JP3476136B2 - Method for producing polyvinyl alcohol film - Google Patents
Method for producing polyvinyl alcohol filmInfo
- Publication number
- JP3476136B2 JP3476136B2 JP2000135655A JP2000135655A JP3476136B2 JP 3476136 B2 JP3476136 B2 JP 3476136B2 JP 2000135655 A JP2000135655 A JP 2000135655A JP 2000135655 A JP2000135655 A JP 2000135655A JP 3476136 B2 JP3476136 B2 JP 3476136B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- drum
- pva
- weight
- thickness
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims description 81
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims description 80
- 238000004519 manufacturing process Methods 0.000 title description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 238000007127 saponification reaction Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- 238000011144 upstream manufacturing Methods 0.000 claims description 4
- 239000010408 film Substances 0.000 description 132
- 239000002994 raw material Substances 0.000 description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 12
- 230000010287 polarization Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- -1 ethylene, propylene, 1-butene Chemical class 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 235000011187 glycerol Nutrition 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000004043 dyeing Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000002834 transmittance Methods 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
- 229940031957 lauric acid diethanolamide Drugs 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229920001567 vinyl ester resin Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 2
- 238000003672 processing method 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
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000004804 winding Methods 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
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- ICCVOKMKWYGITK-UHFFFAOYSA-N 1-(2-methylprop-2-enoylamino)propane-1-sulfonic acid Chemical compound CCC(S(O)(=O)=O)NC(=O)C(C)=C ICCVOKMKWYGITK-UHFFFAOYSA-N 0.000 description 1
- IAUGBVWVWDTCJV-UHFFFAOYSA-N 1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CCC(S(O)(=O)=O)NC(=O)C=C IAUGBVWVWDTCJV-UHFFFAOYSA-N 0.000 description 1
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 1
- QJJDJWUCRAPCOL-UHFFFAOYSA-N 1-ethenoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOC=C QJJDJWUCRAPCOL-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- PGYJSURPYAAOMM-UHFFFAOYSA-N 2-ethenoxy-2-methylpropane Chemical compound CC(C)(C)OC=C PGYJSURPYAAOMM-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- KFTHUBZIEMOORC-UHFFFAOYSA-N 2-methylbut-2-enamide Chemical compound CC=C(C)C(N)=O KFTHUBZIEMOORC-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-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
- QCTQFNOOTWQBSI-UHFFFAOYSA-N C(C)(=O)OC(=C)C.C(=C)[Si](OC)(OC)OC Chemical compound C(C)(=O)OC(=C)C.C(=C)[Si](OC)(OC)OC QCTQFNOOTWQBSI-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- GDFCSMCGLZFNFY-UHFFFAOYSA-N Dimethylaminopropyl Methacrylamide Chemical compound CN(C)CCCNC(=O)C(C)=C GDFCSMCGLZFNFY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- DKNPRRRKHAEUMW-UHFFFAOYSA-N Iodine aqueous Chemical compound [K+].I[I-]I DKNPRRRKHAEUMW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 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
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229920006197 POE laurate Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 235000012745 brilliant blue FCF Nutrition 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 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
- 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
- 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
- BLZSRIYYOIZLJL-UHFFFAOYSA-N ethenyl pentanoate Chemical compound CCCCC(=O)OC=C BLZSRIYYOIZLJL-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-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
- 238000001704 evaporation Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229940077844 iodine / potassium iodide Drugs 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid 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
- 238000005259 measurement Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 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
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-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
- ADTJPOBHAXXXFS-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]prop-2-enamide Chemical compound CN(C)CCCNC(=O)C=C ADTJPOBHAXXXFS-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- XTNMKCFFSXJRQE-UHFFFAOYSA-N n-ethenylethenamine Chemical class C=CNC=C XTNMKCFFSXJRQE-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
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 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
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-OUBTZVSYSA-N potassium-40 Chemical compound [40K] ZLMJMSJWJFRBEC-OUBTZVSYSA-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
- WPPDXAHGCGPUPK-UHFFFAOYSA-N red 2 Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=2C=3C4=CC=C5C6=CC=C7C8=C(C=9C=CC=CC=9)C9=CC=CC=C9C(C=9C=CC=CC=9)=C8C8=CC=C(C6=C87)C(C=35)=CC=2)C4=C1C1=CC=CC=C1 WPPDXAHGCGPUPK-UHFFFAOYSA-N 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
- 238000005728 strengthening Methods 0.000 description 1
- UZZYXUGECOQHPU-UHFFFAOYSA-N sulfuric acid monooctyl ester Natural products CCCCCCCCOS(O)(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 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
- 239000010409 thin film Substances 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
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polarising Elements (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Moulding By Coating Moulds (AREA)
Description
【発明の詳細な説明】
【０００１】
【発明の属する技術分野】本発明は、偏光フィルムの製
造素材として有用なポリビニルアルコールフィルムの製
造法に関するものである。
【０００２】
【従来の技術】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とともに、液晶
ディスプレイ（ＬＣＤ）の基本的な構成要素である。こ
のＬＣＤの適用分野も、初期の頃の電卓および腕時計等
の小型機器から、近年ではラップトップパソコン、ワー
プロ、液晶カラープロジェクター、車載用ナビゲーショ
ンシステム、液晶テレビ等の広範囲に広がり、大画面で
使用されるようになってきたことから、従来品以上に大
画面における偏光性能の均一性に優れた偏光板が求めら
れている。
【０００３】偏光板は、一般にポリビニルアルコールフ
ィルム（以下、これを「ＰＶＡフィルム」と略記し、ま
た、これの原料であるポリビニルアルコールをポリビニ
ルアルコール系重合体と言い、これを「ＰＶＡ」と略記
することがある）を一軸延伸し、染色することにより製
造した偏光フィルムの両面に、三酢酸セルロース（ＴＡ
Ｃ）膜などの保護膜を貼り合わせた構成としている。
【０００４】
【発明が解決しようとする課題】偏光板の偏光性能を均
一とするためには、ＰＶＡフィルムを均一に延伸するこ
と、ムラなく貼り合わせることなど多くの注意点がある
が、最も重要な点は偏光フィルムの素材となるＰＶＡフ
ィルムの厚みを均一にすることである。ＰＶＡフィルム
の厚みが均一でない場合には精密延伸を行っても、大面
積において均一な偏光性能が得られない。ＰＶＡフィル
ムの厚みを均一とするため、ＰＶＡの希薄溶液で流延製
膜することが行われているが、十分な厚み均一性は得ら
れていない。
【０００５】そこで本発明の目的は、偏光フィルムを製
造するときの素材として有用で、大面積においても厚み
均一性に優れたＰＶＡフィルムを得ることができるＰＶ
Ａフィルムの製造法を提供することにある。
【０００６】
【課題を解決するための手段】上記目的を達成するた
め、本発明の偏光フィルム用ＰＶＡフィルムの製造法
は、ドラム製膜機を用いて、重合度が５００以上でけん
化度が９０モル％以上のＰＶＡおよびそのポリビニルア
ルコール１００重量部に対して１〜３０重量部の多価ア
ルコールを含有する製膜原料からＰＶＡフィルムを製造
する際に、製膜原料が供給される最上流側に位置するド
ラムの表面の温度斑を２℃以下とした。ここで、温度斑
とは、ドラムの表面温度を所定間隔置きに点測定したと
きの最大値と最小値の温度差を言う。
【０００７】
【発明の実施の形態】以下、本発明について詳細に説明
する。本発明でドラム製膜機とは、例えば１個以上の回
転するドラムを用い、これらドラムのうち最上流側に位
置する第１ドラムの周面に、溶液または溶融状態のＰＶ
Ａを含有する製膜原料を供給し、乾燥してＰＶＡフィル
ムとし、このＰＶＡフィルムを下流側のドラムの周面上
を通過させながら順次乾燥させて、ＰＶＡフィルムを製
造するもののことを言う。このドラム製膜機には、乾燥
装置や調湿装置及び巻き取り装置などが付設される。ま
た、それぞれの駆動にはモータや変速機などが使用され
て速度調整される。乾燥温度は５０℃〜１５０℃が一般
的である。
【０００８】前記ドラムによるＰＶＡフィルムの乾燥手
段は、加熱乾燥が効率的で、幅方向に均一な乾燥が得ら
れるならば特に限定されないが、液状熱媒体やガス状熱
媒体などを用いて外部から熱源を供給するタイプ、ヒー
タや誘導加熱コイルなどの熱源を内蔵するタイプ及びこ
れらの組み合わせによるタイプなどがある。
【０００９】以上のドラム製膜時には、前記第１ドラム
の表面の温度斑（温度差）は２℃以下とすることが必要
であり、１℃以下が好ましく、０．８℃以下がより好ま
しく、０．５℃以下がさらに好ましい。ＰＶＡを含有す
る製膜原料が直接供給される第１ドラムの表面の温度斑
が小さいほど、厚みが均一な平滑性に優れたＰＶＡフィ
ルムが得られる。このとき、温度斑が２℃より大きい
と、製膜原料が均一に乾燥されないため、厚み均一性に
優れたＰＶＡフィルムを得ることは困難である。
【００１０】第１ドラムの温度斑を少なくする方法とし
ては特に制限はないが、例えば液状熱媒体を熱源とする
タイプでは、ドラムの内面に平行またはスパイラル状の
流路を有するジャケットなどを設ける方法、ガス状熱媒
体を熱源とするタイプでは、ドラムの内部のドレンを強
制的に排除したりして温度コントロール精度を向上させ
る真空蒸気発生装置などを設置する方法、ヒータや誘導
加熱コイルなどを熱源とするタイプでは、熱源の間隔を
狭くする方法、及びこれらの方法を組み合わせた方法な
どが用いられる。なお、ドラム内に特殊構造を有しない
空洞でタンク方式の熱媒循環ドラムでは、ドラム内の熱
媒の充填具合、循環する熱媒のショートパスなどによっ
てドラム表面の温度斑が大きくなったり、ドラム表面の
温度が熱媒の温度より低下する場合があるため好ましく
ない。
【００１１】本発明のＰＶＡフィルムを構成するポリビ
ニルアルコール系重合体（ＰＶＡ）としては、ビニルエ
ステル系モノマー重合して得られたビニルエステル系重
合体をけん化し、ビニルエステル単位をビニルアルコー
ル単位としたものを用いることができる。このビニルエ
ステル系モノマーとしては、例えば、ギ酸ビニル、酢酸
ビニル、プロピオン酸ビニル、バレリン酸ビニル、ラウ
リン酸ビニル、ステアリン酸ビニル、安息香酸ビニル、
ピバリン酸ビニル、バーサティック酸ビニル等を挙げる
ことができ、これらのなかでも酢酸ビニルを用いるのが
好ましい。
【００１２】ビニルエステル系モノマーを共重合させる
際に、必要に応じて、共重合可能なモノマーを、本発明
の趣旨を損なわない範囲内（好ましくは１５モル％以
下、より好ましくは５モル％以下の割合）で共重合させ
ることもできる。
【００１３】このようなビニルエステル系モノマーと共
重合可能なモノマーとしては、例えば、エチレン、プロ
ピレン、１−ブテン、イソブテン等の炭素数３〜３０の
オレフィン類；アクリル酸およびその塩；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
−エチルへキシル、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；メタクリル酸およ
びその塩；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
へキシル、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；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および
その塩、アクリルアミドプロピルジメチルアミンおよび
その塩、Ｎ−メチロールアクリルアミドおよびその誘導
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およびその
塩、メタクリルアミドプロピルジメチルアミンおよびそ
の塩、Ｎ−メチロールメタクリルアミドおよびその誘導
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
ン酸およびその塩またはそのエステル；イタコン酸およ
びその塩またはそのエステル；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、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−ビニルアミド類を挙げることが
できる。
【００１４】前記ＰＶＡフィルムを構成するＰＶＡの平
均重合度は、フィルムの強度の点から５００以上とする
が、偏光性能の点からは１０００以上がより好ましく、
２０００以上がさらに好ましく、３５００以上が特に好
ましい。一方、ＰＶＡの重合度の上限は、フィルムの製
膜性の点から１００００以下が好ましい。
【００１５】前記ＰＶＡの重合度（Ｐ）はＪＩＳ Ｋ
６７２６に準じて測定される。すなわち、ＰＶＡを再け
ん化し、精製した後、３０℃の水中で測定した極限粘度
［η］（単位：ｄＬ／ｇ、Ｌはリットル）から次式によ
り求められる。Ｐ＝（［η］×１０3 ／８．２９）
(1/0.62)
【００１６】前記ＰＶＡフィルムを構成するＰＶＡのけ
ん化度は、偏光膜の耐久性の点から９０モル％以上とす
るが、９５モル％以上がより好ましく、９８モル％以上
がさらに好ましい。また、ＰＶＡフィルムの染色性の点
からは９９．９９モル％以下が好ましい。前記けん化度
とは、けん化によりビニルアルコール単位に変換されう
る単位の中で、実際にビニルアルコール単位にけん化さ
れている単位の割合を示したものである。なお、ＰＶＡ
のケン化度は、ＪＩＳ記載の方法により測定を行った。
【００１７】前記ＰＶＡフィルムを製造する際には、可
塑剤として多価アルコールを添加することとする。多価
アルコールとしては、例えば、エチレングリコール、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を挙げることができ、こ
れらのうち１種または２種以上を使用できる。これらの
中でも延伸性の向上効果からエチレングリコールまたは
グリセリンが好適に使用される。
【００１８】多価アルコールの添加量は、ＰＶＡ１００
重量部に対して１〜３０重量部とするが、３〜２５重量
部がさらに好ましく、５〜２０重量部が特に好ましい。
１重量部より少ないと染色性や延伸性が低下する場合が
あり、３０重量部より多いとフィルムが柔軟になりすぎ
て取り扱い性が低下する場合がある。
【００１９】また、前記ＰＶＡフィルムを製造する際に
は、界面活性剤を添加することが好ましい。界面活性剤
の種類としては特に限定はないが、アニオン性またはノ
ニオン性の界面活性剤が好ましい。アニオン性界面活性
剤としては、例えば、ラウリン酸カリウムなどのカルボ
ン酸型、オクチルサルフェートなどの硫酸エステル型、
ドデシルベンゼンスルホネートなどのスルホン酸型のア
ニオン性界面活性剤が好適である。ノニオン性界面活性
剤としては、例えば、ポリオキシエチレンオレイルエー
テルなど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など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などのアルキルエ
ステル型、ポリオキシエチレンラウリルアミノエーテル
などのアルキルアミン型、ポリオキシエチレンラウリン
酸アミドなど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などのポリプロピレング
リコールエーテル型、オレイン酸ジエタノールアミドな
ど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などのアリルフェニルエーテル型な
どのノニオン性界面活性剤が好適である。これらの界面
活性剤の１種または２種以上の組み合わせで使用するこ
とができる。
【００２０】界面活性剤の添加量としては、ＰＶＡ１０
０重量部に対して０．０１〜１重量部が好ましく、０．
０２〜０．５重量部がより好ましく、０．０５〜０．３
重量部が特に好ましい。０．０１重量部より少ないと延
伸性向上や染色性向上の効果が現れにくく、１重量部よ
り多いとフィルム表面に溶出してブロッキングの原因に
なり、取り扱い性が低下する場合がある。
【００２１】前記ＰＶＡフィルムを製造する際に使用さ
れるＰＶＡを含有する製膜原料の揮発分濃度は５０〜９
０重量％が好ましく、５５〜８０重量％がより好まし
い。揮発分濃度が５０％より小さいと粘度が高くなるた
め製膜が困難となる場合がある。一方、揮発分濃度が９
０％より大きいと粘度が低くなりすぎてＰＶＡフィルム
の厚み均一性が損なわれ易くなる。
【００２２】前記ＰＶＡフィルムは、例えば、製膜原料
をホッパープレート、Ｔ−ダイ、Ｉ−ダイ、リップコー
ターダイなどから最上流側に位置する第１ドラムの周面
に吐出し、このドラム上で含有水分を蒸発させて製膜し
て後工程に送り、さらに乾燥および調湿を行って適切な
ＰＶＡフィルムに調整して巻き取ることにより製造でき
る。
【００２３】ＰＶＡフィルムの厚みは２０〜１５０μｍ
が好ましく、４０〜１２０μｍがより好ましい。
【００２４】前記ＰＶＡフィルムから偏光フィルムを製
造するには、例えばＰＶＡフィルムを染色、一軸延伸、
固定処理、乾燥処理、さらに必要に応じて熱処理を行え
ばよい。各工程の順序は特に限定はなく、また染色と一
軸延伸などの二つの工程を同時に実施しても構わない。
また、各工程を複数回繰り返しても良い。
【００２５】染色は、一軸延伸の前、一軸延伸と同時、
一軸延伸後のいずれでも可能であるが、ＰＶＡは一軸延
伸により結晶化度が上がりやすく染色性が低下すること
があるため、一軸延伸に先立つ任意の工程または一軸延
伸工程中において染色するのが好ましい。
【００２６】染色に用いる染料としては、ヨウ素−ヨウ
化カリウムまたはDirect black 17、19、154 ；Direct
brown 44 、106 、195 、210 、223 ；Direct red 2、2
3、28、31、37、39、79、81、240 、242 、247 ；Direc
t blue 1 、15、22、78、90、98、151 、168 、202 、2
36 、249 、270 ；Direct violet 9 、12、51、98；Dir
ect green 1、85；Direct yellow 8 、12、44、86、8
7；Direct orange 26、39、106 、107 等の二色性染料
などが使用できる。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。
【００２７】前記ＰＶＡフィルムの長さ方向に行う一軸
延伸は、湿式延伸法または乾熱延伸法を使用でき、温水
中（前記染料を含有する溶液や後記固定処理浴中でもよ
い）でまたは吸水後のＰＶＡフィルムを用いて空気中で
行ってもよい。延伸倍率は４倍以上が好ましく、５倍以
上が特に好ましい。延伸倍率が４倍より小さいと、実用
的に十分な偏光性能や耐久性能が得られにくい。延伸温
度は特に限定されないが、ＰＶＡフィルムを温水中で延
伸（湿式延伸）する場合は３０〜９０℃が、また乾熱延
伸する場合は５０〜１８０℃が好適である。延伸後のＰ
ＶＡフィルムの厚みは、３〜７５μｍが好ましく、１０
〜５０μｍがより好ましい。
【００２８】前記ＰＶＡフィルムへの上記染料の吸着を
強固にすることを目的に、固定処理を行う。固定処理に
使用する処理浴には、通常ホウ酸およびホウ素化合物が
添加される。また、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。
【００２９】前記ＰＶＡフィルムの乾燥処理（熱処理）
は３０〜１５０℃で行うのが好ましく、５０〜１５０℃
で行うのがより好ましい。
【００３０】以上のようにして得られた偏光フィルム
は、通常、その両面または片面に、光学的に透明で、か
つ機械的強度を有した保護膜を張り合わせて偏光板とし
て使用される。保護膜としては、通常セルロースアセテ
ート系フィルム、アクリル系フィルム、ポリエステル系
フィルム等が使用される。
【００３１】
【実施例】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。実施例および比較例に記載したドラム表面温度
斑、ＰＶＡフィルムの厚み斑、二色性比は以下の方法に
より測定し、偏光フィルムの加工は以下の方法で実施し
た。
【００３２】ドラム表面の温度斑：温度斑は、ドラムの
表面温度の均一性を評価するためのもので、ドラム循環
熱媒の温度または真空蒸気発生装置により発生したスチ
ーム圧力を、ドラム表面温度が８５℃になるように設定
し、５ｍ／分の周速度で２時間原料を供給せずに空運転
を行った後、運転を停止し、その直後、安立計器株式会
社製デジタル表面温度計を用いて、ドラム表面温度を幅
方向５ｃｍ間隔で全幅にわたって測定した後、さらに流
れ方向１ｍ間隔で同様に全幅にわたって測定し、ドラム
表面温度の最大値と最小値の差を算出した。
【００３３】ＰＶＡフィルムの厚み斑：厚み斑は、ＰＶ
Ａフィルムの厚み均一性を評価するためのもので、アン
リツ株式会社製フィルムシックネステスタＫＧ６０１Ａ
を用いて、ＰＶＡフィルムの幅方向１．５ｍにわたって
フィルムの厚みを測定した。なお、フィルムの厚みは、
流れ方向２５ｃｍ間隔の３ヵ所で測定し、最大値と最小
値の差を算出した。
【００３４】二色性比：得られた偏光フィルムの偏光性
能を評価する指数として二色性比を使用した。この二色
性比は、日本電子機械工業会規格（ＥＩＡＪ）ＬＤ−２
０１−１９８３に準拠し、分光光度計を用いて、Ｃ光
源、２度視野にて測定・計算して得た透過率ＴS （％）
と偏光度Ｐ（％）を使用して下記の式から求めた。
二色性比＝ｌｏｇ（ＴS ／１００−ＴS ／１００×Ｐ／
１００）／ｌｏｇ（ＴS／１００＋ＴS ／１００×Ｐ／
１００）
【００３５】偏光フィルムの加工方法：ＰＶＡフィルム
を予備膨潤、染色、洗浄、一軸延伸、固定処理、乾燥、
熱処理の順に処理して偏光フィルムを作成した。すなわ
ち、ＰＶＡフィルムを３０℃の水中に１分間浸漬して予
備膨潤し、ヨウ素／ヨウ化カリウムの重量比を１／１
０、ヨウ素濃度を５０ｇ／Ｌとした３０℃のホウ酸４重
量％の水溶液中に４分間浸漬し、３０℃の水中で０．５
分浸漬して洗浄し、ホウ酸４重量％の５０℃の水溶液中
で延伸倍率５．０倍に一軸延伸を行った。続いて、ヨウ
化カリウム４０ｇ／Ｌ、ホウ酸４０ｇ／Ｌの４０℃の水
溶液中に５分間浸漬して固定処理を行った。この後ＰＶ
Ａフィルムを取り出し、定長下、４０℃で熱風乾燥し、
さらに１００℃で３分間熱処理を行った。
【００３６】実施例１
けん化度９９．９モル％で重合度４０００のＰＶＡ１０
０重量部、グリセリン１０重量部、ラウリン酸ジエタノ
ールアミド０．１重量部および水からなる揮発分８０重
量％の製膜原料を金属ドラム内に真空蒸気発生装置によ
り発生したスチームを吹き込んだ表面温度８５℃のドラ
ムに流延し、製膜した。空運転時のドラムの表面温度は
８４．８℃、温度斑は０．５℃であった。さらに金属ロ
ール表面の製膜原料を１００℃の熱風で乾燥し、平均厚
さ７５．２μｍ、厚み斑２．２μｍのＰＶＡフィルムを
得た。
【００３７】このＰＶＡフィルムを使用して偏光フィル
ムに加工したところ、その中央部の厚みは２８μｍ、透
過率は４３．１％、偏光度は９９．６％、二色性比は４
２．３であった。また、この偏光フィルムの１ｍ四方を
クロスニコル状態の２枚の偏光板の間に４５°の角度に
置き、透過光を目視で観察すると、光学斑はほとんど認
められなかった。
【００３８】実施例２
けん化度９９．９モル％で重合度２４００のＰＶＡ１０
０重量部、グリセリン１０重量部、ラウリン酸ジエタノ
ールアミド０．１重量部および水からなる揮発分７２重
量％の製膜原料を、金属ドラム内の表面にスパイラル状
の流路を有するジャケット構造の表面温度８５℃の熱媒
循環ドラムに吐出し、製膜した。空運転時のドラムの表
面温度は８４．５℃、温度斑は０．８℃であった。さら
に金属ロール表面の製膜原料を９０℃の熱風で乾燥し、
平均厚さ７４．８μｍ、厚み斑２．９μｍのＰＶＡフィ
ルムを得た。
【００３９】このＰＶＡフィルムを使用して偏光フィル
ムに加工したところ、その中央部の厚みは２７μｍ、透
過率は４３．５％、偏光度は９９．２％、二色性比は３
９．５であった。また、この偏光フィルムの１ｍ四方を
クロスニコル状態の２枚の偏光板の間に４５°の角度に
置き、透過光を目視で観察すると、幅１〜３ｍｍ、長さ
１０〜３０ｍｍの細長い楕円状の薄い光学斑が１個確認
された。
【００４０】実施例３
けん化度９９．９モル％で重合度１７００のＰＶＡ１０
０重量部、グリセリン１０重量部、ラウリン酸ジエタノ
ールアミド０．１重量部および水からなる揮発分５８重
量％の製膜原料を、８５℃の実施例２で使用した金属ド
ラムと同じ構造で、スパイラル定数の低いドラムに吐出
し、製膜した。空運転時のドラムの表面温度は８３．９
℃、温度斑は０．９℃であった。さらに金属ロール表面
の製膜原料を８５℃の熱風で乾燥し、平均厚さ７４．９
μｍ、厚み斑３．１μｍのＰＶＡフィルムを得た。
【００４１】このＰＶＡフィルムを使用して偏光フィル
ムに加工したところ、その中央部の厚みは２６μｍ、透
過率は４３．２％、偏光度は９９．１％、二色性比は３
６．８であった。また、この偏光フィルムの１ｍ四方を
クロスニコル状態の２枚の偏光板の間に４５°の角度に
置き、透過光を目視で観察すると、幅５〜１０ｍｍ、長
さ２０〜８０ｍｍの細長い楕円状の非常に薄い光学斑が
３個確認された。
【００４２】比較例１
けん化度９９．９モル％で重合度４０００のＰＶＡ１０
０重量部、グリセリン１０重量部、ラウリン酸ジエタノ
ールアミド０．１重量部および水からなる揮発分７８重
量％の製膜原料を、表面温度８５℃のドラム内に特殊構
造を有しない空洞でタンク方式の熱媒循環ドラムに流延
し、製膜した。空運転時のドラムの表面温度は８１．６
℃、温度斑は３．３℃であった。さらに金属ロール表面
の製膜原料を１２０℃の熱風で乾燥し、平均厚さ７４．
６μｍ、厚み斑８．４μｍのＰＶＡフィルムを得た。
【００４３】このＰＶＡフィルムを使用して偏光フィル
ムに加工したところ、その中央部の厚みは２７μｍ、透
過率は４３．０％、偏光度は９９．７％、二色性比は４
３．７であった。また、この偏光フィルムの１ｍ四方を
クロスニコル状態の２枚の偏光板の間に４５°の角度に
置き、透過光を目視で観察すると、幅５〜２０ｍｍ、長
さ５０〜１５０ｍｍの縞状、楕円状、及び不定形な光学
斑が８個確認された。
【００４４】比較例２
けん化度９９．９モル％で重合度２４００のＰＶＡ１０
０重量部、グリセリン１０重量部、ラウリン酸ジエタノ
ールアミド０．１重量部および水からなる揮発分７４重
量％の製膜原料を、表面温度８５℃の比較例１と同じ構
造で比較例１とは別のドラムに吐出し、製膜した。空運
転時のドラムの表面温度は８１．７℃、温度斑は４．０
℃であった。さらに金属ロール表面の製膜原料を１００
℃の熱風で乾燥し、平均厚さ７５．１μｍ、厚み斑９．
５μｍのＰＶＡフィルムを得た。
【００４５】このＰＶＡフィルムを使用して偏光フィル
ムに加工したところ、その中央部の厚みは２７μｍ、透
過率は４３．７％、偏光度は９９．０％、二色性比は３
８．９であった。この偏光フィルムの１ｍ四方をクロス
ニコル状態の２枚の偏光板の間に４５°の角度に置き、
透過光を目視で観察すると、幅５〜２０ｍｍ、長さ３０
〜１５０ｍｍの縞状、楕円状、及び不定形な光学斑が８
個確認された。
【００４６】比較例３
けん化度９９．９モル％で重合度１７００のＰＶＡ１０
０重量部、グリセリン１０重量部、ラウリン酸ジエタノ
ールアミド０．１重量部および水からなる揮発分６６重
量％の製膜原料を、表面温度８５℃の実施例１で使用し
た金属ドラムに吐出し、製膜した。空運転時のドラム表
面温度は８１．６℃、温度斑は３．３℃であった。さら
に金属ロール表面の製膜原料を８５℃の熱風で乾燥し、
平均厚さ７５．５μｍ、厚み斑８．８μｍのＰＶＡフィ
ルムを得た。
【００４７】このＰＶＡフィルムを使用して偏光フィル
ムに加工したところ、その中央部の厚みは２６μｍ、透
過率は４３．４％、偏光度は９８．９％、二色性比は３
６．３であった。この偏光フィルムの１ｍ四方をクロス
ニコル状態の２枚の偏光板の間に４５°の角度に置き、
透過光を目視で観察すると、幅５〜２０ｍｍ、長さ３０
〜３００ｍｍの縞状、楕円状、及び不定形な光学斑が１
１個確認された。
【００４８】以上の実施例１〜３および比較例１〜３の
結果を下記の表１に示す。
【００４９】
【表１】
【００５０】上記表１において、◎は光学斑がなくて最
も優れているもの、○は若干の光学斑はあるものの実際
の使用は可能であるもの、×は光学斑が多くて使用不能
のものを示している。
【００５１】上記の表１から明らかなように、製膜原料
が供給される最上流側に位置するドラムの表面の温度斑
を２℃より大きくすると、ＰＶＡフィルムの厚み斑が大
となって厚みの均一性が得られず、これより得られる偏
光フィルムに多くの光学斑が発生する。このことから、
ＰＶＡフィルムの厚み斑を小として、光学斑の少ない偏
光性能に優れた偏光フィルムを得るためには、前記ドラ
ムの表面の温度斑を２℃以下にする必要のあることが理
解できる。
【００５２】
【発明の効果】以上のように本発明によれば、大面積に
おいても厚み均一性に優れた平滑なＰＶＡフィルムを得
ることができ、また、このＰＶＡフィルムから光学斑の
少ない偏光性能に優れた偏光フィルムを得ることができ
る。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyvinyl alcohol film useful as a material for producing a polarizing film. 2. Description of the Related Art A polarizing plate having a function of transmitting and blocking light is a fundamental component of a liquid crystal display (LCD) together with a liquid crystal having a function of switching light. The field of application of this LCD has expanded from small devices such as calculators and watches in the early days to recent years, such as laptop computers, word processors, liquid crystal color projectors, in-vehicle navigation systems, and liquid crystal televisions. As a result, there has been a demand for a polarizing plate that is more excellent in uniformity of polarization performance on a large screen than conventional products. [0003] The polarizing plate is generally a polyvinyl alcohol film (hereinafter abbreviated as "PVA film", and the polyvinyl alcohol as a raw material thereof is referred to as a polyvinyl alcohol polymer, which is abbreviated as "PVA". Is sometimes uniaxially stretched and dyed, and cellulose triacetate (TA
C) A structure in which a protective film such as a film is bonded. [0004] In order to make the polarizing performance of the polarizing plate uniform, there are many precautions such as uniform stretching of the PVA film and bonding without unevenness. The important point is to make the thickness of the PVA film used as the material of the polarizing film uniform. If the thickness of the PVA film is not uniform, uniform polarization performance cannot be obtained over a large area even when precision stretching is performed. In order to make the thickness of the PVA film uniform, casting is performed with a dilute solution of PVA, but sufficient thickness uniformity has not been obtained. Accordingly, an object of the present invention is to provide a PVA film which is useful as a material for producing a polarizing film and which can provide a PVA film having excellent thickness uniformity even in a large area.
An object of the present invention is to provide a method for producing an A film. [0006] In order to achieve the above object, a method for producing a PVA film for a polarizing film of the present invention uses a drum film forming machine and a polymer having a degree of polymerization of 500 or more.
Having a degree of conversion of 90 mol% or more and polyvinyl alcohol
1 to 30 parts by weight of polyvalent alcohol per 100 parts by weight of
When producing a PVA film from a film forming raw material containing rucol , the temperature unevenness on the surface of the drum located on the most upstream side where the film forming raw material is supplied was set to 2 ° C. or less. Here, the temperature unevenness refers to a temperature difference between the maximum value and the minimum value when the surface temperature of the drum is measured at predetermined intervals. Hereinafter, the present invention will be described in detail. In the present invention, the drum film forming machine refers to, for example, one or more rotating drums, and a solution or a molten PV
A film-forming raw material containing A is supplied and dried to form a PVA film, and the PVA film is sequentially dried while passing over the peripheral surface of a downstream drum to produce a PVA film. The drum film forming machine is provided with a drying device, a humidity control device, a winding device, and the like. The speed of each drive is adjusted using a motor, a transmission, or the like. The drying temperature is generally from 50C to 150C. [0008] The means for drying the PVA film by the drum is not particularly limited as long as heat drying is efficient and uniform drying in the width direction can be obtained. There are a type that supplies a heat source, a type that incorporates a heat source such as a heater and an induction heating coil, and a type that combines these. At the time of the above-mentioned drum film formation, the temperature unevenness (temperature difference) on the surface of the first drum needs to be 2 ° C. or less, preferably 1 ° C. or less, more preferably 0.8 ° C. or less. 0.5 ° C. or lower is more preferable. As the temperature unevenness on the surface of the first drum to which the PVA-containing film-forming raw material is directly supplied is smaller, a PVA film having a uniform thickness and excellent in smoothness can be obtained. At this time, if the temperature unevenness is larger than 2 ° C., the film forming raw material is not dried uniformly, so that it is difficult to obtain a PVA film having excellent thickness uniformity. There is no particular limitation on the method of reducing the temperature unevenness of the first drum. For example, in the case of a type using a liquid heat medium as a heat source, a method of providing a jacket having a parallel or spiral flow path on the inner surface of the drum is provided. In the case of using a gaseous heat medium as the heat source, a method of installing a vacuum steam generator to improve the temperature control accuracy by forcibly removing the drain inside the drum or installing a heater or induction heating coil as the heat source In such a case, a method of narrowing the interval between heat sources, a method combining these methods, and the like are used. In the case of a tank-type heat medium circulating drum having no special structure inside the drum, the temperature unevenness on the drum surface increases due to the filling condition of the heat medium in the drum, the short path of the circulating heat medium, or the drum. This is not preferable because the temperature of the surface may be lower than the temperature of the heat medium. As the polyvinyl alcohol-based polymer (PVA) constituting the PVA film of the present invention, a vinyl ester-based polymer obtained by polymerization of a vinyl ester-based monomer is saponified to convert the vinyl ester unit into a vinyl alcohol unit. Can be used. Examples of the vinyl ester monomer include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl laurate, vinyl stearate, vinyl benzoate,
Examples thereof include vinyl pivalate and vinyl versatate, and among these, vinyl acetate is preferably used. When copolymerizing a vinyl ester-based monomer, if necessary, a copolymerizable monomer may be used within a range that does not impair the purpose of the present invention (preferably 15 mol% or less, more preferably 5 mol% or less. ). Examples of such a monomer copolymerizable with the vinyl ester monomer include olefins having 3 to 30 carbon atoms such as ethylene, propylene, 1-butene and isobutene; acrylic acid and its salts; methyl acrylate , Ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, acrylic acid 2
Acrylates such as ethylhexyl, dodecyl acrylate and octadecyl acrylate; methacrylic acid and salts thereof; methyl methacrylate, ethyl methacrylate;
Methacrylates such as n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate And acrylamide,
Acrylamide derivatives such as N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetone acrylamide, acrylamidopropanesulfonic acid and its salts, acrylamidopropyldimethylamine and its salts, N-methylolacrylamide and its derivatives; methacryl Amide, N-
Methacrylamide derivatives such as methyl methacrylamide, N-ethyl methacrylamide, methacrylamidopropanesulfonic acid and salts thereof, methacrylamidopropyldimethylamine and salts thereof, N-methylol methacrylamide and derivatives thereof; N-vinylformamide, N-vinyl N-vinylamides such as acetamide and N-vinylpyrrolidone; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i
-Butyl vinyl ether, t-butyl vinyl ether,
Vinyl ethers such as dodecyl vinyl ether and stearyl vinyl ether; nitriles such as acrylonitrile and methacrylonitrile; vinyl chloride, vinylidene chloride;
Vinyl halides such as vinyl fluoride and vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; maleic acid and its salts or esters; itaconic acid and its salts or esters; vinylsilyl compounds such as vinyltrimethoxysilane Isopropenyl acetate, N-
Examples include N-vinylamides such as vinylformamide, N-vinylacetamide, and N-vinylpyrrolidone. The average degree of polymerization of the PVA constituting the PVA film is 500 or more in view of the strength of the film.
However , from the viewpoint of polarization performance, 1000 or more is more preferable,
It is more preferably at least 2,000, particularly preferably at least 3,500. On the other hand, the upper limit of the degree of polymerization of PVA is preferably 10,000 or less from the viewpoint of film forming properties. The degree of polymerization (P) of the PVA is JIS K
It is measured according to 6726. That is, after PVA is re-saponified and purified, the intrinsic viscosity [η] (unit: dL / g, L is liter) measured in water at 30 ° C. is determined by the following equation. P = ([η] × 10 3 /8.29)
(1 / 0.62) The degree of saponification of the PVA constituting the PVA film is 90 mol% or more from the viewpoint of the durability of the polarizing film .
However , it is more preferably at least 95 mol%, even more preferably at least 98 mol%. Further, from the viewpoint of the dyeability of the PVA film, the content is preferably 99.99 mol% or less. The degree of saponification indicates the ratio of units actually saponified to vinyl alcohol units among units that can be converted into vinyl alcohol units by saponification. In addition, PVA
Was measured by the method described in JIS. [0017] When manufacturing the PVA film, and adding a polyhydric alcohol as a plasticizer. Examples of the polyhydric alcohol include ethylene glycol, glycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, and the like, and one or more of these can be used. Among them, ethylene glycol or glycerin is preferably used from the viewpoint of the effect of improving the stretchability. The amount of the polyhydric alcohol added is PVA 100
The amount is from 1 to 30 parts by weight, more preferably from 3 to 25 parts by weight, and particularly preferably from 5 to 20 parts by weight.
If the amount is less than 1 part by weight, the dyeing properties and the stretchability may decrease. If the amount is more than 30 parts by weight, the film may be too flexible and the handleability may decrease. When producing the PVA film, it is preferable to add a surfactant. The type of the surfactant is not particularly limited, but an anionic or nonionic surfactant is preferable. As the anionic surfactant, for example, carboxylic acid type such as potassium laurate, sulfate type such as octyl sulfate,
Sulfonic acid type anionic surfactants such as dodecylbenzenesulfonate are preferred. Nonionic surfactants include, for example, alkyl ether types such as polyoxyethylene oleyl ether, alkyl phenyl ether types such as polyoxyethylene octyl phenyl ether, alkyl ester types such as polyoxyethylene laurate, and polyoxyethylene lauryl amino. Alkylamine type such as ether, alkylamide type such as polyoxyethylene lauric amide, polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether, alkanolamide type such as oleic acid diethanolamide, polyoxyalkylene allyl phenyl ether Nonionic surfactants such as allyl phenyl ether type are preferred. One or a combination of two or more of these surfactants can be used. The amount of the surfactant added is PVA 10
0.01 to 1 part by weight is preferable for 0 part by weight, and 0.1 to 1 part by weight is preferable.
02 to 0.5 part by weight is more preferable, and 0.05 to 0.3 part by weight.
Part by weight is particularly preferred. If the amount is less than 0.01 part by weight, the effect of improving the stretchability and the dyeing property is difficult to appear, and if it is more than 1 part by weight, it is eluted on the film surface to cause blocking, and the handleability may be reduced. The volatile matter concentration of the PVA-containing film-forming raw material used for producing the PVA film is 50 to 9%.
0% by weight is preferred, and 55-80% by weight is more preferred. If the volatile matter concentration is less than 50%, the viscosity may be high, and thus film formation may be difficult. On the other hand, when the volatile matter concentration is 9
If it is more than 0%, the viscosity becomes too low, and the uniformity of the thickness of the PVA film tends to be impaired. For the PVA film, for example, a film forming raw material is discharged from a hopper plate, a T-die, an I-die, a lip coater die, etc. onto the peripheral surface of a first drum located at the most upstream side, and is formed on the drum. The film can be manufactured by evaporating the contained water to form a film, sending the film to a subsequent step, drying and controlling the humidity, adjusting the film to an appropriate PVA film, and winding the film. The thickness of the PVA film is 20 to 150 μm
Is preferable, and 40 to 120 μm is more preferable. In order to produce a polarizing film from the PVA film, for example, a PVA film is dyed, uniaxially stretched,
Fixing treatment, drying treatment and, if necessary, heat treatment may be performed. The order of each step is not particularly limited, and two steps such as dyeing and uniaxial stretching may be performed simultaneously.
Further, each step may be repeated a plurality of times. The dyeing is performed before the uniaxial stretching, simultaneously with the uniaxial stretching,
Although any method can be used after uniaxial stretching, PVA is preferably dyed in any step prior to uniaxial stretching or during the uniaxial stretching step because the degree of crystallinity tends to increase due to uniaxial stretching and the dyeability may decrease. . The dye used for dyeing is iodine-potassium iodide or Direct black 17, 19, 154;
brown 44, 106, 195, 210, 223; Direct red 2, 2
3, 28, 31, 37, 39, 79, 81, 240, 242, 247; Direc
t blue 1, 15, 22, 78, 90, 98, 151, 168, 202, 2
36, 249, 270; Direct violet 9, 12, 51, 98; Dir
ect green 1, 85; Direct yellow 8, 12, 44, 86, 8
7; Dichroic dyes such as Direct orange 26, 39, 106 and 107 can be used. Dyeing can be usually performed by immersing the PVA film in a solution containing the dye, but the processing conditions and processing method are not particularly limited. The uniaxial stretching performed in the length direction of the PVA film may be performed by a wet stretching method or a dry heat stretching method, and may be performed in warm water (which may be in a solution containing the dye or in a fixing bath described below) or after absorbing water. It may be performed in air using a PVA film. The stretching ratio is preferably at least 4 times, particularly preferably at least 5 times. When the stretching ratio is smaller than 4 times, it is difficult to obtain practically sufficient polarization performance and durability performance. The stretching temperature is not particularly limited, but is preferably 30 to 90 ° C. when the PVA film is stretched in warm water (wet stretching), and 50 to 180 ° C. when the dry stretching is performed by dry heat. P after stretching
The thickness of the VA film is preferably 3 to 75 μm,
-50 μm is more preferable. For the purpose of strengthening the adsorption of the dye to the PVA film, a fixing treatment is performed. Usually, boric acid and a boron compound are added to the treatment bath used for the fixing treatment. Further, an iodine compound may be added to the treatment bath as needed. Drying (heat treatment) of the PVA film
Is preferably performed at 30 to 150 ° C., and 50 to 150 ° C.
It is more preferable to carry out. The polarizing film obtained as described above is usually used as a polarizing plate by laminating an optically transparent protective film having mechanical strength on both surfaces or one surface thereof. As the protective film, a cellulose acetate film, an acrylic film, a polyester film or the like is usually used. EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. Drum surface temperature unevenness, PVA film thickness unevenness, and dichroic ratio described in Examples and Comparative Examples were measured by the following methods, and processing of the polarizing film was performed by the following methods. Temperature unevenness on the surface of the drum: The temperature unevenness is used to evaluate the uniformity of the surface temperature of the drum, and the temperature of the drum circulating heat medium or the steam pressure generated by the vacuum steam generator is used to determine the temperature of the drum surface. The temperature was set to 85 ° C., and after idling without supplying the raw material at a peripheral speed of 5 m / min for 2 hours, the operation was stopped, and immediately thereafter, a digital surface thermometer manufactured by Anritsu Keiki Co., Ltd. was used. After measuring the drum surface temperature over the entire width at intervals of 5 cm in the width direction, the drum surface temperature was also measured over the entire width at intervals of 1 m in the flow direction, and the difference between the maximum value and the minimum value of the drum surface temperature was calculated. Thickness unevenness of PVA film: Thickness unevenness is caused by PV
A for evaluating the thickness uniformity of the A film, and a film thick nest tester KG601A manufactured by Anritsu Corporation.
Was used to measure the thickness of the PVA film over a width of 1.5 m in the width direction. The thickness of the film is
The measurement was performed at three points at intervals of 25 cm in the flow direction, and the difference between the maximum value and the minimum value was calculated. Dichroic ratio: The dichroic ratio was used as an index for evaluating the polarizing performance of the obtained polarizing film. This dichroic ratio is based on the standards of the Electronic Machinery Manufacturers Association of Japan (EIAJ) LD-2.
According to 01-1983, transmittance Ts (%) obtained by measuring and calculating with a C light source and a 2 degree field of view using a spectrophotometer
And the degree of polarization P (%). Dichroic ratio = log (TS / 100−TS / 100 × P /
100) / log (TS / 100 + TS / 100 × P /
100) Processing method of polarizing film: Preliminary swelling, dyeing, washing, uniaxial stretching, fixing treatment, drying,
A polarizing film was prepared by treating in the order of heat treatment. That is, the PVA film was immersed in water at 30 ° C. for 1 minute to pre-swell, and the weight ratio of iodine / potassium iodide was reduced to 1/1.
0, immersed in a 4% by weight aqueous solution of boric acid at 30 ° C. with an iodine concentration of 50 g / L for 4 minutes, and 0.5% in water at 30 ° C.
After immersion for a minute, the film was uniaxially stretched in a 50% aqueous solution of 4% by weight of boric acid at a stretching ratio of 5.0 times. Subsequently, a fixation treatment was performed by immersing in a 40 g / L aqueous solution of 40 g / L of potassium iodide and 40 g / L of boric acid for 5 minutes. After this, PV
A film is taken out and dried with hot air at 40 ° C. under constant length.
Further, heat treatment was performed at 100 ° C. for 3 minutes. Example 1 PVA10 having a degree of saponification of 99.9 mol% and a degree of polymerization of 4000
A surface temperature at which steam generated by a vacuum steam generator was blown into a metal drum was fed a film forming material consisting of 0 parts by weight, 10 parts by weight of glycerin, 0.1 part by weight of lauric acid diethanolamide and water and having a volatile content of 80% by weight. The film was cast on a drum at ° C to form a film. The surface temperature of the drum during idling was 84.8 ° C, and the temperature spot was 0.5 ° C. Further, the film forming raw material on the surface of the metal roll was dried with hot air at 100 ° C. to obtain a PVA film having an average thickness of 75.2 μm and an uneven thickness of 2.2 μm. When this PVA film was processed into a polarizing film, the thickness at the center was 28 μm, the transmittance was 43.1%, the degree of polarization was 99.6%, and the dichroic ratio was 4
2.3. Further, when a 1 m square of this polarizing film was placed at an angle of 45 ° between two polarizing plates in a crossed Nicols state, and transmitted light was visually observed, almost no optical spot was observed. Example 2 PVA 10 having a saponification degree of 99.9 mol% and a polymerization degree of 2400
0 parts by weight, 10 parts by weight of glycerin, 0.1 part by weight of lauric acid diethanolamide, and a film forming raw material having a volatile content of 72% by weight of water were coated on a surface inside a metal drum with a spiral channel on the surface of a jacket structure. The film was discharged onto a heating medium circulation drum at a temperature of 85 ° C. to form a film. The surface temperature of the drum during idling was 84.5 ° C, and the temperature spot was 0.8 ° C. Further, the film forming raw material on the surface of the metal roll is dried with hot air at 90 ° C.
A PVA film having an average thickness of 74.8 μm and a thickness unevenness of 2.9 μm was obtained. When this PVA film was processed into a polarizing film, the thickness at the center was 27 μm, the transmittance was 43.5%, the degree of polarization was 99.2%, and the dichroic ratio was 3
9.5. Moreover, when 1 m square of this polarizing film is placed at an angle of 45 ° between two polarizing plates in a crossed Nicols state, and the transmitted light is visually observed, a thin, elongated, oval thin film having a width of 1 to 3 mm and a length of 10 to 30 mm is obtained. One optical spot was confirmed. Example 3 PVA 10 having a saponification degree of 99.9 mol% and a polymerization degree of 1700
0 parts by weight, 10 parts by weight of glycerin, 0.1 part by weight of lauric acid diethanolamide, and 58% by weight of a water-soluble film-forming raw material having the same structure as the metal drum used in Example 2 at 85 ° C. The film was discharged onto a drum having a low constant to form a film. The drum surface temperature during idle operation was 83.9.
° C and the temperature spot were 0.9 ° C. Further, the film forming raw material on the surface of the metal roll was dried with hot air at 85 ° C. to have an average thickness of 74.9.
A PVA film having a thickness of 3.1 μm and a thickness variation of 3.1 μm was obtained. When this PVA film was processed into a polarizing film, the thickness at the center was 26 μm, the transmittance was 43.2%, the degree of polarization was 99.1%, and the dichroic ratio was 3
6.8. Further, when a 1 m square of this polarizing film is placed at an angle of 45 ° between two polarizing plates in a crossed Nicols state, and the transmitted light is visually observed, an elongated elliptical emergency having a width of 5 to 10 mm and a length of 20 to 80 mm is obtained. 3 thin optical spots were observed. Comparative Example 1 PVA10 having a degree of saponification of 99.9 mol% and a degree of polymerization of 4000
0 parts by weight, 10 parts by weight of glycerin, 0.1 parts by weight of lauric acid diethanolamide and 78% by weight of a water-soluble film-forming raw material in a drum having a surface temperature of 85 ° C. in a drum having no special structure in a tank system And a film was formed. The surface temperature of the drum during idling is 81.6
° C and the temperature spot were 3.3 ° C. Further, the raw material for film formation on the surface of the metal roll was dried with hot air at 120 ° C. to obtain an average thickness of 74.degree.
A PVA film having a thickness of 6 μm and a thickness unevenness of 8.4 μm was obtained. When this PVA film was processed into a polarizing film, the thickness at the center was 27 μm, the transmittance was 43.0%, the degree of polarization was 99.7%, and the dichroic ratio was 4
3.7. Moreover, when 1 m square of this polarizing film is placed at an angle of 45 ° between two polarizing plates in a crossed Nicols state, and the transmitted light is visually observed, a striped shape having a width of 5 to 20 mm and a length of 50 to 150 mm, an elliptical shape is obtained. , And eight irregular optical spots were confirmed. Comparative Example 2 PVA10 having a saponification degree of 99.9 mol% and a polymerization degree of 2400
A film-forming material consisting of 0 parts by weight, 10 parts by weight of glycerin, 0.1 part by weight of lauric acid diethanolamide, and 74% by weight of volatile matter and water was used. The film was discharged onto another drum to form a film. The drum surface temperature during idle operation was 81.7 ° C, and the temperature spot was 4.0.
° C. Further, 100 parts of the film forming material on the metal roll surface
8. Dry with hot air at ℃, average thickness 75.1 μm, thickness unevenness 9.
A 5 μm PVA film was obtained. When this PVA film was processed into a polarizing film, the thickness at the center was 27 μm, the transmittance was 43.7%, the degree of polarization was 99.0%, and the dichroic ratio was 3
8.9. 1 m square of this polarizing film is placed at an angle of 45 ° between two polarizing plates in a crossed Nicols state,
When the transmitted light is visually observed, the width is 5 to 20 mm and the length is 30.
8 striped, elliptical and irregular optical spots of ~ 150 mm
Was confirmed. Comparative Example 3 PVA10 having a saponification degree of 99.9 mol% and a polymerization degree of 1700
0 parts by weight, 10 parts by weight of glycerin, 0.1 part by weight of lauric acid diethanolamide and 66% by weight of a volatile matter formed of water were discharged onto the metal drum used in Example 1 having a surface temperature of 85 ° C. A film was formed. The drum surface temperature during idling was 81.6 ° C, and the temperature spot was 3.3 ° C. Further, the film forming raw material on the surface of the metal roll is dried with hot air of 85 ° C.
A PVA film having an average thickness of 75.5 μm and a thickness unevenness of 8.8 μm was obtained. When this PVA film was processed into a polarizing film, the thickness at the center was 26 μm, the transmittance was 43.4%, the degree of polarization was 98.9%, and the dichroic ratio was 3
6.3. 1 m square of this polarizing film is placed at an angle of 45 ° between two polarizing plates in a crossed Nicols state,
When the transmitted light is visually observed, the width is 5 to 20 mm and the length is 30.
1-300mm striped, elliptical and irregular optical spots
One was confirmed. The results of Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 1 below. [Table 1] In Table 1 above, 最 も indicates that there is no optical unevenness and is excellent, は indicates that there is some optical unevenness but that actual use is possible, and X indicates that there are many optical unevenness and cannot be used. Is shown. As is apparent from Table 1 above, when the temperature unevenness on the surface of the drum located on the most upstream side where the film forming raw material is supplied is larger than 2 ° C., the thickness unevenness of the PVA film becomes large and the thickness becomes large. Cannot be obtained, and many optical spots are generated on the obtained polarizing film. From this,
It can be understood that the temperature unevenness on the surface of the drum needs to be 2 ° C. or less in order to reduce the thickness unevenness of the PVA film and obtain a polarizing film excellent in polarization performance with little optical unevenness. As described above, according to the present invention, it is possible to obtain a smooth PVA film having excellent thickness uniformity even in a large area, and to obtain a polarizing performance with less optical spots from this PVA film. It is possible to obtain a polarizing film excellent in quality
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０８Ｌ 29:04 Ｃ０８Ｌ 29:04 (56)参考文献 特開 平10−315255（ＪＰ，Ａ) 特開 平６−138319（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B29C 41/00 - 41/52 ──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. 7 Identification code FI C08L 29:04 C08L 29:04 (56) References JP-A-10-315255 (JP, A) JP-A-6-138319 (JP) , A) (58) Fields investigated (Int. Cl. 7 , DB name) B29C 41/00-41/52
Claims (1)
以上でけん化度が９０モル％以上のポリビニルアルコー
ルおよびそのポリビニルアルコール１００重量部に対し
て１〜３０重量部の多価アルコールを含有する製膜原料
からポリビニルアルコールフィルムを製造する際に、製
膜原料が供給される最上流側に位置するドラムの表面の
温度斑を２℃以下としたことを特徴とする偏光フィルム
用ポリビニルアルコールフィルムの製造法。(57) [Claims] [Claim 1] Using a drum film forming machine , the polymerization degree is 500
In the above, the saponification degree is at least 90 mol% with respect to polyvinyl alcohol and 100 parts by weight of polyvinyl alcohol
When producing a polyvinyl alcohol film from a film-forming material containing 1 to 30 parts by weight of a polyhydric alcohol , the temperature unevenness on the surface of the drum located on the most upstream side where the film-forming material is supplied is 2 ° C. or less. Polarizing film characterized by the following:
Of producing polyvinyl alcohol film for use .
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|---|---|---|---|
| JP2000135655A JP3476136B2 (en) | 2000-05-09 | 2000-05-09 | Method for producing polyvinyl alcohol film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000135655A JP3476136B2 (en) | 2000-05-09 | 2000-05-09 | Method for producing polyvinyl alcohol film |
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| Publication Number | Publication Date |
|---|---|
| JP2001315139A JP2001315139A (en) | 2001-11-13 |
| JP3476136B2 true JP3476136B2 (en) | 2003-12-10 |
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| JP2002103357A (en) * | 2000-07-24 | 2002-04-09 | Fuji Photo Film Co Ltd | Solution film-making method and polarizing plate, etc. |
| KR100416924B1 (en) * | 2001-12-24 | 2004-01-31 | 신화오플라주식회사 | Polarizing film having ultraviolet absorbing ability and its production |
| JP4531574B2 (en) * | 2004-01-26 | 2010-08-25 | 日本合成化学工業株式会社 | Method for producing polyvinyl alcohol film and method for producing polarizing film using the film |
| TWI272409B (en) * | 2005-02-04 | 2007-02-01 | Optimax Tech Corp | Polarizing film and its manufacturing method |
| KR100962543B1 (en) | 2008-06-20 | 2010-06-14 | 동아대학교 산학협력단 | Method for producing Polyvinyl alcohol polarizing film iodinated at solution state before casting |
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