CN117826308A - Optical film and preparation method thereof - Google Patents
Optical film and preparation method thereof Download PDFInfo
- Publication number
- CN117826308A CN117826308A CN202311856362.6A CN202311856362A CN117826308A CN 117826308 A CN117826308 A CN 117826308A CN 202311856362 A CN202311856362 A CN 202311856362A CN 117826308 A CN117826308 A CN 117826308A
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- China
- Prior art keywords
- liquid crystal
- layer
- crystal polymer
- optical film
- light
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- 239000012788 optical film Substances 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000010410 layer Substances 0.000 claims abstract description 257
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 158
- 229920000106 Liquid crystal polymer Polymers 0.000 claims abstract description 139
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims abstract description 139
- 239000002245 particle Substances 0.000 claims abstract description 75
- 150000001875 compounds Chemical class 0.000 claims abstract description 59
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 239000000758 substrate Substances 0.000 claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 230000028161 membrane depolarization Effects 0.000 claims abstract description 16
- 230000031700 light absorption Effects 0.000 claims abstract description 5
- 239000002356 single layer Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 230000003287 optical effect Effects 0.000 claims description 62
- 238000000576 coating method Methods 0.000 claims description 49
- 239000011248 coating agent Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 36
- 239000002052 molecular layer Substances 0.000 claims description 30
- -1 benzoin ethers Chemical class 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000011358 absorbing material Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 238000001723 curing Methods 0.000 claims description 13
- 238000000016 photochemical curing Methods 0.000 claims description 10
- 230000010287 polarization Effects 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 238000004364 calculation method Methods 0.000 claims description 7
- 239000010408 film Substances 0.000 claims description 7
- CVBASHMCALKFME-UHFFFAOYSA-N (4-methoxyphenyl)-diphenylsulfanium Chemical compound C1=CC(OC)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 CVBASHMCALKFME-UHFFFAOYSA-N 0.000 claims description 6
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 6
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004985 Discotic Liquid Crystal Substance Substances 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 6
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 claims description 6
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 6
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 claims description 6
- 238000013007 heat curing Methods 0.000 claims description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052753 mercury Inorganic materials 0.000 claims description 6
- 229920006254 polymer film Polymers 0.000 claims description 6
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 claims description 6
- 239000012953 triphenylsulfonium Substances 0.000 claims description 6
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 229910001507 metal halide Inorganic materials 0.000 claims description 4
- 150000005309 metal halides Chemical class 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- WBUSZOLVSDXDOC-UHFFFAOYSA-M (4-methoxyphenyl)-diphenylsulfanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(OC)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WBUSZOLVSDXDOC-UHFFFAOYSA-M 0.000 claims description 3
- JZDQKBZKFIWSNW-UHFFFAOYSA-N (4-methoxyphenyl)-phenyliodanium Chemical compound C1=CC(OC)=CC=C1[I+]C1=CC=CC=C1 JZDQKBZKFIWSNW-UHFFFAOYSA-N 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 claims description 3
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 3
- KMZHZAAOEWVPSE-UHFFFAOYSA-N 2,3-dihydroxypropyl acetate Chemical compound CC(=O)OCC(O)CO KMZHZAAOEWVPSE-UHFFFAOYSA-N 0.000 claims description 3
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 claims description 3
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 claims description 3
- XBCSOBWHHUHGJE-UHFFFAOYSA-N B([O-])([O-])[O-].B([O-])([O-])[O-].B([O-])([O-])[O-].B([O-])([O-])[O-].C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1 Chemical compound B([O-])([O-])[O-].B([O-])([O-])[O-].B([O-])([O-])[O-].B([O-])([O-])[O-].C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1 XBCSOBWHHUHGJE-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- YZZKZPYXFNAJRM-UHFFFAOYSA-N CC(C)(C)C(C=C1)=CC=C1I.C(C=C1)=CC=C1[I+]C1=CC=CC=C1 Chemical compound CC(C)(C)C(C=C1)=CC=C1I.C(C=C1)=CC=C1[I+]C1=CC=CC=C1 YZZKZPYXFNAJRM-UHFFFAOYSA-N 0.000 claims description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 3
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
An optical film and a preparation method thereof, wherein the optical film adopts a single layer or a plurality of liquid crystal polymer layers, and the raw materials thereof comprise, by mass, 0.5 to 98 percent of liquid crystal polymerizable monomer, 0.5 to 30 percent of chiral compound, 0.1 to 20 percent of anti-dazzle anti-reflection particles, 0 to 20 percent of light absorption material, 0.1 to 70 percent of photoinitiator and 0 to 70 percent of solvent; firstly, preparing an orientation layer, secondly, preparing a liquid crystal mixture layer, then preparing a liquid crystal polymer layer, and finally peeling the prepared liquid crystal polymer layer from a substrate to prepare an optical film or keeping the prepared liquid crystal polymer layer and the substrate layer from peeling, wherein the whole is reserved as the optical film layer; the invention can depolarize the linear polarized light emitted by the display device and realize anti-glare and anti-reflection, and the depolarization rate of 380-760nm wavelength light emitted by the display device can reach more than 95%, and the reflectivity of ambient light is less than 1%. The thickness of the optical film is greatly reduced, the light-emitting efficiency of the display device is improved, and the preparation process is simple.
Description
Technical Field
The invention relates to the technical field of optical elements, in particular to an optical film and a preparation method thereof.
Background
With the development of display technology, people have increasingly used displays, and the influence of display screens such as Liquid Crystal Displays (LCDs) or Organic Light Emitting Diode (OLED) displays on human eye health is attracting attention. Light emitted by the existing OLED and LCD displays is linearly polarized light; research of related professionals shows that compared with natural light, the linear polarized light is easier to cause visual fatigue, in some existing invention technologies, the linear polarized light is converted into circular polarized light by adding a phase delay layer, so that the visual fatigue is relieved, but the phase delay material has high surface reflectivity and is easy to generate glare, so that viewing discomfort is caused. In order to solve the problems of surface reflection and glare, functional layers such as an anti-reflection layer, an anti-glare layer and the like are added on the phase delay layer, and the anti-reflection layer, the anti-glare layer and the like are usually coated with a coating process, so that the process is complex and the cost is high. And the thickness of the display device is increased, the light emitting efficiency is reduced, and the display effect is poor.
CN 111429812A discloses a display device comprising an electrically controlled phase retardation layer, a reflective polarizer, a micro light emitting diode panel and a reflective layer. The electrically controlled phase delay layer has a first side and a second side opposite to each other. The reflective polarizer is arranged on the first side of the electric control phase delay layer. The micro light emitting diode panel is arranged on the second side of the electric control phase delay layer and comprises a circuit substrate and a plurality of micro light emitting diode elements electrically connected to the circuit substrate. The reflecting layer is arranged between the reflecting polarizer and the circuit substrate. The vertical projection of the reflecting layer on the circuit substrate is not overlapped with the vertical projection of the micro light emitting diode elements on the circuit substrate. The invention improves the gray scale number in the low gray scale brightness range through the miniature light-emitting diode display, and can realize the anti-glare and anti-reflection functions without depolarizing the linear polarized light emitted by the display device.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide an optical film and a preparation method thereof, wherein chiral compounds, anti-dazzle anti-reflection particles and the like are added into a liquid crystal mixture, and the linearly polarized light emitted by a display device can be depolarized by combining a preparation process, so that anti-dazzle and anti-reflection can be realized, and a better display effect is realized; the preparation process is simple and is easy for mass production.
In order to achieve the above object, the present invention provides the following technical solutions.
An optical film adopts a single-layer or multi-layer liquid crystal polymer layer, and comprises, by mass, 0.5-98% of liquid crystal polymerizable monomer, 0.5-30% of chiral compound, 0.1-20% of anti-dazzle anti-reflection particles, 0-20% of light absorption material, 0.1-70% of photoinitiator and 0-70% of solvent.
The liquid crystal polymerizable monomer adopts one or more of nematic liquid crystal, discotic liquid crystal or discotic liquid crystal, and when the liquid crystal polymerizable monomer is various, the proportion is arbitrary; the liquid crystal polymerizable monomer at least contains one polymerizable group, and the polymerizable group is any one of alkenyl, alkynyl, epoxy and mercapto.
At least one liquid crystal polymer layer contains anti-glare anti-reflection particles; at least one liquid crystal polymer layer contains chiral compounds; the liquid crystal polymer layers containing anti-dazzle anti-reflection particles and chiral compounds exist in the same liquid crystal polymer layer or different liquid crystal polymer layers; the light absorbing material is blue light absorbing material or blue light or ultraviolet light absorbing material.
The radius of the anti-dazzle anti-reflection particles is between 0.01 and 1 mu m; the anti-dazzle anti-reflection particles are insoluble in any component in the liquid crystal mixture and comprise organic anti-dazzle anti-reflection particles or inorganic anti-dazzle anti-reflection particlesParticles, wherein the inorganic anti-glare anti-reflection particles are TiO 2 Or SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The organic anti-dazzle particles are selected from one or more of polystyrene, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, acrylic ester-styrene copolymer, methyl acrylate-styrene copolymer, methyl methacrylate-styrene copolymer and polyallylphthalate, and when the organic anti-dazzle particles are multiple, the proportion is arbitrary;
the chiral compound is one or more of X1, X2, X3, X4, X5, X6, X7, X8, X9, X10, X11, X12, X13, X14, X15, X16, X17, X18, X19, X20 and X21, and when the chiral compound is a plurality of chiral compounds, the proportion is arbitrary.
The mass fraction of the chiral compound is determined according to the characteristic value HTP of the chiral compound and the deflection angle between the optical axis of an initial liquid crystal molecular layer and the optical axis of a termination liquid crystal molecular layer in the thickness direction of a liquid crystal polymer film layer to be prepared, and the calculation formula is as follows:
Wherein C is the mass fraction of chiral compound in the liquid crystal mixture, d is the thickness of the polymer film, θ is the deflection angle between the optical axis of the initial liquid crystal molecular layer and the optical axis of the final liquid crystal molecular layer in the thickness direction of the polymer film, and HTP is the characteristic value of the chiral compound.
The photoinitiator may be: benzoyl peroxide, azobisisobutyronitrile, benzoin ethers, benzophenones, acetophenones, benzil ketals, diaryliodonium salts, triarylsulfonium salts, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium arsenate, diphenyliodonium tetraborate, 4-methoxyphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenyliodonium hexafluoroarsenate, 4-tert-butylphenyl iodonium diphenyliodonium tetrafluoroborate, 4-tert-butylphenyl iodonium diphenyliodonium hexafluorophosphonate, and 4-tert-butylphenyl) iodonium diphenyliodonium trifluoromethane sulfonate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsonate, triphenylsulfonium tetraborate, 4-methoxyphenyldiphenylsulfonium tetrahydroborate, 4-methoxyphenyldiphenylsulfonium tetrahydrophosphonate, 4-methoxyphenyldiphenylsulfonium tetrahydroarsonate, 4-methoxyphenyldiphenylsulfonium trifluoromethane sulfonate, 4-methoxyphenyldiphenylsulfonium triphenylsulfonium tetraborate, 4-phenylphenylthio diphenylsulfonium hexafluoroarsonate, benzil dimethyl ketal, and bis-phenylphosphine oxide, when the ratio is plural, the ratio therebetween is arbitrary;
The solvent adopts organic solvents including benzene, toluene, xylene, mesitylene, N-butylbenzene, diethylbenzene, tetrahydronaphthalene, methoxybenzene, 1, 2-dimethoxybenzene, cyclohexanone, ethyl acetate, methyl lactate, ethyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-pyrrolidone, chloroform, methylene chloride, carbomethoxy, dichloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene, tertiary butanol, diacetone alcohol, glycerol, glyceryl monoacetate, triethylene glycol, ethylcellosolve and butylcellosolve, N-methyl-2-pyrrolidone, gamma-butyrolactone, N, N-dimethylformamide, N-dimethylacetamide, diethylene glycol monomethyl ether ethyl ester, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, tetrahydrofuran, methylene chloride, chlorobenzene, 1, 2-dichloroethane, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclobutanone, methyl acetate, ethyl acetate, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol methyl ether, ethylene glycol dimethyl ether, and when the solvent is plural, the ratio therebetween is arbitrary.
The preparation method of the optical film specifically comprises the following steps:
step 1, manufacturing an orientation layer: directly rubbing and orienting the substrate, or coating a polyvinyl alcohol layer on the substrate, and rubbing the polyvinyl alcohol layer to obtain an orientation layer; the depth of a groove of the surface travel of the orientation layer formed by friction orientation is between 5nm and 2000 nm;
step 2, preparing a liquid crystal mixture: the liquid crystal polymerizable monomer, the chiral compound, the anti-dazzle anti-reflection particles, the photoinitiator and the solvent are measured according to a proportion and then heated to be above the phase transition temperature of all the liquid crystal polymerizable monomers, stirring is continuously carried out in the heating process until the liquid crystal polymerizable monomer, the chiral compound, the anti-dazzle anti-reflection particles, the photoinitiator and the solvent are uniformly mixed, and the liquid crystal polymerizable monomer is cooled to 10-50 ℃ for standby;
step 3, preparation of a liquid crystal polymer layer: coating the liquid crystal mixture prepared in the step 2 on the orientation layer prepared in the step 1, wherein the thickness of the coating is 100-5000 nm, heating to remove the organic solvent and curing to obtain the liquid crystal polymer, and the heating temperature is 30-150 ℃ and the heating time is 5-1000 s;
and 4, peeling the liquid crystal polymer layer prepared in the step 3 from the substrate layer to obtain the optical film or keeping the liquid crystal polymer layer prepared in the step 3 and the substrate layer from peeling, and leaving the whole to be used as the optical film layer.
The optical film comprises a plurality of liquid crystal polymer layers, when the included angle between the optical axes of the liquid crystal molecular layers of two adjacent liquid crystal polymer layers is zero, after the substrate is oriented, the first liquid crystal mixture is coated on the substrate, and the first liquid crystal polymer layer is obtained after the organic solvent is removed by heating and is solidified; continuously coating a second liquid crystal mixture layer on the first liquid crystal polymer layer, heating to remove the organic solvent, curing to obtain a second liquid crystal polymer layer, and the like until all liquid crystal polymer layers are coated and prepared;
when the optical film comprises a plurality of liquid crystal polymer layers and the included angle between the optical axes of the liquid crystal molecular layers of at least two adjacent liquid crystal polymer layers is not zero, preparing an alignment layer on one liquid crystal polymer layer after coating, coating an adjacent second liquid crystal polymer layer on the alignment layer, and the like until all liquid crystal polymer layers are coated and prepared; the included angle between the relative optical axis of the whole optical film and the optical axis of the linear polarized light emitted by the display device is 45 degrees+/-10 degrees, the birefringence of the liquid crystal is 0.05-0.5, and the thickness of the optical film is 0.01-5 mu m.
When the optical film is formed by a single liquid crystal polymer layer, the phase retardation value of the optical film for incident linear polarized light is controlled by a plurality of factors including the physical property of a liquid crystal material of the liquid crystal polymer layer, the thickness of the liquid crystal polymer, the included angle between the optical axis of an initial liquid crystal molecular layer and the optical axis of a final liquid crystal molecular layer in the thickness direction of the liquid crystal polymer layer, and the included angle between the optical axis of the liquid crystal molecular layer of the incident linear polarized light entering the optical film side and the polarization direction of the incident linear polarized light, and the specific depolarization calculation formula is as follows:
a i ＝cosX i cosφ i +φ i sinφ i t(X i )
c i ＝cosX i sinφ i -φ i cosφ i t(X i )
T＝T i …T 2 T 1 R(φ 0 )
i＝1,2,3,4
S c ＝TS r
In the above formula: characteristic parameters of birefringence of p, q liquid crystal material e i Is the thickness of the ith liquid crystal polymer layer, lambda is the wavelength of light, phi j Is the included angle phi between the molecular optical axis of the initial liquid crystal layer and the molecular optical axis of the ending liquid crystal layer of the jth layer of liquid crystal polymer in the thickness direction 0 S is the included angle between the optical axis of the linear polarization to be retired and the optical axis of liquid crystal molecules of the initial layer of the liquid crystal polymer r Is the Stokes vector representation form of the light to be depolarized, S c The Stokes vector representation form of the to-be-depolarized light wire after passing through the liquid crystal polymer layer; when the optical film is formed by multiple layers of liquid crystal polymers, the influence factors of the phase delay value of the incident linear polarized light also comprise the included angle between the liquid crystal molecular optical axes of two adjacent liquid crystal polymer layers.
And (2) preparing a coating polyvinyl alcohol layer with the thickness of 10-1000 nm by the orientation layer, and forming the orientation layer after the coating is irradiated by linearly polarized light, so that the liquid crystal molecules coated on the orientation layer are arranged perpendicular to the polarization direction of the irradiated linearly polarized light.
The curing process in the step 3 adopts a photo-curing or heat-curing process, wherein the light source used in the photo-curing process has ultraviolet rays and visible rays with the wavelength of 150nm to 800nm, and preferably has ultraviolet rays with the wavelength of 300nm to 400 nm; as a light source for irradiating light, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, and the irradiation amount of light is preferably 1000J/m 2 ～200000J/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The curing temperature in the heat curing process is between 30 and 200 ℃, the heating temperature is between 30 and 150 ℃ and the heating time is 5s1000s; the photo-curing process is preferred.
Compared with the prior art, the invention has the following technical effects:
the optical film can depolarize the linear polarized light emitted by the display device and can realize anti-glare and anti-reflection. By adding chiral compounds into the liquid crystal mixture, the depolarization rate of the prepared optical film for the linear polarized light with 380-760nm wavelength emitted by the display device can reach more than 95%, and the optical film has good reverse wavelength dispersibility;
by adding anti-glare anti-reflection particles into the liquid crystal mixture, the glare reflectivity of the surface of the optical film can be reduced to be less than 1%, and a better display effect is realized;
by adding the harmful blue light absorbing material into the liquid crystal mixture, the absorption of harmful blue light is realized, the absorption efficiency of the harmful blue light wave band with the wavelength of 380-440nm is more than 40%, the thickness of an optical film is not basically increased by adding the anti-glare antireflection particles and absorbing the harmful blue light material, the optical film is attached to the surface of a display emitting linear polarized light, the anti-glare antireflection function can improve the display effect, and the anti-harmful blue light function and the depolarization function can play a role in protecting eyes;
Through a large number of experiments, the proportion of each component in the liquid crystal mixture for preparing the optical film is optimized, wherein the optical film prepared by the liquid crystal mixture has better depolarization, optical film surface reflection reduction and glare when the proportion of each component is as follows: 60-98% of liquid crystal polymerizable monomer, 0.5-10% of chiral compound, 0.5-10% of anti-dazzle anti-reflection particles, 0-10% of light absorption material, 0.1-10% of photoinitiator and 0-30% of solvent;
under the preferable component proportion, the depolarization rate of the optical film can reach more than 95 percent, which is improved by more than 15 percent compared with the prior art; the surface reflection and glare of the optical film are less than 1%, while the surface reflection and glare of the common film are 4-5%, so that the display effect of the optical film is greatly improved.
The optical film is prepared by a coating process, the preparation process is simple, and the mass production is easy.
In summary, by adding chiral compounds, anti-dazzle anti-reflection particles and the like into the liquid crystal mixture and combining the preparation process, the invention can depolarize the linear polarized light emitted by the display device and realize anti-dazzle and anti-reflection, thereby realizing better display effect; the preparation process is simple and is easy for mass production.
Drawings
FIG. 1 is a schematic diagram of a structure for detecting the depolarization rate of an optical film to be measured.
Detailed Description
The following examples illustrate the invention in further detail.
An optical film adopts a single-layer or multi-layer liquid crystal polymer layer, and comprises, by mass, 0.5-98% of liquid crystal polymerizable monomer, 0.5-30% of chiral compound, 0.1-20% of anti-dazzle anti-reflection particles, 0-20% of light absorption material, 0.1-70% of photoinitiator and 0-70% of solvent.
The liquid crystal polymerizable monomer can be one or more of nematic liquid crystal, discotic liquid crystal or discotic liquid crystal, and when the liquid crystal polymerizable monomer is a plurality of liquid crystals, the proportion is arbitrary; the liquid crystal polymerizable monomer at least contains one polymerizable group, and the polymerizable group is any one of alkenyl, alkynyl, epoxy and mercapto; preferably, the polymerizable liquid crystal monomer contains two or more polymerizable groups; at least one liquid crystal polymer layer contains anti-glare anti-reflection particles; at least one liquid crystal polymer layer contains chiral compounds; the liquid crystal polymer layers containing anti-dazzle anti-reflection particles and chiral compounds exist in the same liquid crystal polymer layer or different liquid crystal polymer layers;
The polymerizable liquid crystal monomer contains two or more polymerizable groups such as:
the light absorbing material may be a blue light absorbing material or a blue and ultraviolet light absorbing material, in particular one or more of C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11.
And C1 has the following structural formula:
the structural formula of C2 is as follows:
the structural formula of C3 is as follows:
the structural formula of C4 is as follows:
the structural formula of C5 is as follows:
the structural formula of C6 is as follows:
the structural formula of C7 is as follows:
the structural formula of C8 is as follows:
the structural formula of C9 is as follows:
the structural formula of C10 is as follows:
the structural formula of C11 is as follows:
the radius of the anti-dazzle anti-reflection particles is between 0.01 and 1 mu m; the anti-dazzle anti-reflection particles are insoluble in any component in the liquid crystal mixture and comprise organic anti-dazzle anti-reflection particles or inorganic anti-dazzle anti-reflection particles, wherein the inorganic anti-dazzle anti-reflection particles are TiO 2 Or SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The organic antiglare particles are one or more selected from polystyrene, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, acrylate-styrene copolymer, methyl methacrylate-styrene copolymer and polyallylphthalate, and when the organic antiglare particles are a plurality of organic antiglare particles, the ratio of the organic antiglare particles to the polyallylmelamine is arbitrary.
The chiral compound is one or more of X1, X2, X3, X4, X5, X6, X7, X8, X9, X10, X11, X12, X13, X14, X15, X16, X17, X18, X19, X20 and X21, and when the chiral compound is a plurality of chiral compounds, the proportion is arbitrary; the structural formula of X1 is as follows:
the structural formula of X2 is as follows:
the structural formula of X3 is as follows:
the structural formula of X4 is as follows:
the structural formula of X5 is as follows:
the structural formula of X6 is as follows:
the structural formula of X7 is as follows:
the structural formula of X8 is as follows:
the structural formula of X9 is as follows:
the structural formula of X10 is as follows:
the structural formula of X11 is as follows:
the structural formula of X12 is as follows:
the structural formula of X13 is as follows:
the structural formula of X14 is as follows:
the structural formula of X15 is as follows:
the structural formula of X16 is as follows:
the structural formula of X17 is as follows:
the structural formula of X18 is as follows:
the structural formula of X19 is as follows:
the structural formula of X20 is as follows:
the structural formula of X21 is as follows:
the mass fraction of the chiral compound is determined according to the characteristic value HTP of the chiral compound and the deflection angle between the optical axis of an initial liquid crystal molecular layer and the optical axis of a termination liquid crystal molecular layer in the thickness direction of a liquid crystal polymer film layer to be prepared, and the calculation formula is as follows:
Wherein C is the mass fraction of chiral compound in the liquid crystal mixture, d is the thickness of the polymer film, θ is the deflection angle between the optical axis of the initial liquid crystal molecular layer and the optical axis of the final liquid crystal molecular layer in the thickness direction of the polymer film, and HTP is the characteristic value of the chiral compound.
The photoinitiator may be: benzoyl peroxide, azobisisobutyronitrile, benzoin ethers, benzophenones, acetophenones, benzil ketals, diaryliodonium salts, triarylsulfonium salts, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium arsenate, diphenyliodonium tetraborate, 4-methoxyphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenyliodonium hexafluoroarsenate, 4-tert-butylphenyl iodonium diphenyliodonium tetrafluoroborate, 4-tert-butylphenyl iodonium diphenyliodonium hexafluorophosphonate, and 4-tert-butylphenyl) iodonium diphenyliodonium trifluoromethane sulfonate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsonate, triphenylsulfonium tetraborate, 4-methoxyphenyldiphenylsulfonium tetrahydroborate, 4-methoxyphenyldiphenylsulfonium tetrahydrophosphonate, 4-methoxyphenyldiphenylsulfonium tetrahydroarsonate, 4-methoxyphenyldiphenylsulfonium trifluoromethane sulfonate, 4-methoxyphenyldiphenylsulfonium triphenylsulfonium tetraborate, 4-phenylphenylthio diphenylsulfonium hexafluoroarsonate, benzil dimethyl ketal, and bis-phenylphosphine oxide, when the ratio is plural, the ratio therebetween is arbitrary;
The solvent adopts organic solvents including benzene, toluene, xylene, mesitylene, N-butylbenzene, diethylbenzene, tetrahydronaphthalene, methoxybenzene, 1, 2-dimethoxybenzene, cyclohexanone, ethyl acetate, methyl lactate, ethyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-pyrrolidone, chloroform, methylene chloride, carbomethoxy, dichloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene, tertiary butanol, diacetone alcohol, glycerol, glyceryl monoacetate, triethylene glycol, ethylcellosolve and butylcellosolve, N-methyl-2-pyrrolidone, gamma-butyrolactone, N, N-dimethylformamide, N-dimethylacetamide, diethylene glycol monomethyl ether ethyl ester, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, tetrahydrofuran, methylene chloride, chlorobenzene, 1, 2-dichloroethane, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclobutanone, methyl acetate, ethyl acetate, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol methyl ether, ethylene glycol dimethyl ether, and when the solvent is plural, the ratio therebetween is arbitrary.
The preparation method of the optical film specifically comprises the following steps:
step 1, manufacturing an orientation layer: directly rubbing and orienting the substrate, or coating a polyvinyl alcohol layer on the substrate, and rubbing the polyvinyl alcohol layer to obtain an orientation layer; the depth of a groove of the surface travel of the orientation layer formed by friction orientation is between 5nm and 2000 nm;
step 2, preparing a liquid crystal mixture: the liquid crystal polymerizable monomer, the chiral compound, the anti-dazzle anti-reflection particles, the photoinitiator and the solvent are measured according to a proportion and then heated to be above the phase transition temperature of all the liquid crystal polymerizable monomers, stirring is continuously carried out in the heating process until the liquid crystal polymerizable monomer, the chiral compound, the anti-dazzle anti-reflection particles, the photoinitiator and the solvent are uniformly mixed, and the liquid crystal polymerizable monomer is cooled to 10-50 ℃ for standby;
step 3, preparation of a liquid crystal polymer layer: coating the liquid crystal mixture prepared in the step 2 on the orientation layer prepared in the step 1, wherein the thickness of the coating is 100-5000 nm, heating to remove the organic solvent and curing to obtain the liquid crystal polymer, and the heating temperature is 30-150 ℃ and the heating time is 5-1000 s;
and 4, peeling the liquid crystal polymer layer prepared in the step 3 from the substrate layer to obtain the optical film or keeping the liquid crystal polymer layer prepared in the step 3 and the substrate layer from peeling, and leaving the whole to be used as the optical film layer.
The optical film comprises a plurality of liquid crystal polymer layers, when the included angle between the optical axes of the liquid crystal molecular layers of two adjacent liquid crystal polymer layers is zero, after the substrate is oriented, the first liquid crystal mixture is coated on the substrate, and the first liquid crystal polymer layer is obtained after the organic solvent is removed by heating and is solidified; continuously coating a second liquid crystal mixture layer on the first liquid crystal polymer layer, heating to remove the organic solvent, curing to obtain a second liquid crystal polymer layer, and the like until all liquid crystal polymer layers are coated and prepared;
when the optical film comprises a plurality of liquid crystal polymer layers and the included angle between the optical axes of the liquid crystal molecular layers of at least two adjacent liquid crystal polymer layers is not zero, preparing an alignment layer on one liquid crystal polymer layer after coating, coating an adjacent second liquid crystal polymer layer on the alignment layer, and the like until all liquid crystal polymer layers are coated and prepared; the included angle between the relative optical axis of the whole optical film and the optical axis of the linear polarized light emitted by the display device is 45 degrees+/-10 degrees, the birefringence of the liquid crystal is 0.05-0.5, and the thickness of the optical film is 0.01-5 mu m.
When the optical film is formed by a single liquid crystal polymer layer, the phase retardation value of the optical film for incident linear polarized light is controlled by a plurality of factors including the physical property of a liquid crystal material of the liquid crystal polymer layer, the thickness of the liquid crystal polymer, the included angle between the optical axis of an initial liquid crystal molecular layer and the optical axis of a final liquid crystal molecular layer in the thickness direction of the liquid crystal polymer layer, and the included angle between the optical axis of the liquid crystal molecular layer of the incident linear polarized light entering the optical film side and the polarization direction of the incident linear polarized light, and the specific depolarization calculation formula is as follows:
a i ＝cos X i cosφ i +φ i sinφ i t(X i )
c i ＝cos X i sinφ i -φ i cosφ i t(X i )
T＝T i …T 2 T 1 R(φ 0 )
i＝1,2,3,4
S c ＝TS r
Characteristic parameters of birefringence of p and q liquid crystal materials in the formula, e i Is the thickness of the ith liquid crystal polymer layer, lambda is the wavelength of light, phi j Is the included angle phi between the molecular optical axis of the initial liquid crystal layer and the molecular optical axis of the ending liquid crystal layer of the jth layer of liquid crystal polymer in the thickness direction 0 S is the included angle between the optical axis of the linear polarization to be retired and the optical axis of liquid crystal molecules of the initial layer of the liquid crystal polymer r Is the Stokes vector representation form of the light to be depolarized, S c The Stokes vector representation form of the to-be-depolarized light wire after passing through the liquid crystal polymer layer;
when the optical film is formed by multiple layers of liquid crystal polymers, the influence factors of the phase delay value of the incident linear polarized light also comprise the included angle between the liquid crystal molecular optical axes of two adjacent liquid crystal polymer layers.
The curing process in the step 3 adopts a photo-curing or heat-curing process, wherein the light source used in the photo-curing process has ultraviolet rays and visible rays with the wavelength of 150nm to 800nm, and preferably has ultraviolet rays with the wavelength of 300nm to 400 nm; as a light source for irradiating light, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, and the irradiation amount of light is preferably 1000J/m 2 ～200000J/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The curing temperature in the heat curing process is between 30 and 200 ℃, the heating temperature is between 30 and 150 ℃, and the heating time is between 5 and 1000 seconds; the photo-curing process is preferred.
The base material adopts any one of cellulose derivative, polyolefin, polyester, polycarbonate, polyacrylate (acrylic resin), polyarylate, polyethersulfone, polyimide, polyphenylene sulfide, polyphenyl ether, nylon or polystyrene; the substrate thickness is between 5 and 300 μm, preferably 20 to 200 μm, further preferably 20 to 100 μm.
In the preparation of the alignment layer in the step 1, the alignment material coated on the substrate can be replaced by SD1, the thickness of the coating is between 10 and 1000nm, and the alignment layer is formed after the coating is irradiated by linearly polarized light, so that the liquid crystal molecules coated on the alignment layer are arranged perpendicular to the polarization direction of the irradiated linearly polarized light. And SD1 has the following structural formula:
the coating process used when the liquid crystal coating is coated on the substrate can be gravure coating, slit coating, reverse roll coating, rotary coating, ink jet coating, printing coating, knife roll coating, metering rod coating, slot die coating, curtain coating, air knife coating, extrusion die coating, closed doctor blade coating, offset gravure coating, single roll anastomosis coating, reverse anastomosis coating using a small diameter gravure roll, three reverse roll coating, four reverse roll coating, forward roll coating, doctor blade coating, impregnation coating, MB reverse coating and the like, and each layer adopts one coating process and each layer coating process can be the same or different.
In some possible applications, the substrate is an optical grade material, the transparency is high, for example, the light transmittance is greater than 90%, and the liquid crystal polymer layer and the substrate layer prepared in the step 3 can be directly used as an optical film layer under the condition that the substrate does not affect the optical performance of the optical film.
The optical film is selectively provided with other functional layers including an anti-reflection layer, a hardening layer, an anti-fingerprint layer and the like near the outermost side.
When the optical film is prepared by compounding a plurality of liquid crystal polymer layers, the included angle between the optical axes of the liquid crystal molecular layers at the two sides of the contact surface in the adjacent liquid crystal coating can be zero or not, and considering the simplicity of the preparation process, preferably, the included angle between the optical axes of the liquid crystal molecular layers at the two sides of the contact surface in the adjacent liquid crystal coating is zero.
A circular polarizer comprises the optical film; the substrate layer and the optical film may be included, that is, the substrate layer and the optical film may be used as an optical film layer as a whole.
A display device comprises the circular polarizer.
Examples
Example 1
An optical film and a method for preparing the same,
the optical film is a single-layer liquid crystal polymer layer with the thickness of 1.6 mu m, and SiO with different particle diameters are added in the liquid crystal polymer layer 2 And TiO 2 The preparation method of the anti-glare anti-reflection particle comprises the following specific steps:
step 1, manufacturing an orientation layer: directly rubbing and orienting the substrate; the average depth of grooves formed on the surface of the orientation layer formed by friction orientation is 50nm;
step 2, preparing a liquid crystal mixture: the liquid crystal polymerizable monomer, the chiral compound, the anti-dazzle anti-reflection particles, the photoinitiator and the solvent are measured according to a proportion and then heated to be above the phase transition temperature of all the liquid crystal polymerizable monomers, and stirring is continuously carried out in the heating process until the liquid crystal polymerizable monomer, the chiral compound, the anti-dazzle anti-reflection particles, the photoinitiator and the solvent are uniformly mixed, and the liquid crystal polymerizable monomer is cooled to 30 ℃ for standby;
the liquid crystal mixture is obtained by mixing the following raw materials: the content of polymerizable liquid crystal is 80%, the content of anti-glare anti-reflection particles is 3%, the content of light absorbing materials is 7%, the content of chiral compounds is 0.4%, the content of photoinitiator is 4-tert-butylphenyl iodonium diphenyl iodonium tetrafluoroborate, the content of photoinitiator is 2%, the content of organic solvent is propylene glycol monomethyl ether acetate, and the content of photoinitiator is 7.6%;
wherein the polymerizable liquid crystal is prepared by mixing the following polymerizable liquid crystal monomers, and the proportions of the components are as follows (in percentage by mass):
the anti-glare antireflection particles consist of the following particles with different particle diameters (in mass percent):
SiO as described above 2 SiO with different particle sizes in anti-glare antireflection particles 2 The weight portions are as follows:
the TiO described above 2 TiO with different particle sizes in anti-glare antireflection particles 2 The weight portions are as follows:
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the polymethyl methacrylate anti-glare antireflection particles comprise the following polymethyl methacrylate with different molecular equivalent weight parts:
1000-2000 37％
3000-5000 63％
the weight parts of polybutyl methacrylate with different molecular equivalent in the polybutyl methacrylate anti-glare antireflection particles are as follows:
1500-2500 55％
3000-5000 45％
the chiral compound adopts S1, and the structural formula is as follows:
the light-absorbing material is prepared by mixing the following light-absorbing material monomers, and the proportions of the components are as follows (in percentage by mass):
C1 40％
C4 25％
C6 35％；
step 3, preparation of a liquid crystal polymer layer: coating the liquid crystal mixture prepared in the step 2 on the alignment layer prepared in the step 1, wherein the thickness of the coating is 1.73 mu m, heating and curing for 2 minutes at 120 ℃ to ensure that the liquid crystal in the liquid crystal mixture coating is uniformly aligned, removing the organic solvent, and cooling to 90 DEG CAt 100mJ/cm by means of a metal halide lamp 2 Irradiating ultraviolet rays to solidify the liquid crystal mixture coating to form a liquid crystal polymer layer;
and 4, stripping the liquid crystal polymer layer prepared in the step 3 from the substrate layer to obtain the optical film.
Example 2
An optical film and a method for producing the same were carried out according to the method in example 1, except that:
the optical film in example 2 was composed of two layers of liquid crystal polymers, wherein after the first layer of liquid crystal mixture was applied, the second layer of liquid crystal mixture was applied after photo-curing, the first layer of liquid crystal polymer formed from the first layer of liquid crystal mixture had a chiral compound content of 0.18%, an anti-glare and anti-reflection particle content of 0, a polymerizable liquid crystal content of 83.22%, a polymerized first layer of liquid crystal polymer thickness of 0.8 μm, a second layer of liquid crystal polymer formed from the second layer of liquid crystal mixture had a chiral compound content of 0.22%, an anti-glare and anti-reflection particle content of 3%, and a polymerizable liquid crystal content of 80.18%. The thickness of the second liquid crystal polymer layer is 0.4 mu m, and the optical axis of the termination molecular layer of the first liquid crystal polymer layer is parallel to the optical axis of the initial liquid crystal molecular layer of the second liquid crystal polymer layer, namely the included angle is zero.
Example 3
An optical film and a method for producing the same were carried out according to the method in example 1, except that:
the optical film of example 3 was prepared by compounding three layers of liquid crystal polymers, wherein the first layer of liquid crystal polymer had a chiral compound content of 0.20%, an anti-glare antireflection particle content of 4%, a polymerizable liquid crystal content of 79.20%, the first layer of liquid crystal polymer had a thickness of 0.42 μm, the second layer of liquid crystal polymer had a chiral compound content of 0.14%, an anti-glare antireflection particle content of 0, a polymerizable liquid crystal content of 83.26%, the second layer of liquid crystal polymer had a thickness of 0.62 μm, the third layer of liquid crystal polymer had a chiral compound content of 0.10%, an anti-glare antireflection particle content of 3%, a polymerizable liquid crystal content of 80.30%, and the third layer of liquid crystal polymer had a thickness of 0.74 μm,
The optical axis of the termination molecular layer of the first layer of liquid crystal polymer is parallel to the optical axis of the initial liquid crystal molecular layer of the second layer of liquid crystal polymer, namely the included angle is zero. The optical axis of the termination molecular layer of the second liquid crystal polymer is parallel to the optical axis of the initial liquid crystal molecular layer of the third liquid crystal polymer, namely the included angle is zero.
Example 4
An optical film and a method for producing the same were carried out according to the method in example 2, except that:
the chiral compound content in the coated first layer liquid crystal polymer is zero, the anti-dazzle anti-reflection particle content is 4%, the polymerizable liquid crystal content is 79.4%, and the thickness of the first layer liquid crystal polymer is 0.4 mu m. The second layer of liquid crystal polymer contains chiral compound 0.4%, anti-glare and anti-reflection particles 4%, polymerizable liquid crystal 79% and has a thickness of 0.7 μm.
Example 5
An optical film and a method for producing the same were carried out according to the method in example 1, except that:
the organic substrate adopts photo-alignment, a layer of SD1 mixture is coated on the PET substrate, the mass percentage of SD1 in the SD1 mixture is 1%, the content of the organic solvent is 99% of propylene glycol monomethyl ether acetate, after the organic solvent is removed by heating, the organic solvent is irradiated by linearly polarized ultraviolet light, and the arrangement direction of a liquid crystal molecular layer coated on the SD1 layer can be perpendicular to the polarization direction of the irradiated linearly polarized light. The thickness of the alignment layer after removal of the organic solvent was 4nm, which was negligible in the overall thickness.
Example 6
An optical film and a method for producing the same were carried out according to the method in example 2, except that:
after the first layer of liquid crystal mixture is coated and cured, a layer of photo-alignment layer SD1 mixture is coated on the first layer of liquid crystal mixture, and after the organic solvent is removed by heating and the first layer of liquid crystal mixture is irradiated by linear polarized ultraviolet light, an alignment layer is formed. And coating a second layer of liquid crystal mixture on the alignment layer, wherein a certain included angle exists between the optical axis of the ending liquid crystal molecular layer of the first layer of liquid crystal polymer and the optical axis of the initial liquid crystal molecular layer of the second layer of liquid crystal polymer, and the included angle is 15 degrees. The first layer of liquid crystal polymer contains 0.28 percent of chiral compound, 3 percent of anti-glare and anti-reflection particles, 80.12 percent of polymerizable liquid crystal, 1.0 mu m of the first layer of liquid crystal polymer, 0.16 percent of chiral compound, 3 percent of anti-glare and anti-reflection particles, 80.24 percent of polymerizable liquid crystal and 0.2 mu m of the second layer of liquid crystal polymer.
Example 7
An optical film and a method for preparing the same were carried out according to the method in example 1, except that the polymerizable liquid crystal content was 20%, the light absorbing material content was 20%, the antiglare antireflection particle content was 20%, the chiral compound content was 20%, the photoinitiator content was 5%, the organic solvent content was 15%, and the liquid crystal polymer thickness was 1.7 μm;
Wherein the chiral compound adopts S2, and the structural formula is as follows:
example 8
An optical film and a method for preparing the same were carried out according to the method in example 1, except that the polymerizable liquid crystal content was 98%, the anti-glare antireflection particle content was 0.01%, the light absorbing material content was 0.5%, the chiral compound content was 0.1%, the photoinitiator content was 0.1%, the organic solvent content was 1.29%, and the liquid crystal polymer thickness was 2.1 μm;
wherein the chiral compound adopts S3, and the structural formula is as follows:
example 9
An optical film and a method for producing the same were conducted in accordance with the method in example 1, except that the content of the anti-glare antireflection particles was 3%, and the anti-glare antireflection particles were composed of SiO 2 And TiO 2 Composition, siO 2 And TiO 2 Ratio of different particle diameters of anti-glare anti-reflection particlesThe example is the same as example 1, and the mass parts of the two are as follows:
SiO 2 66％
TiO 2 34％
example 10
An optical film and a preparation method thereof are carried out according to the method in the example 1, and the difference is that the content of anti-dazzle anti-reflection particles is 3 percent, the anti-dazzle anti-reflection particles are composed of polymethyl methacrylate and polybutyl methacrylate, the ratio of different molecular weights of the polymethyl methacrylate and the polybutyl methacrylate anti-dazzle anti-reflection particles is the same as the example 1, and the mass parts of the two are as follows:
Polymethyl methacrylate 47%
Polybutylmethacrylate 53%
Example 11
An optical film and a method for producing the same were carried out in accordance with the method in example 1, except that the polymerizable liquid crystal in the liquid crystal mixture was composed of the following polymerizable liquid crystal monomers (parts by mass):
example 12
An optical film and a method for producing the same were carried out in accordance with the method in example 1, except that the polymerizable liquid crystal in the liquid crystal mixture was composed of the following polymerizable liquid crystal monomers (parts by mass):
example 13
An optical film and a method for producing the same were carried out in the same manner as in example 1, except that the base material layer TAC (triacetate fiber film) was 50 μm thick, and the base material layer and the liquid crystal polymer layer were not separated in the fourth step of the production step, and were used as an optical film layer as a whole.
Comparative example
Comparative example 1
An optical film comprises a depolarization layer, a blue light prevention layer, an anti-dazzle layer and an anti-reflection layer, wherein the anti-dazzle layer and the anti-reflection layer are coated on the depolarization layer and the blue light prevention layer through a multilayer coating process. Wherein the depolarizing layer is selected from commercial Di GR-138 with the thickness of 71 μm, the blue light preventing layer is selected from patent CN 105505248A with the thickness of 100 μm, and the thickness of the anti-dazzle layer and the anti-reflection layer of the coating film is 0.5 μm. Wherein the depolarization layer is positioned at the light emergent side close to the display device. The optical film thickness was 171.5. Mu.m.
Comparative example 2
An optical film includes a depolarizing layer and a blue light preventing layer. Wherein the depolarizing layer is selected from commercial Di GR-138, the thickness is 71 μm, the blue light preventing layer is selected from patent CN 105505248A, the thickness is 100 μm, and the depolarizing layer is positioned near the light emitting side of the display device. The optical film thickness was 171. Mu.m.
Performance detection
The thickness, light transmittance, depolarization, glare and unwanted blue light blocking were measured for the optical films of examples 1 to 12 and comparative example 1, and the measurement results are shown in table 1.
The thickness is measured by a profilometer selected from the 3D white light interferometers of Filmetrics, a 10-fold objective lens. The transmittance is measured by a spectrophotometer, the average value of the transmittance of wavelengths within the range of 380-760nm is taken as the data of the transmittance measurement, the depolarization rate is measured by placing an optical film to be measured between two polaroids and rotating the optical film to be measured as shown in the attached figure 1, and the calculation formula is as follows:
in the above formula, P is the depolarization rate, I max And I min Respectively, transmission test opticsThe maximum and minimum light intensities of the film were measured by an optical power meter.
The glare reflectivity was measured by a Jing Yiguang electrical reflectance detector. The harmful blue light blocking rate is measured by a spectrophotometer, and the harmful blue light blocking rate is the average blocking rate of light with the wavelength of 380-440 nm.
Table 1:
as can be seen from table 1, the optical film thickness in examples 1 to 13 was greatly reduced as compared with comparative examples 1 to 2, and a separate blue light preventing layer was used in comparative example 1, and the depolarizing material thereof was a carbonate material, and the birefringence was smaller, resulting in a larger thickness of the optical film. In examples 1 to 13, the thickness of the optical film was greatly reduced by using a liquid crystal material having a large birefringence and compounding a blue light shielding material with a liquid crystal polymer.
As can be seen from table 1, the optical films of examples 1 to 13 have reduced overall thickness and improved light transmittance by combining the anti-glare antireflection and anti-harmful blue light function with the depolarizing layer.
The optical films of examples 1 to 13 were better in depolarization rate by using a liquid crystal material to which chiral compounds were added, since they had better reverse wavelength dispersibility for different wavelengths of light than comparative examples.
Referring to the optical films of examples 1 to 13 in table 1, the optical films of examples 1 to 13 were made to have both a glare reduction reflectance and a harmful blue blocking rate better than those of comparative example 1 by uniformly mixing the anti-glare antireflection particles and the material absorbing the harmful blue light in the liquid crystal polymer.
Claims (10)
1. An optical film, characterized in that: adopts a single-layer or multi-layer liquid crystal polymer layer, and the raw materials comprise, by mass, 0.5-98% of liquid crystal polymerizable monomer, 0.5-30% of chiral compound, 0.1-20% of anti-dazzle anti-reflection particles, 0-20% of light absorption material, 0.1-70% of photoinitiator and 0-70% of solvent.
2. An optical film according to claim 1, wherein: the liquid crystal polymerizable monomer adopts one or more of nematic liquid crystal, discotic liquid crystal or discotic liquid crystal, and when the liquid crystal polymerizable monomer is various, the proportion is arbitrary; the liquid crystal polymerizable monomer at least contains one polymerizable group, and the polymerizable group is any one of alkenyl, alkynyl, epoxy and mercapto; at least one liquid crystal polymer layer contains anti-glare anti-reflection particles; at least one liquid crystal polymer layer contains chiral compounds; the liquid crystal polymer layers containing anti-dazzle anti-reflection particles and chiral compounds exist in the same liquid crystal polymer layer or different liquid crystal polymer layers; the light absorbing material is blue light absorbing material or blue light or ultraviolet light absorbing material.
3. An optical film according to claim 1, wherein: the radius of the anti-dazzle anti-reflection particles is between 0.01 and 1 mu m; the anti-dazzle anti-reflection particles are insoluble in any component in the liquid crystal mixture and comprise organic anti-dazzle anti-reflection particles or inorganic anti-dazzle anti-reflection particles, wherein the inorganic anti-dazzle anti-reflection particles are TiO 2 Or SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The organic anti-dazzle particles are selected from one or more of polystyrene, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, acrylic ester-styrene copolymer, methyl acrylate-styrene copolymer, methyl methacrylate-styrene copolymer and polyallylphthalate, and when the organic anti-dazzle particles are multiple, the proportion is arbitrary;
the chiral compound is one or more of X1, X2, X3, X4, X5, X6, X7, X8, X9, X10, X11, X12, X13, X14, X15, X16, X17, X18, X19, X20 and X21, and when the chiral compound is a plurality of chiral compounds, the proportion is arbitrary.
4. An optical film according to claim 1, wherein: the mass fraction of the chiral compound is determined according to the characteristic value HTP of the chiral compound and the deflection angle between the optical axis of an initial liquid crystal molecular layer and the optical axis of a termination liquid crystal molecular layer in the thickness direction of a liquid crystal polymer film layer to be prepared, and the calculation formula is as follows:
wherein C is the mass fraction of chiral compound in the liquid crystal mixture, d is the thickness of the polymer film, θ is the deflection angle between the optical axis of the initial liquid crystal molecular layer and the optical axis of the final liquid crystal molecular layer in the thickness direction of the polymer film, and HTP is the characteristic value of the chiral compound.
5. An optical film according to claim 1, wherein: the photoinitiator may be: benzoyl peroxide, azobisisobutyronitrile, benzoin ethers, benzophenones, acetophenones, benzil ketals, diaryliodonium salts, triarylsulfonium salts, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium arsenate, diphenyliodonium tetraborate, 4-methoxyphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenyliodonium hexafluoroarsenate, 4-tert-butylphenyl iodonium diphenyliodonium tetrafluoroborate, 4-tert-butylphenyl iodonium diphenyliodonium hexafluorophosphonate, and 4-tert-butylphenyl) iodonium diphenyliodonium trifluoromethane sulfonate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsonate, triphenylsulfonium tetraborate, 4-methoxyphenyldiphenylsulfonium tetrahydroborate, 4-methoxyphenyldiphenylsulfonium tetrahydrophosphonate, 4-methoxyphenyldiphenylsulfonium tetrahydroarsonate, 4-methoxyphenyldiphenylsulfonium trifluoromethane sulfonate, 4-methoxyphenyldiphenylsulfonium triphenylsulfonium tetraborate, 4-phenylphenylthio diphenylsulfonium hexafluoroarsonate, benzil dimethyl ketal, and bis-phenylphosphine oxide, when the ratio is plural, the ratio therebetween is arbitrary;
The solvent adopts organic solvents including benzene, toluene, xylene, mesitylene, N-butylbenzene, diethylbenzene, tetrahydronaphthalene, methoxybenzene, 1, 2-dimethoxybenzene, cyclohexanone, ethyl acetate, methyl lactate, ethyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-pyrrolidone, chloroform, methylene chloride, carbomethoxy, dichloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene, tertiary butanol, diacetone alcohol, glycerol, glyceryl monoacetate, triethylene glycol, ethylcellosolve and butylcellosolve, N-methyl-2-pyrrolidone, gamma-butyrolactone, N, N-dimethylformamide, N-dimethylacetamide, diethylene glycol monomethyl ether ethyl ester, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, tetrahydrofuran, methylene chloride, chlorobenzene, 1, 2-dichloroethane, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclobutanone, methyl acetate, ethyl acetate, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol methyl ether, ethylene glycol dimethyl ether, and when the solvent is plural, the ratio therebetween is arbitrary.
6. The method for producing an optical film according to any one of claims 1 to 5, wherein: the method specifically comprises the following steps:
step 1, manufacturing an orientation layer: directly rubbing and orienting the substrate, or coating a polyvinyl alcohol layer on the substrate, and rubbing the polyvinyl alcohol layer to obtain an orientation layer; the depth of a groove of the surface travel of the orientation layer formed by friction orientation is between 5nm and 2000 nm;
step 2, preparing a liquid crystal mixture: the liquid crystal polymerizable monomer, the chiral compound, the anti-dazzle anti-reflection particles, the photoinitiator and the solvent are measured according to a proportion and then heated to be above the phase transition temperature of all the liquid crystal polymerizable monomers, stirring is continuously carried out in the heating process until the liquid crystal polymerizable monomer, the chiral compound, the anti-dazzle anti-reflection particles, the photoinitiator and the solvent are uniformly mixed, and the liquid crystal polymerizable monomer is cooled to 10-50 ℃ for standby;
step 3, preparation of a liquid crystal polymer layer: coating the liquid crystal mixture prepared in the step 2 on the orientation layer prepared in the step 1, wherein the thickness of the coating is 100-5000 nm, heating to remove the organic solvent and curing to obtain the liquid crystal polymer, and the heating temperature is 30-150 ℃ and the heating time is 5-1000 s;
step 4, stripping the liquid crystal polymer layer prepared in the step 3 from the substrate layer to obtain an optical film; or the liquid crystal polymer layer prepared in the step 3 is not peeled off from the substrate layer, and the whole liquid crystal polymer layer is reserved to be used as an optical film layer.
7. The method for producing an optical film according to claim 6, wherein: the optical film comprises a plurality of liquid crystal polymer layers, when the included angle between the optical axes of the liquid crystal molecular layers of two adjacent liquid crystal polymer layers is zero, after the substrate is oriented, the first liquid crystal mixture is coated on the substrate, and the first liquid crystal polymer layer is obtained after the organic solvent is removed by heating and is solidified; continuously coating a second liquid crystal mixture layer on the first liquid crystal polymer layer, heating to remove the organic solvent, curing to obtain a second liquid crystal polymer layer, and the like until all liquid crystal polymer layers are coated and prepared;
when the optical film comprises a plurality of liquid crystal polymer layers and the included angle between the optical axes of the liquid crystal molecular layers of at least two adjacent liquid crystal polymer layers is not zero, preparing an alignment layer on one liquid crystal polymer layer after coating, coating an adjacent second liquid crystal polymer layer on the alignment layer, and the like until all liquid crystal polymer layers are coated and prepared; the included angle between the relative optical axis of the whole optical film and the optical axis of the linear polarized light emitted by the display device is 45 degrees+/-10 degrees, the birefringence of the liquid crystal is 0.05-0.5, and the thickness of the optical film is 0.01-5 mu m.
8. The method for producing an optical film according to claim 6, wherein: when the optical film is formed by a single liquid crystal polymer layer, the phase retardation value of the optical film for incident linear polarized light is controlled by a plurality of factors including the physical property of a liquid crystal material of the liquid crystal polymer layer, the thickness of the liquid crystal polymer, the included angle between the optical axis of an initial liquid crystal molecular layer and the optical axis of a final liquid crystal molecular layer in the thickness direction of the liquid crystal polymer layer, and the included angle between the optical axis of the liquid crystal molecular layer of the incident linear polarized light entering the optical film side and the polarization direction of the incident linear polarized light, and the specific depolarization calculation formula is as follows:
a i ＝cosX i cosφ i +φ i sinφ i t(X i )
c i ＝cosX i sinφ i -φ i cosφ i t(X i )
T＝T i …T 2 T 1 R(φ 0 )
i＝1,2,3,4
S c ＝TS r
in the above formula: characteristic parameters of birefringence of p, q liquid crystal material e i Is the thickness of the ith liquid crystal polymer layer, lambda is the wavelength of light, phi j Is the included angle phi between the molecular optical axis of the initial liquid crystal layer and the molecular optical axis of the ending liquid crystal layer of the jth layer of liquid crystal polymer in the thickness direction 0 S is the included angle between the optical axis of the linear polarization to be retired and the optical axis of liquid crystal molecules of the initial layer of the liquid crystal polymer r Is the Stokes vector representation form of the light to be depolarized, S c The Stokes vector representation form of the to-be-depolarized light wire after passing through the liquid crystal polymer layer; when the optical film is formed by multiple layers of liquid crystal polymers, the influence factors of the phase delay value of the incident linear polarized light also comprise the included angle between the liquid crystal molecular optical axes of two adjacent liquid crystal polymer layers.
9. The method for producing an optical film according to claim 6, wherein: and (2) preparing a coating polyvinyl alcohol layer with the thickness of 10-1000 nm by the orientation layer, and forming the orientation layer after the coating is irradiated by linearly polarized light, so that the liquid crystal molecules coated on the orientation layer are arranged perpendicular to the polarization direction of the irradiated linearly polarized light.
10. The method for producing an optical film according to claim 6, wherein: the curing process in step 3 adopts photo-curing or heat-curing process, wherein the wavelength of ultraviolet light and visible light with 150-800 nm, preferably 30, of the light source used in the photo-curing processUltraviolet light of 0nm to 400 nm; as a light source for irradiating light, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, and the irradiation amount of light is preferably 1000J/m 2 ～200000J/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The curing temperature in the heat curing process is between 30 and 200 ℃, the heating temperature is between 30 and 150 ℃, and the heating time is between 5 and 1000 seconds; the photo-curing process is preferred.
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