JP2018025798A - Polarizing plate and method for manufacturing the same - Google Patents
Polarizing plate and method for manufacturing the same Download PDFInfo
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- JP2018025798A JP2018025798A JP2017152316A JP2017152316A JP2018025798A JP 2018025798 A JP2018025798 A JP 2018025798A JP 2017152316 A JP2017152316 A JP 2017152316A JP 2017152316 A JP2017152316 A JP 2017152316A JP 2018025798 A JP2018025798 A JP 2018025798A
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- polarizing plate
- polyvinyl alcohol
- modified polyvinyl
- alcohol resin
- water
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 76
- 229920005989 resin Polymers 0.000 claims abstract description 76
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 69
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 69
- 230000001681 protective effect Effects 0.000 claims abstract description 49
- 238000001035 drying Methods 0.000 claims abstract description 47
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 claims abstract description 42
- 239000000853 adhesive Substances 0.000 claims abstract description 41
- 230000001070 adhesive effect Effects 0.000 claims abstract description 41
- 239000012790 adhesive layer Substances 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 23
- 229940015043 glyoxal Drugs 0.000 claims abstract description 23
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 29
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 22
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 12
- 239000011592 zinc chloride Substances 0.000 claims description 11
- 235000005074 zinc chloride Nutrition 0.000 claims description 11
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 61
- 230000003287 optical effect Effects 0.000 abstract description 18
- 230000009467 reduction Effects 0.000 abstract description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 17
- 239000004327 boric acid Substances 0.000 description 17
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 12
- 238000004043 dyeing Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000011630 iodine Substances 0.000 description 12
- 229910052740 iodine Inorganic materials 0.000 description 12
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 12
- 230000006866 deterioration Effects 0.000 description 11
- 238000007127 saponification reaction Methods 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- 230000003628 erosive effect Effects 0.000 description 8
- 238000007654 immersion Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 150000001925 cycloalkenes Chemical class 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 238000010306 acid treatment Methods 0.000 description 5
- 230000008602 contraction Effects 0.000 description 5
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229920002284 Cellulose triacetate Polymers 0.000 description 4
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 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
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000004973 liquid crystal related substance 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
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000694440 Colpidium aqueous Species 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012461 cellulose resin Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DKNPRRRKHAEUMW-UHFFFAOYSA-N Iodine aqueous Chemical compound [K+].I[I-]I DKNPRRRKHAEUMW-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920005994 diacetyl cellulose Polymers 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229940077844 iodine / potassium iodide Drugs 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- -1 methylol group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J129/00—Adhesives based on 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; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/02—Homopolymers or copolymers of unsaturated alcohols
- C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Polarising Elements (AREA)
Abstract
Description
本発明は、優れた耐水性を示し、且つ、光特性の低下を防止できる偏光板及びその製造方法に関する。 The present invention relates to a polarizing plate that exhibits excellent water resistance and can prevent deterioration of optical properties and a method for producing the same.
偏光板は、液晶表示装置を構成する光学部品の一つとして有用に使用されている。偏光板は、通常、偏光子の両面に保護フィルムが積層された構造を有し、液晶表示装置に挿入される。偏光子の一方の面にのみ保護フィルムを設けることも知られているが、多くの場合、他方の面には、単純な保護フィルムではなく、別途の機能として例えば光学機能を有する層が保護フィルムを兼ねて接合される。 The polarizing plate is usefully used as one of the optical components constituting the liquid crystal display device. A polarizing plate usually has a structure in which protective films are laminated on both sides of a polarizer, and is inserted into a liquid crystal display device. It is also known to provide a protective film only on one side of the polarizer, but in many cases, the other side is not a simple protective film but a layer having an optical function as a separate function, for example, a protective film. It is joined as well.
一般的に、ポリビニルアルコールにヨウ素を吸着配向させたヨウ素系フィルムやポリビニルアルコールに二色性染料を吸着配向させた染料系フィルムを偏光子として用い、少なくともフィルムの片面にポリビニルアルコール系樹脂の水溶液（ポリビニルアルコール系接着剤）を用いて形成された接着層を介してトリアセチルセルロース（ＴＡＣ）などの保護フィルムを接合した構成の偏光板が用いられているが、このような構成の偏光板は、湿熱の下で長時間使用したとき、保護フィルムと偏光子の端面が剥離しやすいという問題がある。 In general, an iodine-based film in which iodine is adsorbed and oriented in polyvinyl alcohol or a dye-based film in which dichroic dye is adsorbed and oriented in polyvinyl alcohol is used as a polarizer, and an aqueous polyvinyl alcohol resin solution (at least on one side of the film) A polarizing plate having a configuration in which a protective film such as triacetyl cellulose (TAC) is bonded via an adhesive layer formed using a polyvinyl alcohol-based adhesive) is used. When used for a long time under wet heat, there is a problem that the end surfaces of the protective film and the polarizer are easily peeled off.
これより、偏光子（偏光フィルム）と保護フィルムをポリビニルアルコール系接着剤を用いて接合した後、８０〜１００℃の温度で加熱乾燥することによって耐湿熱性を改良した偏光板が提案されているが、依然として湿熱の下で長時間使用した場合、保護フィルムと偏光子の端面が容易に剥離される問題点が解決されていない。 From this, although a polarizer (polarizing film) and a protective film are bonded using a polyvinyl alcohol-based adhesive, a polarizing plate having improved moisture and heat resistance by heat drying at a temperature of 80 to 100 ° C. has been proposed. However, the problem that the protective film and the end face of the polarizer are easily peeled when used for a long time under wet heat has not been solved.
このような問題点を解決するために、特許文献１には、アセトアセチル基変性ポリビニルアルコール系樹脂、ポリビニルアルコール系樹脂（架橋調節剤）、グリオキサール系（架橋剤）、及び塩化亜鉛（架橋触媒）を含む接着剤組成物を開示している。しかし、前記組成物の場合、架橋調節剤を含むことによって、硬化速度が遅くて、湿熱劣化による偏光度の低下が発生する問題がある。 In order to solve such problems, Patent Document 1 discloses acetoacetyl group-modified polyvinyl alcohol resin, polyvinyl alcohol resin (crosslinking regulator), glyoxal (crosslinking agent), and zinc chloride (crosslinking catalyst). An adhesive composition is disclosed. However, in the case of the said composition, there exists a problem that the cure rate becomes slow and the fall of the polarization degree by wet heat deterioration generate | occur | produces by including a crosslinking regulator.
したがって、湿熱条件の下でも保護フィルムと偏光子の短辺が分離することを防止するために、耐水性に優れ、これによる光特性の低下を防止できる接着剤組成物に対する開発が要求されていることが現況である。 Therefore, in order to prevent the short sides of the protective film and the polarizer from separating even under wet heat conditions, development of an adhesive composition that is excellent in water resistance and can prevent deterioration of optical properties due to this is required. This is the current situation.
前記問題を解決するために、本発明の目的は、優れた耐水性を示し、且つ、光特性の低下を防止できる偏光板及びその製造方法を提供することにある。 In order to solve the above-mentioned problems, an object of the present invention is to provide a polarizing plate that exhibits excellent water resistance and can prevent deterioration of optical properties and a method for producing the same.
前記目的を達成するために、本発明の偏光板は、水分率が２．８〜４．８％であり、アセトアセチル基変性ポリビニルアルコール系樹脂、グリオキサール架橋剤及び２種以上の多価金属イオンの水溶性塩を含む接着剤組成物よりなる接着剤層の厚さが３０〜２００ｎｍであることを特徴とする。 In order to achieve the object, the polarizing plate of the present invention has a moisture content of 2.8 to 4.8%, an acetoacetyl group-modified polyvinyl alcohol resin, a glyoxal crosslinking agent, and two or more kinds of polyvalent metal ions. The thickness of the adhesive layer made of the adhesive composition containing the water-soluble salt is 30 to 200 nm.
また、前記目的を達成するために、本発明による偏光板の製造方法は、（ａ）偏光子の両面にアセトアセチル基変性ポリビニルアルコール系樹脂、グリオキサール架橋剤及び２種以上の多価金属イオンの水溶性塩を含む接着剤組成物が塗布され、接着剤層が生成される段階と、（ｂ）前記接着剤層上に少なくとも一つ以上の保護フィルムがニップロールにより接合され、偏光板が製作される段階と、（ｃ）前記偏光板が少なくとも２個以上の乾燥路を通過して乾燥される段階とを含むことを特徴とする。 In order to achieve the above object, the method for producing a polarizing plate according to the present invention comprises: (a) an acetoacetyl group-modified polyvinyl alcohol resin, a glyoxal crosslinking agent, and two or more polyvalent metal ions on both sides of a polarizer; An adhesive composition containing a water-soluble salt is applied to form an adhesive layer; and (b) at least one protective film is bonded onto the adhesive layer by a nip roll to produce a polarizing plate. And (c) a step in which the polarizing plate is dried by passing through at least two or more drying paths.
本発明による偏光板は、偏光板の水分率及び接着剤層の厚さを調節することによって、光特性の低下を伴わず、耐水性が向上する効果がある。 The polarizing plate according to the present invention has an effect of improving water resistance without decreasing optical characteristics by adjusting the moisture content of the polarizing plate and the thickness of the adhesive layer.
また、本発明による偏光板の製造方法で製造された偏光板も、前記効果を有する。 Moreover, the polarizing plate manufactured with the manufacturing method of the polarizing plate by this invention also has the said effect.
本発明において或る部分が或る構成要素を「含む」というとき、これは、特に反対される記載がない限り、他の構成要素を除くものでなく、他の構成要素をさらに含むことができることを意味する。 In the present invention, when a part “comprises” a certain component, this does not exclude other components and can further include other components unless otherwise stated to the contrary. Means.
以下、本発明の好ましい実施様態を詳しく説明する。
〈偏光板〉
本発明の一実施形態による偏光板は、水分率が２．８〜４．８％であり、アセトアセチル基変性ポリビニルアルコール系樹脂、グリオキサール架橋剤及び２種以上の多価金属イオンの水溶性塩を含む接着剤組成物よりなる接着剤層の厚さを３０〜２００ｎｍとすることによって、同伴される光特性の低下なしに、湿熱条件の下でも保護フィルムと偏光子の短辺が分離することを防止するために耐水性を向上させることができる効果がある。
Hereinafter, preferred embodiments of the present invention will be described in detail.
<Polarizer>
The polarizing plate according to one embodiment of the present invention has a moisture content of 2.8 to 4.8%, an acetoacetyl group-modified polyvinyl alcohol resin, a glyoxal crosslinking agent, and a water-soluble salt of two or more polyvalent metal ions. By making the thickness of the adhesive layer made of the adhesive composition containing 30 to 200 nm, the short sides of the protective film and the polarizer are separated even under wet heat conditions without a reduction in the accompanying optical properties There is an effect that the water resistance can be improved.
前記偏光板の水分率は、すべての乾燥工程を終えた完成された偏光板を１０５℃で２時間熱処理する前／後の重量変化を観察する重量水分率測定法で測定されたことを意味する。 The moisture content of the polarizing plate means that it was measured by a weight moisture content measuring method of observing a change in weight before / after heat treatment at 105 ° C. for 2 hours for the completed polarizing plate after all drying steps were completed. .
本発明において偏光板というのは、当業界において使用される偏光板を意味でき、一例として、偏光子の少なくとも一面上に一つ以上の保護フィルムが接着されたものであることができる。 In the present invention, the polarizing plate can mean a polarizing plate used in the art. For example, one or more protective films can be bonded to at least one surface of a polarizer.
接着剤層
本発明の偏光板は、厚さが３０〜２００ｎｍであり、アセトアセチル基変性ポリビニルアルコール系樹脂、グリオキサール架橋剤及び２種以上の多価金属イオンの水溶性塩を含む接着剤組成物よりなる接着剤層を含むことによって、同伴される光特性の低下なしに、湿熱条件の下でも保護フィルムと偏光子の短辺が分離することを防止するために耐水性を向上させることができる効果があり、前記接着剤層の厚さが３０ｎｍ未満の場合、外見上の問題が発生し得、２００ｎｍを超過する場合、湿熱劣化が発生し、光特性が低下する問題が発生し得る。
Adhesive Layer The polarizing plate of the present invention has a thickness of 30 to 200 nm, and contains an acetoacetyl group-modified polyvinyl alcohol resin, a glyoxal crosslinking agent, and a water-soluble salt of two or more polyvalent metal ions. By including an adhesive layer comprising, the water resistance can be improved in order to prevent separation of the short sides of the protective film and the polarizer even under wet heat conditions without deterioration of the entrained light characteristics. If the thickness of the adhesive layer is less than 30 nm, an appearance problem may occur. If the thickness exceeds 200 nm, wet heat deterioration may occur, and the optical characteristics may deteriorate.
前記接着剤組成物は、アセトアセチル基変性ポリビニルアルコール系樹脂及びグリオキサール架橋剤を含むＡ液と、アセトアセチル基変性ポリビニルアルコール系樹脂及び２種以上の多価金属イオンの水溶性塩を含むＢ液と、を含み、前記Ａ液及びＢ液を混合して製造され得る。 The adhesive composition includes a liquid A containing an acetoacetyl group-modified polyvinyl alcohol resin and a glyoxal crosslinking agent, and a liquid B containing an acetoacetyl group-modified polyvinyl alcohol resin and a water-soluble salt of two or more polyvalent metal ions. And can be produced by mixing the liquid A and the liquid B.
前記Ａ液及びＢ液のそれぞれに含まれるアセトアセチル基変性ポリビニルアルコール系樹脂は、水（蒸留水）と混合し、水溶液の形態で混合され得、前記Ａ液及びＢ液のそれぞれに含まれるアセトアセチル基変性ポリビニルアルコール系樹脂の固形分の含量は、前記アセトアセチル基変性ポリビニルアルコール系樹脂水溶液１００重量％に対して、２．５〜４．５重量％で含まれることによって、同伴される光特性の低下なしに、湿熱条件の下でも保護フィルムと偏光子の短辺が分離することを防止するために耐水性を向上させることができる効果がある。具体的に、前記Ａ液及びＢ液のそれぞれに含まれるアセトアセチル基変性ポリビニルアルコール系樹脂の固形分の含量が２．５％未満の場合、耐水性効果が低下する問題が発生し得、４．５％を超過する場合、光学特性が低下する問題が発生し得る。 The acetoacetyl group-modified polyvinyl alcohol resin contained in each of the liquid A and the liquid B can be mixed with water (distilled water) and mixed in the form of an aqueous solution. The acetoacetate contained in each of the liquid A and liquid B The light content accompanying the solid content of the acetyl group-modified polyvinyl alcohol resin is 2.5 to 4.5% by weight with respect to 100% by weight of the acetoacetyl group-modified polyvinyl alcohol resin aqueous solution. There is an effect that the water resistance can be improved in order to prevent the short sides of the protective film and the polarizer from separating even under wet heat conditions without deterioration of the characteristics. Specifically, when the content of the solid content of the acetoacetyl group-modified polyvinyl alcohol resin contained in each of the liquid A and liquid B is less than 2.5%, there may be a problem that the water resistance effect decreases. If it exceeds 0.5%, there may be a problem that the optical characteristics are deteriorated.
アセトアセチル基変性ポリビニルアルコール系樹脂
本発明の接着剤層に含まれる接着剤組成物は、アセトアセチル基変性ポリビニルアルコール系樹脂を含むことによって、保護フィルムと偏光子の接着力を向上させることができる。
Acetoacetyl group-modified polyvinyl alcohol resin The adhesive composition contained in the adhesive layer of the present invention can improve the adhesion between the protective film and the polarizer by including the acetoacetyl group-modified polyvinyl alcohol resin. .
前記アセトアセチル基変性ポリビニルアルコール系樹脂は、カルボキシ基変性、メチロール基変性、アミノ基変性などのような変性されたポリビニルアルコール樹脂に比べて反応性が高い官能基を含有していて、 耐久性の向上の面において優れている。 The acetoacetyl group-modified polyvinyl alcohol resin contains a functional group having a higher reactivity than modified polyvinyl alcohol resin such as carboxy group modification, methylol group modification, amino group modification, and the like. Excellent in terms of improvement.
前記アセトアセチル基変性ポリビニルアルコール系樹脂は、ポリビニルアルコール系樹脂とジケテン（ｄｉｋｅｔｅｎｅ）を公知の方法で反応させて得られる。具体的に、ポリビニルアルコール系樹脂を酢酸などの溶媒中に分散させた後、これにジケテンを添加する方法、ポリビニルアルコール系樹脂をジメチルホルムアミドまたはジオキサンなどの溶媒にあらかじめ溶解させた後、これにジケテンを添加する方法、またはポリビニルアルコール系樹脂にジケテンガスまたは液状ジケテンを直接接触させる方法などによって得られる。 The acetoacetyl group-modified polyvinyl alcohol resin is obtained by reacting a polyvinyl alcohol resin and diketene by a known method. Specifically, after a polyvinyl alcohol-based resin is dispersed in a solvent such as acetic acid, diketene is added thereto, the polyvinyl alcohol-based resin is dissolved in a solvent such as dimethylformamide or dioxane in advance, and then diketene is added thereto. Or a method of directly contacting a diketene gas or liquid diketene with a polyvinyl alcohol resin.
前記アセトアセチル基変性ポリビニルアルコール系樹脂は、アセトアセチル基変性度が０．１モル％以上のものであれば、特に制限されず、好ましくは０．１〜４０モル％、より好ましくは１〜２０モル％、最も好ましくは２〜７モル％であることが良い。前記アセトアセチル基の変性度が０．１モル％未満の場合には、接着剤層の耐水性が不十分なので、不適合であり、前記アセトアセチル基の変性度が４０モル％を超過する場合には、耐水性の向上効果が極めて低い。 The acetoacetyl group-modified polyvinyl alcohol resin is not particularly limited as long as the acetoacetyl group modification degree is 0.1 mol% or more, preferably 0.1 to 40 mol%, more preferably 1 to 20%. It is good that it is mol%, most preferably 2-7 mol%. When the modification degree of the acetoacetyl group is less than 0.1 mol%, the adhesive layer has insufficient water resistance, which is incompatible, and when the modification degree of the acetoacetyl group exceeds 40 mol%. Has an extremely low effect of improving water resistance.
前記アセトアセチル基変性ポリビニルアルコール系樹脂のケン化度は、特に制限されないが、８０モル％以上であることが好ましく、また、８５モル％以上であることがより好ましい。前記アセトアセチル基変性ポリビニルアルコール系樹脂のケン化度が前記範囲未満の場合、十分な水溶性が発現しにくくなるため、接着性が低下する問題が発生し得る。 The saponification degree of the acetoacetyl group-modified polyvinyl alcohol resin is not particularly limited, but is preferably 80 mol% or more, and more preferably 85 mol% or more. When the saponification degree of the acetoacetyl group-modified polyvinyl alcohol-based resin is less than the above range, sufficient water solubility is difficult to be exhibited, so that a problem of lowering adhesiveness may occur.
前記アセトアセチル基変性ポリビニルアルコール系樹脂の重合度は、１００〜１，５００内にあることが好ましい。前記アセトアセチル基変性ポリビニルアルコール系樹脂の重合度が前記範囲内の場合、偏光板における偏光子と保護フィルムの間の接着力を向上させる効果がある。 The degree of polymerization of the acetoacetyl group-modified polyvinyl alcohol resin is preferably within a range from 100 to 1,500. When the polymerization degree of the acetoacetyl group-modified polyvinyl alcohol resin is within the above range, there is an effect of improving the adhesive force between the polarizer and the protective film in the polarizing plate.
前記アセトアセチル基変性ポリビニルアルコール系樹脂は、具体的に、Ｚ−１００、Ｚ−２００、Ｚ−２００Ｈ、Ｚ−２１０、Ｚ−２２０及びＺ−３２０（日本合成化学Ｇｏｈｓｅｆｉｍｅｒ社）などが挙げられるが、これに限定されない。 Specific examples of the acetoacetyl group-modified polyvinyl alcohol-based resin include Z-100, Z-200, Z-200H, Z-210, Z-220 and Z-320 (Nippon Synthetic Chemical Co., Ltd. Gohsheimer). However, the present invention is not limited to this.
グリオキサール架橋剤
本発明の接着剤層に含まれる接着剤組成物は、グリオキサール架橋剤を含む。
前記グリオキサール系架橋剤が含まれる場合、前記グリオキサール系架橋剤内のアルデヒド基が前記アセトアセチル基変性ポリビニルアルコール系樹脂だけでなく、偏光子、保護フィルム内に含まれたヒドロキシ基と縮合反応をすることによって、接着剤組成物の架橋度を向上させて、これを利用して接合される偏光子と保護フィルム間の接着力及び耐水性を向上させる効果がある。
Glyoxal crosslinking agent The adhesive composition contained in the adhesive layer of the present invention contains a glyoxal crosslinking agent.
When the glyoxal crosslinking agent is included, the aldehyde group in the glyoxal crosslinking agent undergoes a condensation reaction with not only the acetoacetyl group-modified polyvinyl alcohol resin, but also a hydroxyl group contained in the polarizer and the protective film. Thus, there is an effect of improving the degree of cross-linking of the adhesive composition and improving the adhesive force and water resistance between the polarizer and the protective film to be bonded using this.
前記グリオキサール系架橋剤の含量は、前記Ａ液に一緒に含まれるアセトアセチル基変性ポリビニルアルコール系樹脂の固形分１００重量部に対してグリオキサール系架橋剤３０〜７０重量部で含まれることができる。前記グリオキサール系架橋剤の含量が前記範囲未満の場合、前記グリオキサール系架橋剤を含む接着剤組成物よりなる接着剤層の耐水性が低下する問題が発生し得、前記範囲を超過する場合、調液安定性が低下する問題が発生し得る。 The content of the glyoxal crosslinking agent may be 30 to 70 parts by weight of the glyoxal crosslinking agent with respect to 100 parts by weight of the solid content of the acetoacetyl group-modified polyvinyl alcohol resin contained together in the liquid A. When the content of the glyoxal crosslinking agent is less than the above range, there may be a problem that the water resistance of the adhesive layer made of the adhesive composition containing the glyoxal crosslinking agent is deteriorated. The problem that liquid stability falls may generate | occur | produce.
多価金属イオンの水溶性塩
本発明の接着剤層に含まれる接着剤組成物は、２種以上の多価金属イオンの水溶性塩を含むことによって、前記グリオキサール系架橋剤の効果を増進させて、これを含む接着剤組成物の架橋度を向上させるだけでなく、これを利用して接着される偏光子と保護フィルム間の架橋度を向上させる効果がある。これにより、前記接着剤層の接着力及び耐水性を向上させることができ、これと同伴される光学耐久性の低下をも防止できる効果がある。
Water-soluble salt of polyvalent metal ions The adhesive composition contained in the adhesive layer of the present invention contains two or more water-soluble salts of polyvalent metal ions, thereby enhancing the effect of the glyoxal crosslinking agent. In addition to improving the degree of cross-linking of the adhesive composition containing the same, there is an effect of improving the degree of cross-linking between the polarizer and the protective film to be bonded using this. Thereby, the adhesive force and water resistance of the adhesive layer can be improved, and the optical durability accompanied by this can be prevented from being lowered.
前記多価金属イオンの水溶性塩は、具体的に、塩化亜鉛、塩化コバルト、塩化マグネシウム、酢酸マグネシウム、硝酸アルミニウム、硝酸亜鉛及び硫酸亜鉛よりなる群から選択され得、架橋触媒の役目に優れた塩化亜鉛、硝酸亜鉛及び硝酸アルミニウムよりなる群から選択されることがより好ましい。 The water-soluble salt of the polyvalent metal ion may be specifically selected from the group consisting of zinc chloride, cobalt chloride, magnesium chloride, magnesium acetate, aluminum nitrate, zinc nitrate, and zinc sulfate, and has an excellent role as a crosslinking catalyst. More preferably, it is selected from the group consisting of zinc chloride, zinc nitrate and aluminum nitrate.
前記多価金属イオンの水溶性塩が塩化亜鉛を含む場合、その含量は、前記Ｂ液に一緒に含まれるアセトアセチル基変性ポリビニルアルコール系樹脂の固形分１００重量部に対して、２〜１０重量部で含まれることができる。前記塩化亜鉛の含量が前記範囲未満の場合、前記塩化亜鉛を含む接着剤組成物よりなる接着剤層の耐水性が十分でない問題が発生し得、前記範囲を超過する場合、調液安定性が低下する問題が発生し得る。 When the water-soluble salt of the polyvalent metal ion contains zinc chloride, the content thereof is 2 to 10% by weight with respect to 100 parts by weight of the solid content of the acetoacetyl group-modified polyvinyl alcohol resin contained in the solution B. Can be included in parts. When the content of the zinc chloride is less than the above range, there may be a problem that the water resistance of the adhesive layer made of the adhesive composition containing the zinc chloride is not sufficient. Decreasing problems can occur.
前記多価金属イオンの水溶性塩が硝酸亜鉛乃至硝酸アルミニウムを含む場合、その含量は、前記Ｂ液に含まれるアセトアセチル基変性ポリビニルアルコール系樹脂の固形分１００重量部に対して、３０〜９０重量部で含まれることができる。前記硝酸亜鉛乃至硝酸アルミニウムの含量が前記範囲未満の場合、前記硝酸亜鉛乃至硝酸アルミニウムを含む接着剤組成物よりなる接着剤層の耐水性が十分ではない問題が発生し得、前記範囲を超過する場合、調液安定性が低下する問題が発生し得る。 When the water-soluble salt of the polyvalent metal ion contains zinc nitrate or aluminum nitrate, the content thereof is 30 to 90 with respect to 100 parts by weight of the solid content of the acetoacetyl group-modified polyvinyl alcohol resin contained in the liquid B. It can be included in parts by weight. When the content of the zinc nitrate or aluminum nitrate is less than the above range, there may be a problem that the water resistance of the adhesive layer made of the adhesive composition containing the zinc nitrate or aluminum nitrate is not sufficient and exceeds the above range. In such a case, there may occur a problem that the preparation stability is lowered.
本発明の接着剤層に含まれる接着剤組成物の２０℃においての粘度は、３〜２５ｍＰａ・ｓｅｃ範囲内であることが好ましい。接着剤組成物の粘度が３ｍＰａ・ｓｅｃ未満の場合には、前記接着剤組成物よりなる接着剤層の耐水性を充分に発現できず、粘度が２５ｍＰａ・ｓｅｃを超過する場合、前記接着剤層を含む偏光板の光学特性が低下する問題点がある。 The viscosity at 20 ° C. of the adhesive composition contained in the adhesive layer of the present invention is preferably in the range of 3 to 25 mPa · sec. When the viscosity of the adhesive composition is less than 3 mPa · sec, the adhesive layer made of the adhesive composition cannot sufficiently exhibit water resistance, and when the viscosity exceeds 25 mPa · sec, the adhesive layer There exists a problem that the optical characteristic of the polarizing plate containing this falls.
前記接着剤組成物は、本発明の効果を阻害しない範囲で、可塑剤、シランカップリング剤、帯電防止剤、微粒子、広がり性を良好にするアルコール、レーベリング剤などの添加剤をさらに含むことができる。 The adhesive composition further includes additives such as a plasticizer, a silane coupling agent, an antistatic agent, fine particles, alcohol for improving spreadability, and a labeling agent, as long as the effects of the present invention are not impaired. Can do.
前記接着剤組成物の形態は、特に制限されないが、被着体である偏光子及び保護フィルムの表面に均一な接着剤層を形成するためには、液型であることが好ましい。このような液型の接着剤としては、各種溶剤の溶液型または分散液型を使用でき、基材の塗工性の面を考慮すると、溶液型が好ましく、安定性の面を考慮すると、水を溶媒とする溶液型または分散液型が好適である。 The form of the adhesive composition is not particularly limited, but is preferably a liquid type in order to form a uniform adhesive layer on the surfaces of the polarizer and the protective film that are adherends. As such a liquid type adhesive, a solution type or a dispersion type of various solvents can be used. In consideration of the coating property of the substrate, the solution type is preferable, and in consideration of the stability, A solution type or a dispersion type using as a solvent is preferred.
偏光子（偏光フィルム）
偏光子を形成するためのポリビニルアルコール系樹脂は、ポリ酢酸ビニル系樹脂をケン化することによって得られる。ポリ酢酸ビニル系樹脂としては、酢酸ビニルの単独重合体であるポリ酢酸ビニル以外に、酢酸ビニルとそれに共重合可能な他の単量体との共重合体などが挙げられる。酢酸ビニルに共重合される他の単量体としては、例えば不飽和カルボン酸類、不飽和スルホン酸類、オレフィン類、ビニルエーテル類、アンモニウム基を有するアクリルアミド類などが挙げられる。ポリビニルアルコール系樹脂のケン化度は、通常、８５〜１００モル％、好ましくは９８モル％以上である。このポリビニルアルコール系樹脂は、さらに変性されていてもよく、例えばアルデヒド類で変性されたポリビニル重合体やポリビニルアセタールなどをも使用できる。偏光子を構成するポリビニルアルコール系樹脂の平均重合度は、通常、１，０００〜１０，０００、好ましくは１，５００〜５，０００である。
Polarizer (polarizing film)
A polyvinyl alcohol-based resin for forming a polarizer can be obtained by saponifying a polyvinyl acetate-based resin. Examples of the polyvinyl acetate-based resin include a copolymer of vinyl acetate and another monomer copolymerizable therewith, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate. Examples of other monomers copolymerized with vinyl acetate include unsaturated carboxylic acids, unsaturated sulfonic acids, olefins, vinyl ethers, and acrylamides having an ammonium group. The degree of saponification of the polyvinyl alcohol resin is usually 85 to 100 mol%, preferably 98 mol% or more. This polyvinyl alcohol resin may be further modified, and for example, a polyvinyl polymer or polyvinyl acetal modified with aldehydes may be used. The average degree of polymerization of the polyvinyl alcohol resin constituting the polarizer is usually 1,000 to 10,000, preferably 1,500 to 5,000.
このようなポリビニルアルコール系樹脂をフィルム上に製膜したもの（ポリビニルアルコール系樹脂フィルム）が偏光子の原反フィルムに用いられる。ポリビニルアルコール系樹脂を製膜する方法は、特に限定されず、公知された製膜方法を採用できる。原反となるポリビニルアルコール系樹脂フィルムの膜厚は、特に限定されないが、例えば１０〜１５０μｍであることができる。 What formed such a polyvinyl alcohol-type resin on the film (polyvinyl alcohol-type resin film) is used for the raw film of a polarizer. The method for forming the polyvinyl alcohol-based resin is not particularly limited, and a known film forming method can be employed. Although the film thickness of the polyvinyl alcohol-type resin film used as a raw fabric is not specifically limited, For example, it can be 10-150 micrometers.
偏光子は、通常、このような原反となるポリビニルアルコール系樹脂フィルムを一軸延伸する工程、ポリビニルアルコール系樹脂フィルムを二色性色素で染色し、該二色性色素を吸着させる工程、二色性色素が吸着されたポリビニルアルコール系樹脂フィルムをホウ酸水溶液で処理する工程、及び該ホウ酸水溶液による処理後に水洗する工程を含む方法によって製造され得る。 A polarizer is usually a step of uniaxially stretching a polyvinyl alcohol-based resin film that becomes such a raw material, a step of dyeing a polyvinyl alcohol-based resin film with a dichroic dye, and adsorbing the dichroic dye, two-color It can be manufactured by a method including a step of treating a polyvinyl alcohol-based resin film adsorbed with a functional dye with an aqueous boric acid solution and a step of washing with water after the treatment with the aqueous boric acid solution.
一軸延伸は、染色前に行ってもよく、染色と同時に行ってもよく、染色後に行ってもよい。一軸延伸を染色後に行う場合には、一軸延伸をホウ酸処理前に行ってもよく、ホウ酸処理中に行ってもよく、ホウ酸処理後に行ってもよい。もちろん、これら複数のステップにより一軸延伸を行うことも可能である。一軸延伸においては、原反フィルムを異なるロールの間で一軸延伸してもよく、熱ロールを利用して一軸延伸してもよい。また、大気中で延伸を行うなどの乾式延伸であってもよく、溶剤で膨潤させた状態で延伸を行う湿式延伸であってもよい。延伸倍率は、通常、３〜８倍である。 Uniaxial stretching may be performed before dyeing, may be performed simultaneously with dyeing, or may be performed after dyeing. When uniaxial stretching is performed after dyeing, uniaxial stretching may be performed before boric acid treatment, may be performed during boric acid treatment, or may be performed after boric acid treatment. Of course, it is also possible to perform uniaxial stretching by these plural steps. In uniaxial stretching, the raw film may be uniaxially stretched between different rolls, or may be uniaxially stretched using a hot roll. Further, it may be dry stretching such as stretching in the air, or may be wet stretching in which stretching is performed in a state swollen with a solvent. The draw ratio is usually 3 to 8 times.
ポリビニルアルコール系樹脂フィルムを二色性色素で染色するためには、例えば二色性色素を含有する水溶液にポリビニルアルコール系樹脂フィルムを浸漬できる。二色性色素として、具体的には、ヨウ素または二色性染料が使用され得る。また、ポリビニルアルコール系樹脂フィルムは、染色処理前に、水に浸漬処理を行うことが好ましい。 In order to dye a polyvinyl alcohol resin film with a dichroic dye, for example, the polyvinyl alcohol resin film can be immersed in an aqueous solution containing the dichroic dye. Specifically, iodine or a dichroic dye can be used as the dichroic dye. Moreover, it is preferable that the polyvinyl alcohol-type resin film is immersed in water before the dyeing process.
二色性色素としてヨウ素を使用する場合は、通常、ヨウ素及びヨウ化カリウムを含有する水溶液にポリビニルアルコール系樹脂フィルムを浸漬し、染色する方法が採用される。この水溶液におけるヨウ素の含有量は、通常、水１００重量部当たり０．０１〜１重量部であり、ヨウ化カリウムの含有量は、通常、水１００重量部当たり０．５〜２０重量部である。染色に使用する水溶液の温度は、通常、２０〜４０℃であり、また、この水溶液への浸漬時間は、通常、２０〜１８００秒である。 When iodine is used as the dichroic dye, a method of immersing and dyeing a polyvinyl alcohol resin film in an aqueous solution containing iodine and potassium iodide is usually employed. The content of iodine in this aqueous solution is usually 0.01 to 1 part by weight per 100 parts by weight of water, and the content of potassium iodide is usually 0.5 to 20 parts by weight per 100 parts by weight of water. . The temperature of the aqueous solution used for dyeing is usually 20 to 40 ° C., and the immersion time in this aqueous solution is usually 20 to 1800 seconds.
二色性色素として二色性染料を使用する場合は、通常、水溶性二色性染料を含む水溶液にポリビニルアルコール系樹脂フィルムを浸漬し、染色する方法が採用される。この水溶液における二色性染料の含有量は、水１００重量部当たり通常１×１０−４〜１０重量部、好ましくは１×１０−３〜１重量部である。この水溶液は、硫酸ナトリウムなどの無機塩を染色補助剤として含有することもできる。染色に利用する染料水溶液の温度は、通常、２０〜８０℃であり、また、この水溶液に対する浸漬時間は、通常、１０〜１，８００秒である。 When a dichroic dye is used as the dichroic dye, a method of immersing and dyeing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye is usually employed. The content of the dichroic dye in this aqueous solution is usually 1 × 10 −4 to 10 parts by weight, preferably 1 × 10 −3 to 1 part by weight per 100 parts by weight of water. This aqueous solution can also contain an inorganic salt such as sodium sulfate as a dyeing auxiliary. The temperature of the aqueous dye solution used for dyeing is usually 20 to 80 ° C., and the immersion time in this aqueous solution is usually 10 to 1,800 seconds.
二色性色素による染色後のホウ酸処理は、染色されたポリビニルアルコール系樹脂フィルムをホウ酸含有水溶液に浸漬することによって行われる。ホウ酸含有水溶液におけるホウ酸の量は、水１００重量部当たり、通常、２〜１５重量部、好ましくは５〜１２重量部である。二色性色素としてヨウ素を使用する場合には、このホウ酸含有水溶液は、ヨウ化カリウムを含むことが好ましい。ホウ酸含有水溶液におけるヨウ化カリウムの量は、水１００重量部当たり、通常、０．１〜１５重量部、好ましくは５〜１２重量部である。ホウ酸含有水溶液への浸漬時間は、通常、６０〜１、２００秒、好ましくは１５０〜６００秒、より好ましくは２００〜４００秒である。ホウ酸含有水溶液の温度は、通常、５０℃以上であり、好ましくは５０〜８５℃、より好ましくは６０〜８０℃である。 The boric acid treatment after dyeing with a dichroic dye is performed by immersing the dyed polyvinyl alcohol-based resin film in a boric acid-containing aqueous solution. The amount of boric acid in the boric acid-containing aqueous solution is usually 2 to 15 parts by weight, preferably 5 to 12 parts by weight, per 100 parts by weight of water. When iodine is used as the dichroic dye, the boric acid-containing aqueous solution preferably contains potassium iodide. The amount of potassium iodide in the boric acid-containing aqueous solution is usually 0.1 to 15 parts by weight, preferably 5 to 12 parts by weight per 100 parts by weight of water. The immersion time in the boric acid-containing aqueous solution is usually 60 to 1,200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds. The temperature of the boric acid-containing aqueous solution is usually 50 ° C. or higher, preferably 50 to 85 ° C., more preferably 60 to 80 ° C.
ホウ酸処理後のポリビニルアルコール系樹脂フィルムは、通常、水洗処理される。水洗処理は、例えばホウ酸処理されたポリビニルアルコール系樹脂フィルムを水に浸漬することによって行われる。水洗処理における水の温度は、通常、５〜４０℃であり、浸漬時間は、通常、１〜１２０秒である。水洗後には、乾燥処理が実施され、偏光子が得られる。乾燥処理は、通常、熱風乾燥機や遠赤外線ヒーターを利用して行われる。乾燥処理の温度は、通常、３０〜１００℃、好ましくは５０〜８０℃である。乾燥処理の時間は、通常、６０〜６００秒であり、好ましくは１２０〜６００秒である。 The polyvinyl alcohol resin film after the boric acid treatment is usually washed with water. The water washing treatment is performed, for example, by immersing a boric acid-treated polyvinyl alcohol resin film in water. The water temperature in the water washing treatment is usually 5 to 40 ° C., and the immersion time is usually 1 to 120 seconds. After washing with water, a drying process is performed to obtain a polarizer. The drying process is usually performed using a hot air dryer or a far infrared heater. The temperature of the drying treatment is usually 30 to 100 ° C, preferably 50 to 80 ° C. The time for the drying treatment is usually 60 to 600 seconds, preferably 120 to 600 seconds.
かくして、ポリビニルアルコール系樹脂フィルムに一軸延伸、二色性色素による染色及びホウ酸処理が行われ、偏光子が得られる。この偏光子の厚さは、通常、５〜４０μｍの範囲内、好ましくは１０〜３５μｍの範囲内である。 Thus, the polyvinyl alcohol resin film is uniaxially stretched, dyed with a dichroic dye, and treated with boric acid to obtain a polarizer. The thickness of this polarizer is usually in the range of 5 to 40 μm, preferably in the range of 10 to 35 μm.
保護フィルム
前記保護フィルムは具体的に、セルロース系樹脂フィルム、シクロオレフィン系樹脂フィルム、アクリル系樹脂フィルム、ポリエステル系樹脂フィルムなど各種透明樹脂フィルムを使用できる。
Protective film Specifically, as the protective film, various transparent resin films such as a cellulose resin film, a cycloolefin resin film, an acrylic resin film, and a polyester resin film can be used.
前記保護フィルムとしてセルロース系樹脂フィルムを使用する場合は、セルロースの少なくとも一部がエステル化された酢酸セルロース系樹脂であることが好ましい。例えばトリアセチルセルロース、ジアセチルセルロース、セルロースアセテートプロピオネートなどが挙げられる。 When a cellulose resin film is used as the protective film, it is preferably a cellulose acetate resin in which at least a part of cellulose is esterified. For example, triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate and the like can be mentioned.
前記シクロオレフィン系樹脂は、例えばノルボルネンや多環ノルボルネン系単量体のようなシクロオレフィンの単量体ユニットを有する熱可塑性の樹脂であり、前記シクロオレフィンの開環重合体や２種以上のシクロオレフィンを利用した開環共重合体の水素添加物であってもよく、シクロオレフィンと鎖状オレフィンやビニル基を有する芳香族化合物との付加共重合体であってもよい。また、シクロオレフィン系樹脂に極性基が導入されていてもよい。 The cycloolefin resin is a thermoplastic resin having a cycloolefin monomer unit such as norbornene or a polycyclic norbornene monomer, and the cycloolefin ring-opening polymer or two or more kinds of cycloolefin resins. A hydrogenated product of a ring-opening copolymer using an olefin may be used, or an addition copolymer of a cycloolefin and a chain olefin or an aromatic compound having a vinyl group may be used. Moreover, the polar group may be introduce | transduced into cycloolefin type resin.
接着剤組成物を利用した偏光子と保護フィルムとの接合方法は、特に限定されず、例えば流延法、メイヤバーコーティング法、グラビアコーティング法、ダイコーティング法、浸漬コーティング法、噴霧法などによって偏光子及び／または保護フィルムの接着面に接着剤組成物を塗布し、両方を重畳させる方法が挙げられる。前記流延法というのは、被塗布物である偏光子または保護フィルムを略垂直方向、略水平方向、または両方間の傾斜方向に移動させながら、その表面に接着剤組成物を塗布する方法である。 The bonding method of the polarizer and the protective film using the adhesive composition is not particularly limited. For example, polarized light can be obtained by casting method, Mayer bar coating method, gravure coating method, die coating method, dip coating method, spraying method, or the like. The method of apply | coating an adhesive composition to the adhesion surface of a child and / or a protective film, and superimposing both 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 in a substantially vertical direction, a substantially horizontal direction, or an inclined direction between both. is there.
前記接着剤組成物を塗布した後、偏光子と保護フィルムをニップロ−ル（ｎｉｐ ｒｏｌｌ）により挟持して接合させる。 After the adhesive composition is applied, the polarizer and the protective film are sandwiched by nip rolls and bonded.
また、接着性を向上させるために、偏光子及び／または保護フィルムの表面にプラズマ処理、コロナ処理、紫外線照射処理、フレーム処理、ケン化処理などの表面処理を適切に行うこともできる。前記ケン化処理としては、水酸化ナトリウム、水酸化カリウムなどのアルカリ水溶液に浸漬する方法が挙げられる。 Moreover, in order to improve adhesiveness, surface treatments such as plasma treatment, corona treatment, ultraviolet irradiation treatment, flame treatment, and saponification treatment can be appropriately performed on the surface of the polarizer and / or protective film. Examples of the saponification treatment include a method of immersing in an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide.
偏光子と保護フィルムを積層した後には、乾燥処理が実施される。乾燥処理は、例えば熱風を噴霧することによって行われるが、この際の温度は、５０〜１００℃範囲で適宜選択される。
乾燥時間は、通常、３０〜１，０００秒である。
After laminating the polarizer and the protective film, a drying process is performed. The drying process is performed, for example, by spraying hot air, and the temperature at this time is appropriately selected in the range of 50 to 100 ° C.
The drying time is usually 30 to 1,000 seconds.
〈偏光板の製造方法〉
本発明のさらに他の実施形態は、前述した偏光板を製造する方法として、（ａ）偏光子の両面にアセトアセチル基変性ポリビニルアルコール系樹脂、グリオキサール架橋剤及び２種以上の多価金属イオンの水溶性塩を含む接着剤組成物が塗布され、接着剤層が生成される段階と、（ｂ）前記接着剤層上に少なくとも一つ以上の保護フィルムがニップロールにより接合され、偏光板が製作される段階と、（ｃ）前記偏光板が少なくとも２個以上の乾燥路を通過し、乾燥する段階とを含むことを特徴とする。このような方法で偏光板の水分率を２．８〜４．８％とし、偏光板に含まれる接着剤層の厚さを３０〜２００ｎｍに調節することが可能である。したがって、同伴される光特性の低下なしに、湿熱条件の下でも保護フィルムと偏光子の短辺が分離することを防止するために耐水性を向上させることができる効果を有する偏光板を製造できる。
<Production method of polarizing plate>
In another embodiment of the present invention, as a method for producing the above-described polarizing plate, (a) an acetoacetyl group-modified polyvinyl alcohol resin, a glyoxal crosslinking agent and two or more kinds of polyvalent metal ions are formed on both sides of a polarizer. An adhesive composition containing a water-soluble salt is applied to form an adhesive layer; and (b) at least one protective film is bonded onto the adhesive layer by a nip roll to produce a polarizing plate. And (c) the polarizing plate passes through at least two or more drying paths and is dried. By such a method, the moisture content of the polarizing plate is adjusted to 2.8 to 4.8%, and the thickness of the adhesive layer included in the polarizing plate can be adjusted to 30 to 200 nm. Accordingly, it is possible to produce a polarizing plate having an effect of improving water resistance in order to prevent separation of the short sides of the protective film and the polarizer even under wet heat conditions without deterioration of the entrained light characteristics. .
本発明の偏光板製造方法について、以下に別の記載がない限り、偏光板の構成要素は、前述した偏光板の構成要素を使用できる。 About the polarizing plate manufacturing method of this invention, unless there is another description below, the component of a polarizing plate mentioned above can be used for the component of a polarizing plate.
前記（ｂ）段階で、ニップロールというのは、偏光子の少なくとも一面上に保護フィルムを接着させる機械であって、偏光子や保護フィルムの上下面の方向にそれぞれ少なくとも１個以上のニップロールが位置し得、前記偏光子や保護フィルムの上下面に位置するニップロールがそれらの間を通過する偏光子及び保護フィルムに圧力をかけることによって、保護フィルムが偏光子に接着され得る。 In the step (b), the nip roll is a machine for adhering a protective film on at least one surface of the polarizer, and at least one nip roll is positioned in the direction of the upper and lower surfaces of the polarizer and the protective film. In addition, the protective film can be adhered to the polarizer by applying pressure to the polarizer and the protective film that pass between the nip rolls positioned on the upper and lower surfaces of the polarizer and the protective film.
前記偏光子と保護フィルム間の接着のために加えられるニップロールの圧力、すなわちニップ圧は、０．３〜０．９ＭＰａであることができ、前記ニップ圧が前記範囲未満の場合、偏光子と保護フィルム間の接着剤層が本発明の構成である２００ｎｍを超過し、湿熱劣化が発生し、光特性が低下し、前記ニップ圧が前記範囲を超過する場合、接着剤層が本発明の構成である３０ｎｍ未満になって、外見不良が発生し得る。 The pressure of the nip roll applied for adhesion between the polarizer and the protective film, that is, the nip pressure may be 0.3 to 0.9 MPa, and when the nip pressure is less than the range, the polarizer and the protection are protected. When the adhesive layer between the films exceeds 200 nm, which is the configuration of the present invention, wet heat deterioration occurs, optical characteristics are deteriorated, and the nip pressure exceeds the above range, the adhesive layer is the configuration of the present invention. When the thickness is less than 30 nm, appearance defects may occur.
ニップロールを通過する偏光子や保護フィルムの上面と接触するニップロール上の一部面及び前記偏光子や保護フィルムの下面と接触するニップロール上の一部面との間隔、すなわちニップギャップ（ｎｉｐ ｇａｐ）は、−１５００〜−５００μｍであることができる。前記ニップギャップが前記範囲未満の場合、前記接着剤層の厚さが本発明の構成である３０ｎｍ未満になって、外見不良が発生し得、前記範囲を超過する場合、前記接着剤層の厚さが本発明の構成である２００ｎｍを超過し、湿熱劣化が発生し、光特性が低下する問題が発生し得る。この際、前記ニップギャップの測定のために使用される偏光子や保護フィルムの上下面に位置するニップロールは、互いに最も近接したものとする。 The distance between the partial surface on the nip roll that contacts the upper surface of the polarizer and the protective film passing through the nip roll and the partial surface on the nip roll that contacts the lower surface of the polarizer and the protective film, that is, the nip gap is −1500 to −500 μm. When the nip gap is less than the range, the thickness of the adhesive layer is less than 30 nm, which is the configuration of the present invention, and appearance defects may occur. When the nip gap exceeds the range, the thickness of the adhesive layer When the length exceeds 200 nm, which is the configuration of the present invention, wet heat deterioration may occur, and a problem may occur in which optical characteristics deteriorate. At this time, the nip rolls positioned on the upper and lower surfaces of the polarizer and the protective film used for measuring the nip gap are assumed to be closest to each other.
前記（ｂ）段階で、偏光子の少なくとも一面上に接着された保護フィルムがニップロールにより接合された偏光板は、前記（ｃ）段階で、少なくとも２個以上の乾燥路を通過して乾燥され得、本発明では、便宜のために、多数の乾燥路を偏光板が通過する順に第１乾燥路、第２乾燥路、第３乾燥路などと命名する。前記乾燥路は、熱風を使用でき、偏光板が少なくとも２個以上の乾燥路を通過するに際して、後続段階の乾燥路内の熱風の温度が、一段階前の乾燥路内の熱風の温度より高いことが好ましい。例えば、第１乾燥路内の熱風の温度より第２乾燥路内の熱風の温度が高い。より具体的に、第１乾燥路内の熱風の温度は、５０℃以下であることが好ましく、多数の乾燥路のうち最後の乾燥路内の熱風の温度は、８０℃以上であることが好ましい。前記第１乾燥路内の温度が５０℃を超過する場合、急激な水分蒸発によって湿熱劣化が発生し、光特性が低下し、最後の乾燥路内の熱風の温度が８０℃未満の場合、偏光板の水分率が高くなって、経時によって光学特性が低下する問題が発生し得る。 In the step (b), the polarizing plate in which the protective film bonded on at least one surface of the polarizer is bonded by a nip roll may be dried through at least two or more drying paths in the step (c). In the present invention, for convenience, the first drying path, the second drying path, the third drying path, and the like are named in the order in which the polarizing plates pass through the many drying paths. The drying path can use hot air, and when the polarizing plate passes through at least two or more drying paths, the temperature of the hot air in the subsequent drying path is higher than the temperature of the hot air in the previous drying path. It is preferable. For example, the temperature of the hot air in the second drying path is higher than the temperature of the hot air in the first drying path. More specifically, the temperature of the hot air in the first drying path is preferably 50 ° C. or lower, and the temperature of the hot air in the last drying path among the many drying paths is preferably 80 ° C. or higher. . When the temperature in the first drying path exceeds 50 ° C., wet heat deterioration occurs due to rapid moisture evaporation, the light characteristics deteriorate, and when the temperature of the hot air in the last drying path is less than 80 ° C., polarized light The moisture content of the plate becomes high, and there may be a problem that optical characteristics deteriorate with time.
〈画像表示装置〉
本発明の他の様態は、前述した偏光板が具備される画像表示装置である。
本発明の画像表示装置は、前記偏光板を具備したものであって、具体的な例を取ると、液晶ディスプレイ、ＯＬＥＤ、フレキシブルディスプレイなどが挙げられるが、これに限定されない。
<Image display device>
Another aspect of the present invention is an image display device including the polarizing plate described above.
The image display device of the present invention includes the polarizing plate, and specific examples include a liquid crystal display, an OLED, and a flexible display, but are not limited thereto.
以下、本発明の理解を助けるために好ましい実施例を提示するが、以下の実施例は、本発明を例示するものに過ぎず、本発明の範疇及び技術思想の範囲内で多様な変更及び修正が可能であることは、当業者にとって明白であり、このような変形及び修正が添付の特許請求範囲に属することも、当然なことである。以下の実施例及び比較例において、含量を示す「％」及び「部」は、特に言及しない限り、重量基準である。 Hereinafter, preferred embodiments will be presented to assist the understanding of the present invention. However, the following embodiments are merely illustrative of the present invention, and various changes and modifications may be made within the scope and spirit of the present invention. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims. In the following Examples and Comparative Examples, “%” and “part” indicating the content are based on weight unless otherwise specified.
製造例
製造例１．偏光子の製造
平均重合度が２，４００であり、ケン化度が９９．９モル％以上である７５μｍ厚さのポリビニルアルコールフィルムを乾式で約５倍に一軸延伸し、延伸状態を維持したまま、６０℃の水（蒸留水）に１分間浸漬した後、ヨウ素／ヨウ化カリウム／蒸留水の重量比が０．０５／５／１００である２８℃の水溶液で６０秒間浸漬した。その後、ヨウ化カリウム／ホウ酸／蒸留水の重量比が８．５／８．５／１００である７２℃水溶液に３００秒間浸漬し、２６℃の蒸留水で２０秒間洗浄した後、６５℃で乾燥し、ＰＶＡ系フィルムにヨウ素が吸着配向された偏光子を製造した。
Production example
Production Example 1 The production average polymerization degree of the polarizer is 2,400, and a 75 μm-thick polyvinyl alcohol film having a saponification degree of 99.9 mol% or more is uniaxially stretched about 5 times by a dry method, and the stretched state is maintained. After immersing in 60 ° C. water (distilled water) for 1 minute, it was immersed in a 28 ° C. aqueous solution having a weight ratio of iodine / potassium iodide / distilled water of 0.05 / 5/100 for 60 seconds. Then, after immersing in a 72 ° C. aqueous solution having a weight ratio of potassium iodide / boric acid / distilled water of 8.5 / 8.5 / 100 for 300 seconds, washed with distilled water at 26 ° C. for 20 seconds, and then at 65 ° C. It dried and manufactured the polarizer by which iodine was adsorbed and oriented to the PVA-type film.
製造例２．保護フィルムの製造
トリアセチルセルロース系フィルムであるＫＣ８ＵＸ（コニカ社、Ｔ）をケン化して使用した。
Production Example 2 Production of protective film KC8UX (Konica, T), which is a triacetyl cellulose film, was used after saponification.
製造例３．接着剤組成物の製造
Ａ液組成物の製造：水（蒸留水）にケン化度が９９．２モル％であるアセトアセチル基変性ポリビニルアルコール系樹脂（ゴーセノールＺ２００、日本合成化学工業株式会社）を溶解し、固形分の含量が表１のような水溶液を製造した。前記水溶液にグリオキサール架橋剤４０％水溶液（大井化金）を表１に記載した含量によって追加した後、混合し、接着剤Ａ液組成物を製造した。
Production Example 3 Manufacture of adhesive composition Manufacture of liquid composition A: An acetoacetyl group-modified polyvinyl alcohol resin (Gocenol Z200, Nippon Synthetic Chemical Industry Co., Ltd.) having a saponification degree of 99.2 mol% in water (distilled water). An aqueous solution having a solid content as shown in Table 1 was dissolved. A 40% aqueous solution of glyoxal crosslinking agent (Oi Kagane) was added to the aqueous solution according to the content described in Table 1, and then mixed to produce an adhesive A liquid composition.
Ｂ液組成物の製造：水（蒸留水）にケン化度が９９．２モル％であるアセトアセチル基変性ポリビニルアルコール系樹脂（ゴーセノールＺ２００、日本合成化学工業株式会社）を溶解し、固形分の含量が表１のような水溶液を製造した。前記水溶液に多価金属イオンの水溶性塩として、塩化亜鉛（大井化金）及び硝酸亜鉛（大井化金）を表１に記載した含量によって追加した後、混合し、接着剤Ｂ液組成物を製造した。 Production of B liquid composition: An acetoacetyl group-modified polyvinyl alcohol resin having a saponification degree of 99.2 mol% (Gosenol Z200, Nippon Synthetic Chemical Industry Co., Ltd.) is dissolved in water (distilled water) to obtain a solid content. An aqueous solution having a content as shown in Table 1 was produced. After adding zinc chloride (Oi Kagane) and zinc nitrate (Oi Kagane) as the water-soluble salt of polyvalent metal ions to the aqueous solution according to the contents shown in Table 1, they are mixed, and the adhesive B liquid composition is added. Manufactured.
前記製造されたＡ液組成物及びＢ液組成物を常温で混合し、約３０分間撹拌し、接着剤組成物を製造した。 The manufactured A liquid composition and B liquid composition were mixed at room temperature and stirred for about 30 minutes to prepare an adhesive composition.
実施例１〜８及び比較例１〜７：偏光板の製造
前記製造例１で製造された偏光子の両面に表１に記載した含量で前記製造例３の方法を利用して製造された接着剤組成物を塗布した後、前記製造例２の保護フィルムをニップロールを利用して接合させた。この際、工程条件（ニップ圧、ニップギャップ）は、表１のようにし、ニップロールにより接合された偏光板は、乾燥路内の熱風乾燥機を利用して乾燥した。乾燥過程は、総５段階で進行され、第１乾燥路内の熱風の温度及び第５乾燥路内の熱風の温度は、表１のようにし、その他、第２乾燥路内の熱風の温度は、５０℃、第３乾燥路内の熱風の温度は、７０℃、第４乾燥路内の熱風の温度は、７５℃にして、各乾燥路内で５分間乾燥し、最終偏光板を製造した。かくして製造された偏光板の水分率及び前記偏光板に含まれる接着剤層の厚さを測定し、表１に一緒に記載した。
Examples 1 to 8 and Comparative Examples 1 to 7: Manufacture of polarizing plates Adhesives manufactured using the method of Preparation Example 3 with the contents shown in Table 1 on both sides of the polarizer manufactured in Preparation Example 1 After coating the agent composition, the protective film of Production Example 2 was bonded using a nip roll. At this time, the process conditions (nip pressure, nip gap) were as shown in Table 1, and the polarizing plate bonded by the nip roll was dried using a hot air dryer in the drying path. The drying process proceeds in a total of five stages. The temperature of the hot air in the first drying path and the temperature of the hot air in the fifth drying path are as shown in Table 1, and the temperature of the hot air in the second drying path is 50 ° C., the temperature of the hot air in the third drying path is 70 ° C., the temperature of the hot air in the fourth drying path is 75 ° C., and drying is performed in each drying path for 5 minutes to produce the final polarizing plate. . The moisture content of the polarizing plate thus produced and the thickness of the adhesive layer contained in the polarizing plate were measured and listed together in Table 1.
この際、前記偏光板の水分率は、１０５℃で２時間行った熱処理の前／後の重量変化を観察する重量水分率測定法で測定した。 At this time, the moisture content of the polarizing plate was measured by a weight moisture content measurement method of observing a change in weight before / after the heat treatment performed at 105 ° C. for 2 hours.
実験例
実験例１．接着力評価（カッター評価）
前記製造された偏光板を１時間常温で放置した後、偏光板の各フィルムの間（偏光子と偏光子保護フィルムの間）にカッターの刃を入れ、刃を押し進めたときの刃が入る方式を以下の基準で評価し、その結果を表２に示した。
◎：カッターの刃がいずれのフィルム間にも入らない。
○：刃を押し進めたとき、少なくともいずれか一方のフィルム間に刃が１〜２ｍｍ入ったときに止まる。
△：刃を押し進めたとき、少なくともいずれか一方のフィルム間に刃が３〜５ｍｍ入ったときに止まる。
×：刃を押し進めたとき、少なくともいずれか一方のフィルム間に刃が無理なく入る。
Experimental example
Experimental Example 1 Adhesive strength evaluation (cutter evaluation)
After leaving the manufactured polarizing plate at room temperature for 1 hour, a cutter blade is inserted between each film of the polarizing plate (between the polarizer and the polarizer protective film), and the blade is inserted when the blade is pushed forward. Were evaluated according to the following criteria, and the results are shown in Table 2.
A: The cutter blade does not enter between any films.
○: When the blade is pushed forward, it stops when the blade enters 1 to 2 mm between at least one of the films.
Δ: When the blade is pushed forward, it stops when the blade enters 3 to 5 mm between at least one of the films.
X: When the blade is pushed forward, the blade enters between at least one of the films without difficulty.
実験例２．耐水性評価
２３℃、相対湿度５５％の環境下で２４時間放置した各偏光板に対して、以下のような方法で耐温水性実験を行い、耐水性を評価した。
Experimental Example 2. Water resistance evaluation Each polarizing plate which was allowed to stand for 24 hours in an environment of 23 ° C. and 55% relative humidity was subjected to a warm water resistance test by the following method to evaluate the water resistance.
偏光板の吸収軸を長辺として５×２ｃｍのサイズに偏光板を切断してサンプルとし、その長辺方向の寸法を正確に測定した。この際、前記サンプルは、偏光フィルムに吸着されたヨウ素に起因して全面にわたって均一に特有の色を示している。図１は、耐水性の評価方法を模式的に示す図であり、（Ａ）は、温水浸漬前のサンプル１、（Ｂ）は、温水浸漬後のサンプル１を示す。図１（Ａ）に示されたように、サンプルの一短辺側を把持具５で把持し、長さ方向の８割程度を６０℃の水槽に浸漬し、８時間維持した。その後、サンプル１を水槽から取り出して水分を拭き取った。 The polarizing plate was cut into a size of 5 × 2 cm with the absorption axis of the polarizing plate as the long side to obtain a sample, and the dimension in the long side direction was accurately measured. At this time, the sample shows a unique color uniformly over the entire surface due to iodine adsorbed on the polarizing film. FIG. 1 is a diagram schematically illustrating a water resistance evaluation method, in which (A) shows sample 1 before hot water immersion, and (B) shows sample 1 after hot water immersion. As shown in FIG. 1 (A), one short side of the sample was gripped by the gripper 5, and about 80% of the length direction was immersed in a 60 ° C. water bath and maintained for 8 hours. Then, the sample 1 was taken out from the water tank and the water | moisture content was wiped off.
前記のような温水浸漬によって偏光板の偏光子４は収縮する。前記偏光子４の収縮程度を、サンプル１の短辺の中央においての末端部１ａ（保護フィルムの終端）から収縮した偏光子４の端部までの距離を測定することによって評価し、収縮長さとした。また、図１（Ｂ）に示されたように、温水浸漬によって偏光板の中央に位置する偏光子４が収縮されることによって、保護フィルムの間に偏光子４の周縁部からヨウ素が溶出し、サンプル１の周縁部に色が抜けた部分３が生ずる。このような脱色程度をサンプル１の短辺の中央においての収縮した偏光子４の末端部から偏光板特有の色が残っている領域までの距離を測定することによって評価し、ヨウ素が抜けた長さとした。前記収縮長さとヨウ素が抜けた長さとの和を総浸食長さｘとした。総浸食長さｘとは、サンプル１の短辺の中央においてのサンプル１の端部１ａから偏光板特有の色が残っている領域までの距離である。収縮長さ、ヨウ素の抜けた長さ及び総浸食長さｘが小さいほど、水の存在下においての接着性が高いと判断できる。総浸食長さｘによって以下４段階で評価し、その結果を表２に記載した。
◎：総浸食長さｘが０．１ｍｍ未満
○：総浸食長さｘが０．１ｍｍ以上０．５ｍｍ未満
△：総浸食長さｘが０．５ｍｍ以上２ｍｍ未満
×：総浸食長さｘが２ｍｍ以上
The polarizer 4 of the polarizing plate contracts by the warm water immersion as described above. The degree of contraction of the polarizer 4 is evaluated by measuring the distance from the end 1a (end of the protective film) at the center of the short side of the sample 1 to the end of the contracted polarizer 4, and the contraction length did. In addition, as shown in FIG. 1B, iodine is eluted from the peripheral portion of the polarizer 4 between the protective films by contraction of the polarizer 4 located at the center of the polarizing plate by immersion in warm water. In the peripheral edge of the sample 1, a portion 3 where the color is lost is generated. The degree of such decolorization was evaluated by measuring the distance from the end of the contracted polarizer 4 at the center of the short side of the sample 1 to the region where the color peculiar to the polarizing plate remains, and the length from which iodine was lost. Say it. The sum of the contraction length and the length from which iodine was removed was defined as the total erosion length x. The total erosion length x is the distance from the end 1a of the sample 1 at the center of the short side of the sample 1 to the region where the color peculiar to the polarizing plate remains. It can be judged that the adhesiveness in the presence of water is higher as the contraction length, the iodine removal length, and the total erosion length x are smaller. The total erosion length x was evaluated in the following four stages, and the results are shown in Table 2.
◎: Total erosion length x is less than 0.1 mm ○: Total erosion length x is 0.1 mm or more and less than 0.5 mm Δ: Total erosion length x is 0.5 mm or more and less than 2 mm ×: Total erosion length x is 2mm or more
実験例３．透過率、偏光度（％）
製造された偏光板を４ｃｍ×４ｃｍのサイズに切断して試験片を作製し、この試験片を測定ホルダーに付着させた後、紫外可視光線分光計（Ｖ−７１００、ＪＡＳＣＯ社製造）を利用して測定し、その結果を表２に記載した。
Experimental Example 3. Transmittance, degree of polarization (%)
The manufactured polarizing plate was cut into a size of 4 cm × 4 cm to prepare a test piece. After attaching the test piece to a measurement holder, an ultraviolet-visible light spectrometer (V-7100, manufactured by JASCO) was used. The results are shown in Table 2.
表２を参照すると、アセトアセチル変性ポリビニルアルコール系樹脂の水溶液内の固形分の含量が、本発明の好ましい範囲（２．５〜４．５重量％）未満の場合（比較例１）、本発明の好ましい範囲を満足する場合（実施例１〜８）より偏光板の水分率が不足で、耐水性が劣り、前記範囲を超過する場合（比較例２）、偏光板の水分率が増加し、偏光板に含まれる接着剤層の厚さが厚くなって、光特性が低下する問題が発生することを確認した。また、本発明の偏光板の工程条件（ニップ圧やニップギャップ）が本発明の範囲を逸脱する場合（比較例３〜４）、本発明において要求する偏光板の水分率や偏光板に含まれる接着剤層の厚さ範囲を逸脱する偏光板が製造されることを確認し、これにより、耐水性や光特性が低下することを確認した。偏光板の乾燥過程中に第１乾燥路内の熱風の温度が本発明の温度範囲（５０℃以下）を超過する場合（実施例７）、本発明において要求する偏光板の水分率及び偏光板に含まれる接着剤層の厚さ範囲は満足させることができたが、前記温度範囲を満足する（実施例１〜６及び８）場合より光特性が多少低下する問題が発生し、第５乾燥路内の熱風の温度範囲に対して本発明の温度範囲（８０℃以上）を逸脱する場合（比較例５）、本発明において要求する偏光板の水分率が超過し、耐水性及び光特性の低下が現われたことを確認した。また、多価金属イオンの水溶性塩を１種だけ使用する場合（比較例６及び７）、耐水性が低下することを確認した。 Referring to Table 2, when the solid content in the aqueous solution of the acetoacetyl-modified polyvinyl alcohol resin is less than the preferred range (2.5 to 4.5% by weight) of the present invention (Comparative Example 1), the present invention. When the preferable range is satisfied (Examples 1 to 8), the moisture content of the polarizing plate is insufficient and the water resistance is inferior. When the above range is exceeded (Comparative Example 2), the moisture content of the polarizing plate increases. It was confirmed that the adhesive layer included in the polarizing plate was thickened, causing a problem that the optical characteristics deteriorated. Moreover, when the process conditions (nip pressure or nip gap) of the polarizing plate of the present invention deviate from the scope of the present invention (Comparative Examples 3 to 4), the water content of the polarizing plate required in the present invention and the polarizing plate are included. It was confirmed that a polarizing plate deviating from the thickness range of the adhesive layer was produced, and thereby, it was confirmed that the water resistance and optical properties were lowered. When the temperature of the hot air in the first drying path exceeds the temperature range of the present invention (50 ° C. or lower) during the drying process of the polarizing plate (Example 7), the moisture content of the polarizing plate and the polarizing plate required in the present invention The thickness range of the adhesive layer contained in the film could be satisfied, but there was a problem that the optical characteristics were somewhat lower than when the temperature range was satisfied (Examples 1 to 6 and 8). When the temperature range of the present invention (80 ° C. or higher) deviates from the temperature range of the hot air in the road (Comparative Example 5), the moisture content of the polarizing plate required in the present invention is exceeded, and the water resistance and light characteristics of It was confirmed that a drop appeared. In addition, when only one water-soluble salt of polyvalent metal ion was used (Comparative Examples 6 and 7), it was confirmed that the water resistance was lowered.
Claims (15)
前記偏光板の水分率が２．８〜４．８％であり、
前記接着剤層は、アセトアセチル基変性ポリビニルアルコール系樹脂、グリオキサール架橋剤及び２種以上の多価金属イオンの水溶性塩を含む接着剤組成物よりなり、厚さが３０〜２００ｎｍであることを特徴とする偏光板。 In a polarizing plate comprising a protective film bonded to at least one surface of a polarizer via an adhesive layer,
The polarizing plate has a moisture content of 2.8 to 4.8%,
The adhesive layer is made of an adhesive composition containing an acetoacetyl group-modified polyvinyl alcohol resin, a glyoxal cross-linking agent, and a water-soluble salt of two or more polyvalent metal ions, and has a thickness of 30 to 200 nm. A characteristic polarizing plate.
前記塩化亜鉛の含量は、前記Ｂ液に含まれるアセトアセチル基変性ポリビニルアルコール系樹脂の固形分総１００重量部に対して、２〜１０重量部で含まれることを特徴とする請求項２に記載の偏光板。 The water-soluble salt of the polyvalent metal ion includes two or more selected from the group consisting of zinc chloride, zinc nitrate and aluminum nitrate,
The content of the zinc chloride is 2 to 10 parts by weight with respect to a total solid content of 100 parts by weight of the acetoacetyl group-modified polyvinyl alcohol resin contained in the B liquid. Polarizing plate.
前記硝酸亜鉛乃至硝酸アルミニウムの含量は、前記Ｂ液に含まれるアセトアセチル基変性ポリビニルアルコール系樹脂の固形分総１００重量部に対して、３０〜９０重量部で含まれることを特徴とする請求項２に記載の偏光板。 The water-soluble salt of the polyvalent metal ion includes two or more selected from the group consisting of zinc chloride, zinc nitrate and aluminum nitrate,
The content of the zinc nitrate or aluminum nitrate is 30 to 90 parts by weight with respect to 100 parts by weight of the total solid content of the acetoacetyl group-modified polyvinyl alcohol resin contained in the liquid B. 2. The polarizing plate according to 2.
（ａ）偏光子の両面にアセトアセチル基変性ポリビニルアルコール系樹脂、グリオキサール架橋剤及び２種以上の多価金属イオンの水溶性塩を含む接着剤組成物が塗布され、接着剤層が生成される段階と、
（ｂ）前記接着剤層上に少なくとも一つ以上の保護フィルムがニップロールにより接合され、偏光板が製作される段階と、
（ｃ）前記偏光板が少なくとも２個以上の乾燥路を通過し、乾燥される段階と、を含むことを特徴とする偏光板の製造方法。 In the method for producing a polarizing plate, the moisture content of the polarizing plate is 2.8 to 4.8%, and the thickness of the adhesive layer contained in the polarizing plate is 30 to 200 nm.
(A) An adhesive composition containing an acetoacetyl group-modified polyvinyl alcohol resin, a glyoxal cross-linking agent, and a water-soluble salt of two or more polyvalent metal ions is applied to both surfaces of the polarizer to form an adhesive layer Stages,
(B) at least one protective film is bonded onto the adhesive layer by a nip roll, and a polarizing plate is manufactured;
(C) The polarizing plate includes a step of passing through at least two drying paths and being dried.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020137839A1 (en) * | 2018-12-25 | 2020-07-02 | 日東電工株式会社 | Polarizer and method for manufacturing same |
| JP2020106834A (en) * | 2018-12-25 | 2020-07-09 | 日東電工株式会社 | Polarizer and method for manufacturing the same |
| WO2021049217A1 (en) * | 2019-09-12 | 2021-03-18 | 住友化学株式会社 | Polarizer |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002221619A (en) * | 2001-01-25 | 2002-08-09 | Gunze Ltd | Polarizing plate |
| JP2005326531A (en) * | 2004-05-13 | 2005-11-24 | Nitto Denko Corp | Polarizing plate equipped with protecting film, manufacturing method therefor, and image display device using polarizing plate |
| JP2008129258A (en) * | 2006-11-20 | 2008-06-05 | Nitto Denko Corp | Method for producing polarizing plate, polarizing plate, optical film and image display device |
| JP2008180765A (en) * | 2007-01-23 | 2008-08-07 | Sumitomo Chemical Co Ltd | Manufacturing method of polarizing film |
| JP2008257025A (en) * | 2007-04-06 | 2008-10-23 | Sumitomo Chemical Co Ltd | Polarizing plate, optical member provided with the same and liquid crystal display device |
| JP2010091811A (en) * | 2008-10-08 | 2010-04-22 | Sumitomo Chemical Co Ltd | High contrast polarizing plate and liquid crystal display apparatus |
| JP2012047799A (en) * | 2010-08-24 | 2012-03-08 | Nitto Denko Corp | Manufacturing method of polarizer |
| JP2012516469A (en) * | 2009-06-24 | 2012-07-19 | エルジー・ケム・リミテッド | Retardation film, method for producing the same, and liquid crystal display device including the same |
| US20130162935A1 (en) * | 2011-12-21 | 2013-06-27 | Eun Kyeong SEO | Polarizing plate and liquid crystal display including the same |
| KR20130078607A (en) * | 2011-12-30 | 2013-07-10 | 제일모직주식회사 | Adhesive composition for polarizing plate |
| WO2016002808A1 (en) * | 2014-07-02 | 2016-01-07 | 住友化学株式会社 | Adhesive composition and polarizing plate containing same |
| WO2016035822A1 (en) * | 2014-09-03 | 2016-03-10 | 住友化学株式会社 | Adhesive composition and polarizing plate manufactured using same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4849563B2 (en) * | 2007-08-07 | 2012-01-11 | 住友化学株式会社 | Polarizing plate and manufacturing method thereof |
| JP4762320B2 (en) * | 2009-02-20 | 2011-08-31 | 住友化学株式会社 | Liquid crystal display |
| KR102282040B1 (en) * | 2014-07-02 | 2021-07-28 | 수미토모 케미칼 컴퍼니 리미티드 | Adhesive composition and polarizing plate comprising the same |
-
2016
- 2016-08-08 KR KR1020160100725A patent/KR101775594B1/en active IP Right Grant
-
2017
- 2017-08-07 CN CN201710668721.3A patent/CN107703577B/en active Active
- 2017-08-07 JP JP2017152316A patent/JP6945380B2/en active Active
- 2017-08-08 TW TW106126685A patent/TWI729183B/en active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002221619A (en) * | 2001-01-25 | 2002-08-09 | Gunze Ltd | Polarizing plate |
| JP2005326531A (en) * | 2004-05-13 | 2005-11-24 | Nitto Denko Corp | Polarizing plate equipped with protecting film, manufacturing method therefor, and image display device using polarizing plate |
| JP2008129258A (en) * | 2006-11-20 | 2008-06-05 | Nitto Denko Corp | Method for producing polarizing plate, polarizing plate, optical film and image display device |
| JP2008180765A (en) * | 2007-01-23 | 2008-08-07 | Sumitomo Chemical Co Ltd | Manufacturing method of polarizing film |
| JP2008257025A (en) * | 2007-04-06 | 2008-10-23 | Sumitomo Chemical Co Ltd | Polarizing plate, optical member provided with the same and liquid crystal display device |
| JP2010091811A (en) * | 2008-10-08 | 2010-04-22 | Sumitomo Chemical Co Ltd | High contrast polarizing plate and liquid crystal display apparatus |
| JP2012516469A (en) * | 2009-06-24 | 2012-07-19 | エルジー・ケム・リミテッド | Retardation film, method for producing the same, and liquid crystal display device including the same |
| JP2012047799A (en) * | 2010-08-24 | 2012-03-08 | Nitto Denko Corp | Manufacturing method of polarizer |
| US20130162935A1 (en) * | 2011-12-21 | 2013-06-27 | Eun Kyeong SEO | Polarizing plate and liquid crystal display including the same |
| KR20130078607A (en) * | 2011-12-30 | 2013-07-10 | 제일모직주식회사 | Adhesive composition for polarizing plate |
| WO2016002808A1 (en) * | 2014-07-02 | 2016-01-07 | 住友化学株式会社 | Adhesive composition and polarizing plate containing same |
| WO2016035822A1 (en) * | 2014-09-03 | 2016-03-10 | 住友化学株式会社 | Adhesive composition and polarizing plate manufactured using same |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020137839A1 (en) * | 2018-12-25 | 2020-07-02 | 日東電工株式会社 | Polarizer and method for manufacturing same |
| JP2020106834A (en) * | 2018-12-25 | 2020-07-09 | 日東電工株式会社 | Polarizer and method for manufacturing the same |
| CN113287043A (en) * | 2018-12-25 | 2021-08-20 | 日东电工株式会社 | Polarizing element and method for manufacturing the same |
| JP7046901B2 (en) | 2018-12-25 | 2022-04-04 | 日東電工株式会社 | Polarizer and its manufacturing method |
| CN113287043B (en) * | 2018-12-25 | 2024-01-09 | 日东电工株式会社 | Polarizing element and manufacturing method thereof |
| WO2021049217A1 (en) * | 2019-09-12 | 2021-03-18 | 住友化学株式会社 | Polarizer |
| JP2021043370A (en) * | 2019-09-12 | 2021-03-18 | 住友化学株式会社 | Polarizer |
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