WO2017078095A1 - Polarizer and method for manufacturing same - Google Patents
Polarizer and method for manufacturing same Download PDFInfo
- Publication number
- WO2017078095A1 WO2017078095A1 PCT/JP2016/082663 JP2016082663W WO2017078095A1 WO 2017078095 A1 WO2017078095 A1 WO 2017078095A1 JP 2016082663 W JP2016082663 W JP 2016082663W WO 2017078095 A1 WO2017078095 A1 WO 2017078095A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polarizer
- film
- degree
- axis direction
- stretching
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 238000000034 method Methods 0.000 title description 21
- 238000010521 absorption reaction Methods 0.000 claims abstract description 49
- 230000008602 contraction Effects 0.000 claims abstract description 34
- 230000005540 biological transmission Effects 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims description 74
- 238000004043 dyeing Methods 0.000 claims description 31
- 230000000295 complement effect Effects 0.000 claims description 26
- 230000008961 swelling Effects 0.000 claims description 22
- 238000002835 absorbance Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 230000001681 protective effect Effects 0.000 claims description 19
- 230000031700 light absorption Effects 0.000 abstract 4
- 239000010408 film Substances 0.000 description 103
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 229910052740 iodine Inorganic materials 0.000 description 27
- 239000011630 iodine Substances 0.000 description 27
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 24
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 23
- 230000010287 polarization Effects 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 16
- 230000003287 optical effect Effects 0.000 description 14
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- -1 polyethylene terephthalate Polymers 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 239000004327 boric acid Substances 0.000 description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 description 9
- 150000001639 boron compounds Chemical class 0.000 description 9
- 230000001186 cumulative effect Effects 0.000 description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
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- 230000000694 effects Effects 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- 238000007602 hot air drying Methods 0.000 description 4
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 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 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical compound CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 description 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- 241000694440 Colpidium aqueous Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 241000656145 Thyrsites atun Species 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 238000007611 bar coating method Methods 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
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
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- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
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- 238000000151 deposition Methods 0.000 description 1
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- 238000007607 die coating method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
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- 239000003822 epoxy resin Substances 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- JTHNLKXLWOXOQK-UHFFFAOYSA-N n-propyl vinyl ketone Natural products CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000642 polymer 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
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000002265 prevention Effects 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
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000002335 surface treatment layer Substances 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
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 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
-
- 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
- B29D11/0074—Production of other optical elements not provided for in B29D11/00009- B29D11/0073
- B29D11/00788—Producing optical films
-
- 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
-
- 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
Definitions
- the present invention relates to a polarizer and a method for producing the same, and more particularly to a polarizer having excellent optical characteristics and a small shrinkage force in the absorption axis (stretching) direction and a method for producing the same.
- Polarizers used in various image display devices such as liquid crystal display devices (LCD), electroluminescence (EL) display devices, plasma display devices (PDP), field emission display devices (FED), OLEDs, etc.
- a polyvinyl alcohol (PVA) film includes a polarizer in which an iodine compound or a dichroic polarizing material is adsorbed and oriented, and a polarizer protective film is sequentially laminated on one surface of the polarizer.
- the other surface of the child has a multilayer structure in which a polarizer protective film, an adhesive layer bonded to another member, and a release film are sequentially laminated.
- a polarizer constituting a polarizing plate is applied to an image display device, and is basically required to have both high transmittance and degree of polarization in order to provide an image having excellent color reproducibility.
- a polarizer was manufactured by modifying the polyvinyl alcohol film itself or using a non-sublimation dichroic dye in place of the sublimable iodine polarization element.
- a polarizer usually has a polarizing function by orienting an internal molecular arrangement in a predetermined direction by stretching a film for forming a polarizer produced using a polymer. Therefore, the stretching process is an indispensable process when manufacturing a polarizer.
- Japanese Published Patent Application No. 2010-145866 discloses a method of manufacturing a polarizer with a small shrinkage stress, but it does not present a satisfactory alternative to the above problem.
- An object of the present invention is to provide a polarizer having an excellent degree of polarization and a small shrinkage force in the absorption axis direction, and a method for producing the same.
- the degree of orientation is 0.250 to 0.400, the contraction force in the absorption axis direction is 3.5 N / 2 mm or less,
- the degree of orientation is a polarizer obtained from Equation 1 below: (Wherein, A MD is the absorbance of infrared light polarized in the absorption axis direction of the polarizer, A TD is the absorbance of infrared light polarized in the transmission axis direction of the polarizer, A large is the A MD the absorbance of the higher one of a TD, a small the absorbance of the lower of a MD and a TD).
- the cross-linking step includes a first cross-linking step of stretching the polarizer forming film to 2.00 to 3.00 times, and a first forming step of stretching the polarizer forming film to 1.00 times or less after the first cross-linking step. 2 cross-linking steps,
- the polarizer forming film is stretched at a stretch ratio that is higher than the stretch ratio of the second cross-linking step and lower than the stretch ratio of the first cross-linking step.
- a polarizing plate comprising the polarizer according to 1 or 2 and a polarizer protective film bonded to at least one surface of the polarizer.
- the polarizer of the present invention exhibits a small contraction force in the absorption axis direction while having excellent optical characteristics without deterioration of other physical properties by having an orientation degree in a predetermined range and a contraction force in the absorption axis direction. be able to.
- the method for producing a polarizer of the present invention can produce the polarizer according to the present invention by stretching the film for forming a polarizer at a stretching ratio in a specific range in the crosslinking step and the complementary color step.
- a stretching ratio usually, the higher the degree of stretching, the higher the degree of orientation. In order to realize excellent polarization characteristics, it is necessary to increase the stretching ratio.
- the higher the stretching ratio the greater the contraction force in the stretching (absorption axis) direction. . Therefore, there is a trade-off relationship between the realization of a high degree of orientation and the contraction force in the low absorption axis direction.
- the method for producing a polarizer of the present invention can adjust the range of the degree of orientation while having a low shrinkage force in the absorption axis direction, and as a result, while having a high degree of polarization.
- a polarizer having a small contraction force in the absorption axis direction can be manufactured.
- the degree of orientation is 0.250 to 0.400, and the contraction force in the absorption axis direction is 3.5 N / 2 mm or less, so that the polarizer has excellent optical characteristics and small contraction force in the absorption axis direction. And a manufacturing method thereof.
- the inventors of the present application manufactured a polarizer that simultaneously satisfies a high degree of orientation and a small shrinkage force in the absorption axis direction through a method of manufacturing a polarizer capable of adjusting the degree of orientation.
- a polarizer having a small contraction force in the absorption axis direction can be obtained without a decrease in the polarization degree.
- the polarizer of the present invention may have an orientation degree of 0.250 to 0.400, preferably 0.300 to 0.400. If the degree of orientation is less than 0.250, the degree of polarization decreases, and if it exceeds 0.400, there is a problem that the contraction force in the absorption axis direction increases and the warpage of the polarizer increases.
- the stretching ratio in the first crosslinking step is controlled to 2.00 to 3.00 times and the total cumulative stretching ratio is controlled to 5.0 times or more. Can be adjusted.
- the degree of orientation according to the present invention is the difference between the absorbance of infrared light (IR) polarized in the absorption axis direction (MD direction) of the polarizer and the absorbance of infrared light polarized in the transmission axis direction (TD direction) of the polarizer.
- IR infrared light
- MD direction absorption axis direction
- TD direction transmission axis direction
- AMD is the absorbance of infrared light polarized in the absorption axis direction (MD direction) of the polarizer
- a TD is the absorbance of infrared light polarized in the transmission axis direction (TD direction) of the polarizer.
- a large is the absorbance of the higher one of a MD and a TD
- a small the absorbance of the lower of a MD and a TD.
- the absorbance of infrared light can be measured by, for example, a Fourier transform infrared spectrophotometer (FT-IR).
- FT-IR Fourier transform infrared spectrophotometer
- the wave number of the infrared light can be set to 1290 cm ⁇ 1 , for example.
- the polarizer of the present invention may have a low contraction force in the absorption axis direction, and the contraction force in the absorption axis direction may be 3.5 N / 2 mm or less.
- the contraction force in the absorption axis direction is 3.5 N / 2 mm or less, deformation of the polarizer can be effectively prevented.
- the lower the shrinkage force in the absorption axis direction the better. Therefore, the lower limit thereof is not particularly limited, and may be, for example, 2 N / 2 mm or more, 1 N / 2 mm or more, or 0.1 N / 2 mm or more.
- the stretching ratio of the first crosslinking step is 2.00 to 3.00 times, and the stretching ratio of the second crosslinking step is 1. It is possible to adjust by controlling at less than 0.000 times.
- the thickness of the polarizer of the present invention may be 5 to 30 ⁇ m, preferably 10 to 28 ⁇ m, more preferably 15 to 26 ⁇ m. When the thickness of the polarizer is in the above range, both low shrinkage force in the absorption axis direction of the polarizer and handling properties can be achieved.
- the present invention also provides a method for manufacturing the above-described polarizer.
- the method for producing a polarizer of the present invention includes swelling, dyeing, stretching, cross-linking, complementary color and drying steps of a polarizer-forming film, and the cross-linking step is 2.00 to 3.00 times the polarizer-forming film.
- the film for forming a polarizer is stretched at a stretch ratio that is higher than the stretch ratio of the cross-linking step and lower than the stretch ratio of the first cross-linking step.
- the degree of orientation of the polarizer and the contraction force in the absorption axis direction can be adjusted to realize a high polarization degree and a small contraction force in the absorption axis direction.
- a film that can be dyed with a dichroic substance for example, iodine
- a dichroic substance for example, iodine
- polyvinyl alcohol film partially saponified polyvinyl alcohol film; polyethylene terephthalate film, ethylene-vinyl acetate copolymer film, ethylene-vinyl alcohol copolymer film, cellulose film, partially A hydrophilic polymer film such as a saponified film, or a polyene oriented film such as a dehydrated polyvinyl alcohol film or a dehydrochlorinated polyvinyl chloride film can be used.
- a polyvinyl alcohol film is preferable because it not only has an excellent effect of enhancing the uniformity of the degree of polarization in the plane, but also has an excellent dyeing affinity for iodine.
- the method for producing a polarizer according to the present invention may include a swelling step, a dyeing step, a crosslinking step, a complementary color step, a stretching step, a water washing step, and a drying step, and can be classified according to a stretching method.
- a dry stretching method, a wet stretching method, or a hybrid stretching method in which the above-mentioned two kinds of stretching methods are mixed can be used.
- the manufacturing method of the polarizer of this invention is demonstrated taking the wet extending
- the remaining steps except the drying step are the states in which the film for forming the polarizer is immersed in a constant temperature bath (bath) filled with one or more solutions each selected from various types of solutions. Can be done.
- the swelling step is performed by immersing the unstretched polarizer-forming film in a swelling tank filled with a swelling aqueous solution before dyeing it, and depositing impurities on the surface of the polarizer-forming film, such as impurities or antiblocking agents.
- impurities such as impurities or antiblocking agents.
- an aqueous solution for swelling known in the art can be used without particular limitation.
- water pure water, deionized water
- glycerin or potassium iodide When is added, processability can be improved along with swelling of the polymer film.
- the content of glycerin is preferably 5% by weight or less and the content of potassium iodide is preferably 10% by weight or less with respect to 100% by weight of water.
- the temperature of the swelling tank is not particularly limited, but may be 20 to 45 ° C, for example, 25 to 40 ° C.
- a performance time known in the art can be applied without particular limitation, and may be, for example, 180 seconds or less, preferably 90 seconds or less. .
- immersion time is in the above range, it is possible to suppress the swelling from becoming excessively saturated, and the breakage due to the softening of the polarizer forming film is prevented, and the adsorption of iodine becomes uniform in the dyeing step.
- the degree of polarization can be improved.
- the stretching step can be performed together with the swelling step.
- the stretching ratio may be about 1.1 to 3.5 times, but is not limited, and preferably 1.5 to 3.0 times. Good. If the draw ratio is less than 1.1 times, wrinkles may occur. If it exceeds 3.5 times, the initial optical characteristics may be weak.
- the dyeing step is a step of immersing the polarizer forming film in a dyeing tank filled with a dichroic substance, for example, an aqueous dyeing solution containing iodine, and adsorbing iodine to the polarizer forming film.
- a dichroic substance for example, an aqueous dyeing solution containing iodine, and adsorbing iodine to the polarizer forming film.
- an aqueous dye solution known in the art can be used without particular limitation, and it can contain water, a water-soluble organic solvent or a mixed solvent thereof and iodine.
- the iodine content may be 0.4 to 400 mmol / L in the aqueous dyeing solution, but is not limited thereto, and is preferably 0.8 to 275 mmol / L, most preferably 1 to 200 mmol / L. Also good.
- the aqueous solution for dyeing may further contain an iodide as a solubilizing agent so that the dyeing efficiency can be improved.
- an iodide known in the art can be used without limitation.
- At least one selected from the group consisting of barium iodide, calcium iodide, tin iodide, and titanium iodide can be included, and among these, potassium iodide is preferable because of its high solubility in water.
- the iodide content may be 0.01 to 10% by weight with respect to 100% by weight of water, but is not limited, and may preferably be 0.1 to 5% by weight.
- boric acid may be added to the dyeing tank in an amount of 0.3 to 5% by weight with respect to 100% by weight of water. Not. When boric acid dyeing tank is less than 0.3 wt%, PVA-I 3 - complex and PVA-I 5 - it may not be effective in increasing the complex content, boric acid dyeing tank 5 If the concentration is higher than% by weight, the risk of film breakage may increase.
- the temperature of the dyeing tank may be 5 to 42 ° C, but is not limited thereto, and may preferably be 10 to 35 ° C.
- the immersion time of the film for forming a polarizer in the dyeing tank is not particularly limited, and may be 1 to 20 minutes, preferably 2 to 10 minutes.
- the stretching step can be performed together with the dyeing step.
- the stretching ratio may be 1.01 to 2.0 times, but is not limited thereto, and preferably 1. It may be 1 to 1.8 times.
- the cumulative stretching ratio up to the dyeing step including the swelling and dyeing step may be 1.2 to 4.0 times. If the cumulative stretch ratio is less than 1.2 times, wrinkles of the film may occur and appearance defects may occur, and if it exceeds 4.0 times, the initial optical characteristics may be fragile.
- the cross-linking step is a step of fixing the adsorbed iodine molecules by immersing the dyed polarizer forming film in an aqueous solution for cross-linking so that the dyeability by physically adsorbed iodine molecules does not deteriorate due to the external environment. It is.
- iodine which is a dichroic dye
- iodine molecules may be detached by a moist heat environment, and sufficient crosslinking reaction is required. Further, in order to orient the iodine molecules located between the molecules of the polarizer-forming film and improve the optical properties, stretching at the largest stretching ratio can be performed in the crosslinking step.
- the crosslinking step includes a first crosslinking step and a second crosslinking step, and at least one of the first and second crosslinking steps is for crosslinking containing a boron compound.
- An aqueous solution can be used. This can improve the optical properties and color durability of the polarizer.
- the aqueous solution for crosslinking a known aqueous crosslinking solution can be used without particular limitation.
- the aqueous solution for crosslinking may contain water as a solvent and a boron compound such as boric acid or sodium borate. It may further contain an organic solvent and iodide that are mutually soluble.
- Boron compounds impart short crosslinks and stiffness to the polarizer, and can suppress wrinkling of the film during the process, improving the handleability of the film and forming the iodine orientation of the polarizer Can play a role.
- the boron compound content may be a content known in the art, and may be, for example, 1 to 10% by weight, preferably 2 to 6% by weight with respect to 100% by weight of water. Good. When the content is less than 1% by weight, the crosslinking effect of the boron compound is reduced, and it may be difficult to impart rigidity to the polarizer. When the content exceeds 10% by weight, the crosslinking reaction of the inorganic crosslinking agent is excessive. When activated, the crosslinking reaction of the organic crosslinking agent may not proceed effectively.
- iodide can be used to maintain the uniformity of the degree of polarization in the plane of the polarizer and to prevent desorption of dyed iodine.
- the iodide may be the same as that used in the dyeing step, and its content may be 0.05 to 15% by weight with respect to 100% by weight of water, but is not limited, preferably May be from 0.5 to 14% by weight. If the content is less than 0.05% by weight, iodine ions in the film may escape and increase the transmittance of the polarizer. If the content exceeds 15% by weight, iodine ions in the aqueous solution may be added to the film. It can penetrate and reduce the transmittance of the polarizer.
- the temperature of the crosslinking tank may be 20 to 70 ° C., but is not limited thereto.
- the immersion time of the film for forming a polarizer in the crosslinking tank may be 1 second to 15 minutes, but is not limited thereto, and may preferably be 5 seconds to 10 minutes.
- the cross-linking step of the present invention includes first and second cross-linking steps, and the stretching step is performed together.
- the stretch ratio of the first crosslinking step is 2.00 to 3.00 times, preferably 2.20 to 2.80 times.
- the first crosslinking step according to the present invention improves the mechanical properties of the polarizer by stretching the polarizer-forming film at a high stretch ratio, and prevents the polarizer-forming film from being broken in the subsequent second crosslinking step. To do. If the stretch ratio of the first crosslinking step is less than 2.00 times, the desired degree of orientation does not appear, so that mechanical properties are not ensured, and if it exceeds 3.00 times, the contraction force in the absorption axis direction may increase. .
- the stretching ratio of the second crosslinking step is 1.00 times or less, preferably 0.80 to 1.00 times, more preferably 0.85 times to 1.00 times.
- the second cross-linking step according to the present invention is a step of relieving the stress generated in the first cross-linking step, and is a step of preventing the polarizer forming film from being broken and reducing the contraction force in the absorption axis direction.
- the stretch ratio of the second crosslinking step exceeds 1.00 times, the film may be broken, and there is a problem that the shrinkage force in the absorption axis direction increases.
- the cumulative stretching ratio of the first and second crosslinking steps may be 1.5 to 3.0 times, and preferably 1.98 to 2.8 times. If the cumulative stretching ratio is less than 1.5 times, the orientation effect of the film for forming a polarizer may be insufficient. If it exceeds 3.0 times, the stress due to stretching increases and the absorption axis increases. Directional contraction force can be increased.
- the complementary color step is a step of stabilizing the iodine complex by orienting the iodine complex located between the molecules in the polarizer-forming film on which the iodine complex is physically adsorbed in the vicinity of the boric acid bridge. . Further, through the complementary color step, the color can be corrected for the polarizer-forming film in which the iodine complex is not sufficiently dyed in the crosslinking step.
- the aqueous solution for complementary color in the complementary color step includes, for example, water as a solvent and a boron compound such as boric acid, and may further include an organic solvent and iodide that are mutually soluble with water.
- the boron compound imparts short crosslinks and rigidity to the polarizer, and suppresses wrinkling of the film during the process, thereby improving the handleability of the film and improving the iodine orientation of the polarizer. Can play a role to form.
- the content of the boron compound may be 1 to 10% by weight with respect to 100% by weight of water, but is not limited thereto, and may preferably be 2 to 6% by weight.
- the content is less than 1% by weight, the crosslinking effect of the boron compound is reduced, and it may be difficult to impart rigidity to the polarizer.
- the content exceeds 10% by weight, the crosslinking reaction of the inorganic crosslinking agent is excessive. When activated, the crosslinking reaction of the organic crosslinking agent may not proceed effectively.
- iodide can be used to maintain the uniformity of the degree of polarization in the plane of the polarizer and to prevent desorption of dyed iodine.
- the iodide may be the same as that used in the dyeing step, and the content may be 0.05 to 15% by weight with respect to 100% by weight of water, but is not limited thereto. Preferably, it may be 0.5 to 11% by weight. If the content is less than 0.05% by weight, iodine ions in the film may escape and increase the transmittance of the polarizer. If the content exceeds 15% by weight, iodine ions in the aqueous solution may be added to the film. It can penetrate and reduce the transmittance of the polarizer.
- the temperature of the complementary color tank may be 20 to 70 ° C.
- the immersion time of the polarizer-forming film in the complementary color tank may be 1 second to 15 minutes, but is not limited thereto, and may preferably be 5 seconds to 10 minutes.
- the complementary color step according to the present invention is performed together with the stretching step, and at this time, the stretching ratio of the complementary color step is higher than the stretching ratio of the second crosslinking step and lower than the stretching ratio of the first crosslinking step.
- the complementary color step according to the present invention maintains a small contraction force in the direction of the absorption axis while realizing a high degree of orientation and improving optical characteristics by stretching a film for forming a polarizer at a relatively high stretch ratio. Can do.
- the stretching ratio of the complementary color step may be 1.01 to 1.25 times, preferably 1.05 to 1.20 times.
- the effect of the complementary color step described above can be excellently exhibited within the range of the stretch ratio. If the draw ratio is less than 1.01, the stabilizing effect of the iodine complex and the orientation degree of the film for forming the polarizer may be lowered. May occur, and production efficiency may be reduced.
- the stretching step may be performed simultaneously with the crosslinking step and the complementary color step as described above, may be performed together with other steps, or may be additionally performed as a separate step.
- the total cumulative draw ratio of the polarizer is preferably 5.0 times or more, for example, preferably 5.0 to 7.0 times, and 5.3 to 6.0. More preferably, it is double.
- the polarizer production method of the present invention is, as necessary, for immersing a film for forming a polarizer, which has been crosslinked and stretched, in a washing tank filled with an aqueous washing solution, and for forming a polarizer in steps up to the washing step.
- a water washing step may be further included to remove unwanted residues such as boric acid attached to the film.
- the aqueous washing solution may be an aqueous washing aqueous solution known in the art without particular limitation, and may be, for example, water, to which an iodide may be further added. Not.
- the temperature of the washing tank may be 10 to 60 ° C, but is not limited thereto, and may preferably be 15 to 40 ° C.
- the water washing step can be omitted, and can be performed each time a step before the water washing step such as the dyeing step or the crosslinking step is completed. Further, it may be repeated one or more times, and the number of repetitions is not particularly limited.
- the drying step is a step of drying the washed film for forming a polarizer, and further improves the orientation of dyed iodine molecules by neck-in by drying. This is a step of obtaining a polarizer having excellent optical characteristics. Neck-in means that the width of the film is narrowed.
- a drying method As a drying method, a drying method known in the art can be used in combination without limitation, and methods such as natural drying, hot air drying, air drying, heat drying, far-infrared drying, and microwave drying can be used. Recently, microwave drying in which only water in the film is activated and dried is newly used, and usually hot air drying is mainly used.
- the temperature at which the hot air drying is performed is not particularly limited, but is preferably performed at a relatively low temperature in order to prevent deterioration of the polarizer, and may be, for example, 20 to 90 ° C., preferably 85 ° C. or less. Preferably, it may be 80 ° C. or lower.
- the time for performing the hot air drying is not particularly limited, and can be performed, for example, for 1 to 10 minutes.
- the polarizer according to the present invention can be provided as a polarizing plate with a polarizer protective film bonded to at least one surface.
- the type of the protective film is not particularly limited as long as it is a film excellent in transparency, mechanical strength, thermal stability, moisture shielding property, isotropy, etc.
- Specific examples include polyethylene terephthalate, polyethylene Polyester resins such as isophthalate and polybutylene terephthalate; Cellulosic resins such as diacetyl cellulose and triacetyl cellulose; Polycarbonate resins; Polyacrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Polystyrene and acrylonitrile Styrene resins such as styrene copolymers; Polyolefin resins such as polyethylene, polypropylene, cyclo- or norbornene-structured polyolefins, ethylene-propylene copolymers; nylons, aromatic polyamides, etc.
- examples include oxymethylene resins; films composed of thermoplastic resins such as epoxy resins, and films composed of blends of the thermoplastic resins can also be used.
- a film made of a thermosetting resin such as (meth) acrylic, urethane, epoxy, or silicon, or an ultraviolet curable resin can be used.
- a film composed of a cellulose resin having a surface saponified with alkali or the like is particularly preferable in view of polarization characteristics or durability.
- the protective film may have a function of the following optical layer.
- the structure of the polarizing plate is not particularly limited, and various types of optical layers that can satisfy necessary optical characteristics may be laminated on a polarizer.
- a structure in which a protective film for protecting a polarizer is laminated on at least one surface of a polarizer; a hard coating layer, an antireflection layer, an anti-adhesion layer, a diffusion prevention layer, an antiglare layer on at least one surface of the polarizer or on the protective film A structure in which a surface treatment layer such as a layer is laminated; a structure in which an alignment liquid crystal layer for compensating a viewing angle or another functional film is laminated on at least one surface of a polarizer or a protective film Good.
- a wave plate such as an optical film such as a polarization conversion device, a reflector, a semi-transmissive reflector, a half-wave plate or a quarter-wave plate used for forming various image display devices.
- the polarizing plate has a structure in which a protective film is laminated on one surface of a polarizer, and a reflective polarizing plate or a semi-transmissive polarizing plate in which a reflector or a semi-transmissive reflector is laminated on the laminated protective film.
- Bonding of the polarizer and the polarizer protective film may be performed using an adhesive composition. Bonding of the polarizer and the protective film using the adhesive composition can be performed by an appropriate method, such as casting method, Mayer bar coating method, gravure coating method, die coating method, dip coating method, spraying method, etc.
- coating an adhesive composition to the adhesive surface of a polarizing film and / or a protective film, and making both overlap is mentioned.
- the casting method is a method in which an adhesive composition is applied to the surface of an object to be coated while moving a polarizer or a protective film to be coated in a substantially vertical direction, a substantially horizontal direction, or an oblique direction therebetween. .
- the polarizer and the protective film are sandwiched by nip rolls and bonded.
- the surface of the polarizer and / or the protective film can be appropriately subjected to surface treatment such as plasma treatment, corona treatment, ultraviolet irradiation treatment, flame treatment, saponification treatment.
- surface treatment such as plasma treatment, corona treatment, ultraviolet irradiation treatment, flame treatment, saponification treatment.
- saponification treatment include a method of immersing in an aqueous solution of an alkali such as sodium hydroxide or potassium hydroxide.
- the drying process is performed, for example, by spraying hot air, and the temperature at that time is appropriately selected in the range of 50 to 100 degrees.
- the drying time is usually 30 to 1,000 seconds.
- the polarizing plate according to the present invention is applicable not only to a normal liquid crystal display device but also to various image display devices such as an organic electroluminescence display device (OLED), a plasma display device, and a field emission display device.
- OLED organic electroluminescence display device
- plasma display device a plasma display device
- field emission display device a field emission display device
- Example 1 After a transparent unstretched polyvinyl alcohol film (PE60, KURARAY) having a saponification degree of 99.9% or more was immersed in water (deionized water) at 25 ° C. for 1 minute and 20 seconds to swell (swelling step) Dyeing by immersing in an aqueous dyeing solution at 30 ° C. containing 1.25% by weight of potassium iodide and 0.3% by weight of boric acid for 1.25 mM / L of iodine and 100% by weight of water for 2 minutes and 30 seconds (Staining step).
- P60 transparent unstretched polyvinyl alcohol film having a saponification degree of 99.9% or more was immersed in water (deionized water) at 25 ° C. for 1 minute and 20 seconds to swell (swelling step)
- Dyeing by immersing in an aqueous dyeing solution at 30 ° C. containing 1.25% by weight of potassium iodide and 0.
- the film was stretched at stretch ratios of about 1.7184 times and about 1.5214 times, respectively, and stretched so that the cumulative stretch ratio up to the dyeing tank was 2.614 times.
- an aqueous solution for crosslinking at 56 ° C. containing 13.9% by weight of potassium iodide and 3% by weight of boric acid with respect to 100% by weight of water for 26 seconds for crosslinking (first crosslinking step)
- the film was drawn at a draw ratio of 36 times. Then, while being immersed in a 56 ° C.
- aqueous solution for crosslinking containing 13.9% by weight of potassium iodide and 3% by weight of boric acid with respect to 100% by weight of water for 20 seconds to crosslink (second crosslinking step)
- the film was stretched at a stretching ratio of 0.90.
- the film was stretched 1.08 times while immersed in a complementary color aqueous solution at 40 ° C. containing 5% by weight of potassium iodide and 2% by weight of boric acid with respect to 100% by weight of water (complementary color step).
- the total cumulative draw ratio of the swelling, dyeing, crosslinking, and complementary color steps was set to 6 times.
- the polyvinyl alcohol film was washed with deionized water (water washing step) and then dried in an oven at 80 ° C. for 5 minutes (drying step) to produce a polarizer having a transmittance of 42.5%.
- the thickness of the polarizer was 23 ⁇ m.
- a polarizing plate was manufactured by laminating a triacetyl cellulose (TAC) film on both sides of the manufactured polarizer.
- TAC triacetyl cellulose
- Polarization degree (P) [(T 1 ⁇ T 2 ) / (T 1 + T 2 )] 1/2 (In the formula, T 1 is a parallel transmittance obtained when a pair of polarizers are arranged in a state where the absorption axes are parallel, and T 2 is a case where a pair of polarizers is arranged in a state where the absorption axes are orthogonal to each other. It is the orthogonal transmittance obtained).
- the IR beam is polarized using a polarization ATR apparatus (VeeMAXIII, PIKE, incident angle: 45 °), and the polarized IR beam and the polarizer sample Absorbance is measured with FT-IR so that the MD direction (absorption axis direction) is parallel (A MD ) (Nicolet Continuum XL, Thermo).
- a MD transmission axis direction
- the absorbance is measured by FT-IR so that the polarized IR beam is parallel to the TD direction (transmission axis direction) of the polarizer sample (A TD ).
- Absorbance at 1290 cm ⁇ 1 indicating the difference in absorbance in the MD and TD directions was measured. The measured absorbance was substituted into Equation 1 to obtain the degree of orientation.
- the contraction force in the absorption axis direction per 2 mm width in the transmission axis direction of the polarizer was measured.
- the polarizers produced in the examples and comparative examples were cut to a size of 3.0 cm (absorption axis direction) ⁇ 2 mm (transmission axis direction), and then DMA Q800 (Dynamic mechanical analyzer, TA) at 80 ° C. for 4 hours.
- the shrinkage force in the absorption axis direction was measured at the time of standing. At this time, in order to maintain the polarizer in a flat state before the measurement, the minimum load was applied in the thickness direction of the polarizer.
- the polarizer of the present invention satisfies both the high degree of orientation and the small contraction force in the absorption axis direction and is excellent in the degree of polarization.
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Abstract
Description
前記配向度は下記の数式1から得られる偏光子:
The degree of orientation is a polarizer obtained from Equation 1 below:
前記架橋ステップは、偏光子形成用フィルムを2.00乃至3.00倍に延伸する第1架橋ステップ、及び前記第1架橋ステップ後、偏光子形成用フィルムを1.00倍以下に延伸する第2架橋ステップを含み、
前記補色ステップで、前記第2架橋ステップの延伸比より高く前記第1架橋ステップの延伸比より低い延伸比で偏光子形成用フィルムを延伸する、偏光子の製造方法。 3. Including swelling, dyeing, stretching, cross-linking, complementary color and drying steps of the polarizer-forming film,
The cross-linking step includes a first cross-linking step of stretching the polarizer forming film to 2.00 to 3.00 times, and a first forming step of stretching the polarizer forming film to 1.00 times or less after the first cross-linking step. 2 cross-linking steps,
In the complementary color step, the polarizer forming film is stretched at a stretch ratio that is higher than the stretch ratio of the second cross-linking step and lower than the stretch ratio of the first cross-linking step.
本発明において、配向度を上述の範囲に調整するためには、第1架橋ステップでの延伸比を2.00乃至3.00倍、総累積延伸比を5.0倍以上で制御することにより、調整することができる。 The polarizer of the present invention may have an orientation degree of 0.250 to 0.400, preferably 0.300 to 0.400. If the degree of orientation is less than 0.250, the degree of polarization decreases, and if it exceeds 0.400, there is a problem that the contraction force in the absorption axis direction increases and the warpage of the polarizer increases.
In the present invention, in order to adjust the degree of orientation to the above range, the stretching ratio in the first crosslinking step is controlled to 2.00 to 3.00 times and the total cumulative stretching ratio is controlled to 5.0 times or more. Can be adjusted.
赤外光の吸光度は、たとえば、フーリエ変換赤外分光光度計(FT-IR)で測定することができる。赤外光の波数は、たとえば、1290cm-1とすることができる。
The absorbance of infrared light can be measured by, for example, a Fourier transform infrared spectrophotometer (FT-IR). The wave number of the infrared light can be set to 1290 cm −1 , for example.
膨潤ステップは、未延伸の偏光子形成用フィルムを染色する前に膨潤用水溶液で満たされた膨潤槽に浸漬し、偏光子形成用フィルムの表面上に堆積したほこりまたはブロッキング防止剤のような不純物を取り除き、偏光子形成用フィルムを膨潤させる、延伸効率を向上させ、染色不均一性を防止し、偏光子の物性を向上させるためのステップである。 <Swelling step>
The swelling step is performed by immersing the unstretched polarizer-forming film in a swelling tank filled with a swelling aqueous solution before dyeing it, and depositing impurities on the surface of the polarizer-forming film, such as impurities or antiblocking agents. Are steps for swelling the polarizer forming film, improving the stretching efficiency, preventing uneven dyeing, and improving the physical properties of the polarizer.
染色ステップは、偏光子形成用フィルムを二色性物質、例えばヨウ素を含む染色用水溶液で満たされた染色槽に浸漬させ、偏光子形成用フィルムにヨウ素を吸着させるステップである。 <Dyeing step>
The dyeing step is a step of immersing the polarizer forming film in a dyeing tank filled with a dichroic substance, for example, an aqueous dyeing solution containing iodine, and adsorbing iodine to the polarizer forming film.
架橋ステップは、物理的に吸着されているヨウ素分子による染色性が外部環境によって低下しないように、染色された偏光子形成用フィルムを架橋用水溶液に浸漬させ、吸着されたヨウ素分子を固定させるステップである。 <Crosslinking step>
The cross-linking step is a step of fixing the adsorbed iodine molecules by immersing the dyed polarizer forming film in an aqueous solution for cross-linking so that the dyeability by physically adsorbed iodine molecules does not deteriorate due to the external environment. It is.
補色ステップは、ヨウ素錯体が物理的に吸着されている偏光子形成用フィルムにおける分子と分子との間に位置するヨウ素錯体をホウ酸架橋の近くに配向させてヨウ素錯体を安定化させるステップである。また、補色ステップを通じて、前記架橋ステップにおけるヨウ素錯体の染色が不十分な偏光子形成用フィルムに対して、色を補正することができる。 <Complementary color step>
The complementary color step is a step of stabilizing the iodine complex by orienting the iodine complex located between the molecules in the polarizer-forming film on which the iodine complex is physically adsorbed in the vicinity of the boric acid bridge. . Further, through the complementary color step, the color can be corrected for the polarizer-forming film in which the iodine complex is not sufficiently dyed in the crosslinking step.
本発明において、延伸ステップは前述したように架橋ステップ及び補色ステップと同時に行われてもよく、その他のステップとも共に行われてもよく、別のステップとして追加的に行われてもよい。 <Extension step>
In the present invention, the stretching step may be performed simultaneously with the crosslinking step and the complementary color step as described above, may be performed together with other steps, or may be additionally performed as a separate step.
本発明の偏光子の製造方法は必要に応じて、架橋及び延伸が完了した偏光子形成用フィルムを、水洗用水溶液で満たされた水洗槽に浸漬させ、水洗ステップまでのステップで偏光子形成用フィルムに付着した、ホウ酸のような不要な残留物を取り除く水洗ステップをさらに含んでいてもよい。 <Washing step>
The polarizer production method of the present invention is, as necessary, for immersing a film for forming a polarizer, which has been crosslinked and stretched, in a washing tank filled with an aqueous washing solution, and for forming a polarizer in steps up to the washing step. A water washing step may be further included to remove unwanted residues such as boric acid attached to the film.
本発明の製造方法において、乾燥ステップは、水洗された偏光子形成用フィルムを乾燥させるステップであって、乾燥によるネックイン(neck-in)で、染着されたヨウ素分子の配向をより向上させ、光学特性に優れた偏光子を得るステップである。なお、ネックインとは、フィルムの幅が狭くなることである。 <Drying step>
In the production method of the present invention, the drying step is a step of drying the washed film for forming a polarizer, and further improves the orientation of dyed iodine molecules by neck-in by drying. This is a step of obtaining a polarizer having excellent optical characteristics. Neck-in means that the width of the film is narrowed.
鹸化度が99.9%以上である透明な未延伸のポリビニルアルコールフィルム(PE60、KURARAY社)を25℃の水(脱イオン水)で1分20秒間浸漬して膨潤させた(膨潤ステップ)後、ヨウ素1.25mM/Lと水100重量%に対してヨウ化カリウム1.25重量%、ホウ酸0.3重量%が含有された30℃の染色用水溶液に2分30秒間浸漬して染色した(染色ステップ)。このとき、膨潤及び染色ステップで、それぞれ約1.7184倍、約1.5214倍の延伸比で延伸して、染色槽までの累積延伸比が2.614倍になるように延伸した。次いで、水100重量%に対してヨウ化カリウム13.9重量%、ホウ酸3重量%が含有された56℃の架橋用水溶液に26秒間浸漬して架橋させながら(第1架橋ステップ)、2.36倍の延伸比で延伸した。その後に、水100重量%に対してヨウ化カリウム13.9重量%、ホウ酸3重量%が含有された56℃の架橋用水溶液に20秒間浸漬して架橋させながら(第2架橋ステップ)、0.90倍の延伸比で延伸した。
次いで、水100重量%に対してヨウ化カリウム5重量%、ホウ酸2重量%が含有された40℃の補色用水溶液に10秒浸漬しながら(補色ステップ)、1.08倍に延伸した。 <Example 1>
After a transparent unstretched polyvinyl alcohol film (PE60, KURARAY) having a saponification degree of 99.9% or more was immersed in water (deionized water) at 25 ° C. for 1 minute and 20 seconds to swell (swelling step) Dyeing by immersing in an aqueous dyeing solution at 30 ° C. containing 1.25% by weight of potassium iodide and 0.3% by weight of boric acid for 1.25 mM / L of iodine and 100% by weight of water for 2 minutes and 30 seconds (Staining step). At this time, in the swelling and dyeing steps, the film was stretched at stretch ratios of about 1.7184 times and about 1.5214 times, respectively, and stretched so that the cumulative stretch ratio up to the dyeing tank was 2.614 times. Next, while immersing in an aqueous solution for crosslinking at 56 ° C. containing 13.9% by weight of potassium iodide and 3% by weight of boric acid with respect to 100% by weight of water for 26 seconds for crosslinking (first crosslinking step), 2 The film was drawn at a draw ratio of 36 times. Then, while being immersed in a 56 ° C. aqueous solution for crosslinking containing 13.9% by weight of potassium iodide and 3% by weight of boric acid with respect to 100% by weight of water for 20 seconds to crosslink (second crosslinking step), The film was stretched at a stretching ratio of 0.90.
Next, the film was stretched 1.08 times while immersed in a complementary color aqueous solution at 40 ° C. containing 5% by weight of potassium iodide and 2% by weight of boric acid with respect to 100% by weight of water (complementary color step).
下記の表1に記載されたように、延伸比を調節したことを除いては、実施例1と同様の方法で偏光板を製造した。 <Examples 2 to 10 and Comparative Examples 1 to 6>
As described in Table 1 below, a polarizing plate was produced in the same manner as in Example 1 except that the stretching ratio was adjusted.
上記の実施例及び比較例において製造された偏光子の物性を下記の方法で測定し、その結果を下記の表2に示した。 <Test example>
The physical properties of the polarizers produced in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 2 below.
製造された偏光子を4cm×4cmのサイズに切断した後、紫外可視光線分光計(V-7100、JASCO社製)を用いて透過率を測定した。このとき、偏光度は下記の数式2で定義される。
[数式2]
偏光度(P)=[(T1-T2)/(T1+T2)]1/2
(式中、T1は一対の偏光子を吸収軸が平行な状態で配置した場合に得られる平行透過率であり、T2は一対の偏光子を吸収軸が直交する状態で配置した場合に得られる直交透過率である)。 <1. Optical properties (degree of polarization)>
The manufactured polarizer was cut into a size of 4 cm × 4 cm, and the transmittance was measured using an ultraviolet-visible light spectrometer (V-7100, manufactured by JASCO). At this time, the degree of polarization is defined by Equation 2 below.
[Formula 2]
Polarization degree (P) = [(T 1 −T 2 ) / (T 1 + T 2 )] 1/2
(In the formula, T 1 is a parallel transmittance obtained when a pair of polarizers are arranged in a state where the absorption axes are parallel, and T 2 is a case where a pair of polarizers is arranged in a state where the absorption axes are orthogonal to each other. It is the orthogonal transmittance obtained).
製造された偏光子を4cm×4cmのサイズに切断した後、偏光ATR装置(VeeMAXIII、PIKE社、入射角:45゜)を用いてIR beamを偏光させ、偏光されたIR beamと偏光子試料のMD方向(吸収軸方向)とが平行になるようにしてFT-IRで吸光度を測定する(AMD)(Nicolet Continuum XL、Thermo社)。次に、偏光されたIR beamと偏光子試料のTD方向(透過軸方向)とが平行になるようにしてFT-IRで吸光度を測定する(ATD)。
MD及びTD方向において吸光度の差を示す1290cm-1の吸光度を測定した。
測定された吸光度を前記数式1に代入して配向度を得た。 <2. Orientation degree>
After the produced polarizer is cut into a size of 4 cm × 4 cm, the IR beam is polarized using a polarization ATR apparatus (VeeMAXIII, PIKE, incident angle: 45 °), and the polarized IR beam and the polarizer sample Absorbance is measured with FT-IR so that the MD direction (absorption axis direction) is parallel (A MD ) (Nicolet Continuum XL, Thermo). Next, the absorbance is measured by FT-IR so that the polarized IR beam is parallel to the TD direction (transmission axis direction) of the polarizer sample (A TD ).
Absorbance at 1290 cm −1 indicating the difference in absorbance in the MD and TD directions was measured.
The measured absorbance was substituted into Equation 1 to obtain the degree of orientation.
ここでは、偏光子の透過軸方向の幅2mmあたりの、吸収軸方向の収縮力を測定した。実施例及び比較例において製造された偏光子を3.0cm(吸収軸方向)×2mm(透過軸方向)のサイズに切断した後、DMA Q800(Dynamic mechanical analyzer、TA社)により80℃で4時間静置時に吸収軸方向の収縮力を測定した。このとき、測定前に偏光子を平坦な状態に維持するために最小限の荷重を偏光子の厚み方向にかけて測定した。 <3. Contraction force>
Here, the contraction force in the absorption axis direction per 2 mm width in the transmission axis direction of the polarizer was measured. The polarizers produced in the examples and comparative examples were cut to a size of 3.0 cm (absorption axis direction) × 2 mm (transmission axis direction), and then DMA Q800 (Dynamic mechanical analyzer, TA) at 80 ° C. for 4 hours. The shrinkage force in the absorption axis direction was measured at the time of standing. At this time, in order to maintain the polarizer in a flat state before the measurement, the minimum load was applied in the thickness direction of the polarizer.
Claims (7)
- 配向度が0.250乃至0.400であり、吸収軸方向の収縮力が3.5N/2mm以下であり、
前記配向度は下記の数式1から得られる偏光子:
The degree of orientation is a polarizer obtained from Equation 1 below:
- 配向度が0.300乃至0.400である、請求項1に記載の偏光子。 The polarizer according to claim 1, wherein the degree of orientation is 0.300 to 0.400.
- 偏光子形成用フィルムの膨潤、染色、延伸、架橋、補色及び乾燥ステップを含み、
前記架橋ステップは、偏光子形成用フィルムを2.00乃至3.00倍に延伸する第1架橋ステップ、及び前記第1架橋ステップ後、偏光子形成用フィルムを1.00倍以下に延伸する第2架橋ステップを含み、
前記補色ステップで、前記第2架橋ステップの延伸比より高く前記第1架橋ステップの延伸比より低い延伸比で偏光子形成用フィルムを延伸する、偏光子の製造方法。 Including swelling, dyeing, stretching, cross-linking, complementary color and drying steps of the polarizer-forming film,
The cross-linking step includes a first cross-linking step of stretching the polarizer forming film to 2.00 to 3.00 times, and a first forming step of stretching the polarizer forming film to 1.00 times or less after the first cross-linking step. 2 cross-linking steps,
In the complementary color step, the polarizer forming film is stretched at a stretch ratio that is higher than the stretch ratio of the second cross-linking step and lower than the stretch ratio of the first cross-linking step. - 前記第2架橋ステップで、偏光子形成用フィルムを0.85乃至1.00倍に延伸する、請求項3に記載の偏光子の製造方法。 The method for producing a polarizer according to claim 3, wherein in the second crosslinking step, the polarizer-forming film is stretched by 0.85 to 1.00 times.
- 前記補色ステップで、偏光子形成用フィルムを1.01乃至1.25倍に延伸する、請求項3又は4に記載の偏光子の製造方法。 The method for producing a polarizer according to claim 3 or 4, wherein in the complementary color step, the film for forming a polarizer is stretched by 1.01 to 1.25 times.
- 請求項1又は2に記載の偏光子及び前記偏光子の少なくとも一面に接合された偏光子保護フィルムを含む偏光板。 A polarizing plate comprising the polarizer according to claim 1 or 2 and a polarizer protective film bonded to at least one surface of the polarizer.
- 請求項6に記載の偏光板を含む画像表示装置。 An image display device comprising the polarizing plate according to claim 6.
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