CN112789528A - Polarizing plate, method for manufacturing the same, and image display device including the same - Google Patents
Polarizing plate, method for manufacturing the same, and image display device including the same Download PDFInfo
- Publication number
- CN112789528A CN112789528A CN201980063096.7A CN201980063096A CN112789528A CN 112789528 A CN112789528 A CN 112789528A CN 201980063096 A CN201980063096 A CN 201980063096A CN 112789528 A CN112789528 A CN 112789528A
- Authority
- CN
- China
- Prior art keywords
- stretching
- pva
- laminate
- polarizing plate
- polarizing film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 75
- 230000001681 protective effect Effects 0.000 claims abstract description 65
- 230000010287 polarization Effects 0.000 claims abstract description 29
- 230000008859 change Effects 0.000 claims abstract description 17
- 239000011521 glass Substances 0.000 claims abstract description 14
- 239000012790 adhesive layer Substances 0.000 claims abstract description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 150
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 150
- 229920005989 resin Polymers 0.000 claims description 147
- 239000011347 resin Substances 0.000 claims description 147
- 239000010410 layer Substances 0.000 claims description 77
- 229920005992 thermoplastic resin Polymers 0.000 claims description 75
- 238000002834 transmittance Methods 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 238000004043 dyeing Methods 0.000 claims description 42
- 239000000178 monomer Substances 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 21
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 17
- 230000035699 permeability Effects 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 230000000007 visual effect Effects 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000010408 film Substances 0.000 description 201
- 239000000758 substrate Substances 0.000 description 75
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 51
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 43
- 239000004327 boric acid Substances 0.000 description 43
- 239000000243 solution Substances 0.000 description 39
- 239000007788 liquid Substances 0.000 description 28
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 26
- 229910052740 iodine Inorganic materials 0.000 description 26
- 239000011630 iodine Substances 0.000 description 26
- 239000011248 coating agent Substances 0.000 description 23
- 238000000576 coating method Methods 0.000 description 23
- 239000000853 adhesive Substances 0.000 description 20
- 230000001070 adhesive effect Effects 0.000 description 20
- 230000003287 optical effect Effects 0.000 description 20
- 150000004820 halides Chemical class 0.000 description 19
- 238000010521 absorption reaction Methods 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 10
- -1 polyethylene terephthalate Polymers 0.000 description 9
- 238000007127 saponification reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001925 cycloalkenes Chemical class 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
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 238000012937 correction Methods 0.000 description 5
- 239000006059 cover glass Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000002093 peripheral effect Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229920002284 Cellulose triacetate Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- DKNPRRRKHAEUMW-UHFFFAOYSA-N Iodine aqueous Chemical compound [K+].I[I-]I DKNPRRRKHAEUMW-UHFFFAOYSA-N 0.000 description 4
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000005401 electroluminescence Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 4
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000007602 hot air drying Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000002096 quantum dot Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 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 2
- 229920008790 Amorphous Polyethylene terephthalate Polymers 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000003522 acrylic cement Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000002156 mixing Methods 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
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 239000012192 staining solution Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- 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 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- 239000004593 Epoxy Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-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
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 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
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920005603 alternating copolymer Polymers 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
- 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
- 239000012461 cellulose resin Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 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
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 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
- 125000005462 imide group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229920002050 silicone resin Polymers 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
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002335 surface treatment layer Substances 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
- 238000012360 testing method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00634—Production of filters
- B29D11/00644—Production of filters polarizing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/0073—Optical laminates
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- 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
- H10K59/50—OLEDs integrated with light modulating elements, e.g. with electrochromic elements, photochromic elements or liquid crystal elements
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
- Nonlinear Science (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Ophthalmology & Optometry (AREA)
- Mechanical Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Mathematical Physics (AREA)
- Theoretical Computer Science (AREA)
- Polarising Elements (AREA)
- Laminated Bodies (AREA)
Abstract
Provided is a polarizing plate having excellent durability even in a severe heating environment. The polarizing plate of the present inventionComprising a polarizing film having a thickness of 8 μm or less and protective films disposed on both sides of the polarizing film, wherein the amount of change in polarization degree Δ P, expressed by the following formula, after the polarizing film is left at 100 ℃ for 60 hours with glass plates attached to both surfaces via adhesive layers is-1.0% to 0.0%: Δ P (%) ═ P60‑P0. Here, P0For degree of polarization before heating, P60The polarization degree after heating for 60 hours.
Description
Technical Field
The present invention relates to a polarizing plate, a method for manufacturing the same, and an image display device including the same.
Background
In a liquid crystal display device, which is a typical image display device, polarizing films (typically, a polarizing film laminate (for example, a polarizing plate) including a polarizing film and an optical functional layer) are disposed on both sides of a liquid crystal cell in accordance with an image forming method. In addition, along with the spread of thin displays, a display (OLED) having an organic EL panel mounted thereon and a display (QLED) using a display panel using an inorganic light emitting material such as quantum dots have been proposed. As a method for producing a polarizing film, for example, the following methods are proposed: a polarizing film is obtained on a resin substrate by stretching a laminate having the resin substrate and a polyvinyl alcohol (PVA) resin layer, and then performing a dyeing treatment (for example, patent document 1). Since a polarizing film having a small thickness can be obtained by such a method, it is attracting attention because it contributes to the thinning of an image display device in recent years. However, the optical characteristics of the conventional thin polarizing film as described above are insufficient, and further improvement in the optical characteristics of the thin polarizing film is required. Further, in recent years, the use of image display devices has been greatly expanded, and for example, the use of image display devices for vehicle use (for example, car navigation devices and rear monitors) has been expanded. Accordingly, the polarizing film laminate is required to have excellent durability in a severe heating environment (for example, in a high-temperature environment), and a polarizing film laminate capable of realizing such durability have been demanded.
Documents of the prior art
Patent document
Patent document 1: japanese Kohyo publication No. 2012-516468
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made to solve the above conventional problems, and a main object thereof is to provide a polarizing plate having excellent durability even in a severe heating environment.
Means for solving the problems
The polarizing plate comprises a polarizing film having a thickness of 8 [ mu ] m or less and protective films disposed on both sides of the polarizing film, wherein the amount of change in polarization degree [ Delta ] P, expressed by the following formula, after the polarizing plate is left at 100 ℃ for 60 hours with glass plates attached to both surfaces via adhesive layers, is-1.0% to 0.0%:
ΔP(％)＝P60-P0
here, P0For degree of polarization before heating, P60The polarization degree after heating for 60 hours.
In one embodiment, the polarizing plate has a monomer transmittance change Δ Ts of 0.0% to 1.5% after being left at 100 ℃ for 60 hours with glass plates attached to both surfaces thereof via an adhesive layer, as represented by the following formula:
ΔTs(％)＝Ts60-Ts0
here, Ts0For the monomer transmittance before heating, Ts60The monomer transmittance after heating for 60 hours.
In one embodiment, the monomer transmittance Ts is041.8 to 43.0 percent.
In one embodiment, the protective film has a moisture permeability of 200g/m224h or less.
According to other aspects of the present invention, an image display apparatus is provided. The image display device includes a display unit, and the polarizing plate disposed on a visual recognition side of the display unit.
In one embodiment, the image display device is configured for in-vehicle use.
According to another aspect of the present invention, there is provided a method of manufacturing a polarizing plate. The manufacturing method comprises the following steps: forming a polyvinyl alcohol resin layer containing a polyvinyl alcohol resin and containing an iodide or sodium chloride on one side of a long thermoplastic resin base material to form a laminate; subjecting the laminate to an in-air auxiliary stretching treatment, a dyeing treatment, an in-water stretching treatment, and a drying shrinkage treatment of shrinking by 2% or more in the width direction by heating while conveying the laminate in the longitudinal direction, in this order, thereby producing a polarizing film from the polyvinyl alcohol resin layer; and laminating protective films on both sides of the polarizing film.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a polarizing film that is thin and has excellent durability even under severe heating environments (for example, small changes in polarization degree and monomer transmittance before and after heating) can be obtained by using a combination of addition of a halide (typically potassium iodide) to a polyvinyl alcohol (PVA) resin, two-stage stretching including aerial auxiliary stretching and underwater stretching, and drying and shrinking by a heating roller. By using such a polarizing film, a polarizing plate having excellent durability even under severe heating environments can be realized.
Drawings
Fig. 1 is a schematic cross-sectional view of a polarizing plate according to one embodiment of the present invention.
Fig. 2 is a schematic diagram showing an example of the drying shrinkage treatment using a heating roller.
Detailed Description
Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.
A. Integral constitution of polarizing plate
Fig. 1 is a schematic cross-sectional view of a polarizing plate according to one embodiment of the present invention. The polarizing plate 100 has a polarizing film 11 and protective films 12 and 13 disposed on both sides of the polarizing film 11. Either one of the protective films 12 and 13 may be omitted depending on the purpose, desired configuration, and the like. In the embodiment of the present invention, the polarizing film is typically a polyvinyl alcohol (PVA) -based resin film containing a dichroic substance (e.g., iodine), and has a thickness of 8 μm or less.
In an embodiment of the present invention, the polarizing plate has a change Δ P in polarization degree represented by the following formula of-1.0% to 0.0% after being left at 100 ℃ for 60 hours with glass plates attached to both sides via an adhesive layer:
ΔP(％)＝P60-P0
here, P0For degree of polarization before heating, P60The polarization degree after heating for 60 hours. That is, the polarizing plate according to the embodiment of the present invention has a feature that the reduction in polarization degree is small even when it is placed in a severe heating environment such as 100 ℃. The Δ P is preferably-0.5% to 0.0%, more preferably-0.2% to 0.0%. The polarizing plate preferably has a monomer transmittance change Δ Ts of 0.0% to 1.5% after being left at 100 ℃ for 60 hours with glass plates attached to both surfaces thereof via an adhesive layer, as represented by the following formula:
ΔTs(％)＝Ts60-Ts0
here, Ts0For the monomer transmittance before heating, Ts60The monomer transmittance after heating for 60 hours. That is, the polarizing plate according to the embodiment of the present invention preferably has a characteristic that the increase in the transmittance of the monomer is small even when it is left under a severe heating environment such as 100 ℃. Δ Ts is preferably 0.0% to 1.0%, more preferably 0.0% to 0.7%. Here, the degree of polarization and the monomer transmittance are characteristics of a polarizing film substantially, but the constituent elements other than the polarizing film in the polarizing plate do not substantially affect the degree of polarization and the monomer transmittance, and therefore the degree of polarization and the monomer transmittance of the polarizing film are substantially equal to those of the polarizing plate. It is presumed that such a feature of the polarizing plate can be achieved by the following mechanism of the polarizing film: iodine in polarizing film is PVA/I3-Complex (absorption near 480 nm), PVA/I5-Complex (having absorption near 600 nm), iodide ion (near 210nm in the ultraviolet region) without complex formationHaving absorption), and the like, and the result is mainly due to PVA/I3-Complex and PVA/I5-The complex compound causes the polarizing film to exhibit absorption dichroism under visible light. In general, under high temperature conditions, PVA/I5-The complex becomes unstable, PVA/I5-The amount of complex is reduced. As a result, a phenomenon (heating to red) occurs in which the polarizing film and the polarizing film laminate (for example, polarizing plate) turn red in the cross nicol state. Further, when an image display device is configured by attaching a polarizing plate to a display cell via an adhesive, a high-temperature and high-humidity state occurs due to moisture contained in the polarizing plate and the adhesive, and thus PVA/I3-Complex and PVA/I5-The deterioration of the complex becomes remarkable, and in addition to the reddening by heating described above, the reduction in the degree of polarization and the increase in the monomer transmittance become remarkable. According to an embodiment of the present invention, as described later, a polyvinyl alcohol (PVA) I/I can be obtained under a severe heating environment by combining addition of a halide (typically potassium iodide) to a PVA-based resin, two-stage stretching including in-air auxiliary stretching and underwater stretching, and drying and shrinking by a heated roller3-Complex and PVA/I5-A polarizing film having excellent stability of the complex. As a result, a polarizing plate having excellent durability even under severe heating environments (typically, reddening is suppressed, and changes in polarization degree and monomer transmittance are small) can be realized.
B. Polarizing film
As described above, the polarizing film is composed of a PVA-based resin film containing a dichroic substance (e.g., iodine). The polarizing film is substantially a PVA-based resin film having iodine adsorbed and oriented. As the PVA-based resin forming the PVA-based resin film, any and appropriate resin can be used. Examples thereof include polyvinyl alcohol and ethylene-vinyl alcohol copolymers. Polyvinyl alcohol is obtained by saponifying polyvinyl acetate. The ethylene-vinyl alcohol copolymer is obtained by saponifying an ethylene-vinyl acetate copolymer. The saponification degree of the PVA resin is usually 85 mol% to 100 mol%, preferably 95.0 mol% to 99.95 mol%, and more preferably 99.0 mol% to 99.93 mol%. The degree of saponification can be determined in accordance with JIS K6726-. By using the PVA-based resin having such a saponification degree, a polarizing film having excellent durability can be obtained. If the degree of saponification is too high, gelation may occur.
The iodine concentration in the polarizing film is 5.0 wt% or more, preferably 5.0 wt% to 12.0 wt%, more preferably 5.5 wt% to 10.0 wt%. In the present specification, the "iodine concentration" refers to the amount of all iodine contained in the polarizing film. More specifically, iodine is represented by I in a polarizing film-、I2、I3 -、PVA/I3-Complex, PVA/I5-When the complex or the like is present, the iodine concentration in the present specification means the concentration of iodine including all of these forms. The iodine concentration is calculated from, for example, the fluorescent X-ray intensity and the film (polarizing film) thickness based on the fluorescent X-ray analysis. According to the embodiment of the present invention, in the polarizing film having such a high iodine concentration, excellent durability under a severe heating environment can be achieved.
As described above, the thickness of the polarizing film is 8 μm or less, preferably 1 to 8 μm, more preferably 1 to 7 μm, and further preferably 2 to 5 μm. According to the embodiment of the present invention, excellent durability under a severe heating environment can be achieved in such a very thin polarizing film.
The polarizing film preferably exhibits absorption dichroism at an arbitrary wavelength of 380nm to 780 nm. Monomer transmittance (monomer transmittance before heating) Ts of polarizing film0Preferably 41.8% to 43.0%, more preferably 41.9% to 42.8%. Polarization degree (polarization degree before heating) P of polarizing film0Preferably 99.900% or more, more preferably 99.950% or more. Typically, the above-mentioned monomer transmittance is a Y value measured by an ultraviolet-visible spectrophotometer and corrected for the photosensitivity. Typically, the degree of polarization is determined by the following equation based on the parallel transmittance Tp and the orthogonal transmittance Tc, which are measured using an ultraviolet-visible spectrophotometer and corrected for visibility.
Polarization degree (%) { (Tp-Tc)/(Tp + Tc) }1/2×100
In one embodiment, typically, the transmittance of a thin polarizing film of 8 μm or less is set to be in a polarizing rangeThe laminate of the optical film (refractive index of the surface: 1.53) and the protective film (refractive index: 1.50) was measured by an ultraviolet-visible spectrophotometer. The reflectance at the interface of each layer may change depending on the refractive index of the surface of the polarizing film and/or the refractive index of the surface of the protective film in contact with the air interface, and as a result, the measured value of the transmittance may change. Therefore, when a protective film having a refractive index other than 1.50 is used, for example, the measured value of the transmittance can be corrected based on the refractive index of the surface of the protective film in contact with the air interface. Specifically, the correction value C of the transmittance uses the reflectance R of polarized light parallel to the transmission axis at the interface of the protective film and the air layer1(transmission axis reflectance) and is expressed by the following equation.
C＝R1-R0
R0＝((1.50-1)2/(1.50+1)2)×(T1/100)
R1＝((n1-1)2/(n1+1)2)×(T1/100)
Here, R0Is a transmission axis reflectance, n, when a protective film having a refractive index of 1.50 is used1The refractive index of the protective film used, T1Is the transmittance of the polarizing film. For example, when a substrate having a surface refractive index of 1.53 (a cycloolefin film, a film with a hard coat layer, or the like) is used as the protective film, the correction amount C reaches about 0.2%. In this case, the transmittance obtained by the measurement can be converted into the transmittance when a protective film having a surface refractive index of 1.50 is used by adding 0.2%. The transmittance T of the polarizing film is calculated based on the above formula1The amount of change in correction value C when the change is 2% is 0.03% or less, and the influence of the transmittance of the polarizing film on the value of correction value C is limited. Further, when the protective film has absorption other than surface reflection, appropriate correction can be made in accordance with the amount of absorption.
As the polarizing film, any and appropriate polarizing film can be used. Typically, the polarizing film can be produced using a laminate of two or more layers.
Specific examples of the polarizing film obtained using the laminate include a polarizing film obtained using a laminate of a resin substrate and a PVA-based resin layer applied to the resin substrate. A polarizing film obtained by using a laminate of a resin substrate and a PVA-based resin layer formed on the resin substrate by coating can be produced by: for example, a laminate of a resin substrate and a PVA-based resin layer is obtained by applying a PVA-based resin solution to a resin substrate and drying the solution to form a PVA-based resin layer on the resin substrate; the laminate was stretched and dyed to obtain a polarizing film from the PVA-based resin layer. In the present embodiment, typically, the stretching includes immersing the laminate in an aqueous boric acid solution and stretching. Further, the stretching may further include, as necessary: the laminate is subjected to in-air stretching at an elevated temperature (e.g., 95 ℃ or higher) prior to stretching in the aqueous boric acid solution. The obtained resin substrate/polarizing film laminate may be used as it is (that is, the resin substrate may be used as a protective layer for the polarizing film), or the resin substrate may be peeled from the resin substrate/polarizing film laminate and an arbitrary and appropriate protective layer suitable for the purpose may be laminated on the peeled surface. Details of a method for producing such a polarizing film are described in, for example, japanese patent laid-open No. 2012-73580. The entire disclosure of this publication is incorporated herein by reference.
Typically, the polarizing film may be produced by a method including the following operations: forming a polyvinyl alcohol resin layer containing a halide and a polyvinyl alcohol resin on one side of a long thermoplastic resin base material to form a laminate; and subjecting the laminate to an in-air auxiliary stretching treatment, a dyeing treatment, an underwater stretching treatment, and a drying shrinkage treatment of shrinking the laminate by 2% or more in the width direction by heating while conveying the laminate in the longitudinal direction in this order. This makes it possible to obtain a thin polarizing film having excellent durability even in a severe heating environment. The process for producing a polarizing film is described in detail in section E below as a process included in the process for producing a polarizing plate.
C. Protective film
The protective films 12 and 13 are formed of any and appropriate film that can be used as a protective film for a polarizing film. Specific examples of the material to be the main component of the film include cellulose resins such as Triacetylcellulose (TAC); transparent resins such as polyester, polyvinyl alcohol, polycarbonate, polyamide, polyimide, polyether sulfone, polysulfone, polystyrene, polynorbornene, polyolefin, (meth) acrylic, and acetate resins. Further, thermosetting resins such as (meth) acrylic, urethane, (meth) acrylic urethane, epoxy, and silicone resins, ultraviolet-curable resins, and the like can be mentioned. In addition, for example, a glassy polymer such as a siloxane polymer can be cited. Further, the polymer film described in Japanese patent application laid-open No. 2001-343529 (WO01/37007) may be used. As a material of the film, for example, a resin composition containing a thermoplastic resin having a substituted or unsubstituted imide group in a side chain and a thermoplastic resin having a nitrile group and a substituted or unsubstituted phenyl group in a side chain can be used, and for example, a resin composition containing an alternating copolymer of isobutylene and N-methylmaleimide and an acrylonitrile-styrene copolymer can be mentioned. The polymer film may be, for example, an extrusion molded product of the above resin composition. The protective film is preferably made of a cycloolefin resin such as polynorbornene resin. This is because an appropriate moisture permeability can be achieved.
The protective film preferably has a moisture permeability of 200g/m224h or less, more preferably 100g/m224h or less, more preferably 50g/m224h or less, particularly preferably 20g/m224h or less. The lower the moisture permeability is, the more preferable the lower the moisture permeability is, the lower the moisture permeability may be, for example, 2g/m224 h. If the moisture permeability is in such a range, reddening can be further suppressed under a high-temperature environment, and changes in the degree of polarization and the monomer transmittance can be further reduced. The moisture permeability was measured according to the moisture permeability test (cup method) of JIS Z0208.
When the polarizing plate 100 is applied to an image display device, the protective film (outer protective film) 12 disposed on the side opposite to the display cell may be subjected to surface treatment such as hard coating treatment, antireflection treatment, anti-blocking treatment, and antiglare treatment as needed. Further, if necessary, the outer protective film 12 may be subjected to a process of improving visibility when visually recognized through polarized sunglasses (typically, a (elliptical) polarizing function is provided, and an ultra-high retardation is provided). By performing such processing, even when the display screen is visually recognized through a polarized lens such as a polarized sunglass, excellent visual recognition can be achieved. Such a polarizing plate can be suitably applied to an in-vehicle image display device because the visibility of a driver of a vehicle wearing sunglasses is excellent.
Typically, the thickness of the outer protective film 12 is 300 μm or less, preferably 100 μm or less, more preferably 5 to 80 μm, and still more preferably 10 to 60 μm. When the surface treatment is performed, the thickness of the outer protective film is a thickness including the thickness of the surface treatment layer.
When the polarizing plate 100 is applied to an image display device, the thickness of the protective film (inner protective film) 13 disposed on the display cell side is preferably 5 μm to 200 μm, more preferably 10 μm to 100 μm, and still more preferably 10 μm to 60 μm. In 1 embodiment, the inner protective film is preferably optically isotropic. In the present specification, "optically isotropic" means: the in-plane retardation Re (550) is 0nm to 10nm, and the retardation Rth (550) in the thickness direction is-10 nm to +10 nm. In another embodiment, the inner protective film is a retardation layer having an arbitrary and appropriate retardation value. In this case, the in-plane retardation Re (550) of the retardation layer is, for example, 110nm to 150 nm. "Re (550)" is an in-plane retardation measured at 23 ℃ with light having a wavelength of 550nm, and is obtained by the formula Re ═ nx-ny × d. "Rth (550)" is a phase difference in the thickness direction measured at 23 ℃ by light having a wavelength of 550nm, and is obtained by the formula Rth ═ nx-nz) × d. Here, "nx" is a refractive index in a direction in which the in-plane refractive index is maximized (i.e., the slow axis direction), "ny" is a refractive index in a direction orthogonal to the slow axis in the plane (i.e., the fast axis direction), "nz" is a refractive index in the thickness direction, and "d" is the thickness (nm) of the layer (film).
D. Polarizing plate with cover glass
As described above, the polarizing plate according to the embodiment of the present invention is excellent in durability even in a state of being sandwiched between glass plates and under a severe heating environment, and therefore, can be suitably configured as a polarizing plate with cover glass. Typically, a polarizing plate with cover glass includes: the polarizing plate according to any one of items A to C, and a cover glass laminated on the viewing side (the side of the outer protective film 12) of the polarizing plate with an interlayer filler interposed therebetween. The interlayer filler is made of an arbitrary and appropriate adhesive. Examples of the interlayer filler include those described in japanese patent No. 6071459. The description of this publication is incorporated herein by reference. The thickness of the interlayer filler is preferably 50 to 300. mu.m, more preferably 100 to 250. mu.m. The cover glass is conventionally known in the art, and therefore, a detailed description thereof will be omitted.
E. Method for manufacturing polarizing plate
The method for manufacturing a polarizing plate according to one embodiment of the present invention includes: forming a polyvinyl alcohol resin layer containing a polyvinyl alcohol resin and containing an iodide or sodium chloride on one side of a long thermoplastic resin base material to form a laminate; subjecting the laminate to an in-air auxiliary stretching treatment, a dyeing treatment, an in-water stretching treatment, and a drying shrinkage treatment of shrinking by 2% or more in the width direction by heating while conveying the laminate in the longitudinal direction, in this order, thereby producing a polarizing film from the polyvinyl alcohol resin layer; and laminating protective films on both sides of the polarizing film. The content of the halide in the PVA-based resin layer is preferably 5 to 20 parts by weight based on 100 parts by weight of the PVA-based resin. The drying shrinkage treatment is preferably carried out using a heated roller, and the temperature of the heated roller is preferably 60 to 120 ℃. According to this production method, a polarizing film that is thin and has excellent durability even under severe heating environments can be obtained, and as a result, a polarizing plate that has excellent durability even under severe heating environments can be obtained. In particular, a polarizing film having excellent durability even under severe heating environments and suppressed variations in optical characteristics can be obtained by producing a laminate including a halide-containing PVA-based resin layer, stretching the laminate in multiple stages including in-air assisted stretching and underwater stretching, and heating the stretched laminate with a heating roller. Specifically, by using a heating roller in the drying and shrinking treatment step, the entire laminate can be uniformly shrunk while the laminate is conveyed. Thus, the polarizing film as described above can be stably produced.
E-1 preparation of laminate
As a method for producing a laminate of the thermoplastic resin substrate and the PVA-based resin layer, any and appropriate method can be adopted. It is preferable that: the PVA-based resin layer is formed on the thermoplastic resin substrate by applying a coating solution containing a halide and a PVA-based resin to the surface of the thermoplastic resin substrate and drying the coating solution. As described above, the content of the halide in the PVA-based resin layer is preferably 5 to 20 parts by weight based on 100 parts by weight of the PVA-based resin.
As a method for applying the coating liquid, any and appropriate method can be adopted. Examples thereof include roll coating, spin coating, wire bar coating, dip coating, die coating, curtain coating, spray coating, and knife coating (comma coating). The coating/drying temperature of the coating liquid is preferably 50 ℃ or higher.
The thickness of the PVA resin layer is preferably 3 to 40 μm, and more preferably 3 to 20 μm.
Before the PVA-based resin layer is formed, the thermoplastic resin substrate may be subjected to a surface treatment (for example, corona treatment), 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.
E-1-1. thermoplastic resin base Material
The thickness of the thermoplastic resin substrate is preferably 20 to 300. mu.m, more preferably 50 to 200. mu.m. If the thickness is less than 20 μm, it may be difficult to form the PVA based resin layer. If it exceeds 300 μm, for example, in the underwater stretching treatment described later, it may take a long time for the thermoplastic resin substrate to absorb water and an excessive load may be required for stretching.
The water absorption of the thermoplastic resin substrate is preferably 0.2% or more, and more preferably 0.3% or more. The thermoplastic resin base material absorbs water, and the water functions as a plasticizer to plasticize the resin. As a result, the tensile stress can be greatly reduced, and the film can be stretched to a high magnification. On the other hand, the water absorption of the thermoplastic resin substrate is preferably 3.0% or less, and more preferably 1.0% or less. By using such a thermoplastic resin substrate, it is possible to prevent problems such as a significant decrease in dimensional stability of the thermoplastic resin substrate during production and deterioration in appearance of the obtained polarizing film. Further, the base material can be prevented from being broken when stretched in water or the PVA-based resin layer can be prevented from being peeled from the thermoplastic resin base material. The water absorption of the thermoplastic resin base material can be adjusted by, for example, introducing a modifying group into the constituent material. The water absorption is a value determined in accordance with JIS K7209.
The glass transition temperature (Tg) of the thermoplastic resin substrate is preferably 120 ℃ or lower. By using such a thermoplastic resin substrate, the crystallization of the PVA-based resin layer can be suppressed, and the stretchability of the laminate can be sufficiently ensured. Further, when the plasticization of the thermoplastic resin substrate by water is considered and the underwater stretching is favorably performed, it is more preferably 100 ℃ or lower, and still more preferably 90 ℃ or lower. On the other hand, the glass transition temperature of the thermoplastic resin substrate is preferably 60 ℃ or higher. By using such a thermoplastic resin substrate, when a coating liquid containing the PVA-based resin is applied and dried, defects such as deformation (for example, generation of irregularities, slackening, wrinkles, and the like) of the thermoplastic resin substrate can be prevented, and a laminate can be produced satisfactorily. Further, the PVA-based resin layer can be favorably stretched at an appropriate temperature (for example, about 60 ℃). The glass transition temperature of the thermoplastic resin substrate can be adjusted by, for example, heating using a crystallized material in which a modifying group is introduced into a constituent material. The glass transition temperature (Tg) is a value determined in accordance with JIS K7121.
As the constituent material of the thermoplastic resin substrate, any and appropriate thermoplastic resin can be used. Examples of the thermoplastic resin include ester resins such as polyethylene terephthalate resins, cycloolefin resins such as norbornene resins, olefin resins such as polypropylene resins, polyamide resins, polycarbonate resins, and copolymer resins thereof. Of these, norbornene resin and amorphous polyethylene terephthalate resin are preferable.
In one embodiment, an amorphous (noncrystalline) polyethylene terephthalate-based resin is preferably used. Among them, amorphous (hardly crystallized) polyethylene terephthalate resin is particularly preferably used. Specific examples of the amorphous polyethylene terephthalate resin include copolymers further containing isophthalic acid and/or cyclohexane dicarboxylic acid as dicarboxylic acids; and a copolymer comprising cyclohexanedimethanol and diethylene glycol as diols.
In a preferred embodiment, the thermoplastic resin substrate is composed of a polyethylene terephthalate resin having an isophthalic acid unit. This is because: the thermoplastic resin substrate is extremely excellent in stretchability and is suppressed in crystallization during stretching. This is considered to be because the introduction of the isophthalic acid unit imparts a large curve to the main chain. The polyethylene terephthalate resin has a terephthalic acid unit and an ethylene glycol unit. The content ratio of the isophthalic acid unit is preferably 0.1 mol% or more, and more preferably 1.0 mol% or more, based on the total of all the repeating units. This is because: a thermoplastic resin base material having extremely excellent stretchability can be obtained. On the other hand, the content ratio of the isophthalic acid unit is preferably 20 mol% or less, more preferably 10 mol% or less, based on the total of all the repeating units. By setting such a content ratio, the crystallinity can be increased favorably in the drying shrinkage treatment described later.
The thermoplastic resin substrate may be stretched in advance (before the PVA-based resin layer is formed). In one embodiment, the stretching is performed in the transverse direction of the long thermoplastic resin base material. The transverse direction is preferably a direction orthogonal to the stretching direction of the laminate described later. In the present specification, "orthogonal" also includes the case of substantially orthogonal. Here, "substantially orthogonal" includes a case of 90 ° ± 5.0 °, preferably 90 ° ± 3.0 °, and more preferably 90 ° ± 1.0 °.
The stretching temperature of the thermoplastic resin substrate is preferably from Tg-10 ℃ to Tg +50 ℃ as compared with the glass transition temperature (Tg). The stretch ratio of the thermoplastic resin base material is preferably 1.5 to 3.0 times.
As the method for stretching the thermoplastic resin substrate, any and appropriate method can be adopted. Specifically, the fixed end stretching may be performed, or the free end stretching may be performed. The stretching method may be dry or wet. The stretching of the thermoplastic resin substrate may be performed in one stage, or may be performed in a plurality of stages. When the stretching is performed in a plurality of stages, the stretching ratio is the product of the stretching ratios of the respective stages.
E-1-2 coating liquid
As described above, the coating liquid contains a halide and a PVA-based resin. Typically, the coating liquid is a solution obtained by dissolving the halide and the PVA-based resin in a solvent. Examples of the solvent include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, various glycols, polyhydric alcohols such as trimethylolpropane, and amines such as ethylenediamine and diethylenetriamine. These may be used alone or in combination of two or more. Among these, water is preferable. The concentration of the PVA based resin in the solution is preferably 3 to 20 parts by weight based on 100 parts by weight of the solvent. With such a resin concentration, a uniform coating film can be formed which adheres closely to the thermoplastic resin substrate. The content of the halide in the coating liquid is preferably 5 to 20 parts by weight based on 100 parts by weight of the PVA-based resin. By incorporating a halide into the coating liquid (as a result, the PVA-based resin layer), when the PVA-based resin layer is immersed in a liquid, disturbance of the orientation of the polyvinyl alcohol molecules and reduction in the orientation can be suppressed as compared with the case where the PVA-based resin layer does not contain a halide. This can improve the optical properties of the polarizing film obtained through a treatment step of immersing the laminate in a liquid, such as dyeing treatment and underwater stretching treatment.
Additives may be compounded into the coating liquid. Examples of the additive include a plasticizer and a surfactant. Examples of the plasticizer include polyhydric alcohols such as ethylene glycol and glycerin. Examples of the surfactant include nonionic surfactants. These can be used for the purpose of further improving the uniformity, dyeability and stretchability of the PVA-based resin layer obtained.
The PVA-based resin is as described in the above item B.
The average polymerization degree of the PVA-based resin can be appropriately selected according to the purpose. The average polymerization degree is usually 1000 to 10000, preferably 1200 to 4500, and more preferably 1500 to 4300. The average polymerization degree can be determined in accordance with JIS K6726-.
As the halide, any and suitable halide can be used. For example, iodide and sodium chloride may be cited. As the iodide, for example, potassium iodide, sodium iodide and lithium iodide are cited. Among these, potassium iodide is preferable.
The amount of the halide in the coating liquid is preferably 5 to 20 parts by weight based on 100 parts by weight of the PVA-based resin, and more preferably 10 to 15 parts by weight based on 100 parts by weight of the PVA-based resin. When the amount of the halide exceeds 20 parts by weight based on 100 parts by weight of the PVA-based resin, the halide may bleed out, and the finally obtained polarizing film may become cloudy.
In general, since the PVA-based resin layer is stretched, the orientation of polyvinyl alcohol molecules in the PVA-based resin is high, and when the stretched PVA-based resin layer is immersed in a liquid containing water, the orientation of polyvinyl alcohol molecules may be disturbed, and the orientation may be lowered. In particular, when a laminate of a thermoplastic resin and a PVA-based resin layer is stretched in an aqueous boric acid solution, the orientation degree tends to be remarkably decreased when the laminate is stretched in an aqueous boric acid solution at a relatively high temperature in order to stabilize the stretching of the thermoplastic resin. For example, while stretching of a PVA film monomer in an aqueous boric acid solution is generally performed at 60 ℃, stretching of a laminate of a-PET (thermoplastic resin substrate) and a PVA-based resin layer is performed at a high temperature of about 70 ℃, and in this case, the orientation of PVA at the initial stage of stretching may be reduced in a stage before it is improved by underwater stretching. On the other hand, by producing a laminate of a PVA-based resin layer containing a halide and a thermoplastic resin substrate and stretching the laminate at a high temperature in air (auxiliary stretching) before stretching the laminate in an aqueous boric acid solution, crystallization of the PVA-based resin in the PVA-based resin layer of the laminate after the auxiliary stretching can be promoted. As a result, in the case where the PVA-based resin layer is immersed in a liquid, disturbance of the orientation of the polyvinyl alcohol molecules and reduction of the orientation can be suppressed as compared with the case where the PVA-based resin layer does not contain a halide. This can improve the optical properties of the polarizing film obtained through a treatment step of immersing the laminate in a liquid, such as dyeing treatment and underwater stretching treatment.
E-2. auxiliary stretching treatment in air
In particular, in order to obtain high optical characteristics, a two-stage stretching method in which dry stretching (auxiliary stretching) and stretching in an aqueous boric acid solution are combined is selected. By introducing the auxiliary stretching as in the two-stage stretching, the thermoplastic resin substrate can be stretched while suppressing crystallization, the problem of the reduction in stretchability due to excessive crystallization of the thermoplastic resin substrate in the subsequent stretching in an aqueous boric acid solution can be solved, and the laminate can be stretched to a higher magnification. Conventionally, when a PVA-based resin is coated on a thermoplastic resin substrate, in order to suppress the influence of the glass transition temperature of the thermoplastic resin substrate, it is necessary to lower the coating temperature as compared with the case of coating the PVA-based resin on a metal drum, and as a result, there is a possibility that crystallization of the PVA-based resin becomes relatively low and sufficient optical characteristics cannot be obtained. In contrast, by introducing the auxiliary stretching, even when the PVA-based resin is applied to the thermoplastic resin, the crystallinity of the PVA-based resin can be improved, and high optical characteristics can be realized. Further, by improving the orientation of the PVA-based resin in advance, when the PVA-based resin is immersed in water in a subsequent dyeing step or stretching step, problems such as a decrease in the orientation and dissolution of the PVA-based resin can be prevented, and high optical characteristics can be realized.
The stretching method of the air-assisted stretching may be fixed-end stretching (for example, a method of stretching using a tenter) or free-end stretching (for example, a method of stretching using a tenter)A method of uniaxially stretching the laminate by passing it between rollers having different peripheral speeds), free end stretching can be positively employed in order to obtain high optical characteristics. In one embodiment, the in-flight stretching process includes a heated roller stretching step of stretching the laminate by a circumferential speed difference between heated rollers while conveying the laminate in a longitudinal direction thereof. Typically, the in-air stretching process includes a zone stretching process and a heated roll stretching process. The order of the zone stretching step and the heated roller stretching step is not limited, and the zone stretching step may be performed first, or the heated roller stretching step may be performed first. The segment stretching process may be omitted. In one embodiment, the zone stretching step and the heated roller stretching step are performed in this order. In addition, in another embodiment, in the tenter stretching machine, stretching is performed by holding the film end portions and expanding the distance between the tenters along the moving direction (expansion of the distance between the tenters becomes the stretching magnification). At this time, the distance of the tenter in the width direction (direction perpendicular to the moving direction) is set to be arbitrarily close. It is preferable to set the stretching ratio in the moving direction so as to be closer to the free end of the sheet. In the case of free end stretching, the shrinkage in the width direction (1/stretching ratio)1/2To calculate.
The aerial auxiliary stretching may be performed in one stage or may be performed in a plurality of stages. When the stretching is performed in a plurality of stages, the stretching ratio is the product of the stretching ratios of the respective stages. The stretching direction in the in-air auxiliary stretching is preferably substantially the same as the stretching direction in the underwater stretching.
The stretching ratio in the air-assisted stretching is preferably 2.0 to 3.5 times. The maximum stretching ratio in the case of combining the in-air auxiliary stretching and the underwater stretching is preferably 5.0 times or more, more preferably 5.5 times or more, and still more preferably 6.0 times or more, with respect to the original length of the laminate. In the present specification, the "maximum stretching ratio" refers to the stretching ratio immediately before the laminate breaks, and refers to the stretching ratio at which the laminate is separately observed to break, and is a value lower than this value by 0.2.
The stretching temperature of the in-air auxiliary stretching may be set to an arbitrary and appropriate value depending on the material for forming the thermoplastic resin base material, the stretching method, and the like. The stretching temperature is preferably not less than the glass transition temperature (Tg) of the thermoplastic resin substrate, more preferably not less than the glass transition temperature (Tg) +10 ℃ of the thermoplastic resin substrate, and particularly preferably not less than Tg +15 ℃. On the other hand, the upper limit of the stretching temperature is preferably 170 ℃. By stretching at such a temperature, rapid progress of crystallization of the PVA-based resin can be suppressed, and defects caused by the crystallization (for example, inhibition of orientation of the PVA-based resin layer by stretching) can be suppressed.
E-3. insolubilization
If necessary, after the in-air auxiliary stretching treatment, the insolubilization treatment is performed before the stretching treatment in water and the dyeing treatment. Typically, the insolubilization treatment is performed by immersing the PVA-based resin layer in an aqueous boric acid solution. By performing insolubilization treatment, water resistance can be imparted to the PVA-based resin layer, and the PVA can be prevented from being degraded in orientation when immersed in water. The concentration of the aqueous boric acid solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water. The liquid temperature of the insolubilization bath (aqueous boric acid solution) is preferably 20 to 50 ℃.
E-4 dyeing treatment
Typically, the dyeing treatment is performed by dyeing the PVA-based resin layer with iodine. Specifically, iodine is adsorbed to the PVA-based resin layer. Examples of the adsorption method include a method in which the PVA-based resin layer (laminate) is immersed in a dyeing solution containing iodine, a method in which the dyeing solution is applied to the PVA-based resin layer, and a method in which the dyeing solution is sprayed to the PVA-based resin layer. A method of immersing the laminate in a dyeing solution (dyeing bath) is preferred. This is because iodine can be adsorbed well.
The staining solution is preferably an aqueous iodine solution. The amount of iodine blended is preferably 0.05 to 0.5 parts by weight based on 100 parts by weight of water. In order to increase the solubility of iodine in water, it is preferable to blend an iodide into the aqueous iodine solution. Examples of the iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and titanium iodide. Among these, potassium iodide is preferable. The amount of the iodide is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight, based on 100 parts by weight of water. In order to suppress dissolution of the PVA-based resin, the dyeing liquid is preferably dyed at a liquid temperature of 20 to 50 ℃. When the PVA-based resin layer is immersed in the dyeing liquid, the immersion time is preferably 5 seconds to 5 minutes, and more preferably 30 seconds to 90 seconds, in order to ensure the transmittance of the PVA-based resin layer.
The dyeing conditions (concentration, liquid temperature, and immersion time) may be set so that the monomer transmittance of the finally obtained polarizing film is 43.5% or more and the polarization degree is 99.940% or more. As such dyeing conditions, preferred are: an iodine aqueous solution is used as a staining solution, and the content ratio of iodine to potassium iodide in the iodine aqueous solution is set to 1: 5-1: 20. The content ratio of iodine to potassium iodide in the iodine aqueous solution is preferably 1: 5-1: 10. This makes it possible to obtain a polarizing film having the above-described optical characteristics.
When the dyeing treatment is continuously performed after the treatment (typically, insolubilization treatment) of immersing the laminate in a treatment bath containing boric acid, the boric acid contained in the treatment bath is mixed into the dyeing bath, and the concentration of the boric acid in the dyeing bath changes with time, and as a result, the dyeing property may be unstable. In order to suppress the instability of dyeing properties as described above, the upper limit of the boric acid concentration in the dyeing bath is adjusted so as to be preferably 4 parts by weight, more preferably 2 parts by weight, based on 100 parts by weight of water. On the other hand, the lower limit of the boric acid concentration of the dyeing bath is preferably 0.1 part by weight, more preferably 0.2 part by weight, and further preferably 0.5 part by weight, based on 100 parts by weight of water. In one embodiment, the dyeing treatment is performed using a dyeing bath previously compounded with boric acid. This can reduce the rate of change in the boric acid concentration when the boric acid in the treatment bath is mixed into the dyeing bath. The compounding amount of boric acid previously compounded into the dyeing bath (i.e., the content of boric acid not originating from the above-mentioned treatment bath) is preferably 0.1 to 2 parts by weight, more preferably 0.5 to 1.5 parts by weight, relative to 100 parts by weight of water.
E-5. Cross-linking treatment
If necessary, a crosslinking treatment is performed after the dyeing treatment and before the stretching treatment in water. Typically, the crosslinking treatment is performed by immersing the PVA-based resin layer in an aqueous boric acid solution. By performing the crosslinking treatment, water resistance can be imparted to the PVA-based resin layer, and the PVA can be prevented from being degraded in orientation when immersed in high-temperature water during subsequent underwater stretching. The concentration of the aqueous boric acid solution is preferably 1 to 5 parts by weight with respect to 100 parts by weight of water. In addition, when the crosslinking treatment is performed after the dyeing treatment, it is preferable to further contain an iodide. By adding an iodide, elution of iodine adsorbed to the PVA-based resin layer can be suppressed. The amount of the iodide is preferably 1 to 5 parts by weight based on 100 parts by weight of water. Specific examples of the iodide are as described above. The liquid temperature of the crosslinking bath (aqueous boric acid solution) is preferably 20 ℃ to 50 ℃.
E-6 stretching treatment in water
The underwater stretching treatment is performed by immersing the laminate in a stretching bath. By the underwater stretching treatment, the thermoplastic resin substrate and the PVA resin layer can be stretched at a temperature lower than the glass transition temperature (typically, about 80 ℃) of the PVA resin layer, and the PVA resin layer can be stretched to a high magnification while suppressing crystallization thereof. As a result, a polarizing film having excellent optical characteristics can be produced.
The laminate may be stretched by any suitable method. Specifically, the stretching may be performed at a fixed end or at a free end (for example, a method of uniaxially stretching the laminate by passing the laminate between rollers having different peripheral speeds). Free end stretching is preferably chosen. The stretching of the laminate may be performed in one stage, or may be performed in a plurality of stages. When the stretching is performed in a plurality of stages, the stretching ratio (maximum stretching ratio) of the laminate described later is the product of the stretching ratios in the respective stages.
The underwater stretching is preferably performed by immersing the laminate in an aqueous boric acid solution (stretching in an aqueous boric acid solution). By using an aqueous boric acid solution as a stretching bath, rigidity capable of withstanding the tension applied during stretching and water resistance not dissolving in water can be imparted to the PVA-based resin layer. Specifically, boric acid can be crosslinked with the PVA-based resin by generating a tetrahydroxyborate anion in an aqueous solution and by means of a hydrogen bond. As a result, rigidity and water resistance can be imparted to the PVA-based resin layer, and the PVA-based resin layer can be stretched well, whereby a polarizing film having excellent optical characteristics can be produced.
The aqueous boric acid solution is preferably obtained by dissolving boric acid and/or a borate in water as a solvent. The boric acid concentration is preferably 1 to 10 parts by weight, more preferably 2.5 to 6 parts by weight, and particularly preferably 3 to 5 parts by weight, based on 100 parts by weight of water. By setting the boric acid concentration to 1 part by weight or more, the dissolution of the PVA-based resin layer can be efficiently suppressed, and a polarizing film with higher characteristics can be produced. In addition to boric acid or a borate, an aqueous solution obtained by dissolving a boron compound such as borax, glyoxal, glutaraldehyde, or the like in a solvent may be used.
The iodide is preferably compounded into the above-mentioned stretching bath (aqueous boric acid solution). By adding an iodide, elution of iodine adsorbed to the PVA-based resin layer can be suppressed. Specific examples of the iodide are as described above. The concentration of the iodide is preferably 0.05 to 15 parts by weight, more preferably 0.5 to 8 parts by weight, based on 100 parts by weight of water.
The drawing temperature (liquid temperature of the drawing bath) is preferably 40 to 85 ℃ and more preferably 60 to 75 ℃. At such a temperature, the PVA-based resin layer can be stretched to a high magnification while suppressing dissolution thereof. Specifically, as described above, the glass transition temperature (Tg) of the thermoplastic resin substrate is preferably 60 ℃ or higher based on the relationship with the formation of the PVA-based resin layer. In this case, if the stretching temperature is less than 40 ℃, there is a possibility that the thermoplastic resin substrate cannot be satisfactorily stretched even when plasticization of the thermoplastic resin substrate by water is considered. On the other hand, as the temperature of the stretching bath is higher, the solubility of the PVA-based resin layer is higher, and thus excellent optical characteristics may not be obtained. The immersion time of the laminate in the stretching bath is preferably 15 seconds to 5 minutes.
The stretching ratio by underwater stretching is preferably 1.5 times or more, more preferably 3.0 times or more. The total stretch ratio of the laminate is preferably 5.0 times or more, and more preferably 5.5 times or more, the original length of the laminate. By realizing such a high stretching ratio, a polarizing film having extremely excellent optical characteristics can be produced. Such a high stretch ratio can be achieved by using an underwater stretching method (stretching in an aqueous boric acid solution).
E-7 drying shrinkage treatment
The drying shrinkage treatment may be performed by heating the entire zone to heat the zone, or may be performed by heating the transport roller (using a so-called hot roller) (hot roller drying method). Both are preferably used. By drying the laminate using a heating roller, the laminate can be efficiently prevented from being warped by heating, and a polarizing film having excellent appearance can be produced. Specifically, by drying the laminate in a state where the laminate is along the heating roller, the crystallization of the thermoplastic resin substrate can be efficiently promoted to increase the crystallinity, and the crystallinity of the thermoplastic resin substrate can be favorably increased even at a low drying temperature. As a result, the thermoplastic resin substrate has increased rigidity and is resistant to shrinkage of the PVA-based resin layer due to drying, and warpage is suppressed. Further, since the laminate can be dried while maintaining a flat state by using the heating roller, not only warpage but also wrinkles can be suppressed. At this time, the laminate is shrunk in the width direction by the drying shrinkage treatment, and the optical properties can be improved. This is because: the orientation of PVA and PVA/iodine complex can be efficiently improved. The shrinkage in the width direction of the laminate by the drying shrinkage treatment is preferably 2% to 10%, more preferably 2% to 8%, and particularly preferably 4% to 6%. By using the heating roller, the laminate can be continuously shrunk in the width direction while being conveyed, and high productivity can be achieved. Further, the optical characteristics can be improved by shrinking the laminate in the width direction by the drying shrinkage treatment.
Fig. 2 is a schematic diagram showing an example of the drying shrinkage process. In the drying shrinkage process, the laminate 200 is dried while being conveyed by the conveying rollers R1 to R6 and the guide rollers G1 to G4 heated to a predetermined temperature. In the illustrated example, the conveying rollers R1 to R6 are disposed so as to alternately and continuously heat the surface of the PVA resin layer and the surface of the thermoplastic resin substrate, but the conveying rollers R1 to R6 may be disposed so as to continuously heat only one surface (for example, the surface of the thermoplastic resin substrate) of the laminate 200.
The drying conditions can be controlled by adjusting the heating temperature of the conveying roller (temperature of the heating roller), the number of heating rollers, the time of contact with the heating roller, and the like. The temperature of the heating roller is preferably 60 to 120 ℃, more preferably 65 to 100 ℃, and particularly preferably 70 to 80 ℃. The crystallinity of the thermoplastic resin can be favorably increased, warpage can be favorably suppressed, and an optical laminate having extremely excellent durability can be produced. The temperature of the heating roller can be measured by a contact thermometer. In the example shown in the figure, 6 conveying rollers are provided, but there is no particular limitation as long as there are a plurality of conveying rollers. The number of the conveying rollers is usually 2 to 40, preferably 4 to 30. The contact time (total contact time) between the laminate and the heating roller is preferably 1 to 300 seconds, more preferably 1 to 20 seconds, and still more preferably 1 to 10 seconds.
The heating roller may be installed in a heating furnace (for example, an oven) or may be installed in a general production line (room temperature environment). Preferably, the heating furnace is provided with an air blowing means. By using drying by the heating roller and hot air drying in combination, a rapid temperature change between the heating rollers can be suppressed, and the shrinkage in the width direction can be easily controlled. The temperature of the hot air drying is preferably 30 to 100 ℃. The hot air drying time is preferably 1 second to 300 seconds. The wind speed of the hot wind is preferably about 10m/s to 30 m/s. The wind speed is the wind speed in the heating furnace, and can be measured by a digital wind speed meter of a miniature blade type.
E-8 other treatment
It is preferable to perform the washing treatment after the stretching treatment in water and before the drying shrinkage treatment. Typically, the cleaning treatment is performed by immersing the PVA-based resin layer in an aqueous potassium iodide solution.
E-9 preparation of polarizing plate
In this manner, the PVA-based resin layer forms a polarizing film, and a polarizing film/thermoplastic resin substrate laminate can be produced. In one embodiment, the polarizing film/thermoplastic resin substrate laminate is directly used as a polarizing plate. In this case, the thermoplastic resin substrate can function as a protective film. In another embodiment, a protective film is attached to the polarizing film surface of the laminate of the polarizing film/thermoplastic resin substrate, and a polarizing plate having a structure of protective film/polarizing film/thermoplastic resin substrate can be obtained. In this case, the thermoplastic resin substrate can also function as a protective film (one protective film). In another embodiment, a protective film is attached to the surface of the polarizing film/thermoplastic resin substrate laminate, and then the thermoplastic resin substrate is peeled off, thereby obtaining a polarizing plate having a protective film/polarizing film structure. In another embodiment, a polarizing plate having a structure of a protective film/a polarizing film/another protective film can be obtained by attaching a protective film to the surface of a polarizing film/thermoplastic resin substrate laminate, peeling the thermoplastic resin substrate, and attaching another protective film to the peeled surface. For example, an arbitrary and appropriate adhesive can be used for attaching the polarizing film and the protective film. Specific examples of the adhesive include an active energy ray-curable adhesive (typically, an ultraviolet-curable adhesive) and an aqueous adhesive.
F. Image display device
The polarizing plate according to the embodiment of the present invention is applicable to an image display device. Accordingly, the present invention also includes an image display device. The image display device of the present invention includes a display unit and a polarizing plate disposed on a visual recognition side of the display unit. Typical examples of the image display device include a liquid crystal display device, an organic Electroluminescence (EL) display device, and a quantum dot display device. The polarizing plate according to the embodiment of the present invention has a significant effect in a severe heating environment, and therefore, the image display device is preferably an image display device that can be used in a severe heating environment. A typical example of such an image display device is a vehicle-mounted image display device. Since the image display device has a structure known in the art, detailed description thereof is omitted.
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. Unless otherwise specified, "parts" and "%" in examples and comparative examples are based on weight.
(1) Thickness of
The measurement was carried out using an interferometric film thickness meter (available under the name "MCPD-3000" available from Otsuka electronics Co., Ltd.).
(2) Variation of monomer transmittance and polarization degree in high temperature environment
With respect to the samples (glass plate/adhesive/protective film/polarizing film/protective film/adhesive/glass plate) corresponding to the image display devices obtained in examples and comparative examples, a monomer transmittance Ts was measured using an ultraviolet-visible spectrophotometer (Otsuka Denshi, LPF-200)0Parallel transmittance Tp0And orthogonal transmittance Tc0. These Ts0、Tp0And Tc0The Y value is measured with a 2-degree visual field (C light source) of JIS Z8701 and corrected for visual sensitivity. The measurement wavelength is 380nm to 780 nm.
Tp is obtained by the following formula0And Tc0Determining the degree of polarization P0。
Degree of polarization P0(％)＝{(TP0-Tc0)/(TP0+Tc0)}1/2×100
Next, the sample corresponding to the image display device was left to stand in a hot air oven at a temperature of 100 ℃ for 60 hours to heat the sample, and the monomer transmittance Ts after heating was measured in the same manner as described above60And P60The monomer transmittance change Δ Ts and the polarization degree change Δ P before and after heating were obtained from the following equations.
ΔTs(％)＝Ts60-Ts0
ΔP(％)＝P60-P0
Example 1-1 to example 1-6
1. Production of polarizing film
As the thermoplastic resin substrate, an amorphous ethylene terephthalate isophthalate copolymer film (thickness: 100 μm) having a long length and a water absorption of 0.75% and a Tg of about 75 ℃ was used. One surface of the resin substrate was subjected to corona treatment.
To 100 parts by weight of a PVA-based resin obtained by mixing polyvinyl alcohol (having a polymerization degree of 4200 and a saponification degree of 99.2 mol%) and acetoacetyl-modified PVA (trade name "GOHSEFIMER Z410" manufactured by Nippon synthetic chemical industries, Ltd.) at a ratio of 9:1, 13 parts by weight of potassium iodide was added to prepare an aqueous PVA solution (coating solution).
The PVA aqueous solution was applied to the corona-treated surface of the resin substrate, and dried at 60 ℃.
The resultant laminate was uniaxially stretched to 2.4 times along the longitudinal (longitudinal) free end in an oven at 130 ℃ between rolls having different peripheral speeds (in-air auxiliary stretching treatment).
Next, the laminate was immersed in an insolubilization bath (an aqueous boric acid solution prepared by adding 4 parts by weight of boric acid to 100 parts by weight of water) at a liquid temperature of 40 ℃ for 30 seconds (insolubilization treatment).
Next, the polarizing film obtained finally was immersed in a dyeing bath (aqueous iodine solution prepared by mixing 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 ℃ for 60 seconds while adjusting the concentration so that the monomer transmittance (Ts) of the polarizing film obtained finally became 41.9% to 42.8% (dyeing treatment).
Next, the substrate was immersed in a crosslinking bath (aqueous boric acid solution prepared by adding 3 parts by weight of potassium iodide and 5 parts by weight of boric acid to 100 parts by weight of water) at a liquid temperature of 40 ℃ for 30 seconds (crosslinking treatment).
Thereafter, the laminate was uniaxially stretched in the longitudinal direction (longitudinal direction) at a total stretching ratio of 5.5 times between rolls having different peripheral speeds while being immersed in an aqueous boric acid solution (boric acid concentration of 4.0 wt%) having a liquid temperature of 70 ℃.
Thereafter, the laminate was immersed in a cleaning bath (aqueous solution containing 4 parts by weight of potassium iodide per 100 parts by weight of water) at a liquid temperature of 20 ℃.
Thereafter, the sheet was brought into contact with a SUS heating roller having a surface temperature of 75 ℃ for about 2 seconds while being dried in an oven maintained at 90 ℃ (drying shrinkage treatment). The shrinkage in the width direction of the laminate was 5.2% by the drying shrinkage treatment.
In this manner, a polarizing film having a thickness of 5 μm was formed on the resin substrate. The same procedure was repeated except that the concentration of the dyeing bath was changed as described above, thereby producing 6 polarizing films in total having different monomer transmittances.
2. Manufacture of polarizing plate
A cycloolefin film (ZF-14 manufactured by ZEON Co., Ltd., Japan) having a water vapor permeability of 10 g/(m) was adhered as a protective film A on the surface (the surface opposite to the resin substrate) of each of the polarizing films obtained as described above with an ultraviolet-curable adhesive to form a protective film A224 h)). Specifically, the curable adhesive was applied so that the total thickness thereof became 1.0 μm, and was applied using a roll mill. Thereafter, the adhesive is cured by irradiating UV light from the protective film side. Next, the resin substrate was peeled off, and a cycloolefin film (ZF-12 manufactured by ZEON Co., Ltd., Japan) having a thickness of 23 μm and a moisture permeability of 10 g/(m) was formed as a protective film B224h)) was adhered to the release surface with an ultraviolet-curable adhesive and cured to produce a polarizing plate having a structure of protective film a/polarizing film/protective film B.
3. Production of sample for image display device
The polarizing plate obtained as described above was cut into a size of 45cm × 40cm so that the absorption axis of the polarizer became a long side, and a glass plate was attached to the surface on the side of the protective film B via an adhesive (an acrylic-free adhesive having a thickness of 200 μm, manufactured by ritonac electric corporation, under the trade name "luciac CS 9868"), and further, a glass plate was attached to the surface on the side of the transparent film a via an acrylic adhesive layer having a thickness of 20 μm, to prepare an image display device-corresponding sample. The obtained image display device-corresponding sample was subjected to the evaluation in (2) above. The results are shown in Table 1.
Example 2-1 to example 2-2
For conditioning dyeing bathsTwo polarizing films having different monomer transmittances were prepared at different concentrations, and a cellulose triacetate film (manufactured by Konika-Menten, Inc.; "KC 2 CT"; having a moisture permeability of 1200 g/(m) was used as the protective film B using the polarizing films and having a thickness of 20 μm224h)), a sample for an image display device was produced in the same manner as in example 1 except for the above. The obtained image display device-corresponding sample was subjected to the same evaluation as in example 1. The results are shown in Table 1.
Comparative examples 1-1 to 1-7
A total of 7 polarizing films having different monomer transmittances were produced in the same manner as in example 1, except that potassium iodide was not used in the coating liquid and the concentration of the dyeing bath was adjusted to change the monomer transmittance. A sample corresponding to an image display device was produced in the same manner as in example 1, except that these polarizing films were used. The obtained image display device-corresponding sample was subjected to the same evaluation as in example 1. The results are shown in Table 1.
Comparative example 2-1 to comparative example 2-2
Two polarizing films having different monomer transmittances were produced in the same manner as in example 1, except that the concentration of the dyeing bath was adjusted to change the monomer transmittance. A sample corresponding to an image display device was produced in the same manner as in example 1, except that these polarizing films were used. The obtained image display device-corresponding sample was subjected to the same evaluation as in example 1. The results are shown in Table 1.
[ reference example 1]
1. Fabrication of polarizing elements
A polyvinyl alcohol film having an average polymerization degree of 2,400, a saponification degree of 99.9 mol% and a thickness of 30 μm was prepared. The polyvinyl alcohol film was swollen by immersing it in a swelling bath (water bath) at 20 ℃ for 30 seconds while the peripheral speed ratio was varied, and stretched 2.4 times in the transport direction (swelling step), and then, while immersing it in a dyeing bath (aqueous solution having an iodine concentration of 0.03 wt% and a potassium iodide concentration of 0.3 wt%) at 30 ℃ for 45 seconds to dye it, the original polyvinyl alcohol film (polyvinyl alcohol film which was not stretched at all in the transport direction) was stretched 3.7 times in the transport direction (dyeing step). Next, the dyed polyvinyl alcohol film was immersed in a crosslinking bath (aqueous solution having a boric acid concentration of 3.0 wt% and a potassium iodide concentration of 3.0 wt%) at 40 ℃ for 20 seconds, and stretched 4.2 times in the transport direction based on the original polyvinyl alcohol film (crosslinking step). The obtained polyvinyl alcohol film was immersed in a stretching bath (an aqueous solution having a boric acid concentration of 4.0 wt% and a potassium iodide concentration of 5.0 wt%) at 64.5 ℃ for 50 seconds, stretched 6.0 times in the transport direction based on the original polyvinyl alcohol film (stretching step), and then immersed in a cleaning bath (an aqueous solution having a potassium iodide concentration of 3.0 wt%) at 20 ℃ for 5 seconds (cleaning step). The washed polyvinyl alcohol film was dried at 30 ℃ for 2 minutes to produce a polarizing plate.
2. Manufacture of polarizing plate
As the adhesive, an aqueous solution containing a polyvinyl alcohol resin having an acetoacetyl group (average polymerization degree of 1,200, saponification degree of 98.5 mol%, acetoacetylation degree of 5 mol%) and methylolmelamine at a weight ratio of 3:1 was used. Using this adhesive, a cycloolefin film (ZT-12 manufactured by ZEON Co., Ltd., Japan) having a moisture permeability of 10 g/(m) was adhered as a transparent protective film C on one surface of the obtained polarizing plate by a roll coater224h)), a cellulose triacetate film having a hard coat layer and a thickness of 40 μm (moisture permeability of 340 g/(m) was attached as a protective film D to the other side of the polarizer224 hours), and a product of Konika Mentada corporation under the trade name "KC 4 UYW"), and then dried by heating in an oven (at 60 ℃ for 10 minutes), to prepare a polarizing plate having a structure of a protective film C/polarizer/protective film D.
3. Production of sample for image display device
The polarizing plate obtained as described above was cut into a size of 45cm × 40cm so that the absorption axis of the polarizer became a long side, and a glass plate was attached to the surface on the side of the protective film D via an adhesive (an acrylic-free adhesive having a thickness of 200 μm, manufactured by ritonac electric corporation, under the trade name "luciac CS 9868"), and further, a glass plate was attached to the surface on the side of the transparent film C via an acrylic adhesive layer having a thickness of 20 μm, to prepare an image display device-corresponding sample. The obtained image display device-corresponding sample was subjected to the evaluation in (2) above. The results are shown in Table 1.
[ Table 1]
As is clear from table 1: the Δ P and Δ Ts of the samples (substantially polarizing plates) corresponding to the image display device of the examples of the present invention were both significantly smaller than those of the comparative examples, and the changes in optical characteristics were also small in a severe heating environment, and the durability was also excellent. That is, in a polarizing plate including a thin polarizing film, by using a specific polarizing film obtained by the method described in the present specification, durability under a severe heating environment can be significantly improved. Further, when examples 1-5 and 1-6 in which the polarizing films had the same degree of monomer transmittance were compared with examples 2-1 and 2-2, it was found that: by using a COP having a small moisture permeability as the protective film, the durability is further improved. Further, as is clear from reference example 1: the problem of durability in such a severe heating environment is a problem specific to a polarizing plate including a thin polarizing film.
Industrial applicability
The polarizing plate of the present invention is suitably used for image display devices such as liquid crystal display devices, organic EL display devices, and quantum dot display devices, and is particularly suitably used for image display devices that are used in severe heating environments (for example, in-vehicle image display devices).
Description of the reference numerals
11 polarizing film
12 protective film
13 protective film
100 polarizing plate
Claims (7)
1. A polarizing plate comprising a polarizing film having a thickness of 8 μm or less and protective films disposed on both sides of the polarizing film,
a change amount [ Delta ] P of polarization degree represented by the following formula is-1.0% to 0.0% after the glass plate is left at 100 ℃ for 60 hours with both surfaces thereof bonded with the adhesive layer,
ΔP(％)＝P60-P0
here, P0For degree of polarization before heating, P60The polarization degree after heating for 60 hours.
2. The polarizing plate according to claim 1, wherein a change in monomer transmittance Δ Ts represented by the following formula after standing at 100 ℃ for 60 hours in a state where glass plates are bonded on both sides with an adhesive layer interposed therebetween is 0.0 to 1.5%,
ΔTs(％)＝Ts60-Ts0
here, Ts0For the monomer transmittance before heating, Ts60The monomer transmittance after heating for 60 hours.
3. The polarizing plate of claim 2, wherein the monomer transmittance Ts is041.8 to 43.0 percent.
4. The polarizing plate according to any one of claims 1 to 3, wherein the protective film has a moisture permeability of 200g/m224h or less.
5. An image display device comprising a display unit and the polarizing plate according to any one of claims 1 to 4 disposed on a visual recognition side of the display unit.
6. The image display device according to claim 5, which is configured for an in-vehicle use.
7. A method for manufacturing the polarizing plate according to any one of claims 1 to 4, comprising:
forming a polyvinyl alcohol resin layer containing a polyvinyl alcohol resin and containing an iodide or sodium chloride on one side of a long thermoplastic resin base material to form a laminate;
subjecting the laminate to an in-air auxiliary stretching treatment, a dyeing treatment, an in-water stretching treatment, and a drying shrinkage treatment of shrinking by 2% or more in the width direction by heating while conveying the laminate in the longitudinal direction, in this order, thereby producing a polarizing film from the polyvinyl alcohol resin layer; and
protective films are laminated on both sides of the polarizing film.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018178258 | 2018-09-25 | ||
| JP2018-178258 | 2018-09-25 | ||
| PCT/JP2019/020712 WO2020066125A1 (en) | 2018-09-25 | 2019-05-24 | Polarizing plate and manufacturing method therefor and image display device including polarizing plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112789528A true CN112789528A (en) | 2021-05-11 |
| CN112789528B CN112789528B (en) | 2023-08-29 |
Family
ID=69949954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980063096.7A Active CN112789528B (en) | 2018-09-25 | 2019-05-24 | Polarizing plate, method for manufacturing the same, and image display device including the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP7376494B2 (en) |
| KR (1) | KR20210063325A (en) |
| CN (1) | CN112789528B (en) |
| WO (1) | WO2020066125A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021167948A (en) * | 2020-04-08 | 2021-10-21 | 日東電工株式会社 | Polarization film |
| JP2021170044A (en) * | 2020-04-14 | 2021-10-28 | 日東電工株式会社 | Polarization membrane and polarization film |
| JP7240364B2 (en) * | 2020-08-27 | 2023-03-15 | 日東電工株式会社 | Polarizing plate, manufacturing method thereof, and polarizing plate with retardation layer and image display device using the polarizing plate |
| JP2022112802A (en) * | 2021-01-22 | 2022-08-03 | 日東電工株式会社 | Method of manufacturing polarizing plate, method of manufacturing image display device, and method of adjusting transmittance of polarizing film |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004020636A (en) * | 2002-06-12 | 2004-01-22 | Kuraray Co Ltd | Method of manufacturing polarizing film |
| JP2012058383A (en) * | 2010-09-07 | 2012-03-22 | Nitto Denko Corp | Method for producing thin polarizing film |
| WO2013047884A1 (en) * | 2011-09-27 | 2013-04-04 | 住友化学株式会社 | Polarizing plate and method for manufacturing same |
| CN103389535A (en) * | 2012-05-11 | 2013-11-13 | 日东电工株式会社 | Method for manufacturing polarizing film, polarizing film, polarizing plate and image display device |
| JP2015191224A (en) * | 2014-03-31 | 2015-11-02 | 日東電工株式会社 | Stretched laminate manufacturing method, stretched laminate, polarizing film manufacturing method, and polarizing film |
| CN106873068A (en) * | 2015-11-20 | 2017-06-20 | 住友化学株式会社 | Polarization plates and image display device |
| WO2017130656A1 (en) * | 2016-01-29 | 2017-08-03 | 住友化学株式会社 | Production method for polarizing plates |
| JPWO2017047408A1 (en) * | 2015-09-18 | 2018-07-05 | 住友化学株式会社 | Composite polarizing plate and liquid crystal panel using the same |
| CN111095051A (en) * | 2017-09-13 | 2020-05-01 | 日东电工株式会社 | Polarizing plate, polarizing plate roll, and method for producing polarizing film |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4430096A1 (en) * | 1994-08-25 | 1996-02-29 | Agfa Gevaert Ag | Thermostable polarizers |
| JP3783971B2 (en) * | 1995-10-11 | 2006-06-07 | 日東電工株式会社 | Optical film and liquid crystal display device |
| JP5593551B2 (en) | 2009-01-30 | 2014-09-24 | エルジー・ケム・リミテッド | POLARIZING ELEMENT, POLARIZING PLATE, IMAGE DISPLAY DEVICE, AND POLARIZING ELEMENT MANUFACTURING METHOD |
| TWI656011B (en) | 2014-03-14 | 2019-04-11 | 日東電工股份有限公司 | Laminated body, extended laminated body, manufacturing method of extended laminated body, manufacturing method of optical film laminated body including polarizing film using these, and polarizing film |
| CN105247395B (en) * | 2014-03-26 | 2018-09-14 | Lg化学株式会社 | The method of polarization element of the manufacture containing local bleached area, the method for manufacturing the method for polarization element roller and manufacturing monolithic polarizing element |
| CN108700700B (en) * | 2016-02-26 | 2021-01-05 | 日东电工株式会社 | Polarizer, single-sided protective polarizing film, polarizing film with adhesive layer, image display device, and continuous production method therefor |
| WO2018025717A1 (en) * | 2016-08-03 | 2018-02-08 | 住友化学株式会社 | Laminate film |
| WO2018038028A1 (en) * | 2016-08-22 | 2018-03-01 | 株式会社クラレ | Polarizing plate |
-
2019
- 2019-05-24 KR KR1020217007034A patent/KR20210063325A/en not_active Application Discontinuation
- 2019-05-24 WO PCT/JP2019/020712 patent/WO2020066125A1/en active Application Filing
- 2019-05-24 JP JP2020547953A patent/JP7376494B2/en active Active
- 2019-05-24 CN CN201980063096.7A patent/CN112789528B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004020636A (en) * | 2002-06-12 | 2004-01-22 | Kuraray Co Ltd | Method of manufacturing polarizing film |
| JP2012058383A (en) * | 2010-09-07 | 2012-03-22 | Nitto Denko Corp | Method for producing thin polarizing film |
| WO2013047884A1 (en) * | 2011-09-27 | 2013-04-04 | 住友化学株式会社 | Polarizing plate and method for manufacturing same |
| CN103389535A (en) * | 2012-05-11 | 2013-11-13 | 日东电工株式会社 | Method for manufacturing polarizing film, polarizing film, polarizing plate and image display device |
| JP2015191224A (en) * | 2014-03-31 | 2015-11-02 | 日東電工株式会社 | Stretched laminate manufacturing method, stretched laminate, polarizing film manufacturing method, and polarizing film |
| JPWO2017047408A1 (en) * | 2015-09-18 | 2018-07-05 | 住友化学株式会社 | Composite polarizing plate and liquid crystal panel using the same |
| CN106873068A (en) * | 2015-11-20 | 2017-06-20 | 住友化学株式会社 | Polarization plates and image display device |
| WO2017130656A1 (en) * | 2016-01-29 | 2017-08-03 | 住友化学株式会社 | Production method for polarizing plates |
| CN111095051A (en) * | 2017-09-13 | 2020-05-01 | 日东电工株式会社 | Polarizing plate, polarizing plate roll, and method for producing polarizing film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2020066125A1 (en) | 2021-08-30 |
| CN112789528B (en) | 2023-08-29 |
| WO2020066125A1 (en) | 2020-04-02 |
| TW202012153A (en) | 2020-04-01 |
| KR20210063325A (en) | 2021-06-01 |
| JP7376494B2 (en) | 2023-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI461759B (en) | Polarizing membrane and polarizing film | |
| TWI801599B (en) | Polarizing film and method for manufacturing polarizing film | |
| CN112789528B (en) | Polarizing plate, method for manufacturing the same, and image display device including the same | |
| CN111316142B (en) | Polarizing film, polarizing plate, and method for producing polarizing film | |
| JP2020076968A (en) | Polarizing plate with retardation layer and image display using the same | |
| JP2020064290A (en) | Polarizing plate with phase difference layer and image display device using the same | |
| JP2023116527A (en) | Polarizer, method of manufacturing the same, and optical laminate comprising the same | |
| CN111095055B (en) | Polarizing film, polarizing plate, and method for producing polarizing film | |
| CN111108417B (en) | Polarizing film, polarizing plate, and method for producing polarizing film | |
| JP2020064291A (en) | Polarizing plate with phase difference layer and image display device using the same | |
| JP2020064293A (en) | Polarizing plate with phase difference layer and image display device using the same | |
| JP7219017B2 (en) | Method for manufacturing polarizing film | |
| CN113646676A (en) | Polarizing film, polarizing plate, and method for producing polarizing film | |
| JP2020064298A (en) | Polarizing plate with phase difference layer and image display device using the same | |
| JP2020064292A (en) | Polarizing plate with phase difference layer and image display device using the same | |
| WO2023218822A1 (en) | Method for producing polarizing film | |
| WO2023218821A1 (en) | Method for producing polarizing film | |
| TWI844544B (en) | Polarizing plate and its manufacturing method, and image display device containing the polarizing plate | |
| WO2023218820A1 (en) | Method for producing polarizing film | |
| WO2022158088A1 (en) | Polarizing plate manufacturing method, image display device manufacturing method, and method for adjusting transmittance of polarizing film | |
| WO2020080173A1 (en) | Polarizing plate with phase difference layer, and image display device using this | |
| WO2020080171A1 (en) | Polarizing plate with phase difference layer, and image display device using this | |
| WO2020080172A1 (en) | Polarizing plate with phase difference layer, and image display device using this | |
| WO2020080188A1 (en) | Polarizing plate with retardation layer and image display device using same | |
| JP2023050226A (en) | Method for producing polarizing film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |