WO2019208611A1 - Film optique, stratifié optique et dispositif flexible d'affichage d'images - Google Patents
Film optique, stratifié optique et dispositif flexible d'affichage d'images Download PDFInfo
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- WO2019208611A1 WO2019208611A1 PCT/JP2019/017345 JP2019017345W WO2019208611A1 WO 2019208611 A1 WO2019208611 A1 WO 2019208611A1 JP 2019017345 W JP2019017345 W JP 2019017345W WO 2019208611 A1 WO2019208611 A1 WO 2019208611A1
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- Prior art keywords
- optical film
- film
- reflection
- formula
- optical
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- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- XMSVKICKONKVNM-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3,4-diamine Chemical compound C1CC2(N)C(N)CC1C2 XMSVKICKONKVNM-UHFFFAOYSA-N 0.000 description 1
- VIQRCOQXIHFJND-UHFFFAOYSA-N bicyclo[2.2.2]oct-2-ene Chemical compound C1CC2CCC1C=C2 VIQRCOQXIHFJND-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- BEQNOZDXPONEMR-UHFFFAOYSA-N cadmium;oxotin Chemical compound [Cd].[Sn]=O BEQNOZDXPONEMR-UHFFFAOYSA-N 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000003098 cholesteric effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 229920005994 diacetyl cellulose Polymers 0.000 description 1
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical compound C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-UHFFFAOYSA-N 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- HRHKULZDDYWVBE-UHFFFAOYSA-N indium;oxozinc;tin Chemical compound [In].[Sn].[Zn]=O HRHKULZDDYWVBE-UHFFFAOYSA-N 0.000 description 1
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- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
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- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- LSACYLWPPQLVSM-UHFFFAOYSA-N isobutyric acid anhydride Chemical compound CC(C)C(=O)OC(=O)C(C)C LSACYLWPPQLVSM-UHFFFAOYSA-N 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- BBDGYADAMYMJNO-UHFFFAOYSA-N n-butyl-n-ethylbutan-1-amine Chemical compound CCCCN(CC)CCCC BBDGYADAMYMJNO-UHFFFAOYSA-N 0.000 description 1
- VEBPYKMCKZTFPJ-UHFFFAOYSA-N n-butyl-n-propylbutan-1-amine Chemical compound CCCCN(CCC)CCCC VEBPYKMCKZTFPJ-UHFFFAOYSA-N 0.000 description 1
- WUQGUKHJXFDUQF-UHFFFAOYSA-N naphthalene-1,2-dicarbonyl chloride Chemical compound C1=CC=CC2=C(C(Cl)=O)C(C(=O)Cl)=CC=C21 WUQGUKHJXFDUQF-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- HVNWRBWNOPYOER-UHFFFAOYSA-N pentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C(C)C(C(O)=O)C(C(O)=O)CC(O)=O HVNWRBWNOPYOER-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010897 surface acoustic wave method Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OAXARSVKYJPDPA-UHFFFAOYSA-N tert-butyl 4-prop-2-ynylpiperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(CC#C)CC1 OAXARSVKYJPDPA-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical group [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- 239000001003 triarylmethane dye Substances 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical class O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/14—Polyamide-imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
-
- 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
- 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
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/50—OLEDs integrated with light modulating elements, e.g. with electrochromic elements, photochromic elements or liquid crystal elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
Definitions
- the present invention relates to an optical film containing at least one selected from the group consisting of polyimide, polyamide and polyamideimide.
- optical films containing polyimide resins have been used as functional films for imparting functions to image display devices such as televisions, personal computers, smartphones, tab reds, and electronic paper. Since the user of such an image display device visually recognizes an image displayed directly by an optical film applied to the display device, the optical film is required to have an excellent film appearance.
- Defective film appearance includes, for example, defects derived from the composition of the optical film and defects derived from the manufacturing method of the optical film.
- the former is, for example, a defect in which an appearance (more specifically, silica particles or the like) interacts with visible light to deteriorate the appearance.
- the optical film is manufactured by the roll-to-roll method, which is excellent in mass productivity, for example, the optical film is not smoothly fed out from the roll due to inappropriate tack of the optical film. Is a defect that causes a scratch on the surface of the optical film due to sliding. For this reason, the latter requires the feeding stability (unwinding stability) of the optical film.
- an optical film including a polyimide resin and silica particles as described in Patent Document 1 May not be compatible at a high level.
- an object of the present invention is to provide an optical film having excellent feeding stability and excellent film appearance, an optical laminate including the optical film, and a flexible image display device.
- the present inventors have found that in an optical film containing at least one selected from the group consisting of polyimide, polyamide and polyamideimide, reflection (SCE) b * / reflection (SCI) ) It has been found that the above problem can be solved by adjusting b * within a predetermined range, and the present invention has been completed. That is, the present invention includes the following aspects.
- reflection (SCE) b * indicates b * in the L * a * b * color system of light reflected from the optical film obtained by the SCE method
- reflection (SCI) b * is SCI.
- the b * in the L * a * b * color system of the light reflected from the optical film determined by the method is shown] Satisfying the optical film.
- Ra represents a three-dimensional distance between the silica particles and at least one selected from the group consisting of the polyimide, the polyamide, and the polyamideimide in a solubility parameter space
- a flexible image display device comprising the optical laminate according to [8].
- the flexible image display device according to [9] further including a polarizing plate.
- the optical laminated body and flexible image display apparatus containing the optical film which combined the outstanding feeding stability and the outstanding film external appearance can be provided.
- the optical film of the present invention contains at least one selected from the group consisting of polyimide, polyamide and polyamideimide, and has the formula (1) 0.04 ⁇ reflection (SCE) b * / reflection (SCI) b * ⁇ 1.50 (1)
- reflection (SCE) b * indicates b * in the L * a * b * color system of light reflected from the optical film obtained by the SCE method
- reflection (SCI) b * is SCI.
- the b * in the L * a * b * color system of the light reflected from the optical film determined by the method is shown] Meet.
- the ratio [reflection (SCE) b * / reflection (SCI) b *] of the formula (1) of the optical film is preferably 0.05 or more, more preferably from the viewpoint of further improving the feeding stability and / or the film appearance. Is 0.1 or more, more preferably 0.13 or more.
- the ratio [reflection (SCE) b * / reflection (SCI) b *] of the formula (1) of the optical film is preferably 1.4 or less from the viewpoint of further improving the feeding stability and / or the film appearance. More preferably, it is 1.2 or less, More preferably, it is 1.1 or less. A plurality of these upper limit values and lower limit values can be arbitrarily combined.
- the reflection (SCE) b * of the optical film is b * in the L * a * b * color system of the light reflected by the optical film, which is determined by the SCE (Special Component Excluded) method.
- SCE Specific Component Excluded
- B * Refers to the b * value of the color system.
- the reflection (SCE) b * is preferably ⁇ 2.5 or more, preferably ⁇ 2.4 or more, more preferably ⁇ 2.3 or more.
- the reflection (SCE) b * is preferably ⁇ 0.08 or less, preferably ⁇ 0.1 or less, more preferably ⁇ 0.3 or less. A plurality of these upper limit values and lower limit values can be arbitrarily combined.
- the reflection (SCE) b * of the optical film can be measured using, for example, a spectrocolorimeter. The measurement method can be measured by the method described in the examples.
- the reflection (SCI) b * of the optical film is b * in the L * a * b * color system of the light reflected from the optical film, which is obtained by SCI (special component included) method.
- SCI special component included
- the reflection (SCI) b * is preferably ⁇ 2.9 or more, more preferably ⁇ 2.7 or more, and further preferably ⁇ 2.5 or more.
- the reflection (SCI) b * is preferably ⁇ 1.4 or less, more preferably ⁇ 1.6 or less, and still more preferably ⁇ 2.0 or less. A plurality of these upper limit values and lower limit values can be arbitrarily combined.
- the reflection (SCI) b * of the optical film can be measured using, for example, a spectrocolorimeter. The measurement method can be measured by the method described in the examples.
- Examples of means for adjusting the numerical value of the formula (1) within a predetermined numerical range include means for reducing the interaction between white light and components in the optical film.
- means for reducing the interaction for example, the film thickness of the optical film, the addition of additives (more specifically, silica particles, ultraviolet absorbers, brighteners, etc.), the characteristics of the additives (more specifically, Specifically, there may be mentioned means for adjusting the particle diameter, surface modification, content, etc.) within a predetermined range.
- the adjustment of the particle diameter, surface modification, and content of the silica particles enables the silica particles to be less likely to aggregate in the optical film and to exist in the form of primary particles, so the silica particles are uniform in the optical film. It becomes easy to disperse.
- the optical film of the present invention preferably has the formula (2) Reflection (SCE) a * / Reflection (SCI) a * ⁇ 2.5 (2)
- Reflection (SCE) a * indicates a * in the L * a * b * color system of light reflected from the optical film obtained by the SCE method
- reflection (SCI) a * is SCI.
- the a * in the L * a * b * color system of the light reflected from the optical film determined by the method is shown] Meet.
- the optical film satisfies the formula (2), the feeding stability and / or film appearance of the optical film is further improved.
- the ratio [reflection (SCE) a * / reflection (SCI) a *] of the formula (2) of the optical film is preferably 2.2 or less from the viewpoint of further improving the feeding stability and / or film appearance of the optical film. More preferably, it is 2.0 or less, More preferably, it is 1.8 or less. Further, the ratio [reflection (SCE) a * / reflection (SCI) a *] of the formula (2) of the optical film is preferably from the viewpoint of further improving the feeding stability and / or film appearance of the optical film. It is 0 or more, more preferably 0.1 or more. A plurality of these upper limit values and lower limit values can be arbitrarily combined. Examples of means for adjusting the numerical value of the expression (2) within a predetermined numerical range include means for adjusting the numerical value of the above-described expression (1) within a predetermined numerical range.
- the reflection (SCE) a * of the optical film is a * in the L * a * b * color system of the light reflected by the optical film, which is determined by the SCE method.
- the vertical direction of the optical film plane The CIE 1976 L * a * b * color system a * value of diffuse reflected light excluding specularly reflected light from incident light in the wavelength range of 380 to 780 nm that is incident from a direction inclined at a predetermined angle from Say.
- the reflection (SCE) a * is preferably ⁇ 0.01 or more, preferably 0.0 or more.
- the reflection (SCE) a * is preferably 0.6 or less, preferably 0.5 or less, and more preferably 0.4 or less. A plurality of these upper limit values and lower limit values can be arbitrarily combined.
- the reflection (SCE) a * of the optical film can be measured using, for example, a spectrocolorimeter. The measurement method can be measured by the method described in the examples.
- the reflection (SCI) a * of the optical film is a * in the L * a * b * color system of the light reflected from the optical film obtained by the SCI method.
- the vertical direction of the optical film plane The CIE 1976 L * a * b * color system a * value of reflected light (reflected light including specularly reflected light) with respect to incident light in a wavelength range of 380 to 780 nm, which is incident from a direction inclined at a predetermined angle.
- the reflection (SCI) a * is preferably ⁇ 0.03 or more, more preferably 0.0 or more, and still more preferably 0.1 or more.
- the reflection (SCI) a * is preferably 0.28 or less, more preferably 0.27 or less, and still more preferably 0.26 or less. A plurality of these upper limit values and lower limit values can be arbitrarily combined.
- the reflection (SCI) a * of the optical film can be measured using, for example, a spectrocolorimeter. The measurement method can be measured by the method described in the examples.
- the haze of the optical film of the present invention is preferably 1% or less, more preferably 0.8% or less, still more preferably 0.5% or less, from the viewpoint of further improving the feeding stability and / or film appearance of the optical film. Especially preferably, it is 0.3% or less.
- the haze of the optical film can be measured according to JIS K 7136: 2000. The measuring method will be described in detail in Examples. Since the haze of the optical film indicates the degree of dispersibility of the additive in the optical film, when the haze of the optical film is within the above range, the feeding stability of the optical film and / or the film appearance is excellent.
- the total light transmittance of the optical film of the present invention is preferably 85% or more, more preferably 87% or more, and further preferably 89% or more.
- the total light transmittance of the optical film can be measured according to JIS K 7361-1: 1997. The measuring method will be described in detail in Examples.
- the total light transmittance of the optical film is within the above numerical range, a sufficient film appearance can be secured when the optical film is incorporated in an image display device.
- the total light transmittance of the optical film is in the above numerical range, it is easy to ensure a certain brightness. For example, it is possible to suppress the light emission intensity of the display element and the power consumption of the image display device. Can be reduced.
- the yellowness of the optical film of the present invention is preferably 3.0 or less, more preferably 2.7 or less, and still more preferably 2.5 or less.
- the yellowness of the optical film can be measured according to JIS K 7373: 2006. The measuring method will be described in detail in Examples.
- the film thickness of the optical film of the present invention is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, and further preferably 30 ⁇ m or more.
- the film thickness is preferably 120 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably 80 ⁇ m or less, and particularly preferably 60 ⁇ m or less.
- a film thickness of 30 ⁇ m or more is advantageous from the viewpoint of internal protection when the optical film is used as a device, and a film thickness of 120 ⁇ m or less is advantageous from the viewpoint of folding resistance, cost, transparency, and the like.
- the measuring method will be described in detail in Examples.
- the composition in the optical film causes aggregation and the like due to poor dispersion and lowers the film appearance quality, and solutes in solid systems such as optical films (eg, additives, more specifically For example, an ultraviolet absorber, silica particles, and a brightening agent) and a medium (for example, a resin, more specifically, at least one resin selected from the group consisting of polyimide, polyamide, and polyamideimide).
- optical films eg, additives, more specifically For example, an ultraviolet absorber, silica particles, and a brightening agent
- a medium for example, a resin, more specifically, at least one resin selected from the group consisting of polyimide, polyamide, and polyamideimide.
- HSP Hansen Solubility Parameter
- the optical film of the present invention is based on the formula (3) related to HSP from the viewpoint of suppressing the deterioration of the film appearance quality (particularly, the viewpoint of suppressing the occurrence of whiteish defects).
- Ra ⁇ 8.0 (3) [In formula (3), Ra represents the three-dimensional distance between the solute and the medium in the HSP space] It is preferable to satisfy.
- the optical film of the present invention has a formula (4) related to the HSP from the viewpoint of further suppressing deterioration of the film appearance quality.
- ⁇ t ⁇ 2.0 (4)
- ⁇ t represents a difference of the total ⁇ t of the dispersion term, the polar term and the hydrogen bond term of the HSP between the solute and the medium.
- optical film of the present invention more preferably satisfies all of the formulas (3) to (5) from the viewpoint of further suppressing the deterioration of the film appearance quality.
- the HSP value is calculated using the Hansen Solubility Sphere method (Hansen Solubility Sphere method). Details will be described below.
- the target composition (the solute and the medium) is dissolved or dispersed in a solvent having a known HSP value, and the solubility or dispersibility of the composition in a specific solvent is evaluated.
- the evaluation of solubility and dispersibility is performed by visually determining whether the target composition is dissolved in a solvent and whether it is dispersed. This is done for a plurality of solvents.
- This type of solvent it is preferable to use a [delta] t is widely different solvents, more specifically, is preferably 10 or more, more preferably 15 or more, more preferably 18 or more.
- HSP space a three-dimensional space
- HSP space composed of HSP dispersion term ⁇ d , polar term ⁇ p and hydrogen bond term ⁇ h .
- a sphere in which a solvent in which the composition of the object is dissolved or dispersed is contained on the inside, a solvent in which the composition of the object is not dissolved or dispersed is on the outside, and the radius is minimized is created.
- the center coordinates ( ⁇ d , ⁇ p , ⁇ h ) of the obtained Hansen sphere are defined as the HSP having the composition.
- HSP values when the resin is component 1 and the silica is component 2 ( ⁇ d1 , ⁇ p1 , ⁇ h1 : HSP of component 1 ).
- the values, ⁇ d2 , ⁇ p2 , ⁇ h2 : HSP value of component 2 are calculated.
- the sum ⁇ t of the dispersion term, the polar term and the hydrogen bond term of the HSP and the difference ⁇ t between the component 1 and the component 2 are calculated using the equations (6) and (7), respectively.
- ⁇ t corresponds to Hildebrand HSP.
- ⁇ t 2 ⁇ d 2 + ⁇ p 2 + ⁇ h 2 (6)
- ⁇ t
- ⁇ t is preferably 3.5 or less, more preferably 3.0 or less, still more preferably 2.0 or less, even more preferably 1.0 or less, particularly preferably from the viewpoint of further suppressing deterioration in film appearance quality. Is 0.5 or less.
- the difference ⁇ p in the HSP polarity term between component 1 and component 2 is calculated using equation (8).
- ⁇ p
- (8) ⁇ p is preferably 4.5 or less, more preferably 3.5 or less, still more preferably 3.0 or less, even more preferably 2.0 or less, particularly preferably from the viewpoint of further suppressing deterioration in film appearance quality. Is 1.0 or less.
- the three-dimensional distance Ra (> 0) between the component 1 and the component 2 in the HSP space is calculated using the equation (9).
- Ra 2 4 ( ⁇ d2 ⁇ d1 ) 2 + ( ⁇ p2 ⁇ p1 ) 2 + ( ⁇ h2 ⁇ h1 ) 2 (9) It shows that the affinity of the component 1 and the component 2 is so favorable that Ra value is small.
- the Ra value is preferably 8.0 or less, more preferably 7.0 or less, still more preferably 6.0 or less, and even more preferably 5.5 or less, particularly preferably from the viewpoint of further suppressing deterioration in film appearance quality. Is 5.0 or less.
- the optical film of the present invention contains at least one resin selected from the group consisting of polyimide resins and polyamide resins.
- Polyimide resin is a polymer containing a repeating structural unit containing an imide group (hereinafter sometimes referred to as polyimide), and a polymer containing a repeating structural unit containing both an imide group and an amide group (hereinafter referred to as polyimide).
- polyimide resin refers to a polymer containing a repeating structural unit containing an amide group.
- the polyimide resin preferably has a repeating structural unit represented by the formula (10).
- G is a tetravalent organic group
- A is a divalent organic group.
- the polyimide resin may contain a repeating structural unit represented by two or more types of formula (10) in which G and / or A are different.
- the polyimide resin contains one or more selected from the group consisting of repeating structural units represented by formula (11), formula (12), and formula (13) as long as various physical properties of the optical film are not impaired. Also good.
- G and G 1 are each independently a tetravalent organic group, and may preferably be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group.
- the G and G 1, equation (20), equation (21), equation (22), equation (23), equation (24), equation (25), equation (26), equation (27), formula (28 ) Or a group represented by the formula (29) and a tetravalent hydrocarbon group having 6 or less carbon atoms. Since it is easy to suppress the yellowness (YI value) of the optical film, among them, the formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula The group represented by (26) or formula (27) is preferred.
- Z is a single bond, -O -, - CH 2 - , - CH 2 -CH 2 -, - CH (CH 3) -, - C (CH 3) 2 -, - C (CF 3) 2 -, - Ar -, - SO 2 -, - CO -, - O-Ar-O -, - Ar-O-Ar -, - Ar-CH 2 -Ar -, - Ar-C (CH 3) 2 -Ar- , or —Ar—SO 2 —Ar— is represented.
- Ar represents an arylene group having 6 to 20 carbon atoms which may be substituted with a fluorine atom, and specific examples thereof include a phenylene group.
- G 2 is a trivalent organic group, preferably an organic group that may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group.
- the G 2, equation (20), equation (21), equation (22), equation (23), equation (24), equation (25), equation (26), equation (27), equation (28) or Examples thereof include a group in which any one of the bonds of the group represented by formula (29) is replaced with a hydrogen atom, and a trivalent chain hydrocarbon group having 6 or less carbon atoms.
- G 3 is a divalent organic group, preferably an organic group which may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group.
- the G 3 equation (20), equation (21), equation (22), equation (23), equation (24), equation (25), equation (26), equation (27), equation (28) or Examples of the bond of the group represented by formula (29) include a group in which two that are not adjacent to each other are replaced with hydrogen atoms, and a chain hydrocarbon group having 6 or less carbon atoms.
- A, A 1 , A 2 and A 3 are each independently a divalent organic group, preferably substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group.
- A, A 1 , A 2 and A 3 Formula (30), Formula (31), Formula (32), Formula (33), Formula (34), Formula (35), Formula (36), Formula ( 37) or a group represented by formula (38); a group in which they are substituted with a methyl group, a fluoro group, a chloro group or a trifluoromethyl group; and a chain hydrocarbon group having 6 or less carbon atoms.
- Z 1, Z 2 and Z 3 are each independently a single bond, -O -, - CH 2 - , - CH 2 -CH 2 -, - CH (CH 3) -, - C (CH 3) 2 —, —C (CF 3 ) 2 —, —SO 2 — or —CO— is represented.
- Z 1 and Z 3 are —O— and Z 2 is —CH 2 —, —C (CH 3 ) 2 —, —C (CF 3 ) 2 — or —SO 2 —. is there. It is preferable that the bonding position of each of Z 1 and Z 2 with respect to each ring and the bonding position of each of Z 2 and Z 3 with respect to each ring is a meta position or a para position with respect to each ring.
- the polyimide resin is a polyamideimide having at least a repeating structural unit represented by the formula (10) and a repeating structural unit represented by the formula (13) from the viewpoint of easily improving the visibility (film appearance).
- a polyamide-type resin has at least the repeating structural unit represented by Formula (13).
- the polyimide resin comprises a diamine, a tetracarboxylic acid compound (an acid chloride compound, a tetracarboxylic acid analog such as tetracarboxylic dianhydride), and, if necessary, a dicarboxylic acid compound.
- a tetracarboxylic acid compound an acid chloride compound, a tetracarboxylic acid analog such as tetracarboxylic dianhydride
- a dicarboxylic acid compound a condensation polymer obtained by reacting (polycondensation) (dicarboxylic acid compound analogs such as acid chloride compounds), tricarboxylic acid compounds (tricarboxylic acid compound analogs such as acid chloride compounds and tricarboxylic acid anhydrides) and the like.
- the repeating structural unit represented by formula (10) or formula (11) is usually derived from a diamine and a tetracarboxylic acid compound.
- the repeating structural unit represented by the formula (12) is usually derived from a diamine and a tricarboxylic acid compound.
- the repeating structural unit represented by the formula (13) is usually derived from a diamine and a dicarboxylic acid compound.
- the polyamide resin is a condensed polymer obtained by reacting (polycondensation) a diamine and a dicarboxylic acid compound. That is, the repeating structural unit represented by the formula (13) is usually derived from a diamine and a dicarboxylic acid compound.
- tetracarboxylic acid compound examples include aromatic tetracarboxylic acid compounds such as aromatic tetracarboxylic dianhydride; and aliphatic tetracarboxylic acid compounds such as aliphatic tetracarboxylic dianhydride.
- aromatic tetracarboxylic acid compounds such as aromatic tetracarboxylic dianhydride
- aliphatic tetracarboxylic acid compounds such as aliphatic tetracarboxylic dianhydride.
- a tetracarboxylic acid compound may be used independently and may use 2 or more types together.
- the tetracarboxylic acid compound may be a dianhydride or a tetracarboxylic acid compound analog such as an acid chloride compound.
- aromatic tetracarboxylic dianhydride examples include 4,4′-oxydiphthalic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3, 3'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-Diphenylsulfonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane Dianhydride, 2,2-bis (3,4-dicarboxyphenoxyphenyl) propane dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride, 4,
- Examples of the aliphatic tetracarboxylic dianhydride include cyclic or acyclic aliphatic tetracarboxylic dianhydrides.
- the cycloaliphatic tetracarboxylic dianhydride is a tetracarboxylic dianhydride having an alicyclic hydrocarbon structure, and specific examples thereof include 1,2,4,5-cyclohexanetetracarboxylic dianhydride.
- acyclic aliphatic tetracarboxylic dianhydride examples include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride and the like. These may be used alone or in combination of two or more. Further, a cycloaliphatic tetracarboxylic dianhydride and an acyclic aliphatic tetracarboxylic dianhydride may be used in combination.
- 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene are used from the viewpoint of high transparency and low colorability.
- -2,3,5,6-tetracarboxylic dianhydride and 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride, and mixtures thereof are preferred.
- tricarboxylic acid compound examples include aromatic tricarboxylic acid, aliphatic tricarboxylic acid, and related acid chloride compounds, acid anhydrides, and the like, and two or more kinds may be used in combination. Specific examples include 1,2,4-benzenetricarboxylic acid anhydride; 2,3,6-naphthalenetricarboxylic acid-2,3-anhydride; phthalic acid anhydride and benzoic acid are a single bond, —CH 2 Examples thereof include compounds linked by —, —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, —SO 2 —, or a phenylene group.
- dicarboxylic acid compound examples include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and related acid chloride compounds, acid anhydrides, and the like, and two or more of them may be used in combination.
- terephthalic acid dichloride terephthaloyl chloride (TPC)
- isophthalic acid dichloride naphthalenedicarboxylic acid dichloride; 4,4′-biphenyldicarboxylic acid dichloride; 3,3′-biphenyldicarboxylic acid dichloride; , 4′-oxybis (benzoyl chloride) (OBBC)
- OBBC 4′-oxybis (benzoyl chloride)
- OBBC 4′-oxybis (benzoyl chloride)
- OBBC 4′-oxybis (benzoyl chloride)
- OBBC 4′-oxybis (benzoyl chloride)
- OBBC 4′-oxybis (benzoyl chloride)
- diamines examples include aliphatic diamines, aromatic diamines, and mixtures thereof.
- the “aromatic diamine” represents a diamine in which an amino group is directly bonded to an aromatic ring, and an aliphatic group or other substituent may be included in a part of the structure.
- the aromatic ring may be a single ring or a condensed ring, and examples thereof include, but are not limited to, a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring. Among these, the aromatic ring is preferably a benzene ring.
- the “aliphatic diamine” refers to a diamine in which an amino group is directly bonded to an aliphatic group, and an aromatic ring or other substituent may be included in a part of the structure.
- aliphatic diamine examples include acyclic aliphatic diamines such as hexamethylene diamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, norbornane diamine, 4,4′- And cycloaliphatic diamines such as diaminodicyclohexylmethane. These can be used alone or in combination of two or more.
- aromatic diamines examples include p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, m-xylylenediamine, p-xylylenediamine, 1,5-diaminonaphthalene and 2,6-diaminonaphthalene.
- Aromatic diamines having one aromatic ring such as 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3 ′ -Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis ( 4-Aminophenoxy) benzene, 4,4'-diaminodiph Nylsulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4
- diamines it is preferable to use one or more selected from the group consisting of aromatic diamines having a biphenyl structure from the viewpoint of high transparency and low colorability.
- aromatic diamines having a biphenyl structure from the viewpoint of high transparency and low colorability.
- One selected from the group consisting of 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) benzidine, 4,4'-bis (4-aminophenoxy) biphenyl, and 4,4'-diaminodiphenyl ether It is more preferable to use the above, and it is even more preferable to use 2,2′-bis (trifluoromethyl) benzidine.
- the polyimide resin is prepared by mixing the raw materials such as the diamine, tetracarboxylic acid compound, tricarboxylic acid compound, and dicarboxylic acid compound by a conventional method, for example, a method such as stirring, and then converting the obtained intermediate into an imidization catalyst and If necessary, it can be obtained by imidization in the presence of a dehydrating agent.
- the polyamide-based resin can be obtained by mixing raw materials such as the diamine and dicarboxylic acid compound by a conventional method, for example, a method such as stirring.
- the imidization catalyst used in the imidization step is not particularly limited, but examples thereof include aliphatic amines such as tripropylamine, dibutylpropylamine, and ethyldibutylamine; N-ethylpiperidine, N-propylpiperidine, N-butylpyrrolidine , N-butylpiperidine, and N-propylhexahydroazepine and other alicyclic amines (monocyclic); azabicyclo [2.2.1] heptane, azabicyclo [3.2.1] octane, azabicyclo [2.2 .2] Cycloaliphatic amines (polycyclic) such as octane and azabicyclo [3.2.2] nonane; and 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3- Ethylpyridine, 4-ethylpyridine, 2,4-dimethylpyridine, 2,
- the dehydrating agent used in the imidization step is not particularly limited, and examples thereof include acetic anhydride, propionic anhydride, isobutyric anhydride, pivalic anhydride, butyric anhydride, and isovaleric anhydride.
- the reaction temperature is not particularly limited, but is, for example, 15 to 350 ° C., preferably 20 to 100 ° C.
- the reaction time is not particularly limited, but is, for example, about 10 minutes to 10 hours. If necessary, the reaction may be carried out under an inert atmosphere or under reduced pressure.
- the reaction may be performed in a solvent, and examples of the solvent include those exemplified as the solvent used for preparing the varnish. After the reaction, the polyimide resin or the polyamide resin is purified.
- Examples of the purification method include a method of adding a poor solvent to the reaction solution and precipitating the resin by a reprecipitation method, drying to take out the precipitate, and washing the precipitate with a solvent such as methanol as necessary to dry it.
- a solvent such as methanol as necessary to dry it.
- the production method described in JP-A-2006-199945 or JP-A-2008-163107 may be referred to.
- Commercially available polyimide resins can also be used, and specific examples thereof include Neoprim (registered trademark) manufactured by Mitsubishi Gas Chemical Co., Ltd., and KPI-MX300F manufactured by Kawamura Sangyo Co., Ltd.
- the weight average molecular weight of the polyimide resin or polyamide resin is preferably 200,000 or more, more preferably 250,000 or more, still more preferably 300,000 or more, preferably 600,000 or less, more preferably 500, 000 or less.
- the weight average molecular weight of the polyimide resin or polyamide resin is larger, there is a tendency that high bending resistance when formed into a film tends to be expressed. Therefore, from the viewpoint of improving the bending resistance of the optical film, it is preferable that the weight average molecular weight is not less than the above lower limit.
- the smaller the weight average molecular weight of the polyimide resin or polyamide resin the easier it is to lower the viscosity of the varnish and the easier it is to improve processability.
- the weight average molecular weight is preferably not more than the above upper limit.
- a weight average molecular weight can perform a gel permeation chromatography (GPC) measurement, can be calculated
- the imidation ratio of the polyimide resin is preferably 95 to 100%, more preferably 97 to 100%, still more preferably 98 to 100%, and particularly preferably 100%. From the viewpoint of the stability of the varnish and the mechanical properties of the obtained optical film, it is preferable that the imidization ratio is not less than the above lower limit.
- the imidization rate can be obtained by IR method, NMR method or the like. From the above viewpoint, it is preferable that the imidization ratio of the polyimide resin contained in the varnish is within the above range.
- the polyimide resin or polyamide resin contained in the optical film of the present invention contains a halogen atom such as a fluorine atom, which can be introduced by, for example, the above fluorine-containing substituent.
- a halogen atom such as a fluorine atom
- the polyimide resin or the polyamide resin contains a halogen atom, it is easy to improve the elastic modulus of the optical film and reduce the yellowness (YI value).
- the halogen atom is preferably a fluorine atom.
- Preferred fluorine-containing substituents for incorporating a fluorine atom into a polyimide resin or polyamide resin include, for example, a fluoro group and a trifluoromethyl group.
- the halogen atom content in the polyimide resin or polyamide resin is preferably 1 to 40% by mass, more preferably 5 to 40% by mass, and still more preferably based on the mass of the polyimide resin or polyamide resin. 5 to 30% by mass.
- the halogen atom content is 1% by mass or more, the elastic modulus when formed into a film is further improved, the water absorption is lowered, the yellowness (YI value) is further reduced, and the transparency is easily improved. There exists a tendency for a synthesis
- the content of the polyimide resin and / or the polyamide resin in the optical film is preferably 40% by mass or more, more preferably 50% by mass or more, based on the total mass of the optical film. More preferably, it is 70 mass% or more. It is preferable that the content of the polyimide-based resin and / or the polyamide-based resin is not less than the above lower limit from the viewpoint of easily improving the bending resistance and the like. In addition, content of the polyimide-type resin and / or polyamide-type resin in an optical film is 100 mass% or less normally on the basis of the total mass of an optical film.
- the optical film of the present invention may further contain an additive.
- additives include silica particles, ultraviolet absorbers, brighteners, silica dispersants, antioxidants, pH adjusters, and leveling agents.
- the optical film of the present invention may further contain silica particles as an additive.
- the content of silica particles is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, preferably 60 parts by mass or less, based on the total mass of the optical film. Preferably it is 50 mass parts or less, More preferably, it is 45 mass parts or less.
- content of a silica particle can select and combine arbitrary lower limit values and upper limit values among these upper limit values and lower limit values.
- the silica particles are less likely to aggregate and tend to be uniformly dispersed in the state of primary particles. A reduction in the visibility of the optical film of the invention can be suppressed.
- the particle diameter of the silica particles is preferably 1 nm or more, more preferably 3 nm or more, further preferably 5 nm or more, particularly preferably 8 nm or more, preferably 30 nm or less, more preferably 28 nm or less, still more preferably 25 nm or less, particularly Preferably it is 20 nm or less.
- the particle diameter of the silica particles can be combined by selecting any lower limit value and upper limit value from among these upper limit values and lower limit values. When the content of the silica particles is within the numerical range of the upper limit and / or the lower limit, in the optical film of the present invention, it is difficult to interact with light of a specific wavelength in white light. A reduction in visibility can be suppressed.
- the particle diameter of the silica particles indicates the average primary particle diameter.
- the particle diameter of the silica particles in the optical film can be measured from imaging using a transmission electron microscope (TEM).
- the particle diameter of the silica particles before producing the optical film (for example, before adding to the varnish) can be measured by a laser diffraction particle size distribution meter. The method for measuring the particle diameter of the silica particles will be described in detail in Examples.
- silica particles examples include silica sol in which silica particles are dispersed in an organic solvent or the like, and silica powder prepared by a gas phase method.
- silica sol is preferable from the viewpoint of workability.
- the silica particles may be subjected to a surface treatment.
- silica particles obtained by replacing a water-soluble alcohol-dispersed silica sol with a solvent (more specifically, ⁇ -butyrolactone or the like) may be used.
- the water-soluble alcohol is an alcohol having 3 or less carbon atoms per hydroxy group in one water-soluble alcohol molecule, and examples thereof include methanol, ethanol, 1-propanol, and 2-propanol.
- the surface treatment of the silica particles usually improves the affinity with the polyimide polymer contained in the optical film and improves the dispersibility of the silica particles. Therefore, it is possible to suppress a reduction in visibility of the present invention.
- the optical film of the present invention may further contain an ultraviolet absorber.
- an ultraviolet absorber examples thereof include triazine-based UV absorbers, benzophenone-based UV absorbers, benzotriazole-based UV absorbers, benzoate-based UV absorbers, and cyanoacrylate-based UV absorbers. These may be used alone or in combination of two or more.
- Suitable commercially available ultraviolet absorbers include, for example, Sumisorb (registered trademark) 340 manufactured by Sumika Chemtex Co., Ltd., Adekastab (registered trademark) LA-31 manufactured by ADEKA, and BASF Japan Tinuvin (registered trademark) 1577 and the like.
- the content of the ultraviolet absorber is preferably 1 phr or more and 10 phr or less, more preferably 3 phr or more and 6 phr or less, based on the mass of the optical film of the present invention.
- the optical film of the present invention may further contain a brightening agent.
- the whitening agent can be added, for example, to adjust the color tone when an additive other than the whitening agent is added.
- the brightener include monoazo dyes, triarylmethane dyes, phthalocyanine dyes, and anthraquinone dyes. Among these, anthraquinone dyes are preferable.
- Suitable commercially available brighteners include, for example, Macrolex (registered trademark) Violet B manufactured by LANXESS, Sumiplast (registered trademark) Violet B manufactured by Sumika Chemtex Co., Ltd., and dialresin manufactured by Mitsubishi Chemical Corporation. (Registered trademark) Blue G etc. are mentioned. These may be used alone or in combination of two or more.
- the content of the brightening agent is preferably 5 ppm or more and 40 ppm or less based on the mass of the optical film of the present invention.
- the application of the optical film of the present invention is not particularly limited, and may be used for various applications.
- the optical film of the present invention may be a single layer or a laminate as described above, and the optical film of the present invention may be used as it is, or a laminate with another film. May be used as Since the optical film of the present invention has excellent surface quality, it is useful as an optical film in image display devices and the like.
- the optical film of the present invention is useful as a front plate of an image display device, particularly as a front plate (window film) of a flexible display.
- the flexible display includes, for example, the flexible functional layer and the polyimide film that is stacked on the flexible functional layer and functions as a front plate. That is, the front plate of the flexible display is arranged on the viewing side on the flexible functional layer. This front plate has a function of protecting the flexible functional layer.
- optical film of this invention is not specifically limited, For example, the following processes: (A) a step of preparing a liquid containing the resin and the filler (hereinafter sometimes referred to as varnish) (varnish preparation step); (B) a step of applying a varnish to a substrate to form a coating film (application step), and (c) a step of drying the applied liquid (coating layer) to form an optical film (optical film formation step). ) It can manufacture by the method containing.
- the resin is dissolved in a solvent, and the varnish is prepared by adding the filler and other additives as necessary and stirring and mixing.
- silica which replaced the dispersion liquid of the silica sol containing a silica with the solvent in which the said resin can melt
- the solvent used for preparing the varnish is not particularly limited as long as the resin can be dissolved.
- solvents include amide solvents such as N, N-dimethylacetamide and N, N-dimethylformamide; lactone solvents such as ⁇ -butyrolactone (GBL) and ⁇ -valerolactone; dimethylsulfone, dimethylsulfoxide, sulfolane and the like.
- an amide solvent or a lactone solvent is preferable.
- These solvents can be used alone or in combination of two or more.
- the varnish may contain water, alcohol solvents, ketone solvents, acyclic ester solvents, ether solvents and the like.
- the solid content concentration of the varnish is preferably 1 to 25% by mass, more preferably 5 to 20% by mass.
- a varnish is coated on the substrate to form a coating film by a known coating method.
- Known coating methods include, for example, roll coating methods such as wire bar coating, reverse coating, and gravure coating, die coating, comma coating, lip coating, spin coating, screen coating, fountain coating, dipping, Examples thereof include a spray method and a fluent molding method.
- the optical film can be formed by drying the coating film and peeling it from the substrate. You may perform the drying process which dries an optical film further after peeling.
- the coating film can be dried usually at a temperature of 50 to 350 ° C. If necessary, the coating film may be dried under an inert atmosphere or under reduced pressure.
- base materials are SUS plates for metal, PET films, PEN films, other polyimide resins or polyamide resin films, cycloolefin polymer (COP) films, acrylic films for resins. Etc.
- PET films and COP films are preferable from the viewpoint of excellent smoothness and heat resistance, and PET films are more preferable from the viewpoint of adhesion to optical films and cost.
- the optical laminate of the present invention has the optical film of the present invention and a hard coat layer (protective film) on at least one of the optical films.
- the optical layered body may further have an adhesive layer.
- the optical layered body of the present invention may be configured, for example, by bonding the optical film of the present invention and a hard coat layer via an adhesive layer.
- the thickness of the hard coat layer is not particularly limited, and may be, for example, 2 to 100 ⁇ m. When the thickness of the hard coat layer is in the above range, sufficient scratch resistance can be ensured, the flex resistance is not easily lowered, and the problem of curling due to curing shrinkage tends not to occur. .
- the hard coat layer can be formed by curing a hard coat composition containing a reactive material that can form a crosslinked structure by irradiation with active energy rays or application of thermal energy, and is preferably formed by irradiation with active energy rays. Active energy rays are defined as energy rays that can generate active species by decomposing compounds that generate active species.
- the hard coat composition contains at least one polymer of a radical polymerizable compound and a cationic polymerizable compound.
- the radical polymerizable compound is a compound having a radical polymerizable group.
- the radical polymerizable group possessed by the radical polymerizable compound may be any functional group capable of causing a radical polymerization reaction, such as a group containing a carbon-carbon unsaturated double bond, and specifically, a vinyl group. , (Meth) acryloyl groups and the like.
- the radical polymerizable compound has two or more radical polymerizable groups, these radical polymerizable groups may be the same or different from each other.
- the number of radical polymerizable groups in the molecule of the radical polymerizable compound is preferably 2 or more from the viewpoint of improving the hardness of the hard coat layer.
- the radical polymerizable compound is preferably a compound having a (meth) acryloyl group from the viewpoint of high reactivity, and specifically includes 2 to 6 (meth) acryloyl groups in one molecule. From several hundreds of molecular weights having several (meth) acryloyl groups in molecules called polyfunctional acrylate monomers, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates Thousands of oligomers are mentioned, Preferably, 1 or more types selected from epoxy (meth) acrylate, urethane (meth) acrylate, and polyester (meth) acrylate are mentioned.
- the cationic polymerizable compound is a compound having a cationic polymerizable group such as an epoxy group, an oxetanyl group, or a vinyl ether group.
- the number of cationically polymerizable groups in one molecule of the cationically polymerizable compound is preferably 2 or more, more preferably 3 or more, from the viewpoint of improving the hardness of the hard coat layer.
- the cationic polymerizable compound is preferably a compound having at least one of an epoxy group and an oxetanyl group as a cationic polymerizable group. Cyclic ether groups such as epoxy groups and oxetanyl groups are preferred from the viewpoint of small shrinkage accompanying the polymerization reaction.
- compounds having an epoxy group among the cyclic ether groups are easily available as compounds having various structures, do not adversely affect the durability of the obtained hard coat layer, and easily control the affinity with the radical polymerizable compound.
- the oxetanyl group tends to have a higher degree of polymerization than the epoxy group, speeds up the network formation obtained from the cationically polymerizable compound of the obtained hard coat layer, and mixes with the radically polymerizable compound. Even in the region to be used, there are advantages such as forming an independent network without leaving unreacted monomers in the film.
- a cationically polymerizable compound having an epoxy group for example, a polyglycidyl ether of a polyhydric alcohol having an alicyclic ring, a cyclohexene ring or a cyclopentene ring-containing compound may be used with an appropriate oxidizing agent such as hydrogen peroxide or peracid.
- Alicyclic epoxy resin obtained by epoxidation polyglycidyl ether of aliphatic polyhydric alcohol or alkylene oxide adduct thereof, polyglycidyl ester of aliphatic long-chain polybasic acid, homopolymer of glycidyl (meth) acrylate, Aliphatic epoxy resins such as copolymers; glycidyl esters produced by the reaction of bisphenols such as bisphenol A, bisphenol F and hydrogenated bisphenol A, or derivatives thereof such as alkylene oxide adducts and caprolactone adducts with epichlorohydrin. Ether, and a novolak epoxy resin, glycidyl ether type epoxy resins derived from bisphenols are exemplified.
- the hard coat composition may further include a polymerization initiator.
- the polymerization initiator include radical polymerization initiators, cationic polymerization initiators, radicals and cationic polymerization initiators, which are appropriately selected and used. These polymerization initiators are decomposed by at least one of active energy ray irradiation and heating to generate radicals or cations to advance radical polymerization and cationic polymerization.
- the radical polymerization initiator only needs to be able to release a substance that initiates radical polymerization by at least one of irradiation with active energy rays and heating.
- thermal radical polymerization initiator examples include organic peroxides such as hydrogen peroxide and perbenzoic acid, and azo compounds such as azobisbutyronitrile.
- active energy ray radical polymerization initiators there are Type 1 type radical polymerization initiators that generate radicals by molecular decomposition and Type 2 type radical polymerization initiators that generate radicals by hydrogen abstraction reaction in the presence of tertiary amines. Yes, they are used alone or in combination.
- the cationic polymerization initiator only needs to be capable of releasing a substance that initiates cationic polymerization by irradiation with active energy rays and / or heating.
- aromatic iodonium salts aromatic sulfonium salts, cyclopentadienyl iron (II) complexes and the like can be used. Depending on the structure, they can initiate cationic polymerization either by irradiation with active energy rays or heating, or any of them.
- the content of the polymerization initiator is preferably 0.1 to 10% by mass with respect to 100% by mass of the entire hard coat composition.
- the content of the polymerization initiator is within the above range, curing can be sufficiently advanced, and the mechanical properties and adhesion of the finally obtained coating film can be within a good range, and There is a tendency that poor adhesion due to curing shrinkage, cracking phenomenon and curling phenomenon are difficult to occur.
- the hard coat composition may further include one or more selected from the group consisting of a solvent and an additive.
- the solvent is capable of dissolving or dispersing the polymerizable compound and the polymerization initiator, and does not inhibit the effects of the present invention as long as it is a solvent known as a solvent for a hard coat composition in this technical field. In range, can be used.
- the additive may further include inorganic particles, a leveling agent, a stabilizer, a surfactant, an antistatic agent, a lubricant, an antifouling agent, and the like.
- the laminate of the present invention can be used for, for example, a flexible image display device, and is particularly preferably used for a foldable display device or a rollable display device.
- An example of the manufacturing method of the optical laminated body which has a circularly-polarizing plate is demonstrated.
- an optical film, a polarizing layer, and a retardation layer are separately formed.
- An optical film is produced by the method described above.
- a polarizing layer is formed by laminating an alignment layer, a polarizer, and a protective layer in this order on a protective film as a substrate.
- the ⁇ / 4 retardation plate and the positive C plate are bonded using an adhesive to form a retardation layer.
- the adhesive, the optical film, the polarizing layer, and the retardation layer that are formed are bonded to produce an optical laminate having a circularly polarizing plate.
- the polarizing layer and the retardation layer are bonded so that the absorption axis of the polarizing layer is substantially 45 ° with respect to the slow axis (optical axis) of the retardation layer.
- the optical film / adhesive layer / polarizing layer (protective film / alignment layer / polarizer / protective layer) / adhesive layer / retardation layer ( ⁇ / 4 retardation plate / positive C plate) are laminated in this order.
- An optical laminate having a circularly polarizing plate can be manufactured.
- the optical laminate (hereinafter also referred to as laminate) having the circularly polarizing plate of the present invention includes the optical film of the present invention.
- the laminate having the circularly polarizing plate of the present invention has the formula (39) Transmission b * -reflection (SCE) b * ⁇ 4.0 (39) [In Formula (39), transmission b * represents b * in the L * a * b * color system of light transmitted through the laminate, and reflection (SCE) b * represents the laminate obtained by the SCE method. Indicates b * in the L * a * b * color system of reflected light] Meet.
- the laminate having the circularly polarizing plate of the present invention has excellent visibility because when the formula (39) is satisfied, the light transmission from the light source is large and the reflection of external light is reduced to be close to the neutral hue. .
- the numerical value (transmission b * ⁇ reflection (SCE) b *) of the formula (39) is preferably 4.2 or more, more preferably 4.5 from the viewpoint of further improving the visibility of the laminate having a circularly polarizing plate. More preferably, it is 5.0 or more, and particularly preferably 6.5 or more.
- the transmission b * of the laminate having a circularly polarizing plate is b * in the L * a * b * color system of light that has passed through the laminate having the circularly polarizing plate.
- the transmission b * is preferably 4.0 or more, more preferably 5.0 or more, and still more preferably 6.0 or more.
- the transmission b * of the laminate having a circularly polarizing plate can be measured using an ultraviolet-visible-near-infrared spectrophotometer, and can be measured, for example, by the method described in Examples.
- the reflection (SCE) b * of the laminate having a circularly polarizing plate is b * in the L * a * b * color system of the light reflected from the laminate having the circularly polarizing plate obtained by the SCE method.
- diffuse reflected light excluding regular reflected light out of reflected light with respect to incident light in a wavelength range of 380 to 780 nm, which is incident from a direction inclined at a predetermined angle from the vertical direction of the plane of the laminate having a circularly polarizing plate.
- the CIE 1976 L * a * b * color system b * value is a color system b * value.
- the reflection (SCE) b * is preferably 1.5 or less, preferably 1.0 or less, more preferably 0 or less, particularly preferably ⁇ 1.5.
- the reflection (SCE) b * of the circularly polarizing plate can be measured using a spectrocolorimeter, for example, by the method described in the examples.
- the reflection (SCI) b * of the circularly polarizing plate is b * in the L * a * b * color system of the light reflected from the circularly polarizing plate obtained by the SCI method.
- the reflection (SCI) b * of the circularly polarizing plate can be measured using a spectrocolorimeter, for example, by the method described in the examples.
- the transmission b * -reflection (SCE) b * in the formula (39) is set to the numerical value of the formula (1)
- Means for adjusting within the range, and hue adjustment by changing the composition of the optical film may be mentioned.
- the flexible image display device of the present invention includes the optical laminate of the present invention.
- the flexible image display device includes an optical laminate (a laminate for a flexible image display device) and an organic EL display panel, and the flexible image display device laminate is disposed on the viewing side with respect to the organic EL display panel. It is configured to be bendable.
- the laminate for a flexible image display device may further contain a window, a polarizing plate, and a touch sensor, and the order of stacking thereof is arbitrary.
- the polarizing plates are preferably laminated in the order of the polarizing plates. The presence of a polarizing plate on the viewing side of the touch sensor is preferable because the pattern of the touch sensor is less visible and the visibility of the display image is improved.
- Each member can be laminated
- a light shielding pattern formed on at least one surface of any one of the window, the polarizing plate, and the touch sensor may be provided.
- the polarizing plate may be a circularly polarizing plate.
- the window is disposed on the visual recognition side of the flexible image display device and plays a role of protecting other components from external impacts or environmental changes such as temperature and humidity.
- glass has been used as such a protective layer.
- a window in a flexible image display device is not rigid and hard like glass, and has flexible characteristics.
- the window is made of a flexible transparent substrate and may include a hard coat layer on at least one surface.
- the hard coat layer optionally included in the window is synonymous with the hard coat layer included in the optical laminate described above.
- the transmittance in the visible region of the transparent substrate is usually 70% or more, preferably 80% or more.
- a transparent polymer film can be used as long as the effects of the present invention are not impaired.
- the polymer film used include polyolefins such as cycloolefin derivatives having units of monomers including polyethylene, polypropylene, polymethylpentene, norbornene, or cycloolefin, diacetyl cellulose, triacetyl cellulose, (Modified) celluloses such as propionyl cellulose, acrylics such as methyl methacrylate (co) polymer, polystyrenes such as styrene (co) polymer, acrylonitrile / butadiene / styrene copolymers, acrylonitrile / styrene copolymers , Ethylene-vinyl acetate copolymers, polyvinyl chloride, polyvinyl chloride, polyvinyl chlor
- Examples include films such as stealth, polyamides such as nylon, polyimides, polyamideimides, polyetherimides, polyethersulfones, polysulfones, polyvinyl alcohols, polyvinyl acetals, polyurethanes, epoxy resins, From the viewpoint of excellent transparency and heat resistance, a polyamide, polyamideimide, polyimide, polyester, olefin, acrylic or cellulose film is preferably used. These polymers can be used alone or in admixture of two or more. These films are used unstretched or as uniaxially or biaxially stretched films. It is also preferable to disperse inorganic particles such as silica, organic fine particles, rubber particles and the like in the polymer film.
- the thickness of the transparent substrate is usually 5 to 200 ⁇ m, preferably 20 to 100 ⁇ m.
- a polarizing plate is a functional layer having a function of transmitting only a right or left circularly polarized component by laminating a ⁇ / 4 retardation plate on a linear polarizing plate. For example, external light is converted into right circularly polarized light, the external light that is reflected by the organic EL panel and turned into left circularly polarized light is blocked, and only the light emitting component of the organic EL is transmitted to suppress the influence of the reflected light. Used to make it easier to see.
- the absorption axis of the linearly polarizing plate and the slow axis of the ⁇ / 4 retardation plate need to be 45 ° theoretically, but practically 45 ⁇ 10 °.
- the linearly polarizing plate and the ⁇ / 4 retardation plate do not necessarily have to be laminated adjacent to each other as long as the relationship between the absorption axis and the slow axis satisfies the above range.
- the circular polarization plate in the present invention includes an elliptical polarization plate because it is not always necessary in practice. It is also preferable to improve visibility in a state where polarized sunglasses are applied by further laminating a ⁇ / 4 retardation film on the viewing side of the linearly polarizing plate and making the emitted light circularly polarized.
- the linearly polarizing plate is a functional layer having a function of blocking polarized light having a vibration component perpendicular to the light that is oscillating in the transmission axis direction.
- the linear polarizing plate may include a linear polarizer alone or a linear polarizer and a protective film attached to at least one surface thereof.
- the linear polarizing plate may have a thickness of 200 ⁇ m or less, preferably 0.5 to 100 ⁇ m. When the thickness is in the above range, flexibility tends to be difficult to decrease.
- the linear polarizer may be a film-type polarizer manufactured by dyeing and stretching a polyvinyl alcohol (PVA) film.
- a dichroic dye such as iodine is adsorbed on a PVA-based film oriented by stretching or is stretched in a state of being adsorbed to PVA, whereby the dichroic dye is oriented and exhibits polarizing performance.
- other steps such as swelling, crosslinking with boric acid, washing with an aqueous solution, and drying may be included.
- the stretching or dyeing process may be performed by using a PVA film alone or in a state where it is laminated with another film such as polyethylene terephthalate.
- the thickness of the PVA film used is preferably 10 to 100 ⁇ m, and the draw ratio is preferably 2 to 10 times.
- a liquid crystal coating type polarizer formed by coating a liquid crystal polarizing composition may be used.
- the liquid crystal polarizing composition may include a liquid crystal compound and a dichroic dye compound.
- the liquid crystalline compound only needs to have the property of exhibiting a liquid crystal state.
- the liquid crystalline compound preferably has a higher-order alignment state such as a smectic phase because it can exhibit high polarization performance.
- the liquid crystal compound preferably has a polymerizable functional group.
- the dichroic dye is a dye that is aligned with the liquid crystal compound and exhibits dichroism, and the dichroic dye itself may have liquid crystallinity or have a polymerizable functional group. You can also. Any compound in the liquid crystal polarizing composition has a polymerizable functional group.
- the liquid crystal polarizing composition may further contain an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a crosslinking agent, a silane coupling agent, and the like.
- the circularly polarizing plate may be a liquid crystal polarizing layer.
- the liquid crystal polarizing layer is manufactured by applying a liquid crystal polarizing composition on an alignment film to form a liquid crystal polarizing layer.
- the liquid crystal polarizing layer can be formed thinner than a film-type polarizer.
- the thickness of the liquid crystal polarizing layer may be preferably 0.5 to 10 ⁇ m, more preferably 1 to 5 ⁇ m.
- the alignment film can be produced, for example, by applying an alignment film forming composition on a substrate and imparting alignment by rubbing, polarized light irradiation, or the like.
- the alignment film forming composition may contain a solvent, a crosslinking agent, an initiator, a dispersing agent, a leveling agent, a silane coupling agent and the like in addition to the aligning agent.
- the aligning agent include polyvinyl alcohols, polyacrylates, polyamic acids, and polyimides.
- an aligning agent containing a cinnamate group When applying photo-alignment, it is preferable to use an aligning agent containing a cinnamate group.
- the polymer used as the aligning agent may have a weight average molecular weight of about 10,000 to 1,000,000.
- the thickness of the alignment film is preferably 5 to 10,000 nm, more preferably 10 to 500 nm, from the viewpoint of the alignment regulating force.
- the liquid crystal polarizing layer can be peeled off from the substrate, transferred, and laminated, or the substrate can be laminated as it is. It is also preferable that the base material plays a role as a transparent base material for a protective film, a retardation plate, or a window.
- the protective film may be a transparent polymer film, and materials and additives used for the transparent substrate can be used.
- a cellulose film, an olefin film, an acrylic film, and a polyester film are preferred.
- It may be a coating-type protective film obtained by applying and curing a cationic curing composition such as an epoxy resin or a radical curing composition such as an acrylate.
- plasticizers, ultraviolet absorbers, infrared absorbers, colorants such as pigments and dyes, fluorescent brighteners, dispersants, thermal stabilizers, light stabilizers, antistatic agents, antioxidants, lubricants, solvents, etc. May be included.
- the protective film may have a thickness of 200 ⁇ m or less, preferably 1 to 100 ⁇ m. When the thickness of the protective film is within the above range, the flexibility of the protective film is difficult to decrease.
- the protective film can also serve as a transparent substrate of the window.
- the ⁇ / 4 phase difference plate is a film that gives a phase difference of ⁇ / 4 in a direction (in-plane direction of the film) orthogonal to the traveling direction of incident light.
- the ⁇ / 4 retardation plate may be a stretched retardation plate manufactured by stretching a polymer film such as a cellulose film, an olefin film, or a polycarbonate film. If necessary, retardation adjusting agents, plasticizers, ultraviolet absorbers, infrared absorbers, colorants such as pigments and dyes, fluorescent brighteners, dispersants, thermal stabilizers, light stabilizers, antistatic agents, antioxidants Further, it may contain a lubricant, a solvent and the like.
- the stretchable retardation plate may have a thickness of 200 ⁇ m or less, preferably 1 to 100 ⁇ m. When the thickness is in the above range, the flexibility of the film tends not to decrease.
- a liquid crystal coating type retardation plate formed by applying a liquid crystal composition may be used as another example of the ⁇ / 4 retardation plate.
- the liquid crystal composition includes a liquid crystal compound having a property of exhibiting a liquid crystal state, such as nematic, cholesteric, and smectic. Any compound including a liquid crystal compound in the liquid crystal composition has a polymerizable functional group.
- the liquid crystal-coated retardation plate may further contain an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a crosslinking agent, a silane coupling agent, and the like.
- the liquid crystal coating type retardation plate can be produced by coating and curing a liquid crystal composition on an alignment film to form a liquid crystal retardation layer, as described for the liquid crystal polarizing layer.
- the liquid crystal coated retardation plate can be formed thinner than the stretched retardation plate.
- the thickness of the liquid crystal polarizing layer may be usually 0.5 to 10 ⁇ m, preferably 1 to 5 ⁇ m.
- the liquid crystal coating type retardation plate can be peeled off from the substrate, transferred, and laminated, or the substrate can be laminated as it is. It is also preferable that the base material plays a role as a transparent base material for a protective film, a retardation plate, or a window.
- the positive C plate may be a liquid crystal-coated retardation plate or a stretched retardation plate.
- the retardation in the thickness direction is usually ⁇ 200 to ⁇ 20 nm, preferably ⁇ 140 to ⁇ 40 nm.
- the touch sensor is used as input means.
- Various types of touch sensors such as a resistive film method, a surface acoustic wave method, an infrared method, an electromagnetic induction method, and a capacitance method have been proposed, and any method may be used. Of these, the electrostatic capacity method is preferable.
- the capacitive touch sensor is divided into an active region and a non-active region located in an outer portion of the active region.
- the active area is an area corresponding to an area (display unit) where the screen is displayed on the display panel, and is an area where a user's touch is sensed.
- An inactive area is an area where the screen is not displayed on the display device (non-display area). This is a region corresponding to the display unit.
- the touch sensor includes a flexible substrate; a sensing pattern formed in the active region of the substrate; and a non-active region of the substrate, which is connected to an external driving circuit through the sensing pattern and a pad portion. Each sensing line can be included.
- the substrate having flexible characteristics the same material as the transparent substrate of the window can be used.
- the substrate of the touch sensor preferably has a toughness of 2,000 MPa% or more from the viewpoint of suppressing cracks in the touch sensor. More preferably, the toughness may be 2,000 to 30,000 MPa%.
- the toughness is defined as the area under the curve up to the fracture point in a stress-strain curve obtained through a tensile test of the polymer material.
- the sensing pattern may include a first pattern formed in the first direction and a second pattern formed in the second direction.
- the first pattern and the second pattern are arranged in different directions.
- the first pattern and the second pattern are formed in the same layer, and each pattern must be electrically connected in order to sense a touched point.
- the first pattern is a form in which each unit pattern is connected to each other through a joint, but the second pattern has a structure in which each unit pattern is separated from each other in an island form.
- a separate bridge electrode is required for connection.
- a known transparent electrode material can be applied to the sensing pattern.
- ITO indium tin oxide
- IZO indium zinc oxide
- ZnO zinc oxide
- IZTO indium zinc tin oxide
- IGZO indium gallium zinc oxide
- CTO cadmium tin oxide
- PEDOT poly (3,4-ethylenedithiothiophene)
- carbon nanotube carbon nanotube
- graphene metal wire, and the like.
- ITO indium tin oxide
- IZO indium zinc oxide
- ZnO zinc oxide
- IZTO indium gallium zinc oxide
- IGZO indium gallium zinc oxide
- CTO cadmium tin oxide
- PEDOT poly (3,4-ethylenedithiothiophene
- CNT carbon nanotube
- graphene metal wire, and the like.
- the bridge electrode can be formed on the sensing pattern via the insulating layer and on the insulating layer.
- the bridge electrode is formed on the substrate, and the insulating layer and the sensing pattern can be formed thereon.
- the bridge electrode may be formed of the same material as the sensing pattern, and is formed of a metal such as molybdenum, silver, aluminum, copper, palladium, gold, platinum, zinc, tin, titanium, or an alloy of two or more of these. You can also Since the first pattern and the second pattern must be electrically insulated, an insulating layer is formed between the sensing pattern and the bridge electrode.
- the insulating layer may be formed only between the joint of the first pattern and the bridge electrode, or may be formed in a layer structure covering the sensing pattern.
- the bridge electrode can be connected to the second pattern via a contact hole formed in the insulating layer.
- the touch sensor has a transmittance difference between a pattern area where a pattern is formed and a non-pattern area where a pattern is not formed, specifically, a light transmittance induced by a difference in refractive index in these areas.
- an optical adjustment layer may be further included between the substrate and the electrode, and the optical adjustment layer may include an inorganic insulating material or an organic insulating material.
- the optical adjustment layer can be formed by coating a photocurable composition containing a photocurable organic binder and a solvent on a substrate.
- the photocurable composition may further include inorganic particles.
- the inorganic particles can increase the refractive index of the optical adjustment layer.
- the photocurable organic binder can include, for example, a copolymer of monomers such as an acrylate monomer, a styrene monomer, and a carboxylic acid monomer.
- the photocurable organic binder may be a copolymer including different repeating units such as an epoxy group-containing repeating unit, an acrylate repeating unit, and a carboxylic acid repeating unit.
- Examples of the inorganic particles include zirconia particles, titania particles, and alumina particles.
- the photocurable composition may further contain additives such as a photopolymerization initiator, a polymerizable monomer, and a curing auxiliary agent.
- Adhesive layer (adhesive layer)
- Each layer (window, polarizing plate, touch sensor) forming the laminate for a flexible image display device and a film member (linear polarizing plate, ⁇ / 4 retardation plate, etc.) forming each layer can be formed by an adhesive.
- Adhesives include water based adhesives, organic solvent based, solventless based adhesives, solid adhesives, solvent volatilizing adhesives, moisture curable adhesives, heat curable adhesives, anaerobic curable adhesives, and active energy ray curable adhesives.
- the thickness of the adhesive layer can be appropriately adjusted according to the required adhesive strength and the like, and is usually 0.01 to 500 ⁇ m, preferably 0.1 to 300 ⁇ m.
- the laminate for a flexible image display device includes although there are a plurality, the thickness and the type of pressure-sensitive adhesive used may be the same or different.
- water-based aqueous solvent volatilization type adhesive water-soluble polymers such as polyvinyl alcohol polymers and starches, water-dispersed polymers such as ethylene-vinyl acetate emulsions and styrene-butadiene emulsions can be used as the main polymer.
- a crosslinking agent, a silane compound, an ionic compound, a crosslinking catalyst, an antioxidant, a dye, a pigment, an inorganic filler, an organic solvent, and the like may be blended.
- the aqueous aqueous solvent volatile adhesive is injected between the layers to be bonded and bonded to the adherent layer, and then dried to provide adhesion.
- the thickness of the adhesive layer in the case of using the aqueous aqueous solvent volatilization type adhesive is preferably 0.01 to 10 ⁇ m, more preferably 0.1 to 1 ⁇ m.
- the thickness of each layer and the type of the adhesive may be the same or different.
- the active energy ray-curable adhesive can be formed by curing an active energy ray-curable composition containing a reactive material that irradiates active energy rays to form an adhesive layer.
- the active energy ray-curable composition can contain at least one polymer of a radical polymerizable compound and a cationic polymerizable compound similar to the hard coat composition.
- the radical polymerizable compound is the same as the hard coat composition, and the same kind as the hard coat composition can be used.
- As the radical polymerizable compound used for the adhesive layer a compound having an acryloyl group is preferable. It is also preferable to contain a monofunctional compound in order to lower the viscosity of the adhesive composition.
- the cationic polymerizable compound is the same as that of the hard coat composition, and the same kind as that of the hard coat composition can be used.
- an epoxy compound is particularly preferable.
- a monofunctional compound is particularly preferable.
- the active energy ray composition may further contain a polymerization initiator. Examples of the polymerization initiator include radical polymerization initiators, cationic polymerization initiators, radicals and cationic polymerization initiators, which can be appropriately selected and used.
- These polymerization initiators are decomposed by at least one of active energy ray irradiation and heating to generate radicals or cations to advance radical polymerization and cationic polymerization.
- an initiator capable of initiating at least one of radical polymerization or cationic polymerization by irradiation with active energy rays can be used.
- the active energy ray curable composition further comprises an ion scavenger, an antioxidant, a chain transfer agent, an adhesion promoter, a thermoplastic resin, a filler, a flow viscosity modifier, a plasticizer, an antifoaming solvent, an additive, a solvent. Can be included.
- an ion scavenger an antioxidant, a chain transfer agent, an adhesion promoter, a thermoplastic resin, a filler, a flow viscosity modifier, a plasticizer, an antifoaming solvent, an additive, a solvent.
- the active energy ray curable composition When adhering with the active energy ray curable adhesive, the active energy ray curable composition is applied to one or both of the adherend layers and then bonded, and the active energy ray curable composition is activated through either of the adhering layers or both of the adhering layers. It can be bonded by irradiating with energy rays and curing.
- the thickness of the adhesive layer is preferably 0.01 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m.
- the thickness of each layer and the type of adhesive used may be the same or different.
- the pressure-sensitive adhesives are classified into acrylic pressure-sensitive adhesives, urethane pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives and the like according to the main polymer, and any of them can be used.
- the adhesive may contain a crosslinking agent, a silane compound, an ionic compound, a crosslinking catalyst, an antioxidant, a tackifier, a plasticizer, a dye, a pigment, an inorganic filler, and the like.
- Each component constituting the pressure-sensitive adhesive is dissolved / dispersed in a solvent to obtain a pressure-sensitive adhesive composition, and the pressure-sensitive adhesive composition is coated on a substrate and then dried to form a pressure-sensitive adhesive layer adhesive layer.
- the pressure-sensitive adhesive layer may be directly formed, or a layer separately formed on the substrate can be transferred. In order to cover the adhesive surface before bonding, it is also preferred to use a release film.
- the thickness of the adhesive layer is preferably 1 to 500 ⁇ m, more preferably 2 to 300 ⁇ m.
- the thickness of each layer and the type of the pressure-sensitive adhesive used may be the same or different.
- the light shielding pattern can be applied as at least a part of a bezel or a housing of the flexible image display device. The visibility of the image is improved by concealing the wiring arranged at the edge portion of the flexible image display device by the light shielding pattern and making it difficult to see.
- the light shielding pattern may be a single layer or a multilayer.
- the color of the light-shielding pattern is not particularly limited, and can have various colors such as black, white, and metal color.
- the light shielding pattern can be formed of a pigment for embodying a color and a polymer such as an acrylic resin, an ester resin, an epoxy resin, polyurethane, or silicone. These can be used alone or in a mixture of two or more.
- the light shielding pattern can be formed by various methods such as printing, lithography, and inkjet.
- the thickness of the light shielding pattern is usually 1 to 100 ⁇ m, preferably 2 to 50 ⁇ m. It is also preferable to give a shape such as an inclination in the thickness direction of the light pattern.
- the measurement diameter is LAV: diameter 8 mm
- the measurement conditions are di: 8 °
- de 8 ° (diffuse illumination, 8 ° direction light reception)
- the measurement visual field is 2 °
- the light source is a D65 light source
- the UV conditions are 100% Full.
- the hue refers to a * and b * in the CIE 1976 L * a * b * color space.
- reflection (SCE) a * and reflection (SCI) a * of the optical film were also measured under the same conditions as described above.
- the reflection (SCE) b * and reflection (SCI) b * of the laminate having a circularly polarizing plate are the same as the measurement method of the optical film, except that the object to be measured is changed from an optical film to a laminate having a circularly polarizing plate. Measured. Similarly, reflection (SCE) a * and reflection (SCI) a * were also measured.
- the luminous transmittance Y is a physical property value indicating the brightness of the object color in the XYZ color system.
- the luminous transmittance Y of the SCI SCE method was measured using a spectrocolorimeter (“CM-3700A” manufactured by Konica Minolta, Inc.).
- the transmission b * of the laminate having a circularly polarizing plate was measured in the same manner as the method for measuring an optical film, except that the measurement object was changed from an optical film to a laminate having a circularly polarizing plate. Similarly, the transmission a * of the laminate having a circularly polarizing plate was also measured.
- Total light transmittance and haze of optical film The total light transmittance and haze of the optical film were measured using a fully automatic direct reading haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd. according to JIS K 7361-1: 1997 and JIS K 7136: 2000, respectively. did.
- the measurement sample was produced by cutting the optical films of Examples and Comparative Examples into a size of 30 mm ⁇ 30 mm.
- the particle diameter of the silica particles was calculated from the specific surface area measured by the BET adsorption method according to JIS Z 8830.
- the specific surface area of the powder obtained by drying silica sol at 300 ° C. was measured using a specific surface area measuring device (“Monosorb (registered trademark) MS-16” manufactured by Yuasa Ionics Co., Ltd.).
- the imidation ratio was determined by 1 H-NMR measurement as follows. (1) Pretreatment method An optical film containing a polyimide polymer was dissolved in deuterated dimethyl sulfoxide (DMSO-d 6 ) to give a 2% by mass solution, which was used as a measurement sample.
- DMSO-d 6 deuterated dimethyl sulfoxide
- the imidation ratio of the polyimide resin was determined from these integral values based on the following formula.
- Imidation ratio (%) 100 ⁇ (1 ⁇ ⁇ Int B / Int A )
- ⁇ is the number ratio of benzene protons A to one amide proton in the case of polyamic acid (imidation rate 0%).
- the observed benzene protons are derived from a structure that does not change before and after imidation, and are derived from an amic acid structure remaining in the polyamideimide resin.
- the integral value of benzene proton C that is not affected by Int C was defined as Int C.
- the integrated value of benzene proton D derived from a structure that does not change before and after imidation among the observed benzene protons and affected by the structure derived from the amic acid structure remaining in the polyamide-imide resin was defined as Int D.
- the ⁇ value was determined from the obtained Int C and Int D by the following formula.
- ⁇ Int D / Int C
- the ⁇ value of the above formula and the imidization ratio of the polyimide resin of the above formula were determined for a plurality of polyamideimide resins, and the following correlation formula was obtained from these results.
- Imidization rate (%) k ⁇ ⁇ + 100
- k is a constant.
- ⁇ was substituted into the correlation equation to obtain the imidization ratio (%) of the polyamideimide resin.
- Hansen spheres were prepared from the evaluation results of the solubility of the obtained resin in a solvent using the Hansen dissolving sphere method described above.
- the center coordinate of the obtained Hansen sphere was taken as the HSP value. The results are shown in Table 2.
- methanol-dispersed silica sol (“MA-ST-L” manufactured by Nissan Chemical Industries, Ltd., primary particle diameter 20 to 25 nm) and methanol-dispersed silica sol (silica sol 2, primary particle diameter 10 to 12 nm) are also used.
- silica 1-solvent system dispersibility in a solvent was evaluated in the same manner except that the kind of silica sol as a raw material was changed.
- evaluation criteria 1: The appearance of the mixture is cloudy.
- Appearance of the mixed solution is transparent.
- Hansen spheres were prepared from the results of evaluation of the dispersibility of each silica dispersed in the silica sol using the Hansen dissolution sphere method described above.
- the center coordinate of the obtained Hansen sphere was taken as the HSP value. The results are shown in Table 4.
- silica-1,2 resin of Ra, .DELTA..delta t and .DELTA..delta p are silica respectively (MA-ST-L) - resin system Ra, compared to .DELTA..delta t and .DELTA..delta p, was small. Further, Ra, ⁇ t , and ⁇ p of the silica 1,2-resin system satisfied the expressions (3) to (5), respectively.
- the elastic modulus (tensile elastic modulus) G ′ of the pressure-sensitive adhesive layer was measured by a tensile test based on JIS K 7127 using an electromechanical universal testing machine (Instron). The measurement conditions were a test speed of 5 m / min and a load cell of 5 kN.
- ⁇ When the film edge is unwound from the roll, although the catch is recognized, the film is not scratched and the film is not cut.
- X When the film edge is unwound from the roll, catching is recognized, and the film is scratched or cut.
- a laminated body having a circularly polarizing plate is installed on the surface of a reflecting plate (aluminum plate, reflectance 97%), and an observer can circularly The laminated body which has a board was observed visually. Based on the observation results, the visibility of the laminate having a circularly polarizing plate was evaluated based on the following evaluation criteria. In order from the best, it is indicated by ⁇ , ⁇ and ⁇ .
- evaluation criteria for visibility of a laminate having a circularly polarizing plate ⁇ : No hue change at 45 ° slope compared to the vertical direction on the reflector. ⁇ : Slight hue change at 45 ° slope compared to the vertical direction on the reflector. X: The hue change at a 45 ° slope on the reflector is larger than that in the vertical direction.
- the reaction system temperature is returned to room temperature (25 ° C.), and 649.8 g of DMAc is further charged into the reaction vessel, so that the polymer concentration becomes 10% by weight based on the total weight of the contents in the reaction vessel. Adjusted as follows. Furthermore, 32.27 g of pyridine and 41.65 g of acetic anhydride were put in a reaction vessel, and imidation was performed by stirring at room temperature for 10 hours. The polyimide varnish was taken out from the reaction vessel. The obtained polyimide varnish was dropped into methanol for reprecipitation. The precipitate was removed by filtration and dried to obtain a powder. The obtained powder was further dried by heating to remove the solvent, and polyimide resin 1 was obtained as a solid content. The resulting polyimide resin 1 had a weight average molecular weight of 320,000 and an imidation ratio of 98.6%.
- the resulting reaction solution was cooled to room temperature and poured into a large amount of methanol in the form of a thread to deposit a precipitate.
- the deposited precipitate was taken out, immersed in methanol for 6 hours, and washed with methanol. Next, the precipitate was dried under reduced pressure at 100 ° C. to obtain a polyamideimide resin.
- the weight average molecular weight of the polyamideimide resin was 400,000, and the imidation ratio was 98.8%.
- the resulting reaction solution was cooled to room temperature and poured into a large amount of methanol in the form of a thread to deposit a precipitate.
- the deposited precipitate was taken out, immersed in methanol for 6 hours, and washed with methanol. Next, the precipitate was dried under reduced pressure at 100 ° C. to obtain a polyamideimide resin.
- the obtained polyamide-imide resin had a weight average molecular weight of 365,000 and an imidization ratio of 98.9%.
- ⁇ -butyrolactone-dispersed silica sol (silica sol 1, SGS7 # 09) was obtained.
- the obtained ⁇ -butyrolactone-dispersed silica sol had a solid content of 28.9%.
- the units (wt%) of the contents of the columns “resin” and “silica particles” indicate the ratio (mass%) to the total mass of the resin and silica particles.
- the unit “phr” of the content of the column “ultraviolet absorber” indicates a ratio (% by mass) to the total mass of the resin and silica particles.
- Varnishes 2 to 8 The composition (type and / or content of ingredients) shown in Table 6 was changed, the solvent to be replaced was changed from ⁇ -butyrolactone to N, N-dimethylacetamide, and the resin solid content concentration was changed to 11.0%. Except for the above, varnish 3 was prepared in the same manner as varnish 1. Varnishes 2 and 4 to 8 were prepared in the same manner as Varnish 1 except that the composition (type and / or content of components) shown in Table 6 was changed.
- Example 1 [3-4. Production of optical film]
- the obtained varnish 1 was cast on a PET film (“Cosmo Shine (registered trademark) A4100” manufactured by Toyobo Co., Ltd.) to form a coating film.
- the conveyance speed of PET in fluency molding was 0.3 m / min.
- the coating film was dried by heating at 80 ° C. for 20 minutes and at 90 ° C. for 20 minutes, and the coating film was peeled off from the PET film.
- the polyamideimide film 1 with a thickness of 51 ⁇ m was obtained by heating the coated film for 12 minutes at 200 ° C. while transversely stretching with a tenter.
- Example 2 A polyamideimide film 2 having a film thickness of 29 ⁇ m was obtained in the same manner as in Example 1 except that the film thickness of the coating was changed.
- Example 3 A polyamideimide film 3 having a thickness of 50 ⁇ m was obtained in the same manner as in Example 1 except that the varnish 1 was changed to the varnish 2.
- Example 4 A polyamideimide film 4 having a film thickness of 49 ⁇ m was obtained in the same manner as in Example 1 except that the varnish 1 was changed to the varnish 3.
- Example 5 A polyamideimide film 5 having a thickness of 48 ⁇ m was obtained in the same manner as in Example 1 except that the varnish 1 was changed to the varnish 4.
- Example 6 A polyamideimide film 6 having a film thickness of 48 ⁇ m was obtained in the same manner as in Example 1 except that the varnish 1 was changed to the varnish 5.
- Example 7 A polyimide film 7 having a film thickness of 78 ⁇ m was obtained in the same manner as in Example 1 except that the varnish 1 was changed to the varnish 6.
- Example 1 A polyimide film 8 having a film thickness of 52 ⁇ m was obtained in the same manner as in Example 1 except that the varnish 1 was changed to the varnish 7.
- Example 2 A polyamideimide film 9 having a thickness of 50 ⁇ m was obtained in the same manner as in Example 1 except that the varnish 1 was changed to the varnish 8.
- the appearances of the obtained polyamideimide films 1 to 6 and 9 and the polyimide films 7 and 8 were visually observed to confirm the presence or absence of cloudiness.
- the presence of white turbidity was confirmed only in the polyamideimide film 9, and the presence of white turbidity was not confirmed in the other films.
- optical films of Examples 1 to 7 contained polyamideimide and satisfied the formula (1), and the evaluation of the feeding stability was any of ⁇ , ⁇ , and ⁇ .
- the optical films of Comparative Examples 1 and 2 contained polyamideimide and did not satisfy the formula (1), and the evaluation results of their feeding stability were all x.
- optical films of Examples 1 to 7 are superior in both feeding stability and film appearance as compared with the optical films of Comparative Examples 1 and 2.
- the three-dimensional distance Ra determined by the Hansen dissolution sphere method satisfies the formula (3), and the evaluation results for the suppression of the deterioration of the film appearance quality are all good (good) )Met.
- the three-dimensional distance Ra did not satisfy the formula (3), and the evaluation result of the deterioration suppression of the film appearance quality was x (bad).
- MMA indicates methyl methacrylate.
- HEA represents hydroxyethyl acrylate.
- AA represents acrylic acid.
- the addition amount of a crosslinking agent and SC agent is a mass with respect to 100 parts of monomers.
- the adhesive layer-forming composition 1 was applied to the release-treated surface of the release-treated substrate (polyethylene terephthalate film, thickness 38 ⁇ m) using an applicator to form a coating layer.
- the coating layer was dried at 100 ° C. for 1 minute to form an adhesive layer 1.
- the thickness of the pressure-sensitive adhesive layer 1 was 25 ⁇ m.
- another base material polyethylene terephthalate film, thickness 38 ⁇ m
- it was cured for 7 days under the conditions of a temperature of 23 ° C. and a relative humidity of 50% RH. Thereby, the film provided with the adhesive layer 1 was obtained.
- the elastic modulus G ′ and thickness of the obtained pressure-sensitive adhesive layer 1 were measured. The measurement results are summarized in Table 9.
- the release-treated substrate was peeled off.
- the pressure-sensitive adhesive layer 1 was changed except that the pressure-sensitive adhesive layer-forming composition 1 was changed to the pressure-sensitive adhesive layer-forming composition 2 and the pressure-sensitive adhesive layer-forming composition was applied so that the thickness of the pressure-sensitive adhesive layer was 5 ⁇ m.
- the pressure-sensitive adhesive layer 2 was formed in the same manner as in the above.
- the elastic modulus and thickness of the pressure-sensitive adhesive layer 2 are summarized in Table 9.
- the polymer 1 is a polymer having a photoreactive group composed of the following structural units. From the GPC measurement, the obtained polymer 1 had a molecular weight of 28,200, a dispersity (Mw / Mn) of 1.82, and a monomer content of 0.5%. A solution in which the polymer 1 was dissolved in cyclopentanone at a concentration of 5% by mass was used as the alignment film forming composition.
- the alignment film-forming composition On the protective film (triacetyl cellulose: TAC), the alignment film-forming composition was applied by a bar coating method to form a coating film. The coating film was dried at 80 ° C. for 1 minute. Next, using a UV irradiation apparatus (SPOT CURE SP-7, manufactured by USHIO INC.) And a wire grid (“UIS-27132 ## manufactured by USHIO ELECTRIC CO., LTD.)”, An exposure amount of 100 mJ / cm 2 (365 nm standard) ), The coating film was irradiated with polarized UV light. Thereby, an alignment film was formed on the protective film. The alignment film had alignment performance and the thickness was 100 nm.
- SPOT CURE SP-7 manufactured by USHIO INC.
- UAS-27132 manufactured by USHIO ELECTRIC CO., LTD.
- the polymerizable liquid crystal compound is a polymerizable liquid crystal compound represented by formula (5) [hereinafter also referred to as compound (5)] and a polymerizable liquid crystal compound represented by formula (6) [hereinafter also referred to as compound (6). ] Was used.
- dichroic dye As the dichroic dye, an azo dye described in Examples of JP2013-101328A represented by the following formulas (7), (8), and (9) was used.
- composition for forming a polarizer layer comprises 75 parts by mass of the compound (5), 25 parts by mass of the compound (6), and each of the azo dyes represented by the above formulas (7), (8) and (9) as dichroic dyes.
- the said composition for polarizer formation was apply
- the coating film was heat-dried at 100 ° C. for 2 minutes. Then it was cooled to room temperature.
- the coating film was irradiated with ultraviolet rays under the condition of an integrated light quantity of 1200 mJ / cm 2 (365 nm standard). Thereby, a polarizer was formed on the alignment film.
- the thickness of the polarizer was 3 ⁇ m.
- Compound b-1 represented by the following formula: 80 parts by mass
- Compound b-2 represented by the following formula: 20 parts by mass Polymerization initiator (Irgacure 369, 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one, manufactured by BASF Japan Ltd.): 6 parts by mass Leveling agent (BYK-361N, polyacrylate compound, BYK -Chemie): 0.1 parts by mass Solvent (cyclopentanone): 400 parts by mass
- the alignment film-forming composition was applied onto a first base film (thickness: 100 ⁇ m, polyethylene terephthalate film (PET)) by a bar coating method, and dried by heating in a drying oven at 80 ° C. for 1 minute.
- the resulting dried film was subjected to polarized UV irradiation treatment to form a second alignment film.
- the polarized UV treatment was performed using the UV irradiation apparatus under the condition that the integrated light amount measured at a wavelength of 365 nm was 100 mJ / cm 2 .
- the polarization direction of the polarized UV was 45 ° with respect to the absorption axis of the polarizing layer. In this way, a laminate composed of “first base film / second alignment film” was obtained.
- the thickness of the second alignment film was 100 nm.
- a composition for forming a ⁇ / 4 retardation layer is applied on the second alignment film of the laminate composed of “first base film / second alignment film” by a bar coating method, and then for 1 minute in a 120 ° C. drying oven. After drying by heating, it was cooled to room temperature.
- a phase difference layer was formed by irradiating the obtained dried film with ultraviolet rays having an integrated light quantity of 1000 mJ / cm 2 (based on 365 nm) using the UV irradiation apparatus. It was 2.0 micrometers when the thickness of the obtained phase difference layer was measured with the laser microscope (Olympus Co., Ltd. OLS3000).
- the retardation layer was a ⁇ / 4 plate showing a retardation value of ⁇ / 4 in the in-plane direction.
- a laminate composed of “first base film / second alignment film / ⁇ / 4 retardation layer” was obtained.
- the components shown below were mixed, and the resulting mixture was stirred at 80 ° C. for 1 hour to obtain a composition for forming a positive c retardation layer.
- the alignment film forming composition is applied by a bar coating method onto a second base film (thickness: 100 ⁇ m, polyethylene terephthalate film (PET)), and a drying oven at 90 ° C. The film was heated and dried for 1 minute to form a third alignment film. Then, on the third alignment film, a positive C phase difference layer forming composition was applied by a bar coating method, heated and dried in a drying oven at 90 ° C. for 1 minute, and then using the UV irradiation apparatus in a nitrogen atmosphere, A positive C plate was formed by irradiating ultraviolet rays with an integrated light quantity of 1000 mJ / cm 2 (365 nm reference).
- the phase difference layer is bonded to the opposite side of the first base film of the ⁇ / 4 retardation plate by using the adhesive layer 2 to bond the surface of the positive C plate from which the second base film has been peeled off.
- the formed ⁇ / 4 retardation plate and positive C plate both included a layer cured with the polymerizable liquid crystal compound aligned.
- a laminate 1 was produced using the polyamideimide film 1, the polarizing layer, the pressure-sensitive adhesive layer 1, and the pressure-sensitive adhesive layer 2.
- Laminate 1 was provided with polyamideimide film 1 / adhesive layer 1 / polarizing layer (protective film / alignment film / polarizer / protective layer) / adhesive layer 2 in this order.
- the surface of the polarizing layer from which the first base film was peeled off was bonded to the side opposite to the protective film side through the pressure-sensitive adhesive layer 2.
- the retardation layer is a layer in which a ⁇ / 4 retardation plate (RWP) and a positive C plate (PosiC) are laminated.
- Laminate 1 is polyamideimide film 1 / adhesive layer 1 / polarizing layer (protective film / alignment film / polarizer / protective layer) / adhesive layer 2 / retardation layer ( ⁇ / 4 retardation plate / positive C plate) ) / Adhesive layer 1 in this order.
- the description of the alignment film in the retardation layer is omitted.
- the adhesive layer 2 is interposed through the pressure-sensitive adhesive layer 2 so that the absorption axis of the polarizing layer is substantially 45 ° with respect to the slow axis (optical axis) of the retardation layer.
- the polarizing layer and the retardation layer were bonded together.
- the optical property value was measured and calculated for the laminate having a circularly polarizing plate. Specifically, transmission b *, transmission a *, and reflection (SCE) a *, b *, and Y were measured. From the obtained transmission b *, reflection (SCE) b * and reflection (SCI) b *, transmission b * ⁇ reflection (SCE) b * was calculated. Table 10 summarizes the measurement results and calculation results.
- Example 9 A laminate 2 having a circularly polarizing plate was produced in the same manner as in Example 8 except that the polyamideimide film 5 was applied to the front plate instead of the polyamideimide film 1, and the optical property values were measured and calculated.
- Example 10 A laminate 3 having a circularly polarizing plate was produced in the same manner as in Example 8 except that the polyimide film 7 was applied to the front plate instead of the polyamideimide film 1, and the optical property values were measured and calculated.
- Example 3 A laminate 4 having a circularly polarizing plate was produced in the same manner as in Example 8 except that the polyimide film 8 was applied to the front plate instead of the polyamideimide film 1, and the optical property values were measured and calculated.
- the laminates having the circularly polarizing plates of Examples 8 to 10 satisfied the formula (39), and the evaluation of their visibility was either ⁇ or ⁇ .
- the laminates having the circularly polarizing plates of Examples 8 to 10 also satisfied the formula (40).
- the circularly polarizing plate of Comparative Example 3 did not satisfy the formula (39), and its visibility evaluation was X.
- the laminated body which has the circularly-polarizing plate of the comparative example 3 did not satisfy
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
L'objectif de la présente invention est de proposer un film optique qui combine une excellente stabilité de sortie et une excellente apparence du film, lorsqu'il est utilisé de façon appropriée en tant que film optique dans un dispositif d'affichage d'image. Le film optique contient au moins une substance sélectionnée dans le groupe constitué par les polyimides, les polyamides et les polyamides-imides, et répond à la formule (1). Formule (1) : 0,04 ≤ réfléchie (SCE)b */réfléchie (SCI)b * ≤ 1,5 [dans la formule (1), réfléchie (SCE)b * représente b * dans le système colorimétrique L * a * b * de la lumière réfléchie par le film optique tel que déterminé par le procédé SCE, et réfléchie (SCI)b * représente b * dans le système colorimétrique L * a * b * de la lumière réfléchie par le film optique, déterminé par le procédé SCI.]
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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CN201980028537.XA CN112041708B (zh) | 2018-04-27 | 2019-04-24 | 光学膜、光学层叠体及柔性图像显示装置 |
KR1020207034055A KR20210003876A (ko) | 2018-04-27 | 2019-04-24 | 광학 필름, 광학 적층체 및 플렉시블 화상 표시 장치 |
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JP2018-087231 | 2018-04-27 | ||
JP2018087231 | 2018-04-27 | ||
JP2019048929 | 2019-03-15 | ||
JP2019-048929 | 2019-03-15 |
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WO2019208611A1 true WO2019208611A1 (fr) | 2019-10-31 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2019/017345 WO2019208611A1 (fr) | 2018-04-27 | 2019-04-24 | Film optique, stratifié optique et dispositif flexible d'affichage d'images |
Country Status (5)
Country | Link |
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JP (2) | JP6896787B2 (fr) |
KR (1) | KR20210003876A (fr) |
CN (1) | CN112041708B (fr) |
TW (1) | TW201945472A (fr) |
WO (1) | WO2019208611A1 (fr) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20210079182A1 (en) * | 2019-09-12 | 2021-03-18 | Dupont Electronics, Inc. | Polyimide films and electronic devices |
WO2021166578A1 (fr) * | 2020-02-18 | 2021-08-26 | 住友化学株式会社 | Corps optique multicouche |
JP2021131532A (ja) * | 2020-02-18 | 2021-09-09 | 住友化学株式会社 | 光学積層体 |
WO2022010299A1 (fr) * | 2020-07-10 | 2022-01-13 | 코오롱인더스트리 주식회사 | Film émetteur de lumière et dispositif d'affichage le comprenant |
JP2023066393A (ja) * | 2021-10-28 | 2023-05-15 | エルジー ディスプレイ カンパニー リミテッド | 表示装置 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JPWO2022176884A1 (fr) * | 2021-02-16 | 2022-08-25 | ||
KR102584535B1 (ko) * | 2021-05-27 | 2023-09-27 | 인하대학교 산학협력단 | 흄드 실리카 나노입자를 포함하는 투명 하이브리드 필름 및 그 제조방법 |
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- 2019-04-23 JP JP2019081774A patent/JP6896787B2/ja active Active
- 2019-04-24 KR KR1020207034055A patent/KR20210003876A/ko not_active Application Discontinuation
- 2019-04-24 WO PCT/JP2019/017345 patent/WO2019208611A1/fr active Application Filing
- 2019-04-24 CN CN201980028537.XA patent/CN112041708B/zh active Active
- 2019-04-25 TW TW108114553A patent/TW201945472A/zh unknown
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US20210079182A1 (en) * | 2019-09-12 | 2021-03-18 | Dupont Electronics, Inc. | Polyimide films and electronic devices |
WO2021166578A1 (fr) * | 2020-02-18 | 2021-08-26 | 住友化学株式会社 | Corps optique multicouche |
JP2021131532A (ja) * | 2020-02-18 | 2021-09-09 | 住友化学株式会社 | 光学積層体 |
CN115104048A (zh) * | 2020-02-18 | 2022-09-23 | 住友化学株式会社 | 光学层叠体 |
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WO2022010299A1 (fr) * | 2020-07-10 | 2022-01-13 | 코오롱인더스트리 주식회사 | Film émetteur de lumière et dispositif d'affichage le comprenant |
JP2023066393A (ja) * | 2021-10-28 | 2023-05-15 | エルジー ディスプレイ カンパニー リミテッド | 表示装置 |
Also Published As
Publication number | Publication date |
---|---|
TW201945472A (zh) | 2019-12-01 |
CN112041708B (zh) | 2023-04-04 |
CN112041708A (zh) | 2020-12-04 |
JP2020154274A (ja) | 2020-09-24 |
KR20210003876A (ko) | 2021-01-12 |
JP2021006926A (ja) | 2021-01-21 |
JP6896787B2 (ja) | 2021-06-30 |
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