WO2016201720A1 - 一种液晶垂直取向剂、液晶显示元件以及液晶显示元件的制备方法 - Google Patents

一种液晶垂直取向剂、液晶显示元件以及液晶显示元件的制备方法 Download PDF

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WO2016201720A1
WO2016201720A1 PCT/CN2015/082510 CN2015082510W WO2016201720A1 WO 2016201720 A1 WO2016201720 A1 WO 2016201720A1 CN 2015082510 W CN2015082510 W CN 2015082510W WO 2016201720 A1 WO2016201720 A1 WO 2016201720A1
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liquid crystal
crystal display
carbon
display element
substrate
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PCT/CN2015/082510
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English (en)
French (fr)
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兰松
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深圳市华星光电技术有限公司
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Priority to GB1710848.1A priority Critical patent/GB2549427A/en
Priority to US14/784,727 priority patent/US9963471B2/en
Priority to JP2017540762A priority patent/JP6488396B2/ja
Priority to KR1020177021296A priority patent/KR102015202B1/ko
Publication of WO2016201720A1 publication Critical patent/WO2016201720A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • 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
    • 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
    • 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
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1341—Filling or closing of cells
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/02—Alignment layer characterised by chemical composition
    • 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
    • G02F1/133715—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films by first depositing a monomer
    • 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
    • G02F1/133742—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers for homeotropic alignment
    • 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
    • G02F1/1341—Filling or closing of cells
    • G02F1/13415—Drop filling process

Definitions

  • the present invention relates to the field of liquid crystal display technology, and in particular, to a liquid crystal vertical alignment agent, a liquid crystal display element, and a method for preparing a liquid crystal display element.
  • liquid crystal display technology has rapidly gained popularity with its unique advantages of low power consumption, low radiation, light weight and convenience.
  • liquid crystal displays require a good initial alignment (or initial orientation) of liquid crystal molecules.
  • a liquid crystal alignment film is provided on the surface of the substrate.
  • Vertical alignment (VA) liquid crystal displays are widely used due to their superior performance such as high contrast and fast response time.
  • a conventional vertical alignment liquid crystal display is generally an oriented film of a polyimide (PI) or a polyamic acid film or the like having an alkyl side chain.
  • the commonly used PI oriented film materials are mainly classified into a friction-aligned PI material and a light-aligned PI material.
  • the friction-aligned material is easy to generate dust, static electricity and circuit damage of the liquid crystal display element in the rubbing process; although the optical alignment PI material can avoid static electricity Or dust, but due to the nature of the PI material itself, the heat resistance and aging resistance of the oriented film are poor and the water absorption is high, which is liable to cause deterioration during storage and transportation.
  • the liquid crystal orientation is uneven, and the ability of PI to anchor liquid crystal molecules is also weak, thereby affecting the quality of the panel. More notably, PI materials are more expensive, and the film forming process is more complicated, resulting in higher panel costs.
  • liquid crystal vertical alignment agent a liquid crystal display element, and a method for producing the same, which are inexpensive, stable in performance, and capable of vertically aligning liquid crystal molecules.
  • the first aspect of the present invention provides a liquid crystal vertical alignment agent for replacing the use of an alignment film of polyimide (PI) or the like in the conventional liquid crystal display, and the price of the liquid crystal vertical alignment agent Low cost, stable performance and vertical alignment of liquid crystal molecules.
  • PI polyimide
  • the present invention provides a liquid crystal vertical alignment agent, wherein the molecular formula of the liquid crystal vertical alignment agent is represented by R 2 Si—(OR 1 ) 3 , wherein R 1 is —Si(CH 3 ) 3 , H atom Or an alkyl group having 1 to 5 carbon atoms, and R 2 is a structure of the following formula (E):
  • B 1 is a single bond, -CH 2 - or -(CH 2 ) 2 -, and B 2 is -O-, -COO-*, -OCO-* or -NHCO-*, wherein B 1
  • B 3 is a phenylene group, an alkylene group having 2 to 6 carbon atoms, and a carbon atom having a carbon-carbon double bond or a carbon-carbon triple bond is 3- 8 alkylene
  • B 4 is -O-, -(CO)NH-*, -COO-* or -OCO-*, wherein B 4 has a "*" linkage on the C side and C is a carbon A linear alkyl group having 1 to 10 atoms.
  • the R 1 is -CH 3 , -Si(CH 3 ) 3 or -CH 2 CH 3 .
  • the C is a linear alkyl group having 5 to 8 carbon atoms.
  • the small molecular liquid crystal vertical alignment agent provided by the first aspect of the invention can make the liquid crystal molecules be vertically oriented with respect to the surface of the substrate, and has a strong anchoring effect on the liquid crystal molecules, and can replace the polyacrylamide in the existing liquid crystal display (such as TFT-LCD).
  • An oriented film of an amine (PI) or the like which is inexpensive, has stable properties, and can vertically align liquid crystal molecules.
  • the present invention provides a liquid crystal display element including a liquid crystal display element precursor, the liquid crystal display element precursor including two substrates having a conductive film disposed opposite to each other and disposed between the substrates a liquid crystal medium comprising a liquid crystal vertical alignment agent, a liquid crystal, and a photopolymerizable monomer (abbreviated as RM), wherein the surface of the substrate does not contain a liquid crystal alignment film, and the liquid crystal vertical alignment agent is used in an initial state.
  • RM photopolymerizable monomer
  • the liquid crystal is vertically oriented on a surface of the substrate, and the liquid crystal display element precursor is used to form a liquid crystal display element by irradiating ultraviolet light in a state where a voltage is applied, wherein the liquid crystal vertical alignment agent has a molecular formula of R 2 Si-( OR 1 ) 3 represents that R 1 is -Si(CH 3 ) 3 , H atom or an alkyl group having 1 to 5 carbon atoms, and R 2 is a structure of the following formula (E):
  • B 1 is a single bond, -CH 2 - or -(CH 2 ) 2 -, and B 2 is -O-, -COO-*, -OCO-* or -NHCO-*, wherein B 1
  • B 3 is a phenylene group, an alkylene group having 2 to 6 carbon atoms, and a carbon atom having a carbon-carbon double bond or a carbon-carbon triple bond is 3- 8 alkylene
  • B 4 is -O-, -(CO)NH-*, -COO-* or -OCO-*, wherein B 4 has a "*" linkage on the C side and C is a carbon A linear alkyl group having 1 to 10 atoms.
  • the liquid crystal aligning agent has a mass content of 0.1% to 5% in the liquid crystal medium.
  • the mass fraction of the photopolymerizable monomer RM in the liquid crystal medium is 0.01% to 0.1%.
  • the photopolymerizable monomer RM is or
  • the liquid crystal vertical alignment agent is used to vertically orient the liquid crystal on the surface of the substrate in an initial state before the voltage is applied and ultraviolet light is irradiated, and the initial alignment direction of the entire liquid crystal More consistently, after applying a suitable voltage, the liquid crystal molecules will be deflected, and then, under the irradiation of ultraviolet light of a certain energy, the photopolymerizable monomer RM is polymerized and deposited on the surface of the substrate to reach the anchor liquid crystal molecules ( For the purpose of LC); after the applied voltage is removed, the LC molecules produce a certain pretilt angle to obtain a liquid crystal display element.
  • the liquid crystal display element provided by the second invention of the present invention since the liquid crystal vertical alignment agent is used, the arrangement of the liquid crystal molecules in the vertical direction is relatively uniform and has long-term stability, so that the response speed of the liquid crystal display element is fast and shows good.
  • the electrical properties, transmittance and contrast are excellent in image display performance.
  • the present invention provides a method of fabricating a liquid crystal display device, comprising the steps of:
  • a liquid crystal vertical alignment agent is added to a liquid crystal containing a photopolymerizable monomer to obtain a liquid crystal medium in which a molecular formula of the liquid crystal vertical alignment agent is represented by R 2 Si-(OR 1 ) 3 and R 1 is -Si (CH 3 ) 3 , H atom or an alkyl group having 1 to 5 carbon atoms, and R 2 is a structure of the following formula (E):
  • B 1 is a single bond, -CH 2 - or -(CH 2 ) 2 -, and B 2 is -O-, -COO-*, -OCO-* or -NHCO-*, wherein B 1
  • B 3 is a phenylene group, an alkylene group having 2 to 6 carbon atoms, and a carbon atom having a carbon-carbon double bond or a carbon-carbon triple bond is 3- 8 alkylene
  • B 4 is -O-, -(CO)NH-*, -COO-* or -OCO-*, wherein B 4 has a "*" linkage on the C side and C is a carbon a linear alkyl group having an atomic number of 1-10;
  • the liquid crystal display element precursor is irradiated with ultraviolet light in a state where a voltage is applied to obtain a liquid crystal display element.
  • the liquid crystal medium is injected between the substrates having the conductive film by a liquid crystal dropping (ODF) process.
  • ODF liquid crystal dropping
  • the method for preparing a liquid crystal display element provided by the third aspect of the present invention has the advantages of simple preparation process and strong operability, and replaces the orientation of polyimide (PI) in the existing liquid crystal display element (such as TFT-LCD).
  • the preparation of the film can greatly simplify the preparation process of the liquid crystal display element, reduce the production cost thereof, and improve the display performance of the liquid crystal display element.
  • FIG. 1 is a schematic structural view of a liquid crystal vertical alignment agent in an embodiment of the present invention.
  • FIG. 2 is a schematic view showing a process of preparing a liquid crystal display device according to Embodiment 1 of the present invention, wherein 1 is a CF substrate, the surface of which is the entire surface of the ITO electrode 3, and the substrate 2 on the other side is a TFT substrate, and the surface thereof is A pattern of ITO electrodes, 4 is a liquid crystal, 5 is a photopolymerizable monomer, 6 is a liquid crystal vertical alignment agent, 51 is a polymer formed of a photopolymerizable monomer, and 41 is a formed liquid crystal having a pretilt angle.
  • the present invention provides a liquid crystal vertical alignment agent, wherein the molecular formula of the liquid crystal vertical alignment agent is represented by R 2 Si—(OR 1 ) 3 , wherein R 1 is —Si(CH 3 ) 3 , H atom Or an alkyl group having 1 to 5 carbon atoms, and R 2 is a structure of the following formula (E):
  • B 1 is a single bond, -CH 2 - or -(CH 2 ) 2 -, and B 2 is -O-, -COO-*, -OCO-* or -NHCO-*, wherein B 1
  • B 3 is a phenylene group, an alkylene group having 2 to 6 carbon atoms, and a carbon atom having a carbon-carbon double bond or a carbon-carbon triple bond is 3- 8 alkylene
  • B 4 is -O-, -(CO)NH-*, -COO-* or -OCO-*, wherein B 4 has a "*" linkage on the C side and C is a carbon A linear alkyl group having 1 to 10 atoms.
  • R 1 is a linear or branched alkyl group having 1 to 5 carbon atoms.
  • the R 1 is -CH 3 , -Si(CH 3 ) 3 or -CH 2 CH 3 .
  • the C is a linear alkyl group having 5 to 8 carbon atoms.
  • the liquid crystal vertical alignment agent may have the following structure, but is not limited thereto.
  • the compound represented by the above R 2 Si-(OR 1 ) 3 can be obtained by a method of organic synthesis.
  • the synthesis of the liquid crystal vertical alignment agent of the formula (II) is similar to the synthesis of the liquid crystal vertical alignment agent of the formula (I).
  • the synthesis of the liquid crystal vertical alignment agent of the formula (III) is similar to the synthesis of the liquid crystal vertical alignment agent of the formula (IV).
  • a liquid crystal vertical alignment agent according to a first aspect of the present invention, wherein the liquid crystal vertical alignment agent comprises a head group A, an intermediate group B and a tail group C (as shown in FIG. 1), wherein the head group A is Si (OR 1 ) 3 -, the head group is a polar anchoring group, its main role is to anchor the liquid crystal vertical alignment agent on the surface of the substrate of the liquid crystal display, but the basic mechanism of action may be different due to the difference in the material of the substrate:
  • the role of the ITO conductive film (or electrode) on the substrate is to utilize the lone pair of electrons on the oxygen atoms in the -Si-O- and the indium atoms in the ITO on the substrate surface (external electron arrangement: In:[Kr] 4d 10 5s 2 5p 1 ) or an empty p-orbital or d-orbital hybrid in a tin atom (extra-nuclear electron arrangement: Sn:[Kr]4d 10 5s
  • the role of the head group A is to anchor the surface of the substrate, while the role of the intermediate group B, tail group C is to orient the LC vertical substrate in a steric barrier manner.
  • the small molecular liquid crystal vertical alignment agent provided by the invention can make the liquid crystal molecules be vertically oriented with respect to the surface of the substrate, and has a strong anchoring effect on the liquid crystal molecules, and can replace the polyimide (PI) oriented film in the TFT-LCD, which can be greatly simplified.
  • the preparation process of the TFT-LCD also reduces the production cost of the TFT-LCD and improves the display performance.
  • the present invention provides a liquid crystal display element comprising a liquid crystal display element precursor (liquid crystal display element precursor), the liquid crystal display element precursor comprising two oppositely disposed conductive films a substrate and a liquid crystal medium disposed between the substrates, the liquid crystal medium comprising a liquid crystal vertical alignment agent, a liquid crystal, and a photopolymerizable monomer RM, wherein the surface of the substrate does not contain a liquid crystal alignment film, and the liquid crystal vertical alignment agent is used for The liquid crystal is vertically oriented on the surface of the substrate in an initial state, and the liquid crystal display element precursor is used to irradiate ultraviolet light to form a liquid crystal display element in a state where a voltage is applied, wherein the liquid crystal vertical alignment agent has a molecular formula of R 2 Si-(OR 1 ) 3 represents that R 1 is -Si(CH 3 ) 3 , H atom or an alkyl group having 1 to 5 carbon atoms, and R 2 is a structure of the following formula (E):
  • B 1 is a single bond, -CH 2 - or -(CH 2 ) 2 -, and B 2 is -O-, -COO-*, -OCO-* or -NHCO-*, wherein B 1
  • B 3 is a phenylene group, an alkylene group having 2 to 6 carbon atoms, and a carbon atom having a carbon-carbon double bond or a carbon-carbon triple bond is 3- 8 alkylene
  • B 4 is -O-, -(CO)NH-*, -COO-* or -OCO-*, wherein B 4 has a "*" linkage on the C side and C is a carbon A linear alkyl group having 1 to 10 atoms.
  • R 1 is a linear or branched alkyl group having 1 to 5 carbon atoms.
  • the R 1 is -CH 3 , -Si(CH 3 ) 3 or -CH 2 CH 3 .
  • the C is a linear alkyl group having 5 to 8 carbon atoms.
  • the present invention provides a liquid crystal display element, as shown in FIGS. 2(a) to 2(d), an electrode having a full surface ITO formed on the upper side of the substrate, and an ITO electrode having a pattern formed on the lower side of the substrate (usually It is particularly emphasized that the surface of the two substrates does not contain a PI alignment film, and a liquid crystal medium containing a liquid crystal vertical alignment agent, a liquid crystal, and a photopolymerizable monomer is added between the two substrates.
  • the liquid crystal vertical alignment agent is used for vertically orienting the liquid crystal on the surface of the substrate in an initial state
  • the liquid crystal element of the display element in the state of applying a voltage, causes the LC of different regions to be preset according to an electric field
  • the direction is poured, and then the photopolymerization monomer RM is subjected to ultraviolet photopolymerization under irradiation of ultraviolet light to form a projection having a tilting of the LC, which is deposited on the surface of the substrate to function as an alignment.
  • liquid crystal vertical alignment agents used in the embodiments of the present invention are not polycondensed into polysilanes because the liquid crystal vertical alignment agent is first fixed on the surface of the substrate by a head group or the like, even if UV-irradiated liquid crystals containing double bond groups.
  • the vertical alignment agent cannot form a polysilane because the liquid crystal vertical alignment agent cannot move.
  • the liquid crystal is a nematic liquid crystal.
  • the liquid crystal is a nematic liquid crystal having dielectric anisotropy, and specifically, a dicyanobenzene liquid crystal, a azine liquid crystal, a Schiff base liquid crystal, or an oxidized azo may be used.
  • the mass fraction of the liquid crystal aligning agent in the liquid crystal medium is from 0.1% to 5%.
  • the mass fraction of the photopolymerizable monomer RM in the liquid crystal medium is 0.01% to 0.1%.
  • the photopolymerizable monomer RM is or
  • the substrate is a substrate that is commonly used in the field of liquid crystal display technology, and is not particularly limited as long as it is a substrate having high transparency, and a substrate on which a transparent electrode for driving liquid crystal is formed is preferably formed on the substrate.
  • a glass plate polycarbonate, poly(meth)acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, poly
  • a substrate having a transparent electrode formed on a plastic plate such as olefin, polyethylene terephthalate, (meth)acrylonitrile or cellulose acetate butyrate.
  • a substrate having a line/slit electrode pattern of 1 to 10 ⁇ m on one substrate and a slit pattern or a protrusion pattern on the opposite substrate is used.
  • the steps at the time of production can be simplified, and high transmittance can be obtained.
  • a color filter substrate i.e., a CF substrate
  • an array substrate TFT substrate
  • indium oxide can be used as the transparent electrode substrate provided on one surface - tin oxide (In 2 O 3 -SnO 2) a film made of ITO, conductive tin oxide (SnO 2) made Membrane and the like.
  • the liquid crystal display element precursor after the liquid crystal medium is injected the liquid crystal molecules are vertically aligned on the surface of the substrate, and a voltage is applied between the electrodes of the two substrates of the precursor of the liquid crystal display element, and then irradiated with ultraviolet light.
  • the RM is polymerized to obtain a liquid crystal display element.
  • the applied voltage is 10 to 20 V
  • ultraviolet light (UV) irradiation is performed using a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, etc.
  • the irradiation UV irradiation amount is 0.01 to 1 mW/cm 2 (at a wavelength of 313 nm)
  • it is 0.5 mW/cm 2
  • the UV irradiation time is preferably 80 to 100 s, and after the voltage is removed, it is irradiated with UV light of 0.03 mW/cm 2 for 100 to 120 minutes.
  • the liquid crystal vertical alignment agent is used to vertically orient the liquid crystal on the surface of the substrate in an initial state before the voltage is applied and ultraviolet light is irradiated, and the initial alignment direction of the entire liquid crystal More consistently, after applying a suitable voltage, the liquid crystal molecules will be deflected, and then RM is polymerized and deposited on the surface of the substrate under the irradiation of ultraviolet light of a certain energy to achieve the purpose of anchoring the liquid crystal molecules LC; After the applied voltage is removed, the LC molecules can be made to have a certain pretilt angle to obtain a liquid crystal display element.
  • the liquid crystal vertical alignment agent causes liquid crystal molecules to be vertically aligned on the surface of the substrate.
  • the RM will be irradiated with ultraviolet light.
  • the liquid crystal vertical alignment agent is polymerized to form a polymer network, and the liquid crystal molecules around the polymer network are further anchored; when the liquid crystal vertical alignment agent does not contain a double bond, the ultraviolet light Upon irradiation, polymerization occurs between the RM containing a double bond to form a polymer polymerization network, so that the liquid crystal is generated at a pretilt angle and the response speed is improved.
  • the liquid crystal display element provided by the second invention of the present invention since the liquid crystal vertical alignment agent is used, the arrangement of the liquid crystal molecules in the vertical direction is relatively uniform and has long-term stability, so that the response speed of the liquid crystal display element is fast and shows good.
  • the electrical properties, transmittance and contrast are excellent in image display performance.
  • the present invention provides a method of fabricating a liquid crystal display device, comprising the steps of:
  • a liquid crystal vertical alignment agent is added to a liquid crystal containing a photopolymerizable monomer to obtain a liquid crystal medium, wherein a molecular formula of the liquid crystal vertical alignment agent is represented by R 2 Si-(OR 1 ) 3 and R 1 is -Si (CH 3 ) 3 , H atom or an alkyl group having 1 to 5 carbon atoms, and R 2 is a structure of the following formula (E):
  • B 1 is a single bond, -CH 2 - or -(CH 2 ) 2 -, and B 2 is -O-, -COO-*, -OCO-* or -NHCO-*, wherein B 1
  • B 3 is a phenylene group, an alkylene group having 2 to 6 carbon atoms, and a carbon atom having a carbon-carbon double bond or a carbon-carbon triple bond is 3- 8 alkylene
  • B 4 is -O-, -(CO)NH-*, -COO-* or -OCO-*, wherein B 4 has a "*" linkage on the C side and C is a carbon a linear alkyl group having an atomic number of 1-10;
  • the liquid crystal display element precursor is irradiated with ultraviolet light in a state where a voltage is applied to obtain a liquid crystal display element.
  • R 1 is a linear or branched alkyl group having 1 to 5 carbon atoms.
  • the R 1 is -CH 3 , -Si(CH 3 ) 3 or -CH 2 CH 3 .
  • the C is a linear alkyl group having 5 to 8 carbon atoms.
  • the liquid crystal aligning agent has a mass content of 0.1% to 5% in the liquid crystal medium.
  • the photopolymerizable monomer RM is 0.01% to 0.1% of the mass of the liquid crystal and the photopolymerizable monomer RM.
  • the photopolymerizable monomer RM is or
  • the liquid crystal display device of the present invention can be obtained by a known method. Usually, a pair of substrates not containing a liquid crystal alignment film are placed opposite each other by a spacer, and the peripheral portions of the two substrates are bonded together with a sealant, and the substrate is sealed and sealed. The liquid crystal medium is injected into the gap of the separated container, and the injection hole is closed to form a liquid crystal cell. Then, a polarizing plate was provided on the outer surface of each of the substrates constituting the liquid crystal cell to obtain a liquid crystal display element.
  • sealant for example, an alumina ball-containing epoxy resin or the like as a curing agent and a separator can be used.
  • the method of injecting the liquid crystal medium between the substrates is not particularly limited, and a vacuum method in which a liquid crystal display element is decompressed after the obtained liquid crystal display element is decompressed, a liquid drop method in which liquid crystal is dropped, and a sealing method are used.
  • the liquid crystal medium is injected between the substrates having the conductive film in a liquid crystal dropping (ODF) process.
  • ODF liquid crystal dropping
  • the liquid crystal medium containing the vertical alignment agent and the sealant are successively dropped onto the array substrate or the color filter substrate, and then the array substrate and the color filter substrate are bonded in a precision range of several micrometers under vacuum, and posted.
  • the frame glue is first subjected to UV light irradiation treatment, and then heat curing treatment is performed.
  • liquid crystal molecules are vertically arranged on the substrate surface due to the action of the vertical alignment agent, and the electrodes are applied between the electrodes of the two substrates.
  • the voltage under ultraviolet light, causes a polymerization reaction between RM or between RM and the liquid crystal vertical alignment agent.
  • the applied voltage is 10-20 V
  • ultraviolet (UV) irradiation is performed using a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, etc.
  • the irradiation UV irradiation amount is 0.01 to 1 mW/cm 2 J (at a wavelength of 313 nm). Lower), preferably 0.5 mW/cm 2
  • UV irradiation time is preferably 80 to 120 s, and after removing the voltage, it is irradiated with UV light of 0.03 mW/cm 2 for 100 to 120 minutes.
  • the method for preparing a liquid crystal display element provided by the third aspect of the present invention has the advantages of simple preparation process and high operability, and replaces the polyimide (PI) oriented film in the thin film field effect transistor LCD (TFT-LCD).
  • the preparation can greatly simplify the preparation process of the liquid crystal display element, and also reduce the production cost of the liquid crystal display element, and improve the display performance of the liquid crystal display element.
  • a method for preparing a liquid crystal display element comprising the steps of:
  • a liquid crystal vertical alignment agent represented by the formula (I) is added to a liquid crystal (LC) containing a photopolymerizable monomer RM to obtain a liquid crystal medium, wherein a mass content of the liquid crystal aligning agent in the liquid crystal medium is obtained.
  • LC liquid crystal
  • the mass fraction of the photopolymerizable monomer RM in the liquid crystal medium is 0.05%
  • the structural formula of the photopolymerizable monomer RM is
  • the liquid crystal display element precursor is irradiated with ultraviolet light for 100 s by applying a voltage of 19 V between the electrodes of the two substrates of the display unit precursor, and the energy of the ultraviolet light is 0.5 mW. /cm 2 , after releasing the voltage, it was further irradiated with UV light of 0.03 mW/cm 2 for 120 minutes to obtain a liquid crystal display element TFT-LCD.
  • a schematic structural view of a liquid crystal vertical alignment agent can be represented by FIG. 1, wherein A represents a head group Si (OSi(CH 3 ) 3 ) 3 -, and an intermediate group B is -O-(CH 2 ) 6 -O. -
  • the tail group C is an alkyl group having 6 carbon atoms.
  • the TFT substrate has a SiNx protective film and an ITO conductive film (or referred to as an ITO electrode).
  • the lower TFT substrate has an ITO electrode with a pattern (usually a fishbone type)
  • the CF substrate has an ITO conductive film (or referred to as an ITO electrode).
  • the upper CF substrate has an electrode of the entire surface ITO.
  • the surface of the TFT substrate or the CF substrate does not contain a PI alignment film.
  • step (2) in the initial state, under the action of the liquid crystal vertical alignment agent, the LC molecules are vertically oriented on the surface of the substrate (as shown in Fig. 2(a)).
  • the liquid crystal molecules in different regions are deflected due to the action of the electric field (as shown in FIG. 2(b)), and the LC is preset.
  • the direction of the product is tilted; under the ultraviolet light, the photopolymerization monomer RM undergoes photopolymerization to form a polymer with a leading LC tilt, which is deposited on the surface of the substrate to anchor the LC molecules (Fig. 2(c));
  • the applied voltage is removed and the LC molecules produce a pretilt angle (as shown in Figure 2(d)) to obtain the final liquid crystal display element.
  • a method for preparing a liquid crystal display element comprising the steps of:
  • a liquid crystal vertical alignment agent represented by the formula (III) is added to a liquid crystal (LC) containing a photopolymerizable monomer RM to obtain a liquid crystal medium, wherein a mass content of the liquid crystal alignment agent in the liquid crystal medium is obtained. 0.1%, the mass fraction of the photopolymerizable monomer RM in the liquid crystal medium is 0.01%, and the structural formula of the photopolymerizable monomer RM is
  • the liquid crystal medium is dropped onto the TFT-LCD substrate having the conductive film by ODF (the same as the TFT substrate and the CF substrate of the first embodiment) to obtain a liquid crystal display unit precursor, and the TFT-LCD
  • ODF the same as the TFT substrate and the CF substrate of the first embodiment
  • the liquid crystal display unit is irradiated with ultraviolet light for 80 s by applying a voltage of 19 V between the electrodes of the two substrates of the liquid crystal display unit precursor, and the energy of the ultraviolet light is 1 mW/cm 2 , and the voltage is released.
  • the UV light having an energy of 0.03 mW/cm 2 was irradiated for 110 minutes to obtain a liquid crystal display element TFT-LCD.
  • a method for preparing a liquid crystal display element comprising the steps of:
  • a liquid crystal vertical alignment agent represented by the formula (VI) is added to a liquid crystal (LC) containing a photopolymerizable monomer RM to obtain a liquid crystal medium, wherein a mass content of the liquid crystal aligning agent in the liquid crystal medium is obtained. 5%, the mass fraction of the photopolymerizable monomer RM in the liquid crystal medium is 0.1%, and the structural formula of the photopolymerizable monomer RM is
  • the liquid crystal display element precursor is irradiated with ultraviolet light for 120 s in a state where a voltage of 19 V is applied, and the energy of the ultraviolet light is 0.01 mW. /cm 2 , after releasing the voltage, it was irradiated with UV light of 0.03 mW/cm 2 for 110 min to obtain a liquid crystal display element TFT-LCD.

Abstract

一种液晶垂直取向剂（6），所述液晶垂直取向剂（6）可以使液晶分子（4）相对基板（1，2）表面垂直取向，所述液晶垂直取向剂（6）的价格低廉、性能稳定，对液晶分子（4）的锚定作用较强，可以取代现有液晶显示器中的聚酰亚胺等取向膜，有助于提高液晶显示器的显示性能；还提供了一种液晶显示元件，由于液晶显示元件采用了所述液晶垂直取向剂（6），初始液晶分子（4）在基板（1，2）垂直方向的排列较一致且具有长期稳定性，进而使得液晶显示元件的响应速度快、显示出良好的图像显示性能优异；还提供了一种液晶显示元件的制备方法。

Description

一种液晶垂直取向剂、液晶显示元件以及液晶显示元件的制备方法
本申请要求于2015年06月18日提交中国专利局、申请号为201510341139.7、发明名称为“一种液晶垂直取向剂、液晶显示元件以及液晶显示元件的制备方法”的中国专利申请的优先权，上述在先申请的内容以引入的方式并入本文本中。
技术领域
本发明涉及液晶显示技术领域，尤其涉及一种液晶垂直取向剂、液晶显示元件以及液晶显示元件的制备方法。
背景技术
近年来，液晶显示(LCD)技术以其低功耗、低辐射、轻巧便捷的独特优势迅速得到普及。液晶显示器要获得优质的显像效果，要求液晶分子具有良好的初始排列(或初始取向)。
为了使液晶分子相对基板表面在一定方向上取向，在基板表面设置有液晶取向膜。而垂直取向(VA)液晶显示器因具有较高对比度、快响应时间等优异性能，使得液晶垂直取向技术而被广泛使用。现有的垂直取向液晶显示器通常是以带有烷基侧链的聚酰亚胺(PI)或聚酰胺酸薄膜等作为取向膜。而常用的PI取向膜材料主要分为摩擦配向型PI材料和光配向型PI材料，摩擦配向型材料容易在摩擦工序中产生粉尘、静电及液晶显示元件的电路损坏；光配向PI材料虽然可以避免静电或粉尘，但由于受PI材料自身性质的限制，取向膜的耐热性、耐老化性不佳且吸水性较高，在存储和运送中容易造成变质而导致 液晶取向不均，同时PI锚定液晶分子的能力也较弱，从而影响面板的品质。更值得注意的是，PI材料价格较昂贵，其成膜的工艺也较复杂，导致面板成本提高。
因此，有必要在省去PI取向膜时，提供一种价格低廉、性能稳定且能使液晶分子垂直排列的液晶垂直取向剂、液晶显示元件及其制备方法。
发明内容
有鉴于此，本发明实施例第一方面提供了一种液晶垂直取向剂，用于取代现有的液晶显示器中聚酰亚胺(PI)等取向膜的使用，所述液晶垂直取向剂的价格低廉、性能稳定且能使液晶分子垂直排列。
第一方面，本发明提供了一种液晶垂直取向剂，所述液晶垂直取向剂的分子式用R2Si-(OR1)3表示，其中，R1为-Si(CH3)3、H原子或碳原子数为1-5的烷基，R2为下述式(E)的结构：
-B1-B2-B3-B4-C  (E)，
式(E)中，B1为单键、-CH2-或-(CH2)2-，B2为-O-、-COO-*、-OCO-*或-NHCO-*，其中，B2中带“*”的连接在B3一侧，B3为亚苯基、碳原子数为2-6的亚烷基、含有碳碳双键或碳碳三键的碳原子数为3-8的亚烷基，B4为-O-、-(CO)NH-*、-COO-*或-OCO-*，其中，B4中带“*”的连接在C一侧，C为碳原子数为1-10的直链烷基。
本发明实施方式中，所述R1为-CH3、-Si(CH3)3或-CH2CH3。
本发明实施方式中，所述B3为-C6H4-、碳原子数为2-6的亚烷基、-CH＝CH-或-(CH3)C＝C(CH3)-。
本发明实施方式中，所述C为碳原子数为5-8的直链烷基。
本发明第一方面提供的小分子液晶垂直取向剂，可以使液晶分子相对基板表面垂直取向，对液晶分子的锚定作用较强，可以取代现有液晶显示器(如TFT-LCD)中聚酰亚胺(PI)等取向膜，所述液晶垂直取向剂的价格低廉、性能稳定且能使液晶分子垂直排列。
第二方面，本发明提供了一种液晶显示元件，所述液晶显示元件包括液晶显示元件前体，所述液晶显示元件前体包括相向设置的具有导电膜的两个基板及设置在基板之间的液晶介质，所述液晶介质包含液晶垂直取向剂、液晶、光聚合单体(简称为RM)，其中，所述基板表面不含有液晶取向膜，所述液晶垂直取向剂用于在初始状态下使所述液晶在基板表面垂直取向，所述液晶显示元件前体用于在施加电压的状态下照射紫外光而形成液晶显示元件，其中，所述液晶垂直取向剂的分子式用R2Si-(OR1)3表示，R1为-Si(CH3)3、H原子或碳原子数为1-5的烷基，R2为下述式(E)的结构：
-B1-B2-B3-B4-C  (E)，
式(E)中，B1为单键、-CH2-或-(CH2)2-，B2为-O-、-COO-*、-OCO-*或-NHCO-*，其中，B2中带“*”的连接在B3一侧，B3为亚苯基、碳原子数为2-6的亚烷基、含有碳碳双键或碳碳三键的碳原子数为3-8的亚烷基，B4为-O-、-(CO)NH-*、-COO-*或-OCO-*，其中，B4中带“*”的连接在C一侧，C为碳原子数为1-10的直链烷基。
本发明实施方式中，所述液晶取向剂在所述液晶介质中的质量含量为0.1％-5％。
本发明实施方式中，所述光聚合单体RM在所述液晶介质中的质量分数为0.01％-0.1％。
本发明实施方式中，所述光聚合单体RM为
Figure PCTCN2015082510-appb-000001
或
Figure PCTCN2015082510-appb-000002
本发明第二发明提供的液晶显示元件，在被施加电压和进行紫外光照射前，所述液晶垂直取向剂用于在初始状态下使所述液晶在基板表面垂直取向，整个液晶的初始排列方向较一致，在对其进行施加合适的电压后，液晶分子会发生偏转，之后在一定能量的紫外光的照射下，使得光聚合单体RM聚合后沉积在基板表面，以达到锚定液晶分子(简称LC)的目的；将施加的电压撤去后，LC分子产生一定预倾角，得到液晶显示元件。
本发明第二发明提供的液晶显示元件，由于采用了所述液晶垂直取向剂，使得液晶分子在垂直方向的排列较一致且具有长期稳定性，进而使得液晶显示元件的响应速度快、显示出良好的电性质、透过率和对比度，图像显示性能优异。
第三方面，本发明提供了一种液晶显示元件的制备方法，包括以下步骤：
(1)将液晶垂直取向剂加到含有光聚合单体的液晶中，得到液晶介质，中，所述液晶垂直取向剂的分子式用R2Si-(OR1)3表示，R1为-Si(CH3)3、H原子或碳原子数为1-5的烷基，R2为下述式(E)的结构：
-B1-B2-B3-B4-C  (E)，
式(E)中，B1为单键、-CH2-或-(CH2)2-，B2为-O-、-COO-*、-OCO-*或-NHCO-*，其中，B2中带“*”的连接在B3一侧，B3为亚苯基、碳原子数为2-6的亚烷基、含有碳碳双键或碳碳三键的碳原子数为3-8的亚烷基，B4为-O-、 -(CO)NH-*、-COO-*或-OCO-*，其中，B4中带“*”的连接在C一侧，C为碳原子数为1-10的直链烷基；
(2)将上述液晶介质加入到相向设置的具有导电膜的两个基板之间，得到液晶显示元件前体，其中，所述基板表面不含有液晶取向膜；
(3)在施加电压的状态下，对上述液晶显示元件前体进行照射紫外光，得到液晶显示元件。
本发明实施方式中，步骤(2)中，所述液晶介质以液晶滴下(ODF)工艺注入到具有导电膜的基板之间。
本发明实施例第三方面提供的液晶显示元件的制备方法，所述制备工艺简单、可操作性强，取代了现有液晶显示元件(如TFT-LCD)中聚酰亚胺(PI)等取向膜的制备，可以大大简化液晶显示元件的制备流程，降低了其生产成本，提高了液晶显示元件的显示性能。
附图说明
图1是本发明实施例方式中液晶垂直取向剂的结构示意图；
图2是本发明实施例一所述液晶显示元件的制备过程示意图，其中，1为CF基板，在其表面为整面的ITO电极3，另一侧的基板2为TFT基板，在其表面为一定图案的ITO电极，4为液晶，5为光聚合单体，6为液晶垂直取向剂，51为光聚合单体形成的聚合物，41为形成的带预倾角度的液晶。
具体实施方式
下面结合附图及实施例，对本发明实施例中的技术方案进行清楚、完整地 描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。应当指出，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
第一方面，本发明提供了一种液晶垂直取向剂，所述液晶垂直取向剂的分子式用R2Si-(OR1)3表示，其中，R1为-Si(CH3)3、H原子或碳原子数为1-5的烷基，R2为下述式(E)的结构：
-B1-B2-B3-B4-C  (E)，
式(E)中，B1为单键、-CH2-或-(CH2)2-，B2为-O-、-COO-*、-OCO-*或-NHCO-*，其中，B2中带“*”的连接在B3一侧，B3为亚苯基、碳原子数为2-6的亚烷基、含有碳碳双键或碳碳三键的碳原子数为3-8的亚烷基，B4为-O-、-(CO)NH-*、-COO-*或-OCO-*，其中，B4中带“*”的连接在C一侧，C为碳原子数为1-10的直链烷基。
本发明实施方式中，R1为碳原子数为1-5的直链或支链烷基。
本发明实施方式中，所述R1为-CH3、-Si(CH3)3或-CH2CH3。
本发明实施方式中，所述B3为-C6H4-、碳原子数为2-6的直链亚烷基、-CH＝CH-或-(CH3)C＝C(CH3)-。
本发明优选实施方式中，所述C为碳原子数为5-8的直链烷基。
具体地，液晶垂直取向剂可列举如下的结构，但不限定于此。
Figure PCTCN2015082510-appb-000003
上述R2Si-(OR1)3表示的化合物可以通过有机合成的方法得到。
其中，作为具体的合成例，可列举以下几种R2Si-(OR1)3表示的液晶垂直取向剂的合成路线：
Figure PCTCN2015082510-appb-000004
化合物(I)的具体合成过程如下：
化合物(I)的H1-NMR数据如下：δ(ppm)：0.08(27H)，3.96(2H)，3.56(2H)，3.37(2H)，1.46(2H)，1.29(4H)，1.33(2H)，0.96(3H)。
Figure PCTCN2015082510-appb-000005
本发明实施方式中，如式所示(II)的液晶垂直取向剂的合成与如式(I)所示的液晶垂直取向剂的合成类似。
本发明实施方式中，如式所示(III)的液晶垂直取向剂的合成与如式(IV)所示的液晶垂直取向剂的合成类似。
现提供化合物(IV)的具体合成过程如下：
Figure PCTCN2015082510-appb-000006
化合物(IV)的H1-NMR数据如下：δ(ppm)：0.96(3H)，1.33(2H)，1.29(2H)，1.59(2H)，3.20(2H)，8.0(1H)，8.13(2H)，7.69(2H)，3.55(9H)，3.2(2H)，0.88(2H)；
Figure PCTCN2015082510-appb-000007
化合物(V)的具体合成过程如下：
Figure PCTCN2015082510-appb-000008
化合物(V)的H1-NMR数据如下：δ(ppm)：0.96(3H)，1.33(2H)，1.29(8H)， 1.57(2H)，4.15(2H)，3.55(9H)，8.0(1H)，3.0(2H)，0.84(2H)，7.49(1H)，6.95(1H)；
Figure PCTCN2015082510-appb-000009
化合物(VI)的具体合成过程如下：
Figure PCTCN2015082510-appb-000010
化合物(VI)的H1-NMR数据如下：
Figure PCTCN2015082510-appb-000011
本发明实施例第一方面提供的液晶垂直取向剂，所述液晶垂直取向剂包括头基A、中间基团B和尾部基团C(如附图1所示)，其中，头基A为Si(OR1)3-，头基为极性锚固基团，其主要的作用将液晶垂直取向剂锚固在液晶显示器的基板表面，但因基板材质的不同可能导致其与基本的作用机理不同：①与基板上的ITO导电膜(或称为电极)的作用是利用-Si-O-中氧原子上的孤对电子与基板表面的ITO中的铟原子(核外电子排列：In：[Kr]4d105s25p1)或锡原子(核外电子排列：Sn：[Kr]4d105s25p2)中的空的p轨道或d轨道杂化，以配位键的方式相结合；②与基板上SiNx保护膜的作用机理是利用-Si-O-中的氧原子与SiNx中的氮原子产生分子间作用力；而中间基团和尾部基团的主要作用是类似于PI支链的作用以立体障碍的方式使液晶分子垂直排列。所述液晶垂直取向剂的柔 性尾部基团能够诱导液晶分子长轴垂直于基板排列。
总是，头基A的作用是锚固的基板表面，而中间基团B、尾基C的作用是以立体障碍的方式使得LC垂直基板取向。
本发明提供的小分子液晶垂直取向剂，可以使液晶分子相对基板表面垂直取向，对液晶分子的锚定作用较强，取代TFT-LCD中的聚酰亚胺(PI)取向膜，可以大大简化TFT-LCD的制备流程程，而且还降低了TFT-LCD的生产成本，提高了显示性能。
第二方面，本发明提供了一种液晶显示元件，所述液晶显示元件包括液晶显示元件前体(液晶显示元件前体)，所述液晶显示元件前体包括相向设置的具有导电膜的两个基板及设置在基板之间的液晶介质，所述液晶介质包含液晶垂直取向剂、液晶、光聚合单体RM，其中，所述基板表面不含有液晶取向膜，所述液晶垂直取向剂用于在初始状态下使所述液晶在基板表面垂直取向，所述液晶显示元件前体用于在施加电压的状态下照射紫外光而形成液晶显示元件，，其中，所述液晶垂直取向剂的分子式用R2Si-(OR1)3表示，R1为-Si(CH3)3、H原子或碳原子数为1-5的烷基，R2为下述式(E)的结构：
-B1-B2-B3-B4-C  (E)，
式(E)中，B1为单键、-CH2-或-(CH2)2-，B2为-O-、-COO-*、-OCO-*或-NHCO-*，其中，B2中带“*”的连接在B3一侧，B3为亚苯基、碳原子数为2-6的亚烷基、含有碳碳双键或碳碳三键的碳原子数为3-8的亚烷基，B4为-O-、-(CO)NH-*、-COO-*或-OCO-*，其中，B4中带“*”的连接在C一侧，C为碳原子数为1-10的直链烷基。
本发明实施方式中，R1为碳原子数为1-5的直链或支链烷基。
本发明实施方式中，所述R1为-CH3、-Si(CH3)3或-CH2CH3。
本发明实施方式中，所述B3为-C6H4-、碳原子数为2-6的直链亚烷基、-CH＝CH-或-(CH3)C＝C(CH3)-。
本发明优选实施方式中，所述C为碳原子数为5-8的直链烷基。
本发明提供了一种液晶显示元件如图2(a)～(d)所示，在基板的上侧形成的具有整面ITO的电极，在基板的下侧形成具有一定图案的ITO电极(通常是为鱼骨型)特别强调的是，在两个基板表面不含有PI取向膜，在这两个基板之间添加有液晶介质，所述液晶介质包含液晶垂直取向剂、液晶、光聚合单体RM，其中，液晶垂直取向剂用于在初始状态下使所述液晶在基板表面垂直取向，该显示元件液晶元件在施加电压的状态下，由于电场的作用会使得不同区域的LC朝预先设定的方向倾倒，然后在紫外光的照射下使得光聚合单体RM发生紫外光聚合反应，形成具有引导LC倾倒的凸起物，沉积在基板表面起到配向的作用。
值得注意的是，本发明实施例所用的液晶垂直取向剂之间不会缩聚成聚硅烷，因为液晶垂直取向剂是先通过头基等固定在基板表面，即使UV照射含有双键基团的液晶垂直取向剂，因为液晶垂直取向剂不能移动，因此不可能再形成聚硅烷。
本发明实施方式中，所述液晶为向列型液晶。
本发明优选实施方式中，所述液晶为具有介电各向异性的向列型液晶，具体而言，可以使用二氰基苯类液晶、哒嗪类液晶、席夫碱类液晶、氧化偶氮类液晶、联苯类液晶、苯基环己烷类液晶、嘧啶类液晶、二氧六环类液晶、双环辛烷类液晶、立方烷类液晶等。
本发明实施方式中，所述液晶取向剂在所述液晶介质中的质量分数为0.1％-5％。
本发明实施方式中，所述光聚合单体RM在液晶介质中的质量分数为0.01％-0.1％。
本发明实施方式中，所述光聚合单体RM为
Figure PCTCN2015082510-appb-000012
或
Figure PCTCN2015082510-appb-000013
所述基板为液晶显示技术领域常用的基板，只要是透明性高的基板即可，没有特别限定，优选基板上形成有用于驱动液晶的透明电极的基板。
作为具体例，可例举在玻璃板，聚碳酸酯、聚(甲基)丙烯酸酯、聚醚砜、聚芳酯、聚氨酯、聚砜、聚醚、聚醚酮、三甲基戊烯、聚烯烃、聚对苯二甲酸乙二酯、(甲基)丙烯腈、乙酸丁酸纤维素等塑料板等上形成有透明电极的基板。
优选采用一侧基板上形成1～10μm的线条/狭缝电极图案、在对向基板上未形成狭缝图案或突起图案的结构的基板。通过这样结构的液晶显示元件基板，能够简化制造时的步骤，且能够获得高透射率。
此外，在TFT-LCD中，可使用彩膜基板(即CF基板)和阵列基板(TFT基板)作为基板。
作为基板一面上所设置的透明电极(或者称为透明导电膜)，可以使用氧化铟-氧化锡(In2O3-SnO2)制成的ITO膜、氧化锡(SnO2)制成的导电膜等。
注入了液晶介质后的液晶显示元件前体，液晶分子在基板表面垂直取向，通过对液晶显示元件前体的两基板的电极之间施加电压后，再在紫外光照射 下，使得RM发生聚合反应，得到液晶显示元件。
所施加的电压为10～20V，使用高压汞灯、超高压汞灯、金属卤化物灯等进行紫外光(UV)照射，照射的UV照射量为0.01～1mW/cm2(在波长为313nm下)，优选0.5mW/cm2；UV照射时间优选为80～100s，撤去电压后再用0.03mW/cm2的UV光照射100～120min。
本发明第二发明提供的液晶显示元件，在被施加电压和进行紫外光照射前，所述液晶垂直取向剂用于在初始状态下使所述液晶在基板表面垂直取向，整个液晶的初始排列方向较一致，在对其进行施加合适的电压后，液晶分子会发生偏转，之后在一定能量的紫外光的照射下，使得RM聚合后沉积在基板表面，以达到锚定液晶分子LC的目的；将施加的电压撤去后，可以使LC分子产生一定预倾角，得到液晶显示元件。
具体地，所述液晶垂直取向剂使得液晶分子在基板表面垂直排列，当所述液晶垂直取向剂中含有双键、三键等不饱和键时，在紫外光照射，所述RM会与所述液晶垂直取向剂发生聚合，生成高分子聚合物网络，在该高分子聚合物网络周围的液晶分子会受到其进一步锚定作用；当所述液晶垂直取向剂中不含有双键时，在紫外光照射，所述含有双键的RM之间发生聚合，生成高分子聚合网络，使得液晶产生于预倾角，响应速度提高。
本发明第二发明提供的液晶显示元件，由于采用了所述液晶垂直取向剂，使得液晶分子在垂直方向的排列较一致且具有长期稳定性，进而使得液晶显示元件的响应速度快、显示出良好的电性质、透过率和对比度，图像显示性能优异。
第三方面，本发明提供了一种液晶显示元件的制备方法，包括以下步骤：
(1)将液晶垂直取向剂加到含有光聚合单体的液晶中，得到液晶介质，其中，所述液晶垂直取向剂的分子式用R2Si-(OR1)3表示，R1为-Si(CH3)3、H原子或碳原子数为1-5的烷基，R2为下述式(E)的结构：
-B1-B2-B3-B4-C  (E)，
式(E)中，B1为单键、-CH2-或-(CH2)2-，B2为-O-、-COO-*、-OCO-*或-NHCO-*，其中，B2中带“*”的连接在B3一侧，B3为亚苯基、碳原子数为2-6的亚烷基、含有碳碳双键或碳碳三键的碳原子数为3-8的亚烷基，B4为-O-、-(CO)NH-*、-COO-*或-OCO-*，其中，B4中带“*”的连接在C一侧，C为碳原子数为1-10的直链烷基；
(2)将上述液晶介质加入到相向设置的具有导电膜的两个基板之间，得到液晶显示元件前体，其中，所述基板表面不含有液晶取向膜；
(3)在施加电压的状态下，对上述液晶显示元件前体进行照射紫外光，得到液晶显示元件。
本发明实施方式中，R1为碳原子数为1-5的直链或支链烷基。
本发明实施方式中，所述R1为-CH3、-Si(CH3)3或-CH2CH3。
本发明实施方式中，所述B3为-C6H4-、碳原子数为2-6的直链亚烷基、-CH＝CH-或-(CH3)C＝C(CH3)-。
本发明优选实施方式中，所述C为碳原子数为5-8的直链烷基。
本发明实施方式中，所述液晶取向剂在所述液晶介质中的质量含量为0.1％-5％。
本发明实施方式中，所述光聚合单体RM为所述液晶与所述光聚合单体RM的质量和的0.01％-0.1％。
本发明实施方式中，所述光聚合单体RM为
Figure PCTCN2015082510-appb-000014
或
Figure PCTCN2015082510-appb-000015
通过公知的方法可以得到本发明的液晶显示元件，通常是将不含有液晶取向膜的一对基板通过间隔物相对放置，并将两块基板周边部位用密封剂贴合，向由基板表面和密封剂分割出的盒间隙内注入液晶介质，封闭注入孔，构成液晶盒。然后，在构成液晶盒的各基板外侧面上设置偏振片，制得液晶显示元件。
作为密封剂，可以使用例如作为固化剂和分隔物的含氧化铝球的环氧树脂等。
对往基板之间注入液晶介质的方法没有特别的限定，可例举在对制得的液晶显示元件前体内进行减压后注入液晶的真空法、滴下液晶后进行密封的滴下法等。
本发明优选实施方式中，所述液晶介质以液晶滴下(ODF)工艺注入到具有导电膜的基板之间。
具体地，将上述含有垂直取向剂的液晶介质和框胶先后滴加阵列基板或者彩膜基板上，然后在真空状态下将阵列基板和彩膜基板在数微米的精度范围内进行贴合，贴合好后，要先对框胶进行UV光照射处理后，再进行热固化处理，此时，由于垂直取向剂的作用而使液晶分子在基板表面垂直排列，通过对两基板的电极之间施加电压，在紫外光照射下，使得RM之间或RM与液晶垂直取向剂之间发生聚合反应。
所施加的电压为10-20V，使用高压汞灯、超高压汞灯、金属卤化物灯等进行紫外光(UV)照射，照射的UV照射量为0.01～1mW/cm2J(在波长为313nm下)，优选0.5mW/cm2；UV照射时间优选为80～120s，撤去电压后再用0.03mW/cm2的UV光照射100～120min。
本发明实施例第三方面提供的液晶显示元件的制备方法，所述制备工艺简单、可操作性强，取代了薄膜场效应晶体管LCD(TFT-LCD)中的聚酰亚胺(PI)取向膜的制备，可以大大简化液晶显示元件的的制备流程，而且还降低了液晶显示元件的的生产成本，提高了液晶显示元件的显示性能。
实施例一
一种液晶显示元件的制备方法，包括以下步骤：
(1)将式(I)所示的液晶垂直取向剂加到含有光聚合单体RM的液晶(LC)中，得到液晶介质，其中，所述液晶取向剂在所述液晶介质中的质量含量为1％，所述光聚合单体RM在所述液晶介质中的质量分数为0.05％，所述光聚合单体RM的结构式为
Figure PCTCN2015082510-appb-000016
(2)将上述液晶介质采用ODF工艺滴加到具有ITO导电膜的TFT基板上，并将该基板与另一块具有ITO导电膜的彩膜基板(CF基板)相对放置，并将两块基板周边部位用密封剂贴合，得到液晶显示单元前体，其中，所述两个基板不含PI取向膜；
(3)通过对显示单元前体的两基板的电极之间施加19V电压，在施加19V电压的状态下，对上述液晶显示元件前体进行照射紫外光100s，所述紫外光 的能量为0.5mW/cm2，释放电压后，再用0.03mW/cm2的UV光照射120min，得到液晶显示元件TFT-LCD。
步骤(1)中，液晶垂直取向剂的结构示意图可用图1表示，其中A代表头基Si(OSi(CH3)3)3-，中间基团B为-O-(CH2)6-O-，尾部基团C为碳原子为6的烷基。
步骤(2)中，所述TFT基板具有SiNx保护膜和ITO导电膜(或称为ITO电极)。下侧的TFT基板具有具有一定图案的ITO电极(通常是为鱼骨型)
如本发明所述的，步骤(2)中，所述CF基板具有ITO导电膜(或称为ITO电极)。上层的CF基板具有的整面ITO的电极。
如本发明所述的，TFT基板、CF基板的表面均不含有PI取向膜。
步骤(2)中，初始状态下，在液晶垂直取向剂的作用下，LC分子在基板表面垂直取向(如图2(a)所示)。
步骤(3)中，在对液晶介质的两基板的电极之间施加电压后，由于电场的作用会使得不同区域的液晶分子发生偏转(如图2(b)所示)，LC朝预先设定的方向倾倒；在紫外光照射下，光聚合单体RM发生光聚合反应，，形成具有引导LC倾倒的聚合物，沉积在基板表面，可以锚定LC分子(如图2(c))；最后将施加的电压撤去，LC分子产生预倾角(如图2(d)所示)，得到最终的液晶显示元件。
实施例二
一种液晶显示元件的制备方法，包括以下步骤：
(1)将式(III)所示的液晶垂直取向剂加到含有光聚合单体RM的液晶(LC)中，得到液晶介质，其中，所述液晶取向剂在所述液晶介质中的质量 含量为0.1％，所述光聚合单体RM在所述液晶介质中的质量分数为0.01％，所述光聚合单体RM的结构式为
Figure PCTCN2015082510-appb-000017
(2)将上述液晶介质以ODF的方式滴加到具有导电膜的TFT-LCD基板之间(同实施例1的TFT基板、CF基板)，得到液晶显示单元前体，所述TFT-LCD的两个基板不含PI取向膜；
(3)通过对液晶显示单元前体的两基板的电极之间施加19V电压，对上述液晶显示单元进行照射紫外光80s，所述紫外光的能量为1mW/cm2，释放电压后，再用能量为0.03mW/cm2的UV光照射110min，得到液晶显示元件TFT-LCD。
实施例三
一种液晶显示元件的制备方法，包括以下步骤：
(1)将式(VI)所示的液晶垂直取向剂加到含有光聚合单体RM的液晶(LC)中，得到液晶介质，其中，所述液晶取向剂在所述液晶介质中的质量含量为5％，所述光聚合单体RM在所述液晶介质中的质量分数为0.1％，所述光聚合单体RM的结构式为
Figure PCTCN2015082510-appb-000018
(2)将上述液晶介质以ODF的方式滴加到具有导电膜的TFT基板上，并将该基板与另一块具有导电膜的彩膜基板(即CF基板)相对放置，并将两块基板周边部位用密封剂贴合，得到液晶显示单元前体，所述两个基板不含PI取向膜；
(3)通过对显示单元前体的两基板的电极之间施加19V电压，在施加19V电压的状态下，对上述液晶显示元件前体进行照射紫外光120s，所述紫外光的能量为0.01mW/cm2，释放电压后，再用0.03mW/cm2的UV光照射110min，得到液晶显示元件TFT-LCD。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

  1. 一种液晶 直取向剂，其特征在于，所述液晶 直取向剂的分子式用R2Si-(OR1)3表示，其中，R1为-Si(CH3)3、H原子或碳原子数为1-5的烷基，R2为下述式(E)的结构：
    -B1-B2-B3-B4-C   (E)，
    式(E)中，B1为单键、-CH2-或-(CH2)2-，B2为-O-、-COO-*、-OCO-*或-NHCO-*，其中，B2中带“*”的连接在B3一侧，B3为亚苯基、碳原子数为2-6的亚烷基、含有碳碳双键或碳碳三键的碳原子数为3-8的亚烷基，B4为-O-、-(CO)NH-*、-COO-*或-OCO-*，其中，B4中带“*”的连接在C一侧，C为碳原子数为1-10的直链烷基。
  2. 如权利要求1所述的液晶 直取向剂，其特征在于，所述R1为-CH3、-Si(CH3)3或-CH2CH3。
  3. 如权利要求1所述的液晶 直取向剂，其特征在于，所述B3为-C6H4-、碳原子数为2-6的直链亚烷基、-CH＝CH-或-(CH3)C＝C(CH3)-。
  4. 如权利要求1所述的液晶 直取向剂，其特征在于，所述C为碳原子数为5-8的直链烷基。
  5. 一种液晶显示元件，其特征在于，所述液晶显示元件包括液晶显示元件前体，所述液晶显示元件前体包括相向设置的具有导电膜的两个基板及设置在基板之间的液晶介质，所述液晶介质包含液晶 直取向剂、液晶、光聚合单体，其中，所述基板表面不含有液晶取向膜，所述液晶 直取向剂用于在初始状态下使所述液晶在基板表面 直取向，所述液晶显示元件前体用于在施加电压的状态下照射紫外光而形成液晶显示元件，其中，所述液晶 直取向剂的分 子式所述液晶 直取向剂的分子式用R2Si-(OR1)3表示，R1为-Si(CH3)3、H原子或碳原子数为1-5的烷基，R2为下述式(E)的结构：
    -B1-B2-B3-B4-C   (E)，
    式(E)中，B1为单键、-CH2-或-(CH2)2-，B2为-O-、-COO-*、-OCO-*或-NHCO-*，其中，B2中带“*”的连接在B3一侧，B3为亚苯基、碳原子数为2-6的亚烷基、含有碳碳双键或碳碳三键的碳原子数为3-8的亚烷基，B4为-O-、-(CO)NH-*、或-COO-*，其中，B4中带“*”的连接在C一侧，C为碳原子数为1-10的直链烷基。
  6. 如权利要求5所述的液晶显示元件，其特征在于，所述液晶取向剂在所述液晶介质中的质量含量为0.1％-5％。
  7. 如权利要求5所述的液晶显示元件，其特征在于，所述光聚合单体在所述液晶介质中的质量分数为0.01％-0.1％。
  8. 如权利要求5所述的液晶显示元件，其特征在于，本发明实施方式中，所述光聚合单体为
    Figure PCTCN2015082510-appb-100001
    Figure PCTCN2015082510-appb-100002
  9. 一种液晶显示元件的制备方法，其特征在于，包括以下步骤：
    (1)将液晶 直取向剂加到含有光聚合单体的液晶中，得到液晶介质，其中，所述液晶 直取向剂的分子式用R2Si-(OR1)3表示，R1为-Si(CH3)3、H原子或碳原子数为1-5的烷基，R2为下述式(E)的结构：
    -B1-B2-B3-B4-C   (E)，
    式(E)中，B1为单键、-CH2-或-(CH2)2-，B2为-O-、-COO-*、-OCO-*或-NHCO-*，其中，B2中带“*”的连接在B3一侧，B3为亚苯基、碳原子数为2-6的亚烷基、含有碳碳双键或碳碳三键的碳原子数为3-8的亚烷基，B4为-O-、-(CO)NH-*、-COO-*或-OCO-*，其中，B4中带“*”的连接在C一侧，C为碳原子数为1-10的直链烷基；
    (2)将上述液晶介质加入到相向设置的具有导电膜的两个基板之间，得到液晶显示元件前体，其中，所述基板表面不含有液晶取向膜；
    (3)在施加电压的状态下，对上述液晶显示元件前体进行照射紫外光，得到液晶显示元件。
  10. 如权利要求9所述的液晶显示元件的制备方法，其特征在于，步骤(2)中，所述液晶介质以液晶滴下(ODF)工艺注入到具有导电膜的基板之间。
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Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105647547B (zh) * 2016-01-29 2018-06-05 深圳市华星光电技术有限公司 热敏型交联材料、液晶显示面板的制作方法及液晶显示面板
CN105542796A (zh) * 2016-02-01 2016-05-04 深圳市华星光电技术有限公司 自取向液晶介质组合物及液晶显示面板
CN105936830A (zh) * 2016-04-22 2016-09-14 深圳市华星光电技术有限公司 液晶材料、液晶显示面板的制作方法及液晶显示面板
CN106085464B (zh) * 2016-06-02 2019-01-15 深圳市华星光电技术有限公司 配向膜材料、液晶显示面板的制作方法及液晶显示面板
CN105974683B (zh) * 2016-07-13 2019-09-24 深圳市华星光电技术有限公司 液晶显示面板及其制作方法
CN106753428A (zh) * 2016-12-30 2017-05-31 深圳市华星光电技术有限公司 一种反式pdlc液晶材料组合物、基板及显示器
CN108121116A (zh) * 2017-12-29 2018-06-05 深圳市华星光电半导体显示技术有限公司 一种液晶显示面板的配向方法
CN108485683B (zh) * 2018-05-21 2020-04-28 中节能万润股份有限公司 一种液晶取向剂、液晶取向膜以及液晶显示元件
CN110187565B (zh) * 2019-05-23 2021-11-02 Tcl华星光电技术有限公司 显示器及其制造方法
CN110568645B (zh) * 2019-08-07 2021-07-06 Tcl华星光电技术有限公司 显示面板及显示装置
CN110734771B (zh) 2019-09-27 2022-12-20 江苏三月科技股份有限公司 液晶取向剂、液晶取向膜及液晶显示元件

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007025529A (ja) * 2005-07-21 2007-02-01 Seiko Epson Corp 液晶装置及びその製造方法、並びに電子機器
KR20090059967A (ko) * 2007-12-07 2009-06-11 제일모직주식회사 액정 광배향제, 이를 포함하는 액정 광배향막, 및 이를포함하는 액정 표시 장치
CN101812304A (zh) * 2009-02-19 2010-08-25 Jsr株式会社 液晶取向剂、液晶显示元件及其制造方法
KR101049550B1 (ko) * 2008-09-29 2011-07-14 제일모직주식회사 액정 배향제, 이를 포함하는 액정 배향막, 및 이를 포함하는 액정 표시 장치
CN103064208A (zh) * 2013-01-23 2013-04-24 深圳市华星光电技术有限公司 一种聚合物稳定垂直配向液晶显示面板及液晶显示器
CN103980911A (zh) * 2013-02-07 2014-08-13 Jsr株式会社 液晶取向剂、液晶取向膜以及液晶显示元件及其制造方法

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11125823A (ja) * 1997-10-23 1999-05-11 Matsushita Electric Ind Co Ltd 液晶配向膜とその製造方法およびそれを用いた液晶表示装置とその製造方法
US7070839B2 (en) * 1998-09-16 2006-07-04 Matsushita Electric Industrial Co., Ltd. Functional film, method of fabricating the same, liquid crystal display device using functional film, and method of fabricating the same
JP2000321562A (ja) * 1999-05-12 2000-11-24 Japan Science & Technology Corp リバースモード光スイッチング機能を有する液晶光学装置とその製造方法
JP2002148600A (ja) * 2000-11-14 2002-05-22 Canon Inc 高分子分散型液晶素子及びその製造方法
JP2002148626A (ja) * 2000-11-15 2002-05-22 Chisato Kajiyama 液晶セルおよびその製造方法
JP5078326B2 (ja) * 2005-11-24 2012-11-21 株式会社半導体エネルギー研究所 液晶表示装置の作製方法
WO2009025388A1 (ja) * 2007-08-21 2009-02-26 Jsr Corporation 液晶配向剤、液晶配向膜の製造方法および液晶表示素子
US8865274B2 (en) * 2010-04-02 2014-10-21 Samsung Display Co., Ltd. Liquid crystal display device, alignment film, and methods for manufacturing the same
JP5488146B2 (ja) * 2010-04-08 2014-05-14 大日本印刷株式会社 体積型ホログラム記録用感光性組成物、ｐ偏光回折型偏光分離素子及び液晶体積型ホログラム素子
JP2012058562A (ja) * 2010-09-10 2012-03-22 Seiko Epson Corp 液晶装置、液晶装置の製造方法、及び電子機器
KR101883521B1 (ko) * 2011-05-27 2018-07-30 닛산 가가쿠 고교 가부시키 가이샤 규소계 액정 배향제, 액정 배향막 및 액정 표시 소자
US9234136B2 (en) * 2011-07-07 2016-01-12 Merck Patent Gmbh Liquid-crystalline medium
JP6107661B2 (ja) * 2011-11-17 2017-04-05 日産化学工業株式会社 ケイ素系液晶配向剤、液晶配向膜及び液晶表示素子
JP2015099170A (ja) * 2012-03-05 2015-05-28 シャープ株式会社 液晶表示装置及び液晶表示装置の製造方法
JP6233310B2 (ja) * 2012-08-30 2017-11-22 日産化学工業株式会社 液晶配向処理剤及びそれを用いた液晶表示素子
WO2014073537A1 (ja) * 2012-11-06 2014-05-15 日産化学工業株式会社 液晶配向剤、液晶配向膜及び液晶表示素子
KR101999242B1 (ko) * 2012-11-20 2019-07-11 제이에스알 가부시끼가이샤 액정 배향제, 위상차 필름 및 위상차 필름의 제조 방법
US9726933B2 (en) * 2012-12-17 2017-08-08 Merck Patent Gmbh Liquid-crystal displays and liquid-crystalline media having homeotropic alignment
WO2014196540A1 (ja) * 2013-06-06 2014-12-11 日産化学工業株式会社 アルコキシシラン化合物、液晶配向剤、液晶配向膜及び液晶表示素子
WO2015025911A1 (ja) * 2013-08-21 2015-02-26 日産化学工業株式会社 液晶配向処理剤、液晶配向膜および液晶表示素子

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007025529A (ja) * 2005-07-21 2007-02-01 Seiko Epson Corp 液晶装置及びその製造方法、並びに電子機器
KR20090059967A (ko) * 2007-12-07 2009-06-11 제일모직주식회사 액정 광배향제, 이를 포함하는 액정 광배향막, 및 이를포함하는 액정 표시 장치
KR101049550B1 (ko) * 2008-09-29 2011-07-14 제일모직주식회사 액정 배향제, 이를 포함하는 액정 배향막, 및 이를 포함하는 액정 표시 장치
CN101812304A (zh) * 2009-02-19 2010-08-25 Jsr株式会社 液晶取向剂、液晶显示元件及其制造方法
CN103064208A (zh) * 2013-01-23 2013-04-24 深圳市华星光电技术有限公司 一种聚合物稳定垂直配向液晶显示面板及液晶显示器
CN103980911A (zh) * 2013-02-07 2014-08-13 Jsr株式会社 液晶取向剂、液晶取向膜以及液晶显示元件及其制造方法

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