WO2016190235A1 - Polyvinyl alcohol polymer film and method for producing same - Google Patents
Polyvinyl alcohol polymer film and method for producing same Download PDFInfo
- Publication number
- WO2016190235A1 WO2016190235A1 PCT/JP2016/064993 JP2016064993W WO2016190235A1 WO 2016190235 A1 WO2016190235 A1 WO 2016190235A1 JP 2016064993 W JP2016064993 W JP 2016064993W WO 2016190235 A1 WO2016190235 A1 WO 2016190235A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- pva
- drying
- drying roll
- roll
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims description 180
- 238000001035 drying Methods 0.000 claims abstract description 166
- 238000007599 discharging Methods 0.000 claims abstract description 6
- 239000010408 film Substances 0.000 claims description 307
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 169
- 238000000034 method Methods 0.000 claims description 41
- 239000011550 stock solution Substances 0.000 claims description 38
- 239000012788 optical film Substances 0.000 claims description 27
- 230000002093 peripheral effect Effects 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 description 34
- 230000007547 defect Effects 0.000 description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 21
- 230000003287 optical effect Effects 0.000 description 21
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 238000011282 treatment Methods 0.000 description 17
- -1 ethylene, propylene, 1-butene Chemical class 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 11
- 238000004043 dyeing Methods 0.000 description 10
- 238000007127 saponification reaction Methods 0.000 description 10
- 239000000975 dye Substances 0.000 description 9
- 235000011187 glycerol Nutrition 0.000 description 8
- 239000002356 single layer Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- AOMUHOFOVNGZAN-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CCO)CCO AOMUHOFOVNGZAN-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 239000004327 boric acid Substances 0.000 description 6
- 229940031957 lauric acid diethanolamide Drugs 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229920002689 polyvinyl acetate Polymers 0.000 description 5
- 239000011118 polyvinyl acetate Substances 0.000 description 5
- 229920001567 vinyl ester resin Polymers 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-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
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229940105990 diglycerin Drugs 0.000 description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 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
- 238000011156 evaluation Methods 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920001290 polyvinyl ester Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000758 substrate 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
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- LPMBTLLQQJBUOO-KTKRTIGZSA-N (z)-n,n-bis(2-hydroxyethyl)octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)N(CCO)CCO LPMBTLLQQJBUOO-KTKRTIGZSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-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
- FVSAFCHCUDOKSI-UHFFFAOYSA-N 2-methylprop-2-enamide;propane-1-sulfonic acid Chemical compound CC(=C)C(N)=O.CCCS(O)(=O)=O FVSAFCHCUDOKSI-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000694440 Colpidium aqueous Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-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
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229920006197 POE laurate Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 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
- 230000005856 abnormality Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- FWZUNOYOVVKUNF-UHFFFAOYSA-N allyl acetate Chemical group CC(=O)OCC=C FWZUNOYOVVKUNF-UHFFFAOYSA-N 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920001727 cellulose butyrate Polymers 0.000 description 1
- OHMJKMNGYYWCHB-UHFFFAOYSA-N chembl1368261 Chemical compound OS(=O)(=O)C1=CC(S(O)(=O)=O)=C(N)C2=C(O)C(N=NC3=CC=C(C=C3OC)C=3C=C(C(=CC=3)N=NC=3C(=C4C(N)=C(C=C(C4=CC=3)S(O)(=O)=O)S(O)(=O)=O)O)OC)=CC=C21 OHMJKMNGYYWCHB-UHFFFAOYSA-N 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- DSARWKALPGYFTA-UHFFFAOYSA-L disodium 4-hydroxy-7-[(5-hydroxy-6-phenyldiazenyl-7-sulfonatonaphthalen-2-yl)carbamoylamino]-3-phenyldiazenylnaphthalene-2-sulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(NC(=O)NC=3C=C4C=C(C(N=NC=5C=CC=CC=5)=C(O)C4=CC=3)S([O-])(=O)=O)=CC=C2C(O)=C1N=NC1=CC=CC=C1 DSARWKALPGYFTA-UHFFFAOYSA-L 0.000 description 1
- DDLNJHAAABRHFY-UHFFFAOYSA-L disodium 8-amino-7-[[4-[4-[(4-oxidophenyl)diazenyl]phenyl]phenyl]diazenyl]-2-phenyldiazenyl-3,6-disulfonaphthalen-1-olate Chemical compound [Na+].[Na+].NC1=C(C(=CC2=CC(=C(C(=C12)O)N=NC1=CC=CC=C1)S(=O)(=O)[O-])S(=O)(=O)[O-])N=NC1=CC=C(C=C1)C1=CC=C(C=C1)N=NC1=CC=C(C=C1)O DDLNJHAAABRHFY-UHFFFAOYSA-L 0.000 description 1
- NJDNXYGOVLYJHP-UHFFFAOYSA-L disodium;2-(3-oxido-6-oxoxanthen-9-yl)benzoate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=CC(=O)C=C2OC2=CC([O-])=CC=C21 NJDNXYGOVLYJHP-UHFFFAOYSA-L 0.000 description 1
- VTEBSADXXKSKOE-UHFFFAOYSA-L disodium;4-[[2,4-diamino-5-[[3-[[2,4-diamino-5-[(4-sulfonatophenyl)diazenyl]phenyl]diazenyl]phenyl]diazenyl]phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].[Na+].NC1=CC(N)=C(N=NC=2C=C(C=CC=2)N=NC=2C(=CC(N)=C(N=NC=3C=CC(=CC=3)S([O-])(=O)=O)C=2)N)C=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 VTEBSADXXKSKOE-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical class NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 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
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229940077844 iodine / potassium iodide Drugs 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 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
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 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
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- YMDZGJOTVBKZQK-UHFFFAOYSA-N n,n-dimethylpropan-1-amine;2-methylprop-2-enamide Chemical compound CCCN(C)C.CC(=C)C(N)=O YMDZGJOTVBKZQK-UHFFFAOYSA-N 0.000 description 1
- QQGJWWNPACORPU-UHFFFAOYSA-N n,n-dimethylpropan-1-amine;prop-2-enamide Chemical compound NC(=O)C=C.CCCN(C)C QQGJWWNPACORPU-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- UZZYXUGECOQHPU-UHFFFAOYSA-M n-octyl sulfate Chemical compound CCCCCCCCOS([O-])(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-M 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- 229940067739 octyl sulfate Drugs 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol 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
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- BQHRKYUXVHKLLZ-UHFFFAOYSA-M sodium 7-amino-2-[[4-[(4-aminophenyl)diazenyl]-2-methoxy-5-methylphenyl]diazenyl]-3-sulfonaphthalen-1-olate Chemical compound [Na+].COc1cc(N=Nc2ccc(N)cc2)c(C)cc1N=Nc1c(O)c2cc(N)ccc2cc1S([O-])(=O)=O BQHRKYUXVHKLLZ-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- UZZYXUGECOQHPU-UHFFFAOYSA-N sulfuric acid monooctyl ester Natural products CCCCCCCCOS(O)(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-N 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 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
- 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
- VRVDFJOCCWSFLI-UHFFFAOYSA-K trisodium 3-[[4-[(6-anilino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-5-methoxy-2-methylphenyl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].COc1cc(N=Nc2cc(c3cccc(c3c2)S([O-])(=O)=O)S([O-])(=O)=O)c(C)cc1N=Nc1c(O)c2ccc(Nc3ccccc3)cc2cc1S([O-])(=O)=O VRVDFJOCCWSFLI-UHFFFAOYSA-K 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
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
- B29C41/26—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on a rotating drum
-
- 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
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
- B29C41/52—Measuring, controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- 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
- B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
- B29K2029/14—Polyvinylacetals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/008—Wide strips, e.g. films, webs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2011/00—Optical elements, e.g. lenses, prisms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Definitions
- the present invention is a thin polyvinyl alcohol polymer film capable of producing an optical film such as a polarizing film with few optical defects (hereinafter, “polyvinyl alcohol polymer” may be abbreviated as “PVA”). And a manufacturing method thereof, an optical film such as a polarizing film manufactured from the PVA film, and a manufacturing method of the optical film.
- PVA polyvinyl alcohol polymer
- a polarizing plate having a light transmission and shielding function is one of important components of a liquid crystal display (LCD) together with a liquid crystal having a light switching function.
- LCDs are used in a wide range of 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, tablet terminals, and measuring instruments used indoors and outdoors. It has become. Of these LCD application fields, LCD TVs and LCD monitors are becoming thinner in addition to larger screens. In recent years, tablet terminals, which have been widely used, are becoming thinner. As a means for achieving LCD thinning, it is possible to reduce the thickness of the glass used in the LCD. From the viewpoint of solving the problem of warping of the glass due to the shrinkage stress of the polarizing plate, the polarizing plate is also used. Thinning is required.
- a polarizing plate is generally produced by dyeing and uniaxially stretching a PVA film to produce a polarizing film, and then bonding a protective film such as a cellulose triacetate (TAC) film on the surface of the polarizing film. Therefore, in order to achieve thinning of the polarizing plate, it is required to produce a thin polarizing film using a thinner PVA film, and the specific thickness of the PVA film is 55 ⁇ m or less, further 30 ⁇ m or less. It is requested to do.
- TAC cellulose triacetate
- Patent Document 1 describes that a PVA film having a thickness of about 75 ⁇ m and a thickness spot of about 1.6 to 3.0 ⁇ m was manufactured by the method.
- an object of the present invention is to provide a thin PVA film capable of producing an optical film such as a polarizing film with few optical defects. Moreover, an object of this invention is to provide the optical film with few optical defects manufactured from the said PVA film.
- the number of broken line streaks in the PVA film is set to a specific value or less.
- a film-forming apparatus provided with a plurality of drying rolls whose rotation axes are parallel to each other is used, and a film-forming stock solution containing PVA is formed on the first drying roll located on the most upstream side of the film-forming apparatus.
- the present invention [1] A PVA film having a thickness of 55 ⁇ m or less, and a broken line streak arranged in an approximately straight line in the flow direction of the film with a period of 0.01 to 10 mm over a length of 10 cm or more per 1 m in the width direction of the film 5 or less PVA films; [2] The PVA film of the above [1], having a width of 2 m or more; [3] A method for producing a PVA film having a thickness of 55 ⁇ m or less, wherein a film forming apparatus including a plurality of drying rolls having rotation axes parallel to each other is used, and PVA is included on the first drying roll of the film forming apparatus.
- the film-forming stock solution discharge rate (S 0 ) is set to 2. 5 to 5.0 m / min of production method; [4] The method according to [3] above, wherein the ratio (S 1 / S 0 ) of the peripheral speed (S 1 ) of the first drying roll to the discharge speed (S 0 ) of the film-forming stock solution is 7 or less; [5] The production method of the above [3] or [4], which is a production method of a PVA film having a width of 2 m or more; [6] An optical film produced from the PVA film of [1] or [2] above; [7] The optical film according to [6], which is a polarizing film; [8] A method for producing an optical film, comprising the step of uniaxially stretching using the PVA film of [1] or [2] above; [9] The production method
- a thin PVA film capable of producing an optical film such as a polarizing film with few optical defects, a method for producing the thin PVA film, an optical film with few optical defects produced from the PVA film, and the optical A method of manufacturing a film is provided.
- the PVA film of the present invention has a thickness of 55 ⁇ m or less, and a broken line streak arranged in a direction of 0.01 to 10 mm in a substantially straight line in the flow direction of the film over 10 cm or more in the width direction of the film. No more than 5 per meter.
- the broken line streak that defines the number of the lines is formed by arranging irregularities approximately linearly in the flow direction of the film over 10 cm or more with a period of 0.01 to 10 mm as described above.
- a broken line streak occurs along the flow direction of the film, and the length of one broken line far exceeds 10 cm.
- the length is less than 10 cm, and it is difficult to call a broken line streak.
- those having a length of 10 cm or more are handled as broken lines.
- the protrusions protruding from the film surface are arranged to form unevenness as a result; the recesses recessed from the film surface are arranged, and as a result What forms the unevenness
- the above-mentioned broken line streaks are formed by arranging irregularities with a period of 0.01 to 10 mm substantially linearly in the direction of film flow over 10 cm or more.
- the period means the length of the film in the flow direction of one set of unevenness (a set of one concave portion and one convex portion adjacent to each other).
- the period is in the range of 0.01 to 10 mm.
- the period may be in the range of 0.1 to 5 mm, for example, and may be in the range of 0.2 to 1 mm.
- the difference in thickness between the highest height and the lowest height is often in the range of 1 to 500 nm.
- it may be within the range of 10 to 300 nm, further within the range of 20 to 100 nm, and particularly within the range of 30 to 90 nm.
- the number of the broken line streaks is measured over the entire width direction on the straight line in the width direction passing through an arbitrary position in the flow direction.
- the number can be obtained as the number per 1 m width.
- the presence of the broken line streaks can be confirmed by, for example, a scanning white interference microscope.
- the number of broken lines can be obtained by the method described later in the embodiment.
- the number of the broken line streaks in the width direction per 1 m of the film needs to be 5 or less, preferably 3 or less, and more preferably 2 or less. Preferably, it may be 1.5 or less, and even 1 or less.
- the number of broken lines is within the above range, an optical film with few optical defects can be easily obtained.
- the number of broken lines is preferably 0.05 or more per 1 m in the width direction, more preferably 0.10 or more, still more preferably 0.15 or more, and 0.20 The above is most preferable.
- PVA forming the PVA film examples include PVA (unmodified PVA) obtained by saponifying polyvinyl ester obtained by polymerizing vinyl ester, modified PVA obtained by graft copolymerization with a comonomer on the main chain of PVA, vinyl A so-called polyvinyl acetal resin in which a part of hydroxyl groups of modified PVA, unmodified PVA or modified PVA produced by saponifying a modified polyvinyl ester obtained by copolymerization of an ester and a comonomer is crosslinked with aldehydes such as formalin, butyraldehyde, and benzaldehyde And so on.
- the amount of modification in the PVA is preferably 15 mol% or less, and more preferably 5 mol% or less.
- vinyl ester used in the production of PVA examples include vinyl acetate, vinyl formate, vinyl laurate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatate, vinyl stearate, vinyl benzoate and the like. Can be mentioned. These vinyl esters can be used alone or in combination. Of these vinyl esters, vinyl acetate is preferred from the viewpoint of productivity.
- Examples of the comonomer described above include olefins having 2 to 30 carbon atoms such as ethylene, propylene, 1-butene and isobutene (such as ⁇ -olefin); acrylic acid or a salt thereof; methyl acrylate, ethyl acrylate, Acrylic esters such as n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, etc.
- olefins having 2 to 30 carbon atoms such as ethylene, propylene, 1-butene and isobutene (such as ⁇ -olefin); acrylic acid or a salt thereof; methyl acrylate, ethyl acrylate, Acrylic esters such as n-propyl acrylate,
- acrylic acid having 1 to 18 carbon atoms of acrylic acid methacrylic acid or a salt thereof; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i -Butyl, t-butyl methacrylate, Methacrylic acid esters such as 2-ethylhexyl crylate, dodecyl methacrylate, octadecyl methacrylate (for example, alkyl esters of 1 to 18 carbon atoms of methacrylic acid); acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N Acrylamide derivatives such as dimethyl acrylamide, diacetone acrylamide, acrylamide propane sulfonic acid or salts thereof, acrylamide propyl dimethylamine or salts thereof, N-methylol acrylamide or derivatives thereof; methacrylamide, N
- the average degree of polymerization of PVA is preferably 1,000 or more, more preferably 1,500 or more, and still more preferably 2,000 or more, from the viewpoint of polarization performance and durability of the polarizing film to be obtained.
- the average degree of polymerization is preferably 8,000 or less, particularly preferably 6,000 or less, from the viewpoint of easy production of a homogeneous PVA film and stretchability.
- the “average degree of polymerization” of PVA in the present specification refers to the average degree of polymerization measured according to JIS K6726-1994, and is the limit measured in water at 30 ° C. after re-saponifying and purifying PVA. Determined from viscosity.
- the saponification degree of PVA is preferably 95.0 mol% or more, more preferably 98.0 mol% or more, and further preferably 99.0 mol% or more from the viewpoint of the polarizing performance and durability of the obtained polarizing film.
- the “degree of saponification” of PVA in the present specification refers to the vinyl in relation to the total number of moles of structural units (typically vinyl ester units) and vinyl alcohol units that can be converted into vinyl alcohol units by saponification. The ratio (mol%) occupied by the number of moles of alcohol units.
- the degree of saponification of PVA can be measured according to the description of JIS K6726-1994.
- the PVA constituting the PVA film may be one type of PVA, or may be one or more of two or more types of PVA that are different from each other in average polymerization degree, saponification degree, modification degree, and the like. Good.
- the PVA content in the PVA film is preferably in the range of 50 to 100% by mass, more preferably in the range of 80 to 100% by mass, and in the range of 85 to 100% by mass. Further preferred.
- the PVA film preferably contains a plasticizer because it can improve mechanical properties such as impact strength, process passability during secondary processing, and stretchability.
- Preferred plasticizers include polyhydric alcohols, and specific examples include ethylene glycol, glycerin, diglycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, and the like.
- the PVA film can contain one or more of these plasticizers.
- these plasticizers one or more of glycerin, diglycerin, and ethylene glycol are preferably used from the viewpoint of stretchability improvement effect when the PVA film is stretched and used, and glycerin is more preferable. Preferably used.
- the content of the plasticizer in the PVA film is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and more preferably 5 parts by mass or more with respect to 100 parts by mass of PVA contained in the PVA film. Is more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 15 parts by mass or less.
- the content is 1 part by mass or more, the stretchability of the PVA film can be further improved.
- the content is 30 parts by mass or less, it is possible to prevent the PVA film from becoming too flexible and handling properties from being lowered.
- the PVA film preferably contains a surfactant from the viewpoints of handleability and improvement of peelability from the film forming apparatus when the PVA film is produced.
- a surfactant from the viewpoints of handleability and improvement of peelability from the film forming apparatus when the PVA film is produced.
- anionic surfactant examples include carboxylic acid types such as potassium laurate; sulfate ester types such as octyl sulfate; and sulfonic acid types such as dodecylbenzene sulfonate.
- nonionic surfactants include alkyl ether types such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; alkyl phenyl ether types such as polyoxyethylene octyl phenyl ether; alkyl ester types such as polyoxyethylene laurate.
- Alkylamine type such as polyoxyethylene lauryl amino ether
- alkylamide type such as polyoxyethylene lauric acid amide
- polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether
- alkanolamide type alkanolamide type
- allyl phenyl ether type such as polyoxyalkylene allyl phenyl ether.
- the PVA film can contain one or more of these surfactants.
- these surfactants nonionic surfactants are preferred because of their excellent effect of reducing film surface abnormalities during film formation, and alkanolamide type surfactants are particularly preferred, and aliphatic carboxylic acids (for example, More preferred are dialkanolamides (for example, diethanolamide) of C8-30 saturated or unsaturated aliphatic carboxylic acid.
- the content of the surfactant in the PVA film is such that the handleability of the PVA film and the peelability from the film forming apparatus when producing the PVA film can be further improved, and the occurrence of blocking can be reduced. It is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, still more preferably 0.05 parts by mass or more, and 1 part by mass with respect to 100 parts by mass of PVA. It is preferable that the amount be 0.5 parts by mass or less, more preferably 0.3 parts by mass or less.
- the PVA film further contains other components such as antioxidants, ultraviolet absorbers, lubricants, colorants, antiseptics, antifungal agents, other polymer compounds other than those described above, and moisture as necessary. May be.
- the PVA film can contain one or more of these other components.
- the thickness of the PVA film needs to be 55 ⁇ m or less, preferably 40 ⁇ m or less, 30 ⁇ m or less, and further 20 ⁇ m or less. It may be. Broken line streaks are more likely to be a problem in thinner PVA films, and the effects of the present invention are particularly prominent in PVA films having such thickness.
- the lower limit of the thickness of the PVA film is not particularly limited, but considering the handleability of the PVA film, the process passability during the production of the optical film, the optical performance of the resulting optical film (such as the polarizing performance of the polarizing film),
- the thickness is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and further preferably 10 ⁇ m or more.
- the thickness of the PVA film can be obtained as an average value obtained by measuring the thicknesses at arbitrary five locations.
- the shape of the PVA film is not particularly limited, but a more uniform PVA film can be continuously and smoothly manufactured, and is also used continuously when an optical film such as a polarizing film is manufactured using the PVA film. It is preferable that the film is a long film.
- the long film is preferably in the form of a film roll by winding it around a cylindrical core.
- the length of the PVA film (the length in the flow direction) is not particularly limited, and can be set as appropriate according to the use, etc., but is continuously unwound from the film roll and used. In some cases, the longer the length of the PVA film, the more the loss when switching the film roll can be reduced.
- the length is preferably 500 m or more, more preferably 1,000 m or more. Is more preferably 8,000 m or more, particularly preferably 8,000 m or more. Although there is no restriction
- thermoplastic resin film Even if it is a single layer form (single layer film), or in the form of a laminated body like the PVA film formed by the coating method etc. on the thermoplastic resin film, for example
- a single-layered form is preferred from the viewpoints of the effects of the present invention being more prominent, the complexity of laminating (coating and the like) work, and the cost of the thermoplastic resin film.
- the width of the PVA film is not particularly limited, and can be set as appropriate according to the use of the PVA film or an optical film such as a polarizing film produced from the PVA film. From the point of progress, it is suitable for these uses when the width of the PVA film is 2 m or more, more preferably 3 m or more, and even more preferably 4 m or more. On the other hand, if the width of the PVA film is too large, it is likely to be difficult to perform uniaxial stretching uniformly when an optical film is produced by a device that has been put to practical use. Therefore, the width of the PVA film may be 7 m or less. preferable.
- the manufacturing method of the PVA film of this invention is not specifically limited, According to the manufacturing method of the following this invention, the PVA film of this invention can be manufactured smoothly continuously.
- the manufacturing method of the present invention for manufacturing a PVA film having a thickness of 55 ⁇ m or less includes a plurality of drying rolls whose rotation axes are parallel to each other (in order from the most upstream side to the downstream side, the first drying roll, 2), a film-forming stock solution containing PVA is discharged in the form of a film on the first drying roll of the film-forming apparatus and dried, followed by second drying.
- This is a production method in which when the PVA film is formed by further drying with a drying roll after the roll, the discharge rate (S 0 ) of the raw film forming solution is set to 2.5 to 5.0 m / min.
- a film-forming apparatus including a plurality of drying rolls whose rotation axes are parallel to each other is used, and a film-forming stock solution containing PVA is discharged into a film on the first drying roll of the film-forming apparatus. It dries, and it further dries with the drying roll after the 2nd drying roll following the downstream of the said 1st drying roll, and forms a PVA film.
- the number of drying rolls is preferably 3 or more, more preferably 4 or more, and further preferably 5 to 30.
- the plurality of drying rolls are preferably formed from a metal such as nickel, chromium, copper, iron, stainless steel, and the like, and in particular, the surface of the drying roll is formed from a metal material that is resistant to corrosion and has a specular gloss. More preferably. In order to increase the durability of the drying roll, it is more preferable to use a drying roll plated with a single layer or a combination of two or more layers such as a nickel layer, a chromium layer, and a nickel / chromium alloy layer.
- first drying roll contact surface a film surface that does not contact the first drying roll
- first drying roll non-contact surface a film surface that does not contact the first drying roll
- a film-forming stock solution containing PVA may be discharged (cast) into a film form on the first drying roll using (film-form casting apparatus).
- the discharge rate (S 0 ) of the film-forming stock solution needs to be 2.5 to 5.0 m / min.
- the peripheral speed of the first drying roll against the discharge rate of the film-forming solution (S 0) the ratio of (S 1) (S 1 / S 0) Increasing or conversely increasing the film-forming stock solution discharge speed (S 0 ), while the film-forming stock solution discharge speed (S 0 ) has a peripheral speed (S 1 ) of the first drying roll.
- the PVA film having the same thickness can be produced at a specific production rate by reducing the ratio (S 1 / S 0 ) of the present invention
- the present inventors have developed a thin PVA film having a thickness of 55 ⁇ m or less.
- the discharge speed (S 0 ) of the film-forming stock solution is preferably 2.6 m / min or more, and preferably 2.7 m / min or more, for the reason that the number of broken lines can be further reduced. Is more preferable, and it is still more preferable that it is 2.8 m / min or more. On the other hand, if the discharge rate (S 0 ) of the film-forming stock solution is too high, it tends to be difficult to stably produce the PVA film.
- the discharge rate (S 0 ) of the film-forming stock solution is It is preferably 4.8 m / min or less, more preferably 4.5 m / min or less, still more preferably 4.2 m / min or less, and particularly preferably 4.0 m / min or less. preferable.
- the discharge rate (S 0 ) of the film-forming stock solution means the linear velocity in the flow direction of the film-forming stock solution, and the volume per unit time of the film-forming stock solution discharged from the film-like discharge device is the film-like discharge rate. It can be determined by dividing by the opening area of the slit portion of the device (product of the slit width of the film-like discharge device and the average value of the slit opening).
- a film-forming stock solution containing a PVA film can be prepared by mixing PVA with a liquid medium to form a solution, or by melting PVA pellets containing the liquid medium or the like to form a melt.
- the liquid medium used in this case include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylenediamine, and diethylenetriamine. These liquid media are used alone. Or two or more of them may be used in combination. Among these, water, dimethyl sulfoxide, or a mixture of both are preferably used, and water is more preferably used.
- the film-forming stock solution is preferably blended with one or more of the plasticizers, surfactants, and other components as described above in the description of the PVA film in the above-mentioned amounts.
- the volatile fraction of the film-forming stock solution used for the production of the PVA film is preferably in the range of 50 to 90% by mass, more preferably in the range of 55 to 80% by mass, and 60 to 75% by mass. More preferably within the range. If the volatile fraction of the film-forming stock solution is too low, the viscosity of the film-forming stock solution may become too high, making filtration and defoaming difficult, or making the film itself difficult. On the other hand, if the volatile fraction of the film-forming stock solution is too high, the viscosity becomes too low and the thickness uniformity of the PVA film may be impaired.
- the volatile fraction of the film-forming stock solution in this specification refers to the volatile fraction obtained by the following formula [I].
- Volatile fraction (% by mass) of the film-forming stock solution ⁇ (Wa ⁇ Wb) / Wa ⁇ ⁇ 100 [I] (In the formula, Wa represents the mass (g) of the film-forming stock solution, and Wb represents the mass (g) when the film-forming stock solution of Wa (g) was dried in an electrothermal dryer at 105 ° C. for 16 hours.)
- the surface temperature of the first drying roll is not particularly limited, but it is preferably in the range of 70 to 120 ° C., and in the range of 80 to 105 ° C., from the viewpoint of film drying uniformity and productivity. Is more preferable, and it is still more preferable to be in the range of 85 to 95 ° C.
- the film-forming stock solution discharged in the form of a film may be dried on the first drying roll only by heating from the first drying roll, the first drying roll non-contact surface is simultaneously heated with the first drying roll. It is preferable from the viewpoints of uniform drying property, drying speed, and the like to dry by blowing hot air onto the film and applying heat from both sides of the film.
- the temperature of the hot air blown on the non-contact surface of the first drying roll of the film is preferably 50 to 150 ° C., more preferably 70 to 120 ° C. from the viewpoint of drying efficiency, drying uniformity, and the like. More preferably, it is -95 ° C. Further, the dew point temperature of the hot air blown on the non-contact surface of the first drying roll of the film is preferably 5 to 20 ° C., and more preferably 10 to 15 ° C.
- the method for blowing hot air to the non-contact surface of the first drying roll of the film is not particularly limited, and the hot air having a uniform wind speed and uniform temperature is uniformly applied to the non-contact surface of the first drying roll, preferably the entire surface thereof. Any of the methods that can be sprayed can be employed, and among them, the nozzle method, the current plate method, or a combination thereof is preferably employed.
- the blowing direction of the hot air to the first drying roll non-contact surface of the film was substantially along the circumferential shape of the first drying roll non-contact surface of the film, even in the direction facing the first drying roll non-contact surface.
- the direction may be the direction (direction substantially along the circumference of the roll surface of the first drying roll) or the other direction.
- the film when the film is dried on the first drying roll, it is preferable to exhaust the volatile matter generated from the film by drying and the hot air after spraying.
- the exhaust method is not particularly limited, but it is preferable to employ an exhaust method that does not cause wind speed spots and temperature spots of hot air sprayed on the non-contact surface of the first drying roll of the film.
- the peripheral speed (S 1 ) of the first drying roll can be within the range of 12 to 35 m / min because the number of broken lines can be further reduced and the stability during production is excellent.
- the peripheral speed (S 1 ) of the first drying roll is more preferably 15 m / min or more, more preferably 30 m / min or less, and still more preferably 28 m / min or less. 26 m / min or less is particularly preferable.
- the ratio (S 1 / S 0 ) of the peripheral speed (S 1 ) of the first drying roll to the discharge speed (S 0 ) of the film-forming stock solution can further reduce the number of broken lines and can be stable during production. From the viewpoint of excellent properties, it is preferably 7 or less, more preferably 6.8 or less, still more preferably 6.5 or less, particularly preferably 6.3 or less, It is preferably more than 3, more preferably more than 5, still more preferably more than 5.2, particularly preferably more than 5.5, and most preferably more than 6.
- the film-forming stock solution discharged in the form of a film on the first drying roll is dried on the first drying roll, and the volatile content rate of the film (the volatile content rate of the film at the time of peeling from the first drying roll) is preferable. Is peeled from the first drying roll when it is 5 to 30% by mass, more preferably 7 to 20% by mass, and still more preferably 8 to 15% by mass. When the volatile content of the film at the time of peeling from the first drying roll is 5% by mass or more, the difference in drying speed between the first drying roll contact surface and the first drying roll non-contact surface becomes large. It can suppress that a film becomes easy to curl.
- the volatile fraction of the film in the present specification refers to the volatile fraction determined by the following formula [II].
- Film volatile content (mass%) ⁇ (Wc ⁇ Wd) / Wc ⁇ ⁇ 100 [II]
- Wc represents the mass (g) of the sample collected from the film
- Wd is the sample of Wc (g) placed in a vacuum dryer at a temperature of 50 ° C. and a pressure of 0.1 kPa or less and dried for 4 hours.
- It represents mass (g) at the time.
- the film dried to a volatile content of preferably 5 to 30% by mass on the first drying roll is peeled off from the first drying roll, and this time, the non-contact surface of the first drying roll is opposed to the second drying roll.
- the film is preferably dried with a second drying roll.
- the film dried by the second drying roll is peeled off from the second drying roll, and the third drying roll, the fourth drying roll, the fifth drying roll, etc., depending on the number of drying rolls provided in the film forming apparatus, etc. * What is necessary is just to dry sequentially by several drying rolls, such as.
- each drying roll from the second drying roll to the final drying roll is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, from the viewpoint of uniform drying properties, drying speed, etc. More preferably, it is preferably less than 100 ° C, more preferably less than 90 ° C, still more preferably less than 85 ° C, and particularly preferably less than 80 ° C.
- the heat treatment can be performed using a heat treatment roll or other known heat treatment apparatus.
- the heat treatment roll there may be one heat treatment roll or a plurality of heat treatment rolls.
- the surface temperature of the heat treatment roll is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and more preferably 110 ° C. or higher, because a PVA film having a moderately advanced crystallization and excellent hot water resistance can be obtained. More preferably it is.
- the surface temperature of the heat treatment roll is preferably 150 ° C. or lower, more preferably 140 ° C. or lower, and further preferably 130 ° C. or lower.
- the heat treatment time it is preferably in the range of 3 to 60 seconds, more preferably in the range of 5 to 30 seconds, because the target PVA film can be produced more smoothly. preferable.
- the film forming apparatus described above may have a hot air drying device, a humidity control device, or the like as necessary.
- the film obtained as described above is further subjected to humidity conditioning treatment, cutting of both end portions (ear portions) of the film, if necessary, and finally wound into a roll with a predetermined length. It can be set as the PVA film of invention.
- the volatile content of the PVA film finally obtained by the above-described series of treatments is preferably in the range of 1 to 5% by mass, and more preferably in the range of 2 to 4% by mass.
- the PVA film of this invention is a polarizing film and retardation. It is preferably used as an original film for producing an optical film such as a film. Such an optical film can be produced, for example, by applying a treatment such as uniaxial stretching using the PVA film of the present invention.
- the method for producing a polarizing film using the PVA film of the present invention as a raw film is not particularly limited, and any conventionally employed method may be employed. Examples of such a method include a method of dyeing and uniaxially stretching a PVA film or uniaxially stretching a PVA film containing a dye.
- a method of subjecting the PVA film of the present invention to dyeing, uniaxial stretching, fixing treatment, drying treatment, and heat treatment as necessary can be mentioned.
- the order of dyeing and uniaxial stretching is not particularly limited, and dyeing may be performed before uniaxial stretching, dyeing may be performed simultaneously with uniaxial stretching, or dyeing may be performed after uniaxial stretching.
- steps such as uniaxial stretching and dyeing may be repeated a plurality of times.
- the rupture at the time of uniaxial stretching is performed by performing uniaxial stretching in a state where the thermoplastic resin film is laminated. It can be further reduced.
- Examples of the dye used for dyeing the PVA film include iodine or a dichroic organic dye (for example, DirectBlack 17, 19, 154; DirectBrown 44, 106, 195, 210, 223; DirectRed 2, 23, 28, 31, 37, 39. 79, 81, 240, 242, 247; DirectBlue 1, 15, 22, 78, 90, 98, 151, 168, 202, 236, 249, 270; DirectViolet 9, 12, 51, 98; DirectGreen 1, 85; Direct Yellow 8, 12, 44, 86, 87; dichroic dyes such as Direct Orange 26, 39, 106, 107) can be used. These dyes can be used alone or in combination of two or more. Dyeing can usually be performed by immersing the PVA film in a solution containing the dye, but the treatment conditions and treatment method are not particularly limited.
- the uniaxial stretching of the PVA film may be performed by either a wet stretching method or a dry heat stretching method, but the wet stretching method is preferred from the viewpoint of the performance and quality stability of the obtained polarizing film.
- the wet stretching method include a method of stretching a PVA film in pure water, an aqueous solution containing various components such as an additive and an aqueous medium, or an aqueous dispersion in which various components are dispersed.
- Uniaxial stretching by a wet stretching method Specific examples of the method include a method of uniaxially stretching in warm water containing boric acid, a method of uniaxially stretching in a solution containing the above-described dye or a fixing treatment bath described later, and the like.
- Uniaxial stretching is preferably performed in the flow direction of the PVA film.
- the stretching temperature for uniaxial stretching is not particularly limited, but in the case of wet stretching, a temperature in the range of preferably 20 to 90 ° C, more preferably 25 to 70 ° C, and even more preferably 30 to 65 ° C is adopted. In the case of hot stretching, a temperature within the range of 50 to 180 ° C. is preferably employed.
- the stretching ratio of uniaxial stretching (the total stretching ratio in the case of performing uniaxial stretching in multiple stages) is preferably stretched as much as possible from the point of polarization performance until just before the film is cut, and specifically 4 times or more. It is preferably 5 times or more, more preferably 5.5 times or more.
- the upper limit of the stretching ratio is not particularly limited as long as the film is not broken, but is preferably 8.0 times or less in order to perform uniform stretching.
- the thickness of the uniaxially stretched film is preferably 1 to 30 ⁇ m, particularly 3 to 25 ⁇ m.
- the said thickness can measure
- fixing treatment is often performed in order to strengthen the adsorption of the dye to the uniaxially stretched film.
- a method of immersing the film in a fixing treatment bath to which boric acid and / or boron compound is added is generally widely adopted. In that case, you may add an iodine compound in a processing bath as needed.
- the film subjected to the uniaxial stretching treatment or the uniaxial stretching treatment and the fixing treatment is then subjected to a drying treatment (heat treatment).
- the temperature of the drying treatment (heat treatment) is preferably 30 to 150 ° C., particularly 50 to 140 ° C. If the temperature of the drying treatment (heat treatment) is too low, the dimensional stability of the obtained polarizing film tends to be lowered, while if too high, the polarizing performance is likely to deteriorate due to the decomposition of the dye.
- a polarizing film can be obtained by bonding optically transparent protective films having mechanical strength to both surfaces or one surface of the polarizing film obtained as described above.
- a cellulose triacetate (TAC) film, an acetic acid / cellulose butyrate (CAB) film, an acrylic film, a polyester film, or the like is used.
- a PVA adhesive or a urethane adhesive is generally used, and among them, a PVA adhesive is preferably used.
- the polarizing plate obtained as described above can be used as a component of a liquid crystal display device after being coated with an acrylic adhesive or the like and then bonded to a glass substrate.
- a retardation film, a viewing angle improving film, a brightness improving film, or the like may be bonded simultaneously.
- Optical defects in polarizing film After appropriately dividing the polarizing film in the width direction, place the polarizing film in an orthogonal direction between polarizing plates for observation (two layers of parallel Nicols, polarization degree of 99.99% or more), and visually observe the degree of optical defects. The following criteria were used for evaluation. ⁇ : No or almost no optical defects can be found. ⁇ : Optical defects can be found easily. XX: Optical defects can be found very easily.
- Example 1 [Production of PVA film] It consists of 100 parts by mass of PVA (average polymerization degree 2,400, saponification degree 99.9 mol%) obtained by saponifying polyvinyl acetate, 12 parts by mass of glycerol, 0.1 part by mass of lauric acid diethanolamide, and water.
- a film-forming stock solution having a volatile content of 70% by mass was discharged from a T-type slit die at a discharge speed (S 0 ) of 2.8 m / min, and a film-forming apparatus provided with a plurality of drying rolls and heat treatment rolls whose rotation axes were parallel to each other.
- iodine / potassium iodide aqueous solution containing potassium iodide at a concentration of 3% by mass (2 3) and then immersed in a boric acid / potassium iodide aqueous solution at 30 ° C. containing 3% by weight of boric acid and 3% by weight of potassium iodide.
- Boric acid / potassium iodide aqueous solution at 63 ° C.
- Example 2 It consists of 100 parts by mass of PVA (average polymerization degree 2,400, saponification degree 99.9 mol%) obtained by saponifying polyvinyl acetate, 12 parts by mass of glycerol, 0.1 part by mass of lauric acid diethanolamide, and water.
- a film-forming stock solution having a volatile content rate of 66 mass% was discharged from a T-shaped slit die at a discharge speed (S 0 ) of 2.8 m / min, and a film-forming apparatus comprising a plurality of drying rolls and heat treatment rolls whose rotation axes were parallel to each other.
- heat treatment is performed with a heat treatment roll having a surface temperature of 115 ° C., and both end portions (ear portions) are cut and wound on a cylindrical core to finally have a thickness of 40.6 ⁇ m, a length of 2,000 m, and a width.
- a long PVA film single layer film having 2.6 m and a volatile content (water content) of 2% by mass was produced.
- the unevenness having a height difference of 50 to 60 nm was approximately 10 cm or more in a straight line in the film flow direction with a period of 0.3 to 0.7 mm.
- Comparative Example 1 It consists of 100 parts by mass of PVA (average polymerization degree 2,400, saponification degree 99.9 mol%) obtained by saponifying polyvinyl acetate, 12 parts by mass of glycerol, 0.1 part by mass of lauric acid diethanolamide, and water.
- a film-forming stock solution having a volatilization rate of 66% by mass was discharged from a T-type slit die at a discharge speed (S 0 ) of 2.4 m / min, and a film-forming apparatus comprising a plurality of drying rolls and heat treatment rolls whose rotation axes were parallel to each other.
- Comparative Example 2 It consists of 100 parts by mass of PVA (average polymerization degree 2,400, saponification degree 99.9 mol%) obtained by saponifying polyvinyl acetate, 12 parts by mass of glycerol, 0.1 part by mass of lauric acid diethanolamide, and water.
- a film-forming stock solution having a volatile content rate of 66% by mass is discharged from a T-shaped slit die at a discharge speed (S 0 ) of 2.0 m / min. 1 film is discharged onto a drying roll (peripheral speed (S 1 ) 15 m / min), and hot air of 90 ° C.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Optics & Photonics (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polarising Elements (AREA)
- Moulding By Coating Moulds (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The present invention pertains to a PVA film having a thickness of 55 μm or less wherein the PVA film has five or fewer dashed-line stripes, arranged substantially linearly over 10 cm or more in the direction of flow of the film with the irregularities having a period of 0.01-10 mm, per 1 m of the widthwise direction of the film; and to a method for producing a PVA film having a thickness of 55 μm or less wherein the production method uses a film-forming apparatus equipped with a plurality of drying rolls, the rotating axes of which are mutually parallel, and the discharge speed (SO) of the film-forming solution is 2.5-5.0 m/min when a PVA film is produced by discharging in film form a film-forming solution containing PVA onto a first drying roll of the film-forming apparatus and drying, then also drying by the second and subsequent drying rolls.
Description
本発明は、光学的欠陥の少ない偏光フィルム等の光学フィルムを製造することのできる薄型のポリビニルアルコール系重合体フィルム（以下、「ポリビニルアルコール系重合体」を「ＰＶＡ」と略記することがある）とその製造方法、当該ＰＶＡフィルムから製造した偏光フィルム等の光学フィルム、および、当該光学フィルムの製造方法に関する。
The present invention is a thin polyvinyl alcohol polymer film capable of producing an optical film such as a polarizing film with few optical defects (hereinafter, “polyvinyl alcohol polymer” may be abbreviated as “PVA”). And a manufacturing method thereof, an optical film such as a polarizing film manufactured from the PVA film, and a manufacturing method of the optical film.
光の透過および遮蔽機能を有する偏光板は、光のスイッチング機能を有する液晶などとともに、液晶ディスプレイ（ＬＣＤ）の重要な構成要素の１つである。ＬＣＤは、電卓および腕時計等の小型機器、ノートパソコン、液晶モニター、液晶カラープロジェクター、液晶テレビ、車載用ナビゲーションシステム、携帯電話、タブレット端末、屋内外で用いられる計測機器などの広範囲において用いられるようになっている。これらＬＣＤの適用分野のうち液晶テレビや液晶モニターなどでは大画面化に加えて薄型化が進んでいる。また近年、普及が目覚しいタブレット端末においても薄型化が進んでいる。ＬＣＤの薄型化を達成するための手段としてＬＣＤに用いられるガラスを薄型化することが挙げられるが、これに伴う偏光板の収縮応力によるガラスの反りの問題を解消する観点から、偏光板にも薄型化が求められている。
A polarizing plate having a light transmission and shielding function is one of important components of a liquid crystal display (LCD) together with a liquid crystal having a light switching function. LCDs are used in a wide range of 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, tablet terminals, and measuring instruments used indoors and outdoors. It has become. Of these LCD application fields, LCD TVs and LCD monitors are becoming thinner in addition to larger screens. In recent years, tablet terminals, which have been widely used, are becoming thinner. As a means for achieving LCD thinning, it is possible to reduce the thickness of the glass used in the LCD. From the viewpoint of solving the problem of warping of the glass due to the shrinkage stress of the polarizing plate, the polarizing plate is also used. Thinning is required.
偏光板は、一般に、ＰＶＡフィルムに染色および一軸延伸を施して偏光フィルムを製造した後、その偏光フィルムの表面に、三酢酸セルロース（ＴＡＣ）フィルムなどの保護膜を貼り合わせることによって製造される。したがって偏光板の薄型化を達成するために、より薄いＰＶＡフィルムを用いて薄型の偏光フィルムを製造することが求められており、具体的なＰＶＡフィルムの厚みについて、５５μｍ以下、さらには３０μｍ以下とすることが求められている。
A polarizing plate is generally produced by dyeing and uniaxially stretching a PVA film to produce a polarizing film, and then bonding a protective film such as a cellulose triacetate (TAC) film on the surface of the polarizing film. Therefore, in order to achieve thinning of the polarizing plate, it is required to produce a thin polarizing film using a thinner PVA film, and the specific thickness of the PVA film is 55 μm or less, further 30 μm or less. It is requested to do.
これまでにＰＶＡフィルムを製造するための様々な方法が知られている。例えば、ＰＶＡを含有する製膜原料を、ドラム製膜機の回転するドラム上またはベルト式製膜機の走行するベルト上に吐出して乾燥してＰＶＡフィルムを製造する際に、ドラムまたはベルトの速度と製膜原料の吐出速度との速度比を１～５とすることによって、大面積においても厚みが均一で平滑性に優れたＰＶＡフィルムを製造することができることが知られている（特許文献１参照）。具体的に特許文献１には、当該方法によって、厚みが７５μｍ程度で厚み斑が１．６～３．０μｍ程度のＰＶＡフィルムを製造したことが記載されている。
So far, various methods for producing a PVA film are known. For example, when a PVA film is produced by discharging a film-forming raw material containing PVA onto a rotating drum of a drum film-forming machine or a belt running on a belt-type film-forming machine and drying it, It is known that a PVA film having a uniform thickness and excellent smoothness can be produced even in a large area by setting the speed ratio of the speed and the film forming raw material discharge speed to 1 to 5 (patent document) 1). Specifically, Patent Document 1 describes that a PVA film having a thickness of about 75 μm and a thickness spot of about 1.6 to 3.0 μm was manufactured by the method.
上記のとおり、より薄型のＰＶＡフィルムが求められているが、従来の製膜方法によって単純に薄型のＰＶＡフィルムを製膜した場合には、フィルムの流れ方向に沿ってナノメートルオーダーの凹凸が複数配列した破線状のスジ（破線スジ）が多数発生するという新たな問題が生じる。本発明者らは、このような破線スジが多数存在する従来の薄型のＰＶＡフィルムを用いると、得られる光学フィルムにおいて光学的欠陥が多発することを認識した。
As described above, there is a demand for a thinner PVA film. However, when a thin PVA film is simply formed by a conventional film forming method, there are a plurality of irregularities on the order of nanometers along the flow direction of the film. There arises a new problem that a large number of arranged broken lines (broken lines) are generated. The present inventors have recognized that when a conventional thin PVA film having many such broken line stripes is used, optical defects frequently occur in the obtained optical film.
そこで本発明は、光学的欠陥の少ない偏光フィルム等の光学フィルムを製造することのできる薄型のＰＶＡフィルムを提供することを目的とする。また本発明は当該ＰＶＡフィルムから製造した光学的欠陥の少ない光学フィルムを提供することを目的とする。
Therefore, an object of the present invention is to provide a thin PVA film capable of producing an optical film such as a polarizing film with few optical defects. Moreover, an object of this invention is to provide the optical film with few optical defects manufactured from the said PVA film.
上記の目的を達成すべく本発明者らが鋭意検討した結果、薄型のＰＶＡフィルムを用いて偏光フィルム等の光学フィルムを製造する際に、当該ＰＶＡフィルムにおける破線スジの本数を特定数値以下にすることにより、光学的欠陥の少ない光学フィルムが容易に得られることを見出した。またこれと併せて、回転軸が互いに平行な複数の乾燥ロールを備える製膜装置を使用し、当該製膜装置の最上流側に位置する第１乾燥ロール上にＰＶＡを含む製膜原液を膜状に吐出して乾燥し、当該第１乾燥ロールの下流側に続く第２乾燥ロール以降の乾燥ロールで更に乾燥して薄型のＰＶＡフィルムを製造する際に、製膜原液の吐出速度（Ｓ０）を特定の範囲にすることにより、破線スジの本数の少ない従来にない薄型のＰＶＡフィルムを円滑に連続して製造することができることを見出した。本発明者らはこれらの知見に基づいて、さらに検討を重ねて本発明を完成させた。
As a result of intensive studies by the present inventors to achieve the above object, when manufacturing an optical film such as a polarizing film using a thin PVA film, the number of broken line streaks in the PVA film is set to a specific value or less. Thus, it has been found that an optical film with few optical defects can be easily obtained. In addition, a film-forming apparatus provided with a plurality of drying rolls whose rotation axes are parallel to each other is used, and a film-forming stock solution containing PVA is formed on the first drying roll located on the most upstream side of the film-forming apparatus. When a thin PVA film is produced by further drying with a drying roll after the second drying roll following the downstream side of the first drying roll to produce a thin PVA film, the film forming stock solution discharge speed (S 0 ) In a specific range, it has been found that an unprecedented thin PVA film with a small number of broken lines can be produced smoothly and continuously. Based on these findings, the present inventors have further studied and completed the present invention.
すなわち、本発明は、
［１］厚みが５５μｍ以下のＰＶＡフィルムであって、凹凸が０．０１～１０ｍｍの周期でフィルムの流れ方向に略直線状に１０ｃｍ以上にわたり配列してなる破線スジが、フィルムの幅方向１ｍあたり５本以下である、ＰＶＡフィルム；
［２］幅が２ｍ以上である、上記［１］のＰＶＡフィルム；
［３］厚みが５５μｍ以下のＰＶＡフィルムの製造方法であって、回転軸が互いに平行な複数の乾燥ロールを備える製膜装置を使用し、当該製膜装置の第１乾燥ロール上にＰＶＡを含む製膜原液を膜状に吐出して乾燥し、それに続く第２乾燥ロール以降の乾燥ロールで更に乾燥してＰＶＡフィルムを製膜する際に、製膜原液の吐出速度（Ｓ０）を２．５～５．０ｍ／分にする、製造方法；
［４］製膜原液の吐出速度（Ｓ０）に対する第１乾燥ロールの周速（Ｓ１）の比（Ｓ１／Ｓ０）を７以下にする、上記［３］の製造方法；
［５］幅が２ｍ以上のＰＶＡフィルムの製造方法である、上記［３］または［４］の製造方法；
［６］上記［１］または［２］のＰＶＡフィルムから製造した光学フィルム；
［７］偏光フィルムである、上記［６］の光学フィルム；
［８］上記［１］または［２］のＰＶＡフィルムを用いて一軸延伸する工程を有する、光学フィルムの製造方法；
［９］偏光フィルムの製造方法である、上記［８］の製造方法；
に関する。 That is, the present invention
[1] A PVA film having a thickness of 55 μm or less, and a broken line streak arranged in an approximately straight line in the flow direction of the film with a period of 0.01 to 10 mm over a length of 10 cm or more per 1 m in the width direction of the film 5 or less PVA films;
[2] The PVA film of the above [1], having a width of 2 m or more;
[3] A method for producing a PVA film having a thickness of 55 μm or less, wherein a film forming apparatus including a plurality of drying rolls having rotation axes parallel to each other is used, and PVA is included on the first drying roll of the film forming apparatus. When forming a PVA film by discharging the film-forming stock solution into a film and drying it, and further drying with subsequent drying rolls after the second drying roll, the film-forming stock solution discharge rate (S 0 ) is set to 2. 5 to 5.0 m / min of production method;
[4] The method according to [3] above, wherein the ratio (S 1 / S 0 ) of the peripheral speed (S 1 ) of the first drying roll to the discharge speed (S 0 ) of the film-forming stock solution is 7 or less;
[5] The production method of the above [3] or [4], which is a production method of a PVA film having a width of 2 m or more;
[6] An optical film produced from the PVA film of [1] or [2] above;
[7] The optical film according to [6], which is a polarizing film;
[8] A method for producing an optical film, comprising the step of uniaxially stretching using the PVA film of [1] or [2] above;
[9] The production method of the above [8], which is a production method of a polarizing film;
About.
［１］厚みが５５μｍ以下のＰＶＡフィルムであって、凹凸が０．０１～１０ｍｍの周期でフィルムの流れ方向に略直線状に１０ｃｍ以上にわたり配列してなる破線スジが、フィルムの幅方向１ｍあたり５本以下である、ＰＶＡフィルム；
［２］幅が２ｍ以上である、上記［１］のＰＶＡフィルム；
［３］厚みが５５μｍ以下のＰＶＡフィルムの製造方法であって、回転軸が互いに平行な複数の乾燥ロールを備える製膜装置を使用し、当該製膜装置の第１乾燥ロール上にＰＶＡを含む製膜原液を膜状に吐出して乾燥し、それに続く第２乾燥ロール以降の乾燥ロールで更に乾燥してＰＶＡフィルムを製膜する際に、製膜原液の吐出速度（Ｓ０）を２．５～５．０ｍ／分にする、製造方法；
［４］製膜原液の吐出速度（Ｓ０）に対する第１乾燥ロールの周速（Ｓ１）の比（Ｓ１／Ｓ０）を７以下にする、上記［３］の製造方法；
［５］幅が２ｍ以上のＰＶＡフィルムの製造方法である、上記［３］または［４］の製造方法；
［６］上記［１］または［２］のＰＶＡフィルムから製造した光学フィルム；
［７］偏光フィルムである、上記［６］の光学フィルム；
［８］上記［１］または［２］のＰＶＡフィルムを用いて一軸延伸する工程を有する、光学フィルムの製造方法；
［９］偏光フィルムの製造方法である、上記［８］の製造方法；
に関する。 That is, the present invention
[1] A PVA film having a thickness of 55 μm or less, and a broken line streak arranged in an approximately straight line in the flow direction of the film with a period of 0.01 to 10 mm over a length of 10 cm or more per 1 m in the width direction of the film 5 or less PVA films;
[2] The PVA film of the above [1], having a width of 2 m or more;
[3] A method for producing a PVA film having a thickness of 55 μm or less, wherein a film forming apparatus including a plurality of drying rolls having rotation axes parallel to each other is used, and PVA is included on the first drying roll of the film forming apparatus. When forming a PVA film by discharging the film-forming stock solution into a film and drying it, and further drying with subsequent drying rolls after the second drying roll, the film-forming stock solution discharge rate (S 0 ) is set to 2. 5 to 5.0 m / min of production method;
[4] The method according to [3] above, wherein the ratio (S 1 / S 0 ) of the peripheral speed (S 1 ) of the first drying roll to the discharge speed (S 0 ) of the film-forming stock solution is 7 or less;
[5] The production method of the above [3] or [4], which is a production method of a PVA film having a width of 2 m or more;
[6] An optical film produced from the PVA film of [1] or [2] above;
[7] The optical film according to [6], which is a polarizing film;
[8] A method for producing an optical film, comprising the step of uniaxially stretching using the PVA film of [1] or [2] above;
[9] The production method of the above [8], which is a production method of a polarizing film;
About.
本発明によれば、光学的欠陥の少ない偏光フィルム等の光学フィルムを製造することのできる薄型のＰＶＡフィルムとその製造方法、当該ＰＶＡフィルムから製造した光学的欠陥の少ない光学フィルム、および、当該光学フィルムの製造方法が提供される。
According to the present invention, a thin PVA film capable of producing an optical film such as a polarizing film with few optical defects, a method for producing the thin PVA film, an optical film with few optical defects produced from the PVA film, and the optical A method of manufacturing a film is provided.
以下、本発明について詳細に説明する。
［ＰＶＡフィルム］
本発明のＰＶＡフィルムは、厚みが５５μｍ以下であり、且つ、凹凸が０．０１～１０ｍｍの周期でフィルムの流れ方向に略直線状に１０ｃｍ以上にわたり配列してなる破線スジが、フィルムの幅方向１ｍあたり５本以下である。 Hereinafter, the present invention will be described in detail.
[PVA film]
The PVA film of the present invention has a thickness of 55 μm or less, and a broken line streak arranged in a direction of 0.01 to 10 mm in a substantially straight line in the flow direction of the film over 10 cm or more in the width direction of the film. No more than 5 per meter.
［ＰＶＡフィルム］
本発明のＰＶＡフィルムは、厚みが５５μｍ以下であり、且つ、凹凸が０．０１～１０ｍｍの周期でフィルムの流れ方向に略直線状に１０ｃｍ以上にわたり配列してなる破線スジが、フィルムの幅方向１ｍあたり５本以下である。 Hereinafter, the present invention will be described in detail.
[PVA film]
The PVA film of the present invention has a thickness of 55 μm or less, and a broken line streak arranged in a direction of 0.01 to 10 mm in a substantially straight line in the flow direction of the film over 10 cm or more in the width direction of the film. No more than 5 per meter.
本発明においてその本数を規定する破線スジは、上記のとおり、凹凸が０．０１～１０ｍｍの周期でフィルムの流れ方向に略直線状に１０ｃｍ以上にわたり配列してなるものである。通常、破線スジは、フィルムの流れ方向に沿って発生し１本の破線スジの長さは１０ｃｍをはるかに超えるが、本明細書では、長さが１０ｃｍ未満であって破線スジとはいいにくい欠点と区別するため、便宜上、長さが１０ｃｍ以上のもの（凹凸が上記周期でフィルムの流れ方向に略直線状に１０ｃｍ以上にわたり配列してなるもの）を破線スジとして取り扱うこととする。
In the present invention, the broken line streak that defines the number of the lines is formed by arranging irregularities approximately linearly in the flow direction of the film over 10 cm or more with a period of 0.01 to 10 mm as described above. Usually, a broken line streak occurs along the flow direction of the film, and the length of one broken line far exceeds 10 cm. However, in this specification, the length is less than 10 cm, and it is difficult to call a broken line streak. For the sake of distinction from the defects, for convenience, those having a length of 10 cm or more (those having irregularities arranged substantially linearly in the flow direction of the film over the period of 10 cm or more in the above cycle) are handled as broken lines.
上記の凹凸の種類に特に制限はなく、例えば、フィルム面から突出した凸部が配列することによって、結果として凹凸を形成しているもの；フィルム面から窪んだ凹部が配列することによって、結果として凹凸を形成しているもの；フィルム面から突出した凸部とフィルム面から窪んだ凹部とがそれぞれ交互に配列することによって、結果として凹凸を形成しているもの；などが挙げられる。
There is no particular limitation on the type of the unevenness, for example, the protrusions protruding from the film surface are arranged to form unevenness as a result; the recesses recessed from the film surface are arranged, and as a result What forms the unevenness | corrugation; What forms the unevenness | corrugation as a result by arranging the convex part which protruded from the film surface and the recessed part recessed from the film surface alternately, etc. are mentioned.
上記の破線スジは、凹凸が０．０１～１０ｍｍの周期でフィルムの流れ方向に略直線状に１０ｃｍ以上にわたり配列してなる。ここで、当該周期とは、１組の凹凸（隣り合う１つの凹部と１つの凸部の組）についてのフィルムの流れ方向の長さを意味し、上記の破線スジにおいては、対象とする凹凸の全てにおいて当該周期が０．０１～１０ｍｍの範囲内にある。当該周期は、例えば、０．１～５ｍｍの範囲内であってもよく、更には０．２～１ｍｍの範囲内であってもよい。
The above-mentioned broken line streaks are formed by arranging irregularities with a period of 0.01 to 10 mm substantially linearly in the direction of film flow over 10 cm or more. Here, the period means the length of the film in the flow direction of one set of unevenness (a set of one concave portion and one convex portion adjacent to each other). In all of the cases, the period is in the range of 0.01 to 10 mm. The period may be in the range of 0.1 to 5 mm, for example, and may be in the range of 0.2 to 1 mm.
上記の破線スジを構成する一組の凹凸において、高さが一番高くなる箇所と、高さが一番低くなる箇所とにおける厚みの高低差は、多くの場合、１～５００ｎｍの範囲内であり、例えば、１０～３００ｎｍの範囲内、更には２０～１００ｎｍの範囲内、特に３０～９０ｎｍの範囲内であってもよい。
In a set of irregularities constituting the broken line streaks, the difference in thickness between the highest height and the lowest height is often in the range of 1 to 500 nm. For example, it may be within the range of 10 to 300 nm, further within the range of 20 to 100 nm, and particularly within the range of 30 to 90 nm.
上記の破線スジの本数は、対象とするＰＶＡフィルムについて、流れ方向の任意の一箇所を通過する幅方向の直線上において、当該直線を横切る上記破線スジの本数を、幅方向全体にわたって計測した後に、その本数を当該ＰＶＡフィルムの幅（単位：ｍ）で除すことによって幅１ｍあたりの本数として求めることができる。ここで、破線スジは、例えば、走査型白色干渉顕微鏡などによってその存在を確認することができる。破線スジの本数は、具体的には実施例において後述する方法により求めることができる。
For the target PVA film, the number of the broken line streaks is measured over the entire width direction on the straight line in the width direction passing through an arbitrary position in the flow direction. By dividing the number by the width (unit: m) of the PVA film, the number can be obtained as the number per 1 m width. Here, the presence of the broken line streaks can be confirmed by, for example, a scanning white interference microscope. Specifically, the number of broken lines can be obtained by the method described later in the embodiment.
本発明のＰＶＡフィルムは、上記の破線スジがフィルムの幅方向１ｍあたりの本数として、５本以下であることが必要であり、３本以下であることが好ましく、２本以下であることがより好ましく、１．５本以下、更には１本以下であってもよい。破線スジの本数が上記範囲にあることにより、光学的欠陥の少ない光学フィルムが容易に得られる。一方、５５μｍ以下の薄いＰＶＡフィルムにおいて、破線スジの本数が幅方向１ｍあたり０．０５本未満になるように運転条件を調整した場合、光学フィルムのスジ状の光学的欠陥は少ないが、理由は必ずしも明確ではないがフィルムに厚み斑などの問題を生じやすい傾向がある。そのため、破線スジの本数は幅方向１ｍあたり０．０５本以上であることが好ましく、０．１０本以上であることがより好ましく、０．１５本以上であることが更に好ましく、０．２０本以上であることが最も好ましい。
In the PVA film of the present invention, the number of the broken line streaks in the width direction per 1 m of the film needs to be 5 or less, preferably 3 or less, and more preferably 2 or less. Preferably, it may be 1.5 or less, and even 1 or less. When the number of broken lines is within the above range, an optical film with few optical defects can be easily obtained. On the other hand, in a thin PVA film of 55 μm or less, when the operating conditions are adjusted so that the number of broken line streaks is less than 0.05 per 1 m in the width direction, the optical film has few streak-like optical defects. Although it is not necessarily clear, the film tends to cause problems such as uneven thickness. Therefore, the number of broken lines is preferably 0.05 or more per 1 m in the width direction, more preferably 0.10 or more, still more preferably 0.15 or more, and 0.20 The above is most preferable.
ＰＶＡフィルムを形成するＰＶＡとしては、例えば、ビニルエステルを重合して得られるポリビニルエステルをけん化して得られるＰＶＡ（未変性ＰＶＡ）、ＰＶＡの主鎖にコモノマーをグラフト共重合させた変性ＰＶＡ、ビニルエステルとコモノマーを共重合させた変性ポリビニルエステルをけん化することにより製造した変性ＰＶＡ、未変性ＰＶＡまたは変性ＰＶＡの水酸基の一部をホルマリン、ブチルアルデヒド、ベンズアルデヒドなどのアルデヒド類で架橋したいわゆるポリビニルアセタール樹脂などを挙げることができる。
ＰＶＡフィルムを形成するＰＶＡが変性ＰＶＡである場合は、ＰＶＡにおける変性量は１５モル％以下であることが好ましく、５モル％以下であることがより好ましい。 Examples of PVA forming the PVA film include PVA (unmodified PVA) obtained by saponifying polyvinyl ester obtained by polymerizing vinyl ester, modified PVA obtained by graft copolymerization with a comonomer on the main chain of PVA, vinyl A so-called polyvinyl acetal resin in which a part of hydroxyl groups of modified PVA, unmodified PVA or modified PVA produced by saponifying a modified polyvinyl ester obtained by copolymerization of an ester and a comonomer is crosslinked with aldehydes such as formalin, butyraldehyde, and benzaldehyde And so on.
When the PVA forming the PVA film is a modified PVA, the amount of modification in the PVA is preferably 15 mol% or less, and more preferably 5 mol% or less.
ＰＶＡフィルムを形成するＰＶＡが変性ＰＶＡである場合は、ＰＶＡにおける変性量は１５モル％以下であることが好ましく、５モル％以下であることがより好ましい。 Examples of PVA forming the PVA film include PVA (unmodified PVA) obtained by saponifying polyvinyl ester obtained by polymerizing vinyl ester, modified PVA obtained by graft copolymerization with a comonomer on the main chain of PVA, vinyl A so-called polyvinyl acetal resin in which a part of hydroxyl groups of modified PVA, unmodified PVA or modified PVA produced by saponifying a modified polyvinyl ester obtained by copolymerization of an ester and a comonomer is crosslinked with aldehydes such as formalin, butyraldehyde, and benzaldehyde And so on.
When the PVA forming the PVA film is a modified PVA, the amount of modification in the PVA is preferably 15 mol% or less, and more preferably 5 mol% or less.
ＰＶＡの製造に用いられる前記のビニルエステルとしては、例えば、酢酸ビニル、ギ酸ビニル、ラウリン酸ビニル、プロピオン酸ビニル、酪酸ビニル、ピバリン酸ビニル、バーサティック酸ビニル、ステアリン酸ビニル、安息香酸ビニルなどを挙げることができる。これらのビニルエステルは、単独でまたは組み合わせて使用することができる。これらのビニルエステルのうち、酢酸ビニルが生産性の観点から好ましい。
Examples of the vinyl ester used in the production of PVA include vinyl acetate, vinyl formate, vinyl laurate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatate, vinyl stearate, vinyl benzoate and the like. Can be mentioned. These vinyl esters can be used alone or in combination. Of these vinyl esters, vinyl acetate is preferred from the viewpoint of productivity.
また、前記したコモノマーとしては、例えば、エチレン、プロピレン、１－ブテン、イソブテンなどの炭素数２～３０のオレフィン類（α－オレフィンなど）；アクリル酸またはその塩；アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ－プロピル、アクリル酸ｉ－プロピル、アクリル酸ｎ－ブチル、アクリル酸ｉ－ブチル、アクリル酸ｔ－ブチル、アクリル酸２－エチルヘキシル、アクリル酸ドデシル、アクリル酸オクタデシル等のアクリル酸エステル類（例えば、アクリル酸の炭素数１～１８アルキルエステル等）；メタクリル酸またはその塩；メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ－プロピル、メタクリル酸ｉ－プロピル、メタクリル酸ｎ－ブチル、メタクリル酸ｉ－ブチル、メタクリル酸ｔ－ブチル、メタクリル酸２－エチルヘキシル、メタクリル酸ドデシル、メタクリル酸オクタデシル等のメタクリル酸エステル類（例えば、メタクリル酸の炭素数１～１８アルキルエステル等）；アクリルアミド、Ｎ－メチルアクリルアミド、Ｎ－エチルアクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド、ジアセトンアクリルアミド、アクリルアミドプロパンスルホン酸またはその塩、アクリルアミドプロピルジメチルアミンまたはその塩、Ｎ－メチロールアクリルアミドまたはその誘導体等のアクリルアミド誘導体；メタクリルアミド、Ｎ－メチルメタクリルアミド、Ｎ－エチルメタクリルアミド、メタクリルアミドプロパンスルホン酸またはその塩、メタクリルアミドプロピルジメチルアミンまたはその塩、Ｎ－メチロールメタクリルアミドまたはその誘導体等のメタクリルアミド誘導体；Ｎ－ビニルホルムアミド、Ｎ－ビニルアセトアミド、Ｎ－ビニルピロリドン等のＮ－ビニルアミド類；メチルビニルエーテル、エチルビニルエーテル、ｎ－プロピルビニルエーテル、ｉ－プロピルビニルエーテル、ｎ－ブチルビニルエーテル、ｉ－ブチルビニルエーテル、ｔ－ブチルビニルエーテル、ドデシルビニルエーテル、ステアリルビニルエーテル等のビニルエーテル類；アクリロニトリル、メタクリロニトリル等のニトリル類；塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン等のハロゲン化ビニル類；酢酸アリル、塩化アリル等のアリル化合物；マレイン酸、イタコン酸等の不飽和ジカルボン酸、その塩またはそのエステル等の誘導体；ビニルトリメトキシシラン等のビニルシリル化合物；酢酸イソプロペニル；不飽和スルホン酸またはその誘導体などを挙げることができる。これらの中でもα－オレフィンが好ましく、特にエチレンが好ましい。
Examples of the comonomer described above include olefins having 2 to 30 carbon atoms such as ethylene, propylene, 1-butene and isobutene (such as α-olefin); acrylic acid or a salt thereof; methyl acrylate, ethyl acrylate, Acrylic esters such as n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, etc. For example, acrylic acid having 1 to 18 carbon atoms of acrylic acid); methacrylic acid or a salt thereof; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i -Butyl, t-butyl methacrylate, Methacrylic acid esters such as 2-ethylhexyl crylate, dodecyl methacrylate, octadecyl methacrylate (for example, alkyl esters of 1 to 18 carbon atoms of methacrylic acid); acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N Acrylamide derivatives such as dimethyl acrylamide, diacetone acrylamide, acrylamide propane sulfonic acid or salts thereof, acrylamide propyl dimethylamine or salts thereof, N-methylol acrylamide or derivatives thereof; methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide , Methacrylamide propane sulfonic acid or its salt, methacrylamide propyl dimethylamine or its salt, N-methylol methacrylamide or its Methacrylamide derivatives such as derivatives; N-vinylamides such as N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i -Vinyl ethers such as butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether and stearyl vinyl ether; Nitriles such as acrylonitrile and methacrylonitrile; Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride; Acetic acid Allyl compounds such as allyl and allyl chloride; unsaturated dicarboxylic acids such as maleic acid and itaconic acid; derivatives thereof such as salts or esters thereof; vinyl silanes such as vinyltrimethoxysilane; Le compounds; isopropenyl acetate; an unsaturated sulfonic acid or its derivatives. Of these, α-olefins are preferable, and ethylene is particularly preferable.
ＰＶＡの平均重合度は、得られる偏光フィルムの偏光性能および耐久性などの点から、１，０００以上が好ましく、１，５００以上がより好ましく、２，０００以上が更に好ましい。一方、ＰＶＡの平均重合度の上限について、均質なＰＶＡフィルムの製造の容易性、延伸性などの点から、当該平均重合度は８，０００以下が好ましく、特に６，０００以下が好ましい。
ここで、本明細書におけるＰＶＡの「平均重合度」とは、ＪＩＳ Ｋ６７２６－１９９４に準じて測定される平均重合度をいい、ＰＶＡを再けん化し、精製した後に３０℃の水中で測定した極限粘度から求められる。 The average degree of polymerization of PVA is preferably 1,000 or more, more preferably 1,500 or more, and still more preferably 2,000 or more, from the viewpoint of polarization performance and durability of the polarizing film to be obtained. On the other hand, with respect to the upper limit of the average degree of polymerization of PVA, the average degree of polymerization is preferably 8,000 or less, particularly preferably 6,000 or less, from the viewpoint of easy production of a homogeneous PVA film and stretchability.
Here, the “average degree of polymerization” of PVA in the present specification refers to the average degree of polymerization measured according to JIS K6726-1994, and is the limit measured in water at 30 ° C. after re-saponifying and purifying PVA. Determined from viscosity.
ここで、本明細書におけるＰＶＡの「平均重合度」とは、ＪＩＳ Ｋ６７２６－１９９４に準じて測定される平均重合度をいい、ＰＶＡを再けん化し、精製した後に３０℃の水中で測定した極限粘度から求められる。 The average degree of polymerization of PVA is preferably 1,000 or more, more preferably 1,500 or more, and still more preferably 2,000 or more, from the viewpoint of polarization performance and durability of the polarizing film to be obtained. On the other hand, with respect to the upper limit of the average degree of polymerization of PVA, the average degree of polymerization is preferably 8,000 or less, particularly preferably 6,000 or less, from the viewpoint of easy production of a homogeneous PVA film and stretchability.
Here, the “average degree of polymerization” of PVA in the present specification refers to the average degree of polymerization measured according to JIS K6726-1994, and is the limit measured in water at 30 ° C. after re-saponifying and purifying PVA. Determined from viscosity.
ＰＶＡのけん化度は、得られる偏光フィルムの偏光性能および耐久性などの点から、９５．０モル％以上が好ましく、９８．０モル％以上がより好ましく、９９．０モル％以上が更に好ましい。
ここで、本明細書におけるＰＶＡの「けん化度」とは、けん化によりビニルアルコール単位に変換され得る構造単位（典型的にはビニルエステル単位）とビニルアルコール単位との合計モル数に対して当該ビニルアルコール単位のモル数が占める割合（モル％）をいう。ＰＶＡのけん化度は、ＪＩＳ Ｋ６７２６－１９９４の記載に準じて測定することができる。 The saponification degree of PVA is preferably 95.0 mol% or more, more preferably 98.0 mol% or more, and further preferably 99.0 mol% or more from the viewpoint of the polarizing performance and durability of the obtained polarizing film.
Here, the “degree of saponification” of PVA in the present specification refers to the vinyl in relation to the total number of moles of structural units (typically vinyl ester units) and vinyl alcohol units that can be converted into vinyl alcohol units by saponification. The ratio (mol%) occupied by the number of moles of alcohol units. The degree of saponification of PVA can be measured according to the description of JIS K6726-1994.
ここで、本明細書におけるＰＶＡの「けん化度」とは、けん化によりビニルアルコール単位に変換され得る構造単位（典型的にはビニルエステル単位）とビニルアルコール単位との合計モル数に対して当該ビニルアルコール単位のモル数が占める割合（モル％）をいう。ＰＶＡのけん化度は、ＪＩＳ Ｋ６７２６－１９９４の記載に準じて測定することができる。 The saponification degree of PVA is preferably 95.0 mol% or more, more preferably 98.0 mol% or more, and further preferably 99.0 mol% or more from the viewpoint of the polarizing performance and durability of the obtained polarizing film.
Here, the “degree of saponification” of PVA in the present specification refers to the vinyl in relation to the total number of moles of structural units (typically vinyl ester units) and vinyl alcohol units that can be converted into vinyl alcohol units by saponification. The ratio (mol%) occupied by the number of moles of alcohol units. The degree of saponification of PVA can be measured according to the description of JIS K6726-1994.
ＰＶＡフィルムを構成するＰＶＡは、１種のＰＶＡであってもよいし、平均重合度、けん化度、変性度などのうちの１つまたは２つ以上が互いに異なる２種以上のＰＶＡであってもよい。ＰＶＡフィルムにおけるＰＶＡの含有率は、５０～１００質量％の範囲内であることが好ましく、８０～１００質量％の範囲内であることがより好ましく、８５～１００質量％の範囲内であることが更に好ましい。
The PVA constituting the PVA film may be one type of PVA, or may be one or more of two or more types of PVA that are different from each other in average polymerization degree, saponification degree, modification degree, and the like. Good. The PVA content in the PVA film is preferably in the range of 50 to 100% by mass, more preferably in the range of 80 to 100% by mass, and in the range of 85 to 100% by mass. Further preferred.
ＰＶＡフィルムは衝撃強度等の機械的物性、二次加工時の工程通過性や延伸性を向上させることができることなどから可塑剤を含むことが好ましい。好ましい可塑剤としては多価アルコールが挙げられ、具体的には、例えば、エチレングリコール、グリセリン、ジグリセリン、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、トリメチロールプロパン等が挙げられる。ＰＶＡフィルムは、これらの可塑剤の１種または２種以上を含むことができる。これらの可塑剤の中でも、ＰＶＡフィルムを延伸して使用する際における延伸性向上効果などの観点から、グリセリン、ジグリセリンおよびエチレングリコールのうちの１種または２種以上が好ましく使用され、グリセリンがより好ましく使用される。
The PVA film preferably contains a plasticizer because it can improve mechanical properties such as impact strength, process passability during secondary processing, and stretchability. Preferred plasticizers include polyhydric alcohols, and specific examples include ethylene glycol, glycerin, diglycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, and the like. The PVA film can contain one or more of these plasticizers. Among these plasticizers, one or more of glycerin, diglycerin, and ethylene glycol are preferably used from the viewpoint of stretchability improvement effect when the PVA film is stretched and used, and glycerin is more preferable. Preferably used.
ＰＶＡフィルムにおける可塑剤の含有量は、ＰＶＡフィルムに含まれるＰＶＡ１００質量部に対して、１質量部以上であることが好ましく、３質量部以上であることがより好ましく、５質量部以上であることがさらに好ましく、また、３０質量部以下であることが好ましく、２０質量部以下であることがより好ましく、１５質量部以下であることがさらに好ましい。当該含有量が１質量部以上であることによりＰＶＡフィルムの延伸性をより向上させることができる。一方、当該含有量が３０質量部以下であることにより、ＰＶＡフィルムが柔軟になりすぎて取り扱い性が低下するのを防止することができる。
The content of the plasticizer in the PVA film is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and more preferably 5 parts by mass or more with respect to 100 parts by mass of PVA contained in the PVA film. Is more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 15 parts by mass or less. 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 30 parts by mass or less, it is possible to prevent the PVA film from becoming too flexible and handling properties from being lowered.
ＰＶＡフィルムは、その取り扱い性や、またＰＶＡフィルムを製造する際の製膜装置からの剥離性の向上などの観点から界面活性剤を含むことが好ましい。界面活性剤の種類に特に制限はなく、例えば、アニオン系界面活性剤、ノニオン系界面活性剤などが挙げられる。
The PVA film preferably contains a surfactant from the viewpoints of handleability and improvement of peelability from the film forming apparatus when the PVA film is produced. There is no restriction | limiting in particular in the kind of surfactant, For example, anionic surfactant, a nonionic surfactant, etc. are mentioned.
アニオン系界面活性剤としては、例えば、ラウリン酸カリウム等のカルボン酸型；オクチルサルフェート等の硫酸エステル型；ドデシルベンゼンスルホネート等のスルホン酸型などが挙げられる。
Examples of the anionic surfactant include carboxylic acid types such as potassium laurate; sulfate ester types such as octyl sulfate; and sulfonic acid types such as dodecylbenzene sulfonate.
ノニオン系界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンオレイルエーテル等のアルキルエーテル型；ポリオキシエチレンオクチルフェニルエーテル等のアルキルフェニルエーテル型；ポリオキシエチレンラウレート等のアルキルエステル型；ポリオキシエチレンラウリルアミノエーテル等のアルキルアミン型；ポリオキシエチレンラウリン酸アミド等のアルキルアミド型；ポリオキシエチレンポリオキシプロピレンエーテル等のポリプロピレングリコールエーテル型；ラウリン酸ジエタノールアミド、オレイン酸ジエタノールアミド等のアルカノールアミド型；ポリオキシアルキレンアリルフェニルエーテル等のアリルフェニルエーテル型などが挙げられる。
Examples of nonionic surfactants include alkyl ether types such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; alkyl phenyl ether types such as polyoxyethylene octyl phenyl ether; alkyl ester types such as polyoxyethylene laurate. Alkylamine type such as polyoxyethylene lauryl amino ether; alkylamide type such as polyoxyethylene lauric acid amide; polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether; lauric acid diethanolamide, oleic acid diethanolamide, etc. Examples include alkanolamide type; allyl phenyl ether type such as polyoxyalkylene allyl phenyl ether.
ＰＶＡフィルムは、これらの界面活性剤の１種または２種以上を含むことができる。これらの界面活性剤の中でも、製膜時の膜面異常の低減効果に優れることなどから、ノニオン系界面活性剤が好ましく、特にアルカノールアミド型の界面活性剤がより好ましく、脂肪族カルボン酸（例えば、炭素数８～３０の飽和または不飽和脂肪族カルボン酸など）のジアルカノールアミド（例えば、ジエタノールアミド等）が更に好ましい。
The PVA film can contain one or more of these surfactants. Among these surfactants, nonionic surfactants are preferred because of their excellent effect of reducing film surface abnormalities during film formation, and alkanolamide type surfactants are particularly preferred, and aliphatic carboxylic acids (for example, More preferred are dialkanolamides (for example, diethanolamide) of C8-30 saturated or unsaturated aliphatic carboxylic acid.
ＰＶＡフィルムにおける界面活性剤の含有量は、ＰＶＡフィルムの取り扱い性や、またＰＶＡフィルムを製造する際の製膜装置からの剥離性がより向上し、またブロッキングの発生を低減することができることから、ＰＶＡ１００質量部に対して、０．０１質量部以上であることが好ましく、０．０２質量部以上であることがより好ましく、０．０５質量部以上であることが更に好ましく、また、１質量部以下であることが好ましく、０．５質量部以下であることがより好ましく、０．３質量部以下であることが更に好ましい。
The content of the surfactant in the PVA film is such that the handleability of the PVA film and the peelability from the film forming apparatus when producing the PVA film can be further improved, and the occurrence of blocking can be reduced. It is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, still more preferably 0.05 parts by mass or more, and 1 part by mass with respect to 100 parts by mass of PVA. It is preferable that the amount be 0.5 parts by mass or less, more preferably 0.3 parts by mass or less.
ＰＶＡフィルムは、必要に応じて、酸化防止剤、紫外線吸収剤、滑剤、着色剤、防腐剤、防黴剤、上記した成分以外の他の高分子化合物、水分などの他の成分を更に含んでいてもよい。ＰＶＡフィルムはこれらの他の成分の１種または２種以上を含むことができる。
The PVA film further contains other components such as antioxidants, ultraviolet absorbers, lubricants, colorants, antiseptics, antifungal agents, other polymer compounds other than those described above, and moisture as necessary. May be. The PVA film can contain one or more of these other components.
薄型の光学フィルム（偏光フィルム等）を製造することができることから、ＰＶＡフィルムの厚みは、５５μｍ以下であることが必要であり、４０μｍ以下であることが好ましく、また、３０μｍ以下、さらには２０μｍ以下であってもよい。より薄型のＰＶＡフィルムにおいて破線スジがより問題となりやすく、このような厚みを有するＰＶＡフィルムにおいて本発明の効果が特に顕著に奏される。一方、ＰＶＡフィルムの厚みの下限に特に制限はないが、ＰＶＡフィルムの取り扱い性、光学フィルム製造時の工程通過性、得られる光学フィルムの光学性能（偏光フィルムの偏光性能等）などを考慮すると、当該厚みは３μｍ以上であることが好ましく、５μｍ以上であることがより好ましく、１０μｍ以上であることがさらに好ましい。ＰＶＡフィルムの厚みは、任意の５箇所の厚みを測定しその平均値として求めることができる。
Since a thin optical film (such as a polarizing film) can be produced, the thickness of the PVA film needs to be 55 μm or less, preferably 40 μm or less, 30 μm or less, and further 20 μm or less. It may be. Broken line streaks are more likely to be a problem in thinner PVA films, and the effects of the present invention are particularly prominent in PVA films having such thickness. On the other hand, the lower limit of the thickness of the PVA film is not particularly limited, but considering the handleability of the PVA film, the process passability during the production of the optical film, the optical performance of the resulting optical film (such as the polarizing performance of the polarizing film), The thickness is preferably 3 μm or more, more preferably 5 μm or more, and further preferably 10 μm or more. The thickness of the PVA film can be obtained as an average value obtained by measuring the thicknesses at arbitrary five locations.
ＰＶＡフィルムの形状は特に制限されないが、より均一なＰＶＡフィルムを連続して円滑に製造することができるとともに、それを用いて偏光フィルム等の光学フィルムを製造する場合などにおいても連続して使用することができることから長尺のフィルムであることが好ましい。長尺のフィルムは、円筒状のコアに巻き取るなどしてフィルムロールの形態とすることが好ましい。長尺のフィルムである際においてＰＶＡフィルムの長さ（流れ方向の長さ）は特に制限されず、用途などに応じて適宜設定することができるが、フィルムロールから連続的に巻き出して使用する場合などにおいてＰＶＡフィルムの長さがより長いほどフィルムロールを切り替える際のロスを減らすことができることから、当該長さは５００ｍ以上であることが好ましく、１，０００ｍ以上であることがより好ましく、５，０００ｍ以上であることが更に好ましく、８，０００ｍ以上であることが特に好ましい。当該長さの上限に特に制限はないが、当該長さは例えば３０，０００ｍ以下とすることができる。
The shape of the PVA film is not particularly limited, but a more uniform PVA film can be continuously and smoothly manufactured, and is also used continuously when an optical film such as a polarizing film is manufactured using the PVA film. It is preferable that the film is a long film. The long film is preferably in the form of a film roll by winding it around a cylindrical core. In the case of a long film, the length of the PVA film (the length in the flow direction) is not particularly limited, and can be set as appropriate according to the use, etc., but is continuously unwound from the film roll and used. In some cases, the longer the length of the PVA film, the more the loss when switching the film roll can be reduced. Therefore, the length is preferably 500 m or more, more preferably 1,000 m or more. Is more preferably 8,000 m or more, particularly preferably 8,000 m or more. Although there is no restriction | limiting in particular in the upper limit of the said length, The said length can be 30,000 m or less, for example.
ＰＶＡフィルムの形態に特に制限はなく、単層の形態（単層フィルム）であっても、あるいは、例えば熱可塑性樹脂フィルム上にコート法などによって形成されたＰＶＡフィルムのように積層体の形態であっても、どちらでもよいが、本発明の効果がより一層顕著に奏される点、積層（コート等）作業の煩雑さ・熱可塑性樹脂フィルムのコストなどの観点から単層の形態が好ましい。
There is no restriction | limiting in particular in the form of a PVA film, Even if it is a single layer form (single layer film), or in the form of a laminated body like the PVA film formed by the coating method etc. on the thermoplastic resin film, for example However, a single-layered form is preferred from the viewpoints of the effects of the present invention being more prominent, the complexity of laminating (coating and the like) work, and the cost of the thermoplastic resin film.
ＰＶＡフィルムの幅は特に制限されず、ＰＶＡフィルムや、それから製造される偏光フィルム等の光学フィルムの用途などに応じて適宜設定することができるが、近年、液晶テレビや液晶モニターの大画面化が進んでいる点から、ＰＶＡフィルムの幅を２ｍ以上、より好ましくは３ｍ以上、さらに好ましくは４ｍ以上にしておくと、これらの用途に好適である。一方、ＰＶＡフィルムの幅があまりに大きすぎると実用化されている装置で光学フィルムを製造する場合に一軸延伸を均一に行うことが困難になりやすいので、ＰＶＡフィルムの幅は７ｍ以下であることが好ましい。
The width of the PVA film is not particularly limited, and can be set as appropriate according to the use of the PVA film or an optical film such as a polarizing film produced from the PVA film. From the point of progress, it is suitable for these uses when the width of the PVA film is 2 m or more, more preferably 3 m or more, and even more preferably 4 m or more. On the other hand, if the width of the PVA film is too large, it is likely to be difficult to perform uniaxial stretching uniformly when an optical film is produced by a device that has been put to practical use. Therefore, the width of the PVA film may be 7 m or less. preferable.
［ＰＶＡフィルムの製造方法］
本発明のＰＶＡフィルムの製法は特に限定されないが、以下の本発明の製造方法によれば、本発明のＰＶＡフィルムを円滑に連続して製造することができる。 [PVA film production method]
Although the manufacturing method of the PVA film of this invention is not specifically limited, According to the manufacturing method of the following this invention, the PVA film of this invention can be manufactured smoothly continuously.
本発明のＰＶＡフィルムの製法は特に限定されないが、以下の本発明の製造方法によれば、本発明のＰＶＡフィルムを円滑に連続して製造することができる。 [PVA film production method]
Although the manufacturing method of the PVA film of this invention is not specifically limited, According to the manufacturing method of the following this invention, the PVA film of this invention can be manufactured smoothly continuously.
すなわち、厚みが５５μｍ以下のＰＶＡフィルムを製造するための本発明の製造方法は、回転軸が互いに平行な複数の乾燥ロール（最上流側から下流側に向かって、順次、第１乾燥ロール、第２乾燥ロール・・・と称する）を備える製膜装置を使用し、当該製膜装置の第１乾燥ロール上にＰＶＡを含む製膜原液を膜状に吐出して乾燥し、それに続く第２乾燥ロール以降の乾燥ロールで更に乾燥してＰＶＡフィルムを製膜する際に、製膜原液の吐出速度（Ｓ０）を２．５～５．０ｍ／分にする、製造方法である。
That is, the manufacturing method of the present invention for manufacturing a PVA film having a thickness of 55 μm or less includes a plurality of drying rolls whose rotation axes are parallel to each other (in order from the most upstream side to the downstream side, the first drying roll, 2), a film-forming stock solution containing PVA is discharged in the form of a film on the first drying roll of the film-forming apparatus and dried, followed by second drying. This is a production method in which when the PVA film is formed by further drying with a drying roll after the roll, the discharge rate (S 0 ) of the raw film forming solution is set to 2.5 to 5.0 m / min.
本発明の製造方法では、回転軸が互いに平行な複数の乾燥ロールを備える製膜装置を使用し、当該製膜装置の第１乾燥ロール上にＰＶＡを含む製膜原液を膜状に吐出して乾燥し、当該第１乾燥ロールの下流側に続く第２乾燥ロール以降の乾燥ロールで更に乾燥してＰＶＡフィルムを製膜する。当該製膜装置では、乾燥ロールの数は３個以上であることが好ましく、４個以上であることがより好ましく、５～３０個であることが更に好ましい。
In the production method of the present invention, a film-forming apparatus including a plurality of drying rolls whose rotation axes are parallel to each other is used, and a film-forming stock solution containing PVA is discharged into a film on the first drying roll of the film-forming apparatus. It dries, and it further dries with the drying roll after the 2nd drying roll following the downstream of the said 1st drying roll, and forms a PVA film. In the film forming apparatus, the number of drying rolls is preferably 3 or more, more preferably 4 or more, and further preferably 5 to 30.
複数の乾燥ロールは、例えば、ニッケル、クロム、銅、鉄、ステンレススチールなどの金属から形成されていることが好ましく、特に乾燥ロールの表面が、腐食しにくく、しかも鏡面光沢を有する金属材料から形成されていることがより好ましい。また、乾燥ロールの耐久性を高めるために、ニッケル層、クロム層、ニッケル／クロム合金層などを単層または２層以上組み合わせてメッキした乾燥ロールを用いることがより好ましい。
The plurality of drying rolls are preferably formed from a metal such as nickel, chromium, copper, iron, stainless steel, and the like, and in particular, the surface of the drying roll is formed from a metal material that is resistant to corrosion and has a specular gloss. More preferably. In order to increase the durability of the drying roll, it is more preferable to use a drying roll plated with a single layer or a combination of two or more layers such as a nickel layer, a chromium layer, and a nickel / chromium alloy layer.
第１乾燥ロールから最終乾燥ロールに至る過程におけるフィルムを乾燥する際の加熱方向について、フィルムをより均一に乾燥することができることから、フィルムの任意の部分において、第１乾燥ロールと接触する膜面（以下、「第１乾燥ロール接触面」ということがある）と、第１乾燥ロールと接触しない膜面（以下、「第１乾燥ロール非接触面」ということがある）とが、第１乾燥ロールから最終乾燥ロールまでの各乾燥ロールに交互に対向するように乾燥するのが好ましい。
Since the film can be dried more uniformly with respect to the heating direction when drying the film in the process from the first drying roll to the final drying roll, the film surface in contact with the first drying roll in any part of the film (Hereinafter sometimes referred to as “first drying roll contact surface”) and a film surface that does not contact the first drying roll (hereinafter also referred to as “first drying roll non-contact surface”) are the first drying. It is preferable to dry so as to alternately face each drying roll from the roll to the final drying roll.
製膜装置の第１乾燥ロール上にＰＶＡを含む製膜原液を膜状に吐出するにあたっては、例えば、Ｔ型スリットダイ、ホッパープレート、Ｉ－ダイ、リップコーターダイなどの既知の膜状吐出装置（膜状流延装置）を使用して、ＰＶＡを含む製膜原液を第１乾燥ロール上に膜状に吐出（流延）すればよい。
For discharging a film-forming stock solution containing PVA onto the first drying roll of the film-forming apparatus in the form of a film, for example, known film-like discharging apparatuses such as a T-type slit die, a hopper plate, an I-die, and a lip coater die A film-forming stock solution containing PVA may be discharged (cast) into a film form on the first drying roll using (film-form casting apparatus).
製膜原液の吐出速度（Ｓ０）は２．５～５．０ｍ／分であることが必要である。理論上、製膜原液の吐出速度（Ｓ０）を小さくする一方、製膜原液の吐出速度（Ｓ０）に対する第１乾燥ロールの周速（Ｓ１）の比（Ｓ１／Ｓ０）を大きくすることによっても、あるいはこれとは逆に、製膜原液の吐出速度（Ｓ０）を大きくする一方、製膜原液の吐出速度（Ｓ０）に対する第１乾燥ロールの周速（Ｓ１）の比（Ｓ１／Ｓ０）を小さくすることによっても、同じ厚みを有するＰＶＡフィルムを特定の生産速度で製造することができるが、本発明者らは、厚みが５５μｍ以下の薄型のＰＶＡフィルムを製造する際に製膜原液の吐出速度（Ｓ０）を上記の範囲にすることにより、薄型のＰＶＡフィルムにおいて特に問題となる破線スジの本数の少ない、従来にない薄型のＰＶＡフィルムを、円滑に連続して製造することができることを見出した。当該製膜原液の吐出速度（Ｓ０）は、破線スジの本数をより低減することができるなどの理由から、２．６ｍ／分以上であることが好ましく、２．７ｍ／分以上であることがより好ましく、２．８ｍ／分以上であることが更に好ましい。一方、当該製膜原液の吐出速度（Ｓ０）があまりに高すぎると、ＰＶＡフィルムを安定して製造するのが困難になる傾向があることから、当該製膜原液の吐出速度（Ｓ０）は、４．８ｍ／分以下であることが好ましく、４．５ｍ／分以下であることがより好ましく、４．２ｍ／分以下であることが更に好ましく、４．０ｍ／分以下であることが特に好ましい。なお、製膜原液の吐出速度（Ｓ０）とは製膜原液の流れ方向の線速度を意味し、膜状吐出装置から吐出される製膜原液の単位時間あたりの体積を、当該膜状吐出装置のスリット部の開口面積（膜状吐出装置のスリット幅とスリット開度の平均値との積）で除すことにより求めることができる。
The discharge rate (S 0 ) of the film-forming stock solution needs to be 2.5 to 5.0 m / min. In theory, while reducing the discharge speed of the film-forming solution (S 0), the peripheral speed of the first drying roll against the discharge rate of the film-forming solution (S 0) the ratio of (S 1) (S 1 / S 0) Increasing or conversely increasing the film-forming stock solution discharge speed (S 0 ), while the film-forming stock solution discharge speed (S 0 ) has a peripheral speed (S 1 ) of the first drying roll. Although the PVA film having the same thickness can be produced at a specific production rate by reducing the ratio (S 1 / S 0 ) of the present invention, the present inventors have developed a thin PVA film having a thickness of 55 μm or less. By making the discharge rate (S 0 ) of the film-forming stock solution in the above range when manufacturing the thin PVA film, a thin PVA film that has an unprecedented thin PVA film with a small number of broken lines, which is a problem particularly in the thin PVA film, Continuously manufactured Theft has been found to be able to. The discharge speed (S 0 ) of the film-forming stock solution is preferably 2.6 m / min or more, and preferably 2.7 m / min or more, for the reason that the number of broken lines can be further reduced. Is more preferable, and it is still more preferable that it is 2.8 m / min or more. On the other hand, if the discharge rate (S 0 ) of the film-forming stock solution is too high, it tends to be difficult to stably produce the PVA film. Therefore, the discharge rate (S 0 ) of the film-forming stock solution is It is preferably 4.8 m / min or less, more preferably 4.5 m / min or less, still more preferably 4.2 m / min or less, and particularly preferably 4.0 m / min or less. preferable. The discharge rate (S 0 ) of the film-forming stock solution means the linear velocity in the flow direction of the film-forming stock solution, and the volume per unit time of the film-forming stock solution discharged from the film-like discharge device is the film-like discharge rate. It can be determined by dividing by the opening area of the slit portion of the device (product of the slit width of the film-like discharge device and the average value of the slit opening).
ＰＶＡフィルムを含む製膜原液としては、ＰＶＡを液体媒体と混合して溶液にしたり、液体媒体などを含むＰＶＡペレットを溶融して溶融液にしたりすることなどによって調製することができる。
その際に用いる液体媒体としては、例えば、水、ジメチルスルホキシド、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ－メチルピロリドン、エチレンジアミン、ジエチレントリアミンなどを挙げることができ、これらの液体媒体は、１種を単独で使用してもまたは２種以上を併用してもよい。これらの中でも水、ジメチルスルホキシド、または両者の混合物が好ましく用いられ、特に水がより好ましく用いられる。 A film-forming stock solution containing a PVA film can be prepared by mixing PVA with a liquid medium to form a solution, or by melting PVA pellets containing the liquid medium or the like to form a melt.
Examples of the liquid medium used in this case include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylenediamine, and diethylenetriamine. These liquid media are used alone. Or two or more of them may be used in combination. Among these, water, dimethyl sulfoxide, or a mixture of both are preferably used, and water is more preferably used.
その際に用いる液体媒体としては、例えば、水、ジメチルスルホキシド、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ－メチルピロリドン、エチレンジアミン、ジエチレントリアミンなどを挙げることができ、これらの液体媒体は、１種を単独で使用してもまたは２種以上を併用してもよい。これらの中でも水、ジメチルスルホキシド、または両者の混合物が好ましく用いられ、特に水がより好ましく用いられる。 A film-forming stock solution containing a PVA film can be prepared by mixing PVA with a liquid medium to form a solution, or by melting PVA pellets containing the liquid medium or the like to form a melt.
Examples of the liquid medium used in this case include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylenediamine, and diethylenetriamine. These liquid media are used alone. Or two or more of them may be used in combination. Among these, water, dimethyl sulfoxide, or a mixture of both are preferably used, and water is more preferably used.
製膜原液には、所望により、ＰＶＡフィルムの説明において上記したような、可塑剤、界面活性剤、他の成分などのうちの１種または２種以上を上記した量で配合するのが好ましい。
If desired, the film-forming stock solution is preferably blended with one or more of the plasticizers, surfactants, and other components as described above in the description of the PVA film in the above-mentioned amounts.
ＰＶＡフィルムの製造に用いる製膜原液の揮発分率は、５０～９０質量％の範囲内であることが好ましく、５５～８０質量％の範囲内であることがより好ましく、６０～７５質量％の範囲内であることが更に好ましい。製膜原液の揮発分率があまりに低すぎると、製膜原液の粘度が高くなりすぎて濾過や脱泡が困難になったり、製膜自体が困難になったりする場合がある。一方、製膜原液の揮発分率があまりに高すぎると、粘度が低くなりすぎてＰＶＡフィルムの厚みの均一性が損なわれる場合がある。
ここで、本明細書における「製膜原液の揮発分率」とは、下記の式［Ｉ］により求めた揮発分率をいう。
製膜原液の揮発分率（質量％）＝｛（Ｗａ－Ｗｂ）／Ｗａ｝×１００ ［Ｉ］
（式中、Ｗａは製膜原液の質量（ｇ）を表し、ＷｂはＷａ（ｇ）の製膜原液を１０５℃の電熱乾燥機中で１６時間乾燥した時の質量（ｇ）を表す。） The volatile fraction of the film-forming stock solution used for the production of the PVA film is preferably in the range of 50 to 90% by mass, more preferably in the range of 55 to 80% by mass, and 60 to 75% by mass. More preferably within the range. If the volatile fraction of the film-forming stock solution is too low, the viscosity of the film-forming stock solution may become too high, making filtration and defoaming difficult, or making the film itself difficult. On the other hand, if the volatile fraction of the film-forming stock solution is too high, the viscosity becomes too low and the thickness uniformity of the PVA film may be impaired.
Here, “the volatile fraction of the film-forming stock solution” in this specification refers to the volatile fraction obtained by the following formula [I].
Volatile fraction (% by mass) of the film-forming stock solution = {(Wa−Wb) / Wa} × 100 [I]
(In the formula, Wa represents the mass (g) of the film-forming stock solution, and Wb represents the mass (g) when the film-forming stock solution of Wa (g) was dried in an electrothermal dryer at 105 ° C. for 16 hours.)
ここで、本明細書における「製膜原液の揮発分率」とは、下記の式［Ｉ］により求めた揮発分率をいう。
製膜原液の揮発分率（質量％）＝｛（Ｗａ－Ｗｂ）／Ｗａ｝×１００ ［Ｉ］
（式中、Ｗａは製膜原液の質量（ｇ）を表し、ＷｂはＷａ（ｇ）の製膜原液を１０５℃の電熱乾燥機中で１６時間乾燥した時の質量（ｇ）を表す。） The volatile fraction of the film-forming stock solution used for the production of the PVA film is preferably in the range of 50 to 90% by mass, more preferably in the range of 55 to 80% by mass, and 60 to 75% by mass. More preferably within the range. If the volatile fraction of the film-forming stock solution is too low, the viscosity of the film-forming stock solution may become too high, making filtration and defoaming difficult, or making the film itself difficult. On the other hand, if the volatile fraction of the film-forming stock solution is too high, the viscosity becomes too low and the thickness uniformity of the PVA film may be impaired.
Here, “the volatile fraction of the film-forming stock solution” in this specification refers to the volatile fraction obtained by the following formula [I].
Volatile fraction (% by mass) of the film-forming stock solution = {(Wa−Wb) / Wa} × 100 [I]
(In the formula, Wa represents the mass (g) of the film-forming stock solution, and Wb represents the mass (g) when the film-forming stock solution of Wa (g) was dried in an electrothermal dryer at 105 ° C. for 16 hours.)
第１乾燥ロールの表面温度は特に限定されないが、フィルムの乾燥の均一性、生産性などの観点から、７０～１２０℃の範囲内であることが好ましく、８０～１０５℃の範囲内であることがより好ましく、８５～９５℃の範囲内であることが更に好ましい。
The surface temperature of the first drying roll is not particularly limited, but it is preferably in the range of 70 to 120 ° C., and in the range of 80 to 105 ° C., from the viewpoint of film drying uniformity and productivity. Is more preferable, and it is still more preferable to be in the range of 85 to 95 ° C.
膜状に吐出された製膜原液の第１乾燥ロール上での乾燥は、第１乾燥ロールからの加熱のみによって行ってもよいが、第１乾燥ロールで加熱すると同時に第１乾燥ロール非接触面に熱風を吹き付けて、フィルムの両面から熱を与えて乾燥を行うことが、均一乾燥性、乾燥速度などの点から好ましい。
Although the film-forming stock solution discharged in the form of a film may be dried on the first drying roll only by heating from the first drying roll, the first drying roll non-contact surface is simultaneously heated with the first drying roll. It is preferable from the viewpoints of uniform drying property, drying speed, and the like to dry by blowing hot air onto the film and applying heat from both sides of the film.
第１乾燥ロール上にあるフィルムの第１乾燥ロール非接触面に熱風を吹き付けるにあたっては、第１乾燥ロール非接触面の全領域に対して風速１～１０ｍ／秒の熱風を吹き付けることが好ましく、風速２～８ｍ／秒の熱風を吹き付けることがより好ましく、風速３～８ｍ／秒の熱風を吹き付けることが更に好ましい。第１乾燥ロール非接触面に吹き付ける熱風の風速が小さすぎると、第１乾燥ロール上での乾燥時に水蒸気などの結露が発生し、その水滴がフィルムに滴下して最終的に得られるＰＶＡフィルムに欠点が生じるおそれがある。一方、第１乾燥ロール非接触面に吹き付ける熱風の風速が大きすぎると、最終的に得られるＰＶＡフィルムに厚み斑が発生し、それに伴って染色斑の発生などのトラブルが発生しやすくなる。
In spraying hot air on the first drying roll non-contact surface of the film on the first drying roll, it is preferable to blow hot air at a wind speed of 1 to 10 m / sec over the entire area of the first drying roll non-contact surface, It is more preferable to blow hot air with a wind speed of 2 to 8 m / sec, and it is more preferable to blow hot air with a wind speed of 3 to 8 m / sec. If the wind speed of the hot air sprayed on the non-contact surface of the first drying roll is too small, condensation such as water vapor occurs during drying on the first drying roll, and the water droplets drop on the film to finally obtain the PVA film. There is a risk that defects may occur. On the other hand, when the wind speed of the hot air blown on the non-contact surface of the first drying roll is too high, thickness spots are generated in the finally obtained PVA film, and troubles such as generation of stained spots easily occur.
フィルムの第１乾燥ロール非接触面に吹き付ける熱風の温度は、乾燥効率、乾燥の均一性などの点から、５０～１５０℃であることが好ましく、７０～１２０℃であることがより好ましく、８０～９５℃であることが更に好ましい。またフィルムの第１乾燥ロール非接触面に吹き付ける熱風の露点温度は５～２０℃であることが好ましく、１０～１５℃であることがより好ましい。
The temperature of the hot air blown on the non-contact surface of the first drying roll of the film is preferably 50 to 150 ° C., more preferably 70 to 120 ° C. from the viewpoint of drying efficiency, drying uniformity, and the like. More preferably, it is -95 ° C. Further, the dew point temperature of the hot air blown on the non-contact surface of the first drying roll of the film is preferably 5 to 20 ° C., and more preferably 10 to 15 ° C.
フィルムの第１乾燥ロール非接触面に熱風を吹き付けるための方式は特に制限されず、風速が均一で且つ温度が均一な熱風をフィルムの第１乾燥ロール非接触面、好ましくはその全体に均一に吹き付け得る方式のいずれもが採用でき、そのうちでもノズル方式、整流板方式またはそれらの組み合わせなどが好ましく採用される。フィルムの第１乾燥ロール非接触面への熱風の吹き付け方向は、第１乾燥ロール非接触面に対向する方向であっても、フィルムの第１乾燥ロール非接触面の円周形状にほぼ沿った方向（第１乾燥ロールのロール表面の円周にほぼ沿った方向）であっても、またはそれ以外の方向であってもよい。
The method for blowing hot air to the non-contact surface of the first drying roll of the film is not particularly limited, and the hot air having a uniform wind speed and uniform temperature is uniformly applied to the non-contact surface of the first drying roll, preferably the entire surface thereof. Any of the methods that can be sprayed can be employed, and among them, the nozzle method, the current plate method, or a combination thereof is preferably employed. The blowing direction of the hot air to the first drying roll non-contact surface of the film was substantially along the circumferential shape of the first drying roll non-contact surface of the film, even in the direction facing the first drying roll non-contact surface. The direction may be the direction (direction substantially along the circumference of the roll surface of the first drying roll) or the other direction.
また、第１乾燥ロール上でのフィルムの乾燥時に、乾燥によってフィルムから発生した揮発分と吹き付けた後の熱風を排気することが好ましい。排気の方法は特に制限されないが、フィルムの第１乾燥ロール非接触面に吹き付ける熱風の風速斑および温度斑が生じない排気方法を採用することが好ましい。
Also, when the film is dried on the first drying roll, it is preferable to exhaust the volatile matter generated from the film by drying and the hot air after spraying. The exhaust method is not particularly limited, but it is preferable to employ an exhaust method that does not cause wind speed spots and temperature spots of hot air sprayed on the non-contact surface of the first drying roll of the film.
第１乾燥ロールの周速（Ｓ１）は、破線スジの本数をより低減することができ、また生産時の安定性などにも優れることから、１２～３５ｍ／分の範囲内であることが好ましく、当該第１乾燥ロールの周速（Ｓ１）は、１５ｍ／分以上であることがより好ましく、また、３０ｍ／分以下であることがより好ましく、２８ｍ／分以下であることが更に好ましく、２６ｍ／分以下であることが特に好ましい。
The peripheral speed (S 1 ) of the first drying roll can be within the range of 12 to 35 m / min because the number of broken lines can be further reduced and the stability during production is excellent. Preferably, the peripheral speed (S 1 ) of the first drying roll is more preferably 15 m / min or more, more preferably 30 m / min or less, and still more preferably 28 m / min or less. 26 m / min or less is particularly preferable.
製膜原液の吐出速度（Ｓ０）に対する第１乾燥ロールの周速（Ｓ１）の比（Ｓ１／Ｓ０）は、破線スジの本数をより低減することができ、また生産時の安定性などにも優れることから、７以下であることが好ましく、６．８以下であることがより好ましく、６．５以下であることが更に好ましく、６．３以下であることが特に好ましく、また、３を超えることが好ましく、５を超えることがより好ましく、５．２を超えることが更に好ましく、５．５を超えることが特に好ましく、６を超えることが最も好ましい。
The ratio (S 1 / S 0 ) of the peripheral speed (S 1 ) of the first drying roll to the discharge speed (S 0 ) of the film-forming stock solution can further reduce the number of broken lines and can be stable during production. From the viewpoint of excellent properties, it is preferably 7 or less, more preferably 6.8 or less, still more preferably 6.5 or less, particularly preferably 6.3 or less, It is preferably more than 3, more preferably more than 5, still more preferably more than 5.2, particularly preferably more than 5.5, and most preferably more than 6.
第１乾燥ロール上に膜状に吐出された製膜原液は、第１乾燥ロール上で乾燥され、フィルムの揮発分率（第１乾燥ロールからの剥離時のフィルムの揮発分率）が、好ましくは５～３０質量％、より好ましくは７～２０質量％、更に好ましくは８～１５質量％のときに第１乾燥ロールから剥離される。第１乾燥ロールからの剥離時のフィルムの揮発分率が５質量％以上であることにより、第１乾燥ロール接触面と第１乾燥ロール非接触面との間の乾燥速度の差が大きくなってフィルムがカールしやすくなるのを抑制することができる。また、第１乾燥ロールからの剥離時のフィルムの揮発分率が３０質量％以下であることにより、厚み斑が大きくなるのを抑制することができる。
ここで、本明細書における「フィルムの揮発分率」とは、下記の式［II］により求めた揮発分率をいう。
フィルムの揮発分率（質量％）＝｛（Ｗｃ－Ｗｄ）／Ｗｃ｝×１００ ［II］
（式中、Ｗｃはフィルムから採取したサンプルの質量（ｇ）を表し、ＷｄはＷｃ（ｇ）の前記サンプルを温度５０℃、圧力０．１ｋＰａ以下の真空乾燥機中に入れて４時間乾燥した時の質量（ｇ）を表す。） The film-forming stock solution discharged in the form of a film on the first drying roll is dried on the first drying roll, and the volatile content rate of the film (the volatile content rate of the film at the time of peeling from the first drying roll) is preferable. Is peeled from the first drying roll when it is 5 to 30% by mass, more preferably 7 to 20% by mass, and still more preferably 8 to 15% by mass. When the volatile content of the film at the time of peeling from the first drying roll is 5% by mass or more, the difference in drying speed between the first drying roll contact surface and the first drying roll non-contact surface becomes large. It can suppress that a film becomes easy to curl. Moreover, it can suppress that a thickness spot becomes large because the volatile content rate of the film at the time of peeling from a 1st drying roll is 30 mass% or less.
Here, “the volatile fraction of the film” in the present specification refers to the volatile fraction determined by the following formula [II].
Film volatile content (mass%) = {(Wc−Wd) / Wc} × 100 [II]
(Wc represents the mass (g) of the sample collected from the film, and Wd is the sample of Wc (g) placed in a vacuum dryer at a temperature of 50 ° C. and a pressure of 0.1 kPa or less and dried for 4 hours. (It represents mass (g) at the time.)
ここで、本明細書における「フィルムの揮発分率」とは、下記の式［II］により求めた揮発分率をいう。
フィルムの揮発分率（質量％）＝｛（Ｗｃ－Ｗｄ）／Ｗｃ｝×１００ ［II］
（式中、Ｗｃはフィルムから採取したサンプルの質量（ｇ）を表し、ＷｄはＷｃ（ｇ）の前記サンプルを温度５０℃、圧力０．１ｋＰａ以下の真空乾燥機中に入れて４時間乾燥した時の質量（ｇ）を表す。） The film-forming stock solution discharged in the form of a film on the first drying roll is dried on the first drying roll, and the volatile content rate of the film (the volatile content rate of the film at the time of peeling from the first drying roll) is preferable. Is peeled from the first drying roll when it is 5 to 30% by mass, more preferably 7 to 20% by mass, and still more preferably 8 to 15% by mass. When the volatile content of the film at the time of peeling from the first drying roll is 5% by mass or more, the difference in drying speed between the first drying roll contact surface and the first drying roll non-contact surface becomes large. It can suppress that a film becomes easy to curl. Moreover, it can suppress that a thickness spot becomes large because the volatile content rate of the film at the time of peeling from a 1st drying roll is 30 mass% or less.
Here, “the volatile fraction of the film” in the present specification refers to the volatile fraction determined by the following formula [II].
Film volatile content (mass%) = {(Wc−Wd) / Wc} × 100 [II]
(Wc represents the mass (g) of the sample collected from the film, and Wd is the sample of Wc (g) placed in a vacuum dryer at a temperature of 50 ° C. and a pressure of 0.1 kPa or less and dried for 4 hours. (It represents mass (g) at the time.)
第１乾燥ロール上で好ましくは揮発分率５～３０質量％にまで乾燥したフィルムを第１乾燥ロールから剥離し、今度は、フィルムの第１乾燥ロール非接触面を第２乾燥ロールに対向させて、第２乾燥ロールでフィルムを乾燥するのが好ましい。
The film dried to a volatile content of preferably 5 to 30% by mass on the first drying roll is peeled off from the first drying roll, and this time, the non-contact surface of the first drying roll is opposed to the second drying roll. The film is preferably dried with a second drying roll.
第２乾燥ロールで乾燥したフィルムは、第２乾燥ロールから剥離し、製膜装置に設けた乾燥ロールの数などに応じて、第３乾燥ロール、第４乾燥ロール、第５乾燥ロール、・・・などの複数の乾燥ロールによって順次乾燥すればよい。
The film dried by the second drying roll is peeled off from the second drying roll, and the third drying roll, the fourth drying roll, the fifth drying roll, etc., depending on the number of drying rolls provided in the film forming apparatus, etc. * What is necessary is just to dry sequentially by several drying rolls, such as.
第２乾燥ロールから最終乾燥ロールまでの各乾燥ロールの表面温度は、均一乾燥性、乾燥速度などの点から、４０℃以上であることが好ましく、４５℃以上であることがより好ましく、５０℃以上であることが更に好ましく、また、１００℃未満であることが好ましく、９０℃未満であることがより好ましく、８５℃未満であることが更に好ましく、８０℃未満であることが特に好ましい。
The surface temperature of each drying roll from the second drying roll to the final drying roll is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, from the viewpoint of uniform drying properties, drying speed, etc. More preferably, it is preferably less than 100 ° C, more preferably less than 90 ° C, still more preferably less than 85 ° C, and particularly preferably less than 80 ° C.
上記のようにして最終乾燥ロールでの乾燥を経たフィルムに対して、熱処理を施すことが好ましい。熱処理は熱処理ロールやその他の公知の熱処理装置を使用して行うことができる。熱処理ロールによって熱処理を施す場合、熱処理ロールは１本であっても複数本であってもどちらでもよい。
It is preferable to heat-treat the film that has been dried on the final drying roll as described above. The heat treatment can be performed using a heat treatment roll or other known heat treatment apparatus. When the heat treatment is performed by the heat treatment roll, there may be one heat treatment roll or a plurality of heat treatment rolls.
熱処理ロールの表面温度は、結晶化を適度に進行し耐熱水性に優れたＰＶＡフィルムが得られることから、９０℃以上であることが好ましく、１００℃以上であることがより好ましく、１１０℃以上であることが更に好ましい。また、得られるＰＶＡフィルムの延伸性を向上させる観点から、熱処理ロールの表面温度は１５０℃以下であることが好ましく、１４０℃以下であることがより好ましく、１３０℃以下であることが更に好ましい。
The surface temperature of the heat treatment roll is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and more preferably 110 ° C. or higher, because a PVA film having a moderately advanced crystallization and excellent hot water resistance can be obtained. More preferably it is. Moreover, from the viewpoint of improving the stretchability of the obtained PVA film, the surface temperature of the heat treatment roll is preferably 150 ° C. or lower, more preferably 140 ° C. or lower, and further preferably 130 ° C. or lower.
熱処理時間に特に制限はないが、目的とするＰＶＡフィルムをより円滑に製造することができることから、３～６０秒間の範囲内であることが好ましく、５～３０秒間の範囲内であることがより好ましい。
Although there is no particular limitation on the heat treatment time, it is preferably in the range of 3 to 60 seconds, more preferably in the range of 5 to 30 seconds, because the target PVA film can be produced more smoothly. preferable.
上記の製膜装置は、必要に応じて、熱風乾燥装置、調湿装置などを有していてもよい。
The film forming apparatus described above may have a hot air drying device, a humidity control device, or the like as necessary.
上記のようにして得られたフィルムは、必要に応じて、更に、調湿処理、フィルム両端部（耳部）のカットなどを行い、最後に所定の長さでロール状に巻き取ることにより本発明のＰＶＡフィルムとすることができる。
The film obtained as described above is further subjected to humidity conditioning treatment, cutting of both end portions (ear portions) of the film, if necessary, and finally wound into a roll with a predetermined length. It can be set as the PVA film of invention.
上記した一連の処理によって最終的に得られるＰＶＡフィルムの揮発分率は１～５質量％の範囲内にあることが好ましく、２～４質量％の範囲内にあることがより好ましい。
The volatile content of the PVA film finally obtained by the above-described series of treatments is preferably in the range of 1 to 5% by mass, and more preferably in the range of 2 to 4% by mass.
［ＰＶＡフィルムの用途］
本発明のＰＶＡフィルムの用途に特に制限はないが、本発明のＰＶＡフィルムによれば、光学的欠陥の少ない光学フィルムを製造することができることから、本発明のＰＶＡフィルムは、偏光フィルムや位相差フィルム等の光学フィルムを製造するための原反フィルムとして用いることが好ましい。このような光学フィルムは、例えば、本発明のＰＶＡフィルムを用いて一軸延伸などの処理を施すことにより製造することができる。 [Use of PVA film]
Although there is no restriction | limiting in particular in the use of the PVA film of this invention, According to the PVA film of this invention, since an optical film with few optical defects can be manufactured, the PVA film of this invention is a polarizing film and retardation. It is preferably used as an original film for producing an optical film such as a film. Such an optical film can be produced, for example, by applying a treatment such as uniaxial stretching using the PVA film of the present invention.
本発明のＰＶＡフィルムの用途に特に制限はないが、本発明のＰＶＡフィルムによれば、光学的欠陥の少ない光学フィルムを製造することができることから、本発明のＰＶＡフィルムは、偏光フィルムや位相差フィルム等の光学フィルムを製造するための原反フィルムとして用いることが好ましい。このような光学フィルムは、例えば、本発明のＰＶＡフィルムを用いて一軸延伸などの処理を施すことにより製造することができる。 [Use of PVA film]
Although there is no restriction | limiting in particular in the use of the PVA film of this invention, According to the PVA film of this invention, since an optical film with few optical defects can be manufactured, the PVA film of this invention is a polarizing film and retardation. It is preferably used as an original film for producing an optical film such as a film. Such an optical film can be produced, for example, by applying a treatment such as uniaxial stretching using the PVA film of the present invention.
本発明のＰＶＡフィルムを原反フィルムとして用いて偏光フィルムを製造する際の方法は特に制限されず、従来から採用されているいずれの方法を採用してもよい。このような方法としては、例えば、ＰＶＡフィルムに対して染色および一軸延伸を施したり、染料を含有するＰＶＡフィルムに対して一軸延伸を施したりする方法が挙げられる。偏光フィルムを製造するためのより具体的な方法としては、本発明のＰＶＡフィルムに対して、染色、一軸延伸、固定処理、乾燥処理、更に必要に応じて熱処理を施す方法が挙げられる。染色と一軸延伸の順序は特に限定されず、一軸延伸の前に染色を行ってもよいし、一軸延伸と同時に染色を行ってもよいし、または一軸延伸の後に染色を行ってもよい。また、一軸延伸、染色などの工程は複数回繰り返してもよい。特に一軸延伸を２段以上に分けると均一な延伸を行いやすくなるため好ましい。なおＰＶＡフィルムが熱可塑性樹脂フィルム上に形成されているような積層体の形態を有する場合には、当該熱可塑性樹脂フィルムが積層された状態で一軸延伸を施すことにより、一軸延伸時の破断をより低減することができる。
The method for producing a polarizing film using the PVA film of the present invention as a raw film is not particularly limited, and any conventionally employed method may be employed. Examples of such a method include a method of dyeing and uniaxially stretching a PVA film or uniaxially stretching a PVA film containing a dye. As a more specific method for producing the polarizing film, a method of subjecting the PVA film of the present invention to dyeing, uniaxial stretching, fixing treatment, drying treatment, and heat treatment as necessary can be mentioned. The order of dyeing and uniaxial stretching is not particularly limited, and dyeing may be performed before uniaxial stretching, dyeing may be performed simultaneously with uniaxial stretching, or dyeing may be performed after uniaxial stretching. In addition, steps such as uniaxial stretching and dyeing may be repeated a plurality of times. In particular, it is preferable to divide the uniaxial stretching into two or more stages because uniform stretching is easily performed. In addition, when the PVA film has the form of a laminated body formed on a thermoplastic resin film, the rupture at the time of uniaxial stretching is performed by performing uniaxial stretching in a state where the thermoplastic resin film is laminated. It can be further reduced.
ＰＶＡフィルムの染色に用いる染料としては、ヨウ素または二色性有機染料（例えば、ＤｉｒｅｃｔＢｌａｃｋ １７、１９、１５４；ＤｉｒｅｃｔＢｒｏｗｎ ４４、１０６、１９５、２１０、２２３；ＤｉｒｅｃｔＲｅｄ ２、２３、２８、３１、３７、３９、７９、８１、２４０、２４２、２４７；ＤｉｒｅｃｔＢｌｕｅ １、１５、２２、７８、９０、９８、１５１、１６８、２０２、２３６、２４９、２７０；ＤｉｒｅｃｔＶｉｏｌｅｔ ９、１２、５１、９８；ＤｉｒｅｃｔＧｒｅｅｎ １、８５；ＤｉｒｅｃｔＹｅｌｌｏｗ ８、１２、４４、８６、８７；ＤｉｒｅｃｔＯｒａｎｇｅ ２６、３９、１０６、１０７などの二色性染料）などが使用できる。これらの染料は、１種を単独でまたは２種以上を組み合わせて使用することができる。染色は、通常、ＰＶＡフィルムを上記染料を含有する溶液中に浸漬させることにより行うことができるが、その処理条件や処理方法は特に制限されるものではない。
Examples of the dye used for dyeing the PVA film include iodine or a dichroic organic dye (for example, DirectBlack 17, 19, 154; DirectBrown 44, 106, 195, 210, 223; DirectRed 2, 23, 28, 31, 37, 39. 79, 81, 240, 242, 247; DirectBlue 1, 15, 22, 78, 90, 98, 151, 168, 202, 236, 249, 270; DirectViolet 9, 12, 51, 98; DirectGreen 1, 85; Direct Yellow 8, 12, 44, 86, 87; dichroic dyes such as Direct Orange 26, 39, 106, 107) can be used. These dyes can be used alone or in combination of two or more. Dyeing can usually be performed by immersing the PVA film in a solution containing the dye, but the treatment conditions and treatment method are not particularly limited.
ＰＶＡフィルムの一軸延伸は、湿式延伸法または乾熱延伸法のいずれで行ってもよいが、得られる偏光フィルムの性能および品質の安定性の観点から湿式延伸法が好ましい。湿式延伸法としては、ＰＶＡフィルムを、純水、添加剤や水性媒体等の各種成分を含む水溶液、または各種成分が分散した水分散液中で延伸する方法が挙げられ、湿式延伸法による一軸延伸方法の具体例としては、ホウ酸を含む温水中で一軸延伸する方法、前記した染料を含有する溶液中や後記固定処理浴中で一軸延伸する方法などが挙げられる。また、吸水後のＰＶＡフィルムを用いて空気中で一軸延伸してもよいし、その他の方法で一軸延伸してもよい。一軸延伸はＰＶＡフィルムの流れ方向に行うのが好ましい。
The uniaxial stretching of the PVA film may be performed by either a wet stretching method or a dry heat stretching method, but the wet stretching method is preferred from the viewpoint of the performance and quality stability of the obtained polarizing film. Examples of the wet stretching method include a method of stretching a PVA film in pure water, an aqueous solution containing various components such as an additive and an aqueous medium, or an aqueous dispersion in which various components are dispersed. Uniaxial stretching by a wet stretching method. Specific examples of the method include a method of uniaxially stretching in warm water containing boric acid, a method of uniaxially stretching in a solution containing the above-described dye or a fixing treatment bath described later, and the like. Moreover, you may uniaxially stretch in the air using the PVA film after water absorption, and you may uniaxially stretch by another method. Uniaxial stretching is preferably performed in the flow direction of the PVA film.
一軸延伸する際の延伸温度は特に限定されないが、湿式延伸する場合は好ましくは２０～９０℃、より好ましくは２５～７０℃、更に好ましくは３０～６５℃の範囲内の温度が採用され、乾熱延伸する場合は好ましくは５０～１８０℃の範囲内の温度が採用される。
The stretching temperature for uniaxial stretching is not particularly limited, but in the case of wet stretching, a temperature in the range of preferably 20 to 90 ° C, more preferably 25 to 70 ° C, and even more preferably 30 to 65 ° C is adopted. In the case of hot stretching, a temperature within the range of 50 to 180 ° C. is preferably employed.
一軸延伸の延伸倍率（多段で一軸延伸を行う場合は合計の延伸倍率）は、偏光性能の点からフィルムが切断する直前までできるだけ延伸することが好ましく、具体的には４倍以上であることが好ましく、５倍以上であることがより好ましく、５．５倍以上であることが更に好ましい。延伸倍率の上限はフィルムが破断しない限り特に制限はないが、均一な延伸を行うためには８．０倍以下であることが好ましい。
The stretching ratio of uniaxial stretching (the total stretching ratio in the case of performing uniaxial stretching in multiple stages) is preferably stretched as much as possible from the point of polarization performance until just before the film is cut, and specifically 4 times or more. It is preferably 5 times or more, more preferably 5.5 times or more. The upper limit of the stretching ratio is not particularly limited as long as the film is not broken, but is preferably 8.0 times or less in order to perform uniform stretching.
一軸延伸後のフィルム（偏光フィルム）の厚みは１～３０μｍ、特に３～２５μｍであることが好ましい。なお当該厚みは、任意の５箇所の厚みを測定しその平均値として求めることができる。
The thickness of the uniaxially stretched film (polarizing film) is preferably 1 to 30 μm, particularly 3 to 25 μm. In addition, the said thickness can measure | require thickness of arbitrary 5 places, and can obtain | require it as the average value.
偏光フィルムの製造にあたっては、一軸延伸されたフィルムへの染料の吸着を強固にするために、固定処理を行うことが多い。固定処理は、ホウ酸および／またはホウ素化合物を添加した固定処理浴中にフィルムを浸漬する方法が一般に広く採用されている。その際に、必要に応じて処理浴中にヨウ素化合物を添加してもよい。
In the production of a polarizing film, fixing treatment is often performed in order to strengthen the adsorption of the dye to the uniaxially stretched film. As the fixing treatment, a method of immersing the film in a fixing treatment bath to which boric acid and / or boron compound is added is generally widely adopted. In that case, you may add an iodine compound in a processing bath as needed.
一軸延伸処理、または一軸延伸処理と固定処理を行ったフィルムを次いで乾燥処理（熱処理）するのが好ましい。乾燥処理（熱処理）の温度は３０～１５０℃、特に５０～１４０℃であることが好ましい。乾燥処理（熱処理）の温度が低すぎると、得られる偏光フィルムの寸法安定性が低下しやすくなり、一方、高すぎると染料の分解などに伴う偏光性能の低下が発生しやすくなる。
It is preferable that the film subjected to the uniaxial stretching treatment or the uniaxial stretching treatment and the fixing treatment is then subjected to a drying treatment (heat treatment). The temperature of the drying treatment (heat treatment) is preferably 30 to 150 ° C., particularly 50 to 140 ° C. If the temperature of the drying treatment (heat treatment) is too low, the dimensional stability of the obtained polarizing film tends to be lowered, while if too high, the polarizing performance is likely to deteriorate due to the decomposition of the dye.
以上のようにして得られた偏光フィルムの両面または片面に、光学的に透明で、かつ機械的強度を有する保護膜を貼り合わせて偏光板にすることができる。その場合の保護膜としては、三酢酸セルロース（ＴＡＣ）フィルム、酢酸・酪酸セルロース（ＣＡＢ）フィルム、アクリル系フィルム、ポリエステル系フィルムなどが使用される。また、保護膜を貼り合わせるための接着剤としては、ＰＶＡ系接着剤やウレタン系接着剤などが一般に使用されており、そのうちでもＰＶＡ系接着剤が好ましく用いられる。
A polarizing film can be obtained by bonding optically transparent protective films having mechanical strength to both surfaces or one surface of the polarizing film obtained as described above. As the protective film in this case, a cellulose triacetate (TAC) film, an acetic acid / cellulose butyrate (CAB) film, an acrylic film, a polyester film, or the like is used. Moreover, as an adhesive for laminating a protective film, a PVA adhesive or a urethane adhesive is generally used, and among them, a PVA adhesive is preferably used.
以上のようにして得られた偏光板は、アクリル系などの粘着剤を被覆した後、ガラス基板に貼り合わせて液晶ディスプレイ装置の部品として使用することができる。偏光板をガラス基板に貼り合わせる際に、位相差フィルム、視野角向上フィルム、輝度向上フィルムなどを同時に貼り合わせてもよい。
The polarizing plate obtained as described above can be used as a component of a liquid crystal display device after being coated with an acrylic adhesive or the like and then bonded to a glass substrate. When the polarizing plate is bonded to the glass substrate, a retardation film, a viewing angle improving film, a brightness improving film, or the like may be bonded simultaneously.
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらにより何ら限定されるものではない。なお、以下の実施例、比較例および参考例において採用された各測定・評価方法を以下に示す。
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, each measurement and evaluation method employ | adopted in the following example, the comparative example, and the reference example is shown below.
［破線スジの本数］
測定対象となるＰＶＡフィルムの任意の位置において、流れ方向６０ｃｍ×幅方向全体の区域を設定し、走査型白色干渉顕微鏡（「Ｎｅｗ Ｖｉｅｗ」７３００、ＺＹＧＯ社製）を用いて破線スジであると思われるスジ状欠点近辺の厚みプロファイルを測定し、このスジ状欠点が本発明において規定する破線スジであるか否かを確認した。このようにして、上記区域部分において流れ方向の任意の一箇所を通過する幅方向の直線を横切る破線スジの本数を、当該直線の幅方向全体にわたって計測し、この本数をＰＶＡフィルムの幅で除すことによって、幅１ｍあたりの破線スジの本数を求めた。 [Number of dashed lines]
At an arbitrary position of the PVA film to be measured, an area of 60 cm in the flow direction × the entire width direction is set, and it seems to be a broken line streak using a scanning white interference microscope (“New View” 7300, manufactured by ZYGO). The thickness profile in the vicinity of the streak-like defect was measured, and it was confirmed whether or not the streak-like defect was a broken-line streak defined in the present invention. In this way, the number of broken line lines crossing the width direction straight line passing through one arbitrary position in the flow direction in the area portion is measured over the entire width direction of the line, and this number is divided by the width of the PVA film. Thus, the number of broken lines per 1 m width was obtained.
測定対象となるＰＶＡフィルムの任意の位置において、流れ方向６０ｃｍ×幅方向全体の区域を設定し、走査型白色干渉顕微鏡（「Ｎｅｗ Ｖｉｅｗ」７３００、ＺＹＧＯ社製）を用いて破線スジであると思われるスジ状欠点近辺の厚みプロファイルを測定し、このスジ状欠点が本発明において規定する破線スジであるか否かを確認した。このようにして、上記区域部分において流れ方向の任意の一箇所を通過する幅方向の直線を横切る破線スジの本数を、当該直線の幅方向全体にわたって計測し、この本数をＰＶＡフィルムの幅で除すことによって、幅１ｍあたりの破線スジの本数を求めた。 [Number of dashed lines]
At an arbitrary position of the PVA film to be measured, an area of 60 cm in the flow direction × the entire width direction is set, and it seems to be a broken line streak using a scanning white interference microscope (“New View” 7300, manufactured by ZYGO). The thickness profile in the vicinity of the streak-like defect was measured, and it was confirmed whether or not the streak-like defect was a broken-line streak defined in the present invention. In this way, the number of broken line lines crossing the width direction straight line passing through one arbitrary position in the flow direction in the area portion is measured over the entire width direction of the line, and this number is divided by the width of the PVA film. Thus, the number of broken lines per 1 m width was obtained.
［偏光フィルムの光学的欠陥］
偏光フィルムを幅方向に適宜分割後、観察用偏光板（パラレルニコルに２枚重ねたもの、偏光度９９．９９％以上）の間に直交方向に置き、光学的欠陥の程度を目視で観察して、以下の基準により評価した。
○：光学的欠陥を全くまたはほとんど見つけることができない
×：光学的欠陥を容易に見つけることができる
××：光学的欠陥を極めて容易に見つけることができる [Optical defects in polarizing film]
After appropriately dividing the polarizing film in the width direction, place the polarizing film in an orthogonal direction between polarizing plates for observation (two layers of parallel Nicols, polarization degree of 99.99% or more), and visually observe the degree of optical defects. The following criteria were used for evaluation.
○: No or almost no optical defects can be found. ×: Optical defects can be found easily. XX: Optical defects can be found very easily.
偏光フィルムを幅方向に適宜分割後、観察用偏光板（パラレルニコルに２枚重ねたもの、偏光度９９．９９％以上）の間に直交方向に置き、光学的欠陥の程度を目視で観察して、以下の基準により評価した。
○：光学的欠陥を全くまたはほとんど見つけることができない
×：光学的欠陥を容易に見つけることができる
××：光学的欠陥を極めて容易に見つけることができる [Optical defects in polarizing film]
After appropriately dividing the polarizing film in the width direction, place the polarizing film in an orthogonal direction between polarizing plates for observation (two layers of parallel Nicols, polarization degree of 99.99% or more), and visually observe the degree of optical defects. The following criteria were used for evaluation.
○: No or almost no optical defects can be found. ×: Optical defects can be found easily. XX: Optical defects can be found very easily.
［実施例１］
［ＰＶＡフィルムの製造］
ポリ酢酸ビニルをけん化することにより得られたＰＶＡ（平均重合度２，４００、けん化度９９．９モル％）１００質量部、グリセリン１２質量部、ラウリン酸ジエタノールアミド０．１質量部および水からなる揮発分率７０質量％の製膜原液を、Ｔ型スリットダイから吐出速度（Ｓ０）２．８ｍ／分で、回転軸が互いに平行な複数の乾燥ロールと熱処理ロールを備える製膜装置の第１乾燥ロール（周速（Ｓ１）１７ｍ／分）上に膜状に吐出し、第１乾燥ロール上で、第１乾燥ロール非接触面の全体に９０℃の熱風を５ｍ／秒の風速で吹き付けながら乾燥し、次いで第１乾燥ロールから剥離して、フィルムの任意の部分における表面と裏面とが各乾燥ロールに交互に対向するように第２乾燥ロールから熱処理ロールの直前にある最終乾燥ロールまでの間で更に乾燥した後、最終乾燥ロールから剥離した。次いで、表面温度１２０℃の熱処理ロールで熱処理を行い、両端部（耳部）をカット後、円筒状のコアに巻き取ることにより、最終的に、厚み３０．３μｍ、長さ２，０００ｍ、幅２．６ｍ、揮発分率（水分率）２質量％の長尺のＰＶＡフィルム（単層フィルム）を製造した。
当該ＰＶＡフィルムについて、上記した方法により破線スジの本数を測定したところ、高低差が５０～６０ｎｍの凹凸が、０．３～０．７ｍｍの周期でフィルムの流れ方向に略直線状に１０ｃｍ以上にわたり配列した破線スジが６本（フィルムの幅方向１ｍあたり２．３本）存在することが判明した。以上の結果を表１に示した。 [Example 1]
[Production of PVA film]
It consists of 100 parts by mass of PVA (average polymerization degree 2,400, saponification degree 99.9 mol%) obtained by saponifying polyvinyl acetate, 12 parts by mass of glycerol, 0.1 part by mass of lauric acid diethanolamide, and water. A film-forming stock solution having a volatile content of 70% by mass was discharged from a T-type slit die at a discharge speed (S 0 ) of 2.8 m / min, and a film-forming apparatus provided with a plurality of drying rolls and heat treatment rolls whose rotation axes were parallel to each other. 1 film is discharged onto a drying roll (peripheral speed (S 1 ) 17 m / min), and hot air of 90 ° C. is applied to the entire surface of the first drying roll non-contact on the first drying roll at a wind speed of 5 m / sec. It is dried while sprayed, then peeled off from the first drying roll, and the final drying roll immediately before the heat treatment roll from the second drying roll so that the front and back surfaces of any part of the film are alternately opposed to each drying roll. After further drying up to the roll, it was peeled off from the final drying roll. Next, heat treatment is performed with a heat treatment roll having a surface temperature of 120 ° C., and both end portions (ear portions) are cut and wound on a cylindrical core to finally have a thickness of 30.3 μm, a length of 2,000 m, and a width. A long PVA film (single layer film) having 2.6 m and a volatile content (water content) of 2% by mass was produced.
With respect to the PVA film, when the number of the broken line streaks was measured by the above-described method, the unevenness having a height difference of 50 to 60 nm was approximately 10 cm or more in a straight line in the film flow direction with a period of 0.3 to 0.7 mm. It was found that there were 6 broken-line stripes arranged (2.3 per 1 m in the width direction of the film). The above results are shown in Table 1.
［ＰＶＡフィルムの製造］
ポリ酢酸ビニルをけん化することにより得られたＰＶＡ（平均重合度２，４００、けん化度９９．９モル％）１００質量部、グリセリン１２質量部、ラウリン酸ジエタノールアミド０．１質量部および水からなる揮発分率７０質量％の製膜原液を、Ｔ型スリットダイから吐出速度（Ｓ０）２．８ｍ／分で、回転軸が互いに平行な複数の乾燥ロールと熱処理ロールを備える製膜装置の第１乾燥ロール（周速（Ｓ１）１７ｍ／分）上に膜状に吐出し、第１乾燥ロール上で、第１乾燥ロール非接触面の全体に９０℃の熱風を５ｍ／秒の風速で吹き付けながら乾燥し、次いで第１乾燥ロールから剥離して、フィルムの任意の部分における表面と裏面とが各乾燥ロールに交互に対向するように第２乾燥ロールから熱処理ロールの直前にある最終乾燥ロールまでの間で更に乾燥した後、最終乾燥ロールから剥離した。次いで、表面温度１２０℃の熱処理ロールで熱処理を行い、両端部（耳部）をカット後、円筒状のコアに巻き取ることにより、最終的に、厚み３０．３μｍ、長さ２，０００ｍ、幅２．６ｍ、揮発分率（水分率）２質量％の長尺のＰＶＡフィルム（単層フィルム）を製造した。
当該ＰＶＡフィルムについて、上記した方法により破線スジの本数を測定したところ、高低差が５０～６０ｎｍの凹凸が、０．３～０．７ｍｍの周期でフィルムの流れ方向に略直線状に１０ｃｍ以上にわたり配列した破線スジが６本（フィルムの幅方向１ｍあたり２．３本）存在することが判明した。以上の結果を表１に示した。 [Example 1]
[Production of PVA film]
It consists of 100 parts by mass of PVA (average polymerization degree 2,400, saponification degree 99.9 mol%) obtained by saponifying polyvinyl acetate, 12 parts by mass of glycerol, 0.1 part by mass of lauric acid diethanolamide, and water. A film-forming stock solution having a volatile content of 70% by mass was discharged from a T-type slit die at a discharge speed (S 0 ) of 2.8 m / min, and a film-forming apparatus provided with a plurality of drying rolls and heat treatment rolls whose rotation axes were parallel to each other. 1 film is discharged onto a drying roll (peripheral speed (S 1 ) 17 m / min), and hot air of 90 ° C. is applied to the entire surface of the first drying roll non-contact on the first drying roll at a wind speed of 5 m / sec. It is dried while sprayed, then peeled off from the first drying roll, and the final drying roll immediately before the heat treatment roll from the second drying roll so that the front and back surfaces of any part of the film are alternately opposed to each drying roll. After further drying up to the roll, it was peeled off from the final drying roll. Next, heat treatment is performed with a heat treatment roll having a surface temperature of 120 ° C., and both end portions (ear portions) are cut and wound on a cylindrical core to finally have a thickness of 30.3 μm, a length of 2,000 m, and a width. A long PVA film (single layer film) having 2.6 m and a volatile content (water content) of 2% by mass was produced.
With respect to the PVA film, when the number of the broken line streaks was measured by the above-described method, the unevenness having a height difference of 50 to 60 nm was approximately 10 cm or more in a straight line in the film flow direction with a period of 0.3 to 0.7 mm. It was found that there were 6 broken-line stripes arranged (2.3 per 1 m in the width direction of the film). The above results are shown in Table 1.
［偏光フィルムの製造］
得られたＰＶＡフィルムを巻き出しながら各処理を施して、厚み１２μｍの偏光フィルムを連続的に製造した。
すなわち、ＰＶＡフィルムを３０℃の水中に浸漬している間に元の長さの２．２倍まで流れ方向（ＭＤ）に一軸延伸（１段目延伸）した後、ヨウ素を０．０３質量％およびヨウ化カリウムを３質量％の濃度で含有する３０℃のヨウ素／ヨウ化カリウム水溶液中に浸漬している間に元の長さの３．３倍まで流れ方向（ＭＤ）に一軸延伸（２段目延伸）し、次いでホウ酸を３質量％およびヨウ化カリウムを３質量％の濃度で含有する３０℃のホウ酸／ヨウ化カリウム水溶液中に浸漬している間に元の長さの３．６倍まで流れ方向（ＭＤ）に一軸延伸（３段目延伸）し、次いでホウ酸を４質量％およびヨウ化カリウムを５質量％の濃度で含有する６３℃のホウ酸／ヨウ化カリウム水溶液中に浸漬している間に元の長さの６．７倍まで流れ方向（ＭＤ）に一軸延伸（４段目延伸）し、さらに、ヨウ化カリウムを３質量％の濃度で含有する３０℃のヨウ化カリウム水溶液中に浸漬した後、６０℃の乾燥機で４分間乾燥して偏光フィルムを製造した。
当該偏光フィルムについて、上記した方法により光学的欠陥を評価した。結果を表１に示した。 [Manufacture of polarizing film]
Each process was performed while unwinding the obtained PVA film, and a polarizing film having a thickness of 12 μm was continuously produced.
That is, while the PVA film was immersed in water at 30 ° C., it was uniaxially stretched (stretched in the first stage) in the flow direction (MD) up to 2.2 times the original length, and then 0.03% by mass of iodine. And uniaxially stretching in the flow direction (MD) up to 3.3 times the original length while immersed in a 30 ° C. iodine / potassium iodide aqueous solution containing potassium iodide at a concentration of 3% by mass (2 3) and then immersed in a boric acid / potassium iodide aqueous solution at 30 ° C. containing 3% by weight of boric acid and 3% by weight of potassium iodide. Boric acid / potassium iodide aqueous solution at 63 ° C. which is uniaxially stretched in the flow direction (MD) up to 6 times (third stage stretching) and then contains boric acid at a concentration of 4% by mass and potassium iodide at a concentration of 5% by mass Flow direction (MD) up to 6.7 times the original length while immersed in Then, after immersing in a 30 ° C. aqueous potassium iodide solution containing potassium iodide at a concentration of 3% by mass, it is dried for 4 minutes with a 60 ° C. drier and polarized. A film was produced.
About the said polarizing film, the optical defect was evaluated by the above-mentioned method. The results are shown in Table 1.
得られたＰＶＡフィルムを巻き出しながら各処理を施して、厚み１２μｍの偏光フィルムを連続的に製造した。
すなわち、ＰＶＡフィルムを３０℃の水中に浸漬している間に元の長さの２．２倍まで流れ方向（ＭＤ）に一軸延伸（１段目延伸）した後、ヨウ素を０．０３質量％およびヨウ化カリウムを３質量％の濃度で含有する３０℃のヨウ素／ヨウ化カリウム水溶液中に浸漬している間に元の長さの３．３倍まで流れ方向（ＭＤ）に一軸延伸（２段目延伸）し、次いでホウ酸を３質量％およびヨウ化カリウムを３質量％の濃度で含有する３０℃のホウ酸／ヨウ化カリウム水溶液中に浸漬している間に元の長さの３．６倍まで流れ方向（ＭＤ）に一軸延伸（３段目延伸）し、次いでホウ酸を４質量％およびヨウ化カリウムを５質量％の濃度で含有する６３℃のホウ酸／ヨウ化カリウム水溶液中に浸漬している間に元の長さの６．７倍まで流れ方向（ＭＤ）に一軸延伸（４段目延伸）し、さらに、ヨウ化カリウムを３質量％の濃度で含有する３０℃のヨウ化カリウム水溶液中に浸漬した後、６０℃の乾燥機で４分間乾燥して偏光フィルムを製造した。
当該偏光フィルムについて、上記した方法により光学的欠陥を評価した。結果を表１に示した。 [Manufacture of polarizing film]
Each process was performed while unwinding the obtained PVA film, and a polarizing film having a thickness of 12 μm was continuously produced.
That is, while the PVA film was immersed in water at 30 ° C., it was uniaxially stretched (stretched in the first stage) in the flow direction (MD) up to 2.2 times the original length, and then 0.03% by mass of iodine. And uniaxially stretching in the flow direction (MD) up to 3.3 times the original length while immersed in a 30 ° C. iodine / potassium iodide aqueous solution containing potassium iodide at a concentration of 3% by mass (2 3) and then immersed in a boric acid / potassium iodide aqueous solution at 30 ° C. containing 3% by weight of boric acid and 3% by weight of potassium iodide. Boric acid / potassium iodide aqueous solution at 63 ° C. which is uniaxially stretched in the flow direction (MD) up to 6 times (third stage stretching) and then contains boric acid at a concentration of 4% by mass and potassium iodide at a concentration of 5% by mass Flow direction (MD) up to 6.7 times the original length while immersed in Then, after immersing in a 30 ° C. aqueous potassium iodide solution containing potassium iodide at a concentration of 3% by mass, it is dried for 4 minutes with a 60 ° C. drier and polarized. A film was produced.
About the said polarizing film, the optical defect was evaluated by the above-mentioned method. The results are shown in Table 1.
［実施例２］
ポリ酢酸ビニルをけん化することにより得られたＰＶＡ（平均重合度２，４００、けん化度９９．９モル％）１００質量部、グリセリン１２質量部、ラウリン酸ジエタノールアミド０．１質量部および水からなる揮発分率６６質量％の製膜原液を、Ｔ型スリットダイから吐出速度（Ｓ０）２．８ｍ／分で、回転軸が互いに平行な複数の乾燥ロールと熱処理ロールを備える製膜装置の第１乾燥ロール（周速（Ｓ１）１７ｍ／分）上に膜状に吐出し、第１乾燥ロール上で、第１乾燥ロール非接触面の全体に９０℃の熱風を５ｍ／秒の風速で吹き付けながら乾燥し、次いで第１乾燥ロールから剥離して、フィルムの任意の部分における表面と裏面とが各乾燥ロールに交互に対向するように第２乾燥ロールから熱処理ロールの直前にある最終乾燥ロールまでの間で更に乾燥した後、最終乾燥ロールから剥離した。次いで、表面温度１１５℃の熱処理ロールで熱処理を行い、両端部（耳部）をカット後、円筒状のコアに巻き取ることにより、最終的に、厚み４０．６μｍ、長さ２，０００ｍ、幅２．６ｍ、揮発分率（水分率）２質量％の長尺のＰＶＡフィルム（単層フィルム）を製造した。
当該ＰＶＡフィルムについて、上記した方法により破線スジの本数を測定したところ、高低差が５０～６０ｎｍの凹凸が、０．３～０．７ｍｍの周期でフィルムの流れ方向に略直線状に１０ｃｍ以上にわたり配列した破線スジが５本（フィルムの幅方向１ｍあたり１．９本）存在することが判明した。また、得られたＰＶＡフィルムを用いて、実施例１と同様にして厚み１７μｍの偏光フィルムを製造し、上記した方法により光学的欠陥を評価した。以上の結果を表１に示した。 [Example 2]
It consists of 100 parts by mass of PVA (average polymerization degree 2,400, saponification degree 99.9 mol%) obtained by saponifying polyvinyl acetate, 12 parts by mass of glycerol, 0.1 part by mass of lauric acid diethanolamide, and water. A film-forming stock solution having a volatile content rate of 66 mass% was discharged from a T-shaped slit die at a discharge speed (S 0 ) of 2.8 m / min, and a film-forming apparatus comprising a plurality of drying rolls and heat treatment rolls whose rotation axes were parallel to each other. 1 film is discharged onto a drying roll (peripheral speed (S 1 ) 17 m / min), and hot air of 90 ° C. is applied to the entire surface of the first drying roll non-contact on the first drying roll at a wind speed of 5 m / sec. It is dried while sprayed, then peeled off from the first drying roll, and the final drying roll immediately before the heat treatment roll from the second drying roll so that the front and back surfaces of any part of the film are alternately opposed to each drying roll. After further drying up to the roll, it was peeled off from the final drying roll. Next, heat treatment is performed with a heat treatment roll having a surface temperature of 115 ° C., and both end portions (ear portions) are cut and wound on a cylindrical core to finally have a thickness of 40.6 μm, a length of 2,000 m, and a width. A long PVA film (single layer film) having 2.6 m and a volatile content (water content) of 2% by mass was produced.
With respect to the PVA film, when the number of the broken line streaks was measured by the above-described method, the unevenness having a height difference of 50 to 60 nm was approximately 10 cm or more in a straight line in the film flow direction with a period of 0.3 to 0.7 mm. It was found that there were five broken-line stripes (1.9 lines per 1 m in the width direction of the film). Further, using the obtained PVA film, a polarizing film having a thickness of 17 μm was produced in the same manner as in Example 1, and optical defects were evaluated by the method described above. The above results are shown in Table 1.
ポリ酢酸ビニルをけん化することにより得られたＰＶＡ（平均重合度２，４００、けん化度９９．９モル％）１００質量部、グリセリン１２質量部、ラウリン酸ジエタノールアミド０．１質量部および水からなる揮発分率６６質量％の製膜原液を、Ｔ型スリットダイから吐出速度（Ｓ０）２．８ｍ／分で、回転軸が互いに平行な複数の乾燥ロールと熱処理ロールを備える製膜装置の第１乾燥ロール（周速（Ｓ１）１７ｍ／分）上に膜状に吐出し、第１乾燥ロール上で、第１乾燥ロール非接触面の全体に９０℃の熱風を５ｍ／秒の風速で吹き付けながら乾燥し、次いで第１乾燥ロールから剥離して、フィルムの任意の部分における表面と裏面とが各乾燥ロールに交互に対向するように第２乾燥ロールから熱処理ロールの直前にある最終乾燥ロールまでの間で更に乾燥した後、最終乾燥ロールから剥離した。次いで、表面温度１１５℃の熱処理ロールで熱処理を行い、両端部（耳部）をカット後、円筒状のコアに巻き取ることにより、最終的に、厚み４０．６μｍ、長さ２，０００ｍ、幅２．６ｍ、揮発分率（水分率）２質量％の長尺のＰＶＡフィルム（単層フィルム）を製造した。
当該ＰＶＡフィルムについて、上記した方法により破線スジの本数を測定したところ、高低差が５０～６０ｎｍの凹凸が、０．３～０．７ｍｍの周期でフィルムの流れ方向に略直線状に１０ｃｍ以上にわたり配列した破線スジが５本（フィルムの幅方向１ｍあたり１．９本）存在することが判明した。また、得られたＰＶＡフィルムを用いて、実施例１と同様にして厚み１７μｍの偏光フィルムを製造し、上記した方法により光学的欠陥を評価した。以上の結果を表１に示した。 [Example 2]
It consists of 100 parts by mass of PVA (average polymerization degree 2,400, saponification degree 99.9 mol%) obtained by saponifying polyvinyl acetate, 12 parts by mass of glycerol, 0.1 part by mass of lauric acid diethanolamide, and water. A film-forming stock solution having a volatile content rate of 66 mass% was discharged from a T-shaped slit die at a discharge speed (S 0 ) of 2.8 m / min, and a film-forming apparatus comprising a plurality of drying rolls and heat treatment rolls whose rotation axes were parallel to each other. 1 film is discharged onto a drying roll (peripheral speed (S 1 ) 17 m / min), and hot air of 90 ° C. is applied to the entire surface of the first drying roll non-contact on the first drying roll at a wind speed of 5 m / sec. It is dried while sprayed, then peeled off from the first drying roll, and the final drying roll immediately before the heat treatment roll from the second drying roll so that the front and back surfaces of any part of the film are alternately opposed to each drying roll. After further drying up to the roll, it was peeled off from the final drying roll. Next, heat treatment is performed with a heat treatment roll having a surface temperature of 115 ° C., and both end portions (ear portions) are cut and wound on a cylindrical core to finally have a thickness of 40.6 μm, a length of 2,000 m, and a width. A long PVA film (single layer film) having 2.6 m and a volatile content (water content) of 2% by mass was produced.
With respect to the PVA film, when the number of the broken line streaks was measured by the above-described method, the unevenness having a height difference of 50 to 60 nm was approximately 10 cm or more in a straight line in the film flow direction with a period of 0.3 to 0.7 mm. It was found that there were five broken-line stripes (1.9 lines per 1 m in the width direction of the film). Further, using the obtained PVA film, a polarizing film having a thickness of 17 μm was produced in the same manner as in Example 1, and optical defects were evaluated by the method described above. The above results are shown in Table 1.
［比較例１］
ポリ酢酸ビニルをけん化することにより得られたＰＶＡ（平均重合度２，４００、けん化度９９．９モル％）１００質量部、グリセリン１２質量部、ラウリン酸ジエタノールアミド０．１質量部および水からなる揮発分率６６質量％の製膜原液を、Ｔ型スリットダイから吐出速度（Ｓ０）２．４ｍ／分で、回転軸が互いに平行な複数の乾燥ロールと熱処理ロールを備える製膜装置の第１乾燥ロール（周速（Ｓ１）１８ｍ／分）上に膜状に吐出し、第１乾燥ロール上で、第１乾燥ロール非接触面の全体に９０℃の熱風を５ｍ／秒の風速で吹き付けながら乾燥し、次いで第１乾燥ロールから剥離して、フィルムの任意の部分における表面と裏面とが各乾燥ロールに交互に対向するように第２乾燥ロールから熱処理ロールの直前にある最終乾燥ロールまでの間で更に乾燥した後、最終乾燥ロールから剥離した。次いで、表面温度１１５℃の熱処理ロールで熱処理を行い、両端部（耳部）をカット後、円筒状のコアに巻き取ることにより、最終的に、厚み２９．６μｍ、長さ２，０００ｍ、幅２．６ｍ、揮発分率（水分率）２質量％の長尺のＰＶＡフィルム（単層フィルム）を製造した。
当該ＰＶＡフィルムについて、上記した方法により破線スジの本数を測定したところ、高低差が６０～７０ｎｍの凹凸が、０．３～０．７ｍｍの周期でフィルムの流れ方向に略直線状に１０ｃｍ以上にわたり配列した破線スジが２４本（フィルムの幅方向１ｍあたり９．２本）存在することが判明した。また、得られたＰＶＡフィルムを用いて、実施例１と同様にして厚み１２μｍの偏光フィルムを製造し、上記した方法により光学的欠陥を評価した。以上の結果を表１に示した。 [Comparative Example 1]
It consists of 100 parts by mass of PVA (average polymerization degree 2,400, saponification degree 99.9 mol%) obtained by saponifying polyvinyl acetate, 12 parts by mass of glycerol, 0.1 part by mass of lauric acid diethanolamide, and water. A film-forming stock solution having a volatilization rate of 66% by mass was discharged from a T-type slit die at a discharge speed (S 0 ) of 2.4 m / min, and a film-forming apparatus comprising a plurality of drying rolls and heat treatment rolls whose rotation axes were parallel to each other. 1 film is discharged onto a drying roll (peripheral speed (S 1 ) 18 m / min), and hot air of 90 ° C. is applied to the entire surface of the first drying roll on the first drying roll at a wind speed of 5 m / sec. It is dried while sprayed, then peeled off from the first drying roll, and the final drying roll immediately before the heat treatment roll from the second drying roll so that the front and back surfaces of any part of the film are alternately opposed to each drying roll. After further drying up to the roll, it was peeled off from the final drying roll. Next, heat treatment is performed with a heat treatment roll having a surface temperature of 115 ° C., and both end portions (ear portions) are cut and wound on a cylindrical core to finally have a thickness of 29.6 μm, a length of 2,000 m, and a width. A long PVA film (single layer film) having 2.6 m and a volatile content (water content) of 2% by mass was produced.
With respect to the PVA film, when the number of broken line streaks was measured by the above-described method, unevenness with a height difference of 60 to 70 nm was approximately 10 cm or more in a straight line with a period of 0.3 to 0.7 mm in the flow direction of the film. It was found that there were 24 broken-line stripes arranged (9.2 per 1 m in the width direction of the film). In addition, using the obtained PVA film, a polarizing film having a thickness of 12 μm was produced in the same manner as in Example 1, and optical defects were evaluated by the method described above. The above results are shown in Table 1.
ポリ酢酸ビニルをけん化することにより得られたＰＶＡ（平均重合度２，４００、けん化度９９．９モル％）１００質量部、グリセリン１２質量部、ラウリン酸ジエタノールアミド０．１質量部および水からなる揮発分率６６質量％の製膜原液を、Ｔ型スリットダイから吐出速度（Ｓ０）２．４ｍ／分で、回転軸が互いに平行な複数の乾燥ロールと熱処理ロールを備える製膜装置の第１乾燥ロール（周速（Ｓ１）１８ｍ／分）上に膜状に吐出し、第１乾燥ロール上で、第１乾燥ロール非接触面の全体に９０℃の熱風を５ｍ／秒の風速で吹き付けながら乾燥し、次いで第１乾燥ロールから剥離して、フィルムの任意の部分における表面と裏面とが各乾燥ロールに交互に対向するように第２乾燥ロールから熱処理ロールの直前にある最終乾燥ロールまでの間で更に乾燥した後、最終乾燥ロールから剥離した。次いで、表面温度１１５℃の熱処理ロールで熱処理を行い、両端部（耳部）をカット後、円筒状のコアに巻き取ることにより、最終的に、厚み２９．６μｍ、長さ２，０００ｍ、幅２．６ｍ、揮発分率（水分率）２質量％の長尺のＰＶＡフィルム（単層フィルム）を製造した。
当該ＰＶＡフィルムについて、上記した方法により破線スジの本数を測定したところ、高低差が６０～７０ｎｍの凹凸が、０．３～０．７ｍｍの周期でフィルムの流れ方向に略直線状に１０ｃｍ以上にわたり配列した破線スジが２４本（フィルムの幅方向１ｍあたり９．２本）存在することが判明した。また、得られたＰＶＡフィルムを用いて、実施例１と同様にして厚み１２μｍの偏光フィルムを製造し、上記した方法により光学的欠陥を評価した。以上の結果を表１に示した。 [Comparative Example 1]
It consists of 100 parts by mass of PVA (average polymerization degree 2,400, saponification degree 99.9 mol%) obtained by saponifying polyvinyl acetate, 12 parts by mass of glycerol, 0.1 part by mass of lauric acid diethanolamide, and water. A film-forming stock solution having a volatilization rate of 66% by mass was discharged from a T-type slit die at a discharge speed (S 0 ) of 2.4 m / min, and a film-forming apparatus comprising a plurality of drying rolls and heat treatment rolls whose rotation axes were parallel to each other. 1 film is discharged onto a drying roll (peripheral speed (S 1 ) 18 m / min), and hot air of 90 ° C. is applied to the entire surface of the first drying roll on the first drying roll at a wind speed of 5 m / sec. It is dried while sprayed, then peeled off from the first drying roll, and the final drying roll immediately before the heat treatment roll from the second drying roll so that the front and back surfaces of any part of the film are alternately opposed to each drying roll. After further drying up to the roll, it was peeled off from the final drying roll. Next, heat treatment is performed with a heat treatment roll having a surface temperature of 115 ° C., and both end portions (ear portions) are cut and wound on a cylindrical core to finally have a thickness of 29.6 μm, a length of 2,000 m, and a width. A long PVA film (single layer film) having 2.6 m and a volatile content (water content) of 2% by mass was produced.
With respect to the PVA film, when the number of broken line streaks was measured by the above-described method, unevenness with a height difference of 60 to 70 nm was approximately 10 cm or more in a straight line with a period of 0.3 to 0.7 mm in the flow direction of the film. It was found that there were 24 broken-line stripes arranged (9.2 per 1 m in the width direction of the film). In addition, using the obtained PVA film, a polarizing film having a thickness of 12 μm was produced in the same manner as in Example 1, and optical defects were evaluated by the method described above. The above results are shown in Table 1.
［比較例２］
ポリ酢酸ビニルをけん化することにより得られたＰＶＡ（平均重合度２，４００、けん化度９９．９モル％）１００質量部、グリセリン１２質量部、ラウリン酸ジエタノールアミド０．１質量部および水からなる揮発分率６６質量％の製膜原液を、Ｔ型スリットダイから吐出速度（Ｓ０）２．０ｍ／分で、回転軸が互いに平行な複数の乾燥ロールと熱処理ロールを備える製膜装置の第１乾燥ロール（周速（Ｓ１）１５ｍ／分）上に膜状に吐出し、第１乾燥ロール上で、第１乾燥ロール非接触面の全体に９０℃の熱風を５ｍ／秒の風速で吹き付けながら乾燥し、次いで第１乾燥ロールから剥離して、フィルムの任意の部分における表面と裏面とが各乾燥ロールに交互に対向するように第２乾燥ロールから熱処理ロールの直前にある最終乾燥ロールまでの間で更に乾燥した後、最終乾燥ロールから剥離した。次いで、表面温度１１５℃の熱処理ロールで熱処理を行い、両端部（耳部）をカット後、円筒状のコアに巻き取ることにより、最終的に、厚み３０．３μｍ、長さ２，０００ｍ、幅２．６ｍ、揮発分率（水分率）２質量％の長尺のＰＶＡフィルム（単層フィルム）を製造した。
当該ＰＶＡフィルムについて、上記した方法により破線スジの本数を測定したところ、高低差が８０～９０ｎｍの凹凸が、０．３～０．７ｍｍの周期でフィルムの流れ方向に略直線状に１０ｃｍ以上にわたり配列した破線スジが３７本（フィルムの幅方向１ｍあたり１４．２本）存在することが判明した。また、得られたＰＶＡフィルムを用いて、実施例１と同様にして厚み１２μｍの偏光フィルムを製造し、上記した方法により光学的欠陥を評価した。以上の結果を表１に示した。 [Comparative Example 2]
It consists of 100 parts by mass of PVA (average polymerization degree 2,400, saponification degree 99.9 mol%) obtained by saponifying polyvinyl acetate, 12 parts by mass of glycerol, 0.1 part by mass of lauric acid diethanolamide, and water. A film-forming stock solution having a volatile content rate of 66% by mass is discharged from a T-shaped slit die at a discharge speed (S 0 ) of 2.0 m / min. 1 film is discharged onto a drying roll (peripheral speed (S 1 ) 15 m / min), and hot air of 90 ° C. is applied to the entire surface of the first drying roll non-contact on the first drying roll at a wind speed of 5 m / sec. It is dried while sprayed, then peeled off from the first drying roll, and the final drying roll immediately before the heat treatment roll from the second drying roll so that the front and back surfaces of any part of the film are alternately opposed to each drying roll. After further drying up to the roll, it was peeled off from the final drying roll. Next, heat treatment is performed with a heat treatment roll having a surface temperature of 115 ° C., and both end portions (ear portions) are cut and wound on a cylindrical core to finally have a thickness of 30.3 μm, a length of 2,000 m, and a width. A long PVA film (single layer film) having 2.6 m and a volatile content (water content) of 2% by mass was produced.
With respect to the PVA film, when the number of broken line streaks was measured by the above-described method, unevenness with a height difference of 80 to 90 nm was approximately 10 cm or more in a straight line in the film flow direction with a period of 0.3 to 0.7 mm. It was found that there were 37 broken-line stripes (14.2 per 1 m in the film width direction). In addition, using the obtained PVA film, a polarizing film having a thickness of 12 μm was produced in the same manner as in Example 1, and optical defects were evaluated by the method described above. The above results are shown in Table 1.
ポリ酢酸ビニルをけん化することにより得られたＰＶＡ（平均重合度２，４００、けん化度９９．９モル％）１００質量部、グリセリン１２質量部、ラウリン酸ジエタノールアミド０．１質量部および水からなる揮発分率６６質量％の製膜原液を、Ｔ型スリットダイから吐出速度（Ｓ０）２．０ｍ／分で、回転軸が互いに平行な複数の乾燥ロールと熱処理ロールを備える製膜装置の第１乾燥ロール（周速（Ｓ１）１５ｍ／分）上に膜状に吐出し、第１乾燥ロール上で、第１乾燥ロール非接触面の全体に９０℃の熱風を５ｍ／秒の風速で吹き付けながら乾燥し、次いで第１乾燥ロールから剥離して、フィルムの任意の部分における表面と裏面とが各乾燥ロールに交互に対向するように第２乾燥ロールから熱処理ロールの直前にある最終乾燥ロールまでの間で更に乾燥した後、最終乾燥ロールから剥離した。次いで、表面温度１１５℃の熱処理ロールで熱処理を行い、両端部（耳部）をカット後、円筒状のコアに巻き取ることにより、最終的に、厚み３０．３μｍ、長さ２，０００ｍ、幅２．６ｍ、揮発分率（水分率）２質量％の長尺のＰＶＡフィルム（単層フィルム）を製造した。
当該ＰＶＡフィルムについて、上記した方法により破線スジの本数を測定したところ、高低差が８０～９０ｎｍの凹凸が、０．３～０．７ｍｍの周期でフィルムの流れ方向に略直線状に１０ｃｍ以上にわたり配列した破線スジが３７本（フィルムの幅方向１ｍあたり１４．２本）存在することが判明した。また、得られたＰＶＡフィルムを用いて、実施例１と同様にして厚み１２μｍの偏光フィルムを製造し、上記した方法により光学的欠陥を評価した。以上の結果を表１に示した。 [Comparative Example 2]
It consists of 100 parts by mass of PVA (average polymerization degree 2,400, saponification degree 99.9 mol%) obtained by saponifying polyvinyl acetate, 12 parts by mass of glycerol, 0.1 part by mass of lauric acid diethanolamide, and water. A film-forming stock solution having a volatile content rate of 66% by mass is discharged from a T-shaped slit die at a discharge speed (S 0 ) of 2.0 m / min. 1 film is discharged onto a drying roll (peripheral speed (S 1 ) 15 m / min), and hot air of 90 ° C. is applied to the entire surface of the first drying roll non-contact on the first drying roll at a wind speed of 5 m / sec. It is dried while sprayed, then peeled off from the first drying roll, and the final drying roll immediately before the heat treatment roll from the second drying roll so that the front and back surfaces of any part of the film are alternately opposed to each drying roll. After further drying up to the roll, it was peeled off from the final drying roll. Next, heat treatment is performed with a heat treatment roll having a surface temperature of 115 ° C., and both end portions (ear portions) are cut and wound on a cylindrical core to finally have a thickness of 30.3 μm, a length of 2,000 m, and a width. A long PVA film (single layer film) having 2.6 m and a volatile content (water content) of 2% by mass was produced.
With respect to the PVA film, when the number of broken line streaks was measured by the above-described method, unevenness with a height difference of 80 to 90 nm was approximately 10 cm or more in a straight line in the film flow direction with a period of 0.3 to 0.7 mm. It was found that there were 37 broken-line stripes (14.2 per 1 m in the film width direction). In addition, using the obtained PVA film, a polarizing film having a thickness of 12 μm was produced in the same manner as in Example 1, and optical defects were evaluated by the method described above. The above results are shown in Table 1.
［参考例］
ポリ酢酸ビニルをけん化することにより得られたＰＶＡ（平均重合度２，４００、けん化度９９．９モル％）１００質量部、グリセリン１２質量部、ラウリン酸ジエタノールアミド０．１質量部および水からなる揮発分率６６質量％の製膜原液を、Ｔ型スリットダイから吐出速度（Ｓ０）２．４ｍ／分で、回転軸が互いに平行な複数の乾燥ロールと熱処理ロールを備える製膜装置の第１乾燥ロール（周速（Ｓ１）１１ｍ／分）上に膜状に吐出し、第１乾燥ロール上で、第１乾燥ロール非接触面の全体に９０℃の熱風を５ｍ／秒の風速で吹き付けながら乾燥し、次いで第１乾燥ロールから剥離して、フィルムの任意の部分における表面と裏面とが各乾燥ロールに交互に対向するように第２乾燥ロールから熱処理ロールの直前にある最終乾燥ロールまでの間で更に乾燥した後、最終乾燥ロールから剥離した。次いで、表面温度１０５℃の熱処理ロールで熱処理を行い、両端部（耳部）をカット後、円筒状のコアに巻き取ることにより、最終的に、厚み７４．５μｍ、長さ２，０００ｍ、幅２．６ｍ、揮発分率（水分率）２質量％の長尺のＰＶＡフィルム（単層フィルム）を製造した。
当該ＰＶＡフィルムについて、上記した方法により破線スジの本数を測定しようとしたが、破線スジは見つからなかった。以上の結果を表１に示した。 [Reference example]
It consists of 100 parts by mass of PVA (average polymerization degree 2,400, saponification degree 99.9 mol%) obtained by saponifying polyvinyl acetate, 12 parts by mass of glycerol, 0.1 part by mass of lauric acid diethanolamide, and water. A film-forming stock solution having a volatilization rate of 66% by mass was discharged from a T-type slit die at a discharge speed (S 0 ) of 2.4 m / min. 1 film is discharged onto a drying roll (peripheral speed (S 1 ) 11 m / min), and hot air of 90 ° C. is applied to the entire surface of the first drying roll non-contact on the first drying roll at a wind speed of 5 m / sec. It is dried while sprayed, then peeled off from the first drying roll, and the final drying roll immediately before the heat treatment roll from the second drying roll so that the front and back surfaces of any part of the film are alternately opposed to each drying roll. After further drying up to the roll, it was peeled off from the final drying roll. Next, heat treatment is performed with a heat treatment roll having a surface temperature of 105 ° C., and both end portions (ear portions) are cut and wound on a cylindrical core to finally have a thickness of 74.5 μm, a length of 2,000 m, and a width. A long PVA film (single layer film) having 2.6 m and a volatile content (water content) of 2% by mass was produced.
About the said PVA film, it tried to measure the number of broken line streaks by the above-mentioned method, but the broken line streak was not found. The above results are shown in Table 1.
ポリ酢酸ビニルをけん化することにより得られたＰＶＡ（平均重合度２，４００、けん化度９９．９モル％）１００質量部、グリセリン１２質量部、ラウリン酸ジエタノールアミド０．１質量部および水からなる揮発分率６６質量％の製膜原液を、Ｔ型スリットダイから吐出速度（Ｓ０）２．４ｍ／分で、回転軸が互いに平行な複数の乾燥ロールと熱処理ロールを備える製膜装置の第１乾燥ロール（周速（Ｓ１）１１ｍ／分）上に膜状に吐出し、第１乾燥ロール上で、第１乾燥ロール非接触面の全体に９０℃の熱風を５ｍ／秒の風速で吹き付けながら乾燥し、次いで第１乾燥ロールから剥離して、フィルムの任意の部分における表面と裏面とが各乾燥ロールに交互に対向するように第２乾燥ロールから熱処理ロールの直前にある最終乾燥ロールまでの間で更に乾燥した後、最終乾燥ロールから剥離した。次いで、表面温度１０５℃の熱処理ロールで熱処理を行い、両端部（耳部）をカット後、円筒状のコアに巻き取ることにより、最終的に、厚み７４．５μｍ、長さ２，０００ｍ、幅２．６ｍ、揮発分率（水分率）２質量％の長尺のＰＶＡフィルム（単層フィルム）を製造した。
当該ＰＶＡフィルムについて、上記した方法により破線スジの本数を測定しようとしたが、破線スジは見つからなかった。以上の結果を表１に示した。 [Reference example]
It consists of 100 parts by mass of PVA (average polymerization degree 2,400, saponification degree 99.9 mol%) obtained by saponifying polyvinyl acetate, 12 parts by mass of glycerol, 0.1 part by mass of lauric acid diethanolamide, and water. A film-forming stock solution having a volatilization rate of 66% by mass was discharged from a T-type slit die at a discharge speed (S 0 ) of 2.4 m / min. 1 film is discharged onto a drying roll (peripheral speed (S 1 ) 11 m / min), and hot air of 90 ° C. is applied to the entire surface of the first drying roll non-contact on the first drying roll at a wind speed of 5 m / sec. It is dried while sprayed, then peeled off from the first drying roll, and the final drying roll immediately before the heat treatment roll from the second drying roll so that the front and back surfaces of any part of the film are alternately opposed to each drying roll. After further drying up to the roll, it was peeled off from the final drying roll. Next, heat treatment is performed with a heat treatment roll having a surface temperature of 105 ° C., and both end portions (ear portions) are cut and wound on a cylindrical core to finally have a thickness of 74.5 μm, a length of 2,000 m, and a width. A long PVA film (single layer film) having 2.6 m and a volatile content (water content) of 2% by mass was produced.
About the said PVA film, it tried to measure the number of broken line streaks by the above-mentioned method, but the broken line streak was not found. The above results are shown in Table 1.
Claims (9)
- 厚みが５５μｍ以下のポリビニルアルコール系重合体フィルムであって、凹凸が０．０１～１０ｍｍの周期でフィルムの流れ方向に略直線状に１０ｃｍ以上にわたり配列してなる破線スジが、フィルムの幅方向１ｍあたり５本以下である、ポリビニルアルコール系重合体フィルム。 A broken line streak is a polyvinyl alcohol polymer film having a thickness of 55 μm or less, in which irregularities are arranged in a straight line over a length of 10 cm or more in the film flow direction at a period of 0.01 to 10 mm. A polyvinyl alcohol polymer film having 5 or less per film.
- 幅が２ｍ以上である、請求項１に記載のポリビニルアルコール系重合体フィルム。 The polyvinyl alcohol polymer film according to claim 1, wherein the width is 2 m or more.
- 厚みが５５μｍ以下のポリビニルアルコール系重合体フィルムの製造方法であって、回転軸が互いに平行な複数の乾燥ロールを備える製膜装置を使用し、当該製膜装置の第１乾燥ロール上にポリビニルアルコール系重合体を含む製膜原液を膜状に吐出して乾燥し、それに続く第２乾燥ロール以降の乾燥ロールで更に乾燥してポリビニルアルコール系重合体フィルムを製膜する際に、製膜原液の吐出速度（Ｓ０）を２．５～５．０ｍ／分にする、製造方法。 A method for producing a polyvinyl alcohol polymer film having a thickness of 55 μm or less, wherein a film-forming apparatus comprising a plurality of drying rolls whose rotation axes are parallel to each other is used, and polyvinyl alcohol is formed on the first drying roll of the film-forming apparatus. When forming a polyvinyl alcohol polymer film by discharging a film-forming stock solution containing a polymer into a film and drying it, followed by further drying with a drying roll after the second drying roll, A production method wherein the discharge speed (S 0 ) is 2.5 to 5.0 m / min.
- 製膜原液の吐出速度（Ｓ０）に対する第１乾燥ロールの周速（Ｓ１）の比（Ｓ１／Ｓ０）を７以下にする、請求項３に記載の製造方法。 The manufacturing method according to claim 3, wherein a ratio (S 1 / S 0 ) of a peripheral speed (S 1 ) of the first drying roll to a discharge speed (S 0 ) of the film forming raw solution is 7 or less.
- 幅が２ｍ以上のポリビニルアルコール系重合体フィルムの製造方法である、請求項３または４に記載の製造方法。 The method according to claim 3 or 4, which is a method for producing a polyvinyl alcohol polymer film having a width of 2 m or more.
- 請求項１または２に記載のポリビニルアルコール系重合体フィルムから製造した光学フィルム。 An optical film produced from the polyvinyl alcohol polymer film according to claim 1.
- 偏光フィルムである、請求項６に記載の光学フィルム。 The optical film according to claim 6, which is a polarizing film.
- 請求項１または２に記載のポリビニルアルコール系重合体フィルムを用いて一軸延伸する工程を有する、光学フィルムの製造方法。 A method for producing an optical film, comprising a step of uniaxially stretching using the polyvinyl alcohol polymer film according to claim 1.
- 偏光フィルムの製造方法である、請求項８に記載の製造方法。 The manufacturing method according to claim 8, which is a manufacturing method of a polarizing film.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017520678A JP6716553B2 (en) | 2015-05-28 | 2016-05-20 | Polyvinyl alcohol polymer film and method for producing the same |
| CN202311059168.5A CN117001908A (en) | 2015-05-28 | 2016-05-20 | Polyvinyl alcohol polymer film and method for producing same |
| KR1020177033978A KR102038212B1 (en) | 2015-05-28 | 2016-05-20 | Polyvinyl alcohol polymer film and method for producing same |
| CN201680031048.6A CN107614242A (en) | 2015-05-28 | 2016-05-20 | Polyvinyl alcohol film and its manufacture method |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015108080 | 2015-05-28 | ||
| JP2015-108080 | 2015-05-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2016190235A1 true WO2016190235A1 (en) | 2016-12-01 |
Family
ID=57393821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2016/064993 WO2016190235A1 (en) | 2015-05-28 | 2016-05-20 | Polyvinyl alcohol polymer film and method for producing same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6716553B2 (en) |
| KR (1) | KR102038212B1 (en) |
| CN (2) | CN117001908A (en) |
| TW (1) | TWI741984B (en) |
| WO (1) | WO2016190235A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020138438A1 (en) * | 2018-12-28 | 2020-07-02 | 株式会社クラレ | Water-soluble film, method of manufacturing same, and package |
| WO2020138440A1 (en) * | 2018-12-28 | 2020-07-02 | 株式会社クラレ | Water-soluble film and package |
| WO2020138444A1 (en) * | 2018-12-28 | 2020-07-02 | 株式会社クラレ | Water-soluble film and package |
| WO2020138437A1 (en) * | 2018-12-28 | 2020-07-02 | 株式会社クラレ | Water-soluble film, method of manufacturing same, and package |
| WO2022004343A1 (en) * | 2020-06-29 | 2022-01-06 | 株式会社クラレ | Water-soluble film and packaging |
| WO2022004536A1 (en) * | 2020-06-30 | 2022-01-06 | 株式会社クラレ | Polyvinyl alcohol film and method for manufacturing optical film in which same is used |
| WO2022004535A1 (en) * | 2020-06-30 | 2022-01-06 | 株式会社クラレ | Polyvinyl alcohol film and method for producing optical film using same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6665512B2 (en) * | 2015-12-14 | 2020-03-13 | コニカミノルタ株式会社 | Optical film manufacturing method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52133371A (en) * | 1976-04-30 | 1977-11-08 | Toshiba Machine Co Ltd | Method of forming polyvinyl alcohol film |
| JP2000301555A (en) * | 1999-04-21 | 2000-10-31 | Fuji Photo Film Co Ltd | Method for forming solution film |
| JP2005231185A (en) * | 2004-02-19 | 2005-09-02 | Konica Minolta Opto Inc | Method for producing optical film and optical film |
| JP2006199927A (en) * | 2004-12-21 | 2006-08-03 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol film and polarizing film |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4631474Y1 (en) * | 1968-06-22 | 1971-10-30 | ||
| JP3632928B2 (en) * | 1992-04-27 | 2005-03-30 | 株式会社クラレ | Method and apparatus for producing polyvinyl alcohol polymer film |
| JP3473838B2 (en) | 2000-06-28 | 2003-12-08 | 株式会社クラレ | Method for producing polyvinyl alcohol film |
| JP3823037B2 (en) | 2001-09-27 | 2006-09-20 | 積水化学工業株式会社 | Discharge plasma processing equipment |
-
2016
- 2016-05-20 CN CN202311059168.5A patent/CN117001908A/en active Pending
- 2016-05-20 KR KR1020177033978A patent/KR102038212B1/en active IP Right Grant
- 2016-05-20 CN CN201680031048.6A patent/CN107614242A/en active Pending
- 2016-05-20 WO PCT/JP2016/064993 patent/WO2016190235A1/en active Application Filing
- 2016-05-20 JP JP2017520678A patent/JP6716553B2/en active Active
- 2016-05-25 TW TW105116201A patent/TWI741984B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52133371A (en) * | 1976-04-30 | 1977-11-08 | Toshiba Machine Co Ltd | Method of forming polyvinyl alcohol film |
| JP2000301555A (en) * | 1999-04-21 | 2000-10-31 | Fuji Photo Film Co Ltd | Method for forming solution film |
| JP2005231185A (en) * | 2004-02-19 | 2005-09-02 | Konica Minolta Opto Inc | Method for producing optical film and optical film |
| JP2006199927A (en) * | 2004-12-21 | 2006-08-03 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol film and polarizing film |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2020138438A1 (en) * | 2018-12-28 | 2021-11-11 | 株式会社クラレ | Water-soluble film, its manufacturing method and packaging |
| WO2020138440A1 (en) * | 2018-12-28 | 2020-07-02 | 株式会社クラレ | Water-soluble film and package |
| JPWO2020138440A1 (en) * | 2018-12-28 | 2021-11-11 | 株式会社クラレ | Water-soluble film and packaging |
| WO2020138438A1 (en) * | 2018-12-28 | 2020-07-02 | 株式会社クラレ | Water-soluble film, method of manufacturing same, and package |
| WO2020138437A1 (en) * | 2018-12-28 | 2020-07-02 | 株式会社クラレ | Water-soluble film, method of manufacturing same, and package |
| CN113226941A (en) * | 2018-12-28 | 2021-08-06 | 株式会社可乐丽 | Water-soluble film and package |
| JPWO2020138437A1 (en) * | 2018-12-28 | 2021-11-11 | 株式会社クラレ | Water-soluble film, its manufacturing method and packaging |
| JPWO2020138445A1 (en) * | 2018-12-28 | 2021-11-11 | 株式会社クラレ | Base film for hydraulic transfer and printing film for hydraulic transfer |
| CN113226941B (en) * | 2018-12-28 | 2023-10-27 | 株式会社可乐丽 | Water-soluble film and package |
| WO2020138445A1 (en) * | 2018-12-28 | 2020-07-02 | 株式会社クラレ | Hydraulic transfer base film, and hydraulic transfer printing film |
| WO2020138444A1 (en) * | 2018-12-28 | 2020-07-02 | 株式会社クラレ | Water-soluble film and package |
| JP7336464B2 (en) | 2018-12-28 | 2023-08-31 | 株式会社クラレ | Water-soluble film and packaging |
| JP7240423B2 (en) | 2018-12-28 | 2023-03-15 | 株式会社クラレ | Hydraulic transfer base film and Hydraulic transfer printing film |
| JP7240420B2 (en) | 2018-12-28 | 2023-03-15 | 株式会社クラレ | Water-soluble film, method for producing the same, and package |
| JP7240421B2 (en) | 2018-12-28 | 2023-03-15 | 株式会社クラレ | Water-soluble film, method for producing the same, and package |
| WO2022004343A1 (en) * | 2020-06-29 | 2022-01-06 | 株式会社クラレ | Water-soluble film and packaging |
| WO2022004535A1 (en) * | 2020-06-30 | 2022-01-06 | 株式会社クラレ | Polyvinyl alcohol film and method for producing optical film using same |
| WO2022004536A1 (en) * | 2020-06-30 | 2022-01-06 | 株式会社クラレ | Polyvinyl alcohol film and method for manufacturing optical film in which same is used |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117001908A (en) | 2023-11-07 |
| JP6716553B2 (en) | 2020-07-01 |
| TW201708268A (en) | 2017-03-01 |
| KR20180013908A (en) | 2018-02-07 |
| TWI741984B (en) | 2021-10-11 |
| JPWO2016190235A1 (en) | 2018-03-15 |
| KR102038212B1 (en) | 2019-10-29 |
| CN107614242A (en) | 2018-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6483792B2 (en) | POLYVINYL ALCOHOL POLYMER FILM AND PROCESS FOR PRODUCING THE SAME | |
| JP6716553B2 (en) | Polyvinyl alcohol polymer film and method for producing the same | |
| JP5649820B2 (en) | Polyvinyl alcohol film and method for producing the same | |
| JP6030528B2 (en) | Manufacturing method of polarizing film | |
| TWI765093B (en) | Polyvinyl alcohol film and method for producing same | |
| TWI711635B (en) | Polyvinyl alcohol polymer film and optical film | |
| JP6630677B2 (en) | Polyvinyl alcohol polymer film and method for producing the same | |
| TW200914468A (en) | Polyvinyl alcohol film | |
| JP5680805B1 (en) | POLYVINYL ALCOHOL POLYMER FILM AND PROCESS FOR PRODUCING THE SAME | |
| JP6572236B2 (en) | Polyvinyl alcohol film | |
| JP7375042B2 (en) | Manufacturing method of optical polyvinyl alcohol film | |
| JP2004020635A (en) | Manufacturing method of polyvinyl alcohol film for optical use |
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: 16799940 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 2017520678 Country of ref document: JP Kind code of ref document: A |
|
| ENP | Entry into the national phase |
Ref document number: 20177033978 Country of ref document: KR Kind code of ref document: A |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 16799940 Country of ref document: EP Kind code of ref document: A1 |