CN117581126A - Polarizing plate - Google Patents
Polarizing plate Download PDFInfo
- Publication number
- CN117581126A CN117581126A CN202280045927.XA CN202280045927A CN117581126A CN 117581126 A CN117581126 A CN 117581126A CN 202280045927 A CN202280045927 A CN 202280045927A CN 117581126 A CN117581126 A CN 117581126A
- Authority
- CN
- China
- Prior art keywords
- mass
- polarizing element
- polyvinyl alcohol
- polarizing plate
- polarizing
- 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.)
- Pending
Links
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 129
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 129
- 229920005989 resin Polymers 0.000 claims abstract description 106
- 239000011347 resin Substances 0.000 claims abstract description 106
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 22
- 230000001681 protective effect Effects 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 19
- 238000004736 wide-angle X-ray diffraction Methods 0.000 claims abstract description 13
- 239000000853 adhesive Substances 0.000 claims description 66
- 230000001070 adhesive effect Effects 0.000 claims description 66
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 48
- 229910052796 boron Inorganic materials 0.000 claims description 48
- 239000012790 adhesive layer Substances 0.000 claims description 36
- 239000010410 layer Substances 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000011701 zinc Substances 0.000 claims description 16
- 229910052725 zinc Inorganic materials 0.000 claims description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011247 coating layer Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 230000010287 polarization Effects 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 5
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- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 73
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- -1 iodine ions Chemical class 0.000 description 48
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- 150000001875 compounds Chemical class 0.000 description 20
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 10
- 230000007423 decrease Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
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- 239000001913 cellulose Substances 0.000 description 8
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- 239000003431 cross linking reagent Substances 0.000 description 8
- 239000004973 liquid crystal related substance Substances 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- 150000001639 boron compounds Chemical class 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
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- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 229920005601 base polymer Polymers 0.000 description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 238000009616 inductively coupled plasma Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 150000003751 zinc Chemical class 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
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- 238000000576 coating method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 238000007127 saponification reaction Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229940015043 glyoxal Drugs 0.000 description 3
- 239000005001 laminate film Substances 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011369 resultant mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 3
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 2
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 2
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- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229930195725 Mannitol Natural products 0.000 description 2
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- GMEGXJPUFRVCPX-UHFFFAOYSA-N butylthiourea Chemical compound CCCCNC(N)=S GMEGXJPUFRVCPX-UHFFFAOYSA-N 0.000 description 2
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- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
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- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
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- 238000000149 argon plasma sintering Methods 0.000 description 1
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- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 description 1
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- 229940075444 barium iodide Drugs 0.000 description 1
- RJNJWHFSKNJCTB-UHFFFAOYSA-N benzylurea Chemical compound NC(=O)NCC1=CC=CC=C1 RJNJWHFSKNJCTB-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CNWSQCLBDWYLAN-UHFFFAOYSA-N butylurea Chemical compound CCCCNC(N)=O CNWSQCLBDWYLAN-UHFFFAOYSA-N 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- 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
- 230000001186 cumulative effect Effects 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- LEEHHPPLIOFGSC-UHFFFAOYSA-N cyclohexylthiourea Chemical compound NC(=S)NC1CCCCC1 LEEHHPPLIOFGSC-UHFFFAOYSA-N 0.000 description 1
- WUESWDIHTKHGQA-UHFFFAOYSA-N cyclohexylurea Chemical compound NC(=O)NC1CCCCC1 WUESWDIHTKHGQA-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 1
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- XRVHSOXXNQTWAW-UHFFFAOYSA-N n-(methylcarbamoyl)acetamide Chemical compound CNC(=O)NC(C)=O XRVHSOXXNQTWAW-UHFFFAOYSA-N 0.000 description 1
- GKRZNOGGALENQJ-UHFFFAOYSA-N n-carbamoylacetamide Chemical compound CC(=O)NC(N)=O GKRZNOGGALENQJ-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- ACLZYRNSDLQOIA-UHFFFAOYSA-N o-tolylthiourea Chemical compound CC1=CC=CC=C1NC(N)=S ACLZYRNSDLQOIA-UHFFFAOYSA-N 0.000 description 1
- GJNDMSSZEBNLPU-UHFFFAOYSA-N octadecylurea Chemical compound CCCCCCCCCCCCCCCCCCNC(N)=O GJNDMSSZEBNLPU-UHFFFAOYSA-N 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
- VPJDULFXCAQHRC-UHFFFAOYSA-N prop-2-enylurea Chemical compound NC(=O)NCC=C VPJDULFXCAQHRC-UHFFFAOYSA-N 0.000 description 1
- LJPYJRMMPVFEKR-UHFFFAOYSA-N prop-2-ynylurea Chemical compound NC(=O)NCC#C LJPYJRMMPVFEKR-UHFFFAOYSA-N 0.000 description 1
- ZQZJKHIIQFPZCS-UHFFFAOYSA-N propylurea Chemical compound CCCNC(N)=O ZQZJKHIIQFPZCS-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- SLUHLANJIVXTRQ-UHFFFAOYSA-N pyridin-2-ylthiourea Chemical compound NC(=S)NC1=CC=CC=N1 SLUHLANJIVXTRQ-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012508 resin bead Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
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- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920005992 thermoplastic resin 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
- 150000003609 titanium compounds Chemical class 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- 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
- G02B5/3041—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 comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—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 comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- G02B1/02—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of crystals, e.g. rock-salt, semi-conductors
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B2037/1276—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives water-based adhesive
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Polarising Elements (AREA)
Abstract
The invention aims to provide a polarizing plate which has excellent effect of inhibiting the reduction of polarization degree even when exposed to a high-temperature environment with a temperature of 115 ℃. A polarizing plate comprising a polarizing element and a transparent protective film, wherein the polarizing element is formed by adsorption-orienting a dichroic dye on a polyvinyl alcohol resin layer, and the half-value width of the peak of the polarizing element, as measured by a wide-angle X-ray scattering method, derived from a polyvinyl alcohol crystal is 4.80nm ‑1 The polarizing element includes potassium ions and metal ions other than potassium ions, and the content of the metal ions other than potassium ions is 0.05 mass% or more.
Description
Technical Field
The present invention relates to a polarizing plate.
Background
Liquid crystal display devices (LCDs) are widely used not only for liquid crystal televisions but also for mobile devices such as personal computers and mobile phones, and for vehicle-mounted applications such as car navigation. In general, a liquid crystal display device includes a liquid crystal panel member formed by bonding polarizing plates to both sides of a liquid crystal cell with an adhesive, and displays by controlling light from a backlight member with the liquid crystal panel member. In recent years, organic EL display devices have been widely used for mobile devices such as televisions and cellular phones, and for vehicle-mounted applications such as car navigation, as well as for liquid crystal display devices. In an organic EL display device, a circularly polarizing plate (a laminate including a polarizing element and a λ/4 plate) is sometimes arranged on the viewing side surface of an image display panel in order to suppress reflection of external light by a metal electrode (cathode) and to be observed as a mirror surface.
As described above, opportunities for mounting the polarizing plate on a vehicle as a member of a liquid crystal display device or an organic EL display device are increasing. Polarizing plates used in-vehicle image display devices are often exposed to high-temperature environments in comparison with other mobile applications such as televisions and mobile phones, and are required to have small changes in characteristics at higher temperatures (high-temperature durability).
As a method for producing such a polarizing element having high-temperature durability, for example, patent documents 1 to 2 disclose that a component including a metal salt such as zinc, copper, aluminum, or the like is added to a treatment bath, so that the polarizing element contains the component, thereby improving the durability of the polarizing element. Patent documents 3 to 4 disclose a method for producing a polarizing element in which a component such as an organic titanium compound is added to a treatment bath.
Prior art literature
Patent literature
Patent document 1: international publication No. 2016/117659
Patent document 2: japanese patent laid-open No. 2006-047978
Patent document 3: japanese patent laid-open No. 2008-46257
Patent document 4: japanese patent laid-open No. 6-172554
Disclosure of Invention
Problems to be solved by the invention
However, with the polarizing plate so far, in the case where the temperature of a high-temperature environment is raised to 115 ℃ and exposed to the high-temperature environment for a certain time, the degree of polarization sometimes decreases. The purpose of the present invention is to provide a polarizing plate that has excellent effect of suppressing a decrease in polarization degree even when exposed to a high-temperature environment such as a temperature of 115 ℃.
Means for solving the problems
The present invention provides the following polarizing plate.
[ 1 ] A polarizing plate comprising a polarizing element and a transparent protective film, wherein the polarizing element is formed by adsorbing and aligning a dichroic dye on a polyvinyl alcohol resin layer,
the half value width of the peak from the polyvinyl alcohol crystal measured by the wide angle X-ray scattering method of the polarizing element was 4.80nm -1 The above-mentioned steps are carried out,
the polarizing element contains potassium ions and metal ions other than potassium ions,
in the polarizing element, the content of the metal ions other than potassium ions is 0.05 mass% or more.
The polarizing plate according to [ 2 ], wherein the metal ion comprises at least 1 kind selected from the group consisting of ions of cobalt, nickel, zinc, chromium, aluminum, copper, manganese and iron.
The polarizing plate according to [ 1 ] or [ 2 ], wherein the content of boron in the polarizing element is 3.9 mass% or more and 8.0 mass% or less.
The polarizing plate according to any one of [ 1 ] to [ 3 ], which further comprises an adhesive layer for bonding the polarizing element to the transparent protective film,
the adhesive layer is a coating layer of an aqueous adhesive.
The polarizing plate according to [ 5 ] above, wherein the concentration of methanol in the aqueous adhesive is 10% by mass or more and 70% by mass or less.
The polarizing plate according to [ 4 ] or [ 5 ], wherein the aqueous adhesive comprises a polyvinyl alcohol resin.
The polarizing plate according to any one of [ 4 ] to [ 6 ], wherein the adhesive layer has a thickness of 0.01 μm or more and 7 μm or less.
Effects of the invention
According to the present invention, it is possible to provide a polarizing plate which can suppress a decrease in polarization degree when exposed to a high-temperature environment such as 115 ℃ and has excellent high-temperature durability.
Drawings
FIG. 1 is a graph showing the values obtained by subtracting the scattering spectrum of the background from the scattering spectrum of the measurement sample with respect to the wave number q for the polarizing elements 1 to 3 (polarizers 1 to 3).
Detailed Description
Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.
[ polarizing plate ]
The polarizing plate according to an embodiment of the present invention includes a polarizing element in which a dichroic dye is adsorbed and oriented on a layer containing a polyvinyl alcohol resin, and a transparent protective film. The half-value width of the peak derived from the polyvinyl alcohol crystal measured by the wide-angle X-ray scattering method of the polarizing element was 4.80nm -1 The above. The polarizing element contains potassium ions (hereinafter, sometimes referred to as "1 st metal ion") and metal ions other than potassium ions (hereinafter, sometimes referred to as "2 nd metal ion"), and the content of the 2 nd metal ion is 0.05 mass% or more.
In the polarizing plate of the present embodiment, the half width of the peak from the polyvinyl alcohol crystal measured by the wide-angle X-ray scattering method with respect to the polarizing element and the content of the 2 nd metal ion in the polarizing element are set to be within the above ranges, whereby the decrease in the polarization degree can be suppressed even when exposed to a high-temperature environment for a long period of time.
According to the polarizing plate of the present embodiment, even when exposed to a high temperature environment of, for example, 115 ℃ for 500 hours or more, the decrease in polarization degree can be suppressed.
< polarizing element >
As a polarizing element in which a dichroic dye is adsorbed and oriented to a layer containing a polyvinyl alcohol (PVA) -based resin (also referred to as a "PVA-based resin layer" in this specification), a known polarizing element can be used. As such a polarizing element, a PVA-based resin film is used, and the PVA-based resin film is dyed with a dichroic dye and uniaxially stretched; a polarizing element is formed by using a laminate film obtained by coating a base film with a coating liquid containing a PVA-based resin, dyeing a PVA-based resin layer as a coating layer of the laminate film with a dichroic dye, and uniaxially stretching the laminate film.
The polarizing element is formed of a PVA-based resin obtained by saponifying a polyvinyl acetate-based resin. As the polyvinyl acetate resin, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, copolymers of vinyl acetate and other monomers copolymerizable therewith can be mentioned. Examples of the other copolymerizable monomer include unsaturated carboxylic acids, olefins such as ethylene, vinyl ethers, and unsaturated sulfonic acids.
In the present invention, the PVA-based resin layer is preferably formed of a PVA-based resin having a boron adsorption rate of 5.70 mass% or more. That is, the boron adsorption rate of the PVA-based resin in the stage of dyeing and stretching the raw material is preferably 5.70 mass% or more. By using such a PVA-based resin, the degree of polarization is not easily lowered even when exposed to a high temperature environment such as a temperature of 115 ℃. The boron adsorption rate of the PVA-based resin is preferably 10 mass% or less. By using such a PVA-based resin to produce a polarizing element, it is possible to shorten the treatment time by boric acid treatment without increasing the boric acid concentration in the boric acid treatment tank, to easily obtain a desired polarizing element, and to improve the productivity of the polarizing element. If the boron adsorption rate of the PVA-based resin is 10 mass% or less, a proper amount of boron is introduced into the PVA-based resin layer, and the shrinkage force of the polarizing element is easily reduced. The boron adsorption rate of the PVA-based resin can be measured by the method described in examples described later.
The boron adsorption rate of the PVA-based resin is a characteristic reflecting the interval between molecular chains and the crystal structure in the PVA-based resin. The PVA-based resin having a boron adsorption rate of 5.70 mass% or more is considered to have a wider interval between molecular chains than the PVA-based resin having a boron adsorption rate of less than 5.70 mass%, and is less crystallized. Therefore, it is presumed that boron, the 1 st metal ion, and the 2 nd metal ion easily enter the PVA-based resin layer, and the degree of polarization is not easily reduced in a high temperature environment.
The boron adsorption rate of the PVA-based resin may be adjusted by, for example, subjecting the PVA-based resin to pretreatment such as hot water treatment, acid solution treatment, ultrasonic irradiation treatment, and radiation irradiation treatment at a stage before the polarizing element is manufactured. By these treatments, the interval between molecular chains in the PVA-based resin can be enlarged or the crystal structure can be broken. Examples of the hot water treatment include a treatment of immersing in pure water at 30 to 100℃for 1 to 90 seconds and drying the immersed water. Examples of the acidic solution treatment include a treatment of immersing in an aqueous boric acid solution having a concentration of 10 to 20 mass% for 1 to 90 seconds and drying the immersed boric acid solution. Examples of the ultrasonic treatment include a treatment of irradiating ultrasonic waves of a frequency of 20 to 29kc with an output of 200 to 500W for 30 seconds to 10 minutes. The ultrasonic treatment may be performed in a solvent such as water.
The saponification degree of the PVA-based resin is preferably 85 mol% or more, more preferably 90 mol% or more, and still more preferably 99 mol% to 100 mol%. The polymerization degree of the PVA-based resin is 1000 to 10000, preferably 1500 to 5000. The PVA-based resin may be modified, and may be, for example, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, or the like modified with an aldehyde.
The thickness of the polarizing element of the present embodiment is preferably 5 to 50. Mu.m, more preferably 8 to 28. Mu.m, still more preferably 12 to 22. Mu.m, and most preferably 12 to 15. Mu.m. By setting the thickness of the polarizing element to 5 μm or more, a constitution that realizes desired optical characteristics can be easily made.
The half-value width of the peak from the polyvinyl alcohol crystal measured by the wide-angle X-ray scattering method of the polarizing element of the present invention was 4.80nm -1 The above is preferably 4.82nm -1 The above is more preferably 4.87nm -1 The above. In such a polarizing element, the crystal size of polyvinyl alcohol decreases due to the progress of the crosslinking reaction by boric acid, and as a result, the proportion of amorphous portions increases. Therefore, the content of boron and the 2 nd metal ion described later can be effectively increased. The half-value width of the peak derived from the polyvinyl alcohol crystal as measured by the wide-angle X-ray scattering method may be, for example, 5.0nm -1 The following is given. Such a polarizing element has a high degree of orientation, and therefore can have excellent optical characteristics. The half width of the peak derived from the polyvinyl alcohol crystal measured by the wide-angle X-ray scattering method can be measured by the method described in examples described later. The half width of the peak derived from the polyvinyl alcohol crystal measured by the wide angle X-ray scattering method can be appropriately adjusted depending on the temperature of the stretching bath, the stretching ratio, the boric acid concentration of the crosslinking bath, the saponification degree of the PVA-based resin used as the raw material, and the like.
The content of the 2 nd metal ion in the polarizing element is preferably 0.05 mass% or more and 10.0 mass% or less, more preferably 0.05 mass% or more and 8.0 mass% or less, and still more preferably 0.1 mass% or more and 6.0 mass% or less. When the content of the 2 nd metal ion exceeds 10.0 mass%, the degree of polarization may be lowered in a high-temperature and high-humidity environment. In addition, when the content of the 2 nd metal ion is less than 0.05 mass%, the effect of improving durability in a high-temperature environment may be insufficient. The content of the 2 nd metal ion in the polarizing element can be calculated as a mass fraction (mass%) of the metal element relative to the mass of the polarizing element by, for example, high-frequency inductively coupled plasma (Inductively Coupled Plasma:icp) emission spectrometry. The metal element is considered to exist in the polarizing element in a state that the metal ion or the metal ion forms a crosslinked structure with the constituent element of the polyvinyl alcohol resin, and the content of the 2 nd metal ion is a value calculated as a metal atom.
The 2 nd metal ion is not limited as long as it is a metal ion other than potassium ion, and is preferably an ion of a metal other than alkali metal, and in particular, from the viewpoint of adjusting color tone and imparting durability, it is preferably at least 1 kind of metal ion containing transition metal such as cobalt, nickel, zinc, chromium, aluminum, copper, manganese, iron, and the like. Among these metal ions, zinc ions are preferable from the viewpoints of adjusting color tone, imparting heat resistance, and the like.
The content of boron in the polarizing element is preferably 2.4 mass% or more. The content of boron is preferably 3.9 mass% or more and 8.0 mass% or less, more preferably 4.2 mass% or more and 7.0 mass% or less, and still more preferably 4.4 mass% or more and 6.0 mass% or less. If the boron content of the polarizing element exceeds 8.0 mass%, the shrinkage force of the polarizing element increases, and there is a case where a problem such as peeling occurs between the polarizing element and other members such as a front panel attached to the image display device when the polarizing element is assembled. In addition, when the content of boron is less than 2.4 mass%, desired optical characteristics may not be achieved. The boron content of the polarizing element can be calculated as a mass fraction (mass%) of boron with respect to the mass of the polarizing element by, for example, high-frequency inductively coupled plasma (Inductively Coupled Plasma: ICP) emission spectrometry. The boron is considered to exist in the polarizing element in a state in which boric acid or a component thereof and the polyvinyl alcohol resin form a crosslinked structure, and the content of boron is a value calculated as boron atom (B).
The content of boron in the polarizing element is preferably 2.4 mass% or more and 8.0 mass% or less, and more preferably 3.9 mass% or more and 8.0 mass% or less. By satisfying such a numerical range, the decrease in the degree of polarization is suppressed even in the case of exposure to a high-temperature environment.
The content of potassium ions in the polarizing element is preferably 0.28 mass% or more, more preferably 0.32 mass% or more, further preferably 0.34 mass% or more, from the viewpoint of suppressing a decrease in the degree of polarization in a high-temperature environment, and is preferably 0.60 mass% or less, more preferably 0.55 mass% or less, further preferably 0.50 mass% or less, from the viewpoint of suppressing a change in color tone in a high-temperature environment. The content of potassium ions can be measured by the same method as that of the metal ion 2, and the content of potassium ions is a value calculated as potassium atoms.
Although the detailed mechanism is not clear, it is presumed that the hydroxyl groups of the polyvinyl alcohol in the polarizing element are protected (stabilized) by boric acid crosslinking because the content of boron is large and the content of potassium ions is small as compared with the conventional polarizing element, and that the iodine ions as counter ions in the polarizing element are stabilized by the content of potassium ions in an appropriate amount.
The visibility correction monomer transmittance of the polarizing plate is preferably 38.8% to 44.8%, more preferably 40.4% to 43.2%, and further preferably 40.7% to 43.0%. If the transmittance of the visibility-correcting monomer exceeds 44.8%, deterioration of optical characteristics such as red discoloration may occur in a high-temperature environment, and if the transmittance of the visibility-correcting monomer is less than 38.8%, deterioration of optical characteristics may occur in a high-temperature environment.
The visibility-corrected monomer transmittance can be obtained by measuring the visibility-corrected Y value using a 2-degree field of view (C light source) specified in JIS Z8701-1982. The transmittance of the visibility-correcting monomer can be easily measured by, for example, a spectrophotometer (model: V7100) manufactured by Japanese Spectrophotometer Co., ltd.
The method for producing the polarizing element is not particularly limited, and is typically a method of producing a polyvinyl alcohol resin film which is wound in advance into a roll form by stretching, dyeing, crosslinking, or the like (hereinafter referred to as "production method 1"); a method comprising a step of stretching a laminate obtained by applying a coating liquid containing a polyvinyl alcohol resin onto a base film to form a polyvinyl alcohol resin layer as a coating layer (hereinafter referred to as "production method 2").
The manufacturing method 1 can be manufactured through the following steps: the method for producing a polyvinyl alcohol resin film comprises a step of uniaxially stretching a polyvinyl alcohol resin film, a step of adsorbing a dichroic dye such as iodine by dyeing the polyvinyl alcohol resin film, a step of treating the polyvinyl alcohol resin film adsorbed with the dichroic dye with an aqueous boric acid solution, and a step of washing with water after the treatment with the aqueous boric acid solution.
The content of boron and the content of potassium ions in the polarizing element can be controlled by the concentration of a boron component providing substance such as a boron compound including boric acid, borate, borax, etc. and the concentration of a potassium component providing substance including potassium halide including potassium iodide, etc. in any one of the treatment baths in the swelling step, dyeing step, crosslinking step, stretching step, and washing step, the treatment temperature and the treatment time of each treatment bath. In particular, in the crosslinking step and the stretching step, the boron content can be easily adjusted to a desired range by the treatment conditions such as the concentration of the boron component providing substance. In addition, in the water washing step, the content of boron and the content of potassium ions are easily adjusted to the desired ranges from the viewpoint of being able to dissolve or adsorb the components such as boron and potassium from or to the polyvinyl alcohol resin film, taking into consideration the treatment conditions such as the amount of the boron component providing substance and the amount of the potassium component providing substance used in the dyeing step, the crosslinking step, the stretching step, and the like.
The swelling step is a treatment step of immersing the polyvinyl alcohol resin film in a swelling bath, whereby dirt, a blocking agent, and the like on the surface of the polyvinyl alcohol resin film can be removed, and further, by swelling the polyvinyl alcohol resin film, uneven dyeing can be suppressed. The swelling bath generally uses a medium containing water as a main component, such as water, distilled water, and pure water. The swelling bath may be appropriately added with a surfactant, alcohol, or the like according to a conventional method. In addition, from the viewpoint of controlling the content of potassium in the polarizing element, potassium iodide may be used in the swelling bath, and in this case, the concentration of potassium iodide in the swelling bath is preferably 1.5 mass% or less, more preferably 1.0 mass% or less, and still more preferably 0.5 mass% or less
The temperature of the swelling bath is preferably 10 to 60 ℃, more preferably 15 to 45 ℃, and still more preferably 18 to 30 ℃. Further, since the swelling degree of the polyvinyl alcohol resin film is affected by the temperature of the swelling bath, the immersion time in the swelling bath cannot be determined at all, but is preferably 5 to 300 seconds, more preferably 10 to 200 seconds, and even more preferably 20 to 100 seconds. The swelling step may be performed only 1 time, or may be performed as many times as necessary.
The dyeing step is a treatment step of immersing the polyvinyl alcohol resin film in a dyeing bath (iodine solution), and can adsorb and orient a dichroic substance such as iodine or a dichroic dye to the polyvinyl alcohol resin film. The iodine solution is generally preferably an aqueous iodine solution containing iodine and iodide as a dissolution aid. 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 them, potassium iodide is preferable from the viewpoint of controlling the content of potassium in the polarizing element.
The concentration of iodine in the dyeing bath is preferably 0.01 to 1% by mass, more preferably 0.02 to 0.5% by mass. The concentration of iodide in the dyeing bath is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and even more preferably 0.1 to 3% by mass.
The temperature of the dyeing bath is preferably 10 to 50 ℃, more preferably 15 to 45 ℃, and even more preferably 18 to 30 ℃. Further, since the dyeing degree of the polyvinyl alcohol resin film is affected by the temperature of the dyeing bath, the immersion time in the dyeing bath cannot be defined at all, and is preferably 10 to 300 seconds, more preferably 20 to 240 seconds. The dyeing step may be performed only 1 time, or may be performed as many times as necessary.
The crosslinking step is a treatment step of immersing the polyvinyl alcohol resin film dyed in the dyeing step in a treatment bath (crosslinking bath) containing a boron compound, and crosslinking the polyvinyl alcohol resin film with the boron compound, whereby iodine molecules or dye molecules can be adsorbed to the crosslinked structure. Examples of the boron compound include boric acid, borate, and borax. The crosslinking bath is usually an aqueous solution, but may be a mixed solution of an organic solvent having miscibility with water and water, for example. In addition, from the viewpoint of controlling the content of potassium in the polarizing element, the crosslinking bath preferably contains potassium iodide.
The concentration of the boron compound in the crosslinking bath is preferably 1 to 15% by mass, more preferably 1.5 to 10% by mass, and still more preferably 2 to 5% by mass. In the case of using potassium iodide in the crosslinking bath, the concentration of potassium iodide in the crosslinking bath is preferably 1 to 15% by mass, more preferably 1.5 to 10% by mass, and still more preferably 2 to 5% by mass.
The temperature of the crosslinking bath is preferably 20 to 70 ℃, more preferably 30 to 60 ℃. Further, since the degree of crosslinking of the polyvinyl alcohol resin film is affected by the temperature of the crosslinking bath, the immersion time in the crosslinking bath cannot be defined at all, and is preferably 5 to 300 seconds, more preferably 10 to 200 seconds. The crosslinking step may be performed only 1 time, or may be performed as many times as necessary.
The stretching step is a treatment step of stretching the polyvinyl alcohol resin film in at least one direction to a predetermined magnification. In general, a polyvinyl alcohol resin film is uniaxially stretched in a transport direction (longitudinal direction). The stretching method is not particularly limited, and both wet stretching and dry stretching may be employed. The stretching step may be performed only 1 time, or may be performed as many times as necessary. The stretching step may be performed at any stage in the production of the polarizing element.
The treatment bath (stretching bath) in the wet stretching method may be usually water or a mixed solution of water and an organic solvent having miscibility with water. From the viewpoint of controlling the content of potassium ions in the polarizing element, the stretching bath preferably contains potassium iodide. When potassium iodide is used in the stretching bath, the concentration of potassium iodide in the stretching bath is preferably 1 to 15% by mass, more preferably 2 to 10% by mass, and still more preferably 3 to 6% by mass. In addition, from the viewpoint of suppressing film breakage during stretching, a boron compound may be contained in the treatment bath (stretching bath), and in this case, the concentration of the boron compound in the stretching bath is preferably 1 to 15 mass%, more preferably 1.5 to 10 mass%, and still more preferably 2 to 5 mass%.
The temperature of the stretching bath is not limited, and is at least one ofThe number of the stretching baths is preferably 25 to 80 ℃, more preferably 40 to 80 ℃, still more preferably 50 to 75 ℃, particularly preferably 65 to 75 ℃, and particularly preferably 67 ℃ or higher. If the temperature of the stretching bath is increased, the 2 nd metal ion used in the metal ion treatment step described later is easily held in the PVA-based resin layer. By increasing the temperature of the stretching bath, the PVA can be stretched at a temperature near the softening point of the PVA in the PVA-based resin layer or at a temperature equal to or higher than the softening point of the PVA. As a result, the crystallization ratio of PVA was decreased, or the crystallization of PVA was decreased, the amount of metal ion 2 introduced was increased, and the crosslinking reaction was promoted, whereby the half width of the peak derived from the polyvinyl alcohol crystal as measured by the wide-angle X-ray scattering method was easily set to 4.80nm -1 The above. Further, since the stretching degree of the polyvinyl alcohol resin film is affected by the temperature of the stretching bath, the immersion time in the stretching bath cannot be defined at all, and is preferably 10 to 800 seconds, more preferably 30 to 500 seconds. The stretching step in the wet stretching method may be performed alone, or may be performed together with 1 or more of the swelling step, dyeing step, crosslinking step, and cleaning step, or may be performed in combination. When the treatment is performed together with 1 or more treatment steps, the treatment step of setting the temperature of the treatment bath to the optimum 65 to 75 ℃ in the stretching step is particularly suitable as the crosslinking step. In the case of stretching in a plurality of treatment baths, the temperature of at least one treatment bath is preferably 65 to 75 ℃, and the immersion time in the treatment bath at 65 to 75 ℃ is preferably 40 to 200 seconds.
Examples of the dry stretching method include an inter-roll stretching method, a heated roll stretching method, and a compression stretching method. The dry stretching method may be performed together with the drying step.
The total stretching ratio (cumulative stretching ratio) of the polyvinyl alcohol resin film can be appropriately set according to the purpose, and is preferably 2 to 7 times, more preferably 3 to 6.8 times, and even more preferably 3.5 to 6.5 times.
The cleaning step is a treatment step of immersing the polyvinyl alcohol resin film in a cleaning bath, and can remove foreign matters remaining on the surface of the polyvinyl alcohol resin film. The washing bath generally uses a medium containing water as a main component, such as water, distilled water, and pure water. In addition, from the viewpoint of controlling the content of potassium in the polarizing element, potassium iodide is preferably used in the cleaning bath, and in this case, the concentration of potassium iodide in the cleaning bath is preferably 1 to 10% by mass, more preferably 1.5 to 4% by mass, and even more preferably 1.8 to 3.8% by mass.
The temperature of the cleaning bath is preferably 5 to 50 ℃, more preferably 10 to 40 ℃, still more preferably 15 to 30 ℃. Further, since the degree of cleaning of the polyvinyl alcohol resin film is affected by the temperature of the cleaning bath, the immersion time in the cleaning bath cannot be defined at all, but is preferably 1 to 100 seconds, more preferably 2 to 50 seconds, and still more preferably 3 to 20 seconds. The cleaning step may be performed only 1 time, or may be performed as many times as necessary.
The method for manufacturing a polarizing element may include a metal ion treatment step in the above steps or may include a metal ion treatment step as a step different from the above steps. The metal ion treatment step is performed by immersing the polyvinyl alcohol resin film in an aqueous solution containing a metal salt of the 2 nd metal ion. The metal ion treatment step is performed to contain the 2 nd metal ion in the polyvinyl alcohol resin film.
The 2 nd metal ion is not limited as long as it is a metal ion other than potassium ion, and is preferably an ion of a metal other than alkali metal, and in particular, from the viewpoint of adjusting color tone and imparting durability, at least 1 kind of metal ion containing transition metal such as cobalt, nickel, zinc, chromium, aluminum, copper, manganese, iron, and the like is preferable. Among these metal ions, zinc ions are preferable from the viewpoints of adjusting color tone, imparting heat resistance, and the like. Examples of the zinc salt include zinc halides such as zinc chloride and zinc iodide, zinc sulfate, and zinc acetate.
The metal ion treatment step uses a metal salt solution. In the following, a description will be given of a dipping treatment in a zinc-containing solution as a typical example when an aqueous zinc salt solution is used in the metal ion treatment step.
The concentration of zinc ions in the zinc salt aqueous solution is in the range of 0.1 to 10 mass%, preferably 0.3 to 7 mass%. In addition, when an aqueous solution containing potassium ions and iodide ions by potassium iodide or the like is used as the zinc salt solution, zinc ions are easily impregnated, which is preferable. The concentration of potassium iodide in the zinc salt solution is preferably 0.1 to 10 mass%, more preferably 0.2 to 5 mass%.
When the impregnation treatment is carried out in a zinc-containing solution, the temperature of the zinc-salt solution is generally 1 5 to 85 ℃, preferably 25 to 70 ℃. The impregnation time is usually in the range of 1 to 120 seconds, preferably 3 to 90 seconds. When the impregnation treatment is performed in the zinc-containing solution, the concentration of the zinc-containing solution, the impregnation temperature of the polyvinyl alcohol resin film in the zinc-containing solution, the impregnation time, and other conditions are adjusted so that the zinc content in the polyvinyl alcohol resin film falls within the above-described range. When the impregnation treatment in the zinc-containing solution is performed is not particularly limited. The impregnation treatment in the zinc-containing liquid may be performed alone, or the zinc salt may be allowed to coexist in the dyeing bath, the crosslinking bath, or the stretching bath, and may be performed simultaneously with at least one of the dyeing step, the crosslinking step, or the stretching step.
After each of the above steps, a drying step is finally performed. The drying step is a step of drying the polyvinyl alcohol resin film washed in the washing step to obtain a polarizing element. Drying is carried out by any suitable method, and examples thereof include natural drying, air drying, and heat drying.
The manufacturing method 2 can be manufactured through the following steps: the method for producing a polarizing element comprises a step of applying a coating liquid containing the polyvinyl alcohol resin onto a base film, a step of uniaxially stretching the obtained laminated film, a step of producing a polarizing element by dyeing a polyvinyl alcohol resin layer of the uniaxially stretched laminated film with a dichroic dye and adsorbing the dichroic dye, a step of treating the film adsorbed with a dichroic dye with an aqueous boric acid solution, and a step of washing with water after the treatment with the aqueous boric acid solution. The base film for forming the polarizing element can also be used as a protective layer for the polarizing element. The base film may be peeled off from the polarizing element as needed.
[ transparent protective film ]
The transparent protective film (hereinafter, also simply referred to as "protective film") used in the present embodiment is attached to at least one surface of the polarizing element via an adhesive layer. The transparent protective film is bonded to one or both sides of the polarizing element, and more preferably to both sides.
The protective film may have other optical functions at the same time, or may have a laminated structure in which a plurality of layers are laminated. From the viewpoint of optical characteristics, the film thickness of the protective film is preferably thin, but if too thin, the strength is lowered and the workability is deteriorated. The thickness of the film is preferably 5 to 100. Mu.m, more preferably 10 to 80. Mu.m, and still more preferably 15 to 70. Mu.m.
As the protective film, a cellulose acylate-based film, a film containing a polycarbonate-based resin, a film containing a cycloolefin-based resin such as norbornene, a (meth) acrylic polymer film, a polyester resin-based film such as polyethylene terephthalate, and the like can be used. In the case where the polarizing element has a structure in which the protective films are provided on both surfaces, in the case where the laminating is performed using an aqueous adhesive such as a PVA adhesive, it is preferable that at least one of the protective films is either a cellulose acylate-based film or a (meth) acrylic polymer film in terms of moisture permeability, and among these, cellulose acylate films are preferable.
At least one of the protective films may have a phase difference for the purpose of viewing angle compensation or the like, in which case the film itself may have a phase difference, or may have a phase difference layer in addition, or may be a combination of both.
The film having the phase difference is directly bonded to the polarizing element with an adhesive, but the film having the phase difference may be bonded with an adhesive or an adhesive via another protective film bonded to the polarizing element.
[ adhesive layer ]
Any suitable adhesive may be used as the adhesive constituting the adhesive layer for attaching the protective film to the polarizing element. The adhesive may be an aqueous adhesive, a solvent-based adhesive, an active energy ray-curable adhesive, or the like, and is preferably an aqueous adhesive. From the viewpoint of improving heat resistance, it is also useful that the adhesive layer preferably contains at least one urea compound selected from urea, urea derivatives, thiourea and thiourea derivatives.
The thickness of the adhesive at the time of application may be set to any appropriate value. For example, the setting is performed such that an adhesive layer (coating layer) having a desired thickness can be obtained after curing or after heating (drying). The thickness of the adhesive layer is preferably 0.O1 μm or more and 7 μm or less, more preferably 0.01 μm or more and 5 μm or less, still more preferably 0.01 μm or more and 2 μm or less, and most preferably O.01 μm or more and 1 μm or less.
(aqueous adhesive)
Any suitable aqueous adhesive may be used as the aqueous adhesive. Among them, an aqueous adhesive (PVA-based adhesive) containing a PVA-based resin is preferably used. From the viewpoint of adhesion, the average degree of polymerization of the PVA-based resin contained in the aqueous adhesive is preferably 100 to 5500, more preferably 1000 to 4500. From the viewpoint of adhesion, the average saponification degree is preferably 85 to 100 mol%, and more preferably 90 to 100 mol%.
The PVA-based resin containing an acetoacetyl group is preferable as the PVA-based resin contained in the aqueous adhesive because the PVA-based resin layer has excellent adhesion to the protective film and excellent durability. The acetoacetyl group-containing PVA-based resin can be obtained, for example, by reacting a PVA-based resin with diketene by any method. The degree of acetoacetyl modification of the acetoacetyl-containing PVA resin is typically 0.1 mol% or more, preferably 0.1 mol% to 20 mol%.
The resin concentration of the aqueous adhesive is preferably 0.1 to 15 mass%, more preferably 0.5 to 10 mass%.
The aqueous adhesive may contain a crosslinking agent. As the crosslinking agent, a known crosslinking agent can be used. Examples thereof include water-soluble epoxy compounds, dialdehydes, isocyanates, and the like.
In the case where the PVA-based resin is an acetoacetyl group-containing PVA-based resin, the crosslinking agent is preferably any one of glyoxal, glyoxylate, and methylolmelamine, more preferably any one of glyoxal and glyoxylate, and particularly preferably glyoxal.
The aqueous adhesive may contain an organic solvent. The organic solvent is preferably an alcohol in terms of miscibility with water, and among them, methanol or ethanol is more preferred. The urea compound has a low solubility in water in part, and has a sufficient solubility in alcohol. In this case, it is also one of preferable modes to prepare an adhesive by dissolving a urea compound in an alcohol to prepare an alcohol solution of the urea compound and then adding the alcohol solution of the urea compound to an aqueous PVA solution.
The concentration of methanol in the aqueous adhesive is preferably 10% by mass or more and 70% by mass or less, more preferably 15% by mass or more and 60% by mass or less, and still more preferably 20% by mass or more and 60% by mass or less. Further, by setting the content of methanol to 70 mass% or less, deterioration of the color tone can be suppressed.
(active energy ray-curable adhesive)
The active energy ray-curable adhesive is an adhesive cured by irradiation with active energy rays such as ultraviolet rays, and examples thereof include adhesives containing a polymerizable compound and a photopolymerization initiator, adhesives containing a photoreactive resin, adhesives containing a binder resin and a photoreactive crosslinking agent, and the like. Examples of the polymerizable compound include photopolymerizable monomers such as photocurable epoxy monomers, photocurable acrylic monomers and photocurable urethane monomers, and oligomers derived from these monomers. The photopolymerization initiator may be a compound containing an active species such as a neutral radical, an anionic radical, or a cationic radical generated by irradiation with an active energy ray such as ultraviolet rays.
(Urea-based Compound)
In the case where the adhesive layer contains a urea-based compound, the urea-based compound is at least 1 selected from urea, urea derivatives, thiourea and thiourea derivatives. As a method for containing the urea compound in the adhesive layer, it is preferable to contain the urea compound in the adhesive. In the process of forming the adhesive layer from the adhesive through a drying step or the like, a part of the urea compound may be moved from the adhesive layer to the polarizing element or the like. That is, the polarizing element may contain a urea compound. Among the urea-based compounds, there are water-soluble urea-based compounds and poorly water-soluble urea-based compounds, and any of the urea-based compounds can be used in the adhesive of the present embodiment. When the water-insoluble urea compound is used for an aqueous adhesive, it is preferable to design the dispersing method so as not to cause an increase in haze or the like after forming the adhesive layer.
When the adhesive is an aqueous adhesive containing a PVA-based resin, the amount of the urea compound to be added is preferably 0.1 to 400 parts by mass, more preferably 1 to 200 parts by mass, and even more preferably 3 to 100 parts by mass, relative to 100 parts by mass of the PVA resin.
(Urea derivative)
Urea derivatives are compounds in which at least 1 of the 4 hydrogen atoms of the urea molecule is substituted with a substituent. In this case, the substituent is not particularly limited, and is preferably a substituent containing a carbon atom, a hydrogen atom and an oxygen atom.
Specific examples of urea derivatives include 1-substituted ureas, methyl urea, ethyl urea, propyl urea, butyl urea, isobutyl urea, N-octadecyl urea, 2-hydroxyethyl urea, hydroxy urea, acetyl urea, allyl urea, 2-propynyl urea, cyclohexyl urea, phenyl urea, 3-hydroxyphenyl urea, (4-methoxyphenyl) urea, benzyl urea, benzoyl urea, o-tolyl urea, and p-tolyl urea.
Examples of the 2-substituted urea include 1, 1-dimethylurea, 1, 3-dimethylurea, 1-diethylurea, 1, 3-bis (hydroxymethyl) urea, 1, 3-t-butylurea, 1, 3-dicyclohexylurea, 1, 3-diphenylurea, 1, 3-bis (4-methoxyphenyl) urea, and 1-acetyl-3-methylurea.
Examples of the 4-substituted urea include tetramethylurea, 1, 3-tetraethylurea, 1, 3-tetrabutylurea, and 1, 3-dimethoxy-1, 3-dimethylurea.
(thiourea derivatives)
Thiourea derivatives are compounds in which at least 1 of the 4 hydrogen atoms of the thiourea molecule is substituted with a substituent. In this case, the substituent is not particularly limited, and is preferably a substituent containing a carbon atom, a hydrogen atom and an oxygen atom.
Specific examples of the thiourea derivatives include 1-substituted thiourea, N-methyl thiourea, ethyl thiourea, propyl thiourea, isopropyl thiourea, 1-butyl thiourea, cyclohexyl thiourea, N-acetyl thiourea, N-allyl thiourea, (2-methoxyethyl) thiourea, N-phenylthiourea, (4-methoxyphenyl) thiourea, N- (2-methoxyphenyl) thiourea, N- (1-naphthyl) thiourea, (2-pyridyl) thiourea, o-tolyl thiourea, and p-tolyl thiourea.
Examples of the 2-substituted thiourea include 1, 1-dimethylthiourea, 1, 3-dimethylthiourea, 1-diethylthiourea, 1, 3-dibutylthiourea, 1, 3-diisopropylthiourea, 1, 3-dicyclohexylthiourea, N-diphenylthiourea, N '-diphenylthiourea, 1, 3-bis (o-tolylthio) thiourea, 1, 3-bis (p-tolyl) thiourea, 1-benzyl-3-phenylthiourea, 1-methyl-3-phenylthiourea, and N-allyl-N' - (2-hydroxyethyl) thiourea.
Examples of the 3-substituted thiourea include trimethyl thiourea, and examples of the 4-substituted thiourea include tetramethyl thiourea and 1, 3-tetraethyl thiourea.
Among the urea-based compounds, urea derivatives or thiourea derivatives are preferable, and urea derivatives are more preferable. Among the urea derivatives, 1-substituted urea or 2-substituted urea is preferable, and 1-substituted urea is more preferable. The 2-substituted urea is 1, 1-substituted urea and 1, 3-substituted urea, and more preferably 1, 3-substituted urea.
< layer containing urea-based Compound >
The urea compound is not limited to the case of being contained in the adhesive layer as described above, and may be contained in a layer other than the adhesive layer from the viewpoint of improving the heat resistance of the polarizing plate. As described in the description of the transparent protective film, in recent years, in order to cope with the demand for thinning of the polarizing plate, a polarizing plate having a protective film on only one side of the polarizing element has been developed as another layer. In such a configuration, a cured layer may be laminated on the surface of the polarizing element having no protective film for the purpose of improving physical strength or the like.
In the present embodiment, such a cured layer may contain a urea compound. Generally, such a cured layer is formed from a curable composition containing an organic solvent, but a method of forming such a cured layer from an aqueous solution of an active energy ray-curable polymer composition is described in paragraphs [0020] to [0042] of Japanese patent application laid-open No. 2017-075986. Since many urea compounds are water-soluble, such compositions may contain water-soluble urea compounds.
< adhesive layer >
In order to attach the polarizing plate described above to an image display device, an adhesive layer is generally laminated. The pressure-sensitive adhesive layer is provided for bonding the polarizing plate to the image display device.
The adhesive layer may be composed of 1 layer or 2 or more layers, and preferably 1 layer. The adhesive layer may be composed of an adhesive composition containing a (meth) acrylic resin, a rubber resin, a urethane resin, an ester resin, a silicone resin, and a polyvinyl ether resin as a main component. Among them, an adhesive composition containing a (meth) acrylic resin excellent in transparency, weather resistance, heat resistance and the like as a base polymer is preferable. The adhesive composition may be an active energy ray-curable or a thermosetting type.
As the (meth) acrylic resin (base polymer) used in the adhesive composition, a polymer or copolymer containing 1 or 2 or more monomers among (meth) acrylic esters such as butyl (meth) acrylate, ethyl (meth) acrylate, isooctyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate is suitably used. The polar monomer is preferably copolymerized with the base polymer. Examples of the polar monomer include monomers having a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group, and the like, such as a (meth) acrylic acid compound, a 2-hydroxypropyl (meth) acrylate compound, a hydroxyethyl (meth) acrylate compound, a (meth) acrylamide compound, an N, N-dimethylaminoethyl (meth) acrylate compound, and a glycidyl (meth) acrylate compound.
The adhesive composition may comprise only the above base polymer, but usually also contains a crosslinking agent. Examples of the crosslinking agent include a metal ion which forms a metal salt of a carboxylic acid with a carboxyl group at a valence of 2 or more, a polyamine compound which forms an amide bond with a carboxyl group, a polyepoxide compound or a polyol which forms an ester bond with a carboxyl group, and a polyisocyanate compound which forms an amide bond with a carboxyl group. Among them, polyisocyanate compounds are preferable.
The active energy ray-curable adhesive composition has a property of being cured by irradiation with active energy rays such as ultraviolet rays and electron beams, and has a property of having adhesiveness to an adherend such as a film even before irradiation with active energy rays and being cured by irradiation with active energy rays to adjust an adhesive force. The active energy ray-curable adhesive composition is preferably an ultraviolet ray-curable adhesive composition. The active energy ray-curable adhesive composition contains an active energy ray-polymerizable compound in addition to the base polymer and the crosslinking agent. If necessary, a photopolymerization initiator, a photosensitizer, and the like may be contained.
The adhesive composition may contain fine particles for imparting light scattering properties, beads (resin beads, glass beads, etc.), glass fibers, resins other than the base polymer, tackifiers, fillers (metal powder, other inorganic powder, etc.), antioxidants, ultraviolet absorbers, dyes, pigments, colorants, defoamers, anticorrosive agents, photopolymerization initiators, and other additives.
The adhesive layer may be formed by coating an organic solvent dilution of the above adhesive composition on the surface of a substrate film, an image display unit, or a polarizing plate and drying it. The base film is usually a thermoplastic resin film, and a typical example thereof is a release film subjected to a release treatment. The release film may be, for example, a film obtained by subjecting the surface of a film containing a resin such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, or polyarylate, on which the adhesive layer is formed, to a mold release treatment such as a silicone treatment.
For example, the release film-attached adhesive layer may be laminated on the surface of the polarizing plate by directly applying the adhesive composition to the release treated surface of the release film to form an adhesive layer. The pressure-sensitive adhesive layer may be formed by directly applying the pressure-sensitive adhesive composition to the surface of the polarizing plate, and the release film may be laminated on the outer surface of the pressure-sensitive adhesive layer.
When the pressure-sensitive adhesive layer is provided on the surface of the polarizing plate, the surface activation treatment, for example, plasma treatment, corona treatment, or the like is preferably performed on the bonding surface of the polarizing plate and/or the bonding surface of the pressure-sensitive adhesive layer, and more preferably corona treatment is performed.
Alternatively, an adhesive sheet may be prepared in which the adhesive composition is applied to the 2 nd separator to form an adhesive layer, and the separator is laminated on the formed adhesive layer, and the separator-provided adhesive layer after the 2 nd separator is peeled off from the adhesive sheet may be laminated on the polarizing plate. The 2 nd release film used was a release film having a weaker adhesion to the adhesive layer than the release film and being easily peeled off.
The thickness of the pressure-sensitive adhesive layer is not particularly limited, and is preferably 1 μm or more and 100 μm or less, more preferably 3 μm or more and 50 μm or less, and may be 20 μm or more.
Examples
The present invention will be specifically described below based on examples. The materials, reagents, amounts of materials, proportions thereof, operations and the like shown in the following examples may be appropriately changed without departing from the gist of the present invention. Accordingly, the present invention is not limited to the following examples.
[ measurement method and evaluation method ]
(1) Measurement of the thickness of the polarizing element:
the measurement was performed using a digital micrometer "MH-15M" manufactured by Nikon, inc.
(2) Measurement of visibility-corrected polarization degree, visibility-corrected monomer transmittance, and color tone of polarizing plate:
the visibility correction monomer transmittance, visibility correction polarization degree, and color tone of the polarizing plate were measured using a spectrophotometer with an integrating sphere ("V7100", manufactured by japan spectroscopy corporation, field of view at 2 degrees); and C, measuring the light source.
(3) Determination of boron content of polarizing element
The content of boron in the polarizing element was measured in the following manner. First, 0.2g of the polarizing element was dissolved in 200g of a 1.9 mass% mannitol aqueous solution. Then, the obtained aqueous solution was titrated with 1 mol/L of aqueous sodium hydroxide solution, and the boron content of the polarizing element was calculated from the comparison between the amount of aqueous sodium hydroxide solution required for neutralization and the standard curve.
(4) Measurement of zinc ion content in polarizing element
The content of zinc ions in the polarizing element was measured in the following manner. First, nitric acid was added to a precisely weighed polarizing element, and acid decomposition was performed by a Milestone General microwave sample pretreatment device (ETHOSD), and the resulting solution was used as a measurement solution. The zinc ion content was calculated as the zinc mass relative to the mass of the polarizing element by quantifying the zinc concentration of the measurement solution using an ICP emission spectroscopic analyzer (5110 ICP-OES) manufactured by Agilent Technologies.
(5) Determination of boron adsorption Rate of PVA resin film
The boron adsorption rate in the PVA-based resin film was measured in the following manner. First, a PVA-based resin film cut into square 100mm was immersed in pure water at 30℃for 60 seconds, and then immersed in an aqueous solution at 60℃containing 5 parts of boric acid for 120 seconds. The PVA-based resin film taken out of the aqueous boric acid solution was dried in an oven at 80 ℃ for 11 minutes. The resulting film was subjected to humidity control at 23℃for 24 hours in an atmosphere of 55% RH, to obtain a boron-containing PVA film. The boron-containing PVA-based resin film 0.2g thus obtained was dissolved in 200g of a 1.9 mass% mannitol aqueous solution. Then, the obtained aqueous solution was titrated with 1 mol/L of aqueous sodium hydroxide solution, and the boron content of the PVA-based resin film was calculated from the comparison of the amount of aqueous sodium hydroxide solution required for neutralization and the standard curve. The boron content of the PVA-based resin film thus obtained was used as the boron adsorption rate of the PVA-based resin film.
(6) Measurement of half value width of peak derived from polyvinyl alcohol crystal of polarizing element
< sample for measurement >
A sample in which 10 polarizing elements were laminated so that the absorption axes of the polarizing elements were aligned was prepared as a sample for measurement.
< measurement Using Wide-angle X-ray Scattering method >
The values calculated by the following measuring device and measuring element using Wide-angle X-ray Scattering (Wide-angle X-ray Scattering) method are referred to.
(measurement device)
A NANO-scale X-ray structure evaluation apparatus NANO-Viewer manufactured by Rigaku corporation was used.
(measurement conditions)
X-ray source: cu-kα ray
Camera length: 71mm
Measurement: transmission measurement
X-ray irradiation time: for 10 minutes
(calculation method)
First, background measurement is performed without providing a sample for measurement, a ring-average scattering spectrum is obtained for the obtained two-dimensional scattering pattern, and then the sample for measurement is measured, and a scattering spectrum is obtained in the same manner. Then, the result obtained by subtracting the scattering spectrum of the background from the scattering spectrum of the sample for measurement was identified as a result that the wavenumber q was 15nm -1 The half value width of the peak from the polyvinyl alcohol crystal in the vicinity of the position of (a) was calculated. Fig. 1 is a graph showing values obtained by subtracting a scattering spectrum of a background from a scattering spectrum of a measurement sample, plotted against a wave number q, for polarizing elements 1 to 3 described later. The wavenumber q is at 15nm -1 The peak at the position of (2) is a peak derived from a polyvinyl alcohol crystal. The half-value width is the interval between 2 points of the intensity of 1/2 of the maximum value of the peak.
(7) High temperature durability test (115 ℃ C.)
< preparation of sample for evaluation >
Referring to the example of Japanese patent application laid-open No. 2018-025765, an acrylic adhesive (manufactured by Lindeke Co., ltd.) was applied to one side of a polarizing plate produced in accordance with the steps described later, thereby forming an adhesive layer having a thickness of 25. Mu.m. The polarizing plate having the adhesive layer formed on one side was cut into a size of 40mm×40 mm. An alkali-free glass (trade name "EAGLE XG", manufactured by Corning corporation) was bonded to the surface of the pressure-sensitive adhesive layer, and a sample for evaluation (optical laminate) was produced.
< high temperature durability test >
For the sample for evaluation obtained above, the temperature was 50℃and the pressure was 5kgf/cm 2 (490.3 kPa) for 1 hour. After the sample for evaluation was left to stand at a temperature of 23℃and a relative humidity of 55% for 24 hours, the transmittance of the visibility-correcting monomer, the visibility-correcting polarization degree and the color tone of the polarizing plate were measured, and the results were used as initial values. Next, a high temperature durability test was performed in which the sample for evaluation was stored for 500 hours in a high temperature environment at 115 ℃, and the transmittance of the visibility-correcting monomer, the visibility-correcting polarization degree, and the color tone of the polarizing plate after the high temperature durability test were measured.
The amount of change in the visibility-correcting monomer transmittance, the visibility-correcting polarization degree, and the hue of the polarizing plate is calculated from the visibility-correcting monomer transmittance, the initial value of the visibility-correcting polarization degree, and the hue, and the measured value after the high-temperature endurance test. The change amount Δty of the transmittance of the visibility-correcting monomer and the change amount Δpy of the visibility-correcting polarization degree are calculated as values obtained by subtracting the initial value from the measured value after the high-temperature endurance test. The change amount Δab of the color tone is obtained by the following equation.
Δab＝{(a1-a2) 2 +(b1-b2) 2 } 1/2
Here, a1 and b1 are initial values of color tones, and a2 and b2 are measured values of color tones after the high temperature endurance test.
[ examples 1 and 2 and comparative example 1 ]
(production of polarizing element 1)
A polyvinyl alcohol resin film having a boron adsorption rate of 5.71 mass% and a thickness of 30 μm was immersed in pure water at 21.5℃for 79 seconds (swelling treatment), and then immersed in an aqueous solution at 23℃containing 1.0mM of iodine at a mass ratio of potassium iodide/boric acid/water of 2/2/100 for 151 seconds (dyeing step). Then, in potassium iodide/boric acid/waterThe resultant mixture was immersed in an aqueous solution at 68.5℃for 76 seconds at a mass ratio of 2.5/4/100 (crosslinking step 1). Then, the mixture was immersed in an aqueous solution at 45℃for 11 seconds at a mass ratio of potassium iodide/boric acid/zinc chloride/water of 3/5.5/0.6/100 (the 2 nd crosslinking step, the metal ion treatment step). Then, the resultant was immersed in a cleaning bath to perform cleaning (cleaning step), and dried at 38℃to obtain a polarizing element having a thickness of 12. Mu.m, in which iodine was adsorbed and oriented on polyvinyl alcohol. Stretching was mainly performed in the dyeing step and the 1 st crosslinking step, and the total stretching ratio was 5.85 times. The zinc ion content of the obtained polarizing element was 0.17 mass%, the boron content was 4.62 mass%, and the half width of the peak derived from the polyvinyl alcohol crystal was 4.90nm -1 。
(production of polarizing element 2)
After immersing a polyvinyl alcohol resin film having a thickness of 30 μm and a boron adsorption rate of 5.71 mass% in pure water at 21.5℃for 79 seconds (swelling treatment), the film was immersed in an aqueous solution at 23℃containing 1.OmM iodine at a mass ratio of potassium iodide/boric acid/water of 2/2/100 for 151 seconds (dyeing step). Then, the resultant mixture was immersed in an aqueous solution at 66.5℃for 76 seconds at a mass ratio of potassium iodide/boric acid/water of 2.5/4/100 (crosslinking step 1). Then, the mixture was immersed in an aqueous solution at 45℃for 11 seconds at a mass ratio of potassium iodide/boric acid/zinc chloride/water of 3/5.5/0.6/100 (the 2 nd crosslinking step, the metal ion treatment step). Then, the resultant was immersed in a cleaning bath to perform cleaning (cleaning step), and dried at 38℃to obtain a polarizing element having a thickness of 12. Mu.m, in which iodine was adsorbed and oriented on polyvinyl alcohol. Stretching was mainly performed in the dyeing step and the 1 st crosslinking step, and the total stretching ratio was 5.85 times. The zinc ion content of the obtained polarizing element was 0.17 mass%, the boron content was 4.62 mass%, and the half width of the peak derived from the polyvinyl alcohol crystal was 4.85nm -1 。
(production of polarizing element 3)
A polyvinyl alcohol resin film having a boron adsorption rate of 5.71 mass% and a thickness of 30 μm was immersed in pure water at 21.5℃for 79 seconds (swelling treatment), then immersed in an aqueous solution at 23℃containing 1.OmM iodine at a mass ratio of potassium iodide/boric acid/water of 2/2/100 for 151 seconds (dyeing step) ). Then, the resultant mixture was immersed in an aqueous solution at 60.6℃for 76 seconds at a mass ratio of potassium iodide/boric acid/water of 2.5/4/100 (crosslinking step 1). Then, the mixture was immersed in an aqueous solution at 45℃for 11 seconds at a mass ratio of potassium iodide/boric acid/zinc chloride/water of 3/5.5/0.6/100 (the 2 nd crosslinking step, the metal ion treatment step). Then, the resultant was immersed in a cleaning bath to perform cleaning (cleaning step), and dried at 38℃to obtain a polarizing element having a thickness of 12. Mu.m, in which iodine was adsorbed and oriented on polyvinyl alcohol. Stretching was mainly performed in the dyeing step and the 1 st crosslinking step, and the total stretching ratio was 5.85 times. The zinc ion content of the obtained polarizing element was 0.17 mass%, the boron content was 4.62 mass%, and the half width of the peak derived from the polyvinyl alcohol crystal was 4.75nm -1 。
(preparation of PVA solution for adhesive)
50g of an acetoacetyl group-containing modified PVA resin (manufactured by Mitsubishi chemical corporation: GOHSENX Z-410) was dissolved in 950g of pure water, heated at 90℃for 2 hours, and cooled to room temperature to obtain a PVA solution for adhesives.
(preparation of adhesive 1 for polarizing plate)
The prepared PVA solution for an adhesive, pure water, and methanol were mixed so that the PVA concentration was 3.0%, the methanol concentration was 35%, and the urea concentration was 0.5%, to obtain an adhesive 1 for a polarizing plate.
(saponification of cellulose acylate film)
A commercially available cellulose acylate film TJ40UL (manufactured by Fuji photo Co., ltd.: film thickness 40 μm) was immersed in a 1.5mol/L aqueous NaOH solution (saponification liquid) kept at 55℃for 2 minutes, and the film was washed with water. Then, the membrane was immersed in a sulfuric acid aqueous solution of 0.05mol/L at 25℃for 30 seconds, and further subjected to water washing under running water for 30 seconds, whereby the membrane was brought into a neutral state. Then, the water removal by the air knife was repeated 3 times. After removing water, the film was left in a drying zone at 70 ℃ for 15 seconds and dried, whereby a saponified film was produced.
(production of polarizing plate 1)
On both sides of the polarizing element 1, a saponified cellulose acylate film was bonded with an adhesive 1 for polarizing plates. The thickness of the adhesive layer after drying was adjusted so that the thickness of the adhesive layer was 100nm on both sides. The bonding was performed using a roll laminator. After bonding, the polarizing element 1 was dried at 80℃for 3 minutes, and then bonded to a cellulose acylate film. Thus, a polarizing plate 1 having cellulose acylate films bonded to both surfaces of the polarizing element 1 was obtained.
Polarizing plates 2 and 3 were produced in the same manner except that polarizing element 1 of polarizing plate 1 was changed to polarizing elements 2 and 3.
(production of optical layered bodies 1 to 3)
Referring to the examples of Japanese patent application laid-open No. 2018-025765, an acrylic adhesive (manufacturer: wandeke Co., ltd.) was applied to one side of the polarizing plates 1 to 3 produced as described above, thereby producing optical laminates 1 to 3 having an adhesive layer with a thickness of 25 μm on one side of the polarizing plates.
Example 1
In example 1, a high temperature durability test was performed on the optical laminate 1. The optical laminate 1 had a change in transmittance Δty of 0.6%, a change in visibility-correcting polarization degree Δpy of-0.03%, and a change in color tone Δab of 2.0NBS. The results are shown in Table 1.
Example 2
In example 2, a high temperature durability test was performed on the optical laminate 2. The optical laminate 2 had a change in transmittance Δty of 1.2%, a change in visibility-correcting polarization degree Δpy of-0.03%, and a change in color tone Δab of 2.3NBS. The results are shown in Table 1.
Comparative example 1
The optical laminate 3 had a change in transmittance Δty of 2.6%, a change in visibility-correcting polarization degree Δpy of-0.13%, and a change in hue Δab of 5.3NBS. The results are shown in Table 1.
TABLE 1
It was found that the optical laminates 1 and 2 were superior to the optical laminate 3 in the effect of suppressing the decrease in polarization degree even when exposed to a high-temperature environment at 115 ℃.
Claims (7)
1. A polarizing plate comprising a polarizing element and a transparent protective film, wherein the polarizing element is formed by adsorbing and aligning a dichroic dye on a polyvinyl alcohol resin layer,
the half value width of the peak from the polyvinyl alcohol crystal measured by the wide angle X-ray scattering method of the polarizing element is 4.80nm -1 The above-mentioned steps are carried out,
the polarizing element contains potassium ions and metal ions other than potassium ions,
in the polarizing element, the content of the metal ions other than potassium ions is 0.05 mass% or more.
2. The polarizing plate according to claim 1, wherein the metal ions comprise at least 1 of the group consisting of ions of cobalt, nickel, zinc, chromium, aluminum, copper, manganese, and iron.
3. The polarizing plate according to claim 1 or 2, wherein the content of boron in the polarizing element is 2.4 mass% or more and 8.0 mass% or less.
4. The polarizing plate according to any one of claims 1 to 3, further comprising an adhesive layer for bonding the polarizing element to the transparent protective film,
The adhesive layer is a coating layer of an aqueous adhesive.
5. The polarizing plate according to claim 4, wherein the concentration of methanol in the aqueous adhesive is 10 mass% or more and 70 mass% or less.
6. The polarizing plate according to claim 4 or 5, wherein the aqueous adhesive comprises a polyvinyl alcohol resin.
7. The polarizing plate according to any one of claims 4 to 6, wherein the adhesive layer has a thickness of 0.01 μm or more and 7 μm or less.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-132867 | 2021-08-17 | ||
| JP2021132867A JP2023027631A (en) | 2021-08-17 | 2021-08-17 | Polarizing plate |
| PCT/JP2022/030074 WO2023022020A1 (en) | 2021-08-17 | 2022-08-05 | Polarizing plate |
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| CN117581126A true CN117581126A (en) | 2024-02-20 |
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| JP (1) | JP2023027631A (en) |
| KR (1) | KR20240040733A (en) |
| CN (1) | CN117581126A (en) |
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| JP3323255B2 (en) | 1992-12-07 | 2002-09-09 | 株式会社クラレ | Polarizing film and manufacturing method thereof |
| JP2000035512A (en) * | 1998-07-17 | 2000-02-02 | Sumitomo Chem Co Ltd | Polarizing film |
| JP2006047978A (en) | 2004-06-29 | 2006-02-16 | Nitto Denko Corp | Polarizer, its manufacturing method, polarizing plate, optical film and image display apparatus |
| US7662456B2 (en) * | 2005-12-12 | 2010-02-16 | Eastman Kodak Company | Guarded cover sheet for LCD polarizers and method of making the same |
| JP4702955B2 (en) | 2006-08-11 | 2011-06-15 | 日東電工株式会社 | Polarizing plate and manufacturing method of polarizing plate, optical film and image display device |
| JP2010134448A (en) * | 2008-10-31 | 2010-06-17 | Nippon Synthetic Chem Ind Co Ltd:The | Polarizing plate and method for manufacturing the same |
| JP2016117659A (en) | 2014-12-19 | 2016-06-30 | 五洲薬品株式会社 | New bath additive |
| JP6794106B2 (en) * | 2015-12-07 | 2020-12-02 | 住友化学株式会社 | Method of manufacturing polarizing film |
| JP7448477B2 (en) * | 2018-09-05 | 2024-03-12 | 日本化薬株式会社 | Polarizing elements, polarizing plates and optical members using the same, etc. |
| JP2020126226A (en) * | 2019-02-04 | 2020-08-20 | 住友化学株式会社 | Polarizing plate and display device |
| CN112041715A (en) * | 2019-02-26 | 2020-12-04 | 日东电工株式会社 | Method for manufacturing polarizer, method for manufacturing polarizing film, method for manufacturing laminated polarizing film, method for manufacturing image display panel, and method for manufacturing image display device |
| KR102484683B1 (en) * | 2019-03-29 | 2023-01-05 | 주식회사 엘지화학 | Optical Laminate |
| JP2020166097A (en) * | 2019-03-29 | 2020-10-08 | 株式会社ポラテクノ | Polarizing plate with silica layer and manufacturing method therefor |
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| TW202314302A (en) | 2023-04-01 |
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