WO2017138551A1 - 偏光フィルム及びその製造方法 - Google Patents
偏光フィルム及びその製造方法 Download PDFInfo
- Publication number
- WO2017138551A1 WO2017138551A1 PCT/JP2017/004511 JP2017004511W WO2017138551A1 WO 2017138551 A1 WO2017138551 A1 WO 2017138551A1 JP 2017004511 W JP2017004511 W JP 2017004511W WO 2017138551 A1 WO2017138551 A1 WO 2017138551A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polarizing film
- film
- pva
- stretching
- polyvinyl alcohol
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 202
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 200
- 239000004327 boric acid Substances 0.000 claims abstract description 86
- 238000004132 cross linking Methods 0.000 claims abstract description 62
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 59
- 230000010287 polarization Effects 0.000 claims abstract description 51
- 239000007864 aqueous solution Substances 0.000 claims abstract description 37
- 238000004043 dyeing Methods 0.000 claims abstract description 26
- 230000008961 swelling Effects 0.000 claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 52
- 230000008569 process Effects 0.000 claims description 39
- 238000002834 transmittance Methods 0.000 claims description 37
- 102000003712 Complement factor B Human genes 0.000 claims description 24
- 108090000056 Complement factor B Proteins 0.000 claims description 24
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 21
- 239000011630 iodine Substances 0.000 claims description 21
- 229910052740 iodine Inorganic materials 0.000 claims description 21
- 238000005259 measurement Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910001868 water Inorganic materials 0.000 claims description 18
- 238000004736 wide-angle X-ray diffraction Methods 0.000 claims description 17
- DKNPRRRKHAEUMW-UHFFFAOYSA-N Iodine aqueous Chemical compound [K+].I[I-]I DKNPRRRKHAEUMW-UHFFFAOYSA-N 0.000 claims description 6
- 241000694440 Colpidium aqueous Species 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 230000008602 contraction Effects 0.000 abstract description 8
- 235000019422 polyvinyl alcohol Nutrition 0.000 abstract 5
- 229960002645 boric acid Drugs 0.000 description 82
- 235000010338 boric acid Nutrition 0.000 description 56
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 38
- 239000013078 crystal Substances 0.000 description 26
- 239000000975 dye Substances 0.000 description 21
- 206010042674 Swelling Diseases 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 13
- 239000010410 layer Substances 0.000 description 13
- 238000005315 distribution function Methods 0.000 description 12
- 239000004973 liquid crystal related substance Substances 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- 238000004220 aggregation Methods 0.000 description 9
- 230000002776 aggregation Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- -1 ethylene, propylene, 1-butene Chemical class 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 239000004014 plasticizer Substances 0.000 description 7
- 229920001290 polyvinyl ester Polymers 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 238000007127 saponification reaction Methods 0.000 description 6
- 229920001567 vinyl ester resin Polymers 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000033001 locomotion Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-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
- 150000001241 acetals Chemical group 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 1
- QJJDJWUCRAPCOL-UHFFFAOYSA-N 1-ethenoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOC=C QJJDJWUCRAPCOL-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- PGYJSURPYAAOMM-UHFFFAOYSA-N 2-ethenoxy-2-methylpropane Chemical compound CC(C)(C)OC=C PGYJSURPYAAOMM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- TYHJNQYKZSZYRO-UHFFFAOYSA-N CC(NC=C)=O.C=CN Chemical class CC(NC=C)=O.C=CN TYHJNQYKZSZYRO-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940063013 borate ion Drugs 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920001727 cellulose butyrate Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000012886 linear function Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- ADTJPOBHAXXXFS-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]prop-2-enamide Chemical compound CN(C)CCCNC(=O)C=C ADTJPOBHAXXXFS-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-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
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- AAYRWMCIKCRHIN-UHFFFAOYSA-N propane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CCCS(O)(=O)=O AAYRWMCIKCRHIN-UHFFFAOYSA-N 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
- B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00634—Production of filters
- B29D11/00644—Production of filters polarizing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
- B29K2033/04—Polymers of esters
Definitions
- the present invention relates to a polarizing film comprising a polyvinyl alcohol film containing an iodine dichroic dye and a method for producing the same.
- a polarizing plate having a light transmission and shielding function is a basic component of a liquid crystal display (LCD) together with a liquid crystal that changes a polarization state of light.
- LCD liquid crystal display
- Many polarizing plates have a structure in which a protective film such as a cellulose triacetate (TAC) film is bonded to the surface of a polarizing film.
- TAC cellulose triacetate
- an iodine pigment (I 3 ) is applied to a matrix (a uniaxially stretched oriented film) obtained by uniaxially stretching a polyvinyl alcohol film (hereinafter, “polyvinyl alcohol” may be abbreviated as “PVA”).
- PVA polyvinyl alcohol
- Such a polarizing film can be obtained by uniaxially stretching a PVA film preliminarily containing a dichroic dye, adsorbing a dichroic dye simultaneously with uniaxial stretching of the PVA film, or dichroic after uniaxially stretching the PVA film. Manufactured by adsorbing dyes.
- LCDs are used in a wide range of applications such as small devices such as calculators and watches, notebook computers, liquid crystal monitors, liquid crystal color projectors, liquid crystal televisions, in-vehicle navigation systems, mobile phones, and measuring devices used indoors and outdoors.
- small devices such as calculators and watches, notebook computers, liquid crystal monitors, liquid crystal color projectors, liquid crystal televisions, in-vehicle navigation systems, mobile phones, and measuring devices used indoors and outdoors.
- polarizing films having excellent optical performance.
- Patent Documents 1 to 4 in a method for producing a polarizing film, a PVA film is immersed in water and swelled, dyed with an iodine dichroic dye, then crosslinked in a boric acid aqueous solution and stretched. It is described that a polarizing film having excellent polarization characteristics, uniform optical characteristics, excellent appearance, and the like can be obtained by swelling treatment in a plurality of tanks having different conditions.
- These patent documents describe various techniques for the step of crosslinking in a boric acid aqueous solution and stretching treatment.
- Patent Document 1 describes a method in which the film is immersed in a boric acid aqueous solution at 50 ° C. and stretched 1.5 times.
- Patent Document 2 describes a method in which the film is immersed in a boric acid aqueous solution at 55 ° C. and stretched 2.5 times.
- the Example of patent document 3 describes the method of extending
- the Example of patent document 4 describes the method of extending
- the stretching ratio in the step is 1.1 to 1.3 times and the total stretching ratio is 2.5.
- the stretching ratio in the step is 1.1 to 1.3 times and the total stretching ratio is 2.5.
- the second crosslinking stretching step in a 60 to 70 ° C.
- the stretching ratio in the step is 1.8 to 3.0 times and the total stretching ratio is 6 to
- the problem is solved by providing a method for producing a polarizing film, characterized in that the film is uniaxially stretched to 8 times.
- the maximum stretching stress is preferably 15 N / mm 2 or less. It is also preferable to obtain a polarizing film having a single transmittance of 42 to 45% and a degree of polarization of 99.980% or more. It is also preferable to obtain a polarizing film having a shrinkage stress of 45 N / mm 2 or less.
- the above problem is a polarizing film comprising a polyvinyl alcohol film containing an iodine dichroic dye, When the single transmittance is 43.5%, the degree of polarization is 99.990% or more, and the content (C A ) of the structure factor A in the wide-angle X-ray diffraction measurement is 3 to 4.5%.
- the problem can also be solved by providing a polarizing film having a B content (C B ) of 2.0 to 8.5% and a ratio (C A / C B ) of 0.4 or more. Is done.
- the above-mentioned problem is a polarizing film made of a polyvinyl alcohol film containing an iodine dichroic dye,
- the single transmittance is 42-45%
- the degree of polarization is 99.980% or more
- the content (C A ) of the structure factor A in the wide-angle X-ray diffraction measurement is 3 to 4.5%
- the content (C B ) of the structure factor B is 2
- the problem can also be solved by providing a polarizing film having a ratio of 0.0 to 8.5% and a ratio (C A / C B ) of 0.4 or more.
- the structure factor A is a highly oriented structure factor derived from a polyvinyl alcohol-boron aggregate structure
- the structure factor B is a highly oriented structure factor derived from amorphous polyvinyl alcohol.
- the degree of polymerization of polyvinyl alcohol contained in each stretched film is preferably 2500-3500. It is also preferred that the polarizing film has a shrinkage stress of 45 N / mm 2 or less.
- the polarizing film of the present invention has excellent polarizing performance and low shrinkage stress. Therefore, it can be suitably used for a high-performance liquid crystal display, particularly a liquid crystal display that may be used at high temperatures. Moreover, according to the manufacturing method of this invention, such a polarizing film can be manufactured.
- FIG. 6 is a graph plotting the degree of polarization of the polarizing films obtained in Example 1 and Comparative Examples 1 to 4, 7, and 8 when the single transmittance is 43.5% against the shrinkage stress.
- FIG. 6 is a diagram in which a baseline straight line is drawn on an I (2 ⁇ ) profile.
- FIG. 3 is a diagram in which the corrected I (2 ⁇ ) profile is separated into “PVA amorphous”, “PVA crystal”, and “PVA-boric acid aggregated structure”. It is the figure which plotted the integrated intensity value (A) of "PVA amorphous”, “PVA crystal”, and "PVA-boric acid aggregation structure" obtained by the waveform separation analysis with respect to the azimuth.
- the polarizing film of the present invention is made of a polyvinyl alcohol film containing an iodine dichroic dye, has excellent polarizing performance, and has a small shrinkage stress.
- a polarizing film applies specific manufacturing conditions when a polyvinyl alcohol film (PVA film) is subjected to at least a swelling process, a dyeing process, a first crosslinking stretching process, and a second crosslinking stretching process in this order. Can be manufactured.
- PVA film polyvinyl alcohol film
- the PVA contained in the PVA film used for the production of the polarizing film of the present invention can be obtained by saponifying a polyvinyl ester obtained by polymerizing one or more vinyl esters.
- the vinyl ester include vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate, and isopropenyl acetate.
- vinyl acetate is preferable from the viewpoint of ease of production, availability, and cost of PVA.
- the polyvinyl ester may be obtained using only one or two or more kinds of vinyl esters as a monomer, but one or two as long as the effects of the present invention are not impaired. It may be a copolymer of at least one kind of vinyl ester and another monomer copolymerizable therewith.
- Examples of other monomers copolymerizable with the vinyl ester include ⁇ -olefins having 2 to 30 carbon atoms such as ethylene, propylene, 1-butene and isobutene; (meth) acrylic acid or a salt thereof; (meth) Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, (meth) (Meth) acrylic acid esters such as t-butyl acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate; (meth) acrylamide, N-methyl (meth) Acrylamide, N-ethyl (meth) acrylamide, N, N-
- the proportion of structural units derived from other monomers in the polyvinyl ester is preferably 15 mol% or less, preferably 10 mol% or less, based on the number of moles of all structural units constituting the polyvinyl ester. More preferred is 5 mol% or less.
- the other monomer is a monomer that may promote water solubility of the obtained PVA, such as (meth) acrylic acid or unsaturated sulfonic acid
- the polarizing film In order to prevent PVA from being dissolved in the production process, the proportion of structural units derived from these monomers in the polyvinyl ester is 5 mol% or less based on the number of moles of all structural units constituting the polyvinyl ester. It is preferable that it is 3 mol% or less.
- the PVA used in the present invention may be modified with one or two or more types of graft copolymerizable monomers as long as the effects of the present invention are not impaired.
- examples of the graft copolymerizable monomer include unsaturated carboxylic acids or derivatives thereof; unsaturated sulfonic acids or derivatives thereof; ⁇ -olefins having 2 to 30 carbon atoms, and the like.
- the proportion of structural units derived from the graft copolymerizable monomer in PVA (structural units in the graft modified portion) is preferably 5 mol% or less based on the number of moles of all structural units constituting PVA. .
- PVA may have some of its hydroxyl groups crosslinked or uncrosslinked. Moreover, said PVA may react with aldehyde compounds, such as acetaldehyde and a butyraldehyde, etc. to form an acetal structure, and the said PVA does not react with these compounds and does not form an acetal structure. May be.
- aldehyde compounds such as acetaldehyde and a butyraldehyde, etc.
- the average degree of polymerization of PVA is preferably 2500-3500.
- the average degree of polymerization is more preferably 2600 or more, and more preferably 3300 or less.
- the average degree of polymerization is 2500 or more, a polarizing film having excellent polarizing performance can be easily obtained even when stretched at a high temperature in the second cross-linking stretching step.
- the average degree of polymerization exceeds 3500, it may be difficult to reduce the shrinkage stress of the obtained polarizing film.
- the average degree of polymerization of PVA means the average degree of polymerization measured according to the description of JIS K6726-1994.
- PVA in a polarizing film contains the crosslinked structure by a boric acid, if a boric acid ester is hydrolyzed and removed, there will be no substantial change in the average degree of polymerization of PVA itself.
- the degree of saponification of PVA is preferably 98 mol% or more, more preferably 98.5 mol% or more, and further preferably 99 mol% or more from the viewpoint of the polarizing performance of the polarizing film.
- the degree of saponification of PVA refers to the total number of moles of structural units (typically vinyl ester units) that can be converted into vinyl alcohol units by saponification and the vinyl alcohol units of PVA. The proportion (mol%) occupied by the number of moles of vinyl alcohol units.
- the degree of saponification can be measured according to the description of JIS K6726-1994.
- the PVA content in the PVA film used in the present invention is preferably in the range of 50 to 99% by mass in view of ease of production of the desired polarizing film.
- the content is more preferably 75% by mass or more, further preferably 80% by mass or more, and particularly preferably 85% by mass or more.
- it is more preferable that it is 98 mass% or less, it is more preferable that it is 96 mass% or less, and it is especially preferable that it is 95 mass% or less.
- the PVA film preferably contains a plasticizer from the viewpoint of improving stretchability when it is stretched.
- the plasticizer include polyhydric alcohols such as ethylene glycol, glycerin, propylene glycol, diethylene glycol, diglycerin, triethylene glycol, tetraethylene glycol, and trimethylol propane.
- One or more of the agents can be included. Among these, glycerin is preferable from the viewpoint of the effect of improving stretchability.
- the content of the plasticizer in the PVA film is preferably in the range of 1 to 20 parts by mass with respect to 100 parts by mass of PVA contained therein. When the content is 1 part by mass or more, the stretchability of the PVA film can be further improved. On the other hand, when the content is 20 parts by mass or less, it is possible to prevent the PVA film from becoming too flexible and handling properties from being lowered.
- the content of the plasticizer in the PVA film is more preferably 2 parts by mass or more, further preferably 4 parts by mass or more, and particularly preferably 5 parts by mass or more with respect to 100 parts by mass of PVA. Further, the content of the plasticizer is more preferably 15 parts by mass or less, and further preferably 12 parts by mass or less.
- the PVA film may further contain components such as an antioxidant, an antifreezing agent, a pH adjuster, a hiding agent, a coloring inhibitor, an oil agent, and a surfactant as necessary.
- the thickness of the PVA film used in the production method of the present invention is 5 to 100 ⁇ m. When the thickness is 100 ⁇ m or less, a thin polarizing film can be easily obtained.
- the thickness of the PVA film is preferably 60 ⁇ m or less. On the other hand, when the thickness is less than 5 ⁇ m, it becomes difficult to produce a polarizing film, and uneven dyeing tends to occur.
- the thickness of the PVA film is preferably 7 ⁇ m or more. The thickness here refers to the thickness of the PVA layer in the case of a multilayer film.
- the PVA film may be a single layer film or a multilayer film having a PVA layer and a base resin layer.
- the film thickness is preferably 20 ⁇ m or more, and more preferably 30 ⁇ m or more, in order to ensure handling properties.
- the thickness of the PVA layer can be 20 ⁇ m or less, or 15 ⁇ m or less.
- the thickness of the base resin layer in the multilayer film is usually 20 to 500 ⁇ m.
- the base resin When a multilayer film having a PVA layer and a base resin layer is used as the PVA film, the base resin must be capable of being stretched together with PVA.
- Polyester, polyolefin resin, or the like can be used.
- an amorphous polyester resin is preferable, and an amorphous polyester resin obtained by copolymerizing polyethylene terephthalate and a copolymer component such as isophthalic acid or 1,4-cyclohexanedimethanol is preferably used.
- the surface of the base resin film may be modified, or an adhesive layer may be formed between both layers.
- the shape of the PVA film is not particularly limited, but is preferably a long PVA film because it can be continuously supplied when the polarizing film is produced.
- the length of the long PVA film (length in the long direction) is not particularly limited, and can be set as appropriate according to the use of the polarizing film to be produced. For example, the length is in the range of 5 to 20,000 m. It can be.
- the width of the PVA film is not particularly limited, and can be appropriately set according to the application of the polarizing film to be produced. In recent years, since the enlargement of screens of liquid crystal televisions and liquid crystal monitors has progressed, it is suitable for these applications when the width of the PVA film is 0.5 m or more, more preferably 1.0 m or more. On the other hand, if the width of the PVA film is too wide, it tends to be difficult to uniformly stretch the polarizing film when the polarizing film is produced by a device that has been put to practical use. Therefore, the width of the PVA film is 7 m or less. Is preferred.
- the polarizing film of the present invention is produced using the PVA film described above as a raw material. Specifically, a polarizing film is produced by performing at least a swelling process, a dyeing process, a first crosslinking stretching process, and a second crosslinking stretching process in this order. It is also preferable to perform a washing process and a drying process after the second cross-linking stretching process.
- a swelling process e.g., a dyeing process
- a first crosslinking stretching process e.g., a first crosslinking stretching process
- a second crosslinking stretching process e.g., a washing process after the second cross-linking stretching process.
- the PVA film is first subjected to a swelling process.
- the PVA film is swollen by dipping in water at 10 to 50 ° C.
- the temperature of water is preferably 20 ° C. or higher, and preferably 40 ° C. or lower.
- the time for immersing the PVA film in water is preferably in the range of 0.1 to 5 minutes, and more preferably in the range of 0.5 to 3 minutes. By setting it as such immersion time, a PVA film can be efficiently swollen uniformly.
- the water in which the PVA film is immersed is not limited to pure water, and may be an aqueous solution in which various components are dissolved, or a mixture of water and a water-soluble organic solvent.
- the draw ratio in that case is not particularly limited, but is preferably 1.2 to 2.8 times.
- the draw ratio is more preferably 1.5 times or more, and more preferably 2.5 times or less.
- the dyeing step is provided after the swelling step.
- the PVA film is impregnated with an iodine dichroic dye by dipping in an aqueous solution at 10 to 50 ° C. containing 0.5 to 3 mass% of iodine and potassium iodide in total, and the total draw ratio is 2 Uniaxially stretched to ⁇ 3 times.
- Dyeing is performed by immersing the PVA film in a dyeing bath containing an iodine-based dye.
- the dyebath is prepared by mixing iodine (I 2 ) and potassium iodide (KI) with water. By mixing the iodine and potassium iodide and water, I 3 - and I 5 - it can generate iodine dye such.
- the total content of iodine and potassium iodide in the dyeing bath is 0.5 to 3% by mass in total.
- the total content of iodine and potassium iodide is preferably 0.8% by mass or more, and more preferably 2.5% by mass or less. By dyeing in such a concentration range, it is possible to dye efficiently and uniformly.
- the mass ratio of potassium iodide to iodine is preferably 10 to 200, more preferably 15 to 150.
- the dyeing bath may contain a boron compound such as boric acid such as boric acid and borax, but the content is usually less than 5% by mass in terms of boric acid, and preferably 1% by mass. It is as follows.
- the temperature of the dyeing bath is 10-50 ° C.
- the temperature is preferably 15 ° C. or higher, and more preferably 20 ° C. or higher.
- the temperature is preferably 40 ° C. or lower, and more preferably 30 ° C. or lower.
- the time for immersing the PVA film in the dyeing bath is preferably within a range of 0.1 to 10 minutes, and more preferably within a range of 0.2 to 5 minutes. By setting it as such a time range, the PVA film can be dyed without spots.
- the PVA film is dyed and uniaxially stretched so that the total draw ratio is 2 to 3 times.
- a polarizing film having excellent polarizing performance and low shrinkage stress can be obtained. What is necessary is just to make it the total draw ratio which passed through the process so far including a swelling process and a dyeing process become 2-3 times.
- the draw ratio in the dyeing process should just exceed 1 time, and it is more preferable that it is 1.05 times or more.
- the first crosslinking stretching step and the second crosslinking stretching step are performed after the dyeing step.
- the crystal state and orientation state of the obtained polarizing film can be controlled, and a polarizing film having excellent polarizing performance and low shrinkage stress can be obtained. it can.
- these two cross-linking stretching steps will be described.
- the stretching ratio in the process is 1.1 to 1.3 times and the total stretching ratio is 2.5 to 2.5 in an aqueous solution containing 1 to 5% by mass of boric acid at 40 to 55 ° C.
- Uniaxial stretching is performed so as to be 3.5 times.
- the boric acid aqueous solution into which the PVA film is immersed contains 1 to 5% by mass of boric acid.
- the concentration of boric acid is preferably 1.5% by mass or more, and preferably 4% by mass or less. By setting it as such a density
- the boric acid may be any boric acid or borate ion in an aqueous solution, and either boric acid or borate can be used, but boric acid is preferred.
- the concentration in the case of using a borate is calculated in terms of mass of boric acid (H 3 BO 3 ).
- the aqueous boric acid solution may contain potassium iodide, and the concentration in that case is preferably in the range of 0.01 to 10% by mass. By containing potassium iodide, the polarizing performance of the obtained polarizing film can be adjusted. Potassium iodide may be included in the first crosslinking stretching step, potassium iodide may be included in the second crosslinking stretching step described later, or both steps may be included.
- the temperature of the aqueous boric acid solution in the first cross-linking and stretching step is 40 to 55 ° C.
- the temperature is preferably 42 ° C. or higher, and is preferably 53 ° C. or lower.
- the temperature is too low, the progress of the crosslinking reaction with boric acid becomes insufficient, and the polarizing property of the obtained polarizing film is deteriorated.
- the said temperature is too high, there exists a possibility that PVA may elute from a film. Under such temperature conditions, the film is uniaxially stretched so that the draw ratio is 1.1 to 1.3 times and the total draw ratio is 2.5 to 3.5 times.
- the total draw ratio is preferably 2.6 times or more, and preferably 3.4 times or less.
- the boric acid cross-linking reaction is advanced while slightly uniaxially stretching and appropriately oriented.
- PVA does not elute into the boric acid aqueous solution from the film or the strength of the film is not greatly reduced. It can be stretched to a magnification.
- the stretching ratio in the step is 1.8 to 3.0 times and the total stretching ratio is 6 to It is uniaxially stretched so that it becomes 8 times.
- the composition of the boric acid aqueous solution used can be the same as that used in the first crosslinking and stretching step.
- the temperature of the boric acid aqueous solution is 60 to 70 ° C.
- the temperature is preferably 62 ° C. or higher, and preferably 68 ° C. or lower. If the temperature is too low, the shrinkage stress will increase. On the other hand, when the temperature is too high, PVA is eluted from the film into the boric acid aqueous solution, or the degree of polarization is reduced. Then, uniaxial stretching is performed so that the total stretching ratio is 6 to 8 times and 1.8 to 3.0 times in the temperature range.
- the draw ratio in the second cross-linking stretching step is preferably 2 times or more, and preferably 2.8 times or less.
- the total draw ratio is preferably 6.2 times or more, and preferably 7.8 times or less. That is, the boric acid crosslinking reaction proceeds in a high-temperature boric acid aqueous solution while stretching at a relatively high magnification, and as a result, crystallization and immobilization of the oriented PVA in the drying process are promoted. Thereby, a polarizing film having high polarization performance and low shrinkage stress can be produced.
- maximum stretching stress in the second bridge stretching process is 15N / mm 2 or less.
- the maximum stretching stress is a value obtained by dividing the tensile force applied between adjacent rolls by the cross-sectional area of the raw material PVA film in the second cross-linking stretching step. When using three or more rolls, the maximum tensile force is adopted. By reducing the maximum stretching stress, a polarizing film having a small shrinkage stress can be obtained.
- the maximum stretching stress is more preferably 10 N / mm 2 or less. Usually, the maximum stretching stress is 1 N / mm 2 or more.
- the PVA film when uniaxially stretched, it is performed by changing the peripheral speed between the rolls using a stretching apparatus having a plurality of rolls parallel to each other in the water bath. be able to.
- the cleaning step can be performed by immersing the PVA film in a cleaning bath or by spraying a cleaning liquid on the PVA film.
- Water can be used as the cleaning solution, but these may contain potassium iodide.
- the content of potassium iodide is preferably 0.1 to 10% by mass.
- the temperature of the cleaning liquid is usually 10 to 40 ° C, preferably 15 to 30 ° C.
- the cleaning bath may be used not only in one tank but also in a plurality of tanks. Moreover, the composition of the cleaning liquid in each tank when using a plurality of tanks can be adjusted according to the purpose.
- the temperature in the drying step is not particularly limited, but is preferably 30 to 150 ° C, and more preferably 50 to 130 ° C. A polarizing film excellent in dimensional stability is easily obtained by drying at a temperature within the above range.
- the thickness of the polarizing film of the present invention is preferably 1 to 30 ⁇ m. If the thickness is less than 1 ⁇ m, it may be difficult to produce at a high speed, and more preferably 3 ⁇ m or more. On the other hand, when the thickness exceeds 30 ⁇ m, the stretching tension at the time of stretching may increase and the apparatus may be damaged, and more preferably 25 ⁇ m or less.
- the thickness here refers to the thickness of the PVA layer in the case of a multilayer film.
- the thickness of the polarizing film is preferably 5 ⁇ m or more, and more preferably 7 ⁇ m or more in order to ensure handling properties.
- the thickness of the PVA layer can be 5 ⁇ m or less, or 3 ⁇ m or less.
- the thickness of the base resin layer in the multilayer film is usually 10 to 250 ⁇ m.
- the single transmittance of the polarizing film of the present invention is preferably 42 to 45%. When the single transmittance is less than 42%, the brightness of the liquid crystal display decreases. The single transmittance is more preferably 42.5% or more. On the other hand, it is difficult to obtain a polarizing film having a high degree of polarization with a polarizing film having a single transmittance exceeding 45%, and the single transmittance is more preferably 44.5% or less. Moreover, it is preferable that the polarization degree of the polarizing film of this invention is 99.980% or more. When the degree of polarization is 99.980% or more, the image quality of the liquid crystal display is excellent. The degree of polarization is more preferably 99.982% or more.
- the shrinkage stress of the polarizing film of the present invention is preferably 45 N / mm 2 or less. Due to the small shrinkage stress, the dimensional stability is excellent even when used at high temperatures.
- the shrinkage stress is more preferably 40 N / mm 2 or less.
- the shrinkage stress means a value obtained by dividing a tension when a polarizing film as a sample is fixed and maintained at 80 ° C. for 4 hours by a cross-sectional area of the sample.
- the polarizing film of the present invention preferably has a “degree of polarization when the single transmittance is 43.5%” of 99.990% or more. This value is obtained by calculating the degree of polarization when it is assumed to be 43.5% when the single transmittance (T) of the polarizing film is not 43.5%.
- the polarization degree when the single transmittance is 43.5% is more preferably 99.991% or more, and further preferably 99.992% or more.
- Equation (1) the relationship between the transmittance (T ′) excluding the surface reflection and the single transmittance (T) is expressed by Equation (1).
- the refractive index of PVA was 1.5, and the reflectance at the surface was 4%.
- the relationship among the transmittance (T ′), the degree of polarization (V), and the dichroic ratio (R) is expressed by Equation (2), and Equation (2) is modified from Equation (3).
- the dichroic ratio (R) can be handled as a constant because it hardly varies depending on the dye concentration in a range where the single transmittance (T) does not vary greatly, for example, in the range of 42 to 45%.
- the dichroic ratio (R) of the polarizing film is determined as a constant by solving the equations (1) and (2) using these values.
- T ′ T / (1 ⁇ 0.04) 2 (1)
- R ⁇ ln [T ′ (1 ⁇ V)] ⁇ / ⁇ ln [T ′ (1 + V)] ⁇ (2)
- T ′ [1-V] 1 / (R ⁇ 1) / [1 + V] R / (R ⁇ 1) (3)
- the polarizing film of the present invention has structural features different from those of conventional polarizing films when structural analysis is performed by wide-angle X-ray diffraction (WAXD) measurement. This will be described below.
- WAXD wide-angle X-ray diffraction
- the profile of the X-ray intensity with respect to the diffraction angle (2 ⁇ ) is created by performing WAXD measurement on the polarizing film of the present invention. Then, the peak is divided according to the method described in the following examples. First, it is divided into three components, “PVA crystal”, “PVA amorphous”, and “PVA-boric acid aggregation structure”.
- PVA crystal refers to a PVA chain in a crystalline state
- PVA amorphous refers to a disordered PVA chain that is not in a crystalline state.
- the peak derived from “PVA-boric acid aggregated structure” is a peak known to appear when boric acid is added to PVA. From the structure formed by the interaction between PVA and boric acid, It is thought that this is the diffraction signal.
- an X-ray intensity profile for the azimuth angle ⁇ is created for the three components divided by the above method. This is further divided into three components, that is, a non-oriented component, a low-oriented component, and a highly-oriented component, respectively, so as to be divided into 9 components in total. In this way, the ratio (%) of each component can be determined when the total of the nine components is 100%.
- the highly oriented component of “PVA-boric acid aggregated structure” was designated as structure factor A
- the highly oriented component of “PVA amorphous” was designated as structure factor B. This time, it was found that the structure factor A is a structure necessary for enhancing the polarization performance, and the structure factor B is a causative structure of the shrinkage stress.
- the structure factor A has a structure in which the oriented PVA chain is stabilized by intramolecular or intermolecular crosslinking of boric acid, D. ⁇ Fujiwara et al., Polymer Preprints, Japan, 59, 2, 3043, 2010; D. Fujiwara et al., Polymer Preprints, Japan, 60, 2, 3393, 2011; K. Ohishi et al., Polymer, 51, 687-693, 2010 etc.
- boric acid has the effect of stabilizing polyiodine ions in order to suppress thermal motion and orientation relaxation of the PVA chain. As a result, many polyiodine ions Can be held stably.
- Structure factor B is a structure in which the PVA chain is highly oriented by stretching and frozen as it is. This is due to non-crystallized PVA chains. At a temperature equal to or higher than the glass transition temperature of PVA, molecular mobility increases due to thermal motion, and since there is no restriction by crystals or boric acid, orientation is easily relaxed. Since the structure factor B is highly oriented, the force for relaxing the orientation is large.
- Structure factor A and structure factor B can be controlled by various conditions when producing a polarizing film from a PVA film.
- the structure factor A depends on the boric acid concentration of the crosslinking tank containing boric acid, and the higher the boric acid concentration, the larger the structural factor A.
- the structure factor B depends on the draw ratio, and by reducing the draw ratio, the orientation of the PVA chain can be suppressed and the structure factor B can be reduced.
- the content of structure factor A (C A ) is preferably 3 to 4.5%. When the content (C A ) is 3% or more, excellent polarization performance can be obtained.
- the content (C B ) of the structure factor B is preferably 2.0 to 8.5%, more preferably 2.5 to 8.5%, and 3.0 to 8.5%. Even more preferably, it is particularly preferably 4.5 to 8.5%. When the content (C B ) is 8.5% or less, the shrinkage stress can be reduced.
- the ratio (C A / C B ) between the two is preferably 0.4 or more. By taking a large value for the ratio (C A / C B ), a polarizing film having excellent polarizing performance and low shrinkage stress can be obtained.
- a preferred embodiment of the polarizing film of the present invention is a polarizing film comprising a polyvinyl alcohol film containing an iodine dichroic dye; the degree of polarization when the single transmittance is 43.5% is 99.990% or more.
- the content (C A ) of the structure factor A in the wide-angle X-ray diffraction measurement is 3 to 4.5%
- the content (C B ) of the structure factor B is 2.0 to 8.5%.
- the ratio (C A / C B ) is 0.4 or more.
- polarizing film of the present invention is a polarizing film comprising a polyvinyl alcohol film containing an iodine-based dichroic dye; having a single transmittance of 42 to 45%; and a degree of polarization of 99.980%
- the content (C A ) of structure factor A in the wide-angle X-ray diffraction measurement is 3 to 4.5%
- the content (C B ) of structure factor B is 2.0 to 8.5. %
- the ratio (C A / C B ) is 0.4 or more.
- polarizing film of the present invention is a polarizing film composed of a polyvinyl alcohol film containing an iodine dichroic dye; the degree of polarization when the single transmittance is 43.5% is 99.990% or more. And a polarizing film having a shrinkage stress of 45 N / mm 2 or less.
- polarizing film of the present invention is a polarizing film comprising a polyvinyl alcohol film containing an iodine-based dichroic dye; having a single transmittance of 42 to 45%; and a degree of polarization of 99.980% And a polarizing film having a shrinkage stress of 45 N / mm 2 or less.
- the polarizing film of the present invention is usually used as a polarizing plate by attaching a protective film on both sides or one side.
- the protective film include those that are optically transparent and have mechanical strength. Specifically, for example, cellulose triacetate (TAC) film, acetic acid / cellulose butyrate (CAB) film, acrylic film, and polyester film.
- TAC cellulose triacetate
- CAB acetic acid / cellulose butyrate
- acrylic film acrylic film
- polyester film polyester film.
- a film or the like can be used.
- examples of the adhesive for bonding include a PVA adhesive, a urethane adhesive, and an ultraviolet curable adhesive.
- the polarizing plate thus obtained can be used for a high-performance liquid crystal display (LCD). It is possible to provide a polarizing plate that is bright, has good polarization characteristics, and has excellent dimensional stability even when used under high temperature conditions. Therefore, it can be suitably used as a polarizing plate for various high-performance LCDs, particularly LCDs for mobile use.
- LCD liquid crystal display
- Wide-angle X-ray diffraction (WAXD) measurement of polarizing film Wide angle X-ray diffraction (WAXD) measurement was performed using a D8 Discover apparatus manufactured by Bruker AXS.
- the incident X-ray wavelength was 0.154 nm (Cu target).
- Hi-STAR a position sensitive 2D gas detector, was used as the detector, and the camera distance (distance between sample and detector) was set to approximately 150 mm.
- the X-ray generator used was a filament current of 110 mA, a voltage of 45 kV, and a collimator diameter of 0.5 mm.
- the WAXD measurement was performed under the following conditions. 11 ° for the ⁇ -axis of the sample (the axis set so that the angle between the normal to the polarizing film surface and the X-ray incident direction is ⁇ , generally called the ⁇ -axis), detector position 2 ° axis (the axis set so that the angle between the normal to the detector surface and the incident X-ray direction is 2 ⁇ ) is 22 °, and the ⁇ axis corresponding to rotation in the plane of the polarizing film is 90 ° or Set to 0 °.
- the ⁇ axis coincides with the azimuthal direction in the plane of the polarizing film.
- the stretching direction of the polarizing film is the meridian direction and the vertical direction in the plane is the equator line direction
- the ⁇ axis is 90 °
- diffraction information in the equator line direction is obtained
- ⁇ axis is 0 °
- the meridian direction diffraction information is obtained.
- Diffraction information can be acquired. Diffraction or scattering observed by the detector satisfies the Bragg condition. In the case of this measurement condition, for example, a 110 diffraction signal from the detected PVA crystal is diffraction due to (110) that approximately matches the thickness direction of the polarizing film. The measurement was performed with the ⁇ axis at 90 ° or 0 ° and the X-ray exposure time of 60 minutes.
- WAXD measurement data analysis of polarizing film The obtained two-dimensional photograph of WAXD was converted into a one-dimensional profile of the X-ray intensity I (2 ⁇ ) with respect to 2 ⁇ using GADDS (General Area Detector Diffraction System) software. The 2 ⁇ range was 5 ° to 35 °. Sampling steps were set at 0.05 ° intervals.
- the analysis of the I (2 ⁇ ) profile was performed according to the following procedure. First, the I (2 ⁇ ) profile in the same azimuth range obtained by background measurement was subtracted from the I (2 ⁇ ) profile obtained by measurement of the polarizing film. For the I (2 ⁇ ) profile minus background scattering, as shown in Fig. 3, the baseline connecting the intensity value I (6.5) when the 2 ⁇ position is 6.5 ° and the intensity value I (30.5) when the 2 ⁇ position is 30.5 ° A straight line was generated and further subtracted from the I (2 ⁇ ) profile minus background scatter. The baseline straight line is a linear function passing through two points (6.5, I (6.5)) and (30.5, I (30.5)) on the I (2 ⁇ ) -2 ⁇ coordinate.
- FIG. 4 shows the corrected I (2 ⁇ ) profile obtained by measuring the polarizing film and the poval film.
- the broad and diffuse scattering component observed from 2 ° to 10 ° to 30 ° mainly originates from the amorphous PVA.
- the peak component observed in the range of 19 ° to 21 ° at 2 ⁇ results from diffraction by (1-10) and (110) of the PVA crystal.
- the peak-like component observed from 21 ° to 23 ° in 2 ⁇ appears when boric acid is added to PVA, and formed by the interaction of PVA and boric acid. It is considered to be a diffraction signal from the structure.
- the structure formed by the interaction of PVA and boric acid is referred to as “PVA-boric acid aggregation structure”.
- scattering or diffraction signals from “PVA amorphous”, “PVA crystal”, and “PVA-boric acid aggregation structure” can be expressed by a Gaussian function.
- Gaussian function A, Gaussian function B, and Gaussian function C were used.
- Parameters defining the shape of the Gaussian function were a peak top position x, a peak height h, and a peak width (here, the standard deviation ⁇ of a normal distribution is meant).
- the peak top position x, peak height h, and peak of the three Gaussian functions are matched so that the calculated-I (2 ⁇ ) profile, which is the sum of the three Gaussian functions representing each component, matches the corrected I (2 ⁇ ) profile.
- the diffraction peak shape could be expressed by a Gaussian function and included in the waveform separation analysis into the I (2 ⁇ ) profile. That is, the least square fitting was performed by appropriately adjusting the peak top position x, peak height h, and peak width ⁇ of the Gaussian function.
- FIG. 5 is a plot of the integrated intensity values (A) of “PVA amorphous”, “PVA crystal”, and “PVA-boric acid aggregated structure” obtained by waveform separation analysis versus azimuth.
- the azimuth angle was defined as follows.
- the analysis result of the corrected I (2 ⁇ ) profile in the azimuth range from -5 ° to 5 ° shows the corrected I (2 ⁇ ) profile in the azimuth range from 85 ° to 95 ° with respect to the azimuth angle of 0 °.
- the analysis results were plotted against an azimuth angle of 90 °.
- the azimuth dispersion plot A ( ⁇ ) of the integrated intensity value of each component reflects the orientation state of each component with respect to the stretching direction of the polarizing film.
- the proportion of signals observed at an azimuth angle of 90 ° is the PVA molecular chain in the stretching direction. Is approximately equal to the ratio of the components.
- the ratio of signals observed at an azimuth angle of 0 ° is approximately equal to the ratio of components in which PVA molecular chains are arranged in a direction perpendicular to the stretching direction. That is, FIG. 5 is approximately equal to the distribution function f ( ⁇ ) of the orientation state of each component.
- the distribution function shows a peak shape with a maximum intensity of 90 °.
- the distribution function f1 ( ⁇ ) of the orientation components of “PVA crystal” and “PVA-boric acid aggregate structure” can be expressed by the Lorentz function
- the peak top position is 90 °
- the peak height is h
- the peak half The value range was a variable parameter.
- the distribution function f1 ( ⁇ ) of the orientation component of “PVA amorphous” can be expressed as a linear sum of two Gaussian functions
- the peak top position is 90 °
- the peak height h of each function The full width at half maximum was a variable parameter.
- the azimuth angle ⁇ was in the range of 80 ° to 100 °, that is, the proportion of highly oriented components was determined as follows. First, in the azimuth angle range of 0 ° to 180 °, an integral value of the distribution function f1 ( ⁇ ) of the orientation component was obtained. This was designated as F1. Next, an integral value in the range of the azimuth angle ⁇ in the orientation component distribution function f1 ( ⁇ ) in the range of 80 ° to 100 ° was calculated, and this was defined as F1a. F1-F1a is an integral value of 0 ° to 80 ° and 100 ° to 180 °, and this is defined as F1b.
- F1b is an orientation component having a small degree of orientation. In the azimuth angle range of 0 ° to 180 °, the integral value F2 of the distribution function f2 ( ⁇ ) of the non-oriented component was calculated. Values of F1a, F1b, and F2 were obtained for “PVA amorphous”, “PVA crystal”, and “PVA-boric acid aggregated structure”, respectively.
- F1a is a high orientation component
- F1b is a low orientation component
- F2 is an amount proportional to the non-alignment component.
- PVA Amorphous “PVA Crystal”, “PVA-Boric Acid Aggregation Structure”, each of the high orientation component, low orientation component, non-orientation component, that is, the presence ratio of 9 components is as follows: It was regarded as the ratio of each component to the total sum of integral values.
- F1a-PVA amorphous F1b-PVA amorphous, F2-PVA amorphous, F1a-PVA crystal, F1b-PVA crystal, F2-PVA crystal, F1a-PVA-boric acid aggregated structure, F1b-PVA-boric acid Aggregation structure, F2-PVA-boric acid aggregation structure.
- the high orientation component F1a-PVA-boric acid aggregate structure of “PVA-boric acid aggregate structure” was found to have a high correlation with the polarization performance of the polarizing film as described above. This is because boric acid interacts and stabilizes the highly oriented and extended PVA chain by stretching to promote the formation and retention of polyiodine ions.
- a highly oriented component of “PVA-boric acid aggregated structure” is defined as structure factor A.
- the highly oriented component F1a-PVA amorphous of “PVA amorphous” has a high correlation with the shrinkage stress of the polarizing film.
- shrinkage stress of polarizing film The shrinkage stress was measured using an autograph AG-X with a thermostatic bath manufactured by Shimadzu Corporation and a video extensometer TR ViewX120S. For the measurement, a polarizing film conditioned at 20 ° C./20% RH for 18 hours was used. After the temperature chamber of Autograph AG-X is set to 20 ° C., a polarizing film (15 cm in the length direction and 1.5 cm in the width direction) is attached to the chuck (chuck interval 5 cm). Heating started. The polarizing film was pulled at a speed of 1 mm / min, and when the tension reached 2N, the tension was stopped, and the tension until 4 hours was measured in that state.
- a polarizing film was produced as follows. First, in the swelling step, the PVA film was uniaxially stretched (first-stage stretch) in the length direction (MD) to twice the original length while being immersed in water at a temperature of 30 ° C. for 1 minute. Subsequently, in the dyeing process, while immersed in an aqueous solution containing 0.06% by mass of iodine and 1.4% by mass of potassium iodide at a temperature of 30 ° C. for 1 minute, the length direction is increased up to 2.4 times the original length. (MD) was uniaxially stretched (second-stage stretching).
- the length is increased to 3 times the original length (MD).
- Uniaxial stretching third stage stretching
- the second cross-linking stretching step up to 7 times the original length while immersed in an aqueous solution at a temperature of 65 ° C. containing 2.8% by weight of boric acid and 5% by weight of potassium iodide.
- Uniaxial stretching fourth stage stretching was performed in the length direction (MD).
- the maximum stretching stress in the second cross-linking stretching process was 5.5 N / mm 2 .
- the film was washed by dipping for 10 seconds in an aqueous solution containing boric acid at a concentration of 1.5% by mass and potassium iodide at a concentration of 5% by mass at a temperature of 22 ° C.
- a polarizing film having a thickness of 13.9 ⁇ m was produced by drying with a dryer at 80 ° C. for 90 seconds.
- FIG. 2 is a graph plotting the degree of polarization with respect to shrinkage stress when the polarizing film obtained in Example 1 and Comparative Examples 1 to 4, 7, and 8 has a single transmittance of 43.5%. As can be seen from FIG. That is, in Comparative Examples 1 to 8, if the degree of polarization is increased when the single transmittance is 43.5%, the shrinkage stress increases.
Abstract
Description
前記ポリビニルアルコールフィルムの厚みが5~100μmであり、
前記ポリビニルアルコールフィルムに含まれるポリビニルアルコールの平均重合度が2500~3500であり、
前記膨潤工程において、10~50℃の水に浸漬して前記ポリビニルアルコールフィルムを膨潤させ、
前記染色工程において、ヨウ素及びヨウ化カリウムを合計で0.5~3質量%含む10~50℃の水溶液に浸漬して、ヨウ素系二色性色素を前記ポリビニルアルコールフィルムに含浸させるとともに、総延伸倍率が2~3倍になるように一軸延伸し、
前記第1架橋延伸工程において、1~5質量%のホウ酸を含む40~55℃の水溶液中で、該工程中の延伸倍率が1.1~1.3倍かつ総延伸倍率が2.5~3.5倍になるように一軸延伸し、
引き続き前記第2架橋延伸工程において、1~5質量%のホウ酸を含む60~70℃の水溶液中で、該工程中の延伸倍率が1.8~3.0倍かつ総延伸倍率が6~8倍になるように一軸延伸することを特徴とする偏光フィルムの製造方法を提供することによって解決される。
単体透過率43.5%のときの偏光度が99.990%以上であり、かつ
広角X線回折測定における構造因子Aの含有率(CA)が3~4.5%であり、構造因子Bの含有率(CB)が2.0~8.5%であり、かつ比(CA/CB)が0.4以上であることを特徴とする偏光フィルムを提供することによっても解決される。
単体透過率が42~45%であり、
偏光度が99.980%以上であり、かつ
広角X線回折測定における構造因子Aの含有率(CA)が3~4.5%であり、構造因子Bの含有率(CB)が2.0~8.5%であり、かつ比(CA/CB)が0.4以上であることを特徴とする偏光フィルムを提供することによっても解決される。
T’=T/(1-0.04)2 (1)
R={-ln[T’(1-V)]}/{-ln[T’(1+V)]} (2)
T’=[1-V]1/(R-1)/[1+V]R/(R-1) (3)
以下の実施例及び比較例で得られた偏光フィルムの幅方向の中央部から、偏光フィルムの長手方向に3cm、その垂直方向に1.5cmの長方形のサンプルを採取し、積分球付き分光光度計(日本分光株式会社製「V7100」)を用いて、JIS Z 8722(物体色の測定方法)に準拠し、視感度補正を行った上で、単体透過率(T)および偏光度(V)を計測した。
T’=T/(1-0.04)2 (1)
R={-ln[T’(1-V)]}/{-ln[T’(1+V)]} (2)
T’=[1-V]1/(R-1)/[1+V]R/(R-1) (3)
広角X線回折(Wide Angle X-ray Diffraction : WAXD)測定は、Bruker AXS製のD8 Discover装置を使用して実施した。入射X線波長は0.154nm(Cuターゲット)とした。検出器には位置敏感型2次元ガス検出器のHi-STARを使用し、カメラ距離(試料と検出器間の距離)はおよそ150mmに設定した。X線発生装置のフィラメント電流を110mA、電圧を45kVとし、コリメータ径は0.5mmのものを使用した。
取得したWAXDの2次元写真を、GADDS(General Area Detector Diffraction System)ソフトウェアを使用して、2θに対するX線強度I(2θ)の1次元プロファイルへと変換した。2θ範囲を5°から35°とした。サンプリングのステップは0.05°間隔とした。方位角方向と一致するφ軸範囲は、-5°から5°、5°から15°、15°から25°、25°から35°、35°から45°、45°から55°、55°から65°、65°から75°、75°から85°、85°から95°、95°から105°、105°から115°、115°から125°、125°から135°、135°から145°、145°から155°、155°から165°、165°から175°、175°から185°のように、方位角方向に10°の方位角範囲にて分割してそれぞれI(2θ)プロファイルを得た。偏光フィルムの延伸方向が0°、その垂直方向が90°に対応している。同操作をバックグラウンド散乱データ(偏光フィルムを取り付けずに同条件にて測定したデータ)にも適用した。
(b)2θにおいておよそ17°から21°の範囲における信号は「PVA非晶」と「PVA結晶」から生ずる散乱および回折であり、とくに「PVA結晶」の寄与が大きい。結晶による回折ピーク位置は既知であり、そこでガウス関数Bのピークトップ位置xは固定する。
(c)2θにおいておよそ20°から23°の範囲における信号は「PVA非晶」と「PVA-ホウ酸凝集構造」から生ずる散乱および回折である。とくに「PVA-ホウ酸凝集構造」の寄与が大きい。そこでガウス関数Cのピークトップ位置xを固定する。
(d)「PVA結晶」と「PVA-ホウ酸凝集構造」を適切に分離するために、ガウス関数Bとガウス関数Cのピークの幅は同じ値とする。なぜなら、どのような偏光フィルムを測定しても、17°から21°と20°から23°における回折強度はおよそ等しく、「PVA結晶」による回折ピークと「PVA-ホウ酸凝集構造」による回折ピークの形状には大きな違いがないと見込まれるからである。
(e)上記(a)~(d)を踏まえ、すべての補正したI(2θ)プロファイルを3つのガウス関数の和であるcalculated-I(2θ)プロファイルが良好に再現するような、3つのガウス関数それぞれのピークトップ位置x、ピークの幅σの最適値を探索した。その結果、ガウス関数Aに対してはx=20.0とσ=4.0を、ガウス関数Bに対してはx=19.7とσ=1.3を、ガウス関数Cに対してはx=22.0とσ=1.3を採用したときに、すべての補正したI(2θ)プロファイルを矛盾なく良好に波形分離できることがわかった。ピークトップ位置xとピークの幅σは上述の最適値に固定する。
(f)すべての補正したI(2θ)プロファイルに対して、3つのガウス関数のピーク高さhのみを可変パラメータとして最小自乗フィッティングした。フィッティング範囲は、6.5°から30.5°とした。
収縮応力は島津製作所製の恒温槽付きオートグラフAG-Xとビデオ式伸び計TR ViewX120Sを用いて測定した。測定には20℃/20%RHで18時間調湿した偏光フィルムを使用した。オートグラフAG-Xの恒温槽を20℃にした後、偏光フィルム(長さ方向15cm、幅方向1.5cm)をチャック(チャック間隔5cm)に取り付け、引張り開始と同時に、80℃へ恒温槽の昇温を開始した。偏光フィルムを1mm/minの速さで引張り、張力が2Nに到達した時点で引張りを停止し、その状態で4時間後までの張力を測定した。このとき、熱膨張によってチャック間の距離が変わるため、チャックに標線シールを貼り、ビデオ式伸び計TR ViewX120Sを用いてチャックに貼り付けた標線シールが動いた分だけチャック間の距離を修正できるようにして測定を行った。なお、4時間後の張力の測定値から初期張力2Nを差し引いた値を偏光フィルムの収縮力とし、その値をサンプル断面積で除した値を収縮応力(N/mm2)と定義した。
第2架橋延伸工程における最大延伸応力は、第2架橋延伸工程において隣接するロール間にかかる延伸張力を、その間に設置したテンションロールによって計測し、原料のPVAフィルムの断面積で割った値である。3本以上のロールを用いるときには、その中の最大の引張力を採用する。
PVA(酢酸ビニル重合体のけん化物、重合度3000、けん化度99.9モル%)100質量部、可塑剤としてグリセリン10質量部、界面活性剤としてポリオキシエチレンラウリルエーテル硫酸ナトリウム:0.1質量部および水からなる製膜原液を用いてキャスト製膜することにより、厚み45μmのPVAフィルムのロールを得た。このPVAフィルムに対して、膨潤工程、染色工程、第1架橋延伸工程、第2架橋延伸工程、洗浄工程および乾燥工程を、順次行うことにより偏光フィルムを製造した。偏光フィルム製造装置の模式図を図1に示す。
PVAフィルムの厚さと重合度、第1架橋延伸工程におけるホウ酸水溶液の温度、第1架橋延伸工程後の総延伸倍率、第2架橋延伸工程におけるホウ酸水溶液の温度、第2架橋延伸工程後の総延伸倍率を表1に示すように変更したこと以外は、実施例1と同様にして偏光フィルムを製造した。第2架橋延伸工程における最大延伸応力の値を表1に示す。
2 PVAフィルムロール
3 膨潤工程
4 染色工程
5 第1架橋延伸工程
6 第2架橋延伸工程
7 洗浄工程
8 乾燥工程
9 偏光フィルムロール
Claims (8)
- ポリビニルアルコールフィルムに対し、少なくとも膨潤工程、染色工程、第1架橋延伸工程、第2架橋延伸工程をこの順番に施す偏光フィルムの製造方法であって、
前記ポリビニルアルコールフィルムの厚みが5~100μmであり、
前記ポリビニルアルコールフィルムに含まれるポリビニルアルコールの平均重合度が2500~3500であり、
前記膨潤工程において、10~50℃の水に浸漬して前記ポリビニルアルコールフィルムを膨潤させ、
前記染色工程において、ヨウ素及びヨウ化カリウムを合計で0.5~3質量%含む10~50℃の水溶液に浸漬して、ヨウ素系二色性色素を前記ポリビニルアルコールフィルムに含浸させるとともに、総延伸倍率が2~3倍になるように一軸延伸し、
前記第1架橋延伸工程において、1~5質量%のホウ酸を含む40~55℃の水溶液中で、該工程中の延伸倍率が1.1~1.3倍かつ総延伸倍率が2.5~3.5倍になるように一軸延伸し、
引き続き前記第2架橋延伸工程において、1~5質量%のホウ酸を含む60~70℃の水溶液中で、該工程中の延伸倍率が1.8~3.0倍かつ総延伸倍率が6~8倍になるように一軸延伸することを特徴とする偏光フィルムの製造方法。 - 前記第2架橋延伸工程において、最大延伸応力が15N/mm2以下である請求項1に記載の偏光フィルムの製造方法。
- 単体透過率が42~45%であり、かつ偏光度が99.980%以上である偏光フィルムを得る、請求項1または2に記載の偏光フィルムの製造方法。
- 収縮応力が45N/mm2以下である偏光フィルムを得る、請求項1~3のいずれかに記載の偏光フィルムの製造方法。
- ヨウ素系二色性色素を含むポリビニルアルコールフィルムからなる偏光フィルムであって、
単体透過率43.5%のときの偏光度が99.990%以上であり、かつ
広角X線回折測定における構造因子Aの含有率(CA)が3~4.5%であり、構造因子Bの含有率(CB)が2.0~8.5%であり、かつ比(CA/CB)が0.4以上であることを特徴とする偏光フィルム。
ここで、構造因子Aはポリビニルアルコール-ホウ素凝集構造に由来する高配向性の構造因子であり、構造因子Bは非晶ポリビニルアルコールに由来する高配向性の構造因子である。 - ヨウ素系二色性色素を含むポリビニルアルコールフィルムからなる偏光フィルムであって、
単体透過率が42~45%であり、
偏光度が99.980%以上であり、かつ
広角X線回折測定における構造因子Aの含有率(CA)が3~4.5%であり、構造因子Bの含有率(CB)が2.0~8.5%であり、かつ比(CA/CB)が0.4以上であることを特徴とする偏光フィルム。
ここで、構造因子Aはポリビニルアルコール-ホウ素凝集構造に由来する高配向性の構造因子であり、構造因子Bは非晶ポリビニルアルコールに由来する高配向性の構造因子である。 - 前記偏光フィルムに含まれるポリビニルアルコールの重合度が2500~3500である、請求項5又は6に記載の偏光フィルム。
- 収縮応力が45N/mm2以下である、請求項5~7のいずれかに記載の偏光フィルム。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202410011707.6A CN117724199A (zh) | 2016-02-09 | 2017-02-08 | 偏振膜和其制造方法 |
CN201780010637.0A CN108603974B (zh) | 2016-02-09 | 2017-02-08 | 偏振膜和其制造方法 |
JP2017566971A JP6776275B2 (ja) | 2016-02-09 | 2017-02-08 | 偏光フィルムの製造方法 |
KR1020187025557A KR102163827B1 (ko) | 2016-02-09 | 2017-02-08 | 편광 필름 및 그 제조 방법 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016-023113 | 2016-02-09 | ||
JP2016023113 | 2016-02-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017138551A1 true WO2017138551A1 (ja) | 2017-08-17 |
Family
ID=59564044
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2017/004511 WO2017138551A1 (ja) | 2016-02-09 | 2017-02-08 | 偏光フィルム及びその製造方法 |
Country Status (5)
Country | Link |
---|---|
JP (2) | JP6776275B2 (ja) |
KR (1) | KR102163827B1 (ja) |
CN (2) | CN117724199A (ja) |
TW (1) | TWI671555B (ja) |
WO (1) | WO2017138551A1 (ja) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019086757A (ja) * | 2017-11-01 | 2019-06-06 | 住友化学株式会社 | 偏光フィルムの製造装置 |
JP2019086543A (ja) * | 2017-11-01 | 2019-06-06 | 住友化学株式会社 | 偏光フィルムの製造装置及び偏光フィルムの製造方法 |
JPWO2021095526A1 (ja) * | 2019-11-11 | 2021-05-20 | ||
WO2021095527A1 (ja) * | 2019-11-11 | 2021-05-20 | 日東電工株式会社 | 偏光膜、偏光板および画像表示装置 |
KR20210074319A (ko) | 2018-12-26 | 2021-06-21 | 후지필름 가부시키가이샤 | 적층체 |
JP2021121862A (ja) * | 2019-02-04 | 2021-08-26 | 住友化学株式会社 | 偏光板および表示装置 |
JPWO2020184083A1 (ja) * | 2019-03-08 | 2021-11-25 | 日東電工株式会社 | 偏光膜、偏光板、および該偏光膜の製造方法 |
WO2022113958A1 (ja) * | 2020-11-26 | 2022-06-02 | 株式会社クラレ | 偏光フィルムの製造方法及び偏光フィルム |
WO2023277025A1 (ja) * | 2021-06-29 | 2023-01-05 | 株式会社クラレ | 偏光板、及びそれからなる熱成形体、並びに熱成形体の製造方法 |
KR20230073227A (ko) | 2020-09-30 | 2023-05-25 | 주식회사 쿠라레 | 편광 필름의 제조 방법 |
WO2024004974A1 (ja) * | 2022-06-28 | 2024-01-04 | 株式会社クラレ | 偏光板、熱成形体および熱成形体の製造方法 |
JP7475403B2 (ja) | 2021-09-13 | 2024-04-26 | 住友化学株式会社 | 偏光フィルム及び偏光板 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7284716B2 (ja) * | 2018-01-25 | 2023-05-31 | 株式会社クラレ | 偏光フィルム及びその製造方法 |
TW202104418A (zh) * | 2019-05-09 | 2021-02-01 | 日商可樂麗股份有限公司 | 偏光薄膜及其製造方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006126722A (ja) * | 2004-11-01 | 2006-05-18 | Nitto Denko Corp | 光学フィルムの製造方法、及びそれに用いる製造装置 |
JP2013105036A (ja) * | 2011-11-14 | 2013-05-30 | Nitto Denko Corp | 偏光子の製造方法、偏光子、偏光板、光学フィルムおよび画像表示装置 |
JP2013140324A (ja) * | 2011-12-06 | 2013-07-18 | Nitto Denko Corp | 偏光子の製造方法および偏光板の製造方法 |
WO2014050697A1 (ja) * | 2012-09-26 | 2014-04-03 | 株式会社クラレ | ポリビニルアルコールフィルムおよび偏光フィルム |
JP2016022690A (ja) * | 2014-07-23 | 2016-02-08 | 日東電工株式会社 | 積層体の製造方法 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4229932B2 (ja) | 2004-07-28 | 2009-02-25 | 日東電工株式会社 | 偏光フィルムの製造方法 |
JP4458483B2 (ja) | 2005-03-22 | 2010-04-28 | 日東電工株式会社 | 偏光フィルムの製造方法、偏光フィルム、偏光板及び画像表示装置 |
JP5350368B2 (ja) * | 2008-12-18 | 2013-11-27 | 株式会社クラレ | 偏光フィルムの製造法 |
JP2012003173A (ja) * | 2010-06-21 | 2012-01-05 | Sumitomo Chemical Co Ltd | 偏光フィルム及び偏光板の製造方法 |
JP4691205B1 (ja) * | 2010-09-03 | 2011-06-01 | 日東電工株式会社 | 薄型高機能偏光膜を含む光学フィルム積層体の製造方法 |
JP5667016B2 (ja) * | 2010-09-03 | 2015-02-12 | 日東電工株式会社 | 薄型偏光膜、薄型偏光膜を有する光学積層体、および薄型偏光膜の製造方法 |
JP5701679B2 (ja) * | 2010-09-03 | 2015-04-15 | 日東電工株式会社 | 矩形形状のパネルに偏光膜を有する光学フィルムを順次的に貼り付ける方法及び装置 |
JP5651089B2 (ja) * | 2011-09-09 | 2015-01-07 | 日本化薬株式会社 | 偏光素子、および、偏光板 |
JP6191197B2 (ja) | 2013-03-29 | 2017-09-06 | 住友化学株式会社 | 偏光フィルムの製造方法 |
JP6122337B2 (ja) * | 2013-04-26 | 2017-04-26 | 日東電工株式会社 | 偏光フィルムおよびその製造方法、光学フィルムおよび画像表示装置 |
KR101400132B1 (ko) * | 2013-10-07 | 2014-05-30 | 동우 화인켐 주식회사 | 편광자의 제조 방법 |
CN105917256B (zh) * | 2014-01-28 | 2019-01-15 | 株式会社可乐丽 | 光学膜制造用初始膜 |
-
2017
- 2017-02-08 JP JP2017566971A patent/JP6776275B2/ja active Active
- 2017-02-08 KR KR1020187025557A patent/KR102163827B1/ko active IP Right Grant
- 2017-02-08 CN CN202410011707.6A patent/CN117724199A/zh active Pending
- 2017-02-08 WO PCT/JP2017/004511 patent/WO2017138551A1/ja active Application Filing
- 2017-02-08 CN CN201780010637.0A patent/CN108603974B/zh active Active
- 2017-02-09 TW TW106104206A patent/TWI671555B/zh active
-
2020
- 2020-10-07 JP JP2020169707A patent/JP7284740B2/ja active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006126722A (ja) * | 2004-11-01 | 2006-05-18 | Nitto Denko Corp | 光学フィルムの製造方法、及びそれに用いる製造装置 |
JP2013105036A (ja) * | 2011-11-14 | 2013-05-30 | Nitto Denko Corp | 偏光子の製造方法、偏光子、偏光板、光学フィルムおよび画像表示装置 |
JP2013140324A (ja) * | 2011-12-06 | 2013-07-18 | Nitto Denko Corp | 偏光子の製造方法および偏光板の製造方法 |
WO2014050697A1 (ja) * | 2012-09-26 | 2014-04-03 | 株式会社クラレ | ポリビニルアルコールフィルムおよび偏光フィルム |
JP2016022690A (ja) * | 2014-07-23 | 2016-02-08 | 日東電工株式会社 | 積層体の製造方法 |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019086543A (ja) * | 2017-11-01 | 2019-06-06 | 住友化学株式会社 | 偏光フィルムの製造装置及び偏光フィルムの製造方法 |
JP7120814B2 (ja) | 2017-11-01 | 2022-08-17 | 住友化学株式会社 | 偏光フィルムの製造装置 |
JP7082472B2 (ja) | 2017-11-01 | 2022-06-08 | 住友化学株式会社 | 偏光フィルムの製造装置及び偏光フィルムの製造方法 |
JP2019086757A (ja) * | 2017-11-01 | 2019-06-06 | 住友化学株式会社 | 偏光フィルムの製造装置 |
KR20210074319A (ko) | 2018-12-26 | 2021-06-21 | 후지필름 가부시키가이샤 | 적층체 |
JP2021121862A (ja) * | 2019-02-04 | 2021-08-26 | 住友化学株式会社 | 偏光板および表示装置 |
JPWO2020184083A1 (ja) * | 2019-03-08 | 2021-11-25 | 日東電工株式会社 | 偏光膜、偏光板、および該偏光膜の製造方法 |
JP7267396B2 (ja) | 2019-03-08 | 2023-05-01 | 日東電工株式会社 | 偏光膜、偏光板、および該偏光膜の製造方法 |
JPWO2021095527A1 (ja) * | 2019-11-11 | 2021-05-20 | ||
WO2021095527A1 (ja) * | 2019-11-11 | 2021-05-20 | 日東電工株式会社 | 偏光膜、偏光板および画像表示装置 |
WO2021095526A1 (ja) * | 2019-11-11 | 2021-05-20 | 日東電工株式会社 | 偏光膜、偏光板および画像表示装置 |
CN114730034A (zh) * | 2019-11-11 | 2022-07-08 | 日东电工株式会社 | 偏光膜、偏光板和图像显示装置 |
JPWO2021095526A1 (ja) * | 2019-11-11 | 2021-05-20 | ||
KR20230073227A (ko) | 2020-09-30 | 2023-05-25 | 주식회사 쿠라레 | 편광 필름의 제조 방법 |
WO2022113958A1 (ja) * | 2020-11-26 | 2022-06-02 | 株式会社クラレ | 偏光フィルムの製造方法及び偏光フィルム |
KR20230109718A (ko) | 2020-11-26 | 2023-07-20 | 주식회사 쿠라레 | 편광 필름의 제조 방법 및 편광 필름 |
WO2023277025A1 (ja) * | 2021-06-29 | 2023-01-05 | 株式会社クラレ | 偏光板、及びそれからなる熱成形体、並びに熱成形体の製造方法 |
JP7475403B2 (ja) | 2021-09-13 | 2024-04-26 | 住友化学株式会社 | 偏光フィルム及び偏光板 |
WO2024004974A1 (ja) * | 2022-06-28 | 2024-01-04 | 株式会社クラレ | 偏光板、熱成形体および熱成形体の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
CN108603974B (zh) | 2024-01-16 |
JP7284740B2 (ja) | 2023-05-31 |
JPWO2017138551A1 (ja) | 2018-09-06 |
KR20180111922A (ko) | 2018-10-11 |
JP6776275B2 (ja) | 2020-10-28 |
TWI671555B (zh) | 2019-09-11 |
JP2021012385A (ja) | 2021-02-04 |
KR102163827B1 (ko) | 2020-10-12 |
CN117724199A (zh) | 2024-03-19 |
CN108603974A (zh) | 2018-09-28 |
TW201800781A (zh) | 2018-01-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7284740B2 (ja) | 偏光フィルム | |
JP2017142347A (ja) | 収縮応力の小さい偏光フィルム及びその製造方法 | |
JP5524501B2 (ja) | 偏光子、その製造方法、偏光板、光学フィルムおよび画像表示装置 | |
JP6434309B2 (ja) | 積層体、偏光フィルムおよび偏光フィルムの製造方法 | |
TWI735449B (zh) | 偏光膜製造用聚乙烯醇系樹脂及其製造方法、聚乙烯醇系薄膜及其製造方法、及偏光膜 | |
JP2007137042A (ja) | ポリビニルアルコール系フィルム、およびそれを用いた偏光膜、偏光板 | |
JP6472381B2 (ja) | 光学フィルム製造用原反フィルム | |
JP6655544B2 (ja) | 偏光フィルム | |
KR20160146540A (ko) | 편광 필름 및 그것을 포함하는 편광판 | |
JP6687611B2 (ja) | 偏光板、表示装置および有機エレクトロルミネッセンス表示装置 | |
JP6564702B2 (ja) | 偏光フィルム | |
JP6858499B2 (ja) | 光学フィルムの製造方法 | |
JP4756111B2 (ja) | ポリビニルアルコール系フィルムの製造方法 | |
JP2016126021A (ja) | 偏光フィルムの製造方法 | |
JP6456235B2 (ja) | 偏光フィルムの検査方法 | |
CN109917506B (zh) | 偏振膜 | |
JP5956276B2 (ja) | 偏光フィルムの製造方法 | |
WO2022113958A1 (ja) | 偏光フィルムの製造方法及び偏光フィルム | |
JP2017015415A (ja) | ポリビニルアルコールフィルムの光学斑の評価方法 | |
JP6571955B2 (ja) | ポリビニルアルコールフィルム |
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: 17750272 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2017566971 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20187025557 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020187025557 Country of ref document: KR |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 17750272 Country of ref document: EP Kind code of ref document: A1 |