CN113126369A - Liquid crystal composite film, preparation method thereof and liquid crystal writing board - Google Patents
Liquid crystal composite film, preparation method thereof and liquid crystal writing board Download PDFInfo
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- CN113126369A CN113126369A CN202110384932.0A CN202110384932A CN113126369A CN 113126369 A CN113126369 A CN 113126369A CN 202110384932 A CN202110384932 A CN 202110384932A CN 113126369 A CN113126369 A CN 113126369A
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- 239000002131 composite material Substances 0.000 title claims abstract description 153
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title abstract description 51
- 239000005264 High molar mass liquid crystal Substances 0.000 claims abstract description 93
- 150000001875 compounds Chemical class 0.000 claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000011521 glass Substances 0.000 claims description 109
- 239000002994 raw material Substances 0.000 claims description 51
- 239000000758 substrate Substances 0.000 claims description 44
- 239000000178 monomer Substances 0.000 claims description 38
- 238000002834 transmittance Methods 0.000 claims description 38
- 239000004988 Nematic liquid crystal Substances 0.000 claims description 34
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 17
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 17
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 claims description 16
- 125000006850 spacer group Chemical group 0.000 claims description 16
- UZGCTULFQVGVNS-UHFFFAOYSA-N 4-(4-prop-2-enoyloxybutoxycarbonyloxy)benzoic acid Chemical compound OC(=O)C1=CC=C(OC(=O)OCCCCOC(=O)C=C)C=C1 UZGCTULFQVGVNS-UHFFFAOYSA-N 0.000 claims description 14
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 14
- FQCKIWWAEIOPSD-UHFFFAOYSA-N [3-methyl-4-[4-(6-prop-2-enoyloxyhexoxy)benzoyl]oxyphenyl] 4-(6-prop-2-enoyloxyhexoxy)benzoate Chemical compound C=1C=C(OC(=O)C=2C=CC(OCCCCCCOC(=O)C=C)=CC=2)C(C)=CC=1OC(=O)C1=CC=C(OCCCCCCOC(=O)C=C)C=C1 FQCKIWWAEIOPSD-UHFFFAOYSA-N 0.000 claims description 14
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 14
- -1 polyethylene terephthalate Polymers 0.000 claims description 14
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 claims description 11
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 9
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 9
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 7
- 229920001568 phenolic resin Polymers 0.000 claims description 7
- 239000005011 phenolic resin Substances 0.000 claims description 7
- 239000004642 Polyimide Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920001721 polyimide Polymers 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical group O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 13
- 239000003086 colorant Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 460
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- 239000000203 mixture Substances 0.000 description 68
- 229920002799 BoPET Polymers 0.000 description 65
- 239000000243 solution Substances 0.000 description 41
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- 238000001035 drying Methods 0.000 description 28
- 238000004544 sputter deposition Methods 0.000 description 28
- 238000009210 therapy by ultrasound Methods 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 230000008569 process Effects 0.000 description 23
- 229910052751 metal Inorganic materials 0.000 description 21
- 239000002184 metal Substances 0.000 description 21
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- 239000003292 glue Substances 0.000 description 15
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- 238000005286 illumination Methods 0.000 description 14
- 230000008020 evaporation Effects 0.000 description 13
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000011229 interlayer Substances 0.000 description 10
- 238000005192 partition Methods 0.000 description 10
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 7
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 7
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 7
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 7
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 description 7
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
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- 239000004744 fabric Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 229920002120 photoresistant polymer Polymers 0.000 description 7
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- YMCOIFVFCYKISC-UHFFFAOYSA-N ethoxy-[2-(2,4,6-trimethylbenzoyl)phenyl]phosphinic acid Chemical compound CCOP(O)(=O)c1ccccc1C(=O)c1c(C)cc(C)cc1C YMCOIFVFCYKISC-UHFFFAOYSA-N 0.000 description 5
- 229930192419 itoside Natural products 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
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- 230000007794 irritation Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- RZLXRFDFCORTQM-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCCn1c(=O)n(CCO)c(=O)n(CCO)c1=O Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCCn1c(=O)n(CCO)c(=O)n(CCO)c1=O RZLXRFDFCORTQM-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 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
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
- G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Mathematical Physics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Liquid Crystal (AREA)
Abstract
The invention is suitable for the technical field of liquid crystal materials and display, and provides a liquid crystal composite film, a preparation method thereof and a liquid crystal writing board, wherein the liquid crystal composite film comprises the following components: a first base layer with a conductive layer on one side; a second base layer with conductive layers on both sides; a first polymer liquid crystal composite layer disposed between the first base layer and the second base layer; the third base layer is provided with an insulating layer and a transistor layer on one side close to the second base layer; and a second polymer liquid crystal composite layer disposed between the second base layer and the third base layer; the first polymer liquid crystal composite layer and the second polymer liquid crystal composite layer respectively comprise two chiral compounds with different chiralities. The technical scheme provided by the invention can enable the liquid crystal composite film to reflect light with different colors, increase the reflection wave width of the film, realize rapid and sufficient polymerization, greatly shorten the polymerization time and improve the production efficiency.
Description
Technical Field
The invention belongs to the technical field of liquid crystal materials and display, and particularly relates to a liquid crystal composite film, a preparation method thereof and a liquid crystal writing board.
Background
In recent years, liquid crystal display technology is rapidly developed, and liquid crystal writing boards are widely concerned by people due to the advantages of dustless writing, environmental protection, health, clear handwriting, smooth writing and the like, and are widely applied to the fields of teaching, drawing, meetings and the like. The liquid crystal writing board film is used as a core component of the liquid crystal writing board, and the use experience of the writing board is directly influenced by the performance of the liquid crystal writing board film.
However, the writing board films in the market still have some disadvantages of slow response speed, single color, poor contrast, etc., so how to improve the usability of the liquid crystal writing board films is a scientific problem to be solved urgently in the combination of the current research and study.
Disclosure of Invention
An object of an embodiment of the present invention is to provide a liquid crystal composite film, which is intended to solve the problems in the background art.
The embodiment of the present invention is achieved as follows, a liquid crystal composite film includes a first base layer and a second base layer, a conductive layer is disposed on one side of the first base layer close to the second base layer, and conductive layers are disposed on both sides of the second base layer, wherein the liquid crystal composite film further includes:
a first polymer liquid crystal composite layer disposed between the first base layer and the second base layer;
a third base layer provided with an insulating layer and a transistor (TFT) layer at a side thereof adjacent to the second base layer; and
a second polymer liquid crystal composite layer disposed between the second base layer and the third base layer;
wherein the first polymer liquid crystal composite layer and the second polymer liquid crystal composite layer respectively contain a left-handed chiral compound and a right-handed chiral compound; or the first polymer liquid crystal composite layer and the second polymer liquid crystal composite layer respectively contain a right-handed chiral compound and a left-handed chiral compound.
As a preferable scheme of the embodiment of the present invention, the first base layer and the second base layer are polyethylene terephthalate (PET) films, and have a thickness of 25 to 180 μm, a light transmittance of 86 to 96%, a transverse heat shrinkage rate of 0.05 to 3%, and a longitudinal heat shrinkage rate of 0.05 to 3%.
In another preferred embodiment of the present invention, a hardened layer having an ultraviolet-resistant function is disposed on a side of the first base layer away from the conductive layer, the hardened layer has a hardness of 3H to 10H, and contains at least one ultraviolet absorber selected from UV-326, UV-405, and UV-928.
Specifically, the ultraviolet absorbers account for the hardened layer in parts by weight of UV-326: 0-0.8 parts, UV-405: 0-1.0 part, UV-928: 0 to 1.2 parts of
As another preferable scheme of the embodiment of the invention, each conducting layer is independently a tin oxide (ITO) conducting layer, the resistance of the conducting layer is 15-100 omega, the light transmittance is 89-96%, and the uniformity of the resistance is plus or minus 50 omega
As another preferable scheme of the embodiment of the present invention, the third base layer is a glass layer, and a transistor (TFT) layer, an insulating layer, and a spacer layer are sequentially disposed on one side of the third base layer, which is close to the second base layer; the thickness of the glass layer is 0.1-5 mm, and the light transmittance of the visible light region is 86% -97%.
Specifically, the bottom area of the spacer column layer is 0.25-9 μm2The column height is 5-30 μm, and the interval between columns is 0.2-1.5 mm.
As another preferable scheme of the embodiment of the invention, the transistor layer partially or completely comprises amorphous indium gallium zinc oxide (a-IGZO) and is prepared by adopting a TFT process with 6-12 layers, and each layer isThe transistor size is (0.2-80 μm) × (0.2-80 μm), the Gate line width is 1-35 μm, the Source line width is 1-35 μm, and the on-off current ratio is 102～107The threshold voltage is 10-100V; the insulating layer is a film of polyimide, polyvinyl alcohol, organic silicon resin or phenolic resin, the thickness of the insulating layer is 0.5-15 mu m, and the light transmittance is 75-85%.
As another preferable scheme of the embodiment of the invention, the first polymer liquid crystal composite layer has a thickness of 1 to 35 μm, and comprises the following raw materials in parts by weight: 55-95 parts of nematic liquid crystal, 5-35 parts of polymerizable monomer, 2-30 parts of left-handed chiral compound and 0.8-4.5 parts of first photoinitiator;
the second polymer liquid crystal composite layer is 1-35 mu m in thickness and comprises the following raw materials in parts by weight: 55-95 parts of nematic liquid crystal, 5-35 parts of polymerizable monomer, 2-30 parts of right-handed chiral compound and 0.8-4.5 parts of second photoinitiator;
the nematic liquid crystal has a birefringence of 0.2 to 0.4, a dielectric constant of 25 to 40, and a viscosity of 15 to 70mm2The clearing point is 50-100 ℃, and the threshold voltage V is902-20V, saturation voltage V102-20V, and the water content is 10-260 ppm;
the polymerizable monomer is at least one of 2-phenoxyethyl acrylate, trimethylolpropane trimethacrylate, stearyl methacrylate, tetraethyleneglycol diacrylate and 1, 4-bis- [4- (6-acryloyloxyhexyloxy) benzoyloxy ] -2-methylbenzene, 2-methyl-1, 4 phenylene bis (4- (((4- (acryloyloxy) butoxy) carbonyl) oxy) benzoic acid, and the polymerizable monomer comprises, by weight, 0-5 parts of 2-phenoxyethyl acrylate, 0-5 parts of trimethylolpropane trimethacrylate, 0-5 parts of stearyl methacrylate, 0-10 parts of tetraethyleneglycol diacrylate, 0-10 parts of 1, 4-bis- [4- (6-acryloyloxyhexyloxy) benzoyloxy ] -2-methylbenzene, 0-10 parts of 2-methyl-1, 4-phenylenebis (4- (((4- (acryloyloxy) butoxy) carbonyl) oxy) benzoic acid;
the levorotatory chiral compound is at least one of S5011, S6N, S2011 and S811; the concrete raw materials and parts by weight are as follows: s5011: 0-5 parts of S6N: 0-6 parts, S2011: 0-9 parts, S811: 0 to 30 parts.
The dextrorotatory chiral compound is at least one of R5011, R6N, R2011 and R811; the concrete raw materials and parts by weight are as follows: r5011: 0-5 parts, R6N: 0-6 parts, R2011: 0-9 parts, R811: 0-30 parts of a solvent;
the first photoinitiator is at least one of a, a-dimethoxy-a-phenyl acetophenone, bis-2, 6-difluoro-3-pyrrolylphenyl titanocene and bis (pentafluorophenyl) titanocene; the concrete raw materials and parts by weight are as follows: 0.3-3.0 parts of a, a-dimethoxy-a-phenyl acetophenone, 0.3-3.0 parts of bis 2, 6-difluoro-3-pyrrolylphenyl titanocene and 0.2-1.5 parts of bis (pentafluorophenyl) titanocene;
the second photoinitiator is at least one of a, a-dimethoxy-a-phenylacetophenone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenyl phosphonate and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide; the concrete raw materials and parts by weight are as follows: 0.3-3.0 parts of a, a-dimethoxy-a-phenyl acetophenone, 0.1-2 parts of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 0.2-1.5 parts of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphonate and 0.2-1 part of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide.
Wherein, the structural formula of the partial raw materials is as follows:
2-Phenoxyethyl acrylate
Trimethylolpropane trimethacrylate
Stearyl methacrylate
Tetraethyleneglycol diacrylate
1, 4-bis- [4- (6-acryloyloxyhexyloxy) benzoyloxy ] -2-methylbenzene
2-methyl-1, 4 phenylenebis (4- (((4- (acryloyloxy) butoxy) carbonyl) oxy) benzoic acid
Another objective of the embodiments of the present invention is to provide a method for preparing the liquid crystal composite film, which includes the following steps:
dropwise adding a second polymer liquid crystal composite system comprising a right-handed chiral compound or a left-handed chiral compound onto a third base layer with an insulating layer and a transistor layer arranged on one side, laying a second base layer with conductive layers arranged on both sides on the second polymer liquid crystal composite system, removing air, and curing by ultraviolet irradiation to form a second polymer liquid crystal composite layer between the second base layer and the third base layer;
dropwise adding a first polymer liquid crystal composite system comprising a left-handed chiral compound or a right-handed chiral compound onto a second base layer, laying a first base layer with a conducting layer on one side on the first polymer liquid crystal composite system, removing air, and curing by ultraviolet irradiation to form a first polymer liquid crystal composite layer between the first base layer and the second base layer to obtain the liquid crystal composite film.
Specifically, the preparation method of the liquid crystal composite film can comprise the following steps:
step 1), preparation of a hardened layer:
mixing 1-10 parts of dipentaerythritol pentaacrylate, 1-17 parts of dipentaerythritol hexaacrylate, 3-18 parts of ditrimethylolpropane tetraacrylate, 1-5 parts of 1, 6-hexanediol diglycidyl ether, 2-24 parts of tris (2-hydroxyethyl) isocyanuric acid triacrylate, 1-12 parts of trimethylolpropane triacrylate, 1-14 parts of pentaerythritol triacrylate, 0-0.8 part of UV-326, 0-1.0 part of UV-405, 0-1.2 part of UV-928, 0.5-3 parts of photoinitiator 651 and 0.5-2 parts of photoinitiator 1173, stirring at 300-1100 rpm for 30-50 min, and then carrying out ultrasonic oscillation for 20-60 min, uniformly coating the non-conductive layer on the first layer of PET film, and then using the obtained wet film at room temperature with the power of 15-105 mW/cm.2Polymerizing for 10-30 min by using ultraviolet light, and drying at 55-70 ℃ for 1-5 h to obtain the first base layer with the conductive layer and the hardening layer on two sides respectively.
Step 2), preparation of a TFT layer:
firstly, wiping ultrathin flexible glass with one side coated with ITO by using dust-free cloth stained with a small amount of acetone solution, then putting the glass into a beaker filled with NaOH solution, carrying out ultrasonic treatment for 30-50 min, taking out the glass, putting the substrate into isopropanol solution, carrying out ultrasonic treatment for 20-40 min again, taking out the substrate again, putting the substrate into deionized water, carrying out ultrasonic treatment for 25-60 min, and drying the substrate at 60-75 ℃ for 30-90 min; secondly, uniformly coating a PVA (polyvinyl alcohol) solution with the concentration of 2.5-3.5% on one side of the cleaned ITO (indium tin oxide) of the ultrathin flexible glass, drying at the temperature of 60-80 ℃ for 30-60min, and repeating the process for 2-5 times after drying to obtain insulating layers with different deposition layers; then sputtering the a-IGZO film on the ultrathin flexible glass coated with the insulating layer, wherein the sputtering power is 50-220W, the sputtering time is 400-800 s, the sputtering air pressure is 0.5-3.0 Pa, the target distance is 10-70 mm, and the back vacuum degree is 6 multiplied by 10-3Pa～3×10-3Pa, the substrate temperature is 25-100 ℃; finally, evaporating the ultrathin flexible glass sputtered with the a-IGZO film to form a metal electrode, putting the mask sheet on the glass, and then putting the glass into a metal cavity for evaporation, wherein the vacuum degree of the metal cavity is 7 multiplied by 10- 3Pa～4×10-3Pa, average evaporation rate of
The thickness of the evaporated electrode is 50-80 nm, and a second base layer with a TFT layer arranged on one side is obtained.
Step 3), preparation of an insulating layer:
dissolving any one of polyimide, polyvinyl alcohol, organic silicon resin and phenolic resin in deionized water or an organic solvent, wherein the mass concentration is 7-12%, uniformly coating the solution on the upper side of a TFT layer after filtering and defoaming processes, and then drying the TFT layer for 10-25 min at 70-90 ℃ to obtain the insulating layer.
Step 4), preparing the spacing column layer:
uniformly coating photoresist on the insulating layer obtained in the step 3), preheating for 3-5 min at 85-95 ℃, placing a mask plate on a substrate, exposing under ultraviolet light for 100-180 s at 55-60 ℃, removing the mask plate, dripping developing solution on the mask plate, uniformly coating, and finally performing film hardening treatment for 3-10 min at 90-120 ℃ to obtain the spacer column layer.
Step 5), preparing a first layer or a second layer of polymer liquid crystal composite system:
mixing 55-95 parts of nematic liquid crystal, 5-35 parts of polymerizable monomer, 2-30 parts of levorotatory or dextrorotatory chiral compound and 0.8-4.5 parts of photoinitiator, heating to 50-65 ℃, then oscillating for 15-25 min while hot, then performing ultrasonic treatment for 30-45 min, and repeating for 2-3 times.
Step 6), preparation of the liquid crystal composite film:
uniformly dripping the mixed second polymer liquid crystal composite system into the middle area of one surface of the spacing column layer on the third base layer, and then uniformly dripping the frame sealing glue into the spacing on the third base layerSpreading a second base layer on the second layer of polymer liquid crystal complex system in the edge area of one side of the column layer, removing air, and finally utilizing ultraviolet light with the wavelength of 365nm and the illumination intensity of 1-1000 mW/cm2Irradiating for 10-35 min by using ultraviolet light to form a second polymer liquid crystal composite layer; secondly, uniformly dripping the mixed first polymer liquid crystal composite system into the middle area of a second base layer, uniformly dripping frame sealing glue into the edge area of the second base layer, paving a first PET film layer on the first polymer liquid crystal composite system, removing air, and finally utilizing 398nm ultraviolet light with the wavelength and the illumination intensity of 1-1000 mW/cm2Irradiating for 10-35 min by using ultraviolet light to form a first polymer liquid crystal composite layer, and thus obtaining the liquid crystal composite film.
The embodiment of the invention also aims to provide a liquid crystal composite film prepared by the preparation method.
Another object of the embodiments of the present invention is to provide a liquid crystal writing board of the liquid crystal composite film.
According to the liquid crystal composite film provided by the embodiment of the invention, the polymerized monomer used in the hardened layer on the first base layer of the film is a monomer with high crosslinking density, high wear resistance, high reactivity and low irritation, the wear resistance and the scratch resistance of the film can be obviously improved after polymerization, and meanwhile, because the ultraviolet resistant agent is added in the layer, the ultraviolet aging resistance of the film is greatly improved, and the service life of the film is prolonged. The a-IGZO semiconductor material used by the transistor layer of the thin film has the characteristics of good conductivity, high film forming quality and the like, can remarkably improve the carrier mobility of the TFT, reduces the threshold voltage of a device, and compared with a common ITO conductive layer in the market, the TFT device can remarkably improve the contrast, brightness and response speed of the thin film, can realize the functions of partial erasing and one-key erasing of multiple colors by applying a local electric field, and greatly improves the use performance of the writing board. In addition, the two layers of polymer liquid crystal composite systems of the film are respectively added with a left-handed chiral compound, a right-handed chiral compound and a photoinitiator with characteristic absorption wavelength, so that the film can reflect light with different colors, the reflection wave width of the film is increased, and the film can be matched with ultraviolet irradiation with characteristic wavelength to realize rapid and sufficient polymerization, greatly shorten the polymerization time, improve the production efficiency, and provide new thinking and precious experience for the production and development of high-performance and low-cost liquid crystal writing board films.
Drawings
Fig. 1 is a schematic process diagram of a method for preparing a liquid crystal composite film according to embodiment 1 of the present invention.
In fig. 1, a third base layer; 2. a TFT layer; 3. an insulating layer; 4. a spacer column layer; 5. a third glass thin layer with an insulating layer and a TFT layer on one side; 6. sealing the frame glue; 7. a second polymer liquid crystal composite layer; 8. a second base layer; 9. an ITO conductive layer; 10. a second PET film with ITO conductive layers plated on both sides; 11. a first polymer liquid crystal composite layer; 12. a first layer of PET film with one side plated with an ITO conductive layer; 13. ultraviolet light.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
As shown in fig. 1, this embodiment provides a two-color/two-layer liquid crystal composite film, which comprises a first PET film 12 coated with an ITO conductive layer on one side, a first polymer liquid crystal composite layer 11, a second PET film 10 coated with an ITO conductive layer on both sides, a second polymer liquid crystal composite layer 7, and a third glass thin layer 5 with an insulating layer and a TFT layer on one side, which are connected in sequence from top to bottom.
Specifically, the thickness of the first layer of PET film is 25 μm, the light transmittance is 96%, the transverse heat shrinkage rate is 0.05%, the longitudinal heat shrinkage rate is 0.05%, the resistance value of the ITO conductive layer is 15 omega, and the light transmittance is 96%.
The upper surface of the first layer of PET film (namely the first base layer) is provided with a hardened layer with an anti-ultraviolet function. The hardness of the hardened layer was 3H, and an ultraviolet absorber UV-326 was added.
The thickness of the second layer of PET film (namely the second base layer 8) is 25 μm, the light transmittance is 96%, the transverse heat shrinkage rate is 0.05%, the longitudinal heat shrinkage rate is 0.05%, the resistance of the ITO conductive layer is 15 omega, the resistance uniformity is plus/minus 50 omega, and the light transmittance is 96%.
The third glass thin layer 5 with the insulating layer and the TFT layer on one side is a spacing column layer 4, an insulating layer 3, a TFT layer 2 and a glass thin layer (namely a third base layer 1) which are sequentially connected from top to bottom.
The spacer column layer has a bottom area of 0.25 μm2And the height of the column is 5 mu m, and the space between the spaced columns is 0.2 mm.
The insulating layer is polyimide, the thickness is 0.5 mu m, and the light transmittance is 85%.
The TFT layer is prepared by adopting 6-layer TFT process, the size of each transistor is (0.2 mu m) x (0.2 mu m), the line width of a Gate line is 1 mu m, the line width of a Source line is 1 mu m, and the switching current ratio is 102And a threshold voltage of 100V.
The glass thin layer is made of ultrathin flexible glass, the thickness of the glass thin layer is 0.1mm, and the light transmittance of a visible light region is 97%.
The first polymer liquid crystal composite layer is prepared by mixing the following raw materials: 55g of nematic liquid crystal, 35g of polymerizable monomer mixture, 10g of levorotatory chiral compound mixture and 4.5g of photoinitiator mixture.
The thickness of the first polymer liquid crystal composite layer is 1 mu m.
The nematic liquid crystal has a birefringence of 0.2, a dielectric constant of 25, and a viscosity of 15mm2(s) clearing point of 50 ℃ and threshold voltage V90Is 2V, saturation voltage V10It was 2V and had a water content of 10 ppm.
The polymerizable monomer mixture comprises the following specific raw materials and the following using amounts: 5g of 2-phenoxyethyl acrylate, 5g of trimethylolpropane trimethacrylate, 5g of stearyl methacrylate, 8g of tetraethyleneglycol diacrylate, 3g of 1, 4-bis- [4- (6-acryloyloxyhexyloxy) benzoyloxy ] -2-methylbenzene, and 9g of 2-methyl-1, 4-phenylenebis (4- (((4- (acryloyloxy) butoxy) carbonyl) oxy) benzoic acid.
The levorotatory chiral compound comprises the following specific raw materials in percentage by weight: s5011: 2g, S6N: 3g, S2011: 4g, S811: 1g of the total weight of the composition.
The specific raw materials and the dosage of the photoinitiator mixture are as follows: 0.8g of a, a-dimethoxy-a-phenylacetophenone, 2.5g of bis (2, 6-difluoro-3-pyrrolylphenyltitanocene), and 1.2g of bis (pentafluorophenyl) titanocene.
The second polymer liquid crystal composite layer is prepared by mixing the following raw materials: 55g of nematic liquid crystal, 35g of polymerizable monomer mixture, 10g of dextrorotatory chiral compound mixture and 4.5g of photoinitiator mixture.
The thickness of the second polymer liquid crystal composite layer is 1 mu m.
The nematic liquid crystal has a birefringence of 0.2, a dielectric constant of 25, and a viscosity of 15mm2(s) clearing point of 50 ℃ and threshold voltage V90Is 2V, saturation voltage V1010V, water content 10 ppm.
The polymerizable monomer mixture comprises the following specific raw materials and the following using amounts: 5g of 2-phenoxyethyl acrylate, 5g of trimethylolpropane trimethacrylate, 5g of stearyl methacrylate, 8g of tetraethyleneglycol diacrylate, 3g of 1, 4-bis- [4- (6-acryloyloxyhexyloxy) benzoyloxy ] -2-methylbenzene, and 9g of 2-methyl-1, 4-phenylenebis (4- (((4- (acryloyloxy) butoxy) carbonyl) oxy) benzoic acid.
The right-handed chiral compound comprises the following specific raw materials in parts by weight: r5011: 2g, R6N: 3g, R2011: 4g, R811: 1g of the total weight of the composition.
The photoinitiator mixture consists of one or more of the following photoinitiators, and the specific raw materials and the using amounts are as follows: 1.0g of a, a-dimethoxy-a-phenylacetophenone, 1.5g of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1.2g of ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, and 0.8g of phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide.
The preparation method of the bicolor/double-layer liquid crystal composite film specifically comprises the following steps:
step 1) preparation of ultraviolet-resistant hardened layer
1g of dipentaerythritol pentaacrylate, 1g of dipentaerythritol hexaacrylate, 3g of ditrimethylolpropane tetraacrylate, 1g of 1, 6-hexanediol diglycidyl ether, 2g of tris (2-hydroxyethyl) isocyanurate triacrylate, 1g of trimethylolpropane triacrylate, 1g of pentaerythritol triacrylate, 0.8g of UV-326 and 0.5g of photoinitiator 651, 0.5g of photoinitiator 1173 were mixed, stirred at 300rpm for 30min and then ultrasonically shaken for 20min before being applied uniformly to the non-conductive layer of the first PET film, which was then applied with 15mW/cm at room temperature2Is polymerized for 10min and then dried for 1h at 55 ℃.
Step 2), preparation of TFT layer
Firstly, wiping ultrathin flexible glass with one side coated with ITO by using dust-free cloth with a small amount of acetone solution, then putting the glass into a beaker filled with NaOH solution, carrying out ultrasonic treatment for 30min, taking out the glass, putting the substrate into isopropanol solution, carrying out ultrasonic treatment for 20min again, taking out the substrate again, putting the substrate into deionized water, carrying out ultrasonic treatment for 25min, and drying the substrate at 60 ℃ for 30 min. And secondly, uniformly coating a PVA solution with the concentration of 2.5% on the ITO side of the cleaned ultrathin flexible glass, drying at 60 ℃ for 30min, and repeating the process for 2 times after drying to obtain insulating layers with different deposition layers. Then sputtering the a-IGZO film on the ultrathin flexible glass coated with the insulating layer, wherein the sputtering power is 50W, the sputtering time is 400s, the sputtering pressure is 0.5Pa, the target distance is 10mm, and the back vacuum degree is 6 multiplied by 10-3Pa, and the substrate temperature is 25 ℃. Finally, evaporating the ultrathin flexible glass sputtered with the a-IGZO film to form a metal electrode, putting the mask sheet on the glass, and then putting the glass into a metal cavity for evaporation, wherein the vacuum degree of the metal cavity is 7 multiplied by 10- 3Pa, average evaporation rate of
The thickness of the evaporated electrode was 50 nm.
Step 3) preparation of insulating layer
Dissolving soluble polyimide in an organic solvent, wherein the mass concentration is 7%, uniformly coating the solution on the upper side of a TFT layer after filtering and defoaming processes, and then drying the TFT layer at 70 ℃ for 10 min.
Step 4), preparation of spacer layer
Uniformly coating photoresist on the insulating layer, preheating at 85 ℃ for 3min, placing a mask plate on a substrate, exposing under ultraviolet light for 100s at 55 ℃, removing the mask plate, dripping developing solution on the mask plate, uniformly coating, and finally hardening at 90 ℃ for 3 min.
Step 5) preparation of first layer or second layer Polymer liquid Crystal composite System
Mixing 55g of nematic liquid crystal, 35g of polymerizable monomer mixture, 10g of levorotatory or dextrorotatory chiral compound mixture and 4.5g of photoinitiator mixture, heating to 50 ℃, then oscillating for 15min while hot, then performing ultrasonic treatment for 30min, and repeating for 2 times.
Step 6) preparation of bicolor/double-layer liquid crystal composite film
Uniformly dripping a mixed lower liquid crystal composite system into a middle area of one surface of a partition column of a third interlayer TFT glass layer, uniformly dripping frame sealing glue into an edge area of one surface of the partition column of the three interlayer TFT glass layers, paving a second PET film layer on the lower liquid crystal layer, removing air, and finally utilizing 365nm ultraviolet light with wavelength and 1mW/cm illumination intensity2Irradiating for 10min by using ultraviolet light; secondly, uniformly dripping the mixed upper layer liquid crystal composite system into the middle area of the second layer of PET film, then uniformly dripping the frame sealing glue into the edge area of the second layer of PET film, then paving the first layer of PET film on the upper layer of liquid crystal layer, removing air, and finally utilizing 398nm ultraviolet light with wavelength and 1mW/cm illumination intensity2Irradiating for 10min by using ultraviolet light.
Example 2:
the embodiment provides a bicolor/double-layer liquid crystal composite film which comprises a first PET film, a first polymer liquid crystal composite layer, a second PET film, a second polymer liquid crystal composite layer and a third glass thin layer, wherein the first PET film is coated with an ITO conductive layer on one side, the second PET film is coated with ITO conductive layers on two sides, the second polymer liquid crystal composite layer and the third glass thin layer are sequentially connected from top to bottom, and the single side of the third glass thin layer is provided with an insulating layer and a TFT layer.
The thickness of the first layer of PET film is 180 mu m, the light transmittance is 86%, the transverse thermal shrinkage rate is 3%, the longitudinal thermal shrinkage rate is 3%, the resistance value of the ITO conductive layer is 100 omega, and the light transmittance is 89%.
The upper surface of the first PET film is provided with a hardening layer with an anti-ultraviolet function. The hardness of the cured layer was 10H, and the amount of the ultraviolet absorber UV-405 added was 1.0g in g of the weight of the cured layer.
The thickness of the second layer of PET film is 180 mu m, the light transmittance is 86%, the transverse thermal shrinkage rate is 3%, the longitudinal thermal shrinkage rate is 3%, the resistance value of the ITO conductive layer is 100 omega, the resistance uniformity is plus-minus 50 omega, and the light transmittance is 89%.
The third glass thin layer with the insulating layer and the TFT layer on one side is a spacing column layer, an insulating layer, a TFT layer and a glass thin layer which are sequentially connected from top to bottom.
The spacer column layer has a bottom area of 9 μm2And the height of the column is 30 mu m, and the space between the spaced columns is 1.5 mm.
The insulating layer is polyvinyl alcohol, the thickness is 15 mu m, and the light transmittance is 75%.
The TFT layer is prepared by adopting a 10-layer TFT process, the size of each transistor is (80 mu m) x (80 mu m), the line width of a Gate line is 35 mu m, the line width of a Source line is 35 mu m, and the switching current ratio is 107And a threshold voltage of 10V.
The glass thin layer is made of ultrathin flexible glass, the thickness of the glass thin layer is 5mm, and the light transmittance of a visible light region is 86%.
The first polymer liquid crystal composite layer is prepared by mixing the following raw materials: 95g of nematic liquid crystal, 10g of polymerizable monomer mixture, 30g of levorotatory chiral compound mixture and 0.8g of photoinitiator mixture.
The thickness of the first polymer liquid crystal composite layer is 35 mu m.
The nematic liquid crystal has a birefringence of 0.4, a dielectric constant of 40, and a viscosity of 70mm2(s) clearing point of 100 ℃ and threshold voltage V90Is 12V, saturation voltage V10The water content was 20V and 260 ppm.
The polymerizable monomer mixture comprises the following specific raw materials and the following using amounts: 1g of 2-phenoxyethyl acrylate, 2g of trimethylolpropane trimethacrylate, 2g of stearyl methacrylate, 1g of tetraethyleneglycol diacrylate, 3g of 1, 4-bis- [4- (6-acryloyloxyhexyloxy) benzoyloxy ] -2-methylbenzene, and 1g of 2-methyl-1, 4-phenylenebis (4- (((4- (acryloyloxy) butoxy) carbonyl) oxy) benzoic acid.
The specific raw materials and the dosage of the levorotatory chiral compound are as follows: s5011: 5g, S6N: 6g, S2011: 9g, S811: 10 g.
The specific raw materials and the dosage of the photoinitiator mixture are as follows: 0.3g of a, a-dimethoxy-a-phenylacetophenone, 0.3g of bis (2, 6-difluoro-3-pyrrolylphenyltitanocene), and 0.2g of bis (pentafluorophenyl) titanocene.
The second polymer liquid crystal composite layer is prepared by mixing the following raw materials: 95g of nematic liquid crystal, 10g of polymerizable monomer mixture, 30g of dextrorotatory chiral compound mixture and 0.8g of photoinitiator mixture.
The thickness of the second polymer liquid crystal composite layer is 35 mu m.
The nematic liquid crystal has a birefringence of 0.4, a dielectric constant of 40, and a viscosity of 70mm2(s) clearing point of 100 ℃ and threshold voltage V90Is 20V, saturation voltage V10The water content was 20V and 260 ppm.
The polymerizable monomer mixture comprises the following specific raw materials and the following using amounts: 1g of 2-phenoxyethyl acrylate, 2g of trimethylolpropane trimethacrylate, 2g of stearyl methacrylate, 1g of tetraethyleneglycol diacrylate, 3g of 1, 4-bis- [4- (6-acryloyloxyhexyloxy) benzoyloxy ] -2-methylbenzene, and 1g of 2-methyl-1, 4-phenylenebis (4- (((4- (acryloyloxy) butoxy) carbonyl) oxy) benzoic acid.
The specific raw materials and the dosage of the dextrorotatory chiral compound are as follows: r5011: 5g, R6N: 6g, R2011: 9g, R811: 10 g.
The specific raw materials and the dosage of the photoinitiator mixture are as follows: 0.3g of a, a-dimethoxy-a-phenylacetophenone, 0.1g of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 0.2g of ethyl 2,4, 6-trimethylbenzoylphenylphosphonate and 0.2g of phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide.
The preparation method of the bicolor/double-layer liquid crystal composite film specifically comprises the following steps:
step 1) preparation of ultraviolet-resistant hardened layer
Mixing 10g of dipentaerythritol pentaacrylate, 17g of dipentaerythritol hexaacrylate, 3-18 g of ditrimethylolpropane tetraacrylate, 5g of 1, 6-hexanediol diglycidyl ether, 24g of tris (2-hydroxyethyl) isocyanurate triacrylate, 12g of trimethylolpropane triacrylate, 14g of pentaerythritol triacrylate, 1.0g of UV-405, 3g of photoinitiator 651, and 2g of photoinitiator 1173, stirring at 1100rpm for 50min, ultrasonically oscillating for 60min, uniformly coating the mixture on the non-conductive layer of the first PET film, and coating the obtained wet film with 105mW/cm at room temperature2Is polymerized for 30min and then dried for 5h at 70 ℃.
Step 2), preparation of TFT layer
Firstly, wiping ultrathin flexible glass with one side coated with ITO by using dust-free cloth with a small amount of acetone solution, then putting the glass into a beaker filled with NaOH solution, carrying out ultrasonic treatment for 50min, taking out the glass, putting the substrate into isopropanol solution, carrying out ultrasonic treatment for 40min again, taking out the substrate again, putting the substrate into deionized water, carrying out ultrasonic treatment for 60min, and drying the substrate for 90min at 75 ℃. And secondly, uniformly coating a PVA solution with the concentration of 3.5% on the ITO side of the cleaned ultrathin flexible glass, drying at 80 ℃ for 60min, and repeating the process for 5 times after drying to obtain insulating layers with different deposition layers. Then sputtering the a-IGZO film on the ultrathin flexible glass coated with the insulating layer, wherein the sputtering power is 220W, the sputtering time is 800s, the sputtering pressure is 3.0Pa, the target distance is 70mm, and the back vacuum degree is 3 multiplied by 10-3Pa, and the substrate temperature is 100 ℃. Finally, evaporating the ultrathin flexible glass sputtered with the a-IGZO film to form a metal electrode, putting the mask sheet on the glass, and then putting the glass into a metal cavity for evaporation, wherein the vacuum degree of the metal cavity is 4 multiplied by 10- 3Pa, average evaporation rate of
The thickness of the evaporated electrode was 80 nm.
Step 3) preparation of insulating layer
Dissolving polyvinyl alcohol in deionized water, wherein the mass concentration is 12%, uniformly coating the polyvinyl alcohol on the upper side of the TFT layer after filtration and defoaming processes, and then drying the TFT layer for 25min at 90 ℃.
Step 4), preparation of spacer layer
Uniformly coating photoresist on the insulating layer, preheating at 95 ℃ for 5min, placing a mask plate on a substrate, exposing under ultraviolet light for 180s at 60 ℃, removing the mask plate, dripping developing solution on the mask plate, uniformly coating, and finally hardening at 120 ℃ for 10 min.
Step 5) preparation of first layer or second layer Polymer liquid Crystal composite System
Mixing 95g of nematic liquid crystal, 10g of polymerizable monomer mixture, 30g of levorotatory or dextrorotatory chiral compound mixture and 0.8g of photoinitiator mixture, heating to 65 ℃, then oscillating for 25min while hot, then performing ultrasonic treatment for 45min, and repeating for 3 times.
Step 6) preparation of bicolor/double-layer liquid crystal composite film
Uniformly dripping a mixed lower liquid crystal composite system into a middle area on one surface of a partition column of a third interlayer TFT glass layer, uniformly dripping frame sealing glue into an edge area on one surface of the partition column of the three interlayer TFT glass layers, paving a second PET film layer on the lower liquid crystal layer, removing air, and finally utilizing ultraviolet light with the wavelength of 365nm and the illumination intensity of 1000mW/cm2Ultraviolet light for 35 min; secondly, uniformly dripping the mixed upper layer liquid crystal composite system into the middle area of the second layer of PET film, then uniformly dripping the frame sealing glue into the edge area of the second layer of PET film, then paving the first layer of PET film on the upper layer of liquid crystal layer, removing air, and finally utilizing 398nm ultraviolet light with wavelength and 1000mW/cm illumination intensity2Ultraviolet light for 35 min.
Example 3
The embodiment provides a bicolor/double-layer liquid crystal composite film which comprises a first PET film, a first polymer liquid crystal composite layer, a second PET film, a second polymer liquid crystal composite layer and a third glass thin layer, wherein the first PET film is coated with an ITO conductive layer on one side, the second PET film is coated with ITO conductive layers on two sides, the second polymer liquid crystal composite layer and the third glass thin layer are sequentially connected from top to bottom, and the single side of the third glass thin layer is provided with an insulating layer and a TFT layer.
The thickness of the first layer of PET film is 102.5 mu m, the light transmittance is 91%, the transverse heat shrinkage rate is 1.5%, the longitudinal heat shrinkage rate is 1.5%, the resistance value of the ITO conductive layer is 57.5 omega, and the light transmittance is 92%.
The upper surface of the first PET film is provided with a hardening layer with an anti-ultraviolet function. The hardness of the cured layer was 6.5H, and the amount of the ultraviolet absorber UV-928 in g was 1.2 g.
The thickness of the second layer of PET film is 102.5 mu m, the light transmittance is 91%, the transverse thermal shrinkage rate is 1.5%, the longitudinal thermal shrinkage rate is 1.5%, the resistance value of the ITO conductive layer is 57.5 omega, the resistance uniformity is positive and negative 50 omega, and the light transmittance is 92%.
The third glass thin layer with the insulating layer and the TFT layer on one side is a spacing column layer, an insulating layer, a TFT layer and a glass thin layer which are sequentially connected from top to bottom.
The spacer column layer has a bottom area of 4.65 μm2And the height of the column is 17.5 mu m, and the space between the spaced columns is 0.85 mm.
The insulating layer is made of organic silicon resin, the thickness of the insulating layer is 7.75 mu m, and the light transmittance is 80%.
The TFT layer is prepared by adopting an 8-layer TFT process, the size of each transistor is (40.1 mu m) x (40.1 mu m), the line width of a Gate line is 18 mu m, the line width of a Source line is 18 mu m, and the switching current ratio is 105And a threshold voltage of 55V.
The glass thin layer is made of ultrathin flexible glass, the thickness of the glass thin layer is 2.5mm, and the light transmittance of a visible light region is 91.5%.
The first polymer liquid crystal composite layer is prepared by mixing the following raw materials: 75g of nematic liquid crystal, 25g of polymerizable monomer mixture, 15g of levorotatory chiral compound mixture and 2.0g of photoinitiator mixture.
The thickness of the first polymer liquid crystal composite layer is 18 mu m.
Birefringence of the nematic liquid crystal0.3, a dielectric constant of 32.5 and a viscosity number of 42.5mm2The clearing point is 75 ℃ and the threshold voltage V is90Is 11V, saturation voltage V10The water content was 11V and 135 ppm.
The polymerizable monomer mixture comprises the following specific raw materials and the following using amounts: 2.5g of 2-phenoxyethyl acrylate, 2.5g of trimethylolpropane trimethacrylate, 3g of stearyl methacrylate, 7g of tetraethyleneglycol diacrylate, 8g of 1, 4-bis- [4- (6-acryloyloxyhexyloxy) benzoyloxy ] -2-methylbenzene, and 2g of 2-methyl-1, 4-phenylenebis (4- (((4- (acryloyloxy) butoxy) carbonyl) oxy) benzoic acid.
The specific raw materials and the dosage of the levorotatory chiral compound are as follows: s5011: 2.5g, S6N: 3g, S2011: 4.5g, S811: 5g of the total weight.
The specific raw materials and the dosage of the photoinitiator mixture are as follows: 0.7g of a, a-dimethoxy-a-phenylacetophenone, 0.7g of bis 2, 6-difluoro-3-pyrrolylphenyltitanocene, and 0.6g of bis (pentafluorophenyl) titanocene.
The second polymer liquid crystal composite layer is prepared by mixing the following raw materials: 75g of nematic liquid crystal, 25g of polymerizable monomer mixture, 15g of dextrorotatory chiral compound mixture and 2.0g of photoinitiator mixture.
The thickness of the second polymer liquid crystal composite layer is 18 mu m.
The nematic liquid crystal has a birefringence of 0.3, a dielectric constant of 32.5, and a viscosity of 42.5mm2The clearing point is 75 ℃ and the threshold voltage V is90Is 11V, saturation voltage V10It was 18V and had a water content of 135 ppm.
The polymerizable monomer mixture comprises the following specific raw materials and the following using amounts: 2.5g of 2-phenoxyethyl acrylate, 2.5g of trimethylolpropane trimethacrylate, 3g of stearyl methacrylate, 7g of tetraethyleneglycol diacrylate, 8g of 1, 4-bis- [4- (6-acryloyloxyhexyloxy) benzoyloxy ] -2-methylbenzene, and 2g of 2-methyl-1, 4-phenylenebis (4- (((4- (acryloyloxy) butoxy) carbonyl) oxy) benzoic acid.
The specific raw materials and the dosage of the dextrorotatory chiral compound are as follows: r5011: 2.5g, R6N: 3g, R2011: 4.5g, R811: 5g of the total weight.
The specific raw materials and the dosage of the photoinitiator are as follows: 0.5g of a, a-dimethoxy-a-phenylacetophenone, 0.5g of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 0.5g of ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, and 0.5g of phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide.
The preparation method of the bicolor/double-layer liquid crystal composite film specifically comprises the following steps:
step 1) preparation of ultraviolet-resistant hardened layer
5g of dipentaerythritol pentaacrylate, 8.5g of dipentaerythritol hexaacrylate, 10.5g of ditrimethylolpropane tetraacrylate, 2.5g of 1, 6-hexanediol diglycidyl ether, 13g of tris (2-hydroxyethyl) isocyanurate triacrylate, 6g of trimethylolpropane triacrylate, 7g of pentaerythritol triacrylate and 1.2 of UV-928 and 1.75g of photoinitiator 651, 1.25g of photoinitiator 1173 were mixed, stirred at 700rpm for 40min and then ultrasonically shaken for 40min before being applied uniformly to the non-conductive layer of the first PET film, which was then applied with 60mW/cm at room temperature2Is polymerized for 20min and then dried for 3h at 62.50 ℃.
Step 2), preparation of TFT layer
Firstly, wiping ultrathin flexible glass coated with ITO on one side by using dust-free cloth stained with a small amount of acetone solution, then putting the glass into a beaker filled with NaOH solution, carrying out ultrasonic treatment for 40min, taking out the glass, putting the substrate into isopropanol solution, carrying out ultrasonic treatment for 30min again, taking out the substrate again, putting the substrate into deionized water, carrying out ultrasonic treatment for 42.5min, and drying the substrate for 600min at 67.5 ℃. And secondly, uniformly coating a PVA solution with the concentration of 3% on the ITO side of the cleaned ultrathin flexible glass, drying at 70 ℃ for 45min, and repeating the process for 4 times after drying to obtain insulating layers with different deposition layers. Then sputtering the ultrathin flexible glass coated with the insulating layer with a-IGZO film, wherein the sputtering power is 135W, the sputtering time is 600s, the sputtering pressure is 1.75Pa, the target distance is 40mm, and the back vacuum degree is 4.5 multiplied by 10-3Pa, and the substrate temperature was 62.5 ℃. Finally, evaporating the ultrathin flexible glass sputtered with the a-IGZO film to form a metal electrode, putting a mask sheet on the glass, and putting the glass into a metal cavityEvaporating, wherein the vacuum degree of the metal cavity is 5.5 × 10-3Pa, average evaporation rate of
The thickness of the evaporated electrode was 65 nm.
Step 3) preparation of insulating layer
And (2) uniformly coating the organic silicon resin organic solvent with the mass concentration of 9.5% on the upper side of the TFT layer after filtering and defoaming processes, and then drying the TFT layer at 80 ℃ for 17.5 min.
Step 4), preparation of spacer layer
Uniformly coating photoresist on the insulating layer, preheating at 90 ℃ for 4min, placing a mask plate on a substrate, exposing under ultraviolet light for 140s at the exposure temperature of 57.5 ℃, removing the mask plate, dripping developing solution on the mask plate, uniformly coating, and finally hardening at 105 ℃ for 6.5 min.
Step 5) preparation of first layer or second layer Polymer liquid Crystal composite System
755g of nematic liquid crystal, 25g of polymerizable monomer mixture, 15g of levorotatory or dextrorotatory chiral compound mixture and 2.0g of photoinitiator mixture are mixed, heated to 57.5 ℃, then vibrated for 20min while hot, and then subjected to ultrasound treatment for 37.5min, and the process is repeated for 2 times.
Step 6) preparation of bicolor/double-layer liquid crystal composite film
Uniformly dripping a mixed lower liquid crystal composite system into the middle area of one surface of a partition column of a third interlayer TFT glass layer, uniformly dripping frame sealing glue into the edge area of one surface of the partition column of the three interlayer TFT glass layers, paving a second PET film layer on the lower liquid crystal layer, removing air, and finally utilizing 365nm ultraviolet light with wavelength and 500mW/cm illumination intensity2Irradiating for 22.5min by using ultraviolet light; secondly, uniformly dripping the mixed upper layer liquid crystal composite system to the middle area of the second layer of PET film, then uniformly dripping the frame sealing glue to the edge area of the second layer of PET film, then paving the first layer of PET film on the upper layer of liquid crystal layer, removing air, and finally utilizing the 398nm violet wavelengthExternal light and illumination intensity of 500mW/cm2Irradiating for 22.5min by using ultraviolet light.
Example 4
The embodiment provides a bicolor/double-layer liquid crystal composite film which comprises a first PET film, a first polymer liquid crystal composite layer, a second PET film, a second polymer liquid crystal composite layer and a third glass thin layer, wherein the first PET film is coated with an ITO conductive layer on one side, the second PET film is coated with ITO conductive layers on two sides, the second polymer liquid crystal composite layer and the third glass thin layer are sequentially connected from top to bottom, and the single side of the third glass thin layer is provided with an insulating layer and a TFT layer.
The thickness of the first layer of PET film is 65 μm, the light transmittance is 88%, the transverse heat shrinkage rate is 0.75%, the longitudinal heat shrinkage rate is 0.75%, the resistance value of the ITO conductive layer is 35 omega, and the light transmittance is 90%.
The upper surface of the first PET film is provided with a hardening layer with an anti-ultraviolet function. The hardness of the hardened layer is 5H, ultraviolet absorbers UV-326 and UV-405 are added, and the weight g of the hardened layer is as follows: 0.5g, UV-405: 0.6 g.
The thickness of the second layer of PET film is 65 μm, the light transmittance is 88%, the transverse thermal shrinkage rate is 0.75%, the longitudinal thermal shrinkage rate is 0.75%, the resistance of the ITO conductive layer is 35 Ω, the resistance uniformity is plus-minus 50 Ω, and the light transmittance is 90%.
The third glass thin layer with the insulating layer and the TFT layer on one side is a spacing column layer, an insulating layer, a TFT layer and a glass thin layer which are sequentially connected from top to bottom.
The spacer column layer has a bottom area of 2.0 μm2And the height of the column is 12 mu m, and the spacing between the columns is 0.5 mm.
The insulating layer is phenolic resin, the thickness is 3.5 mu m, and the light transmittance is 78%.
The TFT layer is prepared by adopting a 7-layer TFT process, the size of each transistor is (20 mu m) x (20 mu m), the line width of a Gate line is 9 mu m, the line width of a Source line is 9 mu m, and the switching current ratio is 103And a threshold voltage of 30V.
The glass thin layer is made of ultrathin flexible glass, the thickness of the glass thin layer is 1.2mm, and the light transmittance of a visible light region is 88%.
The first polymer liquid crystal composite layer is prepared by mixing the following raw materials: 65g of nematic liquid crystal, 15g of polymerizable monomer mixture, 20g of levorotatory chiral compound mixture and 1.5g of photoinitiator mixture.
The thickness of the first polymer liquid crystal composite layer is 115 mu m.
The nematic liquid crystal has a birefringence of 0.25, a dielectric constant of 28, and a viscosity of 32mm2(s) clearing point of 62 ℃ and threshold voltage V90Is 6V, saturation voltage V10It was 6V and had a water content of 60 ppm.
The polymerizable monomer mixture comprises the following specific raw materials and the following using amounts: 2g of 2-phenoxyethyl acrylate, 1g of trimethylolpropane trimethacrylate, 3g of stearyl methacrylate, 4g of tetraethyleneglycol diacrylate, 4g of 1, 4-bis- [4- (6-acryloyloxyhexyloxy) benzoyloxy ] -2-methylbenzene, and 1g of 2-methyl-1, 4-phenylenebis (4- (((4- (acryloyloxy) butoxy) carbonyl) oxy) benzoic acid.
The specific raw materials and the dosage of the levorotatory chiral compound are as follows: s5011: 2g, S6N: 1g, S2011: 3g, S811: 14 g.
The specific raw materials and the dosage of the photoinitiator mixture are as follows: 0.3g of a, a-dimethoxy-a-phenylacetophenone, 0.6g of bis (2, 6-difluoro-3-pyrrolylphenyltitanocene), and 0.7g of bis (pentafluorophenyl) titanocene.
The second polymer liquid crystal composite layer is prepared by mixing the following raw materials: 65g of nematic liquid crystal, 15g of polymerizable monomer mixture, 20g of dextrorotatory chiral compound mixture and 1.5g of photoinitiator mixture.
The thickness of the second polymer liquid crystal composite layer is 115 mu m.
The nematic liquid crystal has a birefringence of 0.25, a dielectric constant of 28, and a viscosity of 32mm2(s) clearing point of 62 ℃ and threshold voltage V90Is 6V, saturation voltage V1015V, and the water content was 60 ppm.
The polymerizable monomer mixture comprises the following specific raw materials and the following using amounts: 2g of 2-phenoxyethyl acrylate, 1g of trimethylolpropane trimethacrylate, 3g of stearyl methacrylate, 4g of tetraethyleneglycol diacrylate, 4g of 1, 4-bis- [4- (6-acryloyloxyhexyloxy) benzoyloxy ] -2-methylbenzene, and 1g of 2-methyl-1, 4-phenylenebis (4- (((4- (acryloyloxy) butoxy) carbonyl) oxy) benzoic acid.
The specific raw materials and the dosage of the dextrorotatory chiral compound are as follows: r5011: 2g, R6N: 1g, R2011: 3g, R811: 14 g.
The specific raw materials and the dosage of the photoinitiator mixture are as follows: 0.3g of a, a-dimethoxy-a-phenylacetophenone, 0.4g of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 0.5g of ethyl 2,4, 6-trimethylbenzoylphenylphosphonate and 0.3g of phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide.
The preparation method of the bicolor/double-layer liquid crystal composite film specifically comprises the following steps:
step 1) preparation of ultraviolet-resistant hardened layer
3g of dipentaerythritol pentaacrylate, 6g of dipentaerythritol hexaacrylate, 7g of ditrimethylolpropane tetraacrylate, 2g of 1, 6-hexanediol diglycidyl ether, 8g of tris (2-hydroxyethyl) isocyanurate triacrylate, 3g of trimethylolpropane triacrylate, 4g of pentaerythritol triacrylate, 0.4g of UV-326, 0.6g of UV-405, 0.9g of photoinitiator 651 and 0.8g of photoinitiator 1173 were mixed, stirred at 500rpm for 35min, then shaken ultrasonically for 30min and then applied uniformly to the non-conductive layer of the first PET film, and the resulting wet film was then coated with 38mW/cm at room temperature using a stirrer2Is polymerized for 15min and then dried for 2h at 58 ℃.
Step 2), preparation of TFT layer
Firstly, wiping ultrathin flexible glass coated with ITO on one side by using dust-free cloth stained with a small amount of acetone solution, then putting the glass into a beaker filled with NaOH solution, carrying out ultrasonic treatment for 35min, taking out the glass, putting the substrate into isopropanol solution, carrying out ultrasonic treatment for 25min again, taking out the substrate again, putting the substrate into deionized water, carrying out ultrasonic treatment for 35min, and drying the substrate at 61 ℃ for 45 min. And secondly, uniformly coating a PVA solution with the concentration of 2.7% on the ITO side of the cleaned ultrathin flexible glass, drying at 65 ℃ for 38min, and repeating the process for 3 times after drying to obtain insulating layers with different deposition layers. Then sputtering the ultrathin flexible glass coated with the insulating layer with an a-IGZO film, wherein the sputtering work isThe ratio was 95W, the sputtering time was 500s, the sputtering pressure was 1.1Pa, the target distance was 25mm, and the degree of vacuum of the back side was 4.8X 10-3Pa, and the substrate temperature is 36 ℃. Finally, evaporating the ultrathin flexible glass sputtered with the a-IGZO film to form a metal electrode, putting the mask sheet on the glass, and then putting the glass into a metal cavity for evaporation, wherein the vacuum degree of the metal cavity is 5.9 multiplied by 10-3Pa, average evaporation rate of
The thickness of the evaporated electrode was 62 nm.
Step 3) preparation of insulating layer
Dissolving phenolic resin in an organic solvent, wherein the mass concentration is 8.5%, uniformly coating the phenolic resin on the upper side of a TFT layer after filtering and defoaming processes, and then drying the TFT layer at 75 ℃ for 14.5 min.
Step 4), preparation of spacer layer
Uniformly coating photoresist on the insulating layer, preheating at 87.5 ℃ for 3.5min, placing a mask plate on a substrate, exposing under ultraviolet light for 115s at the exposure temperature of 57 ℃, removing the mask plate, dripping developing solution on the mask plate, uniformly coating, and finally hardening at 98 ℃ for 5 min.
Step 5) preparation of first layer or second layer Polymer liquid Crystal composite System
Mixing 65g of nematic liquid crystal, 15g of polymerizable monomer mixture, 20g of levorotatory or dextrorotatory chiral compound mixture and 1.5g of photoinitiator mixture, heating to 57 ℃, then oscillating for 18min while hot, then performing ultrasonic treatment for 34min, and repeating for 2 times.
Step 6) preparation of bicolor/double-layer liquid crystal composite film
Uniformly dripping a mixed lower liquid crystal composite system into a middle area of one surface of a partition column of a third interlayer TFT glass layer, uniformly dripping frame sealing glue into an edge area of one surface of the partition column of the three interlayer TFT glass layers, paving a second PET film layer on the lower liquid crystal layer, removing air, and finally utilizing 365nm ultraviolet light with wavelength and 225mW/cm illumination intensity2Ultraviolet light irradiation for 17.5min(ii) a Secondly, uniformly dripping the mixed upper layer liquid crystal composite system into the middle area of the second layer of PET film, then uniformly dripping the frame sealing glue into the edge area of the second layer of PET film, then paving the first layer of PET film on the upper layer of liquid crystal layer, removing air, and finally utilizing 398nm ultraviolet light with wavelength and 225mW/cm illumination intensity2Ultraviolet light for 17.5 min.
Example 5
The embodiment provides a bicolor/double-layer liquid crystal composite film which comprises a first PET film, a first polymer liquid crystal composite layer, a second PET film, a second polymer liquid crystal composite layer and a third glass thin layer, wherein the first PET film is coated with an ITO conductive layer on one side, the second PET film is coated with ITO conductive layers on two sides, the second polymer liquid crystal composite layer and the third glass thin layer are sequentially connected from top to bottom, and the single side of the third glass thin layer is provided with an insulating layer and a TFT layer.
The thickness of the first layer of PET film is 150 μm, the light transmittance is 93%, the transverse heat shrinkage rate is 2.4%, the longitudinal heat shrinkage rate is 2.4%, the resistance value of the ITO conductive layer is 82 omega, and the light transmittance is 94%.
The upper surface of the first PET film is provided with a hardening layer with an anti-ultraviolet function. The hardness of the hardened layer is 8H, ultraviolet absorbers UV-326, UV-405 and UV-928 are added, and the weight g number of the hardened layer is UV-326: 0.8g, UV-405: 1.0g, UV-928: 1.2 g.
The thickness of the second layer of PET film is 150 μm, the light transmittance is 93%, the transverse thermal shrinkage rate is 2.4%, the longitudinal thermal shrinkage rate is 2.4%, the resistance of the ITO conductive layer is 82 omega, the resistance uniformity is plus-minus 50 omega, and the light transmittance is 94%.
The third glass thin layer with the insulating layer and the TFT layer on one side is a spacing column layer, an insulating layer, a TFT layer and a glass thin layer which are sequentially connected from top to bottom.
The spacer column layer has a bottom area of 7.5 μm2And the height of the column is 24 mu m, and the spacing between the columns is 1.25 mm.
The insulating layer is polyvinyl alcohol, the thickness is 12.5 mu m, and the light transmittance is 81.5%.
The TFT layer is prepared by adopting a 9-layer TFT process, the size of each transistor is (60 mu m) x (60 mu m), the line width of a Gate line is 27.5 mu m,source line width is 27.5 μm, and on-off current ratio is 106And a threshold voltage of 75V.
The glass thin layer is made of ultrathin flexible glass, the thickness of the glass thin layer is 3.75mm, and the light transmittance of a visible light region is 95%.
The first polymer liquid crystal composite layer is prepared by mixing the following raw materials: 85g of nematic liquid crystal, 25g of polymerizable monomer mixture, 25g of left-handed chiral compound mixture and 4.0g of photoinitiator mixture.
The thickness of the first polymer liquid crystal composite layer is 27.5 mu m.
The nematic liquid crystal has a birefringence of 0.35, a dielectric constant of 37.5, and a viscosity of 58mm2(s) clearing point of 88 deg.C, threshold voltage V90Is 9V, saturation voltage V10It was 17V and had a water content of 220 ppm.
The polymerizable monomer mixture comprises the following specific raw materials and the following using amounts: 3g of 2-phenoxyethyl acrylate, 2g of trimethylolpropane trimethacrylate, 1g of stearyl methacrylate, 7g of tetraethyleneglycol diacrylate, 8g of 1, 4-bis- [4- (6-acryloyloxyhexyloxy) benzoyloxy ] -2-methylbenzene, and 4g of 2-methyl-1, 4-phenylenebis (4- (((4- (acryloyloxy) butoxy) carbonyl) oxy) benzoic acid.
The specific raw materials and the dosage of the levorotatory chiral compound are as follows: s5011: 1g, S6N: 5g, S2011: 3g, S811: 16 g.
The specific raw materials and the dosage of the photoinitiator mixture are as follows: 1.1g of a, a-dimethoxy-a-phenylacetophenone, 2.2g of bis (2, 6-difluoro-3-pyrrolylphenyltitanocene), and 0.7g of bis (pentafluorophenyl) titanocene.
The second polymer liquid crystal composite layer is prepared by mixing the following raw materials: 85g of nematic liquid crystal, 25g of polymerizable monomer mixture, 25g of dextrorotatory chiral compound mixture and 4.0g of photoinitiator mixture.
The thickness of the second polymer liquid crystal composite layer is 27.5 mu m.
The nematic liquid crystal has a birefringence of 0.35, a dielectric constant of 37.5, and a viscosity of 58mm2(s) clearing point of 88 deg.C, threshold voltage V90Is 9V, saturation voltage V10Is at a voltage of 17V and is,the water content was 220 ppm.
The polymerizable monomer mixture comprises the following specific raw materials and the following using amounts: 3g of 2-phenoxyethyl acrylate, 2g of trimethylolpropane trimethacrylate, 1g of stearyl methacrylate, 7g of tetraethyleneglycol diacrylate, 8g of 1, 4-bis- [4- (6-acryloyloxyhexyloxy) benzoyloxy ] -2-methylbenzene, and 4g of 2-methyl-1, 4-phenylenebis (4- (((4- (acryloyloxy) butoxy) carbonyl) oxy) benzoic acid.
The specific raw materials and the dosage of the dextrorotatory chiral compound are as follows: r5011: 1g, R6N: 5g, R2011: 3g, R811: 16 g.
The specific raw materials and the dosage of the photoinitiator mixture are as follows: 0.8g of a, a-dimethoxy-a-phenylacetophenone, 1.0g of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1.6g of ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, and 0.6g of phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide.
The preparation method of the bicolor/double-layer liquid crystal composite film specifically comprises the following steps:
step 1) preparation of ultraviolet-resistant hardened layer
7.5g of dipentaerythritol pentaacrylate, 13.5g of dipentaerythritol hexaacrylate, 14.5g of ditrimethylolpropane tetraacrylate, 4g of 1, 6-hexanediol diglycidyl ether, 19g of tris (2-hydroxyethyl) isocyanurate triacrylate, 10g of trimethylolpropane triacrylate, 11g of pentaerythritol triacrylate and 0.8g of UV-326, 1.0g of UV-405, 1.2 of UV-928 and 2.5g of photoinitiator 651, 1.5g of photoinitiator 1173 were mixed, stirred at 900rpm for 46min first, then shaken ultrasonically for 50min before being applied uniformly to the non-conductive layer of the first PET film, which was then applied with 85mW/cm at room temperature to the non-conductive layer of the first PET film to give a wet film2Was polymerized for 25min and then dried at 66 ℃ for 4 h.
Step 2), preparation of TFT layer
Firstly, wiping ultrathin flexible glass with one side coated with ITO by using dust-free cloth with a small amount of acetone solution, then putting the glass into a beaker filled with NaOH solution, carrying out ultrasonic treatment for 45min, taking out the glass, putting the substrate into isopropanol solution, carrying out ultrasonic treatment for 35min again, taking out the substrate again, and putting the substrate into a beaker filled with NaOH solutionSonicate in deionized water for 48min and dry at 72 for 75 min. And secondly, uniformly coating a PVA solution with the concentration of 3.2% on the ITO side of the cleaned ultrathin flexible glass, drying at 75 ℃ for 52min, and repeating the process for 4 times after drying to obtain insulating layers with different deposition layers. Then sputtering the a-IGZO film on the ultrathin flexible glass coated with the insulating layer, wherein the sputtering power is 190W, the sputtering time is 700s, the sputtering pressure is 2.5Pa, the target distance is 58mm, and the back vacuum degree is 3.8 multiplied by 10-3Pa, and the substrate temperature is 85 ℃. Finally, evaporating the ultrathin flexible glass sputtered with the a-IGZO film to form a metal electrode, putting the mask sheet on the glass, and then putting the glass into a metal cavity for evaporation, wherein the vacuum degree of the metal cavity is 4.7 multiplied by 10- 3Pa, average evaporation rate of
The thickness of the evaporated electrode was 68 nm.
Step 3) preparation of insulating layer
Dissolving polyvinyl alcohol in deionized water, wherein the mass concentration is 10.5%, uniformly coating the solution on the upper side of the TFT layer after filtration and defoaming processes, and then drying the TFT layer at 85 ℃ for 19.5 min.
Step 4), preparation of spacer layer
Uniformly coating photoresist on the insulating layer, preheating at 91.5 ℃ for 4.5min, placing a mask plate on a substrate, exposing under ultraviolet light for 155s at 59 ℃, removing the mask plate, dripping developing solution on the mask plate, uniformly coating, and finally hardening at 110 ℃ for 8.5 min.
Step 5) preparation of first layer or second layer Polymer liquid Crystal composite System
Mixing 85g of nematic liquid crystal, 25g of polymerizable monomer mixture, 25g of left-handed or right-handed chiral compound mixture and 4.0g of photoinitiator mixture, heating to 61.5 ℃, then oscillating for 22.5min while hot, then performing ultrasonic treatment for 41.5min, and repeating for 3 times.
Step 6) preparation of bicolor/double-layer liquid crystal composite film
Firstly, the mixture is mixedUniformly dripping the lower liquid crystal composite system into the middle area of one surface of the partition column of the third interlayer TFT glass layer, then uniformly dripping the frame sealing glue into the edge area of one surface of the partition column of the three interlayer TFT glass layers, paving the second PET film layer on the lower liquid crystal layer, removing air, and finally utilizing 365nm ultraviolet light with wavelength and 775mW/cm illumination intensity2Irradiating for 31.5min by using ultraviolet light; secondly, uniformly dripping the mixed upper layer liquid crystal composite system to the middle area of the second layer of PET film, then uniformly dripping the frame sealing glue to the edge area of the second layer of PET film, then paving the first layer of PET film on the upper layer of liquid crystal layer, removing air, and finally utilizing 398nm ultraviolet light with wavelength and 775mW/cm illumination intensity2The ultraviolet light is used for irradiating for 31.5 min.
Example 6
The embodiment provides a preparation method of a liquid crystal composite film, which comprises the following steps:
step 1), preparation of a hardened layer:
5g of dipentaerythritol pentaacrylate, 10g of dipentaerythritol hexaacrylate, 10g of ditrimethylolpropane tetraacrylate, 3g of 1, 6-hexanediol diglycidyl ether, 10g of tris (2-hydroxyethyl) isocyanurate triacrylate, 5g of trimethylolpropane triacrylate, 7g of pentaerythritol triacrylate and 1.2 of UV-928 and 1g of photoinitiator 651 were mixed and stirred at 700rpm for 40min and then ultrasonically shaken for 40min before being applied uniformly to the non-conductive layer of the first PET film, which was then applied with 50mW/cm at room temperature2Polymerizing for 20min by using ultraviolet light, and drying for 3h at 60 ℃ to obtain the first base layer with the conductive layer and the hardening layer respectively arranged on the two sides.
Step 2), preparation of a TFT layer:
firstly, wiping ultrathin flexible glass with one side coated with ITO by using dust-free cloth with a small amount of acetone solution, then putting the glass into a beaker filled with NaOH solution, carrying out ultrasonic treatment for 40min, taking out the glass, putting the substrate into isopropanol solution, carrying out ultrasonic treatment for 30min again, taking out the substrate again, putting the substrate into deionized water, carrying out ultrasonic treatment for 30min, and drying the substrate for 60min at 70 ℃; then, PVA (polyethylene) was added at a concentration of 3%Enol) solution is evenly coated on one side of the ITO of the cleaned ultrathin flexible glass, the ITO is dried for 45min at 70 ℃, and the process is repeated for 3 times after drying, so that insulating layers with different deposition layers are obtained; then sputtering the ultrathin flexible glass coated with the insulating layer with a-IGZO film, wherein the sputtering power is 100W, the sputtering time is 600s, the sputtering pressure is 2.0Pa, the target distance is 40mm, and the back vacuum degree is 4 multiplied by 10-3Pa, the substrate temperature is 70 ℃; finally, evaporating the ultrathin flexible glass sputtered with the a-IGZO film to form a metal electrode, putting the mask sheet on the glass, and then putting the glass into a metal cavity for evaporation, wherein the vacuum degree of the metal cavity is 5 multiplied by 10-3Pa, average evaporation rate of
The thickness of the evaporated electrode was 70nm, and a second base layer having a TFT layer provided on one side was obtained.
Step 3), preparation of an insulating layer:
dissolving any one of polyimide, polyvinyl alcohol, organic silicon resin and phenolic resin in deionized water or an organic solvent, wherein the mass concentration is 10%, uniformly coating the solution on the upper side of a TFT layer after filtering and defoaming processes, and then drying the TFT layer for 15min at 80 ℃ to obtain the insulating layer.
Step 4), preparing the spacing column layer:
uniformly coating photoresist on the insulating layer obtained in the step 3), preheating at 90 ℃ for 4min, placing a mask plate on a substrate, exposing under ultraviolet light for 140s at 60 ℃, removing the mask plate, dripping developing solution on the mask plate, uniformly coating, and finally hardening at 100 ℃ to obtain the spacer column layer, wherein the developing solution is 6 min.
Step 5), preparing a first layer or a second layer of polymer liquid crystal composite system:
mixing 80g of nematic liquid crystal (same as example 1), 10g of 2-phenoxyethyl acrylate, 6g of R5011 and 4g of bis (pentafluorophenyl) titanocene, heating to 60 ℃, oscillating for 20min while hot, performing ultrasonic treatment for 35min, and repeating for 3 times to obtain a first layer of polymer liquid crystal composite system; 80g of nematic liquid crystal (same as the embodiment 1), 10g of 2-phenoxyethyl acrylate, 6g of S5011 and 4g of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide are mixed, heated to 60 ℃, then vibrated for 20min while hot, and subjected to ultrasonic treatment for 35min, and repeated for 3 times to obtain a second-layer polymer liquid crystal composite system.
Step 6), preparation of the liquid crystal composite film:
uniformly dripping the mixed second-layer polymer liquid crystal composite system into the middle area of one surface of the spacing column layer on the third base layer, uniformly dripping the frame sealing glue into the edge area of one surface of the spacing column layer on the third base layer, paving the second base layer on the second-layer polymer liquid crystal composite system, removing air, and finally utilizing 365nm ultraviolet light with wavelength and 500mW/cm illumination intensity2Irradiating for 20min by using ultraviolet light to form a second polymer liquid crystal composite layer; secondly, uniformly dripping the mixed first layer of polymer liquid crystal composite system to the middle area of a second base layer, then uniformly dripping frame sealing glue to the edge area of the second base layer, then paving a first layer of PET film layer on the first layer of polymer liquid crystal composite system, removing air, and finally utilizing 398nm ultraviolet light with wavelength and illumination intensity of 500mW/cm2Irradiating for 20min by using ultraviolet light to form a first polymer liquid crystal composite layer, and thus obtaining the liquid crystal composite film.
The performance test results of the liquid crystal composite films prepared in the above examples 1 to 5 are shown in the following table 1.
TABLE 1
| Parameter name | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Contrast ratio | 7.9 | 9.7 | 11.5 | 10.3 | 6.9 |
| Reflectivity during writing | 44.8 | 53.9 | 58.7 | 50.6 | 49.5 |
| Response time | 0.87ms | 0.92ms | 0.32ms | 0.72ms | 0.56ms |
| Service life | More than 4 years | More than 5 years | More than 3 years | More than 3 years | More than 4 years |
| Eliminating voltage | 4.7 | 3.6 | 8.7 | 9.5 | 2.5 |
| Temperature range of use | -25～50℃ | -25～50℃ | -25～50℃ | -25～50℃ | -25～50℃ |
| Storage temperature range | -25～60℃ | -25～60℃ | -25～60℃ | -25～60℃ | -25～60℃ |
In addition, in another embodiment of the invention, a liquid crystal writing board is further provided, and the adopted film is the liquid crystal composite film prepared in the embodiment; it should be noted that other structures and circuit designs of the liquid crystal writing board may be the same as those of the liquid crystal writing board in the prior art, which do not belong to the improvement point of the present invention, and therefore, are not described herein again.
In summary, compared with the prior art, the liquid crystal composite film and the preparation method thereof provided by the embodiments of the present invention have the following advantages and effects:
(1) in the embodiment of the invention, the polymerized monomer used in the hardened layer on the first base layer is a monomer with high crosslinking density, high wear resistance, high reactivity and low irritation, the wear resistance and the scratch resistance of the film can be obviously improved after polymerization, and simultaneously, because the ultraviolet resistant agent is added in the layer, the ultraviolet aging resistance of the film is greatly improved, and the service life of the film is prolonged.
(2) The a-IGZO semiconductor material used in the TFT layer in the embodiment of the invention has the characteristics of good conductivity, high film forming quality and the like, can obviously improve the carrier mobility of the TFT and reduce the threshold voltage of the device, compared with the common ITO conductive layer in the market, the TFT device can obviously improve the contrast, brightness and response speed of the film, and can realize the functions of local erasing and one-key erasing of multiple colors by applying a local electric field, thereby greatly improving the service performance of the writing board.
(3) The insulating layer used in the embodiment of the invention has good insulating effect and long service life, and can not only play a role of protecting the TFT layer, but also ensure the uniformity of an applied electric field through uniform coating.
(4) The spacing columns of the spacing column layer used in the embodiment of the invention have good dispersibility, small height difference and stable mechanical property, can effectively ensure the uniform driving voltage of each area, and obviously improve the smoothness of handwriting and the uniformity of power-on display effect during writing.
(5) The raw materials and the proportion of the polymer liquid crystal composite system in the film are the best choices after multiple attempts, so that the effects of high brightness, high reflection wave width and high contrast are achieved, meanwhile, the waste caused by improper use of the raw materials is avoided, and the production cost is saved.
(6) The liquid crystal used in the embodiment of the invention is nematic liquid crystal with low driving voltage and large dielectric constant, on one hand, the low driving voltage can reduce energy loss in the using process and meet the requirement of environmental protection; on the other hand, the large dielectric constant can accelerate the response time of the film and improve the response speed of the tablet.
(7) The polymerizable monomer used in the embodiment of the invention is a polymerization system with polyfunctional group, rigidity and flexibility, so that on one hand, the polymerization effect can be improved, and the polymerization time can be shortened; on the other hand, the stability and flexibility of the polymer network can be increased, and the mechanical property of the film is improved.
(8) According to the invention, the upper and lower layers of polymer liquid crystal composite systems are respectively added with the levorotatory chiral compound, the dextrorotatory chiral compound and the photoinitiator with characteristic absorption wavelength, so that the film can reflect light with different colors, the reflection wave width of the film is increased, and the ultraviolet irradiation with characteristic wavelength can be matched, so that rapid and sufficient polymerization is realized, and the polymerization time is greatly shortened.
(9) The polymerization method used in the embodiment of the invention is a mode of step-by-step irradiation with different wavelengths, so that the polymerization comprehensiveness and uniformity of each layer of polymer liquid crystal composite system are ensured, and the production efficiency of the film is improved.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. The utility model provides a liquid crystal composite film, includes first basic unit and second basic unit, first basic unit is close to one side of second basic unit is equipped with the conducting layer, the both sides of second basic unit all are equipped with the conducting layer, its characterized in that, liquid crystal composite film still includes:
a first polymer liquid crystal composite layer disposed between the first base layer and the second base layer;
the third base layer is provided with an insulating layer and a transistor layer on one side close to the second base layer; and
a second polymer liquid crystal composite layer disposed between the second base layer and the third base layer;
wherein the first polymer liquid crystal composite layer and the second polymer liquid crystal composite layer respectively contain a left-handed chiral compound and a right-handed chiral compound; or the first polymer liquid crystal composite layer and the second polymer liquid crystal composite layer respectively contain a right-handed chiral compound and a left-handed chiral compound.
2. The liquid crystal composite film as claimed in claim 1, wherein the first base layer and the second base layer are polyethylene terephthalate films, and have a thickness of 25-180 μm, a light transmittance of 86-96%, a transverse heat shrinkage rate of 0.05-3%, and a longitudinal heat shrinkage rate of 0.05-3%.
3. The liquid crystal composite film according to claim 1 or 2, wherein a side of the first base layer away from the conductive layer is provided with a hardened layer having an anti-ultraviolet function, the hardened layer has a hardness of 3H to 10H, and the hardened layer contains at least one ultraviolet absorber selected from UV-326, UV-405 and UV-928.
4. The liquid crystal composite film according to claim 1, wherein each conductive layer is independently a tin oxide conductive layer, the resistance of the conductive layer is 15-100 Ω, and the light transmittance is 89-96%.
5. The liquid crystal composite film according to claim 1, wherein the third substrate is a glass layer, and a transistor layer, an insulating layer and a spacer layer are sequentially disposed on one side of the third substrate close to the second substrate; the thickness of the glass layer is 0.1-5 mm, and the light transmittance of the visible light region is 86% -97%.
6. The liquid crystal composite film according to claim 1 or 5, wherein the transistor layer partially or entirely comprises amorphous InGaZn oxide, and each transistor has a size of (0.2-80 μm) x (0.2-80 μm), a Gate line width of 1-35 μm, a Source line width of 1-35 μm, and a switching current ratio of 102~107The threshold voltage is 10-100V; the insulating layer is a film of polyimide, polyvinyl alcohol, organic silicon resin or phenolic resin, the thickness of the insulating layer is 0.5-15 mu m, and the light transmittance is 75-85%.
7. The liquid crystal composite film according to claim 1, wherein the first polymer liquid crystal composite layer comprises the following raw materials in parts by weight: 55-95 parts of nematic liquid crystal, 5-35 parts of polymerizable monomer, 2-30 parts of left-handed chiral compound and 0.8-4.5 parts of first photoinitiator;
the second polymer liquid crystal composite layer comprises the following raw materials in parts by weight: 55-95 parts of nematic liquid crystal, 5-35 parts of polymerizable monomer, 2-30 parts of right-handed chiral compound and 0.8-4.5 parts of second photoinitiator;
the nematic liquid crystal has a birefringence of 0.2 to 0.4, a dielectric constant of 25 to 40, and a viscosity of 15 to 70mm2The clearing point is 50-100 ℃, and the threshold voltage V is902-20V, saturation voltage V102-20V, and the water content is 10-260 ppm;
the polymerizable monomer is at least one of 2-phenoxyethyl acrylate, trimethylolpropane trimethacrylate, stearyl methacrylate, tetraethyleneglycol diacrylate, 1, 4-bis- [4- (6-acryloyloxyhexyloxy) benzoyloxy ] -2-methylbenzene and 2-methyl-1, 4 phenylene bis (4- (((4- (acryloyloxy) butoxy) carbonyl) oxy) benzoic acid;
the levorotatory chiral compound is at least one of S5011, S6N, S2011 and S811;
the dextrorotatory chiral compound is at least one of R5011, R6N, R2011 and R811;
the first photoinitiator is at least one of a, a-dimethoxy-a-phenyl acetophenone, bis-2, 6-difluoro-3-pyrrolylphenyl titanocene and bis (pentafluorophenyl) titanocene;
the second photoinitiator is at least one of a, a-dimethoxy-a-phenylacetophenone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenyl phosphonate and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide.
8. A method for preparing a liquid crystal composite film according to any one of claims 1 to 7, comprising the steps of:
dropwise adding a second polymer liquid crystal composite system comprising a right-handed chiral compound or a left-handed chiral compound onto a third base layer with an insulating layer and a transistor layer arranged on one side, laying a second base layer with conductive layers arranged on both sides on the second polymer liquid crystal composite system, removing air, and curing by ultraviolet irradiation to form a second polymer liquid crystal composite layer between the second base layer and the third base layer;
dropwise adding a first polymer liquid crystal composite system comprising a left-handed chiral compound or a right-handed chiral compound onto a second base layer, laying a first base layer with a conducting layer on one side on the first polymer liquid crystal composite system, removing air, and curing by ultraviolet irradiation to form a first polymer liquid crystal composite layer between the first base layer and the second base layer to obtain the liquid crystal composite film.
9. A liquid crystal composite film produced by the production method as claimed in claim 8.
10. A liquid crystal writing board comprising the liquid crystal composite film according to any one of claims 1 to 7 and 9.
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| CN116199821A (en) * | 2023-01-15 | 2023-06-02 | 西京学院 | Preparation method of liquid crystal material for liquid crystal phased array radar |
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