WO2022158235A1 - Method for producing polarizing film - Google Patents
Method for producing polarizing film Download PDFInfo
- Publication number
- WO2022158235A1 WO2022158235A1 PCT/JP2021/047761 JP2021047761W WO2022158235A1 WO 2022158235 A1 WO2022158235 A1 WO 2022158235A1 JP 2021047761 W JP2021047761 W JP 2021047761W WO 2022158235 A1 WO2022158235 A1 WO 2022158235A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- based resin
- pva
- film
- stretching
- treatment
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 148
- 239000011347 resin Substances 0.000 claims abstract description 148
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 146
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 146
- 238000002834 transmittance Methods 0.000 claims abstract description 51
- 238000004043 dyeing Methods 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 45
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 36
- 238000011282 treatment Methods 0.000 claims description 95
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 70
- 229920005992 thermoplastic resin Polymers 0.000 claims description 66
- 239000000758 substrate Substances 0.000 claims description 61
- 238000010438 heat treatment Methods 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 31
- 150000004820 halides Chemical class 0.000 claims description 17
- 239000010410 layer Substances 0.000 description 67
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 41
- 239000004327 boric acid Substances 0.000 description 41
- 239000011241 protective layer Substances 0.000 description 37
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 33
- 239000007864 aqueous solution Substances 0.000 description 24
- 239000007788 liquid Substances 0.000 description 22
- 230000003287 optical effect Effects 0.000 description 22
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 19
- 229910052740 iodine Inorganic materials 0.000 description 19
- 239000011630 iodine Substances 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 238000002425 crystallisation Methods 0.000 description 15
- 230000008025 crystallization Effects 0.000 description 15
- 238000005401 electroluminescence Methods 0.000 description 13
- 230000010287 polarization Effects 0.000 description 12
- 230000009102 absorption Effects 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 10
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 10
- DKNPRRRKHAEUMW-UHFFFAOYSA-N Iodine aqueous Chemical compound [K+].I[I-]I DKNPRRRKHAEUMW-UHFFFAOYSA-N 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 9
- -1 polyethylene terephthalate Polymers 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 241000209094 Oryza Species 0.000 description 6
- 235000007164 Oryza sativa Nutrition 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 235000009566 rice Nutrition 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 238000007127 saponification reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 150000001925 cycloalkenes Chemical class 0.000 description 4
- 150000004694 iodide salts Chemical class 0.000 description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 238000007602 hot air drying Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- 229920008790 Amorphous Polyethylene terephthalate Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 239000012192 staining solution Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 206010042674 Swelling Diseases 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 description 1
- 229910001638 barium iodide Inorganic materials 0.000 description 1
- 229940075444 barium iodide Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
-
- 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
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8793—Arrangements for polarized light emission
-
- 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 relates to a method for manufacturing a polarizing film.
- the present invention has been made to solve the conventional problems described above, and its main purpose is to provide a polarizing film capable of reducing the power consumption of an organic EL display device.
- a polyvinyl alcohol-based resin film subjecting a polyvinyl alcohol-based resin film to dyeing treatment and stretching treatment, and bringing an aqueous solvent into contact with the surface of the polyvinyl alcohol-based resin film, in this order, and having a wavelength of ⁇ nm
- the ratio of the transmittance after contact to the transmittance of the polyvinyl alcohol resin film before contact with the aqueous solvent has a relationship of ⁇ Ts (415)> ⁇ Ts (470)> ⁇ Ts (550) is provided.
- the temperature of the aqueous solvent is 20°C to 70°C.
- the water content of the polyvinyl alcohol-based resin film with which the aqueous solvent is brought into contact is 15% by weight or less.
- the polyvinyl alcohol-based resin film with which the aqueous solvent is brought into contact has a thickness of 12 ⁇ m or less.
- subjecting the polyvinyl alcohol-based resin film to dyeing treatment and stretching treatment is a polyvinyl alcohol-based resin containing a halide and a polyvinyl alcohol-based resin on one side of a long thermoplastic resin substrate.
- the manufacturing method is a method for manufacturing a polarizing film having a haze of 1% or less.
- a polyvinyl alcohol (PVA) resin film that has undergone dyeing treatment and stretching treatment is subjected to contact treatment with an aqueous solvent.
- a polarizing film obtained by such a manufacturing method can more positively transmit light on the short wavelength side than light on the long wavelength side. Therefore, by using such a polarizing film, even when the amount of blue light emission, which consumes a large amount of power, is reduced, it is possible to suppress the decrease in luminance in the short wavelength region, and as a result, the organic EL display device can be It is possible to achieve both energy saving and high luminance.
- FIG. 4 is a schematic diagram showing an example of drying shrinkage treatment using a heating roll.
- A. Method for producing polarizing film comprises subjecting a polyvinyl alcohol (PVA) resin film to dyeing treatment and stretching treatment (step I), and contacting with an aqueous solvent (step II), in this order, the ratio of the transmittance after contact to the transmittance of the polyvinyl alcohol resin film before contact with the aqueous solvent at a wavelength of ⁇ nm ( ⁇ Ts ( ⁇ )) satisfies the relationship ⁇ Ts(415)> ⁇ Ts(470)> ⁇ Ts(550).
- PVA polyvinyl alcohol
- step II aqueous solvent
- I ⁇ , I 2 , I 3 ⁇ , PVA-I 3 -complex , PVA-I 5 -complex , etc. I ⁇ , I 2 and I 3 - has absorption in the ultraviolet region (for example, wavelengths around 290 nm to 360 nm), and PVA-I 3 -complex and PVA-I 5 -complex have absorptions around wavelengths of 470 nm and 600 nm, respectively.
- step I the PVA-based resin film is subjected to dyeing treatment and stretching treatment, whereby a PVA-based resin film exhibiting absorption dichroism at any wavelength of 380 nm to 780 nm (hereinafter referred to as "unbleached original film" (sometimes referred to as ).
- the unbleached original film is typically in a state capable of functioning as a polarizing film.
- the transmittance of the unbleached original film is preferably 41.0% or more, more preferably 42.0% or more, and still more preferably 42.5%. That's it.
- the transmittance of the unbleached original film is preferably 46.0% or less, more preferably 45.0% or less.
- the degree of polarization of the unbleached original film is preferably 98.0% or more, more preferably 99.0% or more, still more preferably 99.9% or more.
- the degree of polarization of the unbleached original film is preferably 99.998% or less.
- the transmittance is typically a Y value measured using an ultraviolet-visible spectrophotometer and subjected to visibility correction.
- the degree of polarization is typically obtained by the following formula based on the parallel transmittance Tp and the orthogonal transmittance Tc measured using an ultraviolet-visible spectrophotometer and subjected to visibility correction.
- Degree of polarization (%) ⁇ (Tp-Tc)/(Tp+Tc) ⁇ 1/2 ⁇ 100
- the transmittance of a thin polarizing film is typically the polarizing film (surface refractive index: 1.53) and the protective layer (protective film) ( A laminate with a refractive index of 1.50) is measured using an ultraviolet-visible spectrophotometer.
- the reflectance at each layer interface may change, resulting in a change in the measured transmittance. .
- the transmittance measurements may be corrected according to the refractive index of the surface of the protective layer that is in contact with the air interface.
- the transmittance correction value C is expressed by the following formula using the reflectance R 1 (transmission axis reflectance) of polarized light parallel to the transmission axis at the interface between the protective layer and the air layer.
- R 0 ((1.50 ⁇ 1) 2 /(1.50+1) 2 ) ⁇ (T 1 /100)
- R 1 ((n 1 ⁇ 1) 2 /(n 1 +1) 2 ) ⁇ (T 1 /100)
- R 0 is the transmission axis reflectance when a protective layer having a refractive index of 1.50 is used
- n 1 is the refractive index of the protective layer used
- T 1 is the transmittance of the polarizing film. is.
- the correction amount C is approximately 0.2%.
- the transmittance when using a polarizing film with a surface refractive index of 1.53 and a protective layer with a refractive index of 1.50 It is possible to convert to a rate.
- the amount of change in the correction value C when the transmittance T1 of the polarizing film is changed by 2 % is 0.03% or less, and the transmittance of the polarizing film is equal to the correction value C has a limited effect on the value of
- the protective layer has absorption other than surface reflection, appropriate correction can be performed according to the amount of absorption.
- the transmittance (Ts 415 ) of the unbleached original film at a wavelength of 415 nm can be, for example, less than 40%.
- the moisture content of the unbleached original film is typically 15% by weight or less, preferably 12% by weight or less, more preferably 10% by weight or less, and even more preferably 1% to 5% by weight. If the moisture content of the unbleached original film is within this range, it is possible to prevent dissolution, wrinkles, and the like from occurring during contact with the aqueous solvent in step II.
- the thickness of the unbleached original film is typically 25 ⁇ m or less, preferably 12 ⁇ m or less, more preferably 1 ⁇ m to 12 ⁇ m, even more preferably 1 ⁇ m to 7 ⁇ m, still more preferably 2 ⁇ m to 5 ⁇ m.
- step I the single-layer PVA-based resin film is subjected to dyeing treatment and stretching treatment, whereby an unbleached original film can be produced.
- a laminate of two or more layers including a PVA-based resin layer may be subjected to dyeing treatment and stretching treatment to prepare an unbleached original film.
- the unbleached base film prepared using a laminate of two or more layers avoids the occurrence of wrinkles and the like even after contact with an aqueous solvent, and has excellent optical properties (typically, single transmittance and degree of polarization) can be preferably maintained.
- A-1-1 Production of an unbleached original film using a laminate of two or more layers
- a PVA-based resin film containing a halide and a PVA-based resin is elongated. It can be carried out by dyeing and stretching in the state of a laminate with a thermoplastic resin substrate having a shape.
- the unbleached original film is a laminate obtained by forming a PVA-based resin layer (PVA-based resin film) containing a halide and a PVA-based resin on one side of a long thermoplastic resin substrate.
- the laminate is subjected to an auxiliary aerial stretching treatment, a dyeing treatment, an underwater stretching treatment, and a drying shrinkage treatment that shrinks by 2% or more in the width direction by heating while being conveyed in the longitudinal direction, in this order.
- the content of the halide in the PVA-based resin layer is preferably 5 to 20 parts by weight with respect to 100 parts by weight of the PVA-based resin.
- the drying shrinkage treatment is preferably performed using a heating roll, and the temperature of the heating roll is preferably 60°C to 120°C.
- the shrinkage ratio in the width direction of the laminate due to drying shrinkage treatment is preferably 2% or more. According to such a production method, it is possible to obtain an unbleached raw film having a high degree of orientation of the PVA-based resin and excellent optical properties.
- A-1-1-1 Production of Laminate Any appropriate method can be adopted as a method for producing a laminate of a thermoplastic resin substrate and a PVA-based resin layer.
- a coating liquid containing a halide and a PVA-based resin is applied to the surface of the thermoplastic resin substrate and dried to form a PVA-based resin layer on the thermoplastic resin substrate.
- the content of the halide in the PVA-based resin layer is preferably 5 to 20 parts by weight with respect to 100 parts by weight of the PVA-based resin.
- any appropriate method can be adopted as the method of applying the coating liquid. Examples thereof include roll coating, spin coating, wire bar coating, dip coating, die coating, curtain coating, spray coating, and knife coating (comma coating, etc.).
- the coating/drying temperature of the coating liquid is preferably 50° C. or higher.
- the thickness of the PVA-based resin layer is preferably 3 ⁇ m to 40 ⁇ m, more preferably 3 ⁇ m to 20 ⁇ m.
- the thermoplastic resin substrate Before forming the PVA-based resin layer, the thermoplastic resin substrate may be surface-treated (for example, corona treatment, etc.), or an easy-adhesion layer may be formed on the thermoplastic resin substrate. By performing such treatment, the adhesion between the thermoplastic resin substrate and the PVA-based resin layer can be improved.
- surface-treated for example, corona treatment, etc.
- an easy-adhesion layer may be formed on the thermoplastic resin substrate.
- the thickness of the thermoplastic resin substrate is preferably 20 ⁇ m to 300 ⁇ m, more preferably 50 ⁇ m to 200 ⁇ m. If the thickness is less than 20 ⁇ m, it may be difficult to form the PVA-based resin layer. If it exceeds 300 ⁇ m, for example, in the later-described underwater stretching treatment, it may take a long time for the thermoplastic resin substrate to absorb water, and an excessive load may be required for stretching.
- the thermoplastic resin substrate preferably has a water absorption of 0.2% or more, more preferably 0.3% or more.
- Thermoplastic resin substrates can absorb water and be plasticized with the water acting like a plasticizer. As a result, the stretching stress can be greatly reduced, and the film can be stretched at a high draw ratio.
- the water absorption rate of the thermoplastic resin substrate is preferably 3.0% or less, more preferably 1.0% or less.
- thermoplastic resin substrate can be adjusted, for example, by introducing a modifying group into the constituent material.
- the water absorption is a value determined according to JIS K 7209.
- the glass transition temperature (Tg) of the thermoplastic resin substrate is preferably 120°C or less.
- Tg The glass transition temperature of the thermoplastic resin substrate.
- the temperature is preferably 100° C. or lower, more preferably 90° C. or lower.
- the glass transition temperature of the thermoplastic resin substrate is preferably 60°C or higher.
- the PVA-based resin layer can be satisfactorily stretched at a suitable temperature (for example, about 60°C).
- the glass transition temperature of the thermoplastic resin substrate can be adjusted, for example, by heating using a crystallization material that introduces a modifying group into the constituent material.
- the glass transition temperature (Tg) is a value determined according to JIS K 7121.
- thermoplastic resin can be adopted as a constituent material of the thermoplastic resin base material.
- thermoplastic resins include ester resins such as polyethylene terephthalate resins, cycloolefin resins such as norbornene resins, olefin resins such as polypropylene, polyamide resins, polycarbonate resins, and copolymer resins thereof. is mentioned. Among these, norbornene-based resins and amorphous polyethylene terephthalate-based resins are preferred.
- an amorphous (not crystallized) polyethylene terephthalate resin is preferably used.
- amorphous (difficult to crystallize) polyethylene terephthalate resin is particularly preferably used.
- Specific examples of amorphous polyethylene terephthalate resins include copolymers further containing isophthalic acid and/or cyclohexanedicarboxylic acid as dicarboxylic acids, and copolymers further containing cyclohexanedimethanol or diethylene glycol as glycols.
- the thermoplastic resin base material is composed of a polyethylene terephthalate resin having an isophthalic acid unit.
- a thermoplastic resin substrate is extremely excellent in stretchability and can suppress crystallization during stretching. This is probably because the introduction of the isophthalic acid unit gives the main chain a large bend.
- a polyethylene terephthalate-based resin has a terephthalic acid unit and an ethylene glycol unit.
- the isophthalic acid unit content is preferably 0.1 mol % or more, more preferably 1.0 mol % or more, relative to the total of all repeating units. This is because a thermoplastic resin base material having extremely excellent stretchability can be obtained.
- the isophthalic acid unit content is preferably 20 mol % or less, more preferably 10 mol % or less, relative to the total of all repeating units.
- the degree of crystallinity can be favorably increased in the drying shrinkage treatment described later.
- the thermoplastic resin substrate may be stretched in advance (before forming the PVA-based resin layer). In one embodiment, it is stretched in the transverse direction of the elongated thermoplastic resin substrate.
- the lateral direction is preferably a direction perpendicular to the stretching direction of the laminate described below.
- perpendicular also includes the case of being substantially perpendicular.
- substantially orthogonal includes 90° ⁇ 5.0°, preferably 90° ⁇ 3.0°, more preferably 90° ⁇ 1.0°.
- the stretching temperature of the thermoplastic resin substrate is preferably Tg-10°C to Tg+50°C with respect to the glass transition temperature (Tg).
- the draw ratio of the thermoplastic resin substrate is preferably 1.5 to 3.0 times.
- thermoplastic resin base material Any appropriate method can be adopted as a method for stretching the thermoplastic resin base material.
- the drawing may be fixed end drawing or free end drawing.
- the stretching method may be a dry method or a wet method.
- the stretching of the thermoplastic resin substrate may be performed in one step or in multiple steps. When performing in multiple stages, the above-mentioned draw ratio is the product of the draw ratios in each step.
- the coating liquid contains a halide and a PVA-based resin, as described above.
- the coating liquid is typically a solution in which the halide and the PVA-based resin are dissolved in a solvent.
- solvents include water, dimethylsulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, various glycols, polyhydric alcohols such as trimethylolpropane, and amines such as ethylenediamine and diethylenetriamine. These can be used alone or in combination of two or more. Among these, water is preferred.
- the concentration of the PVA-based resin in the solution is preferably 3 to 20 parts by weight with respect to 100 parts by weight of the solvent. With such a resin concentration, it is possible to form a uniform coating film in close contact with the thermoplastic resin substrate.
- the content of the halide in the coating liquid is preferably 5 to 20 parts by weight with respect to 100 parts by weight of the PVA-based resin.
- Additives may be added to the coating liquid.
- additives include plasticizers and surfactants.
- plasticizers include polyhydric alcohols such as ethylene glycol and glycerin.
- Surfactants include, for example, nonionic surfactants. These can be used for the purpose of further improving the uniformity, dyeability and stretchability of the obtained PVA-based resin layer.
- any appropriate resin can be adopted as the PVA-based resin.
- Examples include polyvinyl alcohol and ethylene-vinyl alcohol copolymers.
- Polyvinyl alcohol is obtained by saponifying polyvinyl acetate.
- An ethylene-vinyl alcohol copolymer is obtained by saponifying an ethylene-vinyl acetate copolymer.
- the degree of saponification of the PVA-based resin is usually 85 mol% to 100 mol%, preferably 95.0 mol% to 99.95 mol%, more preferably 99.0 mol% to 99.93 mol%. .
- the degree of saponification can be determined according to JIS K 6726-1994. By using a PVA-based resin having such a degree of saponification, an unbleached original film having excellent durability can be obtained. If the degree of saponification is too high, gelation may occur.
- the average degree of polymerization of the PVA-based resin can be appropriately selected according to the purpose.
- the average degree of polymerization is usually 1,000 to 10,000, preferably 1,200 to 4,500, more preferably 1,500 to 4,300.
- the average degree of polymerization can be determined according to JIS K 6726-1994.
- halide any appropriate halide can be adopted as the halide.
- examples include iodide and sodium chloride.
- Iodides include, for example, potassium iodide, sodium iodide, and lithium iodide. Among these, potassium iodide is preferred.
- the amount of the halide in the coating liquid is preferably 5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the PVA resin, and more preferably 10 parts by weight to 15 parts by weight with respect to 100 parts by weight of the PVA resin. Department. If the amount of the halide exceeds 20 parts by weight with respect to 100 parts by weight of the PVA-based resin, the halide may bleed out and the finally obtained unbleached original film may become cloudy.
- the orientation of the polyvinyl alcohol molecules in the PVA-based resin layer increases. orientation may be disturbed and the orientation may be lowered.
- the laminate is stretched in boric acid water at a relatively high temperature in order to stabilize the stretching of the thermoplastic resin substrate.
- the film is stretched, the tendency of the degree of orientation to decrease is remarkable.
- the stretching of a single PVA film in boric acid water is generally carried out at 60° C.
- the stretching of a laminate of A-PET (thermoplastic resin substrate) and a PVA-based resin layer is It is carried out at a high temperature of about 70° C., and in this case, the orientation of PVA at the initial stage of stretching may be lowered before it is increased by stretching in water.
- the crystallization of the PVA-based resin in the PVA-based resin layer of the laminate after auxiliary stretching can be promoted.
- the PVA-based resin layer is immersed in a liquid, the disturbance of the orientation of the polyvinyl alcohol molecules and the deterioration of the orientation can be suppressed compared to the case where the PVA-based resin layer does not contain a halide.
- This makes it possible to improve the optical properties of the unbleached base film obtained through a treatment step in which the laminate is immersed in a liquid, such as dyeing treatment and stretching treatment in water.
- A-1-1-2 Aerial Auxiliary Stretching
- a two-stage stretching method combining dry stretching (auxiliary stretching) and stretching in boric acid solution is selected.
- auxiliary stretching such as two-step stretching, it is possible to stretch while suppressing crystallization of the thermoplastic resin substrate, and excessive crystallization of the thermoplastic resin substrate in the subsequent stretching in boric acid water. It is possible to solve the problem that stretchability is reduced by stretching, and stretch the laminate at a higher magnification.
- the stretching method of the in-air auxiliary stretching may be fixed edge stretching (e.g., a method of stretching using a tenter stretching machine) or free edge stretching (e.g., a method of uniaxially stretching the laminate through rolls having different peripheral speeds).
- free-end drawing may be positively employed in order to obtain high optical properties.
- the in-air stretching process includes a heating roll stretching step in which the laminate is stretched by a peripheral speed difference between heating rolls while being conveyed in the longitudinal direction.
- the air drawing process typically includes a zone drawing process and a hot roll drawing process.
- the order of the zone stretching process and the heating roll stretching process is not limited, and the zone stretching process may be carried out first, or the heating roll stretching process may be carried out first.
- the zone drawing step may be omitted. In one embodiment, the zone drawing step and the heated roll drawing step are performed in this order.
- the laminate is stretched by gripping the ends of the laminate and widening the distance between the tenters in the machine direction in a tenter stretching machine (the widening of the distance between the tenters is the stretching ratio). At this time, the distance between the tenters in the width direction (perpendicular to the machine direction) is set to be arbitrarily close.
- the draw ratio in the machine direction can be set to be closer to the free end draw.
- the shrinkage ratio in the width direction is calculated by (1/stretching ratio) 1/2 .
- Aerial auxiliary stretching may be performed in one step or in multiple steps. When it is carried out in multiple stages, the draw ratio is the product of the draw ratios in each step.
- the stretching direction in the in-air auxiliary stretching is preferably substantially the same as the stretching direction in the underwater stretching.
- the draw ratio in the in-air auxiliary drawing is preferably 2.0 to 3.5 times.
- the maximum draw ratio when the auxiliary drawing in the air and the drawing in water are combined is preferably 5.0 times or more, more preferably 5.5 times or more, and still more preferably 6.0 times the original length of the laminate. That's it.
- the term "maximum draw ratio" refers to the draw ratio immediately before the laminate breaks, and is 0.2 lower than the draw ratio at which the laminate breaks.
- the stretching temperature for the in-air auxiliary stretching can be set to any appropriate value depending on the material for forming the thermoplastic resin base material, the stretching method, and the like.
- the stretching temperature is preferably the glass transition temperature (Tg) of the thermoplastic resin substrate or higher, more preferably the glass transition temperature (Tg) of the thermoplastic resin substrate + 10°C or higher, and particularly preferably Tg + 15°C or higher.
- the upper limit of the stretching temperature is preferably 170°C.
- the crystallization index of the PVA-based resin after auxiliary stretching in air is preferably 1.3 to 1.8, more preferably 1.4 to 1.7.
- an insolubilization treatment is performed after the auxiliary stretching treatment in the air and before the stretching treatment in water or the dyeing treatment.
- the insolubilization treatment is typically performed by immersing the PVA-based resin layer in an aqueous boric acid solution.
- the insolubilization treatment imparts water resistance to the PVA-based resin layer, and prevents deterioration of the orientation of the PVA when immersed in water.
- the concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water.
- the liquid temperature of the insolubilizing bath is preferably 20°C to 50°C.
- the dyeing treatment is typically performed by dyeing the PVA-based resin layer with a dichroic substance (typically iodine). Specifically, it is carried out by allowing the PVA-based resin layer to adsorb iodine.
- adsorption method include a method of immersing the PVA-based resin layer (laminate) in a dyeing solution containing iodine, a method of coating the PVA-based resin layer with the dyeing solution, and a method of applying the dyeing solution to the PVA-based resin layer.
- a spraying method and the like can be mentioned.
- a preferred method is to immerse the laminate in a dyeing solution (dyeing bath). This is because iodine can be well adsorbed.
- the staining solution is preferably an iodine aqueous solution.
- the amount of iodine compounded is preferably 0.05 to 0.5 parts by weight per 100 parts by weight of water.
- an iodide to the iodine aqueous solution.
- iodides include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and titanium iodide. etc.
- potassium iodide is preferred.
- the amount of iodide compounded is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight, per 100 parts by weight of water.
- the liquid temperature of the dyeing liquid during dyeing is preferably 20° C. to 50° C. in order to suppress the dissolution of the PVA-based resin.
- the immersion time is preferably 5 seconds to 5 minutes, more preferably 30 seconds to 90 seconds, in order to ensure the transmittance of the PVA-based resin layer.
- the dyeing conditions can be set so that the single transmittance of the finally obtained unbleached raw film has a desired value.
- the content ratio of iodine and potassium iodide in the aqueous iodine solution is preferably 1:5 to 1:10.
- the boric acid contained in the treatment bath is mixed into the dyeing bath.
- the boric acid concentration in the dyeing bath may change over time, resulting in unstable dyeability.
- the upper limit of the boric acid concentration in the dyeing bath is preferably 4 parts by weight, more preferably 2 parts by weight with respect to 100 parts by weight of water. adjusted.
- the lower limit of the boric acid concentration in the dyeing bath is preferably 0.1 parts by weight, more preferably 0.2 parts by weight, and still more preferably 0.5 parts by weight with respect to 100 parts by weight of water. is.
- the dyeing process is performed using a dyeing bath pre-blended with boric acid. This can reduce the rate of change in boric acid concentration when the boric acid in the treatment bath is mixed into the dyeing bath.
- the amount of boric acid blended in advance in the dyeing bath (that is, the content of boric acid not derived from the treatment bath) is preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of water. , more preferably 0.5 to 1.5 parts by weight.
- A-1-1-5 A-1-1-5.
- Crosslinking Treatment If necessary, a crosslinking treatment is applied after the dyeing treatment and before the underwater stretching treatment.
- the cross-linking treatment is typically performed by immersing the PVA-based resin layer in an aqueous solution of boric acid.
- the cross-linking treatment imparts water resistance to the PVA-based resin layer, and prevents deterioration of the orientation of the PVA when immersed in high-temperature water in the subsequent underwater stretching.
- the concentration of the boric acid aqueous solution is preferably 1 to 5 parts by weight with respect to 100 parts by weight of water.
- the amount of iodide compounded is preferably 1 to 5 parts by weight per 100 parts by weight of water. Specific examples of iodides are as described above.
- the liquid temperature of the cross-linking bath is preferably 20°C to 50°C.
- thermoplastic resin substrate and the PVA-based resin layer can be stretched at a temperature lower than the glass transition temperature (typically, about 80° C.), and the PVA-based resin layer undergoes its crystallization. It can be stretched at a high magnification while suppressing the As a result, an unbleached original film having excellent optical properties can be produced.
- any appropriate method can be adopted as the method for stretching the laminate. Specifically, fixed-end stretching or free-end stretching (for example, a method of uniaxially stretching a laminate by passing it between rolls having different peripheral speeds) may be used. Free-end drawing is preferably chosen.
- the laminate may be stretched in one step or in multiple steps. When the stretching is performed in multiple stages, the draw ratio (maximum draw ratio) of the laminate described below is the product of the draw ratios in each step.
- the stretching in water is preferably carried out by immersing the laminate in an aqueous boric acid solution (stretching in boric acid water).
- an aqueous boric acid solution as the stretching bath, the PVA-based resin layer can be imparted with rigidity to withstand tension applied during stretching and water resistance that does not dissolve in water.
- boric acid can form a tetrahydroxyborate anion in an aqueous solution and crosslink with a PVA-based resin through hydrogen bonding.
- rigidity and water resistance can be imparted to the PVA-based resin layer, which can be satisfactorily stretched, and an unbleached base film having excellent optical properties can be produced.
- the boric acid aqueous solution is preferably obtained by dissolving boric acid and/or a borate salt in water as a solvent.
- the boric acid concentration is preferably 1 part by weight to 10 parts by weight, more preferably 2.5 parts by weight to 6 parts by weight, and particularly preferably 3 parts by weight to 5 parts by weight with respect to 100 parts by weight of water. is.
- an aqueous solution obtained by dissolving a boron compound such as borax, glyoxal, glutaraldehyde, or the like in a solvent can also be used.
- an iodide is added to the stretching bath (boric acid aqueous solution).
- iodide elution of iodine adsorbed on the PVA-based resin layer can be suppressed.
- Specific examples of iodides are as described above.
- the concentration of iodide is preferably 0.05 to 15 parts by weight, more preferably 0.5 to 8 parts by weight, per 100 parts by weight of water.
- the stretching temperature (liquid temperature of the stretching bath) is preferably 40°C to 85°C, more preferably 60°C to 75°C. At such a temperature, the film can be stretched at a high magnification while suppressing dissolution of the PVA-based resin layer.
- the glass transition temperature (Tg) of the thermoplastic resin substrate is preferably 60° C. or higher in relation to the formation of the PVA-based resin layer. In this case, if the stretching temperature is lower than 40° C., it may not be possible to stretch well even if the plasticization of the thermoplastic resin base material by water is considered.
- the higher the temperature of the stretching bath the higher the solubility of the PVA-based resin layer, which may make it impossible to obtain excellent optical properties.
- the immersion time of the laminate in the stretching bath is preferably 15 seconds to 5 minutes.
- the draw ratio by underwater drawing is preferably 1.5 times or more, more preferably 3.0 times or more.
- the total draw ratio of the laminate is preferably 5.0 times or more, more preferably 5.5 times or more, relative to the original length of the laminate.
- A-1-1-7 Drying Shrinkage Treatment
- a laminate of a long thermoplastic resin base material and a PVA-based resin film is heated while being transported in the longitudinal direction, thereby shrinking the laminate by 2% or more in the width direction.
- the moisture content is preferably 12% by weight or less, and further preferably. It is preferred to dry to 10% by weight or less, even more preferably 1% to 5% by weight.
- the drying shrinkage treatment may be performed by zone heating performed by heating the entire zone, or by heating the transport roll (using a so-called heating roll) (heating roll drying method). Preferably both are used.
- heating roll heating roll drying method
- the crystallization of the thermoplastic resin substrate can be efficiently promoted to increase the degree of crystallinity, which is relatively low. Even at the drying temperature, the degree of crystallinity of the thermoplastic resin substrate can be favorably increased.
- the thermoplastic resin base material has increased rigidity and is in a state capable of withstanding shrinkage of the PVA-based resin layer due to drying, thereby suppressing curling.
- the layered product can be dried while being maintained in a flat state, so that not only curling but also wrinkling can be suppressed.
- the laminate can be shrunk in the width direction by drying shrinkage treatment, thereby improving the optical properties. This is because the orientation of PVA and PVA/iodine complex can be effectively enhanced.
- the shrinkage ratio of the laminate in the width direction due to drying shrinkage treatment is preferably 1% to 10%, more preferably 2% to 8%, and particularly preferably 4% to 6%.
- FIG. 1 is a schematic diagram showing an example of drying shrinkage treatment.
- the laminate 200 is dried while being transported by transport rolls R1 to R6 heated to a predetermined temperature and guide rolls G1 to G4.
- the transport rolls R1 to R6 are arranged so as to alternately and continuously heat the surface of the PVA-based resin layer and the surface of the thermoplastic resin substrate.
- the transport rolls R1 to R6 may be arranged so as to continuously heat only the plastic resin substrate surface).
- the drying conditions can be controlled by adjusting the heating temperature of the transport rolls (the temperature of the heating rolls), the number of heating rolls, the contact time with the heating rolls, and so on.
- the temperature of the heating roll is preferably 60°C to 120°C, more preferably 65°C to 100°C, and particularly preferably 70°C to 80°C.
- the degree of crystallinity of the thermoplastic resin can be favorably increased, curling can be favorably suppressed, and an optical laminate having extremely excellent durability can be produced.
- the temperature of the heating roll can be measured with a contact thermometer. In the illustrated example, six transport rolls are provided, but there is no particular limitation as long as the number of transport rolls is plural. Conveying rolls are usually 2 to 40, preferably 4 to 30 in number.
- the contact time (total contact time) between the laminate and the heating roll is preferably 1 to 300 seconds, more preferably 1 to 20 seconds, still more preferably 1 to 10 seconds.
- the heating roll may be provided in a heating furnace (for example, an oven), or may be provided in a normal production line (under room temperature environment). Preferably, it is provided in a heating furnace equipped with air blowing means.
- a heating furnace equipped with air blowing means.
- the temperature for hot air drying is preferably 20°C to 100°C.
- the hot air drying time is preferably 1 second to 300 seconds.
- the wind speed of the hot air is preferably about 10m/s to 30m/s. The wind speed is the wind speed in the heating furnace and can be measured with a mini-vane digital anemometer.
- A-1-1-8 Other Treatments
- a washing treatment is performed after the underwater stretching treatment and before the drying shrinkage treatment.
- the cleaning treatment is typically performed by immersing the PVA-based resin layer in an aqueous solution of potassium iodide.
- the contact between the unbleached original film and the aqueous solvent in step II may be performed by contacting only one side of the unbleached original film with the aqueous solvent, or by contacting both sides with the aqueous solvent. . Therefore, in one embodiment, the unbleached original film produced using the laminate can be subjected to step II as it is as the laminate of [unbleached original film/thermoplastic resin substrate]. In another embodiment, a protective layer is attached to the surface of the unbleached original film of the laminate of [unbleached original film/thermoplastic resin substrate] to form [protective layer/unbleached original film/thermoplastic resin substrate].
- any suitable function is provided on the substrate side of the laminate of [unbleached base film/thermoplastic resin substrate] or on the protective layer side of the laminate of [protective layer/unbleached base film].
- a layer provided with a layer can also be subjected to step II.
- a long PVA-based resin film is dyed and stretched (typically, uniaxially stretched using a roll stretcher in an aqueous boric acid solution), and then the moisture content is preferably 15% by weight or less, more preferably is 12% by weight or less, more preferably 10% by weight or less, and even more preferably 1% to 5% by weight.
- the dyeing is performed by, for example, immersing the PVA-based resin film in an iodine aqueous solution.
- the draw ratio of the uniaxial drawing is preferably 3 to 7 times. Stretching may be performed after the dyeing treatment, or may be performed while dyeing.
- the PVA-based resin film is subjected to swelling treatment, cross-linking treatment, washing treatment, and the like. For example, by immersing the PVA-based resin film in water and washing it with water before dyeing, it is possible not only to wash away stains and anti-blocking agents on the surface of the PVA-based resin film, but also to swell the PVA-based resin film for dyeing. Unevenness and the like can be prevented.
- the contact between the unbleached original film and the aqueous solvent in step II may be performed by contacting only one surface of the unbleached original film with the aqueous solvent, or by contacting both surfaces with the aqueous solvent. may be broken. Therefore, in one embodiment, the unbleached original film produced using the single-layer PVA-based resin film can be subjected to step II as it is.
- a protective layer is attached to one side of the unbleached original film to prepare a laminate of [protective layer/unbleached original film], and the laminate can be subjected to step II.
- the laminate of [protective layer/unbleached original film] provided with any suitable functional layer (retardation layer, adhesive layer, etc.) on the protective layer side is subjected to step II. can also
- step II the surface of the PVA-based resin film (unbleached original film) that has undergone step I is brought into contact with an aqueous solvent. Upon contact with an aqueous solvent, polyiodine ions forming I ⁇ , I 2 , I 3 - and PVA-I 3 -complexes preferentially over polyiodine ions forming PVA-I 5 -complexes to the unbleached original.
- the transmittance increase rate ( ⁇ Ts( ⁇ )) at the wavelength ⁇ nm satisfies the relationship ⁇ Ts (415) > ⁇ Ts (470) > ⁇ Ts (550) can satisfy
- the aqueous solvent can be, for example, water or a mixture of water and a water-soluble organic solvent.
- Preferred examples of the water-soluble organic solvent include lower monoalcohols having 1 to 4 carbon atoms such as methanol, ethanol, n-propyl alcohol and isopropyl alcohol, and polyhydric alcohols such as glycerin and ethylene glycol.
- the method of contact with the aqueous solvent is not particularly limited, and any suitable method such as immersion, spraying, coating, etc. can be used. Immersion is preferred from the viewpoint of bringing the entire surface of the unbleached original film into contact with the aqueous solvent uniformly.
- the contact time with the aqueous solvent and the temperature of the aqueous solvent during contact can be appropriately set according to desired Ts 415 , Ts 470 and Ts 550 and the like. Increasing the contact time or increasing the temperature of the aqueous solvent tends to increase the transmittance (particularly Ts 415 ).
- the contact time can be, for example, 10 minutes or less, preferably 60 seconds to 9 minutes, more preferably 60 seconds to 4 minutes.
- the temperature of the aqueous solvent can be preferably 20°C to 70°C, more preferably 30°C to 65°C, even more preferably 40°C to 60°C.
- drying treatment may be performed after contact with the aqueous solvent.
- the drying temperature can be, for example, 20°C to 100°C, preferably 30°C to 80°C.
- the moisture content of the dried polarizing film is typically 15% by weight or less, preferably 12% by weight or less, more preferably 10% by weight or less, and still more preferably 1% to 5% by weight. is.
- the polarizing film obtained by the method for producing a polarizing film described in Section A is composed of a PVA-based resin film containing a dichroic substance (typically iodine), and has a wavelength range of at least 415 nm to 550 nm. It has a higher transmittance than the original bleaching film.
- the transmittance increase rate ( ⁇ Ts( ⁇ )) at the wavelength ⁇ nm satisfies the relationship ⁇ Ts(415)> ⁇ Ts(470)> ⁇ Ts(550).
- the transmittance increase rate ( ⁇ Ts(415)) at a wavelength of 415 nm exceeds, for example, 1.05, preferably 1.1 or more, and more preferably 1.10 to 2.2. If ⁇ Ts(415) is within this range, it is possible to reduce the amount of blue light emission that consumes a large amount of power, thereby contributing to energy saving of the organic EL display device.
- Ts 415 and Ts 550 of the polarizing film can be any suitable value depending on the purpose.
- Ts 415 can be, for example, 40% or more, preferably 41% or more, more preferably 42% or more, and can be, for example, 80% or less, preferably 60% or less, more preferably 50% or less.
- Ts 550 may be, for example, 40% or more, preferably 42% or more, more preferably 43% or more, and may be, for example, 70% or less, preferably 60% or less, more preferably 50% or less.
- the polarizing film preferably exhibits absorption dichroism at any wavelength of 380 nm to 780 nm.
- the transmittance of the polarizing film (single transmittance: Ts) is preferably 41% or more, more preferably 42% or more, and still more preferably 42.5% or more.
- the transmittance of the polarizing film is, for example, 65% or less, preferably 50% or less, more preferably 48% or less.
- the polarization degree of the polarizing film is, for example, 40.0% or more, preferably 90.0% or more, more preferably 94.0% or more, still more preferably 96.0% or more, and still more It is preferably 99.0% or more, still more preferably 99.5% or more, and preferably 99.998% or less.
- the above transmittance and degree of polarization are obtained in the same manner as the transmittance and degree of polarization of the unbleached original film.
- the haze of the polarizing film is preferably 1% or less, more preferably 0.8% or less, and even more preferably 0.6% or less. If the haze is within this range, an organic EL display device with a high contrast ratio can be obtained.
- the iodine concentration in the polarizing film is preferably 3% by weight or more, more preferably 4% to 10% by weight, and more preferably 4% to 8% by weight.
- "iodine concentration” means the total amount of iodine contained in the polarizing film. More specifically, iodine exists in the form of I ⁇ , I 2 , I 3 ⁇ , PVA-I 3 -complex , PVA-I 5 -complex , etc. in the polarizing film. , means the concentration of iodine including all these forms.
- the iodine concentration can be calculated, for example, from the fluorescent X-ray intensity and film (polarizing film) thickness obtained by fluorescent X-ray analysis.
- the thickness of the polarizing film is typically 25 ⁇ m or less, preferably 12 ⁇ m or less, more preferably 1 ⁇ m to 12 ⁇ m, even more preferably 1 ⁇ m to 7 ⁇ m, still more preferably 2 ⁇ m to 5 ⁇ m.
- Ts, Tp, and Tc of the PVA-based resin film were defined as Ts, Tp, and Tc of the PVA-based resin film, respectively.
- Ts, Tp and Tc are Y values measured with a 2-degree field of view (C light source) according to JIS Z8701 and subjected to visibility correction.
- the refractive index of the protective layer was 1.53, and the refractive index of the surface of the polarizing film opposite to the protective layer was 1.53. From the obtained Tp and Tc, the degree of polarization P was determined by the following formula.
- Degree of polarization P (%) ⁇ (Tp-Tc)/(Tp+Tc) ⁇ 1/2 ⁇ 100
- the measured Ts at wavelengths of 415 nm, 470 nm and 550 nm were defined as Ts 415 , Ts 470 and Ts 550 , respectively.
- Equivalent measurement can be performed with a spectrophotometer such as "V-7100" manufactured by JASCO Corporation, and equivalent measurement results can be obtained using any spectrophotometer. has been confirmed.
- (3) Moisture content The unbleached raw film immediately after drying (when the laminate is stretched, the stretched substrate is peeled off) is cut into a size of 100 mm ⁇ 100 mm or more, and the weight before processing is measured with an electronic balance. .
- Moisture content [%] (weight before treatment - weight after treatment) / weight before treatment x 100 (4) Haze Measured according to JISK7136 using a product name "Haze meter (NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd.).
- Example 1-1 Preparation of polarizing film and polarizing plate A long roll of PVA-based resin film (manufactured by Kuraray, product name "PE3000") having a thickness of 30 ⁇ m was stretched 2.2 times in the transport direction while being immersed in a water bath at 30°C. While immersed in an aqueous solution of 0.04% by weight of iodine and 0.3% by weight of potassium at 30° C. for dyeing, the film was stretched 3 times with respect to the unstretched film (original length).
- PVA-based resin film manufactured by Kuraray, product name "PE3000”
- a PVA-based resin aqueous solution (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “GOSEFIMER (registered trademark) Z-200”, resin concentration: 3% by weight) was applied to one side of the obtained unbleached raw film a1.
- An olefin film (Zeonor, manufactured by Nippon Zeon Co., Ltd., thickness: 25 ⁇ m) was laminated to obtain an optical laminate having a structure of [unbleached original film a1/protective layer].
- a protective layer provided with a hard coat layer may be used.
- a protective layer for example, a cycloolefin film with a hard coat layer (manufactured by ZEON, product name "G-Film , total thickness of 27 ⁇ m (film thickness of 25 ⁇ m+hard coat layer thickness of 2 ⁇ m), and the like.
- the above optical layered body was cut into a size of 45 mm ⁇ 50 mm and attached to a glass plate via an acrylic pressure-sensitive adhesive layer (thickness 15 ⁇ m) so that the unbleached base film side surface was exposed. was immersed in for 31 hours. Then, by drying at 50° C. for 5 minutes, a polarizing plate having a structure of [polarizing film A1/protective layer] was obtained.
- Example 1-2 A polarizing plate having a structure of [polarizing film A2/protective layer] was obtained in the same manner as in Example 1-1, except that instead of immersing in water at 23° C. for 31 hours, it was immersed in water at 55° C. for 9 minutes. rice field.
- Example 1-3 A polarizing plate having a structure of [polarizing film A3/protective layer] was obtained in the same manner as in Example 1-1, except that instead of immersing in water at 23° C. for 31 hours, it was immersed in water at 60° C. for 4 minutes. rice field.
- Example 1-4 A polarizing plate having a structure of [polarizing film A4/protective layer] was obtained in the same manner as in Example 1-1, except that instead of immersing in water at 23° C. for 31 hours, it was immersed in water at 65° C. for 3 minutes. rice field.
- Example 2-1 A long amorphous isophthalic copolymerized polyethylene terephthalate film (thickness: 100 ⁇ m) having a Tg of about 75° C. was used as the thermoplastic resin substrate, and one side of the resin substrate was subjected to corona treatment.
- Polyvinyl alcohol degree of polymerization: 4,200, degree of saponification: 99.2 mol%
- acetoacetyl-modified PVA manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "GOSEFIMER" were mixed at a ratio of 9:1, and 100 parts by weight of PVA-based resin.
- aqueous PVA solution (coating solution).
- the above PVA aqueous solution was applied to the corona-treated surface of the resin base material and dried at 60° C. to form a PVA-based resin layer having a thickness of 13 ⁇ m, thereby producing a laminate.
- the resulting laminate was uniaxially stretched 2.4 times in the machine direction (longitudinal direction) in an oven at 130° C. (in-air auxiliary stretching treatment).
- the laminate was immersed in an insolubilizing bath (an aqueous boric acid solution obtained by mixing 4 parts by weight of boric acid with 100 parts by weight of water) at a liquid temperature of 40° C.
- crosslinking treatment After that, while immersing the laminate in an aqueous solution of boric acid (boric acid concentration: 4% by weight, potassium iodide concentration: 5% by weight) at a liquid temperature of 70° C., the laminate was moved vertically (longitudinally) between rolls with different peripheral speeds. Uniaxial stretching was performed so that the stretching ratio was 5.5 times (underwater stretching treatment). After that, the laminate was immersed in a washing bath (aqueous solution obtained by blending 4 parts by weight of potassium iodide with 100 parts by weight of water) at a liquid temperature of 20° C. (washing treatment).
- a washing bath aqueous solution obtained by blending 4 parts by weight of potassium iodide with 100 parts by weight of water
- the above optical layered body was cut into a size of 45 mm ⁇ 50 mm, and attached to a glass plate so that the unbleached original film side surface became an exposed surface via an acrylic pressure-sensitive adhesive layer (thickness 15 ⁇ m). for 9 minutes. Then, by drying at 50° C. for 5 minutes, a polarizing plate having a structure of [polarizing film B1/protective layer] was obtained.
- Example 2-2 A polarizing plate having a structure of [polarizing film B2/protective layer] was obtained in the same manner as in Example 2-1, except that instead of immersing in water at 50°C for 9 minutes, it was immersed in water at 55°C for 3 minutes. rice field.
- Example 2-3 A polarizing plate having a structure of [polarizing film B3/protective layer] was obtained in the same manner as in Example 2-1, except that instead of immersing in water at 50°C for 9 minutes, it was immersed in water at 60°C for 2 minutes. rice field.
- Example 2-4 A polarizing plate having a structure of [polarizing film B4/protective layer] was obtained in the same manner as in Example 2-1, except that instead of immersing in water at 50°C for 9 minutes, it was immersed in water at 60°C for 3 minutes. rice field.
- the transmittance increase rate ( ⁇ Ts ( ⁇ )) of the PVA-based resin film at the wavelength ⁇ nm is ⁇ Ts (415) > ⁇ Ts (470 )> ⁇ Ts(550), and the rate of increase in transmittance at a wavelength of 415 nm is large.
- the polarizing film obtained by such a manufacturing method has practically acceptable optical properties (typically, single transmittance and degree of polarization) and has an increased transmittance for short-wavelength light.
- the polarizing film of the present invention can be suitably used in image display devices such as liquid crystal display devices and EL display devices, particularly organic EL display devices.
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Abstract
Description
1つの実施形態において、上記水性溶媒の温度が、20℃~70℃である。
1つの実施形態において、上記水性溶媒を接触させるポリビニルアルコール系樹脂膜の水分率が、15重量%以下である。
1つの実施形態において、上記水性溶媒を接触させるポリビニルアルコール系樹脂膜の厚みが、12μm以下である。
1つの実施形態において、上記ポリビニルアルコール系樹脂膜を染色処理および延伸処理に供することが、長尺状の熱可塑性樹脂基材の片側に、ハロゲン化物とポリビニルアルコール系樹脂とを含むポリビニルアルコール系樹脂膜を形成して積層体とすること、および、該積層体に、空中補助延伸処理と、染色処理と、水中延伸処理と、長手方向に搬送しながら加熱することにより幅方向に2%以上収縮させる乾燥収縮処理と、をこの順に施すことを含む。
1つの実施形態において、上記製造方法が、ヘイズが1%以下の偏光膜の製造方法である。 According to one aspect of the present invention, subjecting a polyvinyl alcohol-based resin film to dyeing treatment and stretching treatment, and bringing an aqueous solvent into contact with the surface of the polyvinyl alcohol-based resin film, in this order, and having a wavelength of λ nm The ratio of the transmittance after contact to the transmittance of the polyvinyl alcohol resin film before contact with the aqueous solvent (ΔTs (λ)) has a relationship of ΔTs (415)>ΔTs (470)>ΔTs (550) is provided.
In one embodiment, the temperature of the aqueous solvent is 20°C to 70°C.
In one embodiment, the water content of the polyvinyl alcohol-based resin film with which the aqueous solvent is brought into contact is 15% by weight or less.
In one embodiment, the polyvinyl alcohol-based resin film with which the aqueous solvent is brought into contact has a thickness of 12 μm or less.
In one embodiment, subjecting the polyvinyl alcohol-based resin film to dyeing treatment and stretching treatment is a polyvinyl alcohol-based resin containing a halide and a polyvinyl alcohol-based resin on one side of a long thermoplastic resin substrate. Forming a membrane to form a laminate, and subjecting the laminate to auxiliary stretching in the air, dyeing, stretching in water, and heating while transporting in the longitudinal direction, thereby shrinking in the width direction by 2% or more. and drying shrinkage treatment to make it dry, and applying in this order.
In one embodiment, the manufacturing method is a method for manufacturing a polarizing film having a haze of 1% or less.
本発明の実施形態による偏光膜の製造方法は、ポリビニルアルコール(PVA)系樹脂膜を染色処理および延伸処理に供すること(工程I)、および、該PVA系樹脂膜の表面に水性溶媒を接触させること(工程II)、をこの順に含み、波長λnmにおける該水性溶媒との接触前の該ポリビニルアルコール系樹脂膜の透過率に対する接触後の透過率の割合(ΔTs(λ))が、ΔTs(415)>ΔTs(470)>ΔTs(550)の関係を満たす。染色後のPVA系樹脂膜中においてヨウ素はI-、I2、I3 -、PVA-I3 -錯体、PVA-I5 -錯体等の形態で存在するところ、I-、I2およびI3 -は紫外領域(例えば、波長290nm~360nm付近)に吸収を有し、PVA-I3 -錯体およびPVA-I5 -錯体はそれぞれ、波長470nm付近および波長600nm付近に吸収を有する。よって、水性溶媒との接触前後においてΔTs(415)>ΔTs(470)>ΔTs(550)の関係が成立することは、PVA系樹脂膜中に存在する全ヨウ素に対してI-、I2、I3 -、およびPVA-I3 -錯体の占める割合が減少(換言すると、PVA-I5 -錯体の占める割合が増加)したことを示すと考えられる。 A. Method for producing polarizing film The method for producing a polarizing film according to an embodiment of the present invention comprises subjecting a polyvinyl alcohol (PVA) resin film to dyeing treatment and stretching treatment (step I), and contacting with an aqueous solvent (step II), in this order, the ratio of the transmittance after contact to the transmittance of the polyvinyl alcohol resin film before contact with the aqueous solvent at a wavelength of λ nm (ΔTs (λ)) satisfies the relationship ΔTs(415)>ΔTs(470)>ΔTs(550). In the PVA-based resin film after dyeing, iodine exists in the form of I − , I 2 , I 3 − , PVA-I 3 -complex , PVA-I 5 -complex , etc., but I − , I 2 and I 3 - has absorption in the ultraviolet region (for example, wavelengths around 290 nm to 360 nm), and PVA-I 3 -complex and PVA-I 5 -complex have absorptions around wavelengths of 470 nm and 600 nm, respectively. Therefore, the fact that the relationship ΔTs (415)>ΔTs (470)>ΔTs (550) holds before and after contact with the aqueous solvent means that I − , I 2 , This is thought to indicate that the ratio of I 3 − and PVA-I 3 -complex decreased (in other words, the ratio of PVA-I 5 -complex increased).
工程Iにおいては、PVA系樹脂膜を染色処理および延伸処理に供し、これにより、波長380nm~780nmのいずれかの波長で吸収二色性を示すPVA系樹脂膜(以下、「未脱色原膜」と称する場合がある)を得る。未脱色原膜は、代表的には、偏光膜として機能し得る状態にある。 A-1. Process I
In step I, the PVA-based resin film is subjected to dyeing treatment and stretching treatment, whereby a PVA-based resin film exhibiting absorption dichroism at any wavelength of 380 nm to 780 nm (hereinafter referred to as "unbleached original film" (sometimes referred to as ). The unbleached original film is typically in a state capable of functioning as a polarizing film.
偏光度(%)={(Tp-Tc)/(Tp+Tc)}1/2×100 In one embodiment, the transmittance of the unbleached original film (single transmittance: Ts) is preferably 41.0% or more, more preferably 42.0% or more, and still more preferably 42.5%. That's it. On the other hand, the transmittance of the unbleached original film is preferably 46.0% or less, more preferably 45.0% or less. The degree of polarization of the unbleached original film is preferably 98.0% or more, more preferably 99.0% or more, still more preferably 99.9% or more. On the other hand, the degree of polarization of the unbleached original film is preferably 99.998% or less. The transmittance is typically a Y value measured using an ultraviolet-visible spectrophotometer and subjected to visibility correction. The degree of polarization is typically obtained by the following formula based on the parallel transmittance Tp and the orthogonal transmittance Tc measured using an ultraviolet-visible spectrophotometer and subjected to visibility correction.
Degree of polarization (%) = {(Tp-Tc)/(Tp+Tc)} 1/2 × 100
C=R1-R0
R0=((1.50-1)2/(1.50+1)2)×(T1/100)
R1=((n1-1)2/(n1+1)2)×(T1/100)
ここで、R0は、屈折率が1.50である保護層を用いた場合の透過軸反射率であり、n1は使用する保護層の屈折率であり、T1は偏光膜の透過率である。例えば、表面屈折率が1.53である基材(シクロオレフィン系フィルム、ハードコート層付きフィルムなど)を保護層として用いる場合、補正量Cは約0.2%となる。この場合、測定により得られた透過率に0.2%を加算することで、表面の屈折率が1.53である偏光膜を屈折率が1.50である保護層を用いた場合の透過率に換算することが可能である。なお、上記式に基づく計算によれば、偏光膜の透過率T1を2%変化させたときの補正値Cの変化量は0.03%以下であり、偏光膜の透過率が補正値Cの値に与える影響は限定的である。また、保護層が表面反射以外の吸収を有する場合は、吸収量に応じて適切な補正を行うことができる。 In one embodiment, the transmittance of a thin polarizing film (unbleached original film) of 12 μm or less is typically the polarizing film (surface refractive index: 1.53) and the protective layer (protective film) ( A laminate with a refractive index of 1.50) is measured using an ultraviolet-visible spectrophotometer. Depending on the refractive index of the surface of the polarizing film and/or the refractive index of the protective layer contacting the air interface, the reflectance at each layer interface may change, resulting in a change in the measured transmittance. . Thus, for example, if a protective layer with a refractive index other than 1.50 is used, the transmittance measurements may be corrected according to the refractive index of the surface of the protective layer that is in contact with the air interface. Specifically, the transmittance correction value C is expressed by the following formula using the reflectance R 1 (transmission axis reflectance) of polarized light parallel to the transmission axis at the interface between the protective layer and the air layer.
C=R 1 -R 0
R 0 = ((1.50−1) 2 /(1.50+1) 2 )×(T 1 /100)
R 1 = ((n 1 −1) 2 /(n 1 +1) 2 )×(T 1 /100)
Here, R 0 is the transmission axis reflectance when a protective layer having a refractive index of 1.50 is used, n 1 is the refractive index of the protective layer used, and T 1 is the transmittance of the polarizing film. is. For example, when a substrate having a surface refractive index of 1.53 (a cycloolefin film, a film with a hard coat layer, etc.) is used as the protective layer, the correction amount C is approximately 0.2%. In this case, by adding 0.2% to the transmittance obtained by the measurement, the transmittance when using a polarizing film with a surface refractive index of 1.53 and a protective layer with a refractive index of 1.50 It is possible to convert to a rate. According to the calculation based on the above formula, the amount of change in the correction value C when the transmittance T1 of the polarizing film is changed by 2 % is 0.03% or less, and the transmittance of the polarizing film is equal to the correction value C has a limited effect on the value of Moreover, when the protective layer has absorption other than surface reflection, appropriate correction can be performed according to the amount of absorption.
二層以上の積層体を用いた未脱色原膜の作製は、例えば、ハロゲン化物とPVA系樹脂とを含むPVA系樹脂膜を長尺状の熱可塑性樹脂基材との積層体の状態で染色処理および延伸処理に供することによって行われ得る。具体的には、未脱色原膜は、長尺状の熱可塑性樹脂基材の片側に、ハロゲン化物とPVA系樹脂とを含むPVA系樹脂層(PVA系樹脂膜)を形成して積層体とすること、および、積層体に、空中補助延伸処理と、染色処理と、水中延伸処理と、長手方向に搬送しながら加熱することにより幅方向に2%以上収縮させる乾燥収縮処理と、をこの順に施すことを含む方法により作製され得る。PVA系樹脂層におけるハロゲン化物の含有量は、好ましくは、PVA系樹脂100重量部に対して5重量部~20重量部である。乾燥収縮処理は、加熱ロールを用いて処理することが好ましく、加熱ロールの温度は、好ましくは、60℃~120℃である。乾燥収縮処理による積層体の幅方向の収縮率は、好ましくは、2%以上である。このような製造方法によれば、PVA系樹脂の配向度が高く、優れた光学特性を有する未脱色原膜を得ることができる。 A-1-1. Production of an unbleached original film using a laminate of two or more layers In the production of an unbleached original film using a laminate of two or more layers, for example, a PVA-based resin film containing a halide and a PVA-based resin is elongated. It can be carried out by dyeing and stretching in the state of a laminate with a thermoplastic resin substrate having a shape. Specifically, the unbleached original film is a laminate obtained by forming a PVA-based resin layer (PVA-based resin film) containing a halide and a PVA-based resin on one side of a long thermoplastic resin substrate. Then, the laminate is subjected to an auxiliary aerial stretching treatment, a dyeing treatment, an underwater stretching treatment, and a drying shrinkage treatment that shrinks by 2% or more in the width direction by heating while being conveyed in the longitudinal direction, in this order. It can be made by a method comprising applying. The content of the halide in the PVA-based resin layer is preferably 5 to 20 parts by weight with respect to 100 parts by weight of the PVA-based resin. The drying shrinkage treatment is preferably performed using a heating roll, and the temperature of the heating roll is preferably 60°C to 120°C. The shrinkage ratio in the width direction of the laminate due to drying shrinkage treatment is preferably 2% or more. According to such a production method, it is possible to obtain an unbleached raw film having a high degree of orientation of the PVA-based resin and excellent optical properties.
熱可塑性樹脂基材とPVA系樹脂層との積層体を作製する方法としては、任意の適切な方法が採用され得る。好ましくは、熱可塑性樹脂基材の表面に、ハロゲン化物とPVA系樹脂とを含む塗布液を塗布し、乾燥することにより、熱可塑性樹脂基材上にPVA系樹脂層を形成する。上記のとおり、PVA系樹脂層におけるハロゲン化物の含有量は、好ましくは、PVA系樹脂100重量部に対して5重量部~20重量部である。 A-1-1-1. Production of Laminate Any appropriate method can be adopted as a method for producing a laminate of a thermoplastic resin substrate and a PVA-based resin layer. Preferably, a coating liquid containing a halide and a PVA-based resin is applied to the surface of the thermoplastic resin substrate and dried to form a PVA-based resin layer on the thermoplastic resin substrate. As described above, the content of the halide in the PVA-based resin layer is preferably 5 to 20 parts by weight with respect to 100 parts by weight of the PVA-based resin.
特に、高い光学特性を得るためには、乾式延伸(補助延伸)とホウ酸水中延伸を組み合わせる、2段延伸の方法が選択される。2段延伸のように、補助延伸を導入することにより、熱可塑性樹脂基材の結晶化を抑制しながら延伸することができ、後のホウ酸水中延伸において熱可塑性樹脂基材の過度の結晶化により延伸性が低下するという問題を解決し、積層体をより高倍率に延伸することができる。さらには、熱可塑性樹脂基材上にPVA系樹脂を塗布する場合、熱可塑性樹脂基材のガラス転移温度の影響を抑制するために、通常の金属ドラム上にPVA系樹脂を塗布する場合と比べて塗布温度を低くする必要があり、その結果、PVA系樹脂の結晶化が相対的に低くなり、十分な光学特性が得られない、という問題が生じ得る。これに対して、補助延伸を導入することにより、熱可塑性樹脂基材上にPVA系樹脂を塗布する場合でも、PVA系樹脂の結晶性を高めることが可能となり、高い光学特性を達成することが可能となる。また、同時にPVA系樹脂の配向性を事前に高めることで、後の染色処理や延伸処理で水に浸漬された時に、PVA系樹脂の配向性の低下や溶解などの問題を防止することができ、高い光学特性を達成することが可能になる。 A-1-1-2. Aerial Auxiliary Stretching In order to obtain particularly high optical properties, a two-stage stretching method combining dry stretching (auxiliary stretching) and stretching in boric acid solution is selected. By introducing auxiliary stretching, such as two-step stretching, it is possible to stretch while suppressing crystallization of the thermoplastic resin substrate, and excessive crystallization of the thermoplastic resin substrate in the subsequent stretching in boric acid water. It is possible to solve the problem that stretchability is reduced by stretching, and stretch the laminate at a higher magnification. Furthermore, when applying the PVA-based resin on the thermoplastic resin substrate, in order to suppress the influence of the glass transition temperature of the thermoplastic resin substrate, compared to the case of applying the PVA-based resin on a normal metal drum As a result, the crystallization of the PVA-based resin becomes relatively low, which may cause a problem that sufficient optical properties cannot be obtained. On the other hand, by introducing auxiliary stretching, it is possible to increase the crystallinity of the PVA-based resin even when the PVA-based resin is applied onto a thermoplastic resin substrate, thereby achieving high optical properties. It becomes possible. At the same time, by increasing the orientation of the PVA-based resin in advance, it is possible to prevent problems such as deterioration of the orientation and dissolution of the PVA-based resin when it is immersed in water in the subsequent dyeing treatment or stretching treatment. , making it possible to achieve high optical properties.
結晶化指数=(IC/IR)
ただし、
IC :測定光を入射して測定したときの1141cm-1の強度
IR :測定光を入射して測定したときの1440cm-1の強度
である。 The stretching temperature for the in-air auxiliary stretching can be set to any appropriate value depending on the material for forming the thermoplastic resin base material, the stretching method, and the like. The stretching temperature is preferably the glass transition temperature (Tg) of the thermoplastic resin substrate or higher, more preferably the glass transition temperature (Tg) of the thermoplastic resin substrate + 10°C or higher, and particularly preferably Tg + 15°C or higher. On the other hand, the upper limit of the stretching temperature is preferably 170°C. By stretching at such a temperature, it is possible to suppress rapid crystallization of the PVA-based resin and suppress problems caused by the crystallization (for example, hindrance of orientation of the PVA-based resin layer due to stretching). can. The crystallization index of the PVA-based resin after auxiliary stretching in air is preferably 1.3 to 1.8, more preferably 1.4 to 1.7. The crystallization index of the PVA-based resin can be measured by the ATR method using a Fourier transform infrared spectrophotometer. Specifically, measurement is performed using polarized light as measurement light, and the crystallization index is calculated according to the following formula using the intensities at 1141 cm −1 and 1440 cm −1 of the obtained spectrum.
Crystallization index = (IC/ IR )
however,
I C : Intensity at 1141 cm −1 when measurement light is incident and measured I R : Intensity at 1440 cm −1 when measurement light is incident and measured.
必要に応じて、空中補助延伸処理の後、水中延伸処理や染色処理の前に、不溶化処理を施す。上記不溶化処理は、代表的には、ホウ酸水溶液にPVA系樹脂層を浸漬することにより行う。不溶化処理を施すことにより、PVA系樹脂層に耐水性を付与し、水に浸漬した時のPVAの配向低下を防止することができる。当該ホウ酸水溶液の濃度は、水100重量部に対して、好ましくは1重量部~4重量部である。不溶化浴(ホウ酸水溶液)の液温は、好ましくは20℃~50℃である。 A-1-1-3. Insolubilization Treatment If necessary, an insolubilization treatment is performed after the auxiliary stretching treatment in the air and before the stretching treatment in water or the dyeing treatment. The insolubilization treatment is typically performed by immersing the PVA-based resin layer in an aqueous boric acid solution. The insolubilization treatment imparts water resistance to the PVA-based resin layer, and prevents deterioration of the orientation of the PVA when immersed in water. The concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water. The liquid temperature of the insolubilizing bath (boric acid aqueous solution) is preferably 20°C to 50°C.
上記染色処理は、代表的には、PVA系樹脂層を二色性物質(代表的には、ヨウ素)で染色することにより行う。具体的には、PVA系樹脂層にヨウ素を吸着させることにより行う。当該吸着方法としては、例えば、ヨウ素を含む染色液にPVA系樹脂層(積層体)を浸漬させる方法、PVA系樹脂層に当該染色液を塗工する方法、当該染色液をPVA系樹脂層に噴霧する方法等が挙げられる。好ましくは、染色液(染色浴)に積層体を浸漬させる方法である。ヨウ素が良好に吸着し得るからである。 A-1-1-4. Dyeing Treatment The dyeing treatment is typically performed by dyeing the PVA-based resin layer with a dichroic substance (typically iodine). Specifically, it is carried out by allowing the PVA-based resin layer to adsorb iodine. Examples of the adsorption method include a method of immersing the PVA-based resin layer (laminate) in a dyeing solution containing iodine, a method of coating the PVA-based resin layer with the dyeing solution, and a method of applying the dyeing solution to the PVA-based resin layer. A spraying method and the like can be mentioned. A preferred method is to immerse the laminate in a dyeing solution (dyeing bath). This is because iodine can be well adsorbed.
必要に応じて、染色処理の後、水中延伸処理の前に、架橋処理を施す。上記架橋処理は、代表的には、ホウ酸水溶液にPVA系樹脂層を浸漬させることにより行う。架橋処理を施すことにより、PVA系樹脂層に耐水性を付与し、後の水中延伸で、高温の水中へ浸漬した際のPVAの配向低下を防止することができる。当該ホウ酸水溶液の濃度は、水100重量部に対して、好ましくは1重量部~5重量部である。また、上記染色処理後に架橋処理を行う場合、さらに、ヨウ化物を配合することが好ましい。ヨウ化物を配合することにより、PVA系樹脂層に吸着させたヨウ素の溶出を抑制することができる。ヨウ化物の配合量は、水100重量部に対して、好ましくは1重量部~5重量部である。ヨウ化物の具体例は、上述のとおりである。架橋浴(ホウ酸水溶液)の液温は、好ましくは20℃~50℃である。 A-1-1-5. Crosslinking Treatment If necessary, a crosslinking treatment is applied after the dyeing treatment and before the underwater stretching treatment. The cross-linking treatment is typically performed by immersing the PVA-based resin layer in an aqueous solution of boric acid. The cross-linking treatment imparts water resistance to the PVA-based resin layer, and prevents deterioration of the orientation of the PVA when immersed in high-temperature water in the subsequent underwater stretching. The concentration of the boric acid aqueous solution is preferably 1 to 5 parts by weight with respect to 100 parts by weight of water. Moreover, when cross-linking treatment is carried out after the dyeing treatment, it is preferable to further add an iodide. By blending iodide, elution of iodine adsorbed on the PVA-based resin layer can be suppressed. The amount of iodide compounded is preferably 1 to 5 parts by weight per 100 parts by weight of water. Specific examples of iodides are as described above. The liquid temperature of the cross-linking bath (boric acid aqueous solution) is preferably 20°C to 50°C.
水中延伸処理は、積層体を延伸浴に浸漬させて行う。水中延伸処理によれば、上記熱可塑性樹脂基材やPVA系樹脂層のガラス転移温度(代表的には、80℃程度)よりも低い温度で延伸し得、PVA系樹脂層を、その結晶化を抑えながら、高倍率に延伸することができる。その結果、優れた光学特性を有する未脱色原膜を製造することができる。 A-1-1-6. Underwater Stretching Treatment Underwater stretching treatment is performed by immersing the laminate in a stretching bath. According to the underwater stretching treatment, the thermoplastic resin substrate and the PVA-based resin layer can be stretched at a temperature lower than the glass transition temperature (typically, about 80° C.), and the PVA-based resin layer undergoes its crystallization. It can be stretched at a high magnification while suppressing the As a result, an unbleached original film having excellent optical properties can be produced.
上記乾燥収縮処理は、例えば、長尺状の熱可塑性樹脂基材とPVA系樹脂膜との積層体を長手方向に搬送しながら加熱することにより、幅方向に2%以上収縮させる。乾燥収縮処理においては、該PVA系樹脂膜の水分率が15重量%以下となるまで乾燥させることが好ましく、安定した外観を得る観点から、より好ましくは水分率が12重量%以下、さらに好ましくは10重量%以下、さらにより好ましくは1重量%~5重量%となるまで乾燥させることが好ましい。 A-1-1-7. Drying Shrinkage Treatment In the drying shrinkage treatment, for example, a laminate of a long thermoplastic resin base material and a PVA-based resin film is heated while being transported in the longitudinal direction, thereby shrinking the laminate by 2% or more in the width direction. In the drying shrinkage treatment, it is preferable to dry the PVA-based resin film until the moisture content becomes 15% by weight or less, and from the viewpoint of obtaining a stable appearance, the moisture content is preferably 12% by weight or less, and further preferably. It is preferred to dry to 10% by weight or less, even more preferably 1% to 5% by weight.
好ましくは、水中延伸処理の後、乾燥収縮処理の前に、洗浄処理を施す。上記洗浄処理は、代表的には、ヨウ化カリウム水溶液にPVA系樹脂層を浸漬させることにより行う。 A-1-1-8. Other Treatments Preferably, a washing treatment is performed after the underwater stretching treatment and before the drying shrinkage treatment. The cleaning treatment is typically performed by immersing the PVA-based resin layer in an aqueous solution of potassium iodide.
単層のPVA系樹脂膜を用いた未脱色原膜の作製は、自己支持性を有する(すなわち、基材による支持を必要としない)長尺状のPVA系樹脂膜を染色および延伸(代表的には、ホウ酸水溶液中でのロール延伸機を用いた一軸延伸)し、次いで、水分率が好ましくは15重量%以下、より好ましくは12重量%以下、さらに好ましくは10重量%以下、さらにより好ましくは1重量%~5重量%となるまで乾燥させることによって行われ得る。上記染色は、例えば、PVA系樹脂膜をヨウ素水溶液に浸漬することにより行われる。上記一軸延伸の延伸倍率は、好ましくは3~7倍である。延伸は、染色処理後に行ってもよいし、染色しながら行ってもよい。また、延伸してから染色してもよい。必要に応じて、PVA系樹脂膜に、膨潤処理、架橋処理、洗浄処理等が施される。例えば、染色の前にPVA系樹脂膜を水に浸漬して水洗することで、PVA系樹脂膜表面の汚れやブロッキング防止剤を洗浄することができるだけでなく、PVA系樹脂膜を膨潤させて染色ムラ等を防止することができる。 A-1-2. Preparation of unbleached original film using single-layer PVA-based resin film ) A long PVA-based resin film is dyed and stretched (typically, uniaxially stretched using a roll stretcher in an aqueous boric acid solution), and then the moisture content is preferably 15% by weight or less, more preferably is 12% by weight or less, more preferably 10% by weight or less, and even more preferably 1% to 5% by weight. The dyeing is performed by, for example, immersing the PVA-based resin film in an iodine aqueous solution. The draw ratio of the uniaxial drawing is preferably 3 to 7 times. Stretching may be performed after the dyeing treatment, or may be performed while dyeing. Moreover, you may dye after extending|stretching. If necessary, the PVA-based resin film is subjected to swelling treatment, cross-linking treatment, washing treatment, and the like. For example, by immersing the PVA-based resin film in water and washing it with water before dyeing, it is possible not only to wash away stains and anti-blocking agents on the surface of the PVA-based resin film, but also to swell the PVA-based resin film for dyeing. Unevenness and the like can be prevented.
工程IIにおいては、工程Iを経たPVA系樹脂膜(未脱色原膜)の表面に水性溶媒を接触させる。水性溶媒との接触により、I-、I2、I3 -およびPVA-I3 -錯体を形成するポリヨウ素イオンがPVA-I5 -錯体を形成するポリヨウ素イオンよりも優先的に未脱色原膜から溶出し、短波長側の透過率がより大きく上昇する結果、波長λnmにおける透過率の上昇率(ΔTs(λ))が、ΔTs(415)>ΔTs(470)>ΔTs(550)の関係を満たすことができる。 A-2. Process II
In step II, the surface of the PVA-based resin film (unbleached original film) that has undergone step I is brought into contact with an aqueous solvent. Upon contact with an aqueous solvent, polyiodine ions forming I − , I 2 , I 3 - and PVA-I 3 -complexes preferentially over polyiodine ions forming PVA-I 5 -complexes to the unbleached original. As a result of elution from the film and a greater increase in the transmittance on the short wavelength side, the transmittance increase rate (ΔTs(λ)) at the wavelength λnm satisfies the relationship ΔTs (415) > ΔTs (470) > ΔTs (550) can satisfy
A項に記載の偏光膜の製造方法によって得られる偏光膜は、二色性物質(代表的には、ヨウ素)を含むPVA系樹脂フィルムで構成され、少なくとも415nm~550nmの波長領域において未脱色原膜よりも上昇した透過率を有する。具体的には、波長λnmにおける透過率の上昇率(ΔTs(λ))がΔTs(415)>ΔTs(470)>ΔTs(550)の関係を満たす。波長415nmにおける透過率の上昇率(ΔTs(415))は、例えば1.05を超え、好ましくは1.1以上であり、より好ましくは1.10~2.2であり得る。ΔTs(415)が当該範囲内であれば、消費電力が大きい青色発光の量を減らして、有機EL表示装置の省エネルギー化に寄与することができる。 B. Polarizing film The polarizing film obtained by the method for producing a polarizing film described in Section A is composed of a PVA-based resin film containing a dichroic substance (typically iodine), and has a wavelength range of at least 415 nm to 550 nm. It has a higher transmittance than the original bleaching film. Specifically, the transmittance increase rate (ΔTs(λ)) at the wavelength λnm satisfies the relationship ΔTs(415)>ΔTs(470)>ΔTs(550). The transmittance increase rate (ΔTs(415)) at a wavelength of 415 nm exceeds, for example, 1.05, preferably 1.1 or more, and more preferably 1.10 to 2.2. If ΔTs(415) is within this range, it is possible to reduce the amount of blue light emission that consumes a large amount of power, thereby contributing to energy saving of the organic EL display device.
(1)厚み
製品名「リニアゲージ MODEL D-10HS」(尾崎製作所社製)を用いて測定した。
(2)単体透過率および偏光度
実施例および比較例で得られたPVA系樹脂膜(偏光膜または未脱色原膜)と保護層との積層体について、PVA系樹脂膜側から、紫外可視分光光度計(大塚電子社製「LPF-200」)を用いて測定した単体透過率Ts、平行透過率Tp、直交透過率Tcをそれぞれ、PVA系樹脂膜のTs、TpおよびTcとした。これらのTs、TpおよびTcは、JIS Z8701の2度視野(C光源)により測定して視感度補正を行なったY値である。なお、保護層の屈折率は1.53であり、偏光膜の保護層とは反対側の表面の屈折率は1.53であった。
得られたTpおよびTcから、下記式により偏光度Pを求めた。
偏光度P(%)={(Tp-Tc)/(Tp+Tc)}1/2×100
また、波長415nm、470nmおよび550nmでの測定されたTsをそれぞれ、Ts415、Ts470およびTs550とした。
なお、分光光度計は、日本分光社製「V-7100」などでも同等の測定をすることが可能であり、いずれの分光光度計を用いた場合であっても同等の測定結果が得られることが確認されている。
(3)水分率
乾燥処理直後の未脱色原膜(積層体で延伸した場合、延伸基材は剥離する)を100mm×100mm以上の大きさに切り出し、電子天秤にて、処理前重量を測定する。その後120℃に保たれた加熱オーブンに2時間投入し、取り出し後の重量(処理後重量)を測定し、下記式により水分率を求めた。
水分率[%]=(処理前重量-処理後重量)/処理前重量×100
(4)ヘイズ
日本電色工業社製、製品名「ヘーズメーター(NDH-5000」を用いて、JISK7136に従って測定した。 EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples. The measurement method of each characteristic is as follows. "Parts" and "%" in Examples and Comparative Examples are by weight unless otherwise specified.
(1) Thickness Measured using the product name “Linear Gauge MODEL D-10HS” (manufactured by Ozaki Seisakusho).
(2) Individual Transmittance and Degree of Polarization For laminates of PVA-based resin films (polarizing films or unbleached original films) and protective layers obtained in Examples and Comparative Examples, ultraviolet-visible spectroscopy was performed from the PVA-based resin film side. Single transmittance Ts, parallel transmittance Tp, and orthogonal transmittance Tc measured using a photometer (“LPF-200” manufactured by Otsuka Electronics Co., Ltd.) were defined as Ts, Tp, and Tc of the PVA-based resin film, respectively. These Ts, Tp and Tc are Y values measured with a 2-degree field of view (C light source) according to JIS Z8701 and subjected to visibility correction. The refractive index of the protective layer was 1.53, and the refractive index of the surface of the polarizing film opposite to the protective layer was 1.53.
From the obtained Tp and Tc, the degree of polarization P was determined by the following formula.
Degree of polarization P (%) = {(Tp-Tc)/(Tp+Tc)} 1/2 × 100
Also, the measured Ts at wavelengths of 415 nm, 470 nm and 550 nm were defined as Ts 415 , Ts 470 and Ts 550 , respectively.
Equivalent measurement can be performed with a spectrophotometer such as "V-7100" manufactured by JASCO Corporation, and equivalent measurement results can be obtained using any spectrophotometer. has been confirmed.
(3) Moisture content The unbleached raw film immediately after drying (when the laminate is stretched, the stretched substrate is peeled off) is cut into a size of 100 mm × 100 mm or more, and the weight before processing is measured with an electronic balance. . After that, it was placed in a heating oven maintained at 120° C. for 2 hours, the weight after removal (weight after treatment) was measured, and the moisture content was determined by the following formula.
Moisture content [%] = (weight before treatment - weight after treatment) / weight before treatment x 100
(4) Haze Measured according to JISK7136 using a product name "Haze meter (NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd.).
1.偏光膜および偏光板の作製
厚み30μmのPVA系樹脂フィルム(クラレ製、製品名「PE3000」)の長尺ロールを、30℃水浴中に浸漬させつつ搬送方向に2.2倍に延伸した後、ヨウ素濃度0.04重量%、カリウム濃度0.3重量%の30℃水溶液中に浸漬して染色しながら、全く延伸していないフィルム(元長)を基準として3倍に延伸した。次いで、この延伸フィルムを、ホウ酸濃度3重量%、ヨウ化カリウム濃度3重量%の30℃の水溶液中に浸漬しながら、元長基準で3.3倍までさらに延伸し、続いて、ホウ酸濃度4重量%、ヨウ化カリウム濃度5重量%の60℃水溶液中に浸漬しながら、元長基準で6倍までさらに延伸し、最後に60℃に保たれたオーブンで5分の乾燥処理を施すことによって、厚み12μmの偏光膜(未脱色原膜a1)を作製した。得られた未脱色原膜a1の水分率は10.0重量%であり、単体透過率は42.5%であった。 [Example 1-1]
1. Preparation of polarizing film and polarizing plate A long roll of PVA-based resin film (manufactured by Kuraray, product name "PE3000") having a thickness of 30 µm was stretched 2.2 times in the transport direction while being immersed in a water bath at 30°C. While immersed in an aqueous solution of 0.04% by weight of iodine and 0.3% by weight of potassium at 30° C. for dyeing, the film was stretched 3 times with respect to the unstretched film (original length). Next, while immersing this stretched film in an aqueous solution of 3% by weight of boric acid and 3% by weight of potassium iodide at 30° C., the stretched film is further stretched to 3.3 times its original length. While immersed in a 60°C aqueous solution with a concentration of 4% by weight and a concentration of potassium iodide of 5% by weight, it is further stretched to 6 times its original length, and finally dried in an oven maintained at 60°C for 5 minutes. Thus, a polarizing film (unbleached original film a1) having a thickness of 12 μm was produced. The obtained unbleached original film a1 had a moisture content of 10.0% by weight and a single transmittance of 42.5%.
23℃の水中に31時間浸漬する代わりに、55℃の水中に9分間浸漬したこと以外は実施例1-1と同様にして、[偏光膜A2/保護層]の構成を有する偏光板を得た。 [Example 1-2]
A polarizing plate having a structure of [polarizing film A2/protective layer] was obtained in the same manner as in Example 1-1, except that instead of immersing in water at 23° C. for 31 hours, it was immersed in water at 55° C. for 9 minutes. rice field.
23℃の水中に31時間浸漬する代わりに、60℃の水中に4分間浸漬したこと以外は実施例1-1と同様にして、[偏光膜A3/保護層]の構成を有する偏光板を得た。 [Example 1-3]
A polarizing plate having a structure of [polarizing film A3/protective layer] was obtained in the same manner as in Example 1-1, except that instead of immersing in water at 23° C. for 31 hours, it was immersed in water at 60° C. for 4 minutes. rice field.
23℃の水中に31時間浸漬する代わりに、65℃の水中に3分間浸漬したこと以外は実施例1-1と同様にして、[偏光膜A4/保護層]の構成を有する偏光板を得た。 [Example 1-4]
A polarizing plate having a structure of [polarizing film A4/protective layer] was obtained in the same manner as in Example 1-1, except that instead of immersing in water at 23° C. for 31 hours, it was immersed in water at 65° C. for 3 minutes. rice field.
実施例1-1と同様にして作製した[未脱色原膜a1/保護層]の構成を有する光学積層体を偏光板とした。 [Comparative Example 1]
An optical laminate having a structure of [unbleached original film a1/protective layer] prepared in the same manner as in Example 1-1 was used as a polarizing plate.
熱可塑性樹脂基材として、長尺状で、Tg約75℃である、非晶質のイソフタル共重合ポリエチレンテレフタレートフィルム(厚み:100μm)を用い、樹脂基材の片面に、コロナ処理を施した。
ポリビニルアルコール(重合度4200、ケン化度99.2モル%)およびアセトアセチル変性PVA(日本合成化学工業社製、商品名「ゴーセファイマー」)を9:1で混合したPVA系樹脂100重量部に、ヨウ化カリウム13重量部を添加したものを水に溶かし、PVA水溶液(塗布液)を調製した。
樹脂基材のコロナ処理面に、上記PVA水溶液を塗布して60℃で乾燥することにより、厚み13μmのPVA系樹脂層を形成し、積層体を作製した。
得られた積層体を、130℃のオーブン内で縦方向(長手方向)に2.4倍に一軸延伸した(空中補助延伸処理)。
次いで、積層体を、液温40℃の不溶化浴(水100重量部に対して、ホウ酸を4重量部配合して得られたホウ酸水溶液)に30秒間浸漬させた(不溶化処理)。
次いで、液温30℃の染色浴(水100重量部に対して、ヨウ素とヨウ化カリウムを1:7の重量比で配合して得られたヨウ素水溶液)に、最終的に得られる未脱色原膜の単体透過率(Ts)が42.3%となるように濃度を調整しながら60秒間浸漬させた(染色処理)。
次いで、液温40℃の架橋浴(水100重量部に対して、ヨウ化カリウムを3重量部配合し、ホウ酸を5重量部配合して得られたホウ酸水溶液)に30秒間浸漬させた(架橋処理)。
その後、積層体を、液温70℃のホウ酸水溶液(ホウ酸濃度4重量%、ヨウ化カリウム濃度5重量%)に浸漬させながら、周速の異なるロール間で縦方向(長手方向)に総延伸倍率が5.5倍となるように一軸延伸を行った(水中延伸処理)。
その後、積層体を液温20℃の洗浄浴(水100重量部に対して、ヨウ化カリウムを4重量部配合して得られた水溶液)に浸漬させた(洗浄処理)。
その後、約90℃に保たれたオーブン中で乾燥しながら、表面温度が約75℃に保たれたSUS製の加熱ロールに接触させた(乾燥収縮処理)。乾燥収縮処理による積層体の幅方向の収縮率は2%であった。
このようにして、樹脂基材上に水分率が4.5%であり、厚み5μmの未脱色原膜を形成し、未脱色原膜の表面にシクロオレフィン系フィルム(日本ゼオン社製、Zeonor、厚み:25μm)をUV硬化型接着剤(厚み1.0μm)により貼り合わせ、その後、樹脂基材を剥離して[未脱色原膜b1/保護層]の構成を有する光学積層体を得た。 [Example 2-1]
A long amorphous isophthalic copolymerized polyethylene terephthalate film (thickness: 100 μm) having a Tg of about 75° C. was used as the thermoplastic resin substrate, and one side of the resin substrate was subjected to corona treatment.
Polyvinyl alcohol (degree of polymerization: 4,200, degree of saponification: 99.2 mol%) and acetoacetyl-modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "GOSEFIMER") were mixed at a ratio of 9:1, and 100 parts by weight of PVA-based resin. was added with 13 parts by weight of potassium iodide and dissolved in water to prepare an aqueous PVA solution (coating solution).
The above PVA aqueous solution was applied to the corona-treated surface of the resin base material and dried at 60° C. to form a PVA-based resin layer having a thickness of 13 μm, thereby producing a laminate.
The resulting laminate was uniaxially stretched 2.4 times in the machine direction (longitudinal direction) in an oven at 130° C. (in-air auxiliary stretching treatment).
Next, the laminate was immersed in an insolubilizing bath (an aqueous boric acid solution obtained by mixing 4 parts by weight of boric acid with 100 parts by weight of water) at a liquid temperature of 40° C. for 30 seconds (insolubilizing treatment).
Next, in a dyeing bath (iodine aqueous solution obtained by blending iodine and potassium iodide at a weight ratio of 1:7 with respect to 100 parts by weight of water) at a liquid temperature of 30 ° C., the finally obtained unbleached original It was immersed for 60 seconds while adjusting the concentration so that the single transmittance (Ts) of the membrane was 42.3% (dyeing treatment).
Next, it was immersed for 30 seconds in a cross-linking bath at a liquid temperature of 40°C (an aqueous solution of boric acid obtained by blending 3 parts by weight of potassium iodide and 5 parts by weight of boric acid with respect to 100 parts by weight of water). (crosslinking treatment).
After that, while immersing the laminate in an aqueous solution of boric acid (boric acid concentration: 4% by weight, potassium iodide concentration: 5% by weight) at a liquid temperature of 70° C., the laminate was moved vertically (longitudinally) between rolls with different peripheral speeds. Uniaxial stretching was performed so that the stretching ratio was 5.5 times (underwater stretching treatment).
After that, the laminate was immersed in a washing bath (aqueous solution obtained by blending 4 parts by weight of potassium iodide with 100 parts by weight of water) at a liquid temperature of 20° C. (washing treatment).
Thereafter, while drying in an oven maintained at about 90° C., it was brought into contact with a heating roll made of SUS whose surface temperature was maintained at about 75° C. (dry shrinkage treatment). The shrinkage rate in the width direction of the laminate due to the drying shrinkage treatment was 2%.
In this way, an unbleached original film having a moisture content of 4.5% and a thickness of 5 μm was formed on the resin substrate, and a cycloolefin film (Zeonor, manufactured by Nippon Zeon Co., Ltd.) was formed on the surface of the unbleached original film. thickness: 25 μm) were bonded together with a UV curable adhesive (thickness: 1.0 μm), and then the resin substrate was peeled off to obtain an optical laminate having a structure of [unbleached base film b1/protective layer].
50℃の水中に9分間浸漬する代わりに、55℃の水に3分間浸漬したこと以外は実施例2-1と同様にして、[偏光膜B2/保護層]の構成を有する偏光板を得た。 [Example 2-2]
A polarizing plate having a structure of [polarizing film B2/protective layer] was obtained in the same manner as in Example 2-1, except that instead of immersing in water at 50°C for 9 minutes, it was immersed in water at 55°C for 3 minutes. rice field.
50℃の水中に9分間浸漬する代わりに、60℃の水に2分間浸漬したこと以外は実施例2-1と同様にして、[偏光膜B3/保護層]の構成を有する偏光板を得た。 [Example 2-3]
A polarizing plate having a structure of [polarizing film B3/protective layer] was obtained in the same manner as in Example 2-1, except that instead of immersing in water at 50°C for 9 minutes, it was immersed in water at 60°C for 2 minutes. rice field.
50℃の水中に9分間浸漬する代わりに、60℃の水に3分間浸漬したこと以外は実施例2-1と同様にして、[偏光膜B4/保護層]の構成を有する偏光板を得た。 [Example 2-4]
A polarizing plate having a structure of [polarizing film B4/protective layer] was obtained in the same manner as in Example 2-1, except that instead of immersing in water at 50°C for 9 minutes, it was immersed in water at 60°C for 3 minutes. rice field.
実施例2-1と同様にして作製した[未脱色原膜b1/保護層]の構成を有する光学積層体を偏光板として用いた。 [Comparative Example 2]
An optical laminate having a structure of [unbleached original film b1/protective layer] prepared in the same manner as in Example 2-1 was used as a polarizing plate.
Claims (6)
- ポリビニルアルコール系樹脂膜を染色処理および延伸処理に供すること、および
該ポリビニルアルコール系樹脂膜の表面に水性溶媒を接触させること、をこの順に含み、
波長λnmにおける該水性溶媒との接触前の該ポリビニルアルコール系樹脂膜の透過率に対する接触後の透過率の割合(ΔTs(λ))が、ΔTs(415)>ΔTs(470)>ΔTs(550)の関係を満たす、偏光膜の製造方法。 subjecting the polyvinyl alcohol-based resin film to dyeing treatment and stretching treatment, and bringing the surface of the polyvinyl alcohol-based resin film into contact with an aqueous solvent in this order,
The ratio of the transmittance after contact to the transmittance of the polyvinyl alcohol resin film before contact with the aqueous solvent at a wavelength of λ nm (ΔTs (λ)) is ΔTs (415) > ΔTs (470) > ΔTs (550) A method for manufacturing a polarizing film that satisfies the relationship of - 前記水性溶媒の温度が、20℃~70℃である、請求項1に記載の製造方法。 The production method according to claim 1, wherein the temperature of the aqueous solvent is 20°C to 70°C.
- 前記水性溶媒を接触させるポリビニルアルコール系樹脂膜の水分率が、15重量%以下である、請求項1または2に記載の製造方法。 The manufacturing method according to claim 1 or 2, wherein the water content of the polyvinyl alcohol-based resin film with which the aqueous solvent is brought into contact is 15% by weight or less.
- 前記水性溶媒を接触させるポリビニルアルコール系樹脂膜の厚みが、12μm以下である、請求項1から3のいずれかに記載の製造方法。 The manufacturing method according to any one of claims 1 to 3, wherein the thickness of the polyvinyl alcohol-based resin film with which the aqueous solvent is brought into contact is 12 µm or less.
- 前記ポリビニルアルコール系樹脂膜を染色処理および延伸処理に供することが、
長尺状の熱可塑性樹脂基材の片側に、ハロゲン化物とポリビニルアルコール系樹脂とを含むポリビニルアルコール系樹脂膜を形成して積層体とすること、および、
該積層体に、空中補助延伸処理と、染色処理と、水中延伸処理と、長手方向に搬送しながら加熱することにより幅方向に2%以上収縮させる乾燥収縮処理と、をこの順に施すこと
を含む、請求項1から4のいずれかに記載の製造方法。 subjecting the polyvinyl alcohol-based resin film to dyeing treatment and stretching treatment,
Forming a polyvinyl alcohol-based resin film containing a halide and a polyvinyl alcohol-based resin on one side of a long thermoplastic resin substrate to form a laminate, and
The laminate is subjected to an in-air auxiliary stretching treatment, a dyeing treatment, an underwater stretching treatment, and a drying shrinkage treatment for shrinking the laminate by 2% or more in the width direction by heating while being conveyed in the longitudinal direction, in this order. , The manufacturing method according to any one of claims 1 to 4. - ヘイズが1%以下の偏光膜の製造方法である、請求項1から5のいずれかに記載の製造方法。 The manufacturing method according to any one of claims 1 to 5, which is a method for manufacturing a polarizing film with a haze of 1% or less.
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