.
- Examples thereof include a cyclic alkyl group of 20 and an alkenyl group having 2 to 20 carbon atoms.
- Examples of the aryl group include a phenyl group having 6 to 20 carbon atoms which may have a substituent and a naphthyl group having 10 to 20 carbon atoms which may have a substituent.
- the heterocyclic group include a 5-membered ring group or a 6-membered ring group containing at least one heteroatom which may have a substituent.
- R 1 and R 2 may be connected to each other to form a ring.
- R 1 and R 2 are preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom
- the reactive group contained in the functional group represented by X is a vinyl group, a (meth) acrylic group, a styryl group, a (meth) acrylamide group, a vinyl ether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and the like. And at least one selected from the group consisting of carboxyl groups.
- the reactive group is a (meth) acrylic group and / or a (meth) acrylamide group.
- the functional group represented by X is preferably a functional group represented by ZZ.
- Z is selected from the group consisting of a vinyl group, a (meth) acrylic group, a styryl group, a (meth) acrylamide group, a vinyl ether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group.
- the following compounds can be used as the copolymerization monomer.
- the copolymerized monomer is used in an amount of more than 0 parts by weight and less than 50 parts by weight with respect to 100 parts by weight of the monomer mixture. It is preferably 0.01 parts by weight or more and less than 50 parts by weight, more preferably 0.05 parts by weight to 20 parts by weight, still more preferably 0.1 parts by weight to 10 parts by weight, and particularly preferably 0. It is 5 parts by weight to 5 parts by weight.
- the acrylic resin has a repeating unit containing a ring structure selected from a lactone ring unit, a glutaric anhydride unit, a glutarimide unit, a maleic anhydride unit and a maleimide (N-substituted maleimide) unit. .. Only one type of the repeating unit including the ring structure may be contained in the repeating unit of the acrylic resin, or two or more types may be contained.
- the lactone ring unit is preferably represented by the following general formula (2):
- R 2 , R 3 and R 4 independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.
- the organic residue may contain an oxygen atom.
- the acrylic resin may be contained only a single lactone ring units may be R 2, R 3 and R 4 in the general formula (2) is contains different lactone ring unit ..
- An acrylic resin having a lactone ring unit is described in, for example, Japanese Patent Application Laid-Open No. 2008-181078, and the description in this publication is incorporated herein by reference.
- the glutarimide unit is preferably represented by the following general formula (3):
- R 11 and R 12 independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms
- R 13 is an alkyl group having 1 to 18 carbon atoms and 3 to 12 carbon atoms.
- the cycloalkyl group of the above, or an aryl group having 6 to 10 carbon atoms is shown.
- R 11 and R 12 are independently hydrogen or methyl groups
- R 13 is a hydrogen, methyl group, butyl group or cyclohexyl group, respectively. More preferably, R 11 is a methyl group, R 12 is hydrogen, and R 13 is a methyl group.
- the acrylic resin may contain only a single glutarimide unit, or may contain a plurality of glutarimide units having different R 11 , R 12 and R 13 in the above general formula (3). ..
- Examples of the acrylic resin having a glutarimide unit include JP-A-2006-309033, JP-A-2006-317560, JP-A-2006-328334, JP-A-2006-337491, and JP-A-2006-337492. It is described in Japanese Patent Application Laid-Open No. 2006-337493 and Japanese Patent Application Laid-Open No. 2006-337569, and the description of the relevant publication is incorporated herein by reference. Note that the glutaric anhydride units, nitrogen atom substituted by R 13 in the general formula (3), except that the oxygen atom, the above description is applied about the glutarimide units.
- the structure of the maleic anhydride unit and the maleimide (N-substituted maleimide) unit is specified from the name, so specific description thereof will be omitted.
- the content ratio of the repeating unit including the ring structure in the acrylic resin is preferably 1 mol% to 50 mol%, more preferably 10 mol% to 40 mol%, and further preferably 20 mol% to 30 mol%.
- the acrylic resin contains the above-mentioned (meth) acrylic monomer-derived repeating unit as the main repeating unit.
- an epoxy resin having an aromatic ring is preferably used as the epoxy resin.
- the adhesion to the polarizing element can be improved when the iodine permeation suppressing layer is arranged adjacent to the polarizer.
- the anchoring force of the pressure-sensitive adhesive layer can be improved.
- the epoxy resin having an aromatic ring include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and other bisphenol type epoxy resins; phenol novolac epoxy resin, cresol novolac epoxy resin, hydroxybenzaldehyde phenol novolac.
- Novolak type epoxy resin such as epoxy resin; polyfunctional epoxy resin such as tetrahydroxyphenylmethane glycidyl ether, tetrahydroxybenzophenone glycidyl ether, epoxidized polyvinylphenol, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type Epoxy resin and the like can be mentioned.
- a bisphenol A type epoxy resin, a biphenyl type epoxy resin, or a bisphenol F type epoxy resin is used. Only one type of epoxy resin may be used, or two or more types may be used in combination.
- the iodine permeation suppressing layer can be formed by applying an organic solvent solution of the above resin to form a coating film, and solidifying or thermosetting the coating film.
- the organic solvent any suitable organic solvent capable of dissolving or uniformly dispersing the acrylic resin can be used.
- the organic solvent include ethyl acetate, toluene, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone, and cyclohexanone.
- the resin concentration of the solution is preferably 3 parts by weight to 20 parts by weight with respect to 100 parts by weight of the solvent. With such a resin concentration, a uniform coating film can be formed.
- the solution may be applied to any suitable substrate or adjacent layers (eg, polarizer, retardation layer).
- the solidified product (iodine permeation suppressing layer) of the coating film formed on the base material is transferred to the adjacent layer.
- the protective layer is directly formed on the adjacent layer by drying (solidifying) the coating film.
- the solution is applied to the adjacent layer and a protective layer is formed directly on the adjacent layer.
- the adhesive layer or the pressure-sensitive adhesive layer required for transfer can be omitted, so that the polarizing plate with a retardation layer can be further thinned.
- Any suitable method can be adopted as the method for applying the solution. Specific examples include a roll coating method, a spin coating method, a wire bar coating method, a dip coating method, a die coating method, a curtain coating method, a spray coating method, and a knife coating method (comma coating method, etc.).
- An iodine permeation inhibitory layer can be formed by solidifying or thermosetting the coating film of the solution.
- the heating temperature for solidification or thermosetting is preferably 100 ° C. or lower, more preferably 50 ° C. to 70 ° C. When the heating temperature is in such a range, it is possible to prevent an adverse effect on the polarizer.
- the heating time can vary depending on the heating temperature. The heating time can be, for example, 1 minute to 10 minutes.
- the iodine permeation suppressing layer may contain any suitable additive depending on the purpose.
- additives include ultraviolet absorbers; leveling agents; antioxidants such as hindered phenol-based, phosphorus-based, and sulfur-based; stabilizers such as light-resistant stabilizers, weather-resistant stabilizers, and heat-stabilizing agents; glass fibers, Reinforcing materials such as carbon fibers; Near infrared absorbers; Flame retardants such as tris (dibromopropyl) phosphate, triallyl phosphate, antimony oxide; Antistatic agents such as anionic, cationic and nonionic surfactants; Inorganic pigments , Organic pigments, colorants such as dyes; organic fillers or inorganic fillers; resin modifiers; organic fillers and inorganic fillers; plasticizers; lubricants; antistatic agents; flame retardants; and the like.
- the type, number, combination, amount of additive, etc. of the additive can be appropriately
- the retardation Rth (550) in the thickness direction of the second retardation layer is preferably ⁇ 50 nm to ⁇ 300 nm, more preferably ⁇ 70 nm to ⁇ 250 nm, still more preferably ⁇ 90 nm to ⁇ 200 nm, and particularly preferably. It is -100 nm to -180 nm.
- the second retardation layer preferably consists of a film containing a liquid crystal material fixed in a homeotropic orientation.
- the liquid crystal material (liquid crystal compound) that can be homeotropically oriented may be a liquid crystal monomer or a liquid crystal polymer.
- Specific examples of the liquid crystal compound and the method for forming the retardation layer include the liquid crystal compounds described in [0020] to [0028] of JP-A-2002-333642 and the method for forming the retardation layer.
- the thickness of the second retardation layer is preferably 0.5 ⁇ m to 10 ⁇ m, more preferably 0.5 ⁇ m to 8 ⁇ m, and even more preferably 0.5 ⁇ m to 5 ⁇ m.
- the conductive layer is an arbitrary suitable base material by any suitable film forming method (for example, vacuum deposition method, sputtering method, CVD method, ion plating method, spray method, etc.). It can be formed by forming a metal oxide film on top of it.
- the metal oxide include indium oxide, tin oxide, zinc oxide, indium-tin composite oxide, tin-antimon composite oxide, zinc-aluminum composite oxide, and indium-zinc composite oxide. Of these, indium-tin composite oxide (ITO) is preferable.
- the thickness of the conductive layer is preferably 50 nm or less, more preferably 35 nm or less.
- the lower limit of the thickness of the conductive layer is preferably 10 nm.
- the conductive layer is transferred from the base material to the first retardation layer (or the iodine permeation suppression layer or the second retardation layer if present), and the conductive layer alone constitutes a polarizing plate with a retardation layer. It may be a layer, and is laminated on the first retardation layer (or the iodine permeation suppression layer or the second retardation layer if present) as a laminate with the base material (base material with a conductive layer). You may.
- the substrate is optically isotropic, and therefore the conductive layer can be used as an isotropic substrate with a conductive layer in a polarizing plate with a retardation layer.
- any suitable isotropic base material can be adopted as the optically isotropic base material (isotropic base material).
- the material constituting the isotropic base material include a material having a resin having no conjugate system such as a norbornene resin and an olefin resin as a main skeleton, and an acrylic resin having a cyclic structure such as a lactone ring and a glutarimide ring. Examples include the material contained in the main chain. When such a material is used, when an isotropic base material is formed, the expression of the phase difference due to the orientation of the molecular chains can be suppressed to be small.
- the thickness of the isotropic base material is preferably 50 ⁇ m or less, more preferably 35 ⁇ m or less. The lower limit of the thickness of the isotropic base material is, for example, 20 ⁇ m.
- the conductive layer and / or the conductive layer of the isotropic base material with the conductive layer can be patterned as needed. By patterning, a conductive portion and an insulating portion can be formed. As a result, electrodes can be formed.
- the electrode can function as a touch sensor electrode that senses contact with the touch panel.
- any suitable method can be adopted. Specific examples of the patterning method include a wet etching method and a screen printing method.
- an embodiment of the present invention includes an image display device using such a polarizing plate with a retardation layer.
- Typical examples of the image display device include a liquid crystal display device and an electroluminescence (EL) display device (for example, an organic EL display device and an inorganic EL display device).
- the image display device according to the embodiment of the present invention includes the polarizing plate with a retardation layer according to the above items A to F on the visible side thereof.
- the polarizing plate with a retardation layer is laminated so that the retardation layer is on the image display cell side (for example, a liquid crystal cell, an organic EL cell, an inorganic EL cell) (so that the polarizer is on the visual recognition side).
- the image display device has a curved shape (substantially a curved display screen) and / or is foldable or foldable.
- Thickness The thickness of 10 ⁇ m or less was measured using an interference film thickness meter (manufactured by Otsuka Electronics Co., Ltd., product name “MCPD-3000”). The thickness exceeding 10 ⁇ m was measured using a digital micrometer (manufactured by Anritsu, product name “KC-351C”).
- an overcoat solution (solid content) containing 99 parts of methyl isobutyl ketone (MIBK), 1 part of pentaerythritol tetraacrylate (PETA), and 0.03 part of a photopolymerization initiator (manufactured by BASF, product name "Irgacure 907"). Concentration: about 1%) was applied to the surface of the silver nanowire coating film using a wire bar so that the wet film thickness was 10 ⁇ m, and dried in an oven at 100 ° C. for 5 minutes.
- MIBK methyl isobutyl ketone
- PETA pentaerythritol tetraacrylate
- a photopolymerization initiator manufactured by BASF, product name "Irgacure 907”
- the overcoat coating film was cured by irradiating with active energy rays to prepare a metal film having a composition of PET film / silver nanowire layer / overcoat layer (thickness 100 nm).
- This metal film was attached to a glass plate having a thickness of 0.5 mm using an adhesive (15 ⁇ m) to obtain a metal film / adhesive / glass plate laminate.
- a non-contact resistance measuring instrument manufactured by Napuson, product name "EC-80"
- the polarizing plates with retardation layers obtained in Examples and Comparative Examples were bonded to the surface of the overcoat layer of the metal film of the laminated body to prepare a test sample.
- the resistance value of this test sample was measured with a non-contact resistance measuring instrument and used as the initial resistance value. Further, after subjecting the test sample to a reliability test (placed in an environment of 85 ° C. and 85% RH for 48 hours and then left in an environment of 23 ° C. and 55% RH for 2 hours), the resistance value is the same as above. Was measured.
- the resistance value increase rate was calculated by the following formula.
- Resistance value increase rate (%) ⁇ (resistance value after reliability test-initial resistance value) / initial resistance value ⁇ x 100 Furthermore, it was evaluated according to the following criteria. Good: Resistance increase rate is less than 200% Bad: Resistance increase rate is 200% or more
- Resistance value increase rate (%) ⁇ (resistance value after reliability test-initial resistance value) / initial resistance value ⁇ x 100 Furthermore, it was evaluated according to the following criteria. Excellent: Resistance increase rate is less than 200% Good: Resistance increase rate is 200% or more and less than 2000% Bad: Resistance increase rate is 2000% or more
- thermoplastic resin base material an amorphous isophthalic copolymerized polyethylene terephthalate film (thickness: 100 ⁇ m) having a long shape, a water absorption of 0.75%, and a Tg of about 75 ° C. was used.
- One side of the resin base material was corona-treated.
- a PVA aqueous solution (coating solution) was prepared by dissolving 13 parts by weight of potassium iodide in water.
- the PVA aqueous solution was applied to the corona-treated surface of the resin base material and dried at 60 ° C. to form a PVA-based resin layer having a thickness of 13 ⁇ m to prepare a laminate.
- the obtained laminate was uniaxially stretched at the free end 2.4 times in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds in an oven at 130 ° C. (aerial auxiliary stretching treatment). Next, the laminate was immersed in an insolubilizing bath at a liquid temperature of 40 ° C.
- HC-COP film as a protective layer was attached to the surface of the polarizer obtained above (the surface opposite to the resin substrate) via an ultraviolet curable adhesive. Specifically, the curable adhesive was coated so as to have a total thickness of 1.0 ⁇ m, and bonded using a roll machine. Then, UV light was irradiated from the protective layer side to cure the adhesive.
- the HC-COP film is a film in which a hard coat (HC) layer (thickness 2 ⁇ m) is formed on a cycloolefin (COP) film (manufactured by Nippon Zeon Corporation, product name “ZF12”, thickness 25 ⁇ m), and is a COP film.
- HC hard coat
- COP cycloolefin
- the surface of a polyethylene terephthalate (PET) film was rubbed with a rubbing cloth and subjected to an orientation treatment.
- the direction of the alignment treatment was set to be 15 ° when viewed from the visual side with respect to the direction of the absorption axis of the polarizer when the polarizing plate was attached.
- the liquid crystal coating liquid was applied to the alignment-treated surface with a bar coater, and the liquid crystal compound was oriented by heating and drying at 90 ° C. for 2 minutes.
- the liquid crystal layer thus formed was irradiated with light of 1 mJ / cm 2 using a metal halide lamp, and the liquid crystal layer was cured to form a liquid crystal oriented solidified layer A on the PET film.
- the protective layer (HC layer / COP film) / adhesive layer / polarizer / adhesive layer / retardation layer (first liquid crystal oriented solidified layer / adhesive layer / second liquid crystal oriented solidified layer).
- an adhesive layer (thickness 15 ⁇ m) is provided on the surface of the iodine permeation suppressing layer, and a protective layer (HC layer / COP film) / adhesive layer / polarizer / adhesive layer / retardation layer (first liquid crystal alignment solidification layer) is provided.
- a polarizing plate with a retardation layer having the constitution of / adhesive layer / second liquid crystal oriented solidified layer) / iodine permeation suppressing layer / adhesive layer was obtained.
- the total thickness of the obtained polarizing plate with a retardation layer was 39.5 ⁇ m.
- the obtained polarizing plate with a retardation layer was subjected to the evaluations (2) and (3) above. Further, regarding metal corrosiveness, it was compared with Comparative Example 1 (described later) in which the iodine permeation suppressing layer was not formed. The results are shown in Tables 1 and 2.
- Methyl methacrylate (MMA, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "methyl methacrylate monomer”) 97.0 parts, 3.0 parts of copolymerization monomer represented by the above general formula (1e), polymerization initiation 0.2 part of the agent (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "2,2'-azobis (isobutyronitrile)”) was dissolved in 200 parts of toluene. Next, a polymerization reaction was carried out for 5.5 hours while heating at 70 ° C. in a nitrogen atmosphere to obtain a boron-containing acrylic resin solution (solid content concentration: 33%).
- MMA manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "methyl methacrylate monomer” 97.0 parts, 3.0 parts of copolymerization monomer represented by the above general formula (1e)
- polymerization initiation 0.2 part of the agent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "2,
- the obtained boron-containing acrylic polymer had a Tg of 110 ° C. and a Mw of 80,000.
- the retardation layer was the same as in Example 1 except that this boron-containing acrylic polymer was used instead of the acrylic resin "B-811" and the thickness of the iodine permeation suppressing layer was 0.3 ⁇ m.
- a polarizing plate with a plate was prepared.
- the obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
- Example 3 A polarizing plate with a retardation layer was produced in the same manner as in Example 2 except that the thickness of the iodine permeation suppressing layer was 0.5 ⁇ m. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
- Example 4 Examples except that a thermoplastic epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name "jER (registered trademark) 1256B40", Tg: 100 ° C., Mw: 45000) was used instead of the acrylic resin "B-811".
- a polarizing plate with a retardation layer was produced in the same manner as in 1.
- the obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
- Example 5 A thermoplastic epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name "jER (registered trademark) YX7200B35", Tg: 150 ° C., Mw: 30000) was used instead of the acrylic resin "B-811", and iodine.
- a polarizing plate with a retardation layer was produced in the same manner as in Example 1 except that the thickness of the permeation suppression layer was 0.3 ⁇ m.
- the obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
- Example 6 A polarizing plate with a retardation layer was produced in the same manner as in Example 5 except that the thickness of the iodine permeation suppressing layer was 0.5 ⁇ m. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
- Example 7 Instead of the acrylic resin "B-811", 15 parts of “B-811” and 85 parts of thermoplastic epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name "jER (registered trademark) YX6954BH30") (solid content conversion) A polarizing plate with a retardation layer was produced in the same manner as in Example 1 except that the above blend was used. The Tg of the blend was 125 ° C. and the Mw was 38,000. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
- Example 8 Example 1-2.
- the resin blend used in Example 7 was applied and dried on the polarizer side of the polarizing plate having the constitution of the protective layer (HC layer / COP film) / adhesive layer / polarizer obtained in the above, and the resin was organic.
- An iodine permeation inhibitory layer (thickness 0.5 ⁇ m) formed as a solidified coating film of the solvent solution was formed.
- the liquid crystal oriented solidified layer A and the liquid crystal oriented solidified layer B are transferred in this order to the surface of the iodine permeation suppressing layer in the same manner as in Example 1, and the protective layer (HC layer / COP film) / adhesive layer / polarizer / iodine permeation
- a polarizing plate with a retardation layer having a structure of an inhibitory layer / adhesive layer / retardation layer (first liquid crystal alignment solidification layer / adhesive layer / second liquid crystal alignment solidification layer) / adhesive layer was obtained.
- the obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
- Example 9 Lamination having a protective layer (HC layer / COP film) / adhesive layer / polarizer / iodine permeation suppressing layer in the same manner as in Example 8 except that the boron-containing acrylic polymer in Example 2 was used. The body was made. Next, a blend of 15 parts of the boron-containing acrylic polymer and 85 parts (solid content equivalent) of the thermoplastic epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name "jER (registered trademark) YX6954BH30”) in Example 2 was used.
- jER registered trademark
- Protective layer (HC layer / COP film) / adhesive layer / polarizer / iodine permeation suppression layer / adhesive layer / retardation layer (first liquid crystal oriented solidifying layer / adhesion) in the same manner as in Example 1 except for the above.
- a polarizing plate with a retardation layer having a structure of an agent layer / a second liquid crystal oriented solidified layer) / an iodine permeation suppressing layer / an adhesive layer was obtained.
- the total thickness of the obtained polarizing plate with a retardation layer was 40 ⁇ m.
- the obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 2.
- Example 10 Fifteen parts of the boron-containing acrylic polymer obtained in Example 2 and a thermoplastic epoxy resin (on the iodine permeation suppressing layer provided between the polarizing element and the retardation layer and adjacent to the polarizing element).
- a polarizing plate with a retardation layer was obtained in the same manner as in Example 9 except that a blend with 85 parts (solid content equivalent) of Mitsubishi Chemical Co., Ltd., trade name "jER (registered trademark) YX6954BH30") was used. ..
- the total thickness of the obtained polarizing plate with a retardation layer was 40 ⁇ m.
- the obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 2.
- Example 11 The iodine permeation suppressing layer formed between the polarizer and the retardation layer at a position adjacent to the polarizer is placed between the polarizer and the retardation layer at a position adjacent to the retardation layer.
- Protective layer HC layer / COP film
- adhesive layer / polarizer / adhesive layer / iodine permeation suppression layer / retardation layer (first liquid crystal oriented solidified layer) in the same manner as in Example 10 except that it was formed.
- a polarizing plate with a retardation layer having the constitution of / adhesive layer / second liquid crystal alignment solidification layer) / iodine permeation suppression layer / pressure-sensitive adhesive layer was obtained.
- the total thickness of the obtained polarizing plate with a retardation layer was 40 ⁇ m.
- the obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 2.
- Example 12 Similar to Example 9, the protective layer (HC) is similar to that of Example 11 except that an iodine permeation suppressing layer is further formed between the polarizer and the retardation layer at a position adjacent to the polarizer.
- a polarizing plate with a retardation layer having a structure of an iodine permeation suppressing layer / an adhesive layer was obtained.
- the total thickness of the obtained polarizing plate with a retardation layer was 40.5 ⁇ m.
- the obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 2.
- Example 1 A polarizing plate with a retardation layer was produced in the same manner as in Example 1 except that the iodine permeation suppressing layer was not formed. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
- the retardation layer is the same as in Example 1 except that the acrylic resin "B-723" (manufactured by Kusumoto Kasei Co., Ltd., Tg: 54 ° C., Mw: 200,000) is used instead of the acrylic resin "B-811".
- a polarizing plate with a polarizing plate was prepared.
- the obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
- Example 4 Same as in Example 1 except that a PVA resin (manufactured by Mitsubishi Chemical Corporation, trade name "Gosenol Z200", Tg: 80 ° C., Mw: 8800) was used instead of the acrylic resin "B-811". A polarizing plate with a retardation layer was produced. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
- the temperature rise and depressurization in the second reactor were started, and the internal temperature was 240 ° C. and the pressure was 0.2 kPa in 50 minutes. Then, the polymerization was allowed to proceed until the stirring power became a predetermined value. When the predetermined power was reached, nitrogen was introduced into the reactor to repressurize, the produced polyester carbonate-based resin was extruded into water, and the strands were cut to obtain pellets.
- the polarizing plate with a retardation layer according to the embodiment of the present invention forms an iodine permeation inhibitory layer composed of a solidified product of an organic solvent solution of a resin having a predetermined Tg and Mw.
- the metal corrosiveness in a high temperature and high humidity environment can be remarkably suppressed. Therefore, it can be seen that the polarizing plate with a retardation layer according to the embodiment of the present invention can suppress corrosion of metal members when applied to an image display device. Further, as is clear from Reference Example 1, such metal corrosiveness is a problem peculiar to a very thin polarizing plate with a retardation layer.
- the polarizing plate with a retardation layer of Examples 9 to 12 of the present invention contains two or three layers of iodine permeation suppression layers, so that it can be used for a long time (200 hours) in a high temperature and high humidity environment. ) Even when it is thrown in, metal corrosiveness can be remarkably suppressed. Therefore, it can be seen that the polarizing plates with retardation layers of Examples 9 to 12 of the present invention can remarkably suppress the corrosion of metal members when applied to an image display device.
- the polarizing plate with a retardation layer of the present invention is suitably used as a circular polarizing plate for a liquid crystal display device, an organic EL display device, and an inorganic EL display device.
- Polarizing plate 11 Polarizer 12 Protective layer 20 Phase difference layer 30
- Adhesive layer 40 Iodine permeation suppression layer 100 Polarizing plate with retardation layer 101 Polarizing plate with retardation layer 102 Polarizing plate with retardation layer 103 Polarizing plate with retardation layer 104 Polarizing plate with retardation layer 105 Polarizing plate with retardation layer
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Polarising Elements (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
Provided is a thin retardation layer–equipped polarizing plate that can suppress the corrosion of a metal member when used in an image display device. This retardation layer–equipped polarizing plate has, in order from the viewing side: a polarizing plate that includes a polarizer; a retardation layer; and an adhesive layer. The retardation layer is an oriented solidified layer of a liquid crystal compound that can circularly or elliptically polarize light. An iodine transmission suppression layer that is formed by solidifying or thermosetting a coating film of an organic solvent solution of a resin is provided between the polarizer and the adhesive layer. The resin that constitutes the iodine transmission suppression layer has a glass transition temperature of at least 85°C and a weight average molecular weight Mw of at least 25000.
Description
本発明は、位相差層付偏光板およびそれを用いた画像表示装置に関する。
The present invention relates to a polarizing plate with a retardation layer and an image display device using the same.
近年、液晶表示装置およびエレクトロルミネセンス(EL)表示装置(例えば、有機EL表示装置、無機EL表示装置)に代表される画像表示装置が急速に普及している。画像表示装置には、代表的には偏光板および位相差板が用いられている。実用的には、偏光板と位相差板とを一体化した位相差層付偏光板が広く用いられているところ(例えば、特許文献1)、最近、画像表示装置の薄型化への要望が強くなるに伴って、位相差層付偏光板についても薄型化の要望が強まっている。位相差層付偏光板の薄型化を目的として、厚みに対する寄与の大きい偏光子の保護層の薄型化(または省略)ならびに位相差フィルムの薄型化が進んでいる。しかし、薄型の位相差層付偏光板を画像表示装置に適用すると、画像表示装置の金属部材(例えば、電極、センサー、配線、金属層)が腐食する場合がある。このような金属部材の腐食は、高温高湿環境下で顕著である。
In recent years, image display devices represented by liquid crystal display devices and electroluminescence (EL) display devices (for example, organic EL display devices and inorganic EL display devices) have rapidly become widespread. A polarizing plate and a retardation plate are typically used in the image display device. Practically, a polarizing plate with a retardation layer in which a polarizing plate and a retardation plate are integrated is widely used (for example, Patent Document 1), and recently, there has been a strong demand for thinner image display devices. As a result, there is an increasing demand for thinner plates with retardation layers. For the purpose of thinning the polarizing plate with a retardation layer, the protective layer of the polarizer, which greatly contributes to the thickness, is thinned (or omitted), and the retardation film is thinned. However, when a thin polarizing plate with a retardation layer is applied to an image display device, metal members (for example, electrodes, sensors, wiring, metal layer) of the image display device may be corroded. Such corrosion of metal members is remarkable in a high temperature and high humidity environment.
本発明は上記従来の課題を解決するためになされたものであり、その主たる目的は、画像表示装置に適用した場合に金属部材の腐食を抑制し得る薄型の位相差層付偏光板を提供することにある。
The present invention has been made to solve the above-mentioned conventional problems, and a main object thereof is to provide a thin polarizing plate with a retardation layer capable of suppressing corrosion of a metal member when applied to an image display device. There is.
本発明の位相差層付偏光板は、偏光子を含む偏光板と、位相差層と、粘着剤層と、を視認側からこの順に有し、該位相差層は円偏光機能または楕円偏光機能を有する液晶化合物の配向固化層である。位相差層付偏光板においては、該偏光子と該粘着剤層との間に、樹脂の有機溶媒溶液の塗布膜の固化物または熱硬化物であるヨウ素透過抑制層が設けられており、該ヨウ素透過抑制層を構成する樹脂のガラス転移温度は85℃以上であり、かつ、重量平均分子量Mwは25000以上である。
1つの実施形態においては、上記ヨウ素透過抑制層は、上記偏光子と上記位相差層との間に設けられている。別の実施形態においては、上記ヨウ素透過抑制層は、上記位相差層と上記粘着剤層との間に設けられている。
1つの実施形態においては、上記ヨウ素透過抑制層は、上記偏光子と上記粘着剤層との間に2層以上設けられている。
1つの実施形態においては、上記ヨウ素透過抑制層の厚みは0.05μm~10μmである。
1つの実施形態においては、上記ヨウ素透過抑制層を構成する樹脂のガラス転移温度は90℃以上である。
1つの実施形態においては、上記ヨウ素透過抑制層を構成する樹脂は、50重量部を超える(メタ)アクリル系単量体と0重量部を超えて50重量部未満の式(1)で表される単量体とを含むモノマー混合物を重合することにより得られる共重合体を含む:
(式中、Xはビニル基、(メタ)アクリル基、スチリル基、(メタ)アクリルアミド基、ビニルエーテル基、エポキシ基、オキセタン基、ヒドロキシル基、アミノ基、アルデヒド基、および、カルボキシル基からなる群より選択される少なくとも1種の反応性基を含む官能基を表し、R1およびR2はそれぞれ独立して、水素原子、置換基を有していてもよい脂肪族炭化水素基、置換基を有していてもよいアリール基、または、置換基を有していてもよいヘテロ環基を表し、R1およびR2は互いに連結して環を形成してもよい)。
1つの実施形態においては、上記位相差層は単一層であり、該位相差層のRe(550)は100nm~190nmであり、該位相差層の遅相軸と上記偏光子の吸収軸とのなす角度は40°~50°である。
1つの実施形態においては、上記位相差層は、第1の液晶化合物の配向固化層と第2の液晶化合物の配向固化層との積層構造を有し;該第1の液晶化合物の配向固化層のRe(550)は200nm~300nmであり、その遅相軸と上記偏光子の吸収軸とのなす角度は10°~20°であり;該第2の液晶化合物の配向固化層のRe(550)は100nm~190nmであり、その遅相軸と該偏光子の吸収軸とのなす角度は70°~80°である。
1つの実施形態においては、上記位相差層付偏光板は、上記位相差層と上記粘着剤層との間に別の位相差層をさらに有し、該別の位相差層の屈折率特性はnz>nx=nyの関係を示す。
1つの実施形態においては、上記位相差層付偏光板は、上記ヨウ素透過抑制層と上記粘着剤層との間に導電層または導電層付等方性基材をさらに有する。
1つの実施形態においては、上記位相差層付偏光板は、総厚みが60μm以下である。
本発明の別の局面によれば、画像表示装置が提供される。この画像表示装置は、上記の位相差層付偏光板を備える。
1つの実施形態においては、上記画像表示装置は、有機エレクトロルミネセンス表示装置または無機エレクトロルミネセンス表示装置である。 The polarizing plate with a retardation layer of the present invention has a polarizing plate containing a polarizer, a retardation layer, and an adhesive layer in this order from the visual side, and the retardation layer has a circular polarization function or an elliptical polarization function. It is an orientation solidification layer of a liquid crystal compound having. In a polarizing plate with a retardation layer, an iodine permeation suppressing layer, which is a solidified or thermosetting film of a coating film of an organic solvent solution of a resin, is provided between the polarizing element and the pressure-sensitive adhesive layer. The glass transition temperature of the resin constituting the iodine permeation suppressing layer is 85 ° C. or higher, and the weight average molecular weight Mw is 25,000 or higher.
In one embodiment, the iodine permeation inhibitory layer is provided between the polarizer and the retardation layer. In another embodiment, the iodine permeation suppressing layer is provided between the retardation layer and the pressure-sensitive adhesive layer.
In one embodiment, the iodine permeation suppressing layer is provided with two or more layers between the polarizer and the pressure-sensitive adhesive layer.
In one embodiment, the iodine permeation inhibitory layer has a thickness of 0.05 μm to 10 μm.
In one embodiment, the glass transition temperature of the resin constituting the iodine permeation suppressing layer is 90 ° C. or higher.
In one embodiment, the resin constituting the iodine permeation suppressing layer is represented by the formula (1) of more than 50 parts by weight (meth) acrylic monomer and more than 0 parts by weight and less than 50 parts by weight. Contains a copolymer obtained by polymerizing a monomer mixture containing a monomer:
(In the formula, X is a group consisting of a vinyl group, a (meth) acrylic group, a styryl group, a (meth) acrylamide group, a vinyl ether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group. Represents a functional group containing at least one reactive group selected, and R 1 and R 2 each independently have a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, and a substituent. It represents an aryl group which may be used, or a heterocyclic group which may have a substituent, and R 1 and R 2 may be linked to each other to form a ring).
In one embodiment, the retardation layer is a single layer, the Re (550) of the retardation layer is 100 nm to 190 nm, and the slow axis of the retardation layer and the absorption axis of the polarizer The angle of formation is 40 ° to 50 °.
In one embodiment, the retardation layer has a laminated structure of an oriented solidified layer of a first liquid crystal compound and an oriented solidified layer of a second liquid crystal compound; an oriented solidified layer of the first liquid crystal compound. The Re (550) of the second liquid crystal compound is 200 nm to 300 nm, and the angle formed by the slow axis thereof and the absorption axis of the polarizer is 10 ° to 20 °; the Re (550) of the orientation solidification layer of the second liquid crystal compound is formed. ) Is 100 nm to 190 nm, and the angle formed by the slow axis thereof and the absorption axis of the polarizer is 70 ° to 80 °.
In one embodiment, the polarizing plate with a retardation layer further has another retardation layer between the retardation layer and the pressure-sensitive adhesive layer, and the refractive index characteristic of the other retardation layer is The relationship of nz> nx = ny is shown.
In one embodiment, the polarizing plate with a retardation layer further has a conductive layer or an isotropic base material with a conductive layer between the iodine permeation suppressing layer and the pressure-sensitive adhesive layer.
In one embodiment, the polarizing plate with a retardation layer has a total thickness of 60 μm or less.
According to another aspect of the present invention, an image display device is provided. This image display device includes the above-mentioned polarizing plate with a retardation layer.
In one embodiment, the image display device is an organic electroluminescence display device or an inorganic electroluminescence display device.
1つの実施形態においては、上記ヨウ素透過抑制層は、上記偏光子と上記位相差層との間に設けられている。別の実施形態においては、上記ヨウ素透過抑制層は、上記位相差層と上記粘着剤層との間に設けられている。
1つの実施形態においては、上記ヨウ素透過抑制層は、上記偏光子と上記粘着剤層との間に2層以上設けられている。
1つの実施形態においては、上記ヨウ素透過抑制層の厚みは0.05μm~10μmである。
1つの実施形態においては、上記ヨウ素透過抑制層を構成する樹脂のガラス転移温度は90℃以上である。
1つの実施形態においては、上記ヨウ素透過抑制層を構成する樹脂は、50重量部を超える(メタ)アクリル系単量体と0重量部を超えて50重量部未満の式(1)で表される単量体とを含むモノマー混合物を重合することにより得られる共重合体を含む:
1つの実施形態においては、上記位相差層は単一層であり、該位相差層のRe(550)は100nm~190nmであり、該位相差層の遅相軸と上記偏光子の吸収軸とのなす角度は40°~50°である。
1つの実施形態においては、上記位相差層は、第1の液晶化合物の配向固化層と第2の液晶化合物の配向固化層との積層構造を有し;該第1の液晶化合物の配向固化層のRe(550)は200nm~300nmであり、その遅相軸と上記偏光子の吸収軸とのなす角度は10°~20°であり;該第2の液晶化合物の配向固化層のRe(550)は100nm~190nmであり、その遅相軸と該偏光子の吸収軸とのなす角度は70°~80°である。
1つの実施形態においては、上記位相差層付偏光板は、上記位相差層と上記粘着剤層との間に別の位相差層をさらに有し、該別の位相差層の屈折率特性はnz>nx=nyの関係を示す。
1つの実施形態においては、上記位相差層付偏光板は、上記ヨウ素透過抑制層と上記粘着剤層との間に導電層または導電層付等方性基材をさらに有する。
1つの実施形態においては、上記位相差層付偏光板は、総厚みが60μm以下である。
本発明の別の局面によれば、画像表示装置が提供される。この画像表示装置は、上記の位相差層付偏光板を備える。
1つの実施形態においては、上記画像表示装置は、有機エレクトロルミネセンス表示装置または無機エレクトロルミネセンス表示装置である。 The polarizing plate with a retardation layer of the present invention has a polarizing plate containing a polarizer, a retardation layer, and an adhesive layer in this order from the visual side, and the retardation layer has a circular polarization function or an elliptical polarization function. It is an orientation solidification layer of a liquid crystal compound having. In a polarizing plate with a retardation layer, an iodine permeation suppressing layer, which is a solidified or thermosetting film of a coating film of an organic solvent solution of a resin, is provided between the polarizing element and the pressure-sensitive adhesive layer. The glass transition temperature of the resin constituting the iodine permeation suppressing layer is 85 ° C. or higher, and the weight average molecular weight Mw is 25,000 or higher.
In one embodiment, the iodine permeation inhibitory layer is provided between the polarizer and the retardation layer. In another embodiment, the iodine permeation suppressing layer is provided between the retardation layer and the pressure-sensitive adhesive layer.
In one embodiment, the iodine permeation suppressing layer is provided with two or more layers between the polarizer and the pressure-sensitive adhesive layer.
In one embodiment, the iodine permeation inhibitory layer has a thickness of 0.05 μm to 10 μm.
In one embodiment, the glass transition temperature of the resin constituting the iodine permeation suppressing layer is 90 ° C. or higher.
In one embodiment, the resin constituting the iodine permeation suppressing layer is represented by the formula (1) of more than 50 parts by weight (meth) acrylic monomer and more than 0 parts by weight and less than 50 parts by weight. Contains a copolymer obtained by polymerizing a monomer mixture containing a monomer:
In one embodiment, the retardation layer is a single layer, the Re (550) of the retardation layer is 100 nm to 190 nm, and the slow axis of the retardation layer and the absorption axis of the polarizer The angle of formation is 40 ° to 50 °.
In one embodiment, the retardation layer has a laminated structure of an oriented solidified layer of a first liquid crystal compound and an oriented solidified layer of a second liquid crystal compound; an oriented solidified layer of the first liquid crystal compound. The Re (550) of the second liquid crystal compound is 200 nm to 300 nm, and the angle formed by the slow axis thereof and the absorption axis of the polarizer is 10 ° to 20 °; the Re (550) of the orientation solidification layer of the second liquid crystal compound is formed. ) Is 100 nm to 190 nm, and the angle formed by the slow axis thereof and the absorption axis of the polarizer is 70 ° to 80 °.
In one embodiment, the polarizing plate with a retardation layer further has another retardation layer between the retardation layer and the pressure-sensitive adhesive layer, and the refractive index characteristic of the other retardation layer is The relationship of nz> nx = ny is shown.
In one embodiment, the polarizing plate with a retardation layer further has a conductive layer or an isotropic base material with a conductive layer between the iodine permeation suppressing layer and the pressure-sensitive adhesive layer.
In one embodiment, the polarizing plate with a retardation layer has a total thickness of 60 μm or less.
According to another aspect of the present invention, an image display device is provided. This image display device includes the above-mentioned polarizing plate with a retardation layer.
In one embodiment, the image display device is an organic electroluminescence display device or an inorganic electroluminescence display device.
本発明の実施形態によれば、薄型の位相差層付偏光板の所定の位置に特定のヨウ素透過抑制層を設けることにより、当該位相差層付偏光板を画像表示装置に適用した場合に金属部材の腐食を抑制することができる。本発明の実施形態に用いられ得るヨウ素透過抑制層は、樹脂の有機溶媒溶液の塗布膜の固化物または熱硬化物であり、当該ヨウ素透過抑制層を構成する樹脂のガラス転移温度は85℃以上であり、かつ、重量平均分子量Mwは25000以上である。
According to the embodiment of the present invention, by providing a specific iodine permeation suppressing layer at a predetermined position of a thin polarizing plate with a retardation layer, a metal when the polarizing plate with a retardation layer is applied to an image display device. Corrosion of members can be suppressed. The iodine permeation suppressing layer that can be used in the embodiment of the present invention is a solidified or thermosetting product of a coating film of an organic solvent solution of a resin, and the glass transition temperature of the resin constituting the iodine permeation suppressing layer is 85 ° C. or higher. And the weight average molecular weight Mw is 25,000 or more.
以下、本発明の実施形態について説明するが、本発明はこれらの実施形態には限定されない。
Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.
(用語および記号の定義)
本明細書における用語および記号の定義は下記の通りである。
(1)屈折率(nx、ny、nz)
「nx」は面内の屈折率が最大になる方向(すなわち、遅相軸方向)の屈折率であり、「ny」は面内で遅相軸と直交する方向(すなわち、進相軸方向)の屈折率であり、「nz」は厚み方向の屈折率である。
(2)面内位相差(Re)
「Re(λ)」は、23℃における波長λnmの光で測定した面内位相差である。例えば、「Re(550)」は、23℃における波長550nmの光で測定した面内位相差である。Re(λ)は、層(フィルム)の厚みをd(nm)としたとき、式:Re(λ)=(nx-ny)×dによって求められる。
(3)厚み方向の位相差(Rth)
「Rth(λ)」は、23℃における波長λnmの光で測定した厚み方向の位相差である。例えば、「Rth(550)」は、23℃における波長550nmの光で測定した厚み方向の位相差である。Rth(λ)は、層(フィルム)の厚みをd(nm)としたとき、式:Rth(λ)=(nx-nz)×dによって求められる。
(4)Nz係数
Nz係数は、Nz=Rth/Reによって求められる。
(5)角度
本明細書において角度に言及するときは、当該角度は基準方向に対して時計回りおよび反時計回りの両方を包含する。したがって、例えば「45°」は±45°を意味する。 (Definition of terms and symbols)
Definitions of terms and symbols herein are as follows.
(1) Refractive index (nx, ny, nz)
"Nx" is the refractive index in the direction in which the in-plane refractive index is maximized (that is, the slow-phase axis direction), and "ny" is the in-plane direction orthogonal to the slow-phase axis (that is, the phase-advance axis direction). Is the refractive index of, and "nz" is the refractive index in the thickness direction.
(2) In-plane phase difference (Re)
“Re (λ)” is an in-plane phase difference measured with light having a wavelength of λ nm at 23 ° C. For example, "Re (550)" is an in-plane phase difference measured with light having a wavelength of 550 nm at 23 ° C. Re (λ) is obtained by the formula: Re (λ) = (nx−ny) × d, where d (nm) is the thickness of the layer (film).
(3) Phase difference in the thickness direction (Rth)
“Rth (λ)” is a phase difference in the thickness direction measured with light having a wavelength of λ nm at 23 ° C. For example, "Rth (550)" is a phase difference in the thickness direction measured with light having a wavelength of 550 nm at 23 ° C. Rth (λ) is obtained by the formula: Rth (λ) = (nx−nz) × d, where d (nm) is the thickness of the layer (film).
(4) Nz coefficient The Nz coefficient is obtained by Nz = Rth / Re.
(5) Angle When referring to an angle herein, the angle includes both clockwise and counterclockwise with respect to the reference direction. Therefore, for example, "45 °" means ± 45 °.
本明細書における用語および記号の定義は下記の通りである。
(1)屈折率(nx、ny、nz)
「nx」は面内の屈折率が最大になる方向(すなわち、遅相軸方向)の屈折率であり、「ny」は面内で遅相軸と直交する方向(すなわち、進相軸方向)の屈折率であり、「nz」は厚み方向の屈折率である。
(2)面内位相差(Re)
「Re(λ)」は、23℃における波長λnmの光で測定した面内位相差である。例えば、「Re(550)」は、23℃における波長550nmの光で測定した面内位相差である。Re(λ)は、層(フィルム)の厚みをd(nm)としたとき、式:Re(λ)=(nx-ny)×dによって求められる。
(3)厚み方向の位相差(Rth)
「Rth(λ)」は、23℃における波長λnmの光で測定した厚み方向の位相差である。例えば、「Rth(550)」は、23℃における波長550nmの光で測定した厚み方向の位相差である。Rth(λ)は、層(フィルム)の厚みをd(nm)としたとき、式:Rth(λ)=(nx-nz)×dによって求められる。
(4)Nz係数
Nz係数は、Nz=Rth/Reによって求められる。
(5)角度
本明細書において角度に言及するときは、当該角度は基準方向に対して時計回りおよび反時計回りの両方を包含する。したがって、例えば「45°」は±45°を意味する。 (Definition of terms and symbols)
Definitions of terms and symbols herein are as follows.
(1) Refractive index (nx, ny, nz)
"Nx" is the refractive index in the direction in which the in-plane refractive index is maximized (that is, the slow-phase axis direction), and "ny" is the in-plane direction orthogonal to the slow-phase axis (that is, the phase-advance axis direction). Is the refractive index of, and "nz" is the refractive index in the thickness direction.
(2) In-plane phase difference (Re)
“Re (λ)” is an in-plane phase difference measured with light having a wavelength of λ nm at 23 ° C. For example, "Re (550)" is an in-plane phase difference measured with light having a wavelength of 550 nm at 23 ° C. Re (λ) is obtained by the formula: Re (λ) = (nx−ny) × d, where d (nm) is the thickness of the layer (film).
(3) Phase difference in the thickness direction (Rth)
“Rth (λ)” is a phase difference in the thickness direction measured with light having a wavelength of λ nm at 23 ° C. For example, "Rth (550)" is a phase difference in the thickness direction measured with light having a wavelength of 550 nm at 23 ° C. Rth (λ) is obtained by the formula: Rth (λ) = (nx−nz) × d, where d (nm) is the thickness of the layer (film).
(4) Nz coefficient The Nz coefficient is obtained by Nz = Rth / Re.
(5) Angle When referring to an angle herein, the angle includes both clockwise and counterclockwise with respect to the reference direction. Therefore, for example, "45 °" means ± 45 °.
A.位相差層付偏光板の全体構成
図1Aは、本発明の1つの実施形態による位相差層付偏光板の概略断面図であり;図1Bは、本発明の別の実施形態による位相差層付偏光板の概略断面図である。図1Aおよび図1Bの位相差層付偏光板100、101はそれぞれ、偏光板10と位相差層20と粘着剤層30とを視認側からこの順に有する。偏光板10は、代表的には、偏光子11と、偏光子11の視認側に配置された保護層12と、を含む。目的に応じて、偏光子11の視認側(保護層12)と反対側に別の保護層(図示せず)が設けられてもよい。位相差層20は、円偏光機能または楕円偏光機能を有する液晶化合物の配向固化層(以下、単に液晶配向固化層と称する場合がある)である。粘着剤層30は最外層として設けられ、位相差層付偏光板は画像表示装置(実質的には、画像表示セル)に貼り付け可能とされている。 A. Overall Configuration of Polarizing Plate with Phase Difference FIG. 1A is a schematic cross-sectional view of a polarizing plate with a retardation layer according to one embodiment of the present invention; FIG. 1B is a polarizing plate with a retardation layer according to another embodiment of the present invention. It is a schematic cross-sectional view of a polarizing plate. The polarizing plates 100 and 101 with a retardation layer of FIGS. 1A and 1B each have a polarizing plate 10, a retardation layer 20, and an adhesive layer 30 in this order from the visual side. The polarizing plate 10 typically includes a polarizing element 11 and a protective layer 12 arranged on the visual side of the polarizing element 11. Depending on the purpose, another protective layer (not shown) may be provided on the side opposite to the visible side (protective layer 12) of the polarizer 11. The retardation layer 20 is an oriented solidified layer of a liquid crystal compound having a circular polarization function or an elliptically polarized function (hereinafter, may be simply referred to as a liquid crystal oriented solidified layer). The pressure-sensitive adhesive layer 30 is provided as the outermost layer, and the polarizing plate with a retardation layer can be attached to an image display device (substantially, an image display cell).
図1Aは、本発明の1つの実施形態による位相差層付偏光板の概略断面図であり;図1Bは、本発明の別の実施形態による位相差層付偏光板の概略断面図である。図1Aおよび図1Bの位相差層付偏光板100、101はそれぞれ、偏光板10と位相差層20と粘着剤層30とを視認側からこの順に有する。偏光板10は、代表的には、偏光子11と、偏光子11の視認側に配置された保護層12と、を含む。目的に応じて、偏光子11の視認側(保護層12)と反対側に別の保護層(図示せず)が設けられてもよい。位相差層20は、円偏光機能または楕円偏光機能を有する液晶化合物の配向固化層(以下、単に液晶配向固化層と称する場合がある)である。粘着剤層30は最外層として設けられ、位相差層付偏光板は画像表示装置(実質的には、画像表示セル)に貼り付け可能とされている。 A. Overall Configuration of Polarizing Plate with Phase Difference FIG. 1A is a schematic cross-sectional view of a polarizing plate with a retardation layer according to one embodiment of the present invention; FIG. 1B is a polarizing plate with a retardation layer according to another embodiment of the present invention. It is a schematic cross-sectional view of a polarizing plate. The polarizing
本発明の実施形態においては、偏光子11と粘着剤層30との間に、ヨウ素透過抑制層40が設けられている。ヨウ素透過抑制層40は、図1Aに示すように偏光子11と位相差層20との間に(すなわち、偏光子11に隣接して)設けられてもよく、図1Bに示すように位相差層20と粘着剤層30との間に設けられてもよい。ヨウ素透過抑制層を偏光子と位相差層との間に設ける場合(特に、偏光子にヨウ素透過抑制層を隣接させる場合)には、高温高湿環境下における偏光子からのヨウ素移行抑制が可能となり信頼性が向上するという利点がある。ヨウ素透過抑制層を位相差層と粘着剤層との間に設ける場合(特に、粘着剤層にヨウ素透過抑制層を隣接させる場合)には、ヨウ素以外の金属腐食に影響すると考えられる成分(例えば、紫外線硬化接着剤中の残渣モノマー成分、光開始剤の分解物)についても同時に粘着剤中への移行を防止可能であり、金属腐食抑制効果がさらに高まるという利点がある。
In the embodiment of the present invention, the iodine permeation suppressing layer 40 is provided between the polarizer 11 and the pressure-sensitive adhesive layer 30. The iodine permeation suppressing layer 40 may be provided between the polarizer 11 and the retardation layer 20 (that is, adjacent to the polarizer 11) as shown in FIG. 1A, and the retardation difference as shown in FIG. 1B. It may be provided between the layer 20 and the pressure-sensitive adhesive layer 30. When the iodine permeation suppressing layer is provided between the polarizer and the retardation layer (particularly when the iodine permeation suppressing layer is adjacent to the polarizer), it is possible to suppress iodine transfer from the polarizer in a high temperature and high humidity environment. It has the advantage of improving reliability. When the iodine permeation suppressing layer is provided between the retardation layer and the pressure-sensitive adhesive layer (particularly when the iodine permeation suppressing layer is adjacent to the pressure-sensitive adhesive layer), components that are considered to affect metal corrosion other than iodine (for example). , Residual monomer component in the ultraviolet curable adhesive, decomposition product of the photoinitiator) can also be prevented from migrating into the adhesive at the same time, and has the advantage of further enhancing the metal corrosion suppressing effect.
位相差層付偏光板においては、偏光子と粘着剤層との間に、ヨウ素透過抑制層が2層以上設けられてもよい(例えば、図4および図5)。位相差層付偏光板が2層以上のヨウ素透過抑制層を有することにより、位相差層付偏光板を画像表示装置に適用した場合に金属部材の腐食を顕著に抑制することができる。
In the polarizing plate with a retardation layer, two or more iodine permeation suppressing layers may be provided between the polarizer and the pressure-sensitive adhesive layer (for example, FIGS. 4 and 5). When the polarizing plate with a retardation layer has two or more iodine permeation suppression layers, corrosion of the metal member can be remarkably suppressed when the polarizing plate with a retardation layer is applied to an image display device.
図4に示す位相差層付偏光板においては、偏光子と粘着剤層との間に、ヨウ素透過抑制層が2層設けられている。図4に示す例においては、ヨウ素透過抑制層は、偏光子11と位相差層20との間、および、位相差層20と粘着剤層30との間に2層が設けられている。1つの実施形態においては、ヨウ素透過抑制層は偏光子に隣接して設けられている。別の実施形態においては、ヨウ素透過抑制層は位相差層に隣接して設けられている。本明細書において「隣接している」とは、接着層等を介さず直接積層されていることをいう。
In the polarizing plate with a retardation layer shown in FIG. 4, two iodine permeation suppressing layers are provided between the polarizer and the pressure-sensitive adhesive layer. In the example shown in FIG. 4, the iodine permeation suppressing layer is provided with two layers, one between the polarizer 11 and the retardation layer 20, and the other between the retardation layer 20 and the pressure-sensitive adhesive layer 30. In one embodiment, the iodine permeation inhibitor layer is provided adjacent to the polarizer. In another embodiment, the iodine permeation inhibitory layer is provided adjacent to the retardation layer. In the present specification, "adjacent" means that they are directly laminated without an adhesive layer or the like.
図5に示す位相差層付偏光板においては、偏光子と粘着剤層との間に、ヨウ素透過抑制層が3層設けられている。図5に示す例においては、ヨウ素透過抑制層は、偏光子11と位相差層20との間に2層が設けられ、位相差層20と粘着剤層30との間に1層が設けられている。偏光子11と位相差層20との間の2層のヨウ素透過抑制層は、一方は偏光子に隣接して設けられ、もう一方は位相差層に隣接して設けられている。
In the polarizing plate with a retardation layer shown in FIG. 5, three iodine permeation suppressing layers are provided between the polarizer and the pressure-sensitive adhesive layer. In the example shown in FIG. 5, the iodine permeation suppressing layer is provided with two layers between the polarizer 11 and the retardation layer 20, and one layer between the retardation layer 20 and the pressure-sensitive adhesive layer 30. ing. The two iodine permeation suppressing layers between the polarizer 11 and the retardation layer 20 are provided adjacent to the polarizer and the other adjacent to the retardation layer.
位相差層付偏光板においては、ヨウ素透過抑制層が4層以上(例えば、4層、5層、6層)であってもよい。ヨウ素透過抑制層の数が多いほど、金属腐食抑制効果を高めることができる。ヨウ素透過抑制層の数は、コスト、製造効率、位相差層付偏光板の総厚み等を考慮して設定され得る。
In the polarizing plate with a retardation layer, the iodine permeation suppressing layer may be 4 or more layers (for example, 4 layers, 5 layers, 6 layers). The larger the number of iodine permeation suppressing layers, the higher the metal corrosion suppressing effect. The number of iodine permeation suppressing layers can be set in consideration of cost, manufacturing efficiency, total thickness of the polarizing plate with a retardation layer, and the like.
ヨウ素透過抑制層は、樹脂の有機溶媒溶液の塗布膜の固化物または熱硬化物である。さらに、ヨウ素透過抑制層を構成する樹脂のガラス転移温度(Tg)は85℃以上であり、かつ、重量平均分子量Mwは25000以上である。このようなヨウ素透過抑制層を位相差層付偏光板の所定の位置に設けることにより、位相差層付偏光板を画像表示装置に適用した場合に偏光子中のヨウ素が画像表示装置(実質的には、画像表示セル)に移行することを顕著に抑制することができる。その結果、画像表示装置の金属部材(例えば、電極、センサー、配線、金属層)の腐食を顕著に抑制することができる。このような効果は、薄型の位相差層付偏光板(代表的には、位相差層が液晶配向固化層である位相差層付偏光板)に特有の効果である。すなわち、本発明者らは、薄型の位相差層付偏光板を画像表示装置に適用した場合に画像表示装置の金属部材が腐食する場合があるという問題を新たに発見し、腐食部分にヨウ素が存在することから、このような金属部材の腐食はヨウ素に起因し得ることを解明した。そして、試行錯誤の結果、ヨウ素の画像表示装置(実質的には、画像表示セル)への移行を防止する手段として、上記のようなヨウ素透過抑制層(特定のTgおよびMwを有する樹脂の有機溶媒溶液の塗布膜の固化層または熱硬化層)が有用であることを見出し、本発明を完成するに至った。すなわち、このような効果は、従来知られていなかった新たな課題を解決するものであり、予期せぬ優れた効果である。さらに、後述するように、ヨウ素透過抑制層は非常に薄く形成することができ、かつ、ヨウ素透過抑制層を設けることにより視認側と反対側の保護層を省略することができるので、これらの相乗的な効果により、位相差層付偏光板のさらなる薄型化にも寄与し得る。
The iodine permeation suppression layer is a solidified product or thermosetting product of a coating film of a resin organic solvent solution. Further, the glass transition temperature (Tg) of the resin constituting the iodine permeation suppressing layer is 85 ° C. or higher, and the weight average molecular weight Mw is 25000 or higher. By providing such an iodine permeation suppressing layer at a predetermined position of the polarizing plate with a retardation layer, when the polarizing plate with a retardation layer is applied to an image display device, iodine in the polarizing element is released to the image display device (substantially The transition to the image display cell) can be remarkably suppressed. As a result, corrosion of metal members (for example, electrodes, sensors, wiring, metal layers) of the image display device can be remarkably suppressed. Such an effect is peculiar to a thin polarizing plate with a retardation layer (typically, a polarizing plate with a retardation layer in which the retardation layer is a liquid crystal oriented solidifying layer). That is, the present inventors have newly discovered a problem that the metal member of the image display device may be corroded when the thin polarizing plate with a retardation layer is applied to the image display device, and iodine is added to the corroded portion. From its presence, it has been clarified that such corrosion of metal parts can be caused by iodine. Then, as a result of trial and error, as a means for preventing the transfer of iodine to the image display device (substantially, the image display cell), the above-mentioned iodine permeation suppressing layer (organic resin having specific Tg and Mw) is used. We have found that the solidified layer or thermosetting layer of the coating film of the solvent solution is useful, and have completed the present invention. That is, such an effect solves a new problem that has not been known in the past, and is an unexpectedly excellent effect. Further, as will be described later, the iodine permeation suppressing layer can be formed very thinly, and by providing the iodine permeation suppressing layer, the protective layer on the side opposite to the viewing side can be omitted. This effect can contribute to further thinning of the polarizing plate with a retardation layer.
図2に示すように、さらに別の実施形態による位相差層付偏光板102においては、別の位相差層50ならびに/あるいは導電層または導電層付等方性基材60が設けられてもよい。別の位相差層50は、代表的には、位相差20と粘着剤層30との間(すなわち、位相差層20の外側)に設けられる。別の位相差層は、代表的には、屈折率特性がnz>nx=nyの関係を示す。導電層または導電層付等方性基材60は、代表的には、ヨウ素透過抑制層40と粘着剤層30との間(すなわち、ヨウ素透過抑制層40の外側)に設けられる。別の位相差層50ならびに導電層または導電層付等方性基材60は、代表的には、位相差層20側からこの順に設けられる。図示例においては、ヨウ素透過抑制層40、位相差層20、別の位相差層50、ならびに導電層または導電層付等方性基材60が視認側からこの順に設けられているが、別の位相差層50が位相差20と粘着剤層30との間に設けられ、導電層または導電層付等方性基材60がヨウ素透過抑制層40と粘着剤層30との間に設けられる限りにおいて、任意の適切な配置順序が採用され得る。別の位相差層50ならびに導電層または導電層付等方性基材60は、代表的には、必要に応じて設けられる任意の層であり、いずれか一方または両方が省略されてもよい。なお、便宜上、位相差層20を第1の位相差層と称し、別の位相差層50を第2の位相差層と称する場合がある。導電層または導電層付等方性基材が設けられる場合、位相差層付偏光板は、画像表示セル(例えば、有機ELセル)と偏光板との間にタッチセンサが組み込まれた、いわゆるインナータッチパネル型入力表示装置に適用され得る。本発明の実施形態においては、導電層または導電層付等方性基材60をヨウ素透過抑制層40の外側に設けることにより、導電層の腐食が顕著に抑制され得る。
As shown in FIG. 2, in the polarizing plate 102 with a retardation layer according to still another embodiment, another retardation layer 50 and / or a conductive layer or an isotropic base material 60 with a conductive layer may be provided. Another retardation layer 50 is typically provided between the retardation 20 and the pressure-sensitive adhesive layer 30 (ie, outside the retardation layer 20). Another retardation layer typically exhibits a relationship in which the refractive index characteristic is nz> nz = ny. The conductive layer or the isotropic base material 60 with the conductive layer is typically provided between the iodine permeation suppressing layer 40 and the pressure-sensitive adhesive layer 30 (that is, outside the iodine permeation suppressing layer 40). Another retardation layer 50 and the conductive layer or the isotropic base material 60 with the conductive layer are typically provided in this order from the retardation layer 20 side. In the illustrated example, the iodine permeation suppressing layer 40, the retardation layer 20, another retardation layer 50, and the conductive layer or the isotropic base material 60 with the conductive layer are provided in this order from the visual side, but different retardation. Any is provided as long as the layer 50 is provided between the phase difference 20 and the pressure-sensitive adhesive layer 30, and the conductive layer or the isotropic base material 60 with the conductive layer is provided between the iodine permeation suppressing layer 40 and the pressure-sensitive adhesive layer 30. Appropriate placement order can be adopted. The other retardation layer 50 and the conductive layer or the isotropic base material 60 with the conductive layer are typically arbitrary layers provided as needed, and one or both of them may be omitted. For convenience, the retardation layer 20 may be referred to as a first retardation layer, and another retardation layer 50 may be referred to as a second retardation layer. When a conductive layer or an isotropic substrate with a conductive layer is provided, the polarizing plate with a retardation layer is a so-called inner touch panel type in which a touch sensor is incorporated between an image display cell (for example, an organic EL cell) and the polarizing plate. Can be applied to input display devices. In the embodiment of the present invention, by providing the conductive layer or the isotropic base material 60 with the conductive layer on the outside of the iodine permeation suppressing layer 40, the corrosion of the conductive layer can be remarkably suppressed.
上記のとおり、第1の位相差層20は液晶配向固化層である。第1の位相差層20は図1A、図1Bおよび図2に示すような単一層であってもよく、図3に示すような第1の液晶配向固化層21と第2の液晶配向固化層22との積層構造を有していてもよい。
As described above, the first retardation layer 20 is a liquid crystal oriented solidifying layer. The first retardation layer 20 may be a single layer as shown in FIGS. 1A, 1B and 2, and the first liquid crystal oriented solidified layer 21 and the second liquid crystal oriented solidified layer as shown in FIG. It may have a laminated structure with 22.
上記の実施形態は適宜組み合わせてもよく、上記の実施形態における構成要素に当業界で自明の改変を加えてもよい。例えば、図1Bの位相差層付偏光板101に第2の位相差層50ならびに/あるいは導電層または導電層付等方性基材60が設けられてもよく;図1Bの位相差層付偏光板101の位相差層20が図3のような2層構造を有していてもよく;図3の位相差層付偏光板103に第2の位相差層50ならびに/あるいは導電層または導電層付等方性基材60が設けられてもよく;図2の位相差層付偏光板102のヨウ素透過抑制層40が位相差層20と導電層または導電層付等方性基材60との間に設けられてもよい。
The above embodiments may be combined as appropriate, and the components of the above embodiments may be modified in a manner that is self-evident in the art. For example, the polarizing plate with a retardation layer 101 of FIG. 1B may be provided with a second retardation layer 50 and / or an isotropic base material 60 with a conductive layer or a conductive layer; the polarizing plate with a retardation layer 101 of FIG. 1B. The retardation layer 20 of the above may have a two-layer structure as shown in FIG. 3; the polarizing plate 103 with the retardation layer of FIG. 3 has a second retardation layer 50 and / or a conductive layer or a conductive layer, etc. A square substrate 60 may be provided; the iodine permeation suppressing layer 40 of the polarizing plate 102 with a retardation layer of FIG. 2 may be provided between the retardation layer 20 and the conductive layer or the isotropic substrate 60 with a conductive layer. good.
本発明の実施形態による位相差層付偏光板は、その他の位相差層をさらに含んでいてもよい。その他の位相差層の光学的特性(例えば、屈折率特性、面内位相差、Nz係数、光弾性係数)、厚み、配置位置等は、目的に応じて適切に設定され得る。
The polarizing plate with a retardation layer according to the embodiment of the present invention may further include other retardation layers. The optical characteristics (for example, refractive index characteristics, in-plane retardation, Nz coefficient, photoelastic coefficient), thickness, arrangement position, and the like of other retardation layers can be appropriately set according to the purpose.
本発明の実施形態による位相差層付偏光板は、枚葉状であってもよく長尺状であってもよい。本明細書において「長尺状」とは、幅に対して長さが十分に長い細長形状を意味し、例えば、幅に対して長さが10倍以上、好ましくは20倍以上の細長形状を含む。長尺状の位相差層付偏光板は、ロール状に巻回可能である。
The polarizing plate with a retardation layer according to the embodiment of the present invention may be single-wafered or elongated. As used herein, the term "long" means an elongated shape having a length sufficiently long with respect to the width, and for example, an elongated shape having a length of 10 times or more, preferably 20 times or more with respect to the width. include. The long-shaped polarizing plate with a retardation layer can be wound in a roll shape.
位相差層付偏光板の総厚みは、好ましくは60μm以下であり、より好ましくは55μm以下であり、さらに好ましくは50μm以下であり、特に好ましくは40μm以下である。総厚みの下限は、例えば28μmであり得る。本発明の実施形態によれば、このようにきわめて薄い位相差層付偏光板を実現することができ、さらに、このようなきわめて薄い位相差層付偏光板を画像表示装置に適用した場合であっても、画像表示装置の金属部材(例えば、電極、センサー、配線、金属層)の腐食を顕著に抑制することができる。また、このような位相差層付偏光板は、きわめて優れた可撓性および折り曲げ耐久性を有し得る。したがって、このような位相差層付偏光板は、湾曲した画像表示装置および/または折り曲げもしくは折り畳み可能な画像表示装置に特に好適に適用され得る。なお、位相差層付偏光板の総厚みとは、偏光板、位相差層(第1の位相差層および存在する場合には第2の位相差層)、ヨウ素透過抑制層およびこれらを積層するための接着剤層または粘着剤層の厚みの合計をいう(すなわち、位相差層付偏光板の総厚みは、導電層または導電層付等方性基材60、ならびに、粘着剤層30およびその表面に仮着され得る剥離フィルムの厚みを含まない)。
The total thickness of the polarizing plate with a retardation layer is preferably 60 μm or less, more preferably 55 μm or less, further preferably 50 μm or less, and particularly preferably 40 μm or less. The lower limit of the total thickness can be, for example, 28 μm. According to the embodiment of the present invention, it is possible to realize such an extremely thin polarizing plate with a retardation layer, and further, when such a polarizing plate with an extremely thin retardation layer is applied to an image display device. However, corrosion of metal members (for example, electrodes, sensors, wirings, metal layers) of the image display device can be remarkably suppressed. Further, such a polarizing plate with a retardation layer can have extremely excellent flexibility and bending durability. Therefore, such a polarizing plate with a retardation layer can be particularly preferably applied to a curved image display device and / or a foldable or foldable image display device. The total thickness of the polarizing plate with a retardation layer is the polarizing plate, the retardation layer (the first retardation layer and the second retardation layer if present), the iodine permeation suppression layer, and the layers thereof. The total thickness of the adhesive layer or the pressure-sensitive adhesive layer for the purpose (that is, the total thickness of the polarizing plate with the retardation layer is the conductive layer or the isotropic base material 60 with the conductive layer, and the pressure-sensitive adhesive layer 30 and its surface. Does not include the thickness of the release film that can be temporarily attached).
実用的には、粘着剤層30の表面には、位相差層付偏光板が使用に供されるまで、剥離フィルムが仮着されていることが好ましい。剥離フィルムを仮着することにより、粘着剤層を保護するとともに、位相差層付偏光板のロール形成が可能となる。
Practically, it is preferable that a release film is temporarily attached to the surface of the pressure-sensitive adhesive layer 30 until a polarizing plate with a retardation layer is used. By temporarily attaching the release film, the pressure-sensitive adhesive layer can be protected and a roll of the polarizing plate with a retardation layer can be formed.
以下、位相差層付偏光板の構成要素について、より詳細に説明する。なお、粘着剤層30については業界で周知の構成が採用され得るので、粘着剤層の詳細な構成については記載を省略する。
Hereinafter, the components of the polarizing plate with a retardation layer will be described in more detail. Since a structure well known in the industry can be adopted for the pressure-sensitive adhesive layer 30, the detailed structure of the pressure-sensitive adhesive layer will be omitted.
B.偏光板
B-1.偏光子
偏光子は、代表的には、二色性物質を含むポリビニルアルコール(PVA)系樹脂フィルムで構成される。偏光子の厚みは、好ましくは1μm~8μmであり、より好ましくは1μm~7μmであり、さらに好ましくは2μm~5μmである。偏光子の厚みがこのような範囲であれば、位相差層付偏光板の薄型化に大きく貢献し得る。さらに、このような偏光子を用いる薄型の位相差層付偏光板において、本発明の効果が顕著である。 B. Polarizing plate B-1. Polarizer The polarizer is typically composed of a polyvinyl alcohol (PVA) -based resin film containing a dichroic substance. The thickness of the polarizer is preferably 1 μm to 8 μm, more preferably 1 μm to 7 μm, and even more preferably 2 μm to 5 μm. If the thickness of the polarizer is in such a range, it can greatly contribute to the thinning of the polarizing plate with a retardation layer. Further, the effect of the present invention is remarkable in a thin polarizing plate with a retardation layer using such a polarizer.
B-1.偏光子
偏光子は、代表的には、二色性物質を含むポリビニルアルコール(PVA)系樹脂フィルムで構成される。偏光子の厚みは、好ましくは1μm~8μmであり、より好ましくは1μm~7μmであり、さらに好ましくは2μm~5μmである。偏光子の厚みがこのような範囲であれば、位相差層付偏光板の薄型化に大きく貢献し得る。さらに、このような偏光子を用いる薄型の位相差層付偏光板において、本発明の効果が顕著である。 B. Polarizing plate B-1. Polarizer The polarizer is typically composed of a polyvinyl alcohol (PVA) -based resin film containing a dichroic substance. The thickness of the polarizer is preferably 1 μm to 8 μm, more preferably 1 μm to 7 μm, and even more preferably 2 μm to 5 μm. If the thickness of the polarizer is in such a range, it can greatly contribute to the thinning of the polarizing plate with a retardation layer. Further, the effect of the present invention is remarkable in a thin polarizing plate with a retardation layer using such a polarizer.
偏光子のホウ酸含有量は、好ましくは10重量%以上であり、より好ましくは13重量%~25重量%である。偏光子のホウ酸含有量がこのような範囲であれば、後述のヨウ素含有量との相乗的な効果により、貼り合わせ時のカール調整の容易性を良好に維持し、かつ、加熱時のカールを良好に抑制しつつ、加熱時の外観耐久性を改善することができる。ホウ酸含有量は、例えば、中和法から下記式を用いて、単位重量当たりの偏光子に含まれるホウ酸量として算出することができる。
The boric acid content of the polarizer is preferably 10% by weight or more, more preferably 13% by weight to 25% by weight. When the boric acid content of the polarizer is in such a range, the ease of curl adjustment at the time of bonding is well maintained due to the synergistic effect with the iodine content described later, and the curl at the time of heating is maintained. It is possible to improve the appearance durability at the time of heating while satisfactorily suppressing the above. The boric acid content can be calculated as, for example, the amount of boric acid contained in the polarizer per unit weight by using the following formula from the neutralization method.
偏光子のヨウ素含有量は、好ましくは2重量%以上であり、より好ましくは2重量%~10重量%である。偏光子のヨウ素含有量がこのような範囲であれば、上記のホウ酸含有量との相乗的な効果により、貼り合わせ時のカール調整の容易性を良好に維持し、かつ、加熱時のカールを良好に抑制しつつ、加熱時の外観耐久性を改善することができる。本明細書において「ヨウ素含有量」とは、偏光子(PVA系樹脂フィルム)中に含まれるすべてのヨウ素の量を意味する。より具体的には、偏光子中においてヨウ素はヨウ素イオン(I-)、ヨウ素分子(I2)、ポリヨウ素イオン(I3
-、I5
-)等の形態で存在するところ、本明細書におけるヨウ素含有量は、これらの形態をすべて包含したヨウ素の量を意味する。ヨウ素含有量は、例えば、蛍光X線分析の検量線法により算出することができる。なお、ポリヨウ素イオンは、偏光子中でPVA-ヨウ素錯体を形成した状態で存在している。このような錯体が形成されることにより、可視光の波長範囲において吸収二色性が発現し得る。具体的には、PVAと三ヨウ化物イオンとの錯体(PVA・I3
-)は470nm付近に吸光ピークを有し、PVAと五ヨウ化物イオンとの錯体(PVA・I5
-)は600nm付近に吸光ピークを有する。結果として、ポリヨウ素イオンは、その形態に応じて可視光の幅広い範囲で光を吸収し得る。一方、ヨウ素イオン(I-)は230nm付近に吸光ピークを有し、可視光の吸収には実質的には関与しない。したがって、PVAとの錯体の状態で存在するポリヨウ素イオンが、主として偏光子の吸収性能に関与し得る。
The iodine content of the polarizer is preferably 2% by weight or more, more preferably 2% by weight to 10% by weight. When the iodine content of the polarizer is in such a range, the ease of curl adjustment at the time of bonding is well maintained due to the synergistic effect with the above boric acid content, and the curl at the time of heating is maintained. It is possible to improve the appearance durability at the time of heating while satisfactorily suppressing the above. As used herein, the term "iodine content" means the amount of all iodine contained in the polarizer (PVA-based resin film). More specifically, iodine during polarizers iodide ion (I -), molecular iodine (I 2), polyiodine ion (I 3 -, I 5 - ) where present in the form of such, herein Iodine content means the amount of iodine that includes all of these forms. The iodine content can be calculated, for example, by the calibration curve method of fluorescent X-ray analysis. The polyiodine ion exists in a state in which a PVA-iodine complex is formed in the polarizer. By forming such a complex, absorption dichroism can be exhibited in the wavelength range of visible light. Specifically, a complex of PVA and tri-iodide ion (PVA · I 3 -) has a light absorption peak around 470 nm, a complex of PVA and five iodide ion (PVA · I 5 -) is 600nm near Has an absorptive peak. As a result, polyiodine ions can absorb light in a wide range of visible light, depending on their morphology. On the other hand, iodide ion (I − ) has an absorption peak near 230 nm and is not substantially involved in the absorption of visible light. Therefore, polyiodine ions present in the form of a complex with PVA may be mainly involved in the absorption performance of the polarizer.
偏光子は、好ましくは、波長380nm~780nmのいずれかの波長で吸収二色性を示す。偏光子の単体透過率Tsは、好ましくは40%~48%であり、より好ましくは41%~46%である。偏光子の偏光度Pは、好ましくは97.0%以上であり、より好ましくは99.0%以上であり、さらに好ましくは99.9%以上である。上記単体透過率は、代表的には、紫外可視分光光度計を用いて測定し、視感度補正を行なったY値である。上記偏光度は、代表的には、紫外可視分光光度計を用いて測定して視感度補正を行なった平行透過率Tpおよび直交透過率Tcに基づいて、下記式により求められる。
偏光度(%)={(Tp-Tc)/(Tp+Tc)}1/2×100 The polarizer preferably exhibits absorption dichroism at any wavelength of 380 nm to 780 nm. The simple substance transmittance Ts of the polarizer is preferably 40% to 48%, more preferably 41% to 46%. The degree of polarization P of the polarizer is preferably 97.0% or more, more preferably 99.0% or more, and further preferably 99.9% or more. The simple substance transmittance is typically a Y value measured using an ultraviolet-visible spectrophotometer and corrected for luminosity factor. The degree of polarization is typically obtained by the following formula based on the parallel transmittance Tp and the orthogonal transmittance Tc measured by using an ultraviolet-visible spectrophotometer and corrected for luminosity factor.
Polarization degree (%) = {(Tp-Tc) / (Tp + Tc)} 1/2 × 100
偏光度(%)={(Tp-Tc)/(Tp+Tc)}1/2×100 The polarizer preferably exhibits absorption dichroism at any wavelength of 380 nm to 780 nm. The simple substance transmittance Ts of the polarizer is preferably 40% to 48%, more preferably 41% to 46%. The degree of polarization P of the polarizer is preferably 97.0% or more, more preferably 99.0% or more, and further preferably 99.9% or more. The simple substance transmittance is typically a Y value measured using an ultraviolet-visible spectrophotometer and corrected for luminosity factor. The degree of polarization is typically obtained by the following formula based on the parallel transmittance Tp and the orthogonal transmittance Tc measured by using an ultraviolet-visible spectrophotometer and corrected for luminosity factor.
Polarization degree (%) = {(Tp-Tc) / (Tp + Tc)} 1/2 × 100
偏光子は、代表的には、二層以上の積層体を用いて作製され得る。積層体を用いて得られる偏光子の具体例としては、樹脂基材と当該樹脂基材に塗布形成されたPVA系樹脂層との積層体を用いて得られる偏光子が挙げられる。樹脂基材と当該樹脂基材に塗布形成されたPVA系樹脂層との積層体を用いて得られる偏光子は、例えば、PVA系樹脂溶液を樹脂基材に塗布し、乾燥させて樹脂基材上にPVA系樹脂層を形成して、樹脂基材とPVA系樹脂層との積層体を得ること;当該積層体を延伸および染色してPVA系樹脂層を偏光子とすること;により作製され得る。延伸は、代表的には積層体をホウ酸水溶液中に浸漬させて延伸することを含む。さらに、延伸は、必要に応じて、ホウ酸水溶液中での延伸の前に積層体を高温(例えば、95℃以上)で空中延伸することをさらに含み得る。得られた樹脂基材/偏光子の積層体はそのまま用いてもよく(すなわち、樹脂基材を偏光子の保護層としてもよく)、樹脂基材/偏光子の積層体から樹脂基材を剥離し、当該剥離面に目的に応じた任意の適切な保護層を積層して用いてもよい。このような偏光子の製造方法の詳細は、例えば特開2012-73580号公報、特許第6470455号に記載されている。これらの公報は、その全体の記載が本明細書に参考として援用される。
The polarizer can typically be made using a laminate of two or more layers. Specific examples of the polarizer obtained by using the laminate include a polarizer obtained by using a laminate of a resin base material and a PVA-based resin layer coated and formed on the resin base material. The polarizer obtained by using the laminate of the resin base material and the PVA-based resin layer coated and formed on the resin base material is, for example, a resin base material obtained by applying a PVA-based resin solution to the resin base material and drying the resin base material. It is produced by forming a PVA-based resin layer on the PVA-based resin layer to obtain a laminate of a resin base material and a PVA-based resin layer; stretching and dyeing the laminate to make the PVA-based resin layer a polarizer. obtain. Stretching typically involves immersing the laminate in an aqueous boric acid solution for stretching. Further, stretching may further include, if necessary, stretching the laminate in the air at a high temperature (eg, 95 ° C. or higher) prior to stretching in boric acid aqueous solution. The obtained resin substrate / polarizer laminate may be used as it is (that is, the resin substrate may be used as a protective layer for the polarizer), and the resin substrate is peeled off from the resin substrate / polarizer laminate. Then, an arbitrary appropriate protective layer according to the purpose may be laminated on the peeled surface. Details of the method for producing such a polarizer are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580 and Japanese Patent No. 6470455. The entire description of these publications is incorporated herein by reference.
偏光子の製造方法は、代表的には、長尺状の熱可塑性樹脂基材の片側に、ハロゲン化物とポリビニルアルコール系樹脂とを含むポリビニルアルコール系樹脂層を形成して積層体とすること、および、上記積層体に、空中補助延伸処理と、染色処理と、水中延伸処理と、長手方向に搬送しながら加熱することにより幅方向に2%以上収縮させる乾燥収縮処理と、をこの順に施すことを含む。これにより、非常に薄型で、優れた光学特性を有するとともに光学特性のバラつきが抑制された偏光子が提供され得る。すなわち、補助延伸を導入することにより、熱可塑性樹脂上にPVAを塗布する場合でも、PVAの結晶性を高めることが可能となり、高い光学特性を達成することが可能となる。また、同時にPVAの配向性を事前に高めることで、後の染色工程や延伸工程で水に浸漬された時に、PVAの配向性の低下や溶解などの問題を防止することができ、高い光学特性を達成することが可能になる。さらに、PVA系樹脂層を液体に浸漬した場合において、PVA系樹脂層がハロゲン化物を含まない場合に比べて、ポリビニルアルコール分子の配向の乱れ、および配向性の低下が抑制され得る。これにより、染色処理および水中延伸処理など、積層体を液体に浸漬して行う処理工程を経て得られる偏光子の光学特性を向上し得る。さらに、乾燥収縮処理により積層体を幅方向に収縮させることにより、光学特性を向上させることができる。
A typical method for producing a polarizer is to form a polyvinyl alcohol-based resin layer containing a halide and a polyvinyl alcohol-based resin on one side of a long thermoplastic resin base material to form a laminate. Then, the laminated body is subjected to an aerial auxiliary stretching treatment, a dyeing treatment, an underwater stretching treatment, and a drying shrinkage treatment in which the laminate is shrunk by 2% or more in the width direction by heating while being conveyed in the longitudinal direction. including. This makes it possible to provide a polarizer that is extremely thin, has excellent optical characteristics, and suppresses variations in optical characteristics. That is, by introducing the auxiliary stretching, even when PVA is applied on the thermoplastic resin, the crystallinity of PVA can be enhanced, and high optical characteristics can be achieved. At the same time, by increasing the orientation of PVA in advance, it is possible to prevent problems such as deterioration of PVA orientation and dissolution when immersed in water in a subsequent dyeing step or stretching step, resulting in high optical characteristics. Will be possible to achieve. Further, when the PVA-based resin layer is immersed in a liquid, the disorder of the orientation of the polyvinyl alcohol molecules and the decrease in the orientation can be suppressed as compared with the case where the PVA-based resin layer does not contain a halide. This makes it possible to improve the optical characteristics of the polarizer obtained through a treatment step of immersing the laminate in a liquid, such as a dyeing treatment and a stretching treatment in water. Further, the optical characteristics can be improved by shrinking the laminated body in the width direction by the drying shrinkage treatment.
B-2.保護層
保護層12は、偏光子の保護層として使用できる任意の適切なフィルムで形成される。当該フィルムの主成分となる材料の具体例としては、トリアセチルセルロース(TAC)等のセルロース系樹脂や、ポリエステル系、ポリビニルアルコール系、ポリカーボネート系、ポリアミド系、ポリイミド系、ポリエーテルスルホン系、ポリスルホン系、ポリスチレン系、ポリノルボルネン系、ポリオレフィン系、(メタ)アクリル系、アセテート系等の透明樹脂等が挙げられる。また、(メタ)アクリル系、ウレタン系、(メタ)アクリルウレタン系、エポキシ系、シリコーン系等の熱硬化型樹脂または紫外線硬化型樹脂等も挙げられる。この他にも、例えば、シロキサン系ポリマー等のガラス質系ポリマーも挙げられる。また、特開2001-343529号公報(WO01/37007)に記載のポリマーフィルムも使用できる。このフィルムの材料としては、例えば、側鎖に置換または非置換のイミド基を有する熱可塑性樹脂と、側鎖に置換または非置換のフェニル基ならびにニトリル基を有する熱可塑性樹脂を含有する樹脂組成物が使用でき、例えば、イソブテンとN-メチルマレイミドからなる交互共重合体と、アクリロニトリル・スチレン共重合体とを有する樹脂組成物が挙げられる。当該ポリマーフィルムは、例えば、上記樹脂組成物の押出成形物であり得る。 B-2. Protective layer Theprotective layer 12 is formed of any suitable film that can be used as a protective layer for the polarizer. Specific examples of the material that is the main component of the film include cellulose-based resins such as triacetyl cellulose (TAC), polyester-based, polyvinyl alcohol-based, polycarbonate-based, polyamide-based, polyimide-based, polyethersulfone-based, and polysulfone-based. , Polyester-based, polycarbonate-based, polyolefin-based, (meth) acrylic-based, acetate-based transparent resins and the like. Further, thermosetting resins such as (meth) acrylic, urethane, (meth) acrylic urethane, epoxy, and silicone, or ultraviolet curable resins can also be mentioned. In addition to this, for example, glassy polymers such as siloxane-based polymers can also be mentioned. Further, the polymer film described in JP-A-2001-343529 (WO01 / 37007) can also be used. As the material of this film, for example, a resin composition containing a thermoplastic resin having a substituted or unsubstituted imide group in the side chain and a thermoplastic resin having a substituted or unsubstituted phenyl group and a nitrile group in the side chain. Can be used, and examples thereof include a resin composition having an alternating copolymer composed of isobutene and N-methylmaleimide and an acrylonitrile / styrene copolymer. The polymer film can be, for example, an extruded product of the above resin composition.
保護層12は、偏光子の保護層として使用できる任意の適切なフィルムで形成される。当該フィルムの主成分となる材料の具体例としては、トリアセチルセルロース(TAC)等のセルロース系樹脂や、ポリエステル系、ポリビニルアルコール系、ポリカーボネート系、ポリアミド系、ポリイミド系、ポリエーテルスルホン系、ポリスルホン系、ポリスチレン系、ポリノルボルネン系、ポリオレフィン系、(メタ)アクリル系、アセテート系等の透明樹脂等が挙げられる。また、(メタ)アクリル系、ウレタン系、(メタ)アクリルウレタン系、エポキシ系、シリコーン系等の熱硬化型樹脂または紫外線硬化型樹脂等も挙げられる。この他にも、例えば、シロキサン系ポリマー等のガラス質系ポリマーも挙げられる。また、特開2001-343529号公報(WO01/37007)に記載のポリマーフィルムも使用できる。このフィルムの材料としては、例えば、側鎖に置換または非置換のイミド基を有する熱可塑性樹脂と、側鎖に置換または非置換のフェニル基ならびにニトリル基を有する熱可塑性樹脂を含有する樹脂組成物が使用でき、例えば、イソブテンとN-メチルマレイミドからなる交互共重合体と、アクリロニトリル・スチレン共重合体とを有する樹脂組成物が挙げられる。当該ポリマーフィルムは、例えば、上記樹脂組成物の押出成形物であり得る。 B-2. Protective layer The
位相差層付偏光板は、後述するように代表的には画像表示装置の視認側に配置され、保護層12は、代表的にはその視認側に配置される。したがって、保護層12には、必要に応じて、ハードコート処理、反射防止処理、スティッキング防止処理、アンチグレア処理等の表面処理が施されていてもよい。さらに/あるいは、保護層12には、必要に応じて、偏光サングラスを介して視認する場合の視認性を改善する処理(代表的には、(楕)円偏光機能を付与すること、超高位相差を付与すること)が施されていてもよい。このような処理を施すことにより、偏光サングラス等の偏光レンズを介して表示画面を視認した場合でも、優れた視認性を実現することができる。したがって、位相差層付偏光板は、屋外で用いられ得る画像表示装置にも好適に適用され得る。
As will be described later, the polarizing plate with a retardation layer is typically arranged on the visible side of the image display device, and the protective layer 12 is typically arranged on the visible side. Therefore, the protective layer 12 may be subjected to surface treatment such as hard coat treatment, antireflection treatment, anti-sticking treatment, and anti-glare treatment, if necessary. Further / or, if necessary, the protective layer 12 is provided with a process for improving visibility when visually recognizing through polarized sunglasses (typically, a (elliptical) circular polarization function is provided, and an ultra-high phase difference is provided. May be given). By performing such a process, excellent visibility can be realized even when the display screen is visually recognized through a polarized lens such as polarized sunglasses. Therefore, the polarizing plate with a retardation layer can be suitably applied to an image display device that can be used outdoors.
保護層の厚みは、好ましくは10μm~50μm、より好ましくは10μm~30μmである。なお、表面処理が施されている場合、外側保護層の厚みは、表面処理層の厚みを含めた厚みである。
The thickness of the protective layer is preferably 10 μm to 50 μm, more preferably 10 μm to 30 μm. When the surface treatment is applied, the thickness of the outer protective layer is the thickness including the thickness of the surface treatment layer.
C.第1の位相差層
第1の位相差層20は、上記のとおり、液晶配向固化層である。液晶化合物を用いることにより、得られる位相差層のnxとnyとの差を非液晶材料に比べて格段に大きくすることができるので、所望の面内位相差を得るための位相差層の厚みを格段に小さくすることができる。その結果、位相差層付偏光板のさらなる薄型化を実現することができる。本明細書において「液晶配向固化層」とは、液晶化合物が層内で所定の方向に配向し、その配向状態が固定されている層をいう。なお、「配向固化層」は、後述のように液晶モノマーを硬化させて得られる配向硬化層を包含する概念である。本実施形態においては、代表的には、棒状の液晶化合物が第1の位相差層の遅相軸方向に並んだ状態で配向している(ホモジニアス配向)。 C. First Phase Difference Layer Thefirst retardation layer 20 is a liquid crystal oriented solidifying layer as described above. By using the liquid crystal compound, the difference between nx and ny of the obtained retardation layer can be made much larger than that of the non-liquid crystal material, so that the thickness of the retardation layer for obtaining a desired in-plane retardation can be obtained. Can be made much smaller. As a result, it is possible to further reduce the thickness of the polarizing plate with a retardation layer. As used herein, the term "liquid crystal oriented solidified layer" refers to a layer in which a liquid crystal compound is oriented in a predetermined direction within the layer and the oriented state is fixed. The "oriented solidified layer" is a concept including an oriented cured layer obtained by curing a liquid crystal monomer as described later. In the present embodiment, the rod-shaped liquid crystal compounds are typically oriented in a state of being aligned in the slow-phase axial direction of the first retardation layer (homogeneous orientation).
第1の位相差層20は、上記のとおり、液晶配向固化層である。液晶化合物を用いることにより、得られる位相差層のnxとnyとの差を非液晶材料に比べて格段に大きくすることができるので、所望の面内位相差を得るための位相差層の厚みを格段に小さくすることができる。その結果、位相差層付偏光板のさらなる薄型化を実現することができる。本明細書において「液晶配向固化層」とは、液晶化合物が層内で所定の方向に配向し、その配向状態が固定されている層をいう。なお、「配向固化層」は、後述のように液晶モノマーを硬化させて得られる配向硬化層を包含する概念である。本実施形態においては、代表的には、棒状の液晶化合物が第1の位相差層の遅相軸方向に並んだ状態で配向している(ホモジニアス配向)。 C. First Phase Difference Layer The
液晶化合物としては、例えば、液晶相がネマチック相である液晶化合物(ネマチック液晶)が挙げられる。このような液晶化合物として、例えば、液晶ポリマーや液晶モノマーが使用可能である。液晶化合物の液晶性の発現機構は、リオトロピックでもサーモトロピックでもどちらでもよい。液晶ポリマーおよび液晶モノマーは、それぞれ単独で用いてもよく、組み合わせてもよい。
Examples of the liquid crystal compound include a liquid crystal compound (nematic liquid crystal) in which the liquid crystal phase is a nematic phase. As such a liquid crystal compound, for example, a liquid crystal polymer or a liquid crystal monomer can be used. The liquid crystal expression mechanism of the liquid crystal compound may be either lyotropic or thermotropic. The liquid crystal polymer and the liquid crystal monomer may be used alone or in combination.
液晶化合物が液晶モノマーである場合、当該液晶モノマーは、重合性モノマーおよび架橋性モノマーであることが好ましい。液晶モノマーを重合または架橋(すなわち、硬化)させることにより、液晶モノマーの配向状態を固定できるからである。液晶モノマーを配向させた後に、例えば、液晶モノマー同士を重合または架橋させれば、それによって上記配向状態を固定することができる。ここで、重合によりポリマーが形成され、架橋により3次元網目構造が形成されることとなるが、これらは非液晶性である。したがって、形成された第1の位相差層は、例えば、液晶性化合物に特有の温度変化による液晶相、ガラス相、結晶相への転移が起きることはない。その結果、第1の位相差層は、温度変化に影響されない、極めて安定性に優れた位相差層となる。
When the liquid crystal compound is a liquid crystal monomer, the liquid crystal monomer is preferably a polymerizable monomer and a crosslinkable monomer. This is because the orientation state of the liquid crystal monomer can be fixed by polymerizing or cross-linking (that is, curing) the liquid crystal monomer. After the liquid crystal monomers are oriented, for example, if the liquid crystal monomers are polymerized or crosslinked with each other, the oriented state can be fixed. Here, the polymer is formed by polymerization, and the three-dimensional network structure is formed by cross-linking, but these are non-liquid crystal. Therefore, the formed first retardation layer does not undergo a transition to a liquid crystal phase, a glass phase, or a crystal phase due to a temperature change peculiar to a liquid crystal compound, for example. As a result, the first retardation layer becomes an extremely stable retardation layer that is not affected by temperature changes.
液晶モノマーが液晶性を示す温度範囲は、その種類に応じて異なる。具体的には、当該温度範囲は、好ましくは40℃~120℃であり、さらに好ましくは50℃~100℃であり、最も好ましくは60℃~90℃である。
The temperature range in which the liquid crystal monomer exhibits liquid crystal properties differs depending on the type. Specifically, the temperature range is preferably 40 ° C. to 120 ° C., more preferably 50 ° C. to 100 ° C., and most preferably 60 ° C. to 90 ° C.
上記液晶モノマーとしては、任意の適切な液晶モノマーが採用され得る。例えば、特表2002-533742(WO00/37585)、EP358208(US5211877)、EP66137(US4388453)、WO93/22397、EP0261712、DE19504224、DE4408171、およびGB2280445等に記載の重合性メソゲン化合物等が使用できる。このような重合性メソゲン化合物の具体例としては、例えば、BASF社の商品名LC242、Merck社の商品名E7、Wacker-Chem社の商品名LC-Sillicon-CC3767が挙げられる。液晶モノマーとしては、例えばネマチック性液晶モノマーが好ましい。
Any suitable liquid crystal monomer can be adopted as the liquid crystal monomer. For example, the polymerizable mesogen compounds described in Special Tables 2002-533742 (WO00 / 37585), EP358208 (US5211877), EP666137 (US4388453), WO93 / 22397, EP02671712, DE19504224, DE4408171, GB2280445 and the like can be used. Specific examples of such a polymerizable mesogen compound include, for example, BASF's trade name LC242, Merck's trade name E7, and Wacker-Chem's trade name LC-Silicon-CC3767. As the liquid crystal monomer, for example, a nematic liquid crystal monomer is preferable.
液晶配向固化層は、所定の基材の表面に配向処理を施し、当該表面に液晶化合物を含む塗工液を塗工して当該液晶化合物を上記配向処理に対応する方向に配向させ、当該配向状態を固定することにより形成され得る。1つの実施形態においては、基材は任意の適切な樹脂フィルムであり、当該基材上に形成された液晶配向固化層は、隣接層(例えば、偏光子、ヨウ素透過抑制層)の表面に転写され得る。
The liquid crystal alignment solidified layer is subjected to an orientation treatment on the surface of a predetermined base material, and a coating liquid containing a liquid crystal compound is applied to the surface to orient the liquid crystal compound in a direction corresponding to the orientation treatment. It can be formed by fixing the state. In one embodiment, the substrate is any suitable resin film and the liquid crystal oriented solidified layer formed on the substrate is transferred to the surface of an adjacent layer (eg, a polarizer, an iodine permeation inhibitory layer). Can be done.
上記配向処理としては、任意の適切な配向処理が採用され得る。具体的には、機械的な配向処理、物理的な配向処理、化学的な配向処理が挙げられる。機械的な配向処理の具体例としては、ラビング処理、延伸処理が挙げられる。物理的な配向処理の具体例としては、磁場配向処理、電場配向処理が挙げられる。化学的な配向処理の具体例としては、斜方蒸着法、光配向処理が挙げられる。各種配向処理の処理条件は、目的に応じて任意の適切な条件が採用され得る。
As the orientation treatment, any appropriate orientation treatment can be adopted. Specific examples thereof include mechanical orientation treatment, physical orientation treatment, and chemical orientation treatment. Specific examples of the mechanical orientation treatment include a rubbing treatment and a stretching treatment. Specific examples of the physical orientation treatment include magnetic field orientation treatment and electric field orientation treatment. Specific examples of the chemical alignment treatment include an orthorhombic deposition method and a photoalignment treatment. As the treatment conditions for various orientation treatments, any appropriate conditions can be adopted depending on the purpose.
液晶化合物の配向は、液晶化合物の種類に応じて液晶相を示す温度で処理することにより行われる。このような温度処理を行うことにより、液晶化合物が液晶状態をとり、基材表面の配向処理方向に応じて当該液晶化合物が配向する。
The orientation of the liquid crystal compound is performed by treating at a temperature indicating the liquid crystal phase according to the type of the liquid crystal compound. By performing such temperature treatment, the liquid crystal compound takes a liquid crystal state, and the liquid crystal compound is oriented according to the orientation treatment direction of the surface of the base material.
配向状態の固定は、1つの実施形態においては、上記のように配向した液晶化合物を冷却することにより行われる。液晶化合物が重合性モノマーまたは架橋性モノマーである場合には、配向状態の固定は、上記のように配向した液晶化合物に重合処理または架橋処理を施すことにより行われる。
In one embodiment, the orientation state is fixed by cooling the liquid crystal compound oriented as described above. When the liquid crystal compound is a polymerizable monomer or a crosslinkable monomer, the orientation state is fixed by subjecting the liquid crystal compound oriented as described above to a polymerization treatment or a crosslinking treatment.
液晶化合物の具体例および配向固化層の形成方法の詳細は、特開2006-163343号公報に記載されている。当該公報の記載は本明細書に参考として援用される。
Specific examples of the liquid crystal compound and details of the method for forming the oriented solidified layer are described in JP-A-2006-163343. The description of this publication is incorporated herein by reference.
1つの実施形態においては、第1の位相差層20は、図1A、図1Bおよび図2に示すように単一層である。第1の位相差層20が単一層で構成される場合、その厚みは、好ましくは0.5μm~7μmであり、より好ましくは1μm~5μmである。液晶化合物を用いることにより、樹脂フィルムよりも格段に薄い厚みで樹脂フィルムと同等の面内位相差を実現することができる。
In one embodiment, the first retardation layer 20 is a single layer as shown in FIGS. 1A, 1B and 2. When the first retardation layer 20 is composed of a single layer, its thickness is preferably 0.5 μm to 7 μm, and more preferably 1 μm to 5 μm. By using the liquid crystal compound, it is possible to realize an in-plane phase difference equivalent to that of the resin film with a thickness much thinner than that of the resin film.
第1の位相差層は、上記のとおり円偏光機能または楕円偏光機能を有する。第1の位相差層は、代表的には、屈折率特性がnx>ny=nzの関係を示す。第1の位相差層は、代表的には偏光板に反射防止特性を付与するために設けられ、第1の位相差層が単一層である場合にはλ/4板として機能し得る。この場合、第1の位相差層の面内位相差Re(550)は、好ましくは100nm~190nm、より好ましくは110nm~170nm、さらに好ましくは130nm~160nmである。なお、ここで「ny=nz」はnyとnzが完全に等しい場合だけではなく、実質的に等しい場合を包含する。したがって、本発明の効果を損なわない範囲で、ny>nzまたはny<nzとなる場合があり得る。
The first retardation layer has a circular polarization function or an elliptically polarization function as described above. The first retardation layer typically shows a relationship in which the refractive index characteristic is nx> ny = nz. The first retardation layer is typically provided to impart antireflection characteristics to the polarizing plate, and can function as a λ / 4 plate when the first retardation layer is a single layer. In this case, the in-plane retardation Re (550) of the first retardation layer is preferably 100 nm to 190 nm, more preferably 110 nm to 170 nm, and even more preferably 130 nm to 160 nm. Here, "ny = nz" includes not only the case where ny and nz are completely equal, but also the case where they are substantially equal. Therefore, ny> nz or ny <nz may occur within a range that does not impair the effects of the present invention.
第1の位相差層のNz係数は、好ましくは0.9~1.5であり、より好ましくは0.9~1.3である。このような関係を満たすことにより、得られる位相差層付偏光板を画像表示装置に用いた場合に、非常に優れた反射色相を達成し得る。
The Nz coefficient of the first retardation layer is preferably 0.9 to 1.5, and more preferably 0.9 to 1.3. By satisfying such a relationship, a very excellent reflected hue can be achieved when the obtained polarizing plate with a retardation layer is used in an image display device.
第1の位相差層は、位相差値が測定光の波長に応じて大きくなる逆分散波長特性を示してもよく、位相差値が測定光の波長に応じて小さくなる正の波長分散特性を示してもよく、位相差値が測定光の波長によってもほとんど変化しないフラットな波長分散特性を示してもよい。1つの実施形態においては、第1の位相差層は、逆分散波長特性を示す。この場合、位相差層のRe(450)/Re(550)は、好ましくは0.8以上1未満であり、より好ましくは0.8以上0.95以下である。このような構成であれば、非常に優れた反射防止特性を実現することができる。
The first retardation layer may exhibit a reverse dispersion wavelength characteristic in which the retardation value increases according to the wavelength of the measurement light, and a positive wavelength dispersion characteristic in which the retardation value decreases according to the wavelength of the measurement light. It may be shown, or may show a flat wavelength dispersion characteristic in which the phase difference value hardly changes with the wavelength of the measurement light. In one embodiment, the first retardation layer exhibits inverse dispersion wavelength characteristics. In this case, the Re (450) / Re (550) of the retardation layer is preferably 0.8 or more and less than 1, and more preferably 0.8 or more and 0.95 or less. With such a configuration, very excellent antireflection characteristics can be realized.
第1の位相差層20の遅相軸と偏光子11の吸収軸とのなす角度θは、好ましくは40°~50°であり、より好ましくは42°~48°であり、さらに好ましくは約45°である。角度θがこのような範囲であれば、上記のように第1の位相差層をλ/4板とすることにより、非常に優れた円偏光特性(結果として、非常に優れた反射防止特性)を有する位相差層付偏光板が得られ得る。
The angle θ formed by the slow axis of the first retardation layer 20 and the absorption axis of the polarizer 11 is preferably 40 ° to 50 °, more preferably 42 ° to 48 °, and even more preferably about. It is 45 °. If the angle θ is in such a range, by using the λ / 4 plate as the first retardation layer as described above, very excellent circular polarization characteristics (as a result, very excellent antireflection characteristics). A polarizing plate with a retardation layer having the above can be obtained.
別の実施形態においては、第1の位相差層20は、図3に示すように第1の液晶配向固化層21と第2の液晶配向固化層22との積層構造を有し得る。この場合、第1の液晶配向固化層21および第2の液晶配向固化層22のいずれか一方がλ/4板として機能し、他方がλ/2板として機能し得る。したがって、第1の液晶配向固化層21および第2の液晶配向固化層22の厚みは、λ/4板またはλ/2板の所望の面内位相差が得られるよう調整され得る。例えば、第1の液晶配向固化層21がλ/2板として機能し、第2の液晶配向固化層22がλ/4板として機能する場合、第1の液晶配向固化層21の厚みは例えば2.0μm~3.0μmであり、第2の液晶配向固化層22の厚みは例えば1.0μm~2.0μmである。この場合、第1の液晶配向固化層の面内位相差Re(550)は、好ましくは200nm~300nmであり、より好ましくは230nm~290nmであり、さらに好ましくは250nm~280nmである。第2の液晶配向固化層の面内位相差Re(550)は、単一層に関して上記で説明したとおりである。第1の液晶配向固化層の遅相軸と偏光子の吸収軸とのなす角度は、好ましくは10°~20°であり、より好ましくは12°~18°であり、さらに好ましくは約15°である。第2の液晶配向固化層の遅相軸と偏光子の吸収軸とのなす角度は、好ましくは70°~80°であり、より好ましくは72°~78°であり、さらに好ましくは約75°である。このような構成であれば、理想的な逆波長分散特性に近い特性を得ることが可能であり、結果として、非常に優れた反射防止特性を実現することができる。第1の液晶配向固化層および第2の液晶配向固化層を構成する液晶化合物、第1の液晶配向固化層および第2の液晶配向固化層の形成方法、光学特性等については、単一層に関して上記で説明したとおりである。
In another embodiment, the first retardation layer 20 may have a laminated structure of the first liquid crystal oriented solidified layer 21 and the second liquid crystal oriented solidified layer 22 as shown in FIG. In this case, either one of the first liquid crystal oriented solidified layer 21 and the second liquid crystal oriented solidified layer 22 may function as a λ / 4 plate, and the other may function as a λ / 2 plate. Therefore, the thicknesses of the first liquid crystal oriented solidified layer 21 and the second liquid crystal oriented solidified layer 22 can be adjusted so as to obtain a desired in-plane phase difference between the λ / 4 plate or the λ / 2 plate. For example, when the first liquid crystal oriented solidified layer 21 functions as a λ / 2 plate and the second liquid crystal oriented solidified layer 22 functions as a λ / 4 plate, the thickness of the first liquid crystal oriented solidified layer 21 is, for example, 2. The thickness is 0.0 μm to 3.0 μm, and the thickness of the second liquid crystal oriented solidifying layer 22 is, for example, 1.0 μm to 2.0 μm. In this case, the in-plane retardation Re (550) of the first liquid crystal oriented solidified layer is preferably 200 nm to 300 nm, more preferably 230 nm to 290 nm, and further preferably 250 nm to 280 nm. The in-plane retardation Re (550) of the second liquid crystal oriented solidified layer is as described above with respect to the single layer. The angle formed by the slow axis of the first liquid crystal oriented solidification layer and the absorption axis of the polarizer is preferably 10 ° to 20 °, more preferably 12 ° to 18 °, and even more preferably about 15 °. Is. The angle formed by the slow axis of the second liquid crystal oriented solidification layer and the absorption axis of the polarizer is preferably 70 ° to 80 °, more preferably 72 ° to 78 °, and even more preferably about 75 °. Is. With such a configuration, it is possible to obtain characteristics close to the ideal reverse wavelength dispersion characteristic, and as a result, it is possible to realize extremely excellent antireflection characteristics. The liquid crystal compounds constituting the first liquid crystal oriented solidified layer and the second liquid crystal oriented solidified layer, the method for forming the first liquid crystal oriented solidified layer and the second liquid crystal oriented solidified layer, the optical characteristics, and the like are described above with respect to the single layer. As explained in.
D.ヨウ素透過抑制層
ヨウ素透過抑制層は、上記のとおり、樹脂の有機溶媒溶液の塗布膜の固化物または熱硬化物である。このような構成であれば、厚みを非常に薄く(例えば、10μm以下に)することができる。ヨウ素透過抑制層の厚みは、好ましくは0.05μm~10μmであり、より好ましくは0.08μm~5μmであり、さらに好ましくは0.1μm~1μmであり、特に好ましくは0.2μm~0.7μmである。さらに、このような構成であれば、ヨウ素透過抑制層を隣接層(例えば、偏光子、位相差層)に直接(すなわち、接着剤層または粘着剤層を介することなく)形成することができる。本発明の実施形態によれば、上記のとおり偏光子、位相差層およびヨウ素透過抑制層が非常に薄く、かつ、ヨウ素透過抑制層を積層するための接着剤層または粘着剤層を省略することができるので、位相差層付偏光板の総厚みをきわめて薄くすることができる。さらに、このようなヨウ素透過抑制層は、水溶液または水分散体のような水系の塗布膜の固化物に比べて吸湿性および透湿性が小さいので加湿耐久性に優れるという利点を有する。その結果、高温高湿環境下においても光学特性を維持し得る、耐久性に優れた位相差層付偏光板を実現することができる。また、このようなヨウ素透過抑制層は、例えば紫外線硬化性樹脂の硬化物に比べて紫外線照射による偏光板(偏光子)に対する悪影響を抑制することができる。ヨウ素透過抑制層は、好ましくは、樹脂の有機溶媒溶液の塗布膜の固化物である。固化物は、硬化物に比べてフィルム成形時の収縮が小さい、および、残存モノマー等が含まれないのでフィルム自体の劣化が抑制され、かつ、残存モノマー等に起因する偏光板(偏光子)に対する悪影響を抑制することができる。 D. Iodine permeation suppression layer The iodine permeation suppression layer is, as described above, a solidified product or a thermosetting product of a coating film of an organic solvent solution of a resin. With such a configuration, the thickness can be made very thin (for example, 10 μm or less). The thickness of the iodine permeation inhibitory layer is preferably 0.05 μm to 10 μm, more preferably 0.08 μm to 5 μm, still more preferably 0.1 μm to 1 μm, and particularly preferably 0.2 μm to 0.7 μm. Is. Further, with such a configuration, the iodine permeation suppressing layer can be formed directly (that is, without an adhesive layer or an adhesive layer) directly on the adjacent layer (for example, a polarizer or a retardation layer). According to the embodiment of the present invention, as described above, the polarizer, the retardation layer and the iodine permeation suppressing layer are very thin, and the adhesive layer or the pressure-sensitive adhesive layer for laminating the iodine permeation suppressing layer is omitted. Therefore, the total thickness of the polarizing plate with a retardation layer can be made extremely thin. Further, such an iodine permeation suppressing layer has an advantage that it is excellent in humidification durability because it has a smaller hygroscopicity and moisture permeability than a solidified water-based coating film such as an aqueous solution or an aqueous dispersion. As a result, it is possible to realize a polarizing plate with a retardation layer having excellent durability, which can maintain optical characteristics even in a high temperature and high humidity environment. Further, such an iodine permeation suppressing layer can suppress an adverse effect on a polarizing plate (polarizer) due to ultraviolet irradiation as compared with a cured product of, for example, an ultraviolet curable resin. The iodine permeation inhibitory layer is preferably a solidified coating film of a resin organic solvent solution. The solidified product has a smaller shrinkage during film molding than the cured product, and since it does not contain residual monomers, deterioration of the film itself is suppressed, and the solidified product has a resistance to a polarizing plate (polarizer) caused by the residual monomers and the like. The adverse effect can be suppressed.
ヨウ素透過抑制層は、上記のとおり、樹脂の有機溶媒溶液の塗布膜の固化物または熱硬化物である。このような構成であれば、厚みを非常に薄く(例えば、10μm以下に)することができる。ヨウ素透過抑制層の厚みは、好ましくは0.05μm~10μmであり、より好ましくは0.08μm~5μmであり、さらに好ましくは0.1μm~1μmであり、特に好ましくは0.2μm~0.7μmである。さらに、このような構成であれば、ヨウ素透過抑制層を隣接層(例えば、偏光子、位相差層)に直接(すなわち、接着剤層または粘着剤層を介することなく)形成することができる。本発明の実施形態によれば、上記のとおり偏光子、位相差層およびヨウ素透過抑制層が非常に薄く、かつ、ヨウ素透過抑制層を積層するための接着剤層または粘着剤層を省略することができるので、位相差層付偏光板の総厚みをきわめて薄くすることができる。さらに、このようなヨウ素透過抑制層は、水溶液または水分散体のような水系の塗布膜の固化物に比べて吸湿性および透湿性が小さいので加湿耐久性に優れるという利点を有する。その結果、高温高湿環境下においても光学特性を維持し得る、耐久性に優れた位相差層付偏光板を実現することができる。また、このようなヨウ素透過抑制層は、例えば紫外線硬化性樹脂の硬化物に比べて紫外線照射による偏光板(偏光子)に対する悪影響を抑制することができる。ヨウ素透過抑制層は、好ましくは、樹脂の有機溶媒溶液の塗布膜の固化物である。固化物は、硬化物に比べてフィルム成形時の収縮が小さい、および、残存モノマー等が含まれないのでフィルム自体の劣化が抑制され、かつ、残存モノマー等に起因する偏光板(偏光子)に対する悪影響を抑制することができる。 D. Iodine permeation suppression layer The iodine permeation suppression layer is, as described above, a solidified product or a thermosetting product of a coating film of an organic solvent solution of a resin. With such a configuration, the thickness can be made very thin (for example, 10 μm or less). The thickness of the iodine permeation inhibitory layer is preferably 0.05 μm to 10 μm, more preferably 0.08 μm to 5 μm, still more preferably 0.1 μm to 1 μm, and particularly preferably 0.2 μm to 0.7 μm. Is. Further, with such a configuration, the iodine permeation suppressing layer can be formed directly (that is, without an adhesive layer or an adhesive layer) directly on the adjacent layer (for example, a polarizer or a retardation layer). According to the embodiment of the present invention, as described above, the polarizer, the retardation layer and the iodine permeation suppressing layer are very thin, and the adhesive layer or the pressure-sensitive adhesive layer for laminating the iodine permeation suppressing layer is omitted. Therefore, the total thickness of the polarizing plate with a retardation layer can be made extremely thin. Further, such an iodine permeation suppressing layer has an advantage that it is excellent in humidification durability because it has a smaller hygroscopicity and moisture permeability than a solidified water-based coating film such as an aqueous solution or an aqueous dispersion. As a result, it is possible to realize a polarizing plate with a retardation layer having excellent durability, which can maintain optical characteristics even in a high temperature and high humidity environment. Further, such an iodine permeation suppressing layer can suppress an adverse effect on a polarizing plate (polarizer) due to ultraviolet irradiation as compared with a cured product of, for example, an ultraviolet curable resin. The iodine permeation inhibitory layer is preferably a solidified coating film of a resin organic solvent solution. The solidified product has a smaller shrinkage during film molding than the cured product, and since it does not contain residual monomers, deterioration of the film itself is suppressed, and the solidified product has a resistance to a polarizing plate (polarizer) caused by the residual monomers and the like. The adverse effect can be suppressed.
さらに、ヨウ素透過抑制層を構成する樹脂のガラス転移温度(Tg)は85℃以上であり、かつ、重量平均分子量Mwは25000以上である。当該樹脂のTgおよびMwがこのような範囲であれば、ヨウ素透過抑制層を樹脂の有機溶媒溶液の塗布膜の固化物または熱硬化物で構成することによる効果との相乗的な効果により、非常に薄いにもかかわらず、偏光子中のヨウ素の画像表示セルへの移行を顕著に抑制することができる。結果として、位相差層付偏光板を画像表示装置に適用した場合に金属部材の腐食を顕著に抑制することができる。当該樹脂のTgは、好ましくは90℃以上であり、より好ましくは100℃以上であり、さらに好ましくは110℃以上であり、特に好ましくは120℃以上である。Tgの上限は、例えば200℃であり得る。また、当該樹脂のMwは、好ましくは30000以上であり、より好ましくは35000以上であり、さらに好ましくは40000以上である。Mwの上限は、例えば150000であり得る。
Further, the glass transition temperature (Tg) of the resin constituting the iodine permeation suppressing layer is 85 ° C. or higher, and the weight average molecular weight Mw is 25000 or higher. When the Tg and Mw of the resin are in such a range, the effect synergistically with the effect of forming the iodine permeation suppressing layer with a solidified product or a thermosetting material of a coating film of an organic solvent solution of the resin is extremely effective. Despite its thinness, the transfer of iodine in the polarizer to the image display cell can be significantly suppressed. As a result, when the polarizing plate with a retardation layer is applied to an image display device, corrosion of the metal member can be remarkably suppressed. The Tg of the resin is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, still more preferably 110 ° C. or higher, and particularly preferably 120 ° C. or higher. The upper limit of Tg can be, for example, 200 ° C. The Mw of the resin is preferably 30,000 or more, more preferably 35,000 or more, and further preferably 40,000 or more. The upper limit of Mw can be, for example, 150,000.
ヨウ素透過抑制層を構成する樹脂としては、有機溶媒溶液の塗布膜の固化物または熱硬化物を形成可能であり、かつ上記のようなTgおよびMwを有する限りにおいて、任意の適切な熱可塑性樹脂または熱硬化性樹脂を用いることができる。好ましくは、熱可塑性樹脂である。熱可塑性樹脂としては、例えば、アクリル系樹脂、エポキシ系樹脂が挙げられる。アクリル系樹脂とエポキシ系樹脂とを組み合わせて用いてもよい。以下、ヨウ素透過抑制層に用いられ得るアクリル系樹脂およびエポキシ系樹脂の代表例を説明する。
As the resin constituting the iodine permeation suppressing layer, any suitable thermoplastic resin can be formed as long as it can form a solidified product or a thermosetting product of a coating film of an organic solvent solution and has Tg and Mw as described above. Alternatively, a thermosetting resin can be used. A thermoplastic resin is preferable. Examples of the thermoplastic resin include acrylic resins and epoxy resins. Acrylic resin and epoxy resin may be used in combination. Hereinafter, typical examples of the acrylic resin and the epoxy resin that can be used for the iodine permeation suppressing layer will be described.
アクリル系樹脂は、代表的には、直鎖または分岐構造を有する(メタ)アクリル酸エステル系単量体由来の繰り返し単位を主成分として含有する。本明細書において、(メタ)アクリルとは、アクリルおよび/またはメタクリルをいう。アクリル系樹脂は、目的に応じた任意の適切な共重合単量体由来の繰り返し単位を含有し得る。共重合単量体(共重合モノマー)としては、例えば、カルボキシル基含有モノマー、ヒドロキシル基含有モノマー、アミド基含有モノマー、芳香環含有(メタ)アクリレート、複素環含有ビニル系モノマーが挙げられる。モノマー単位の種類、数、組み合わせおよび共重合比等を適切に設定することにより、上記所定のMwを有するアクリル系樹脂が得られ得る。
Acrylic resins typically contain a repeating unit derived from a (meth) acrylic acid ester-based monomer having a linear or branched structure as a main component. As used herein, the term (meth) acrylic refers to acrylic and / or methacryl. The acrylic resin may contain repeating units derived from any suitable copolymerized monomer depending on the intended purpose. Examples of the copolymerization monomer (copolymerization monomer) include a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an amide group-containing monomer, an aromatic ring-containing (meth) acrylate, and a heterocyclic ring-containing vinyl-based monomer. By appropriately setting the type, number, combination, copolymerization ratio, etc. of the monomer units, an acrylic resin having the above-mentioned predetermined Mw can be obtained.
<ホウ素含有アクリル系樹脂>
アクリル系樹脂は、1つの実施形態においては、50重量部を超える(メタ)アクリル系単量体と0重量部を超えて50重量部未満の式(1)で表される単量体(以下、共重合単量体と称する場合がある)とを含むモノマー混合物を重合することにより得られる共重合体(以下、ホウ素含有アクリル系樹脂と称する場合がある)を含む:
(式中、Xはビニル基、(メタ)アクリル基、スチリル基、(メタ)アクリルアミド基、ビニルエーテル基、エポキシ基、オキセタン基、ヒドロキシル基、アミノ基、アルデヒド基、および、カルボキシル基からなる群より選択される少なくとも1種の反応性基を含む官能基を表し、R1およびR2はそれぞれ独立して、水素原子、置換基を有していてもよい脂肪族炭化水素基、置換基を有していてもよいアリール基、または、置換基を有していてもよいヘテロ環基を表し、R1およびR2は互いに連結して環を形成してもよい)。
<Boron-containing acrylic resin>
In one embodiment, the acrylic resin is a (meth) acrylic monomer having a weight of more than 50 parts by weight and a monomer having a weight of more than 0 parts by weight and less than 50 parts by weight (hereinafter, represented by the formula (1)). , May be referred to as a copolymerized monomer) and a copolymer obtained by polymerizing a monomer mixture (hereinafter, may be referred to as a boron-containing acrylic resin).
(In the formula, X is a group consisting of a vinyl group, a (meth) acrylic group, a styryl group, a (meth) acrylamide group, a vinyl ether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group. Represents a functional group containing at least one reactive group selected, and R 1 and R 2 each independently have a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, and a substituent. It represents an aryl group which may be used, or a heterocyclic group which may have a substituent, and R 1 and R 2 may be linked to each other to form a ring).
アクリル系樹脂は、1つの実施形態においては、50重量部を超える(メタ)アクリル系単量体と0重量部を超えて50重量部未満の式(1)で表される単量体(以下、共重合単量体と称する場合がある)とを含むモノマー混合物を重合することにより得られる共重合体(以下、ホウ素含有アクリル系樹脂と称する場合がある)を含む:
In one embodiment, the acrylic resin is a (meth) acrylic monomer having a weight of more than 50 parts by weight and a monomer having a weight of more than 0 parts by weight and less than 50 parts by weight (hereinafter, represented by the formula (1)). , May be referred to as a copolymerized monomer) and a copolymer obtained by polymerizing a monomer mixture (hereinafter, may be referred to as a boron-containing acrylic resin).
ホウ素含有アクリル系樹脂は、代表的には下記式で表される繰り返し単位を有する。式(1)で表される共重合単量体と(メタ)アクリル系単量体とを含むモノマー混合物を重合することにより、ホウ素含有アクリル系樹脂は側鎖にホウ素を含む置換基(例えば、下記式中kの繰り返し単位)を有する。これにより、ヨウ素透過抑制層を偏光子に隣接して配置した場合に偏光子との密着性が向上し得る。このホウ素を含む置換基は、ホウ素含有アクリル系樹脂に連続して(すなわち、ブロック状に)含まれていてもよく、ランダムに含まれていてもよい。
(式中、R6は任意の官能基を表し、jおよびkは1以上の整数を表す)。
The boron-containing acrylic resin typically has a repeating unit represented by the following formula. By polymerizing a monomer mixture containing the copolymerization monomer represented by the formula (1) and the (meth) acrylic monomer, the boron-containing acrylic resin has a substituent containing boron in the side chain (for example,). It has a repeating unit of k in the following formula). As a result, when the iodine permeation suppressing layer is arranged adjacent to the polarizer, the adhesion to the polarizer can be improved. The boron-containing substituent may be continuously (that is, in a block shape) contained in the boron-containing acrylic resin, or may be randomly contained.
(In the formula, R 6 represents an arbitrary functional group, and j and k represent integers of 1 or more).
<(メタ)アクリル系単量体>
(メタ)アクリル系単量体としては任意の適切な(メタ)アクリル系単量体を用いることができる。例えば、直鎖または分岐構造を有する(メタ)アクリル酸エステル系単量体、および、環状構造を有する(メタ)アクリル酸エステル系単量体が挙げられる。 <(Meta) acrylic monomer>
Any suitable (meth) acrylic monomer can be used as the (meth) acrylic monomer. For example, a (meth) acrylic acid ester-based monomer having a linear or branched structure and a (meth) acrylic acid ester-based monomer having a cyclic structure can be mentioned.
(メタ)アクリル系単量体としては任意の適切な(メタ)アクリル系単量体を用いることができる。例えば、直鎖または分岐構造を有する(メタ)アクリル酸エステル系単量体、および、環状構造を有する(メタ)アクリル酸エステル系単量体が挙げられる。 <(Meta) acrylic monomer>
Any suitable (meth) acrylic monomer can be used as the (meth) acrylic monomer. For example, a (meth) acrylic acid ester-based monomer having a linear or branched structure and a (meth) acrylic acid ester-based monomer having a cyclic structure can be mentioned.
直鎖または分岐構造を有する(メタ)アクリル酸エステル系単量体としては、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸メチル2-エチルヘキシル、(メタ)アクリル酸2-ヒドロキシエチル等が挙げられる。好ましくは、(メタ)アクリル酸メチルが用いられる。(メタ)アクリル酸エステル系単量体は、1種のみを用いてもよく、2種以上を組み合わせて用いてもよい。
Examples of the (meth) acrylic acid ester-based monomer having a linear or branched structure include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic acid. Examples thereof include isopropyl, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and the like. .. Preferably, methyl (meth) acrylate is used. As the (meth) acrylic acid ester-based monomer, only one type may be used, or two or more types may be used in combination.
環状構造を有する(メタ)アクリル酸エステル系単量体としては、例えば、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸ベンジル、(メタ)アクリル酸イソボルニル、(メタ)アクリル酸1-アダマンチル、(メタ)アクリル酸ジシクロペンテニル、(メタ)アクリル酸ジシクロペンテニルオキシエチル、(メタ)アクリル酸ジシクロペンタニル、ビフェニル(メタ)アクリレート、o-ビフェニルオキシエチル(メタ)アクリレート、o-ビフェニルオキシエトキシエチル(メタ)アクリレート、m-ビフェニルオキシエチルアクリレート、p-ビフェニルオキシエチル(メタ)アクリレート、o-ビフェニルオキシ-2-ヒドロキシプロピル(メタ)アクリレート、p-ビフェニルオキシ-2-ヒドロキシプロピル(メタ)アクリレート、m-ビフェニルオキシ-2-ヒドロキシプロピル(メタ)アクリレート、N-(メタ)アクリロイルオキシエチル-o-ビフェニル=カルバマート、N-(メタ)アクリロイルオキシエチル-p-ビフェニル=カルバマート、N-(メタ)アクリロイルオキシエチル-m-ビフェニル=カルバマート、o-フェニルフェノールグリシジルエーテルアクリレート等のビフェニル基含有モノマー、ターフェニル(メタ)アクリレート、o-ターフェニルオキシエチル(メタ)アクリレート等が挙げられる。好ましくは、(メタ)アクリル酸1-アダマンチル、(メタ)アクリル酸ジシクロペンタニルが用いられる。これらの単量体を用いることにより、ガラス転移温度の高い重合体が得られる。これらの単量体は1種のみを用いてもよく、2種以上を組み合わせて用いてもよい。
Examples of the (meth) acrylate-based monomer having a cyclic structure include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, and ( Dicyclopentenyl acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, biphenyl (meth) acrylate, o-biphenyloxyethyl (meth) acrylate, o-biphenyloxyethoxy Ethyl (meth) acrylate, m-biphenyloxyethyl acrylate, p-biphenyloxyethyl (meth) acrylate, o-biphenyloxy-2-hydroxypropyl (meth) acrylate, p-biphenyloxy-2-hydroxypropyl (meth) acrylate , M-biphenyloxy-2-hydroxypropyl (meth) acrylate, N- (meth) acryloyloxyethyl-o-biphenyl = carbamate, N- (meth) acryloyloxyethyl-p-biphenyl = carbamate, N- (meth) Examples thereof include biphenyl group-containing monomers such as acryloyloxyethyl-m-biphenyl = carbamate and o-phenylphenol glycidyl ether acrylate, terphenyl (meth) acrylate, and o-terphenyloxyethyl (meth) acrylate. Preferably, 1-adamantyl (meth) acrylate and dicyclopentanyl (meth) acrylate are used. By using these monomers, a polymer having a high glass transition temperature can be obtained. Only one kind of these monomers may be used, or two or more kinds thereof may be used in combination.
また、上記(メタ)アクリル酸エステル系単量体に代えて、(メタ)アクリロイル基を有するシルセスキオキサン化合物を用いてもよい。シルセスキオキサン化合物を用いることにより、ガラス転移温度が高いアクリル系重合体が得られる。シルセスキオキサン化合物は、種々の骨格構造、例えば、カゴ型構造、ハシゴ型構造、ランダム構造などの骨格を持つものが知られている。シルセスキオキサン化合物は、これらの構造を1種のみを有するものでもよく、2種以上を有するものでもよい。シルセスキオキサン化合物は1種のみを用いてもよく、2種以上を組み合わせて用いてもよい。
Further, instead of the above (meth) acrylic acid ester-based monomer, a silsesquioxane compound having a (meth) acryloyl group may be used. By using the silsesquioxane compound, an acrylic polymer having a high glass transition temperature can be obtained. The silsesquioxane compound is known to have various skeletal structures, for example, a basket-shaped structure, a ladder-shaped structure, and a random structure. The silsesquioxane compound may have only one of these structures, or may have two or more of these structures. Only one type of silsesquioxane compound may be used, or two or more types may be used in combination.
(メタ)アクリロイル基を含有するシルセスキオキサン化合物として、例えば、東亜合成株式会社SQシリーズのMACグレード、および、ACグレードを用いることができる。MACグレードは、メタクリロイル基を含有するシルセスキオキサン化合物であり、具体的には、例えば、MAC-SQ TM-100、MAC-SQ SI-20、MAC-SQ HDM等が挙げられる。ACグレードは、アクリロイル基を含有するシルセスキオキサン化合物であり、具体的には、例えば、AC-SQ TA-100、AC-SQ SI-20等が挙げられる。
As the silsesquioxane compound containing a (meth) acryloyl group, for example, MAC grade and AC grade of Toagosei Co., Ltd. SQ series can be used. The MAC grade is a silsesquioxane compound containing a methacryloyl group, and specific examples thereof include MAC-SQ TM-100, MAC-SQ SI-20, and MAC-SQ HDM. The AC grade is a silsesquioxane compound containing an acryloyl group, and specific examples thereof include AC-SQ TA-100 and AC-SQ SI-20.
(メタ)アクリル系単量体は、モノマー混合物100重量部に対して、50重量部を超えて用いられる。
The (meth) acrylic monomer is used in an amount of more than 50 parts by weight with respect to 100 parts by weight of the monomer mixture.
<共重合単量体>
共重合単量体としては、上記式(1)で表される単量体が用いられる。このような共重合単量体を用いることにより、得られる重合体の側鎖にホウ素を含む置換基が導入される。共重合単量体は1種のみを用いてもよく、2種以上を組み合わせて用いてもよい。 <Copolymerization monomer>
As the copolymerization monomer, a monomer represented by the above formula (1) is used. By using such a copolymerization monomer, a substituent containing boron is introduced into the side chain of the obtained polymer. Only one type of copolymerization monomer may be used, or two or more types may be used in combination.
共重合単量体としては、上記式(1)で表される単量体が用いられる。このような共重合単量体を用いることにより、得られる重合体の側鎖にホウ素を含む置換基が導入される。共重合単量体は1種のみを用いてもよく、2種以上を組み合わせて用いてもよい。 <Copolymerization monomer>
As the copolymerization monomer, a monomer represented by the above formula (1) is used. By using such a copolymerization monomer, a substituent containing boron is introduced into the side chain of the obtained polymer. Only one type of copolymerization monomer may be used, or two or more types may be used in combination.
上記式(1)における脂肪族炭化水素基としては、置換基を有していてもよい炭素数1~20の直鎖または分岐のアルキル基、置換基を有していてもよい炭素数3~20の環状アルキル基、炭素数2~20のアルケニル基が挙げられる。上記アリール基としては、置換基を有していてもよい炭素数6~20のフェニル基、置換基を有していてもよい炭素数10~20のナフチル基等が挙げられる。ヘテロ環基としては、置換基を有していてもよい少なくとも1つのヘテロ原子を含む5員環基または6員環基が挙げられる。なお、R1およびR2は互いに連結して環を形成してもよい。R1およびR2は、好ましくは水素原子、もしくは、炭素数1~3の直鎖または分岐のアルキル基であり、より好ましくは水素原子である。
The aliphatic hydrocarbon group in the above formula (1) may have a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and 3 to 3 carbon atoms which may have a substituent. Examples thereof include a cyclic alkyl group of 20 and an alkenyl group having 2 to 20 carbon atoms. Examples of the aryl group include a phenyl group having 6 to 20 carbon atoms which may have a substituent and a naphthyl group having 10 to 20 carbon atoms which may have a substituent. Examples of the heterocyclic group include a 5-membered ring group or a 6-membered ring group containing at least one heteroatom which may have a substituent. R 1 and R 2 may be connected to each other to form a ring. R 1 and R 2 are preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.
Xで表される官能基が含む反応性基は、ビニル基、(メタ)アクリル基、スチリル基、(メタ)アクリルアミド基、ビニルエーテル基、エポキシ基、オキセタン基、ヒドロキシル基、アミノ基、アルデヒド基、および、カルボキシル基からなる群より選択される少なくとも1種である。好ましくは、反応性基は(メタ)アクリル基および/または(メタ)アクリルアミド基である。これらの反応性基を有することにより、ヨウ素透過抑制層を偏光子に隣接して配置した場合に偏光子との密着性がさらに向上し得る。
The reactive group contained in the functional group represented by X is a vinyl group, a (meth) acrylic group, a styryl group, a (meth) acrylamide group, a vinyl ether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and the like. And at least one selected from the group consisting of carboxyl groups. Preferably, the reactive group is a (meth) acrylic group and / or a (meth) acrylamide group. By having these reactive groups, the adhesion to the polarizer can be further improved when the iodine permeation inhibitory layer is arranged adjacent to the polarizer.
1つの実施形態においては、Xで表される官能基は、Z-Y-で表される官能基であることが好ましい。ここで、Zはビニル基、(メタ)アクリル基、スチリル基、(メタ)アクリルアミド基、ビニルエーテル基、エポキシ基、オキセタン基、ヒドロキシル基、アミノ基、アルデヒド基、および、カルボキシル基からなる群より選択される少なくとも1種の反応性基を含む官能基を表し、Yはフェニレン基またはアルキレン基を表す。
In one embodiment, the functional group represented by X is preferably a functional group represented by ZZ. Here, Z is selected from the group consisting of a vinyl group, a (meth) acrylic group, a styryl group, a (meth) acrylamide group, a vinyl ether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group. Represents a functional group containing at least one reactive group, where Y represents a phenylene group or an alkylene group.
共重合単量体としては、具体的には以下の化合物を用いることができる。
Specifically, the following compounds can be used as the copolymerization monomer.
共重合単量体は、モノマー混合物100重量部に対して、0重量部を超えて50重量部未満の含有量で用いられる。好ましくは0.01重量部以上50重量部未満であり、より好ましくは0.05重量部~20重量部であり、さらに好ましくは0.1重量部~10重量部であり、特に好ましくは0.5重量部~5重量部である。
The copolymerized monomer is used in an amount of more than 0 parts by weight and less than 50 parts by weight with respect to 100 parts by weight of the monomer mixture. It is preferably 0.01 parts by weight or more and less than 50 parts by weight, more preferably 0.05 parts by weight to 20 parts by weight, still more preferably 0.1 parts by weight to 10 parts by weight, and particularly preferably 0. It is 5 parts by weight to 5 parts by weight.
<ラクトン環等含有アクリル系樹脂>
<Acrylic resin containing lactone ring, etc.>
アクリル系樹脂は、別の実施形態においては、ラクトン環単位、無水グルタル酸単位、グルタルイミド単位、無水マレイン酸単位およびマレイミド(N-置換マレイミド)単位から選択される環構造を含む繰り返し単位を有する。環構造を含む繰り返し単位は、1種類のみがアクリル系樹脂の繰り返し単位に含まれていてもよく、2種類以上が含まれていてもよい。
In another embodiment, the acrylic resin has a repeating unit containing a ring structure selected from a lactone ring unit, a glutaric anhydride unit, a glutarimide unit, a maleic anhydride unit and a maleimide (N-substituted maleimide) unit. .. Only one type of the repeating unit including the ring structure may be contained in the repeating unit of the acrylic resin, or two or more types may be contained.
ラクトン環単位は、好ましくは、下記一般式(2)で表される:
The lactone ring unit is preferably represented by the following general formula (2):
グルタルイミド単位は、好ましくは、下記一般式(3)で表される:
The glutarimide unit is preferably represented by the following general formula (3):
一般式(3)において、R11およびR12は、それぞれ独立して、水素または炭素数1~8のアルキル基を示し、R13は、炭素数1~18のアルキル基、炭素数3~12のシクロアルキル基、または炭素数6~10のアリール基を示す。一般式(3)において、好ましくは、R11およびR12は、それぞれ独立して水素またはメチル基であり、R13は水素、メチル基、ブチル基またはシクロヘキシル基である。より好ましくは、R11はメチル基であり、R12は水素であり、R13はメチル基である。アクリル系樹脂には、単一のグルタルイミド単位のみが含まれていてもよく、上記一般式(3)におけるR11、R12およびR13が異なる複数のグルタルイミド単位が含まれていてもよい。グルタルイミド単位を有するアクリル系樹脂は、例えば、特開2006-309033号公報、特開2006-317560号公報、特開2006-328334号公報、特開2006-337491号公報、特開2006-337492号公報、特開2006-337493号公報、特開2006-337569号公報に記載されており、当該公報の記載は本明細書に参考として援用される。なお、無水グルタル酸単位については、上記一般式(3)におけるR13で置換された窒素原子が酸素原子となること以外は、グルタルイミド単位に関する上記の説明が適用される。
In the general formula (3), R 11 and R 12 independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 13 is an alkyl group having 1 to 18 carbon atoms and 3 to 12 carbon atoms. The cycloalkyl group of the above, or an aryl group having 6 to 10 carbon atoms is shown. In the general formula (3), preferably R 11 and R 12 are independently hydrogen or methyl groups, and R 13 is a hydrogen, methyl group, butyl group or cyclohexyl group, respectively. More preferably, R 11 is a methyl group, R 12 is hydrogen, and R 13 is a methyl group. The acrylic resin may contain only a single glutarimide unit, or may contain a plurality of glutarimide units having different R 11 , R 12 and R 13 in the above general formula (3). .. Examples of the acrylic resin having a glutarimide unit include JP-A-2006-309033, JP-A-2006-317560, JP-A-2006-328334, JP-A-2006-337491, and JP-A-2006-337492. It is described in Japanese Patent Application Laid-Open No. 2006-337493 and Japanese Patent Application Laid-Open No. 2006-337569, and the description of the relevant publication is incorporated herein by reference. Note that the glutaric anhydride units, nitrogen atom substituted by R 13 in the general formula (3), except that the oxygen atom, the above description is applied about the glutarimide units.
無水マレイン酸単位およびマレイミド(N-置換マレイミド)単位については、名称から構造が特定されるので、具体的な説明は省略する。
The structure of the maleic anhydride unit and the maleimide (N-substituted maleimide) unit is specified from the name, so specific description thereof will be omitted.
アクリル系樹脂における環構造を含む繰り返し単位の含有割合は、好ましくは1モル%~50モル%、より好ましくは10モル%~40モル%、さらに好ましくは20モル%~30モル%である。なお、アクリル系樹脂は、主たる繰り返し単位として、上記の(メタ)アクリル系単量体由来の繰り返し単位を含む。
The content ratio of the repeating unit including the ring structure in the acrylic resin is preferably 1 mol% to 50 mol%, more preferably 10 mol% to 40 mol%, and further preferably 20 mol% to 30 mol%. The acrylic resin contains the above-mentioned (meth) acrylic monomer-derived repeating unit as the main repeating unit.
<エポキシ樹脂>
エポキシ樹脂としては、好ましくは芳香族環を有するエポキシ樹脂が用いられる。芳香族環を有するエポキシ樹脂をエポキシ樹脂として用いることにより、ヨウ素透過抑制層を偏光子に隣接して配置した場合に偏光子との密着性が向上し得る。さらに、ヨウ素透過抑制層に隣接して粘着剤層を配置した場合に、粘着剤層の投錨力が向上し得る。芳香族環を有するエポキシ樹脂としては、例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂などのビスフェノール型エポキシ樹脂;フェノールノボラックエポキシ樹脂、クレゾールノボラックエポキシ樹脂、ヒドロキシベンズアルデヒドフェノールノボラックエポキシ樹脂などのノボラック型のエポキシ樹脂;テトラヒドロキシフェニルメタンのグリシジルエーテル、テトラヒドロキシベンゾフェノンのグリシジルエーテル、エポキシ化ポリビニルフェノールなどの多官能型のエポキシ樹脂、ナフトール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂などが挙げられる。好ましくは、ビスフェノールA型エポキシ樹脂、ビフェニル型エポキシ樹脂、ビスフェノールF型エポキシ樹脂が用いられる。エポキシ樹脂は1種のみを用いてもよく、2種以上を組み合わせて用いてもよい。 <Epoxy resin>
As the epoxy resin, an epoxy resin having an aromatic ring is preferably used. By using an epoxy resin having an aromatic ring as the epoxy resin, the adhesion to the polarizing element can be improved when the iodine permeation suppressing layer is arranged adjacent to the polarizer. Further, when the pressure-sensitive adhesive layer is arranged adjacent to the iodine permeation suppressing layer, the anchoring force of the pressure-sensitive adhesive layer can be improved. Examples of the epoxy resin having an aromatic ring include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and other bisphenol type epoxy resins; phenol novolac epoxy resin, cresol novolac epoxy resin, hydroxybenzaldehyde phenol novolac. Novolak type epoxy resin such as epoxy resin; polyfunctional epoxy resin such as tetrahydroxyphenylmethane glycidyl ether, tetrahydroxybenzophenone glycidyl ether, epoxidized polyvinylphenol, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type Epoxy resin and the like can be mentioned. Preferably, a bisphenol A type epoxy resin, a biphenyl type epoxy resin, or a bisphenol F type epoxy resin is used. Only one type of epoxy resin may be used, or two or more types may be used in combination.
エポキシ樹脂としては、好ましくは芳香族環を有するエポキシ樹脂が用いられる。芳香族環を有するエポキシ樹脂をエポキシ樹脂として用いることにより、ヨウ素透過抑制層を偏光子に隣接して配置した場合に偏光子との密着性が向上し得る。さらに、ヨウ素透過抑制層に隣接して粘着剤層を配置した場合に、粘着剤層の投錨力が向上し得る。芳香族環を有するエポキシ樹脂としては、例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂などのビスフェノール型エポキシ樹脂;フェノールノボラックエポキシ樹脂、クレゾールノボラックエポキシ樹脂、ヒドロキシベンズアルデヒドフェノールノボラックエポキシ樹脂などのノボラック型のエポキシ樹脂;テトラヒドロキシフェニルメタンのグリシジルエーテル、テトラヒドロキシベンゾフェノンのグリシジルエーテル、エポキシ化ポリビニルフェノールなどの多官能型のエポキシ樹脂、ナフトール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂などが挙げられる。好ましくは、ビスフェノールA型エポキシ樹脂、ビフェニル型エポキシ樹脂、ビスフェノールF型エポキシ樹脂が用いられる。エポキシ樹脂は1種のみを用いてもよく、2種以上を組み合わせて用いてもよい。 <Epoxy resin>
As the epoxy resin, an epoxy resin having an aromatic ring is preferably used. By using an epoxy resin having an aromatic ring as the epoxy resin, the adhesion to the polarizing element can be improved when the iodine permeation suppressing layer is arranged adjacent to the polarizer. Further, when the pressure-sensitive adhesive layer is arranged adjacent to the iodine permeation suppressing layer, the anchoring force of the pressure-sensitive adhesive layer can be improved. Examples of the epoxy resin having an aromatic ring include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and other bisphenol type epoxy resins; phenol novolac epoxy resin, cresol novolac epoxy resin, hydroxybenzaldehyde phenol novolac. Novolak type epoxy resin such as epoxy resin; polyfunctional epoxy resin such as tetrahydroxyphenylmethane glycidyl ether, tetrahydroxybenzophenone glycidyl ether, epoxidized polyvinylphenol, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type Epoxy resin and the like can be mentioned. Preferably, a bisphenol A type epoxy resin, a biphenyl type epoxy resin, or a bisphenol F type epoxy resin is used. Only one type of epoxy resin may be used, or two or more types may be used in combination.
ヨウ素透過抑制層は、上記のような樹脂の有機溶媒溶液を塗布して塗布膜を形成し、当該塗布膜を固化または熱硬化させることにより形成され得る。有機溶媒としては、アクリル系樹脂を溶解または均一に分散し得る任意の適切な有機溶媒を用いることができる。有機溶媒の具体例としては、酢酸エチル、トルエン、メチルエチルケトン(MEK)、メチルイソブチルケトン(MIBK)、シクロペンタノン、シクロヘキサノンが挙げられる。溶液の樹脂濃度は、溶媒100重量部に対して、好ましくは3重量部~20重量部である。このような樹脂濃度であれば、均一な塗布膜を形成することができる。
The iodine permeation suppressing layer can be formed by applying an organic solvent solution of the above resin to form a coating film, and solidifying or thermosetting the coating film. As the organic solvent, any suitable organic solvent capable of dissolving or uniformly dispersing the acrylic resin can be used. Specific examples of the organic solvent include ethyl acetate, toluene, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone, and cyclohexanone. The resin concentration of the solution is preferably 3 parts by weight to 20 parts by weight with respect to 100 parts by weight of the solvent. With such a resin concentration, a uniform coating film can be formed.
溶液は、任意の適切な基材に塗布してもよく、隣接層(例えば、偏光子、位相差層)に塗布してもよい。溶液を基材に塗布する場合には、基材上に形成された塗布膜の固化物(ヨウ素透過抑制層)が隣接層に転写される。溶液を隣接層に塗布する場合には、塗布膜を乾燥(固化)させることにより、隣接層上に保護層が直接形成される。好ましくは、溶液は隣接層に塗布され、隣接層上に保護層が直接形成される。このような構成であれば、転写に必要とされる接着剤層または粘着剤層を省略することができるので、位相差層付偏光板をさらに薄くすることができる。溶液の塗布方法としては、任意の適切な方法を採用することができる。具体例としては、ロールコート法、スピンコート法、ワイヤーバーコート法、ディップコート法、ダイコート法、カーテンコート法、スプレーコート法、ナイフコート法(コンマコート法等)が挙げられる。
The solution may be applied to any suitable substrate or adjacent layers (eg, polarizer, retardation layer). When the solution is applied to the base material, the solidified product (iodine permeation suppressing layer) of the coating film formed on the base material is transferred to the adjacent layer. When the solution is applied to the adjacent layer, the protective layer is directly formed on the adjacent layer by drying (solidifying) the coating film. Preferably, the solution is applied to the adjacent layer and a protective layer is formed directly on the adjacent layer. With such a configuration, the adhesive layer or the pressure-sensitive adhesive layer required for transfer can be omitted, so that the polarizing plate with a retardation layer can be further thinned. Any suitable method can be adopted as the method for applying the solution. Specific examples include a roll coating method, a spin coating method, a wire bar coating method, a dip coating method, a die coating method, a curtain coating method, a spray coating method, and a knife coating method (comma coating method, etc.).
溶液の塗布膜を固化または熱硬化させることにより、ヨウ素透過抑制層が形成され得る。固化または熱硬化の加熱温度は、好ましくは100℃以下であり、より好ましくは50℃~70℃である。加熱温度がこのような範囲であれば、偏光子に対する悪影響を防止することができる。加熱時間は、加熱温度に応じて変化し得る。加熱時間は、例えば1分~10分であり得る。
An iodine permeation inhibitory layer can be formed by solidifying or thermosetting the coating film of the solution. The heating temperature for solidification or thermosetting is preferably 100 ° C. or lower, more preferably 50 ° C. to 70 ° C. When the heating temperature is in such a range, it is possible to prevent an adverse effect on the polarizer. The heating time can vary depending on the heating temperature. The heating time can be, for example, 1 minute to 10 minutes.
ヨウ素透過抑制層(実質的には、上記樹脂の有機溶媒溶液)は、目的に応じて任意の適切な添加剤を含んでいてもよい。添加剤の具体例としては、紫外線吸収剤;レベリング剤;ヒンダードフェノール系、リン系、イオウ系等の酸化防止剤;耐光安定剤、耐候安定剤、熱安定剤等の安定剤;ガラス繊維、炭素繊維等の補強材;近赤外線吸収剤;トリス(ジブロモプロピル)ホスフェート、トリアリルホスフェート、酸化アンチモン等の難燃剤;アニオン系、カチオン系、ノニオン系の界面活性剤等の帯電防止剤;無機顔料、有機顔料、染料等の着色剤;有機フィラーまたは無機フィラー;樹脂改質剤;有機充填剤や無機充填剤;可塑剤;滑剤;帯電防止剤;難燃剤;などが挙げられる。添加剤の種類、数、組み合わせ、添加量等は、目的に応じて適切に設定され得る。
The iodine permeation suppressing layer (substantially, the organic solvent solution of the above resin) may contain any suitable additive depending on the purpose. Specific examples of additives include ultraviolet absorbers; leveling agents; antioxidants such as hindered phenol-based, phosphorus-based, and sulfur-based; stabilizers such as light-resistant stabilizers, weather-resistant stabilizers, and heat-stabilizing agents; glass fibers, Reinforcing materials such as carbon fibers; Near infrared absorbers; Flame retardants such as tris (dibromopropyl) phosphate, triallyl phosphate, antimony oxide; Antistatic agents such as anionic, cationic and nonionic surfactants; Inorganic pigments , Organic pigments, colorants such as dyes; organic fillers or inorganic fillers; resin modifiers; organic fillers and inorganic fillers; plasticizers; lubricants; antistatic agents; flame retardants; and the like. The type, number, combination, amount of additive, etc. of the additive can be appropriately set according to the purpose.
E.第2の位相差層
第2の位相差層は、上記のとおり、屈折率特性がnz>nx=nyの関係を示す、いわゆるポジティブCプレートであり得る。第2の位相差層としてポジティブCプレートを用いることにより、斜め方向の反射を良好に防止することができ、反射防止機能の広視野角化が可能となる。この場合、第2の位相差層の厚み方向の位相差Rth(550)は、好ましくは-50nm~-300nm、より好ましくは-70nm~-250nm、さらに好ましくは-90nm~-200nm、特に好ましくは-100nm~-180nmである。ここで、「nx=ny」は、nxとnyが厳密に等しい場合のみならず、nxとnyが実質的に等しい場合も包含する。すなわち、第2の位相差層の面内位相差Re(550)は10nm未満であり得る。 E. Second Phase Difference Layer The second phase difference layer can be a so-called positive C plate in which the refractive index characteristic shows a relationship of nz> nz = ny as described above. By using the positive C plate as the second retardation layer, it is possible to satisfactorily prevent reflection in the oblique direction, and it is possible to widen the viewing angle of the antireflection function. In this case, the retardation Rth (550) in the thickness direction of the second retardation layer is preferably −50 nm to −300 nm, more preferably −70 nm to −250 nm, still more preferably −90 nm to −200 nm, and particularly preferably. It is -100 nm to -180 nm. Here, "nx = ny" includes not only the case where nx and ny are exactly equal, but also the case where nx and ny are substantially equal. That is, the in-plane retardation Re (550) of the second retardation layer can be less than 10 nm.
第2の位相差層は、上記のとおり、屈折率特性がnz>nx=nyの関係を示す、いわゆるポジティブCプレートであり得る。第2の位相差層としてポジティブCプレートを用いることにより、斜め方向の反射を良好に防止することができ、反射防止機能の広視野角化が可能となる。この場合、第2の位相差層の厚み方向の位相差Rth(550)は、好ましくは-50nm~-300nm、より好ましくは-70nm~-250nm、さらに好ましくは-90nm~-200nm、特に好ましくは-100nm~-180nmである。ここで、「nx=ny」は、nxとnyが厳密に等しい場合のみならず、nxとnyが実質的に等しい場合も包含する。すなわち、第2の位相差層の面内位相差Re(550)は10nm未満であり得る。 E. Second Phase Difference Layer The second phase difference layer can be a so-called positive C plate in which the refractive index characteristic shows a relationship of nz> nz = ny as described above. By using the positive C plate as the second retardation layer, it is possible to satisfactorily prevent reflection in the oblique direction, and it is possible to widen the viewing angle of the antireflection function. In this case, the retardation Rth (550) in the thickness direction of the second retardation layer is preferably −50 nm to −300 nm, more preferably −70 nm to −250 nm, still more preferably −90 nm to −200 nm, and particularly preferably. It is -100 nm to -180 nm. Here, "nx = ny" includes not only the case where nx and ny are exactly equal, but also the case where nx and ny are substantially equal. That is, the in-plane retardation Re (550) of the second retardation layer can be less than 10 nm.
nz>nx=nyの屈折率特性を有する第2の位相差層は、任意の適切な材料で形成され得る。第2の位相差層は、好ましくは、ホメオトロピック配向に固定された液晶材料を含むフィルムからなる。ホメオトロピック配向させることができる液晶材料(液晶化合物)は、液晶モノマーであっても液晶ポリマーであってもよい。当該液晶化合物および当該位相差層の形成方法の具体例としては、特開2002-333642号公報の[0020]~[0028]に記載の液晶化合物および当該位相差層の形成方法が挙げられる。この場合、第2の位相差層の厚みは、好ましくは0.5μm~10μmであり、より好ましくは0.5μm~8μmであり、さらに好ましくは0.5μm~5μmである。
The second retardation layer having a refractive index characteristic of nz> nx = ny can be formed of any suitable material. The second retardation layer preferably consists of a film containing a liquid crystal material fixed in a homeotropic orientation. The liquid crystal material (liquid crystal compound) that can be homeotropically oriented may be a liquid crystal monomer or a liquid crystal polymer. Specific examples of the liquid crystal compound and the method for forming the retardation layer include the liquid crystal compounds described in [0020] to [0028] of JP-A-2002-333642 and the method for forming the retardation layer. In this case, the thickness of the second retardation layer is preferably 0.5 μm to 10 μm, more preferably 0.5 μm to 8 μm, and even more preferably 0.5 μm to 5 μm.
F.導電層または導電層付等方性基材
導電層は、任意の適切な成膜方法(例えば、真空蒸着法、スパッタリング法、CVD法、イオンプレーティング法、スプレー法等)により、任意の適切な基材上に、金属酸化物膜を成膜して形成され得る。金属酸化物としては、例えば、酸化インジウム、酸化スズ、酸化亜鉛、インジウム-スズ複合酸化物、スズ-アンチモン複合酸化物、亜鉛-アルミニウム複合酸化物、インジウム-亜鉛複合酸化物が挙げられる。なかでも好ましくは、インジウム-スズ複合酸化物(ITO)である。 F. A conductive layer or an isotropic base material with a conductive layer The conductive layer is an arbitrary suitable base material by any suitable film forming method (for example, vacuum deposition method, sputtering method, CVD method, ion plating method, spray method, etc.). It can be formed by forming a metal oxide film on top of it. Examples of the metal oxide include indium oxide, tin oxide, zinc oxide, indium-tin composite oxide, tin-antimon composite oxide, zinc-aluminum composite oxide, and indium-zinc composite oxide. Of these, indium-tin composite oxide (ITO) is preferable.
導電層は、任意の適切な成膜方法(例えば、真空蒸着法、スパッタリング法、CVD法、イオンプレーティング法、スプレー法等)により、任意の適切な基材上に、金属酸化物膜を成膜して形成され得る。金属酸化物としては、例えば、酸化インジウム、酸化スズ、酸化亜鉛、インジウム-スズ複合酸化物、スズ-アンチモン複合酸化物、亜鉛-アルミニウム複合酸化物、インジウム-亜鉛複合酸化物が挙げられる。なかでも好ましくは、インジウム-スズ複合酸化物(ITO)である。 F. A conductive layer or an isotropic base material with a conductive layer The conductive layer is an arbitrary suitable base material by any suitable film forming method (for example, vacuum deposition method, sputtering method, CVD method, ion plating method, spray method, etc.). It can be formed by forming a metal oxide film on top of it. Examples of the metal oxide include indium oxide, tin oxide, zinc oxide, indium-tin composite oxide, tin-antimon composite oxide, zinc-aluminum composite oxide, and indium-zinc composite oxide. Of these, indium-tin composite oxide (ITO) is preferable.
導電層が金属酸化物を含む場合、該導電層の厚みは、好ましくは50nm以下であり、より好ましくは35nm以下である。導電層の厚みの下限は、好ましくは10nmである。
When the conductive layer contains a metal oxide, the thickness of the conductive layer is preferably 50 nm or less, more preferably 35 nm or less. The lower limit of the thickness of the conductive layer is preferably 10 nm.
導電層は、上記基材から第1の位相差層(あるいは、ヨウ素透過抑制層または存在する場合には第2の位相差層)に転写されて導電層単独で位相差層付偏光板の構成層とされてもよく、基材との積層体(導電層付基材)として第1の位相差層(あるいは、ヨウ素透過抑制層または存在する場合には第2の位相差層)に積層されてもよい。好ましくは、上記基材は光学的に等方性であり、したがって、導電層は導電層付等方性基材として位相差層付偏光板に用いられ得る。
The conductive layer is transferred from the base material to the first retardation layer (or the iodine permeation suppression layer or the second retardation layer if present), and the conductive layer alone constitutes a polarizing plate with a retardation layer. It may be a layer, and is laminated on the first retardation layer (or the iodine permeation suppression layer or the second retardation layer if present) as a laminate with the base material (base material with a conductive layer). You may. Preferably, the substrate is optically isotropic, and therefore the conductive layer can be used as an isotropic substrate with a conductive layer in a polarizing plate with a retardation layer.
光学的に等方性の基材(等方性基材)としては、任意の適切な等方性基材を採用し得る。等方性基材を構成する材料としては、例えば、ノルボルネン系樹脂やオレフィン系樹脂などの共役系を有さない樹脂を主骨格としている材料、ラクトン環やグルタルイミド環などの環状構造をアクリル系樹脂の主鎖中に有する材料などが挙げられる。このような材料を用いると、等方性基材を形成した際に、分子鎖の配向に伴う位相差の発現を小さく抑えることができる。等方性基材の厚みは、好ましくは50μm以下であり、より好ましくは35μm以下である。等方性基材の厚みの下限は、例えば20μmである。
Any suitable isotropic base material can be adopted as the optically isotropic base material (isotropic base material). Examples of the material constituting the isotropic base material include a material having a resin having no conjugate system such as a norbornene resin and an olefin resin as a main skeleton, and an acrylic resin having a cyclic structure such as a lactone ring and a glutarimide ring. Examples include the material contained in the main chain. When such a material is used, when an isotropic base material is formed, the expression of the phase difference due to the orientation of the molecular chains can be suppressed to be small. The thickness of the isotropic base material is preferably 50 μm or less, more preferably 35 μm or less. The lower limit of the thickness of the isotropic base material is, for example, 20 μm.
上記導電層および/または上記導電層付等方性基材の導電層は、必要に応じてパターン化され得る。パターン化によって、導通部と絶縁部とが形成され得る。結果として、電極が形成され得る。電極は、タッチパネルへの接触を感知するタッチセンサ電極として機能し得る。パターニング方法としては、任意の適切な方法を採用し得る。パターニング方法の具体例としては、ウエットエッチング法、スクリーン印刷法が挙げられる。
The conductive layer and / or the conductive layer of the isotropic base material with the conductive layer can be patterned as needed. By patterning, a conductive portion and an insulating portion can be formed. As a result, electrodes can be formed. The electrode can function as a touch sensor electrode that senses contact with the touch panel. As the patterning method, any suitable method can be adopted. Specific examples of the patterning method include a wet etching method and a screen printing method.
G.画像表示装置
上記A項からF項に記載の位相差層付偏光板は、画像表示装置に適用され得る。したがって、本発明の実施形態は、そのような位相差層付偏光板を用いた画像表示装置を包含する。画像表示装置の代表例としては、液晶表示装置、エレクトロルミネセンス(EL)表示装置(例えば、有機EL表示装置、無機EL表示装置)が挙げられる。本発明の実施形態による画像表示装置は、その視認側に上記A項からF項に記載の位相差層付偏光板を備える。位相差層付偏光板は、位相差層が画像表示セル(例えば、液晶セル、有機ELセル、無機ELセル)側となるように(偏光子が視認側となるように)積層されている。このような画像表示装置は、非常に薄型でありながら金属部材の腐食が顕著に抑制されている。1つの実施形態においては、画像表示装置は、湾曲した形状(実質的には、湾曲した表示画面)を有し、および/または、折り曲げもしくは折り畳み可能である。 G. Image display device The polarizing plate with a retardation layer according to the above items A to F can be applied to an image display device. Therefore, an embodiment of the present invention includes an image display device using such a polarizing plate with a retardation layer. Typical examples of the image display device include a liquid crystal display device and an electroluminescence (EL) display device (for example, an organic EL display device and an inorganic EL display device). The image display device according to the embodiment of the present invention includes the polarizing plate with a retardation layer according to the above items A to F on the visible side thereof. The polarizing plate with a retardation layer is laminated so that the retardation layer is on the image display cell side (for example, a liquid crystal cell, an organic EL cell, an inorganic EL cell) (so that the polarizer is on the visual recognition side). Although such an image display device is extremely thin, corrosion of metal members is remarkably suppressed. In one embodiment, the image display device has a curved shape (substantially a curved display screen) and / or is foldable or foldable.
上記A項からF項に記載の位相差層付偏光板は、画像表示装置に適用され得る。したがって、本発明の実施形態は、そのような位相差層付偏光板を用いた画像表示装置を包含する。画像表示装置の代表例としては、液晶表示装置、エレクトロルミネセンス(EL)表示装置(例えば、有機EL表示装置、無機EL表示装置)が挙げられる。本発明の実施形態による画像表示装置は、その視認側に上記A項からF項に記載の位相差層付偏光板を備える。位相差層付偏光板は、位相差層が画像表示セル(例えば、液晶セル、有機ELセル、無機ELセル)側となるように(偏光子が視認側となるように)積層されている。このような画像表示装置は、非常に薄型でありながら金属部材の腐食が顕著に抑制されている。1つの実施形態においては、画像表示装置は、湾曲した形状(実質的には、湾曲した表示画面)を有し、および/または、折り曲げもしくは折り畳み可能である。 G. Image display device The polarizing plate with a retardation layer according to the above items A to F can be applied to an image display device. Therefore, an embodiment of the present invention includes an image display device using such a polarizing plate with a retardation layer. Typical examples of the image display device include a liquid crystal display device and an electroluminescence (EL) display device (for example, an organic EL display device and an inorganic EL display device). The image display device according to the embodiment of the present invention includes the polarizing plate with a retardation layer according to the above items A to F on the visible side thereof. The polarizing plate with a retardation layer is laminated so that the retardation layer is on the image display cell side (for example, a liquid crystal cell, an organic EL cell, an inorganic EL cell) (so that the polarizer is on the visual recognition side). Although such an image display device is extremely thin, corrosion of metal members is remarkably suppressed. In one embodiment, the image display device has a curved shape (substantially a curved display screen) and / or is foldable or foldable.
以下、実施例によって本発明を具体的に説明するが、本発明はこれら実施例によって限定されるものではない。各特性の測定方法は以下の通りである。なお、特に明記しない限り、実施例および比較例における「部」および「%」は重量基準である。
Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. The measurement method of each characteristic is as follows. Unless otherwise specified, "parts" and "%" in Examples and Comparative Examples are based on weight.
(1)厚み
10μm以下の厚みは、干渉膜厚計(大塚電子社製、製品名「MCPD-3000」)を用いて測定した。10μmを超える厚みは、デジタルマイクロメーター(アンリツ社製、製品名「KC-351C」)を用いて測定した。 (1) Thickness The thickness of 10 μm or less was measured using an interference film thickness meter (manufactured by Otsuka Electronics Co., Ltd., product name “MCPD-3000”). The thickness exceeding 10 μm was measured using a digital micrometer (manufactured by Anritsu, product name “KC-351C”).
10μm以下の厚みは、干渉膜厚計(大塚電子社製、製品名「MCPD-3000」)を用いて測定した。10μmを超える厚みは、デジタルマイクロメーター(アンリツ社製、製品名「KC-351C」)を用いて測定した。 (1) Thickness The thickness of 10 μm or less was measured using an interference film thickness meter (manufactured by Otsuka Electronics Co., Ltd., product name “MCPD-3000”). The thickness exceeding 10 μm was measured using a digital micrometer (manufactured by Anritsu, product name “KC-351C”).
(2)金属腐食性(48時間)
50μmのポリエチレンテレフタレート(PET)フィルムの片面に、銀ナノワイヤー液(MERCK社製、ナノワイヤーサイズ:直径115nm、長さ20μm~50μm、固形分0.5%のイソプロピルアルコール(IPA)溶液)をワイヤーバーでウェット膜厚が15μmになるように塗工し、100℃のオーブンで5分間乾燥し、銀ナノワイヤー塗膜を形成した。次いで、メチルイソブチルケトン(MIBK)99部、ペンタエリスリトールテトラアクリレート(PETA)1部、および光重合開始剤(BASF社製、製品名「イルガキュア907」)0.03部を含むオーバーコート液(固形分濃度:約1%)を、銀ナノワイヤー塗膜の表面にワイヤーバーを用いてウェット膜厚が10μmになるように塗工し、100℃のオーブンで5分間乾燥した。次いで、活性エネルギー線を照射してオーバーコート塗膜を硬化させ、PETフィルム/銀ナノワイヤー層/オーバーコート層(厚み100nm)の構成を有する金属フィルムを作製した。この金属フィルムを、粘着剤(15μm)を用いて厚さ0.5mmのガラス板に貼り合わせ、金属フィルム/粘着剤/ガラス板の積層体を得た。得られた積層体を非接触式抵抗測定器(ナプソン社製、製品名「EC-80」)にて抵抗値を測定したところ、50Ω/□であった。 (2) Metal corrosive (48 hours)
Wire a silver nanowire solution (manufactured by MERCK, nanowire size: diameter 115 nm,length 20 μm to 50 μm, solid content 0.5% isopropyl alcohol (IPA) solution) on one side of a 50 μm polyethylene terephthalate (PET) film. It was coated with a bar so that the wet film thickness was 15 μm, and dried in an oven at 100 ° C. for 5 minutes to form a silver nanowire coating film. Next, an overcoat solution (solid content) containing 99 parts of methyl isobutyl ketone (MIBK), 1 part of pentaerythritol tetraacrylate (PETA), and 0.03 part of a photopolymerization initiator (manufactured by BASF, product name "Irgacure 907"). Concentration: about 1%) was applied to the surface of the silver nanowire coating film using a wire bar so that the wet film thickness was 10 μm, and dried in an oven at 100 ° C. for 5 minutes. Next, the overcoat coating film was cured by irradiating with active energy rays to prepare a metal film having a composition of PET film / silver nanowire layer / overcoat layer (thickness 100 nm). This metal film was attached to a glass plate having a thickness of 0.5 mm using an adhesive (15 μm) to obtain a metal film / adhesive / glass plate laminate. When the resistance value of the obtained laminate was measured with a non-contact resistance measuring instrument (manufactured by Napuson, product name "EC-80"), it was 50Ω / □.
50μmのポリエチレンテレフタレート(PET)フィルムの片面に、銀ナノワイヤー液(MERCK社製、ナノワイヤーサイズ:直径115nm、長さ20μm~50μm、固形分0.5%のイソプロピルアルコール(IPA)溶液)をワイヤーバーでウェット膜厚が15μmになるように塗工し、100℃のオーブンで5分間乾燥し、銀ナノワイヤー塗膜を形成した。次いで、メチルイソブチルケトン(MIBK)99部、ペンタエリスリトールテトラアクリレート(PETA)1部、および光重合開始剤(BASF社製、製品名「イルガキュア907」)0.03部を含むオーバーコート液(固形分濃度:約1%)を、銀ナノワイヤー塗膜の表面にワイヤーバーを用いてウェット膜厚が10μmになるように塗工し、100℃のオーブンで5分間乾燥した。次いで、活性エネルギー線を照射してオーバーコート塗膜を硬化させ、PETフィルム/銀ナノワイヤー層/オーバーコート層(厚み100nm)の構成を有する金属フィルムを作製した。この金属フィルムを、粘着剤(15μm)を用いて厚さ0.5mmのガラス板に貼り合わせ、金属フィルム/粘着剤/ガラス板の積層体を得た。得られた積層体を非接触式抵抗測定器(ナプソン社製、製品名「EC-80」)にて抵抗値を測定したところ、50Ω/□であった。 (2) Metal corrosive (48 hours)
Wire a silver nanowire solution (manufactured by MERCK, nanowire size: diameter 115 nm,
実施例および比較例で得られた位相差層付偏光板を積層体の金属フィルムのオーバーコート層表面に貼り合わせ、試験サンプルとした。この試験サンプルの抵抗値を非接触式抵抗測定器にて測定し、初期抵抗値とした。さらに、試験サンプルを信頼性試験(85℃・85%RHの環境下に48時間置き、その後23℃・55%RHの環境下で2時間放置)に供した後、上記と同様にして抵抗値を測定した。以下の式により抵抗値上昇率を算出した。なお、測定値(抵抗値)が非接触式抵抗測定器の測定限界(1000Ω/□)を超える場合には、測定値を1500Ω/□として仮定した。
抵抗値上昇率(%)={(信頼性試験後の抵抗値-初期抵抗値)/初期抵抗値}×100
さらに、以下の基準で評価した。
良好:抵抗値上昇率が200%未満
不良:抵抗値上昇率が200%以上 The polarizing plates with retardation layers obtained in Examples and Comparative Examples were bonded to the surface of the overcoat layer of the metal film of the laminated body to prepare a test sample. The resistance value of this test sample was measured with a non-contact resistance measuring instrument and used as the initial resistance value. Further, after subjecting the test sample to a reliability test (placed in an environment of 85 ° C. and 85% RH for 48 hours and then left in an environment of 23 ° C. and 55% RH for 2 hours), the resistance value is the same as above. Was measured. The resistance value increase rate was calculated by the following formula. When the measured value (resistance value) exceeds the measurement limit (1000Ω / □) of the non-contact resistance measuring instrument, the measured value is assumed to be 1500Ω / □.
Resistance value increase rate (%) = {(resistance value after reliability test-initial resistance value) / initial resistance value} x 100
Furthermore, it was evaluated according to the following criteria.
Good: Resistance increase rate is less than 200% Bad: Resistance increase rate is 200% or more
抵抗値上昇率(%)={(信頼性試験後の抵抗値-初期抵抗値)/初期抵抗値}×100
さらに、以下の基準で評価した。
良好:抵抗値上昇率が200%未満
不良:抵抗値上昇率が200%以上 The polarizing plates with retardation layers obtained in Examples and Comparative Examples were bonded to the surface of the overcoat layer of the metal film of the laminated body to prepare a test sample. The resistance value of this test sample was measured with a non-contact resistance measuring instrument and used as the initial resistance value. Further, after subjecting the test sample to a reliability test (placed in an environment of 85 ° C. and 85% RH for 48 hours and then left in an environment of 23 ° C. and 55% RH for 2 hours), the resistance value is the same as above. Was measured. The resistance value increase rate was calculated by the following formula. When the measured value (resistance value) exceeds the measurement limit (1000Ω / □) of the non-contact resistance measuring instrument, the measured value is assumed to be 1500Ω / □.
Resistance value increase rate (%) = {(resistance value after reliability test-initial resistance value) / initial resistance value} x 100
Furthermore, it was evaluated according to the following criteria.
Good: Resistance increase rate is less than 200% Bad: Resistance increase rate is 200% or more
(3)金属腐食性(200時間)
実施例および比較例で得られた位相差層付偏光板を、(2)で得られた積層体の金属フィルムのオーバーコート層形成面に貼り合わせ、試験サンプルとした。この試験サンプルの抵抗値を非接触式抵抗測定器にて測定し、初期の抵抗値とした。さらに、試験サンプルを信頼性試験(85℃・85%RHの環境下に200時間置き、その後23℃・55%RHの環境下で2時間放置)に供した後、上記と同様にして抵抗値を測定した。以下の式により抵抗値上昇率を算出した。なお、測定値(抵抗値)が非接触式抵抗測定器の測定限界(1000Ω/□)を超える場合には、測定値を1500Ω/□として仮定した。
抵抗値上昇率(%)={(信頼性試験後の抵抗値-初期抵抗値)/初期抵抗値}×100
さらに、以下の基準で評価した。
優:抵抗値上昇率が200%未満
良:抵抗値上昇率が200%以上2000%未満
不良:抵抗値上昇率が2000%以上 (3) Metal corrosiveness (200 hours)
The polarizing plates with retardation layers obtained in Examples and Comparative Examples were bonded to the overcoat layer forming surface of the metal film of the laminate obtained in (2) to prepare a test sample. The resistance value of this test sample was measured with a non-contact resistance measuring instrument and used as the initial resistance value. Further, after subjecting the test sample to a reliability test (placed in an environment of 85 ° C. and 85% RH for 200 hours and then left in an environment of 23 ° C. and 55% RH for 2 hours), the resistance value is the same as above. Was measured. The resistance value increase rate was calculated by the following formula. When the measured value (resistance value) exceeds the measurement limit (1000Ω / □) of the non-contact resistance measuring instrument, the measured value is assumed to be 1500Ω / □.
Resistance value increase rate (%) = {(resistance value after reliability test-initial resistance value) / initial resistance value} x 100
Furthermore, it was evaluated according to the following criteria.
Excellent: Resistance increase rate is less than 200% Good: Resistance increase rate is 200% or more and less than 2000% Bad: Resistance increase rate is 2000% or more
実施例および比較例で得られた位相差層付偏光板を、(2)で得られた積層体の金属フィルムのオーバーコート層形成面に貼り合わせ、試験サンプルとした。この試験サンプルの抵抗値を非接触式抵抗測定器にて測定し、初期の抵抗値とした。さらに、試験サンプルを信頼性試験(85℃・85%RHの環境下に200時間置き、その後23℃・55%RHの環境下で2時間放置)に供した後、上記と同様にして抵抗値を測定した。以下の式により抵抗値上昇率を算出した。なお、測定値(抵抗値)が非接触式抵抗測定器の測定限界(1000Ω/□)を超える場合には、測定値を1500Ω/□として仮定した。
抵抗値上昇率(%)={(信頼性試験後の抵抗値-初期抵抗値)/初期抵抗値}×100
さらに、以下の基準で評価した。
優:抵抗値上昇率が200%未満
良:抵抗値上昇率が200%以上2000%未満
不良:抵抗値上昇率が2000%以上 (3) Metal corrosiveness (200 hours)
The polarizing plates with retardation layers obtained in Examples and Comparative Examples were bonded to the overcoat layer forming surface of the metal film of the laminate obtained in (2) to prepare a test sample. The resistance value of this test sample was measured with a non-contact resistance measuring instrument and used as the initial resistance value. Further, after subjecting the test sample to a reliability test (placed in an environment of 85 ° C. and 85% RH for 200 hours and then left in an environment of 23 ° C. and 55% RH for 2 hours), the resistance value is the same as above. Was measured. The resistance value increase rate was calculated by the following formula. When the measured value (resistance value) exceeds the measurement limit (1000Ω / □) of the non-contact resistance measuring instrument, the measured value is assumed to be 1500Ω / □.
Resistance value increase rate (%) = {(resistance value after reliability test-initial resistance value) / initial resistance value} x 100
Furthermore, it was evaluated according to the following criteria.
Excellent: Resistance increase rate is less than 200% Good: Resistance increase rate is 200% or more and less than 2000% Bad: Resistance increase rate is 2000% or more
[実施例1]
1.偏光子の作製
熱可塑性樹脂基材として、長尺状で、吸水率0.75%、Tg約75℃である、非晶質のイソフタル共重合ポリエチレンテレフタレートフィルム(厚み:100μm)を用いた。樹脂基材の片面に、コロナ処理を施した。
ポリビニルアルコール(重合度4200、ケン化度99.2モル%)およびアセトアセチル変性PVA(日本合成化学工業社製、商品名「ゴーセファイマーZ410」)を9:1で混合したPVA系樹脂100重量部に、ヨウ化カリウム13重量部を添加したものを水に溶かし、PVA水溶液(塗布液)を調製した。
樹脂基材のコロナ処理面に、上記PVA水溶液を塗布して60℃で乾燥することにより、厚み13μmのPVA系樹脂層を形成し、積層体を作製した。
得られた積層体を、130℃のオーブン内で周速の異なるロール間で縦方向(長手方向)に2.4倍に自由端一軸延伸した(空中補助延伸処理)。
次いで、積層体を、液温40℃の不溶化浴(水100重量部に対して、ホウ酸を4重量部配合して得られたホウ酸水溶液)に30秒間浸漬させた(不溶化処理)。
次いで、液温30℃の染色浴(水100重量部に対して、ヨウ素とヨウ化カリウムを1:7の重量比で配合して得られたヨウ素水溶液)に、最終的に得られる偏光子の単体透過率(Ts)が43.0%以上となるように濃度を調整しながら60秒間浸漬させた(染色処理)。
次いで、液温40℃の架橋浴(水100重量部に対して、ヨウ化カリウムを3重量部配合し、ホウ酸を5重量部配合して得られたホウ酸水溶液)に30秒間浸漬させた(架橋処理)。
その後、積層体を、液温70℃のホウ酸水溶液(ホウ酸濃度4.0重量%、ヨウ化カリウム濃度5重量%)に浸漬させながら、周速の異なるロール間で縦方向(長手方向)に総延伸倍率が5.5倍となるように一軸延伸を行った(水中延伸処理)。
その後、積層体を液温20℃の洗浄浴(水100重量部に対して、ヨウ化カリウムを4重量部配合して得られた水溶液)に浸漬させた(洗浄処理)。
その後、90℃に保たれたオーブン中で乾燥しながら、表面温度が75℃に保たれたSUS製の加熱ロールに約2秒接触させた(乾燥収縮処理)。乾燥収縮処理による積層体の幅方向の収縮率は5.2%であった。
このようにして、樹脂基材上に厚み5μmの偏光子を形成した。 [Example 1]
1. 1. Preparation of Polarizer As the thermoplastic resin base material, an amorphous isophthalic copolymerized polyethylene terephthalate film (thickness: 100 μm) having a long shape, a water absorption of 0.75%, and a Tg of about 75 ° C. was used. One side of the resin base material was corona-treated.
100 weight of PVA-based resin in which polyvinyl alcohol (degree of polymerization 4200, saponification degree 99.2 mol%) and acetacetyl-modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "Gosefimer Z410") are mixed at a ratio of 9: 1. A PVA aqueous solution (coating solution) was prepared by dissolving 13 parts by weight of potassium iodide in water.
The PVA aqueous solution was applied to the corona-treated surface of the resin base material and dried at 60 ° C. to form a PVA-based resin layer having a thickness of 13 μm to prepare a laminate.
The obtained laminate was uniaxially stretched at the free end 2.4 times in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds in an oven at 130 ° C. (aerial auxiliary stretching treatment).
Next, the laminate was immersed in an insolubilizing bath at a liquid temperature of 40 ° C. (an aqueous boric acid solution obtained by blending 4 parts by weight of boric acid with 100 parts by weight of water) for 30 seconds (insolubilization treatment).
Next, in a dyeing bath having a liquid temperature of 30 ° C. (an aqueous iodine solution obtained by mixing iodine and potassium iodide in a weight ratio of 1: 7 with respect to 100 parts by weight of water), the polarizer finally obtained Immersion was carried out for 60 seconds while adjusting the concentration so that the simple substance transmittance (Ts) was 43.0% or more (dyeing treatment).
Next, it was immersed in a cross-linked bath at a liquid temperature of 40 ° C. (an aqueous boric acid solution obtained by blending 3 parts by weight of potassium iodide and 5 parts by weight of boric acid with respect to 100 parts by weight of water) for 30 seconds. (Crossing treatment).
Then, while immersing the laminate in a boric acid aqueous solution (boric acid concentration 4.0% by weight, potassium iodide concentration 5% by weight) at a liquid temperature of 70 ° C., the rolls having different peripheral speeds are subjected to the longitudinal direction (longitudinal direction). The uniaxial stretching was performed so that the total stretching ratio was 5.5 times (underwater stretching treatment).
Then, the laminate was immersed in a washing bath at a liquid temperature of 20 ° C. (an aqueous solution obtained by blending 4 parts by weight of potassium iodide with 100 parts by weight of water) (cleaning treatment).
Then, while drying in an oven kept at 90 ° C., it was brought into contact with a heating roll made of SUS whose surface temperature was kept at 75 ° C. for about 2 seconds (dry shrinkage treatment). The shrinkage rate in the width direction of the laminated body by the drying shrinkage treatment was 5.2%.
In this way, a polarizer having a thickness of 5 μm was formed on the resin substrate.
1.偏光子の作製
熱可塑性樹脂基材として、長尺状で、吸水率0.75%、Tg約75℃である、非晶質のイソフタル共重合ポリエチレンテレフタレートフィルム(厚み:100μm)を用いた。樹脂基材の片面に、コロナ処理を施した。
ポリビニルアルコール(重合度4200、ケン化度99.2モル%)およびアセトアセチル変性PVA(日本合成化学工業社製、商品名「ゴーセファイマーZ410」)を9:1で混合したPVA系樹脂100重量部に、ヨウ化カリウム13重量部を添加したものを水に溶かし、PVA水溶液(塗布液)を調製した。
樹脂基材のコロナ処理面に、上記PVA水溶液を塗布して60℃で乾燥することにより、厚み13μmのPVA系樹脂層を形成し、積層体を作製した。
得られた積層体を、130℃のオーブン内で周速の異なるロール間で縦方向(長手方向)に2.4倍に自由端一軸延伸した(空中補助延伸処理)。
次いで、積層体を、液温40℃の不溶化浴(水100重量部に対して、ホウ酸を4重量部配合して得られたホウ酸水溶液)に30秒間浸漬させた(不溶化処理)。
次いで、液温30℃の染色浴(水100重量部に対して、ヨウ素とヨウ化カリウムを1:7の重量比で配合して得られたヨウ素水溶液)に、最終的に得られる偏光子の単体透過率(Ts)が43.0%以上となるように濃度を調整しながら60秒間浸漬させた(染色処理)。
次いで、液温40℃の架橋浴(水100重量部に対して、ヨウ化カリウムを3重量部配合し、ホウ酸を5重量部配合して得られたホウ酸水溶液)に30秒間浸漬させた(架橋処理)。
その後、積層体を、液温70℃のホウ酸水溶液(ホウ酸濃度4.0重量%、ヨウ化カリウム濃度5重量%)に浸漬させながら、周速の異なるロール間で縦方向(長手方向)に総延伸倍率が5.5倍となるように一軸延伸を行った(水中延伸処理)。
その後、積層体を液温20℃の洗浄浴(水100重量部に対して、ヨウ化カリウムを4重量部配合して得られた水溶液)に浸漬させた(洗浄処理)。
その後、90℃に保たれたオーブン中で乾燥しながら、表面温度が75℃に保たれたSUS製の加熱ロールに約2秒接触させた(乾燥収縮処理)。乾燥収縮処理による積層体の幅方向の収縮率は5.2%であった。
このようにして、樹脂基材上に厚み5μmの偏光子を形成した。 [Example 1]
1. 1. Preparation of Polarizer As the thermoplastic resin base material, an amorphous isophthalic copolymerized polyethylene terephthalate film (thickness: 100 μm) having a long shape, a water absorption of 0.75%, and a Tg of about 75 ° C. was used. One side of the resin base material was corona-treated.
100 weight of PVA-based resin in which polyvinyl alcohol (degree of polymerization 4200, saponification degree 99.2 mol%) and acetacetyl-modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "Gosefimer Z410") are mixed at a ratio of 9: 1. A PVA aqueous solution (coating solution) was prepared by dissolving 13 parts by weight of potassium iodide in water.
The PVA aqueous solution was applied to the corona-treated surface of the resin base material and dried at 60 ° C. to form a PVA-based resin layer having a thickness of 13 μm to prepare a laminate.
The obtained laminate was uniaxially stretched at the free end 2.4 times in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds in an oven at 130 ° C. (aerial auxiliary stretching treatment).
Next, the laminate was immersed in an insolubilizing bath at a liquid temperature of 40 ° C. (an aqueous boric acid solution obtained by blending 4 parts by weight of boric acid with 100 parts by weight of water) for 30 seconds (insolubilization treatment).
Next, in a dyeing bath having a liquid temperature of 30 ° C. (an aqueous iodine solution obtained by mixing iodine and potassium iodide in a weight ratio of 1: 7 with respect to 100 parts by weight of water), the polarizer finally obtained Immersion was carried out for 60 seconds while adjusting the concentration so that the simple substance transmittance (Ts) was 43.0% or more (dyeing treatment).
Next, it was immersed in a cross-linked bath at a liquid temperature of 40 ° C. (an aqueous boric acid solution obtained by blending 3 parts by weight of potassium iodide and 5 parts by weight of boric acid with respect to 100 parts by weight of water) for 30 seconds. (Crossing treatment).
Then, while immersing the laminate in a boric acid aqueous solution (boric acid concentration 4.0% by weight, potassium iodide concentration 5% by weight) at a liquid temperature of 70 ° C., the rolls having different peripheral speeds are subjected to the longitudinal direction (longitudinal direction). The uniaxial stretching was performed so that the total stretching ratio was 5.5 times (underwater stretching treatment).
Then, the laminate was immersed in a washing bath at a liquid temperature of 20 ° C. (an aqueous solution obtained by blending 4 parts by weight of potassium iodide with 100 parts by weight of water) (cleaning treatment).
Then, while drying in an oven kept at 90 ° C., it was brought into contact with a heating roll made of SUS whose surface temperature was kept at 75 ° C. for about 2 seconds (dry shrinkage treatment). The shrinkage rate in the width direction of the laminated body by the drying shrinkage treatment was 5.2%.
In this way, a polarizer having a thickness of 5 μm was formed on the resin substrate.
2.偏光板の作製
上記で得られた偏光子の表面(樹脂基材とは反対側の面)に、保護層としてHC-COPフィルムを、紫外線硬化型接着剤を介して貼り合せた。具体的には、硬化型接着剤の総厚みが1.0μmになるように塗工し、ロール機を使用して貼り合わせた。その後、UV光線を保護層側から照射して接着剤を硬化させた。なお、HC-COPフィルムは、シクロオレフィン(COP)フィルム(日本ゼオン社製、製品名「ZF12」、厚み25μm)にハードコート(HC)層(厚み2μm)が形成されたフィルムであり、COPフィルムが偏光子側となるようにして貼り合わせた。次いで、樹脂基材を剥離し、保護層(HC層/COPフィルム)/接着剤層/偏光子の構成を有する偏光板を得た。 2. Preparation of Polarizing Plate An HC-COP film as a protective layer was attached to the surface of the polarizer obtained above (the surface opposite to the resin substrate) via an ultraviolet curable adhesive. Specifically, the curable adhesive was coated so as to have a total thickness of 1.0 μm, and bonded using a roll machine. Then, UV light was irradiated from the protective layer side to cure the adhesive. The HC-COP film is a film in which a hard coat (HC) layer (thickness 2 μm) is formed on a cycloolefin (COP) film (manufactured by Nippon Zeon Corporation, product name “ZF12”, thickness 25 μm), and is a COP film. Was attached so that it was on the polarizer side. Next, the resin base material was peeled off to obtain a polarizing plate having a structure of a protective layer (HC layer / COP film) / adhesive layer / polarizer.
上記で得られた偏光子の表面(樹脂基材とは反対側の面)に、保護層としてHC-COPフィルムを、紫外線硬化型接着剤を介して貼り合せた。具体的には、硬化型接着剤の総厚みが1.0μmになるように塗工し、ロール機を使用して貼り合わせた。その後、UV光線を保護層側から照射して接着剤を硬化させた。なお、HC-COPフィルムは、シクロオレフィン(COP)フィルム(日本ゼオン社製、製品名「ZF12」、厚み25μm)にハードコート(HC)層(厚み2μm)が形成されたフィルムであり、COPフィルムが偏光子側となるようにして貼り合わせた。次いで、樹脂基材を剥離し、保護層(HC層/COPフィルム)/接着剤層/偏光子の構成を有する偏光板を得た。 2. Preparation of Polarizing Plate An HC-COP film as a protective layer was attached to the surface of the polarizer obtained above (the surface opposite to the resin substrate) via an ultraviolet curable adhesive. Specifically, the curable adhesive was coated so as to have a total thickness of 1.0 μm, and bonded using a roll machine. Then, UV light was irradiated from the protective layer side to cure the adhesive. The HC-COP film is a film in which a hard coat (HC) layer (thickness 2 μm) is formed on a cycloolefin (COP) film (manufactured by Nippon Zeon Corporation, product name “ZF12”, thickness 25 μm), and is a COP film. Was attached so that it was on the polarizer side. Next, the resin base material was peeled off to obtain a polarizing plate having a structure of a protective layer (HC layer / COP film) / adhesive layer / polarizer.
3.位相差層を構成する第1の配向固化層および第2の配向固化層の作製
ネマチック液晶相を示す重合性液晶(BASF社製:商品名「Paliocolor LC242」、下記式で表される)10gと、当該重合性液晶化合物に対する光重合開始剤(BASF社製:商品名「イルガキュア907」)3gとを、トルエン40gに溶解して、液晶組成物(塗工液)を調製した。
ポリエチレンテレフタレート(PET)フィルム(厚み38μm)表面を、ラビング布を用いてラビングし、配向処理を施した。配向処理の方向は、偏光板に貼り合わせる際に偏光子の吸収軸の方向に対して視認側から見て15°方向となるようにした。この配向処理表面に、上記液晶塗工液をバーコーターにより塗工し、90℃で2分間加熱乾燥することによって液晶化合物を配向させた。このようにして形成された液晶層に、メタルハライドランプを用いて1mJ/cm2の光を照射し、当該液晶層を硬化させることによって、PETフィルム上に液晶配向固化層Aを形成した。液晶配向固化層Aの厚みは2.5μm、面内位相差Re(550)は270nmであった。さらに、液晶配向固化層Aは、nx>ny=nzの屈折率分布を有していた。
塗工厚みを変更したこと、および、配向処理方向を偏光子の吸収軸の方向に対して視認側から見て75°方向となるようにしたこと以外は上記と同様にして、PETフィルム上に液晶配向固化層Bを形成した。液晶配向固化層Bの厚みは1.5μm、面内位相差Re(550)は140nmであった。さらに、液晶配向固化層Bは、nx>ny=nzの屈折率分布を有していた。 3. 3. Preparation of First Oriented Solidified Layer and Second Oriented Solidified Layer Constituting the Phase Difference Layer With 10 g of polymerizable liquid crystal (manufactured by BASF: trade name "Pariocolor LC242", represented by the following formula) showing a nematic liquid crystal phase. , 3 g of a photopolymerization initiator (manufactured by BASF: trade name "Irgacure 907") for the polymerizable liquid crystal compound was dissolved in 40 g of toluene to prepare a liquid crystal composition (coating liquid).
The surface of a polyethylene terephthalate (PET) film (thickness 38 μm) was rubbed with a rubbing cloth and subjected to an orientation treatment. The direction of the alignment treatment was set to be 15 ° when viewed from the visual side with respect to the direction of the absorption axis of the polarizer when the polarizing plate was attached. The liquid crystal coating liquid was applied to the alignment-treated surface with a bar coater, and the liquid crystal compound was oriented by heating and drying at 90 ° C. for 2 minutes. The liquid crystal layer thus formed was irradiated with light of 1 mJ / cm 2 using a metal halide lamp, and the liquid crystal layer was cured to form a liquid crystal oriented solidified layer A on the PET film. The thickness of the liquid crystal oriented solidified layer A was 2.5 μm, and the in-plane retardation Re (550) was 270 nm. Further, the liquid crystal oriented solidified layer A had a refractive index distribution of nx> ny = nz.
On the PET film in the same manner as above, except that the coating thickness was changed and the orientation treatment direction was set to be 75 ° when viewed from the visual side with respect to the direction of the absorber's absorption axis. A liquid crystal oriented solidified layer B was formed. The thickness of the liquid crystal oriented solidified layer B was 1.5 μm, and the in-plane retardation Re (550) was 140 nm. Further, the liquid crystal oriented solidified layer B had a refractive index distribution of nx> ny = nz.
ネマチック液晶相を示す重合性液晶(BASF社製:商品名「Paliocolor LC242」、下記式で表される)10gと、当該重合性液晶化合物に対する光重合開始剤(BASF社製:商品名「イルガキュア907」)3gとを、トルエン40gに溶解して、液晶組成物(塗工液)を調製した。
塗工厚みを変更したこと、および、配向処理方向を偏光子の吸収軸の方向に対して視認側から見て75°方向となるようにしたこと以外は上記と同様にして、PETフィルム上に液晶配向固化層Bを形成した。液晶配向固化層Bの厚みは1.5μm、面内位相差Re(550)は140nmであった。さらに、液晶配向固化層Bは、nx>ny=nzの屈折率分布を有していた。 3. 3. Preparation of First Oriented Solidified Layer and Second Oriented Solidified Layer Constituting the Phase Difference Layer With 10 g of polymerizable liquid crystal (manufactured by BASF: trade name "Pariocolor LC242", represented by the following formula) showing a nematic liquid crystal phase. , 3 g of a photopolymerization initiator (manufactured by BASF: trade name "Irgacure 907") for the polymerizable liquid crystal compound was dissolved in 40 g of toluene to prepare a liquid crystal composition (coating liquid).
On the PET film in the same manner as above, except that the coating thickness was changed and the orientation treatment direction was set to be 75 ° when viewed from the visual side with respect to the direction of the absorber's absorption axis. A liquid crystal oriented solidified layer B was formed. The thickness of the liquid crystal oriented solidified layer B was 1.5 μm, and the in-plane retardation Re (550) was 140 nm. Further, the liquid crystal oriented solidified layer B had a refractive index distribution of nx> ny = nz.
4.位相差層の形成
上記2.で得られた偏光板の偏光子表面に、上記3.で得られた液晶配向固化層Aおよび液晶配向固化層Bをこの順に転写した。このとき、偏光子の吸収軸と液晶配向固化層Aの遅相軸とのなす角度が15°、偏光子の吸収軸と液晶配向固化層Bの遅相軸とのなす角度が75°になるようにして転写(貼り合わせ)を行った。なお、それぞれの転写(貼り合わせ)は、上記2.で用いた紫外線硬化型接着剤(厚み1.0μm)を介して行った。このようにして、保護層(HC層/COPフィルム)/接着剤層/偏光子/接着剤層/位相差層(第1の液晶配向固化層/接着剤層/第2の液晶配向固化層)の構成を有する積層体を作製した。 4. Formation of retardation layer 2. On the polarizer surface of the polarizing plate obtained in 3. above. The liquid crystal oriented solidified layer A and the liquid crystal oriented solidified layer B obtained in the above were transferred in this order. At this time, the angle formed by the absorption axis of the polarizer and the slow axis of the liquid crystal oriented solidified layer A is 15 °, and the angle formed by the absorption axis of the polarizer and the slow axis of the liquid crystal oriented solidified layer B is 75 °. Transfer (bonding) was performed in this way. In addition, each transfer (bonding) is performed in the above 2. This was done via the ultraviolet curable adhesive (thickness 1.0 μm) used in. In this way, the protective layer (HC layer / COP film) / adhesive layer / polarizer / adhesive layer / retardation layer (first liquid crystal oriented solidified layer / adhesive layer / second liquid crystal oriented solidified layer). A laminated body having the above-mentioned structure was produced.
上記2.で得られた偏光板の偏光子表面に、上記3.で得られた液晶配向固化層Aおよび液晶配向固化層Bをこの順に転写した。このとき、偏光子の吸収軸と液晶配向固化層Aの遅相軸とのなす角度が15°、偏光子の吸収軸と液晶配向固化層Bの遅相軸とのなす角度が75°になるようにして転写(貼り合わせ)を行った。なお、それぞれの転写(貼り合わせ)は、上記2.で用いた紫外線硬化型接着剤(厚み1.0μm)を介して行った。このようにして、保護層(HC層/COPフィルム)/接着剤層/偏光子/接着剤層/位相差層(第1の液晶配向固化層/接着剤層/第2の液晶配向固化層)の構成を有する積層体を作製した。 4. Formation of retardation layer 2. On the polarizer surface of the polarizing plate obtained in 3. above. The liquid crystal oriented solidified layer A and the liquid crystal oriented solidified layer B obtained in the above were transferred in this order. At this time, the angle formed by the absorption axis of the polarizer and the slow axis of the liquid crystal oriented solidified layer A is 15 °, and the angle formed by the absorption axis of the polarizer and the slow axis of the liquid crystal oriented solidified layer B is 75 °. Transfer (bonding) was performed in this way. In addition, each transfer (bonding) is performed in the above 2. This was done via the ultraviolet curable adhesive (thickness 1.0 μm) used in. In this way, the protective layer (HC layer / COP film) / adhesive layer / polarizer / adhesive layer / retardation layer (first liquid crystal oriented solidified layer / adhesive layer / second liquid crystal oriented solidified layer). A laminated body having the above-mentioned structure was produced.
5.位相差層付偏光板の作製
アクリル系樹脂(楠本化成社製、製品名「B-811」、Tg:110℃、Mw:40000)20部をメチルエチルケトン80部に溶解し、樹脂溶液(20%)を得た。この樹脂溶液を、上記4.で得られた積層体の第2の液晶配向固化層表面にワイヤーバーを用いて塗布し、塗布膜を60℃で5分間乾燥して、樹脂の有機溶媒溶液の塗布膜の固化物として構成されるヨウ素透過抑制層(厚み0.5μm)を形成した。次いで、ヨウ素透過抑制層表面に粘着剤層(厚み15μm)を設け、保護層(HC層/COPフィルム)/接着剤層/偏光子/接着剤層/位相差層(第1の液晶配向固化層/接着剤層/第2の液晶配向固化層)/ヨウ素透過抑制層/粘着剤層の構成を有する位相差層付偏光板を得た。得られた位相差層付偏光板の総厚みは39.5μmであった。得られた位相差層付偏光板を上記(2)および(3)の評価に供した。さらに、金属腐食性に関して、ヨウ素透過抑制層を形成しなかった比較例1(後述)と比較した。結果を表1および表2に示す。 5. Preparation of polarizing plate withretardation layer 20 parts of acrylic resin (manufactured by Kusumoto Kasei Co., Ltd., product name "B-811", Tg: 110 ° C., Mw: 40000) was dissolved in 80 parts of methyl ethyl ketone, and a resin solution (20%) was used. Got This resin solution is applied to the above 4. The surface of the second liquid crystal oriented solidified layer of the laminate obtained in the above was coated with a wire bar, and the coating film was dried at 60 ° C. for 5 minutes to form a solidified coating film of a resin organic solvent solution. An iodine permeation inhibitory layer (thickness 0.5 μm) was formed. Next, an adhesive layer (thickness 15 μm) is provided on the surface of the iodine permeation suppressing layer, and a protective layer (HC layer / COP film) / adhesive layer / polarizer / adhesive layer / retardation layer (first liquid crystal alignment solidification layer) is provided. A polarizing plate with a retardation layer having the constitution of / adhesive layer / second liquid crystal oriented solidified layer) / iodine permeation suppressing layer / adhesive layer was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 39.5 μm. The obtained polarizing plate with a retardation layer was subjected to the evaluations (2) and (3) above. Further, regarding metal corrosiveness, it was compared with Comparative Example 1 (described later) in which the iodine permeation suppressing layer was not formed. The results are shown in Tables 1 and 2.
アクリル系樹脂(楠本化成社製、製品名「B-811」、Tg:110℃、Mw:40000)20部をメチルエチルケトン80部に溶解し、樹脂溶液(20%)を得た。この樹脂溶液を、上記4.で得られた積層体の第2の液晶配向固化層表面にワイヤーバーを用いて塗布し、塗布膜を60℃で5分間乾燥して、樹脂の有機溶媒溶液の塗布膜の固化物として構成されるヨウ素透過抑制層(厚み0.5μm)を形成した。次いで、ヨウ素透過抑制層表面に粘着剤層(厚み15μm)を設け、保護層(HC層/COPフィルム)/接着剤層/偏光子/接着剤層/位相差層(第1の液晶配向固化層/接着剤層/第2の液晶配向固化層)/ヨウ素透過抑制層/粘着剤層の構成を有する位相差層付偏光板を得た。得られた位相差層付偏光板の総厚みは39.5μmであった。得られた位相差層付偏光板を上記(2)および(3)の評価に供した。さらに、金属腐食性に関して、ヨウ素透過抑制層を形成しなかった比較例1(後述)と比較した。結果を表1および表2に示す。 5. Preparation of polarizing plate with
[実施例2]
メタクリル酸メチル(MMA、富士フイルム和光純薬社製、商品名「メタクリル酸メチルモノマー」)97.0部、上記一般式(1e)で表される共重合単量体3.0部、重合開始剤(富士フイルム和光純薬社製、商品名「2,2´-アゾビス(イソブチロニトリル)」)0.2部をトルエン200部に溶解した。次いで、窒素雰囲気下で70℃に加熱しながら5.5時間重合反応を行い、ホウ素含有アクリル系樹脂溶液(固形分濃度:33%)を得た。得られたホウ素含有アクリル系重合体のTgは110℃、Mwは80000であった。このホウ素含有アクリル系重合体をアクリル系樹脂「B-811」の代わりに用いたこと、および、ヨウ素透過抑制層の厚みを0.3μmとしたこと以外は実施例1と同様にして位相差層付偏光板を作製した。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 [Example 2]
Methyl methacrylate (MMA, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "methyl methacrylate monomer") 97.0 parts, 3.0 parts of copolymerization monomer represented by the above general formula (1e), polymerization initiation 0.2 part of the agent (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "2,2'-azobis (isobutyronitrile)") was dissolved in 200 parts of toluene. Next, a polymerization reaction was carried out for 5.5 hours while heating at 70 ° C. in a nitrogen atmosphere to obtain a boron-containing acrylic resin solution (solid content concentration: 33%). The obtained boron-containing acrylic polymer had a Tg of 110 ° C. and a Mw of 80,000. The retardation layer was the same as in Example 1 except that this boron-containing acrylic polymer was used instead of the acrylic resin "B-811" and the thickness of the iodine permeation suppressing layer was 0.3 μm. A polarizing plate with a plate was prepared. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
メタクリル酸メチル(MMA、富士フイルム和光純薬社製、商品名「メタクリル酸メチルモノマー」)97.0部、上記一般式(1e)で表される共重合単量体3.0部、重合開始剤(富士フイルム和光純薬社製、商品名「2,2´-アゾビス(イソブチロニトリル)」)0.2部をトルエン200部に溶解した。次いで、窒素雰囲気下で70℃に加熱しながら5.5時間重合反応を行い、ホウ素含有アクリル系樹脂溶液(固形分濃度:33%)を得た。得られたホウ素含有アクリル系重合体のTgは110℃、Mwは80000であった。このホウ素含有アクリル系重合体をアクリル系樹脂「B-811」の代わりに用いたこと、および、ヨウ素透過抑制層の厚みを0.3μmとしたこと以外は実施例1と同様にして位相差層付偏光板を作製した。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 [Example 2]
Methyl methacrylate (MMA, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "methyl methacrylate monomer") 97.0 parts, 3.0 parts of copolymerization monomer represented by the above general formula (1e), polymerization initiation 0.2 part of the agent (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "2,2'-azobis (isobutyronitrile)") was dissolved in 200 parts of toluene. Next, a polymerization reaction was carried out for 5.5 hours while heating at 70 ° C. in a nitrogen atmosphere to obtain a boron-containing acrylic resin solution (solid content concentration: 33%). The obtained boron-containing acrylic polymer had a Tg of 110 ° C. and a Mw of 80,000. The retardation layer was the same as in Example 1 except that this boron-containing acrylic polymer was used instead of the acrylic resin "B-811" and the thickness of the iodine permeation suppressing layer was 0.3 μm. A polarizing plate with a plate was prepared. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
[実施例3]
ヨウ素透過抑制層の厚みを0.5μmとしたこと以外は実施例2と同様にして位相差層付偏光板を作製した。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 [Example 3]
A polarizing plate with a retardation layer was produced in the same manner as in Example 2 except that the thickness of the iodine permeation suppressing layer was 0.5 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
ヨウ素透過抑制層の厚みを0.5μmとしたこと以外は実施例2と同様にして位相差層付偏光板を作製した。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 [Example 3]
A polarizing plate with a retardation layer was produced in the same manner as in Example 2 except that the thickness of the iodine permeation suppressing layer was 0.5 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
[実施例4]
アクリル系樹脂「B-811」の代わりに熱可塑性エポキシ樹脂(三菱ケミカル株式会社製、商品名「jER(登録商標)1256B40」、Tg:100℃、Mw:45000)を用いたこと以外は実施例1と同様にして位相差層付偏光板を作製した。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 [Example 4]
Examples except that a thermoplastic epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name "jER (registered trademark) 1256B40", Tg: 100 ° C., Mw: 45000) was used instead of the acrylic resin "B-811". A polarizing plate with a retardation layer was produced in the same manner as in 1. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
アクリル系樹脂「B-811」の代わりに熱可塑性エポキシ樹脂(三菱ケミカル株式会社製、商品名「jER(登録商標)1256B40」、Tg:100℃、Mw:45000)を用いたこと以外は実施例1と同様にして位相差層付偏光板を作製した。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 [Example 4]
Examples except that a thermoplastic epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name "jER (registered trademark) 1256B40", Tg: 100 ° C., Mw: 45000) was used instead of the acrylic resin "B-811". A polarizing plate with a retardation layer was produced in the same manner as in 1. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
[実施例5]
アクリル系樹脂「B-811」の代わりに熱可塑性エポキシ樹脂(三菱ケミカル株式会社製、商品名「jER(登録商標)YX7200B35」、Tg:150℃、Mw:30000)を用いたこと、および、ヨウ素透過抑制層の厚みを0.3μmとしたこと以外は実施例1と同様にして位相差層付偏光板を作製した。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 [Example 5]
A thermoplastic epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name "jER (registered trademark) YX7200B35", Tg: 150 ° C., Mw: 30000) was used instead of the acrylic resin "B-811", and iodine. A polarizing plate with a retardation layer was produced in the same manner as in Example 1 except that the thickness of the permeation suppression layer was 0.3 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
アクリル系樹脂「B-811」の代わりに熱可塑性エポキシ樹脂(三菱ケミカル株式会社製、商品名「jER(登録商標)YX7200B35」、Tg:150℃、Mw:30000)を用いたこと、および、ヨウ素透過抑制層の厚みを0.3μmとしたこと以外は実施例1と同様にして位相差層付偏光板を作製した。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 [Example 5]
A thermoplastic epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name "jER (registered trademark) YX7200B35", Tg: 150 ° C., Mw: 30000) was used instead of the acrylic resin "B-811", and iodine. A polarizing plate with a retardation layer was produced in the same manner as in Example 1 except that the thickness of the permeation suppression layer was 0.3 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
[実施例6]
ヨウ素透過抑制層の厚みを0.5μmとしたこと以外は実施例5と同様にして位相差層付偏光板を作製した。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 [Example 6]
A polarizing plate with a retardation layer was produced in the same manner as in Example 5 except that the thickness of the iodine permeation suppressing layer was 0.5 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
ヨウ素透過抑制層の厚みを0.5μmとしたこと以外は実施例5と同様にして位相差層付偏光板を作製した。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 [Example 6]
A polarizing plate with a retardation layer was produced in the same manner as in Example 5 except that the thickness of the iodine permeation suppressing layer was 0.5 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
[実施例7]
アクリル系樹脂「B-811」の代わりに、「B-811」15部と熱可塑性エポキシ樹脂(三菱ケミカル株式会社製、商品名「jER(登録商標)YX6954BH30」)85部(固形分換算)とのブレンドを用いたこと以外は実施例1と同様にして位相差層付偏光板を作製した。当該ブレンドのTgは125℃、Mwは38000であった。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 [Example 7]
Instead of the acrylic resin "B-811", 15 parts of "B-811" and 85 parts of thermoplastic epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name "jER (registered trademark) YX6954BH30") (solid content conversion) A polarizing plate with a retardation layer was produced in the same manner as in Example 1 except that the above blend was used. The Tg of the blend was 125 ° C. and the Mw was 38,000. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
アクリル系樹脂「B-811」の代わりに、「B-811」15部と熱可塑性エポキシ樹脂(三菱ケミカル株式会社製、商品名「jER(登録商標)YX6954BH30」)85部(固形分換算)とのブレンドを用いたこと以外は実施例1と同様にして位相差層付偏光板を作製した。当該ブレンドのTgは125℃、Mwは38000であった。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 [Example 7]
Instead of the acrylic resin "B-811", 15 parts of "B-811" and 85 parts of thermoplastic epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name "jER (registered trademark) YX6954BH30") (solid content conversion) A polarizing plate with a retardation layer was produced in the same manner as in Example 1 except that the above blend was used. The Tg of the blend was 125 ° C. and the Mw was 38,000. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
[実施例8]
実施例1の2.で得られた保護層(HC層/COPフィルム)/接着剤層/偏光子の構成を有する偏光板の偏光子側に、実施例7で使用した樹脂ブレンドを塗布および乾燥して、樹脂の有機溶媒溶液の塗布膜の固化物として構成されるヨウ素透過抑制層(厚み0.5μm)を形成した。ヨウ素透過抑制層の表面に実施例1と同様にして液晶配向固化層Aおよび液晶配向固化層Bをこの順に転写し、保護層(HC層/COPフィルム)/接着剤層/偏光子/ヨウ素透過抑制層/接着剤層/位相差層(第1の液晶配向固化層/接着剤層/第2の液晶配向固化層)/粘着剤層の構成を有する位相差層付偏光板を得た。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 [Example 8]
Example 1-2. The resin blend used in Example 7 was applied and dried on the polarizer side of the polarizing plate having the constitution of the protective layer (HC layer / COP film) / adhesive layer / polarizer obtained in the above, and the resin was organic. An iodine permeation inhibitory layer (thickness 0.5 μm) formed as a solidified coating film of the solvent solution was formed. The liquid crystal oriented solidified layer A and the liquid crystal oriented solidified layer B are transferred in this order to the surface of the iodine permeation suppressing layer in the same manner as in Example 1, and the protective layer (HC layer / COP film) / adhesive layer / polarizer / iodine permeation A polarizing plate with a retardation layer having a structure of an inhibitory layer / adhesive layer / retardation layer (first liquid crystal alignment solidification layer / adhesive layer / second liquid crystal alignment solidification layer) / adhesive layer was obtained. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
実施例1の2.で得られた保護層(HC層/COPフィルム)/接着剤層/偏光子の構成を有する偏光板の偏光子側に、実施例7で使用した樹脂ブレンドを塗布および乾燥して、樹脂の有機溶媒溶液の塗布膜の固化物として構成されるヨウ素透過抑制層(厚み0.5μm)を形成した。ヨウ素透過抑制層の表面に実施例1と同様にして液晶配向固化層Aおよび液晶配向固化層Bをこの順に転写し、保護層(HC層/COPフィルム)/接着剤層/偏光子/ヨウ素透過抑制層/接着剤層/位相差層(第1の液晶配向固化層/接着剤層/第2の液晶配向固化層)/粘着剤層の構成を有する位相差層付偏光板を得た。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 [Example 8]
Example 1-2. The resin blend used in Example 7 was applied and dried on the polarizer side of the polarizing plate having the constitution of the protective layer (HC layer / COP film) / adhesive layer / polarizer obtained in the above, and the resin was organic. An iodine permeation inhibitory layer (thickness 0.5 μm) formed as a solidified coating film of the solvent solution was formed. The liquid crystal oriented solidified layer A and the liquid crystal oriented solidified layer B are transferred in this order to the surface of the iodine permeation suppressing layer in the same manner as in Example 1, and the protective layer (HC layer / COP film) / adhesive layer / polarizer / iodine permeation A polarizing plate with a retardation layer having a structure of an inhibitory layer / adhesive layer / retardation layer (first liquid crystal alignment solidification layer / adhesive layer / second liquid crystal alignment solidification layer) / adhesive layer was obtained. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
[実施例9]
実施例2におけるホウ素含有アクリル系重合体を用いたこと以外は実施例8と同様にして、保護層(HC層/COPフィルム)/接着剤層/偏光子/ヨウ素透過抑制層の構成を有する積層体を作製した。次いで、実施例2におけるホウ素含有アクリル系重合体15部と熱可塑性エポキシ樹脂(三菱ケミカル株式会社製、商品名「jER(登録商標)YX6954BH30」)85部(固形分換算)とのブレンドを用いたこと以外は実施例1と同様にして、保護層(HC層/COPフィルム)/接着剤層/偏光子/ヨウ素透過抑制層/接着剤層/位相差層(第1の液晶配向固化層/接着剤層/第2の液晶配向固化層)/ヨウ素透過抑制層/粘着剤層の構成を有する位相差層付偏光板を得た。得られた位相差層付偏光板の総厚みは40μmであった。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表2に示す。 [Example 9]
Lamination having a protective layer (HC layer / COP film) / adhesive layer / polarizer / iodine permeation suppressing layer in the same manner as in Example 8 except that the boron-containing acrylic polymer in Example 2 was used. The body was made. Next, a blend of 15 parts of the boron-containing acrylic polymer and 85 parts (solid content equivalent) of the thermoplastic epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name "jER (registered trademark) YX6954BH30") in Example 2 was used. Protective layer (HC layer / COP film) / adhesive layer / polarizer / iodine permeation suppression layer / adhesive layer / retardation layer (first liquid crystal oriented solidifying layer / adhesion) in the same manner as in Example 1 except for the above. A polarizing plate with a retardation layer having a structure of an agent layer / a second liquid crystal oriented solidified layer) / an iodine permeation suppressing layer / an adhesive layer was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 40 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 2.
実施例2におけるホウ素含有アクリル系重合体を用いたこと以外は実施例8と同様にして、保護層(HC層/COPフィルム)/接着剤層/偏光子/ヨウ素透過抑制層の構成を有する積層体を作製した。次いで、実施例2におけるホウ素含有アクリル系重合体15部と熱可塑性エポキシ樹脂(三菱ケミカル株式会社製、商品名「jER(登録商標)YX6954BH30」)85部(固形分換算)とのブレンドを用いたこと以外は実施例1と同様にして、保護層(HC層/COPフィルム)/接着剤層/偏光子/ヨウ素透過抑制層/接着剤層/位相差層(第1の液晶配向固化層/接着剤層/第2の液晶配向固化層)/ヨウ素透過抑制層/粘着剤層の構成を有する位相差層付偏光板を得た。得られた位相差層付偏光板の総厚みは40μmであった。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表2に示す。 [Example 9]
Lamination having a protective layer (HC layer / COP film) / adhesive layer / polarizer / iodine permeation suppressing layer in the same manner as in Example 8 except that the boron-containing acrylic polymer in Example 2 was used. The body was made. Next, a blend of 15 parts of the boron-containing acrylic polymer and 85 parts (solid content equivalent) of the thermoplastic epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name "jER (registered trademark) YX6954BH30") in Example 2 was used. Protective layer (HC layer / COP film) / adhesive layer / polarizer / iodine permeation suppression layer / adhesive layer / retardation layer (first liquid crystal oriented solidifying layer / adhesion) in the same manner as in Example 1 except for the above. A polarizing plate with a retardation layer having a structure of an agent layer / a second liquid crystal oriented solidified layer) / an iodine permeation suppressing layer / an adhesive layer was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 40 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 2.
[実施例10]
偏光子と位相差層との間であって、偏光子に隣接した位置に設けられたヨウ素透過抑制層に、実施例2で得られたホウ素含有アクリル系重合体15部と熱可塑性エポキシ樹脂(三菱ケミカル株式会社製、商品名「jER(登録商標)YX6954BH30」)85部(固形分換算)とのブレンドを用いたこと以外は実施例9と同様にして、位相差層付偏光板を得た。得られた位相差層付偏光板の総厚みは40μmであった。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表2に示す。 [Example 10]
Fifteen parts of the boron-containing acrylic polymer obtained in Example 2 and a thermoplastic epoxy resin (on the iodine permeation suppressing layer provided between the polarizing element and the retardation layer and adjacent to the polarizing element). A polarizing plate with a retardation layer was obtained in the same manner as in Example 9 except that a blend with 85 parts (solid content equivalent) of Mitsubishi Chemical Co., Ltd., trade name "jER (registered trademark) YX6954BH30") was used. .. The total thickness of the obtained polarizing plate with a retardation layer was 40 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 2.
偏光子と位相差層との間であって、偏光子に隣接した位置に設けられたヨウ素透過抑制層に、実施例2で得られたホウ素含有アクリル系重合体15部と熱可塑性エポキシ樹脂(三菱ケミカル株式会社製、商品名「jER(登録商標)YX6954BH30」)85部(固形分換算)とのブレンドを用いたこと以外は実施例9と同様にして、位相差層付偏光板を得た。得られた位相差層付偏光板の総厚みは40μmであった。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表2に示す。 [Example 10]
Fifteen parts of the boron-containing acrylic polymer obtained in Example 2 and a thermoplastic epoxy resin (on the iodine permeation suppressing layer provided between the polarizing element and the retardation layer and adjacent to the polarizing element). A polarizing plate with a retardation layer was obtained in the same manner as in Example 9 except that a blend with 85 parts (solid content equivalent) of Mitsubishi Chemical Co., Ltd., trade name "jER (registered trademark) YX6954BH30") was used. .. The total thickness of the obtained polarizing plate with a retardation layer was 40 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 2.
[実施例11]
偏光子と位相差層との間であって、偏光子に隣接した位置に形成されたヨウ素透過抑制層を、偏光子と位相差層との間であって、位相差層に隣接した位置に形成したこと以外は実施例10と同様にして、保護層(HC層/COPフィルム)/接着剤層/偏光子/接着剤層/ヨウ素透過抑制層/位相差層(第1の液晶配向固化層/接着剤層/第2の液晶配向固化層)/ヨウ素透過抑制層/粘着剤層の構成を有する位相差層付偏光板を得た。得られた位相差層付偏光板の総厚みは40μmであった。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表2に示す。 [Example 11]
The iodine permeation suppressing layer formed between the polarizer and the retardation layer at a position adjacent to the polarizer is placed between the polarizer and the retardation layer at a position adjacent to the retardation layer. Protective layer (HC layer / COP film) / adhesive layer / polarizer / adhesive layer / iodine permeation suppression layer / retardation layer (first liquid crystal oriented solidified layer) in the same manner as in Example 10 except that it was formed. A polarizing plate with a retardation layer having the constitution of / adhesive layer / second liquid crystal alignment solidification layer) / iodine permeation suppression layer / pressure-sensitive adhesive layer was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 40 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 2.
偏光子と位相差層との間であって、偏光子に隣接した位置に形成されたヨウ素透過抑制層を、偏光子と位相差層との間であって、位相差層に隣接した位置に形成したこと以外は実施例10と同様にして、保護層(HC層/COPフィルム)/接着剤層/偏光子/接着剤層/ヨウ素透過抑制層/位相差層(第1の液晶配向固化層/接着剤層/第2の液晶配向固化層)/ヨウ素透過抑制層/粘着剤層の構成を有する位相差層付偏光板を得た。得られた位相差層付偏光板の総厚みは40μmであった。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表2に示す。 [Example 11]
The iodine permeation suppressing layer formed between the polarizer and the retardation layer at a position adjacent to the polarizer is placed between the polarizer and the retardation layer at a position adjacent to the retardation layer. Protective layer (HC layer / COP film) / adhesive layer / polarizer / adhesive layer / iodine permeation suppression layer / retardation layer (first liquid crystal oriented solidified layer) in the same manner as in Example 10 except that it was formed. A polarizing plate with a retardation layer having the constitution of / adhesive layer / second liquid crystal alignment solidification layer) / iodine permeation suppression layer / pressure-sensitive adhesive layer was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 40 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 2.
[実施例12]
実施例9と同様に、偏光子と位相差層との間であって、偏光子に隣接した位置にヨウ素透過抑制層をさらに形成したこと以外は実施例11と同様にして、保護層(HC層/COPフィルム)/接着剤層/偏光子/ヨウ素透過抑制層/接着剤層/ヨウ素透過抑制層/位相差層(第1の液晶配向固化層/接着剤層/第2の液晶配向固化層)/ヨウ素透過抑制層/粘着剤層の構成を有する位相差層付偏光板を得た。得られた位相差層付偏光板の総厚みは40.5μmであった。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表2に示す。 [Example 12]
Similar to Example 9, the protective layer (HC) is similar to that of Example 11 except that an iodine permeation suppressing layer is further formed between the polarizer and the retardation layer at a position adjacent to the polarizer. Layer / COP film) / Adhesive layer / Polarizer / Iodine permeation inhibitory layer / Adhesive layer / Iodine permeation inhibitory layer / Phase difference layer (first liquid crystal oriented solidified layer / adhesive layer / second liquid crystal oriented solidified layer) ) / A polarizing plate with a retardation layer having a structure of an iodine permeation suppressing layer / an adhesive layer was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 40.5 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 2.
実施例9と同様に、偏光子と位相差層との間であって、偏光子に隣接した位置にヨウ素透過抑制層をさらに形成したこと以外は実施例11と同様にして、保護層(HC層/COPフィルム)/接着剤層/偏光子/ヨウ素透過抑制層/接着剤層/ヨウ素透過抑制層/位相差層(第1の液晶配向固化層/接着剤層/第2の液晶配向固化層)/ヨウ素透過抑制層/粘着剤層の構成を有する位相差層付偏光板を得た。得られた位相差層付偏光板の総厚みは40.5μmであった。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表2に示す。 [Example 12]
Similar to Example 9, the protective layer (HC) is similar to that of Example 11 except that an iodine permeation suppressing layer is further formed between the polarizer and the retardation layer at a position adjacent to the polarizer. Layer / COP film) / Adhesive layer / Polarizer / Iodine permeation inhibitory layer / Adhesive layer / Iodine permeation inhibitory layer / Phase difference layer (first liquid crystal oriented solidified layer / adhesive layer / second liquid crystal oriented solidified layer) ) / A polarizing plate with a retardation layer having a structure of an iodine permeation suppressing layer / an adhesive layer was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 40.5 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 2.
[比較例1]
ヨウ素透過抑制層を形成しなかったこと以外は実施例1と同様にして位相差層付偏光板を作製した。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 [Comparative Example 1]
A polarizing plate with a retardation layer was produced in the same manner as in Example 1 except that the iodine permeation suppressing layer was not formed. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
ヨウ素透過抑制層を形成しなかったこと以外は実施例1と同様にして位相差層付偏光板を作製した。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 [Comparative Example 1]
A polarizing plate with a retardation layer was produced in the same manner as in Example 1 except that the iodine permeation suppressing layer was not formed. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
[比較例2]
アクリル系樹脂「B-811」の代わりにアクリル系樹脂「B-723」(楠本化成社製、Tg:54℃、Mw:200000)を用いたこと以外は実施例1と同様にして位相差層付偏光板を作製した。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 [Comparative Example 2]
The retardation layer is the same as in Example 1 except that the acrylic resin "B-723" (manufactured by Kusumoto Kasei Co., Ltd., Tg: 54 ° C., Mw: 200,000) is used instead of the acrylic resin "B-811". A polarizing plate with a polarizing plate was prepared. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
アクリル系樹脂「B-811」の代わりにアクリル系樹脂「B-723」(楠本化成社製、Tg:54℃、Mw:200000)を用いたこと以外は実施例1と同様にして位相差層付偏光板を作製した。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 [Comparative Example 2]
The retardation layer is the same as in Example 1 except that the acrylic resin "B-723" (manufactured by Kusumoto Kasei Co., Ltd., Tg: 54 ° C., Mw: 200,000) is used instead of the acrylic resin "B-811". A polarizing plate with a polarizing plate was prepared. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
[比較例3]
アクリル系樹脂「B-811」の代わりに光硬化性エポキシ樹脂(三菱ケミカル株式会社製、商品名「jER(登録商標)828」、光重合開始剤としてサンアプロ社製「CPI100P」を使用)を用いたこと以外は実施例1と同様にして位相差層付偏光板を作製した。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 [Comparative Example 3]
Uses a photocurable epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name "jER (registered trademark) 828", and San Appro "CPI100P" as a photopolymerization initiator) instead of the acrylic resin "B-811". A polarizing plate with a retardation layer was produced in the same manner as in Example 1 except for the above. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
アクリル系樹脂「B-811」の代わりに光硬化性エポキシ樹脂(三菱ケミカル株式会社製、商品名「jER(登録商標)828」、光重合開始剤としてサンアプロ社製「CPI100P」を使用)を用いたこと以外は実施例1と同様にして位相差層付偏光板を作製した。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 [Comparative Example 3]
Uses a photocurable epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name "jER (registered trademark) 828", and San Appro "CPI100P" as a photopolymerization initiator) instead of the acrylic resin "B-811". A polarizing plate with a retardation layer was produced in the same manner as in Example 1 except for the above. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
[比較例4]
アクリル系樹脂「B-811」の代わりにPVA系樹脂(三菱ケミカル株式会社製、商品名「ゴーセノールZ200」、Tg:80℃、Mw:8800)を用いたこと以外は実施例1と同様にして位相差層付偏光板を作製した。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 [Comparative Example 4]
Same as in Example 1 except that a PVA resin (manufactured by Mitsubishi Chemical Corporation, trade name "Gosenol Z200", Tg: 80 ° C., Mw: 8800) was used instead of the acrylic resin "B-811". A polarizing plate with a retardation layer was produced. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
アクリル系樹脂「B-811」の代わりにPVA系樹脂(三菱ケミカル株式会社製、商品名「ゴーセノールZ200」、Tg:80℃、Mw:8800)を用いたこと以外は実施例1と同様にして位相差層付偏光板を作製した。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 [Comparative Example 4]
Same as in Example 1 except that a PVA resin (manufactured by Mitsubishi Chemical Corporation, trade name "Gosenol Z200", Tg: 80 ° C., Mw: 8800) was used instead of the acrylic resin "B-811". A polarizing plate with a retardation layer was produced. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
[参考例1]
1.偏光板の作製
実施例1と同様にして保護層(HC層/COPフィルム)/偏光子の構成を有する偏光板を得た。 [Reference example 1]
1. 1. Preparation of Polarizing Plate A polarizing plate having a protective layer (HC layer / COP film) / polarizing element was obtained in the same manner as in Example 1.
1.偏光板の作製
実施例1と同様にして保護層(HC層/COPフィルム)/偏光子の構成を有する偏光板を得た。 [Reference example 1]
1. 1. Preparation of Polarizing Plate A polarizing plate having a protective layer (HC layer / COP film) / polarizing element was obtained in the same manner as in Example 1.
2.位相差層を構成する位相差フィルムの作製
2-1.ポリエステルカーボネート系樹脂の重合
撹拌翼および100℃に制御された還流冷却器を具備した縦型反応器2器からなるバッチ重合装置を用いて重合を行った。ビス[9-(2-フェノキシカルボニルエチル)フルオレン-9-イル]メタン29.60質量部(0.046mol)、イソソルビド(ISB)29.21質量部(0.200mol)、スピログリコール(SPG)42.28質量部(0.139mol)、ジフェニルカーボネート(DPC)63.77質量部(0.298mol)及び触媒として酢酸カルシウム1水和物1.19×10-2質量部(6.78×10-5mol)を仕込んだ。反応器内を減圧窒素置換した後、熱媒で加温を行い、内温が100℃になった時点で撹拌を開始した。昇温開始40分後に内温を220℃に到達させ、この温度を保持するように制御すると同時に減圧を開始し、220℃に到達してから90分で13.3kPaにした。重合反応とともに副生するフェノール蒸気を100℃の還流冷却器に導き、フェノール蒸気中に若干量含まれるモノマー成分を反応器に戻し、凝縮しないフェノール蒸気は45℃の凝縮器に導いて回収した。第1反応器に窒素を導入して一旦大気圧まで復圧させた後、第1反応器内のオリゴマー化された反応液を第2反応器に移した。次いで、第2反応器内の昇温および減圧を開始して、50分で内温240℃、圧力0.2kPaにした。その後、所定の攪拌動力となるまで重合を進行させた。所定動力に到達した時点で反応器に窒素を導入して復圧し、生成したポリエステルカーボネート系樹脂を水中に押し出し、ストランドをカッティングしてペレットを得た。 2. Preparation of retardation film constituting the retardation layer 2-1. Polymerization of polyester carbonate-based resin Polymerization was carried out using a batch polymerization apparatus consisting of two vertical reactors equipped with a stirring blade and a reflux condenser controlled at 100 ° C. Bis [9- (2-phenoxycarbonylethyl) fluoren-9-yl] 29.60 parts by mass (0.046 mol) of methane, 29.21 parts by mass (0.200 mol) of isosorbide (ISB), spiroglycol (SPG) 42 .28 parts by weight (0.139 mol), diphenyl carbonate (DPC) 63.77 parts by weight (0.298 mol) and calcium acetate monohydrate 1.19 × 10 -2 parts by weight as a catalyst (6.78 × 10 - 5 mol) was charged. After substituting nitrogen under reduced pressure in the reactor, heating was performed with a heat medium, and stirring was started when the internal temperature reached 100 ° C. The internal temperature was brought to 220 ° C. 40 minutes after the start of the temperature rise, and the depressurization was started at the same time as controlling to maintain this temperature, and the temperature was adjusted to 13.3 kPa 90 minutes after reaching 220 ° C. The phenol vapor produced as a by-product of the polymerization reaction was guided to a reflux condenser at 100 ° C., the monomer component contained in a small amount in the phenol vapor was returned to the reactor, and the uncondensed phenol vapor was guided to a condenser at 45 ° C. for recovery. Nitrogen was introduced into the first reactor and the pressure was once restored to atmospheric pressure, and then the oligomerized reaction solution in the first reactor was transferred to the second reactor. Then, the temperature rise and depressurization in the second reactor were started, and the internal temperature was 240 ° C. and the pressure was 0.2 kPa in 50 minutes. Then, the polymerization was allowed to proceed until the stirring power became a predetermined value. When the predetermined power was reached, nitrogen was introduced into the reactor to repressurize, the produced polyester carbonate-based resin was extruded into water, and the strands were cut to obtain pellets.
2-1.ポリエステルカーボネート系樹脂の重合
撹拌翼および100℃に制御された還流冷却器を具備した縦型反応器2器からなるバッチ重合装置を用いて重合を行った。ビス[9-(2-フェノキシカルボニルエチル)フルオレン-9-イル]メタン29.60質量部(0.046mol)、イソソルビド(ISB)29.21質量部(0.200mol)、スピログリコール(SPG)42.28質量部(0.139mol)、ジフェニルカーボネート(DPC)63.77質量部(0.298mol)及び触媒として酢酸カルシウム1水和物1.19×10-2質量部(6.78×10-5mol)を仕込んだ。反応器内を減圧窒素置換した後、熱媒で加温を行い、内温が100℃になった時点で撹拌を開始した。昇温開始40分後に内温を220℃に到達させ、この温度を保持するように制御すると同時に減圧を開始し、220℃に到達してから90分で13.3kPaにした。重合反応とともに副生するフェノール蒸気を100℃の還流冷却器に導き、フェノール蒸気中に若干量含まれるモノマー成分を反応器に戻し、凝縮しないフェノール蒸気は45℃の凝縮器に導いて回収した。第1反応器に窒素を導入して一旦大気圧まで復圧させた後、第1反応器内のオリゴマー化された反応液を第2反応器に移した。次いで、第2反応器内の昇温および減圧を開始して、50分で内温240℃、圧力0.2kPaにした。その後、所定の攪拌動力となるまで重合を進行させた。所定動力に到達した時点で反応器に窒素を導入して復圧し、生成したポリエステルカーボネート系樹脂を水中に押し出し、ストランドをカッティングしてペレットを得た。 2. Preparation of retardation film constituting the retardation layer 2-1. Polymerization of polyester carbonate-based resin Polymerization was carried out using a batch polymerization apparatus consisting of two vertical reactors equipped with a stirring blade and a reflux condenser controlled at 100 ° C. Bis [9- (2-phenoxycarbonylethyl) fluoren-9-yl] 29.60 parts by mass (0.046 mol) of methane, 29.21 parts by mass (0.200 mol) of isosorbide (ISB), spiroglycol (SPG) 42 .28 parts by weight (0.139 mol), diphenyl carbonate (DPC) 63.77 parts by weight (0.298 mol) and calcium acetate monohydrate 1.19 × 10 -2 parts by weight as a catalyst (6.78 × 10 - 5 mol) was charged. After substituting nitrogen under reduced pressure in the reactor, heating was performed with a heat medium, and stirring was started when the internal temperature reached 100 ° C. The internal temperature was brought to 220 ° C. 40 minutes after the start of the temperature rise, and the depressurization was started at the same time as controlling to maintain this temperature, and the temperature was adjusted to 13.3 kPa 90 minutes after reaching 220 ° C. The phenol vapor produced as a by-product of the polymerization reaction was guided to a reflux condenser at 100 ° C., the monomer component contained in a small amount in the phenol vapor was returned to the reactor, and the uncondensed phenol vapor was guided to a condenser at 45 ° C. for recovery. Nitrogen was introduced into the first reactor and the pressure was once restored to atmospheric pressure, and then the oligomerized reaction solution in the first reactor was transferred to the second reactor. Then, the temperature rise and depressurization in the second reactor were started, and the internal temperature was 240 ° C. and the pressure was 0.2 kPa in 50 minutes. Then, the polymerization was allowed to proceed until the stirring power became a predetermined value. When the predetermined power was reached, nitrogen was introduced into the reactor to repressurize, the produced polyester carbonate-based resin was extruded into water, and the strands were cut to obtain pellets.
2-2.位相差フィルムの作製
得られたポリエステルカーボネート系樹脂(ペレット)を80℃で5時間真空乾燥をした後、単軸押出機(東芝機械社製、シリンダー設定温度:250℃)、Tダイ(幅200mm、設定温度:250℃)、チルロール(設定温度:120~130℃)および巻取機を備えたフィルム製膜装置を用いて、厚み135μmの長尺状の樹脂フィルムを作製した。得られた長尺状の樹脂フィルムを、幅方向に、延伸温度133℃、延伸倍率2.8倍で延伸し、厚み53μmの位相差フィルムを得た。得られた位相差フィルムのRe(550)は141nmであり、Re(450)/Re(550)は0.82であり、Nz係数は1.12であった。 2-2. Preparation of retardation film After vacuum-drying the obtained polyester carbonate resin (pellets) at 80 ° C for 5 hours, a single-screw extruder (manufactured by Toshiba Machine Co., Ltd., cylinder set temperature: 250 ° C), T-die (width 200 mm) , Set temperature: 250 ° C.), chill roll (set temperature: 120 to 130 ° C.), and a film forming apparatus equipped with a winder was used to prepare a long resin film having a thickness of 135 μm. The obtained elongated resin film was stretched in the width direction at a stretching temperature of 133 ° C. and a stretching ratio of 2.8 times to obtain a retardation film having a thickness of 53 μm. The Re (550) of the obtained retardation film was 141 nm, the Re (450) / Re (550) was 0.82, and the Nz coefficient was 1.12.
得られたポリエステルカーボネート系樹脂(ペレット)を80℃で5時間真空乾燥をした後、単軸押出機(東芝機械社製、シリンダー設定温度:250℃)、Tダイ(幅200mm、設定温度:250℃)、チルロール(設定温度:120~130℃)および巻取機を備えたフィルム製膜装置を用いて、厚み135μmの長尺状の樹脂フィルムを作製した。得られた長尺状の樹脂フィルムを、幅方向に、延伸温度133℃、延伸倍率2.8倍で延伸し、厚み53μmの位相差フィルムを得た。得られた位相差フィルムのRe(550)は141nmであり、Re(450)/Re(550)は0.82であり、Nz係数は1.12であった。 2-2. Preparation of retardation film After vacuum-drying the obtained polyester carbonate resin (pellets) at 80 ° C for 5 hours, a single-screw extruder (manufactured by Toshiba Machine Co., Ltd., cylinder set temperature: 250 ° C), T-die (width 200 mm) , Set temperature: 250 ° C.), chill roll (set temperature: 120 to 130 ° C.), and a film forming apparatus equipped with a winder was used to prepare a long resin film having a thickness of 135 μm. The obtained elongated resin film was stretched in the width direction at a stretching temperature of 133 ° C. and a stretching ratio of 2.8 times to obtain a retardation film having a thickness of 53 μm. The Re (550) of the obtained retardation film was 141 nm, the Re (450) / Re (550) was 0.82, and the Nz coefficient was 1.12.
3.位相差層付偏光板の作製
上記1.で得られた偏光板の偏光子表面に、上記2.で得られた位相差フィルムを、アクリル系粘着剤(厚み5μm)を介して貼り合わせた。このとき、偏光子の吸収軸と位相差フィルムの遅相軸とが45°の角度をなすようにして貼り合わせた。さらに、位相差層の表面に実施例1と同様の粘着剤層を設けた。このようにして、保護層/接着剤層/偏光子/粘着剤層/位相差層(樹脂フィルムの延伸フィルム)/粘着剤層の構成を有する位相差層付偏光板を得た。得られた位相差層付偏光板の総厚みは91μmであった。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 3. 3. Fabrication of polarizing plate with retardation layer 1. On the polarizer surface of the polarizing plate obtained in 2. above. The retardation film obtained in (1) was bonded via an acrylic pressure-sensitive adhesive (thickness: 5 μm). At this time, the absorption axis of the polarizer and the slow axis of the retardation film were bonded so as to form an angle of 45 °. Further, the same pressure-sensitive adhesive layer as in Example 1 was provided on the surface of the retardation layer. In this way, a polarizing plate with a retardation layer having a structure of a protective layer / adhesive layer / polarizer / pressure-sensitive adhesive layer / retardation layer (stretched film of resin film) / pressure-sensitive adhesive layer was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 91 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
上記1.で得られた偏光板の偏光子表面に、上記2.で得られた位相差フィルムを、アクリル系粘着剤(厚み5μm)を介して貼り合わせた。このとき、偏光子の吸収軸と位相差フィルムの遅相軸とが45°の角度をなすようにして貼り合わせた。さらに、位相差層の表面に実施例1と同様の粘着剤層を設けた。このようにして、保護層/接着剤層/偏光子/粘着剤層/位相差層(樹脂フィルムの延伸フィルム)/粘着剤層の構成を有する位相差層付偏光板を得た。得られた位相差層付偏光板の総厚みは91μmであった。得られた位相差層付偏光板を実施例1と同様の評価に供した。結果を表1および表2に示す。 3. 3. Fabrication of polarizing plate with retardation layer 1. On the polarizer surface of the polarizing plate obtained in 2. above. The retardation film obtained in (1) was bonded via an acrylic pressure-sensitive adhesive (thickness: 5 μm). At this time, the absorption axis of the polarizer and the slow axis of the retardation film were bonded so as to form an angle of 45 °. Further, the same pressure-sensitive adhesive layer as in Example 1 was provided on the surface of the retardation layer. In this way, a polarizing plate with a retardation layer having a structure of a protective layer / adhesive layer / polarizer / pressure-sensitive adhesive layer / retardation layer (stretched film of resin film) / pressure-sensitive adhesive layer was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 91 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Tables 1 and 2.
[評価]
表1から明らかなように、本発明の実施例の位相差層付偏光板は、所定のTgおよびMwを有する樹脂の有機溶媒溶液の塗布物の固化物で構成されたヨウ素透過抑制層を形成することにより、高温高湿環境下における金属腐食性を顕著に抑制できる。したがって、本発明の実施例の位相差層付偏光板は、画像表示装置に適用した場合に金属部材の腐食を抑制し得ることがわかる。さらに、参考例1から明らかなように、このような金属腐食性は、非常に薄型の位相差層付偏光板に特有の課題であることがわかる。 [evaluation]
As is clear from Table 1, the polarizing plate with a retardation layer according to the embodiment of the present invention forms an iodine permeation inhibitory layer composed of a solidified product of an organic solvent solution of a resin having a predetermined Tg and Mw. By doing so, the metal corrosiveness in a high temperature and high humidity environment can be remarkably suppressed. Therefore, it can be seen that the polarizing plate with a retardation layer according to the embodiment of the present invention can suppress corrosion of metal members when applied to an image display device. Further, as is clear from Reference Example 1, such metal corrosiveness is a problem peculiar to a very thin polarizing plate with a retardation layer.
表1から明らかなように、本発明の実施例の位相差層付偏光板は、所定のTgおよびMwを有する樹脂の有機溶媒溶液の塗布物の固化物で構成されたヨウ素透過抑制層を形成することにより、高温高湿環境下における金属腐食性を顕著に抑制できる。したがって、本発明の実施例の位相差層付偏光板は、画像表示装置に適用した場合に金属部材の腐食を抑制し得ることがわかる。さらに、参考例1から明らかなように、このような金属腐食性は、非常に薄型の位相差層付偏光板に特有の課題であることがわかる。 [evaluation]
As is clear from Table 1, the polarizing plate with a retardation layer according to the embodiment of the present invention forms an iodine permeation inhibitory layer composed of a solidified product of an organic solvent solution of a resin having a predetermined Tg and Mw. By doing so, the metal corrosiveness in a high temperature and high humidity environment can be remarkably suppressed. Therefore, it can be seen that the polarizing plate with a retardation layer according to the embodiment of the present invention can suppress corrosion of metal members when applied to an image display device. Further, as is clear from Reference Example 1, such metal corrosiveness is a problem peculiar to a very thin polarizing plate with a retardation layer.
表2から明らかなように、本発明の実施例9~12の位相差層付偏光板は、ヨウ素透過抑制層を2層または3層含むことにより、高温高湿環境下に長時間(200時間)投入された場合においても金属腐食性を顕著に抑制できる。したがって、本発明の実施例9~12の位相差層付偏光板は、画像表示装置に適用した場合に金属部材の腐食を顕著に抑制し得ることがわかる。
As is clear from Table 2, the polarizing plate with a retardation layer of Examples 9 to 12 of the present invention contains two or three layers of iodine permeation suppression layers, so that it can be used for a long time (200 hours) in a high temperature and high humidity environment. ) Even when it is thrown in, metal corrosiveness can be remarkably suppressed. Therefore, it can be seen that the polarizing plates with retardation layers of Examples 9 to 12 of the present invention can remarkably suppress the corrosion of metal members when applied to an image display device.
本発明の位相差層付偏光板は、液晶表示装置、有機EL表示装置および無機EL表示装置用の円偏光板として好適に用いられる。
The polarizing plate with a retardation layer of the present invention is suitably used as a circular polarizing plate for a liquid crystal display device, an organic EL display device, and an inorganic EL display device.
10 偏光板
11 偏光子
12 保護層
20 位相差層
30 粘着剤層
40 ヨウ素透過抑制層
100 位相差層付偏光板
101 位相差層付偏光板
102 位相差層付偏光板
103 位相差層付偏光板
104 位相差層付偏光板
105 位相差層付偏光板 10Polarizing plate 11 Polarizer 12 Protective layer 20 Phase difference layer 30 Adhesive layer 40 Iodine permeation suppression layer 100 Polarizing plate with retardation layer 101 Polarizing plate with retardation layer 102 Polarizing plate with retardation layer 103 Polarizing plate with retardation layer 104 Polarizing plate with retardation layer 105 Polarizing plate with retardation layer
11 偏光子
12 保護層
20 位相差層
30 粘着剤層
40 ヨウ素透過抑制層
100 位相差層付偏光板
101 位相差層付偏光板
102 位相差層付偏光板
103 位相差層付偏光板
104 位相差層付偏光板
105 位相差層付偏光板 10
Claims (14)
- 偏光子を含む偏光板と、位相差層と、粘着剤層と、を視認側からこの順に有し、
該位相差層が円偏光機能または楕円偏光機能を有する液晶化合物の配向固化層であり、
該偏光子と該粘着剤層との間に、樹脂の有機溶媒溶液の塗布膜の固化物または熱硬化物であるヨウ素透過抑制層が設けられており、
該ヨウ素透過抑制層を構成する樹脂のガラス転移温度が85℃以上であり、かつ、重量平均分子量Mwが25000以上である、
位相差層付偏光板。 A polarizing plate containing a polarizer, a retardation layer, and an adhesive layer are provided in this order from the visual side.
The retardation layer is an orientation-solidified layer of a liquid crystal compound having a circular polarization function or an elliptical polarization function.
An iodine permeation suppressing layer, which is a solidified or thermosetting film of a coating film of an organic solvent solution of a resin, is provided between the polarizing element and the pressure-sensitive adhesive layer.
The glass transition temperature of the resin constituting the iodine permeation suppressing layer is 85 ° C. or higher, and the weight average molecular weight Mw is 25,000 or higher.
Polarizing plate with retardation layer. - 前記ヨウ素透過抑制層が、前記偏光子と前記位相差層との間に設けられている、請求項1に記載の位相差層付偏光板。 The polarizing plate with a retardation layer according to claim 1, wherein the iodine permeation suppression layer is provided between the polarizer and the retardation layer.
- 前記ヨウ素透過抑制層が、前記位相差層と前記粘着剤層との間に設けられている、請求項1に記載の位相差層付偏光板。 The polarizing plate with a retardation layer according to claim 1, wherein the iodine permeation suppressing layer is provided between the retardation layer and the pressure-sensitive adhesive layer.
- 前記ヨウ素透過抑制層が、前記偏光子と前記粘着剤層との間に2層以上設けられている、請求項1に記載の位相差層付偏光板。 The polarizing plate with a retardation layer according to claim 1, wherein the iodine permeation suppressing layer is provided in two or more layers between the polarizer and the pressure-sensitive adhesive layer.
- 前記ヨウ素透過抑制層の厚みが0.05μm~10μmである、請求項1から4のいずれかに記載の位相差層付偏光板。 The polarizing plate with a retardation layer according to any one of claims 1 to 4, wherein the iodine permeation suppressing layer has a thickness of 0.05 μm to 10 μm.
- 前記ヨウ素透過抑制層を構成する樹脂のガラス転移温度が90℃以上である、請求項1から5のいずれかに記載の位相差層付偏光板。 The polarizing plate with a retardation layer according to any one of claims 1 to 5, wherein the glass transition temperature of the resin constituting the iodine permeation suppressing layer is 90 ° C. or higher.
- 前記ヨウ素透過抑制層を構成する樹脂が、50重量部を超える(メタ)アクリル系単量体と0重量部を超えて50重量部未満の式(1)で表される単量体とを含むモノマー混合物を重合することにより得られる共重合体を含む、請求項1から6のいずれかに記載の位相差層付偏光板:
- 前記位相差層が単一層であり、
該位相差層のRe(550)が100nm~190nmであり、
該位相差層の遅相軸と前記偏光子の吸収軸とのなす角度が40°~50°である、
請求項1から7のいずれかに記載の位相差層付偏光板。 The retardation layer is a single layer
The Re (550) of the retardation layer is 100 nm to 190 nm.
The angle formed by the slow axis of the retardation layer and the absorption axis of the polarizer is 40 ° to 50 °.
The polarizing plate with a retardation layer according to any one of claims 1 to 7. - 前記位相差層が、第1の液晶化合物の配向固化層と第2の液晶化合物の配向固化層との積層構造を有し、
該第1の液晶化合物の配向固化層のRe(550)が200nm~300nmであり、その遅相軸と前記偏光子の吸収軸とのなす角度が10°~20°であり、
該第2の液晶化合物の配向固化層のRe(550)が100nm~190nmであり、その遅相軸と該偏光子の吸収軸とのなす角度が70°~80°である、
請求項1から7のいずれかに記載の位相差層付偏光板。 The retardation layer has a laminated structure of an orientation-solidified layer of a first liquid crystal compound and an orientation-solidification layer of a second liquid crystal compound.
The Re (550) of the oriented solidification layer of the first liquid crystal compound is 200 nm to 300 nm, and the angle formed by the slow axis thereof and the absorption axis of the polarizer is 10 ° to 20 °.
The Re (550) of the oriented solidified layer of the second liquid crystal compound is 100 nm to 190 nm, and the angle formed by the slow axis thereof and the absorption axis of the polarizer is 70 ° to 80 °.
The polarizing plate with a retardation layer according to any one of claims 1 to 7. - 前記位相差層と前記粘着剤層との間に別の位相差層をさらに有し、該別の位相差層の屈折率特性がnz>nx=nyの関係を示す、請求項1から9のいずれかに記載の位相差層付偏光板。 Claims 1 to 9, wherein another retardation layer is further provided between the retardation layer and the pressure-sensitive adhesive layer, and the refractive index characteristics of the other retardation layer show a relationship of nz> nz = ny. The polarizing plate with a retardation layer according to any one.
- 前記ヨウ素透過抑制層と前記粘着剤層との間に導電層または導電層付等方性基材をさらに有する、請求項1から10のいずれかに記載の位相差層付偏光板。 The polarizing plate with a retardation layer according to any one of claims 1 to 10, further comprising an isotropic base material with a conductive layer or a conductive layer between the iodine permeation suppressing layer and the pressure-sensitive adhesive layer.
- 総厚みが60μm以下である、請求項1から11のいずれかに記載の位相差層付偏光板。 The polarizing plate with a retardation layer according to any one of claims 1 to 11, wherein the total thickness is 60 μm or less.
- 請求項1から12のいずれかに記載の位相差層付偏光板を備える、画像表示装置。 An image display device including the polarizing plate with a retardation layer according to any one of claims 1 to 12.
- 有機エレクトロルミネセンス表示装置または無機エレクトロルミネセンス表示装置である、請求項13に記載の画像表示装置。 The image display device according to claim 13, which is an organic electroluminescence display device or an inorganic electroluminescence display device.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202080094154.5A CN115004066A (en) | 2020-01-24 | 2020-10-20 | Polarizing plate with phase difference layer and image display device using same |
KR1020227020403A KR20220124150A (en) | 2020-01-24 | 2020-10-20 | Polarizing plate with retardation layer and image display device using same |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020009755 | 2020-01-24 | ||
JP2020-009755 | 2020-01-24 | ||
JP2020160882A JP7114664B2 (en) | 2020-01-24 | 2020-09-25 | Polarizing plate with retardation layer and image display device using the same |
JP2020-160882 | 2020-09-25 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2021149311A1 true WO2021149311A1 (en) | 2021-07-29 |
Family
ID=76992938
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2020/039431 WO2021149311A1 (en) | 2020-01-24 | 2020-10-20 | Retardation layer–equipped polarizing plate and image display device using same |
Country Status (3)
Country | Link |
---|---|
KR (1) | KR20220124150A (en) |
CN (1) | CN115004066A (en) |
WO (1) | WO2021149311A1 (en) |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007264586A (en) * | 2006-02-28 | 2007-10-11 | Nitto Denko Corp | Liquid crystal panel and liquid crystal display device |
JP2009192612A (en) * | 2008-02-12 | 2009-08-27 | Nitto Denko Corp | Multilayer optical film, liquid crystal panel using multilayer optical film, and liquid crystal display |
JP2013050583A (en) * | 2011-08-31 | 2013-03-14 | Fujifilm Corp | Polarizing plate, image display apparatus employing the same, and adhesive composition |
WO2013137464A1 (en) * | 2012-03-15 | 2013-09-19 | 富士フイルム株式会社 | Organic el display element comprising optical laminate |
JP2016122054A (en) * | 2014-12-24 | 2016-07-07 | 日東電工株式会社 | Polarizing film with coating layer, polarizing film with adhesive layer, and image display device |
JP2017068235A (en) * | 2015-09-30 | 2017-04-06 | 富士フイルム株式会社 | Polarizing plate protective film, manufacturing method of the same, polarizing plate, and image display device |
JP2017075986A (en) * | 2015-10-13 | 2017-04-20 | 株式会社サンリッツ | Polarizing plate with adhesive layer and manufacturing method of the same, active energy ray curable polymer composition used for the manufacture, and liquid crystal display |
JP2017191203A (en) * | 2016-04-13 | 2017-10-19 | 富士フイルム株式会社 | Laminate and liquid crystal display |
JP2018141962A (en) * | 2017-02-28 | 2018-09-13 | 住友化学株式会社 | Optical laminate |
WO2020111232A1 (en) * | 2018-11-29 | 2020-06-04 | 日東電工株式会社 | Polarizing film with adhesive layer, and image display device |
JP2020126226A (en) * | 2019-02-04 | 2020-08-20 | 住友化学株式会社 | Polarizing plate and display device |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2316828C (en) | 1998-10-30 | 2010-02-23 | Teijin Limited | Retardation film and optical device employing it |
JP5267919B2 (en) * | 2008-08-06 | 2013-08-21 | 住友化学株式会社 | Polarizing plate, optical member, and liquid crystal display device |
JP6321107B2 (en) * | 2016-10-04 | 2018-05-09 | 日東電工株式会社 | Optical laminate and image display device |
KR20200096431A (en) * | 2019-02-04 | 2020-08-12 | 스미또모 가가꾸 가부시키가이샤 | Polarizing plate and display device |
-
2020
- 2020-10-20 KR KR1020227020403A patent/KR20220124150A/en unknown
- 2020-10-20 CN CN202080094154.5A patent/CN115004066A/en active Pending
- 2020-10-20 WO PCT/JP2020/039431 patent/WO2021149311A1/en active Application Filing
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007264586A (en) * | 2006-02-28 | 2007-10-11 | Nitto Denko Corp | Liquid crystal panel and liquid crystal display device |
JP2009192612A (en) * | 2008-02-12 | 2009-08-27 | Nitto Denko Corp | Multilayer optical film, liquid crystal panel using multilayer optical film, and liquid crystal display |
JP2013050583A (en) * | 2011-08-31 | 2013-03-14 | Fujifilm Corp | Polarizing plate, image display apparatus employing the same, and adhesive composition |
WO2013137464A1 (en) * | 2012-03-15 | 2013-09-19 | 富士フイルム株式会社 | Organic el display element comprising optical laminate |
JP2016122054A (en) * | 2014-12-24 | 2016-07-07 | 日東電工株式会社 | Polarizing film with coating layer, polarizing film with adhesive layer, and image display device |
JP2017068235A (en) * | 2015-09-30 | 2017-04-06 | 富士フイルム株式会社 | Polarizing plate protective film, manufacturing method of the same, polarizing plate, and image display device |
JP2017075986A (en) * | 2015-10-13 | 2017-04-20 | 株式会社サンリッツ | Polarizing plate with adhesive layer and manufacturing method of the same, active energy ray curable polymer composition used for the manufacture, and liquid crystal display |
JP2017191203A (en) * | 2016-04-13 | 2017-10-19 | 富士フイルム株式会社 | Laminate and liquid crystal display |
JP2018141962A (en) * | 2017-02-28 | 2018-09-13 | 住友化学株式会社 | Optical laminate |
WO2020111232A1 (en) * | 2018-11-29 | 2020-06-04 | 日東電工株式会社 | Polarizing film with adhesive layer, and image display device |
JP2020126226A (en) * | 2019-02-04 | 2020-08-20 | 住友化学株式会社 | Polarizing plate and display device |
Also Published As
Publication number | Publication date |
---|---|
CN115004066A (en) | 2022-09-02 |
KR20220124150A (en) | 2022-09-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2021024544A1 (en) | Retardation-layer-equipped polarizing plate, and image display device using same | |
JP2024007555A (en) | Polarizing plate having retardation layer and picture display unit using the same | |
JP7114664B2 (en) | Polarizing plate with retardation layer and image display device using the same | |
JP7273769B2 (en) | Polarizing plate, polarizing plate with retardation layer, and image display device using these | |
WO2022185802A1 (en) | Circular polarizing plate and image display device using same | |
WO2021149311A1 (en) | Retardation layer–equipped polarizing plate and image display device using same | |
WO2021149312A1 (en) | Retardation-layer-equipped polarizing plate and image display device using same | |
WO2021149314A1 (en) | Polarizing plate, polarizing plate with retardation layer, and image display device using said plates | |
WO2021149313A1 (en) | Polarizing plate and phase difference layer-equipped polarizing plate, and image display device using same | |
JP7114665B2 (en) | Polarizing plate with retardation layer and image display device using the same | |
WO2022034774A1 (en) | Retardation layer-equipped polarizing plate and image display device using same | |
JP7273768B2 (en) | Polarizing plate, polarizing plate with retardation layer, and image display device using these | |
WO2022074872A1 (en) | Method for manufacturing phase difference layer-equipped polarizing plate | |
KR20230152586A (en) | Laminate and image display device using the same | |
KR20240081356A (en) | Optical laminate and image display apparatus | |
JP2023075748A (en) | Polarizing plate with retardation layer, and image display device using the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20915278 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 20915278 Country of ref document: EP Kind code of ref document: A1 |