WO2022095722A1 - 液晶取向剂及其制备方法、液晶取向膜及其制备方法、液晶盒 - Google Patents

液晶取向剂及其制备方法、液晶取向膜及其制备方法、液晶盒 Download PDF

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WO2022095722A1
WO2022095722A1 PCT/CN2021/125583 CN2021125583W WO2022095722A1 WO 2022095722 A1 WO2022095722 A1 WO 2022095722A1 CN 2021125583 W CN2021125583 W CN 2021125583W WO 2022095722 A1 WO2022095722 A1 WO 2022095722A1
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liquid crystal
crystal aligning
aligning agent
agent according
monomer
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PCT/CN2021/125583
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English (en)
French (fr)
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王胜林
黎厚明
苏江华
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深圳市道尔顿电子材料有限公司
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Priority to US17/772,567 priority Critical patent/US11807794B2/en
Publication of WO2022095722A1 publication Critical patent/WO2022095722A1/zh

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • G02F1/133711—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
    • G02F1/133784—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 rubbing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2250/00—Compositions for preparing crystalline polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/12—Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • 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
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G02F1/13392—Gaskets; Spacers; Sealing of cells spacers dispersed on the cell substrate, e.g. spherical particles, microfibres
    • 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
    • G02F2202/00—Materials and properties
    • G02F2202/28—Adhesive materials or arrangements

Definitions

  • the invention relates to the field of liquid crystal alignment agents, in particular to a liquid crystal alignment agent and a preparation method thereof, a liquid crystal alignment film and a preparation method thereof, and a liquid crystal cell.
  • LCD Liquid Crystal Display
  • the existing liquid crystal displays often have the problem of charge accumulation, which further leads to problems such as residual static electricity, static electricity damage, charge accumulation affecting signal transmission speed, image retention, afterimage, and poor reliability under long-term high temperature and high humidity.
  • the purpose of the present invention is to provide a liquid crystal aligning agent and a preparation method thereof, a liquid crystal alignment film and a preparation method thereof, and a liquid crystal cell, so as to solve the problem of charge accumulation of liquid crystal displays.
  • the present invention provides a liquid crystal aligning agent, comprising: a diamine monomer, a dianhydride monomer, a piperazine monomer and a solvent, and the general structural formula of the piperazine monomer is:
  • R represents an amine group or an acid anhydride group.
  • amine group refers to an organic compound in which the hydrogen atom of ammonia is replaced by an alkyl group.
  • Acid anhydride refers to the acid anhydride of an organic acid, a compound formed by the shrinkage of two monobasic acid molecules or one dibasic acid molecule.
  • the piperazine monomer when R is an amino group, the piperazine monomer constitutes a diamine containing a piperazine structure; when R is an acid anhydride group, the piperazine monomer constitutes a dianhydride containing a piperazine structure.
  • the diamine monomer and the dianhydride monomer will react after mixing to generate polyamic acid, so the liquid crystal aligning agent is also a viscous and transparent polyamide. acid solution.
  • the mole ratio of the piperazine monomer to the diamine monomer is 1-100:100;
  • the piperazine monomer includes one or more of the compounds represented by the following structural formula:
  • the diamine monomer includes a first diamine compound and a second diamine compound
  • the first diamine compound includes at least one of the compounds represented by the general formula I or the general formula II:
  • R represents -H or -CH 3 ;
  • the second diamine compound includes at least one of the compounds whose general structural formula is represented by general formula III or general formula IV:
  • the mole number of the first diamine compound accounts for 0.01-99.9% of the total mole number of the diamine monomer, preferably 10-99.9%, more preferably 50-99.9%;
  • the first diamine compound includes one or more of the following compounds:
  • the second diamine compound includes one or more of the following compounds:
  • the function of the first diamine compound is the basis for synthesizing the alignment agent material, so that the liquid crystal cell has basic electrical properties.
  • the function of the second diamine compound provides the alignment agent material with alignment properties, and the alignment agent material obtained after the reaction can align the liquid crystal after rubbing, so that the liquid crystal cell has a certain pretilt angle.
  • the solid content of the liquid crystal aligning agent is 1-10%
  • the molar ratio of the diamine monomer and the dianhydride monomer is (80-100):(80-100), preferably (90-100):(90-100), more preferably 100 : 100;
  • the solvent includes polar aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, m-cresol and tetrahydrofuran one or more of;
  • polar aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, m-cresol and tetrahydrofuran one or more of;
  • the liquid crystal aligning agent further includes a leveling agent, and the leveling agent includes ethyl acetate, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diacetone alcohol, ethylene glycol butyl ether acetate one or more of;
  • the addition amount of the leveling agent in the liquid crystal aligning agent is 0-80 wt %.
  • the present invention also provides a method for preparing the above liquid crystal aligning agent, comprising: mixing and reacting raw materials including the diamine monomer, the dianhydride monomer, the piperazine monomer and the solvent;
  • the temperature conditions of the reaction are -15°C-100°C, preferably 0°C-80°C, more preferably 20°C-60°C;
  • reaction time is 0.5-48 hours, preferably 1-24 hours, more preferably 2-12 hours;
  • the mixing and reaction are carried out in a protective atmosphere; preferably, the protective atmosphere is argon or nitrogen;
  • the solid content of the reacted system is 10-50%, more preferably 12-40%, further preferably 15-30%;
  • the preparation method further comprises: adding a leveling agent to the reacted system;
  • the preparation method further comprises: further adding the solvent to the reaction system to dilute the reaction system;
  • the solid content of the diluted reaction system is 1-10%.
  • the present invention also provides a method for preparing a liquid crystal alignment film, which includes: after the liquid crystal alignment agent is formed into a film and cured, the liquid crystal alignment film is prepared.
  • the film forming includes: coating the liquid crystal aligning agent on a substrate and removing the solvent by baking;
  • the baking temperature is 60-120°C, and the baking time is 10-20 min;
  • the curing includes: performing imidization treatment on the film-formed substrate at a temperature of 200-250°C; preferably, the imidization treatment time is 30-90 minutes;
  • the preparation method further includes: rubbing the cured film.
  • the present invention also provides a liquid crystal alignment film, which is prepared by the above-mentioned preparation method of the liquid crystal alignment film.
  • the present invention also provides a liquid crystal cell, comprising a first substrate and a second substrate disposed opposite to each other and a liquid crystal material disposed between the first substrate and the second substrate; the first substrate and the liquid crystal material
  • the liquid crystal alignment film is provided on the side in contact and the side in which the second substrate is in contact with the liquid crystal material;
  • the first substrate and the second substrate are sealed and connected by adhesive;
  • the adhesive includes light-curing adhesive and/or heat-curing adhesive;
  • spacer particles are mixed in the adhesive; preferably, the particle size of the spacer particles is 1-20 ⁇ m, more preferably 3-20 ⁇ m.
  • the function of the spacer particles is to form a certain gap between the first substrate and the second substrate to accommodate the liquid crystal material.
  • the first substrate and the second substrate are both ITO glass substrates.
  • liquid crystal aligning agent by adding piperazine monomer to the liquid crystal aligning agent, the volume resistance and surface resistance of the liquid crystal aligning agent material can be reduced, the ability of the aligning agent material to release residual charges can be effectively improved, and the reliability and stability of electronic products can be improved.
  • the liquid crystal cell using the liquid crystal aligning agent of the present invention has the advantages of high voltage holding ratio (VHR), low residual voltage (RDC) and the like.
  • the liquid crystal aligning agent of the present invention can be applied to various types of liquid crystal displays such as TN type (twisted nematic type) and VA type (vertical alignment type).
  • TN type twisted nematic type
  • VA type vertical alignment type
  • compositions, step, method, article or device comprising the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such composition, step, method, article or device elements.
  • Part by weight refers to a basic unit of measurement that represents the mass ratio relationship of multiple components, and 1 part can represent any unit mass, such as 1 g, 2.689 g, and the like. If we say that the weight part of the A component is a part, and the weight part of the B component is b part, it means the ratio of the mass of the A component to the mass of the B component a:b. Or, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number, representing a multiplier factor). Unmistakably, unlike parts by weight, the sum of parts by weight of all components is not limited to a limit of 100 parts.
  • a and/or B includes (A and B) and (A or B).
  • CBDA CBDA
  • DA-3 3,3-(1,4piperazinediyl)diphthalic anhydride, the structural formula is:
  • DN-1 p-phenylenediamine, the structural formula is:
  • DN-2 2,4-diaminobenzene octadecyl ether, the structural formula is:
  • DN-3 Dihydrocholesterol 3,5 diaminobenzoate, the structural formula is:
  • DN-4 1,4-bis(4-aminophenyl)piperazine, the structural formula is:
  • DN-5 1,4-bis(3-methyl-5aminocyclohexyl)piperazine, the structural formula is:
  • the polyamic acid liquid crystal aligning agent solution prepared according to the above preparation method is evenly spin-coated on the clean ITO glass, and then the ITO glass substrate is sequentially pre-baked at a temperature of 60-120°C for 10-20min, and then heated at a temperature of 200-250°C.
  • the polyimide film on the ITO glass substrate is rubbed with a rubbing machine, and the rubbing angle is 45° to obtain a liquid crystal alignment film coated on the ITO glass substrate.
  • the polyamic acid liquid crystal aligning agent solution prepared according to the above preparation method is evenly spin-coated on the clean ITO glass, and then the ITO glass substrate is sequentially pre-baked at a temperature of 60-120°C for 10-20min, and then heated at a temperature of 200-250°C.
  • the polyimide film on the ITO glass substrate is rubbed with a rubbing machine, and the rubbing angle is 45° to obtain a liquid crystal alignment film coated on the ITO glass substrate.
  • the polyamic acid liquid crystal aligning agent solution prepared according to the above preparation method is evenly spin-coated on the clean ITO glass, and then the ITO glass substrate is sequentially pre-baked at a temperature of 60-120°C for 10-20min, and then heated at a temperature of 200-250°C. °C of imidization treatment for 30-90min, and then rubbing the polyimide film on the ITO glass substrate with a rubbing machine, the rubbing angle is 0°, that is, a liquid crystal alignment film coated on the ITO glass substrate is obtained.
  • the polyamic acid liquid crystal aligning agent solution prepared according to the above preparation method is evenly spin-coated on the clean ITO glass, and then the ITO glass substrate is sequentially pre-baked at a temperature of 60-120°C for 10-20min, and then heated at a temperature of 200-250°C. °C of imidization treatment for 30-90min, and then rubbing the polyimide film on the ITO glass substrate with a rubbing machine, the rubbing angle is 0°, that is, a liquid crystal alignment film coated on the ITO glass substrate is obtained.
  • the polyamic acid liquid crystal aligning agent solution prepared according to the above preparation method is evenly spin-coated on the clean ITO glass, and then the ITO glass substrate is sequentially pre-baked at a temperature of 60-120°C for 10-20min, and then heated at a temperature of 200-250°C.
  • the polyimide film on the ITO glass substrate is rubbed with a rubbing machine, and the rubbing angle is 45° to obtain a liquid crystal alignment film coated on the ITO glass substrate.
  • DN-1 9.72 g (0.09 mol), DN-2 3.76 (0.01 mol) and NMP 89.9 g were sequentially added, and stirred at room temperature for 30 minutes to confirm complete dissolution.
  • 13.72 g (0.07 mol) of DA-1 and 11.34 g (0.03 mol) of DA-3 were added successively, and the reaction was stirred at room temperature for 3 hours, and the solid content of the reaction was 30%.
  • the polyamic acid liquid crystal aligning agent solution prepared according to the above preparation method is evenly spin-coated on the clean ITO glass, and then the ITO glass substrate is sequentially pre-baked at a temperature of 60-120°C for 10-20min, and then heated at a temperature of 200-250°C.
  • the polyimide film on the ITO glass substrate is rubbed with a rubbing machine, and the rubbing angle is 45° to obtain a liquid crystal alignment film coated on the ITO glass substrate.
  • the polyamic acid liquid crystal aligning agent solution prepared according to the above preparation method is evenly spin-coated on the clean ITO glass, and then the ITO glass substrate is sequentially pre-baked at a temperature of 60-120°C for 10-20min, and then heated at a temperature of 200-250°C. °C of imidization treatment for 30-90min, and then rubbing the polyimide film on the ITO glass substrate with a rubbing machine, the rubbing angle is 0°, that is, a liquid crystal alignment film coated on the ITO glass substrate is obtained.
  • the polyamic acid liquid crystal aligning agent solution prepared according to the above preparation method is evenly spin-coated on the clean ITO glass, and then the ITO glass substrate is sequentially pre-baked at a temperature of 60-120°C for 10-20min, and then heated at a temperature of 200-250°C. °C of imidization treatment for 30-90min, and then rubbing the polyimide film on the ITO glass substrate with a rubbing machine, the rubbing angle is 0°, that is, a liquid crystal alignment film coated on the ITO glass substrate is obtained.
  • the polyamic acid liquid crystal aligning agent solution prepared by the above preparation method is evenly spin-coated on the clean ITO glass, and then the ITO glass substrate is sequentially pre-baked at a temperature of 60-120°C for 10-20min, and then heated at a temperature of 200-250°C. °C of imidization treatment for 30 to 90 minutes, and then rubbing the polyimide film on the ITO glass substrate with a rubbing machine at a rubbing angle of 45° to obtain a liquid crystal alignment film coated on the ITO glass substrate.
  • thermosetting glue containing 4 ⁇ m spacer particles, so that the rubbing surfaces of the two substrates were opposite and the rubbing directions were orthogonal, and the liquid crystal was poured into the box.
  • the light-curing glue is sealed to obtain a liquid crystal cell.
  • the polyamic acid liquid crystal aligning agent solution prepared according to the above preparation method is evenly spin-coated on the clean ITO glass, and then the ITO glass substrate is sequentially pre-baked at a temperature of 60-120°C for 10-20min, and then heated at a temperature of 200-250°C.
  • the polyimide film on the ITO glass substrate is rubbed with a rubbing machine, and the rubbing angle is 45° to obtain a liquid crystal alignment film coated on the ITO glass substrate.
  • VHR measurement conditions voltage 5V, pulse width 60 ⁇ s/frame, period 1667ms, measurement temperature 60°C;
  • RDC measurement conditions voltage 5V, charging time 2400sec, measurement time 1200sec, measurement temperature 60°C.
  • Test equipment Shintech Optitro-STD (3STN11);
  • Test wavelength 591.4nm
  • Test mode TN/VA mode.
  • Test equipment electrometer/high resistance meter (KEYSIGHT B2985A), sample thickness 5-50 microns, effective area 30-60 cm 2 , test parameters: voltage measurement range 1 ⁇ V-20V, 0.01fA measurement resolution, 2000 readings/s.

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Abstract

本发明提供一种液晶取向剂及其制备方法、液晶取向膜及其制备方法、液晶盒，涉及液晶取向剂领域。本发明通过在液晶取向剂中添加哌嗪单体，能够降低液晶取向剂材料的体阻值与面阻值，有效提升取向剂材料释放残余电荷的能力，进而提高电子产品的可靠性及稳定性。采用本发明液晶取向剂的液晶盒具有高电压保持率、低残留电压等优点。

Description

液晶取向剂及其制备方法、液晶取向膜及其制备方法、液晶盒 技术领域
本发明涉及液晶取向剂领域，尤其涉及一种液晶取向剂及其制备方法、液晶取向膜及其制备方法、液晶盒。
背景技术
随着显示技术的发展，液晶显示器(Liquid Crystal Display，LCD)因具有高画质、省电、机身薄及应用范围广等优点，而被广泛的应用于手机、电视、个人数字助理、数字相机、笔记本电脑、台式计算机等各种消费性电子产品，成为显示装置中的主流。
然而，现有的液晶显示器多存在电荷蓄积的问题，进而导致静电残留、静电击伤、电荷聚积影响讯号传输速度、影像暂留、残像、长时间高温高湿信赖性不佳等问题。
发明内容
本发明的目的在于提供一种液晶取向剂及其制备方法、液晶取向膜及其制备方法、液晶盒，以解决液晶显示器的电荷蓄积问题。
为实现以上目的，本发明提供一种液晶取向剂，包括：二胺单体、二酐单体、哌嗪单体以及溶剂，所述哌嗪单体的结构通式为：
Figure PCTCN2021125583-appb-000001
其中，R表示胺基基团或者酸酐基团。
可以理解的是，胺基指的是氨的氢原子被烷基代替后的有机化合物。酸酐指的是有机酸的酸酐，由两个一元酸分子或一个二元酸分子缩水而成的化合物。
可以理解的是，R为胺基基团时，哌嗪单体即构成了含哌嗪结构的二胺；R为酸酐基团时，哌嗪单体即构成了含哌嗪结构的二酐。
可以理解的是，所述液晶取向剂中，二胺单体与二酐单体混合后会发生反应，生成聚酰胺酸，因此所述液晶取向剂也即为一种粘稠透明聚酰聚酰胺酸溶液。
本发明一些实施例中，所述哌嗪单体与所述二胺单体的摩尔数之比为1～100：100；
优选的，所述哌嗪单体包括下述结构式所示的化合物中的一种或多种：
Figure PCTCN2021125583-appb-000002
本发明一些实施例中，所述二胺单体包括第一二胺化合物和第二二胺化合物；
所述第一二胺化合物包括结构通式为通式Ⅰ或通式Ⅱ所示的化合物中的至少一种：
Figure PCTCN2021125583-appb-000003
通式Ⅰ中，A表示化学键、烷基链C nH 2n，n＝1-20、-O-、-NH-、-S-或-SO 2-，R表示-H或者-CH 3；
Figure PCTCN2021125583-appb-000004
通式Ⅱ中，R表示-H或者-CH 3；
所述第二二胺化合物包括结构通式为通式Ⅲ或通式Ⅳ所示的化合物中的至少一种：
Figure PCTCN2021125583-appb-000005
通式Ⅲ中，R表示烷基链C nH (2n+1)，n＝1-50；
Figure PCTCN2021125583-appb-000006
通式Ⅳ中，R表示烷基链C nH (2n+1)，n＝1-50。
本发明一些实施例中，所述第一二胺化合物的摩尔数占所述二胺单体 的总摩尔数的0.01-99.9％，优选为10-99.9％，更优选为50-99.9％；
优选的，所述第一二胺化合物包括以下化合物中的一种或多种：
Figure PCTCN2021125583-appb-000007
优选的，所述第二二胺化合物包括以下化合物中的一种或多种：
Figure PCTCN2021125583-appb-000008
第一二胺化合物的作用为合成该取向剂材料的基础，使得液晶盒有基本的电性能。第二二胺化合物的作用为该取向剂材料提供取向性能，反应后得到的取向剂材料经摩擦后能对液晶取向，使得液晶盒有一定的预倾角。
本发明一些实施例中，所述液晶取向剂的固含量为1-10％；
优选的，所述二胺单体和所述二酐单体的摩尔比为(80-100)：(80-100)，优选为(90-100)：(90-100)，更优选为100：100；
优选的，所述溶剂包括N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮、间甲酚及四氢呋喃等极性非质子溶剂中的一种或多种；
优选的，所述液晶取向剂还包括流平剂，所述流平剂包括乙酸乙酯、乙二醇单丁醚、二乙二醇二乙醚、二丙酮醇、乙二醇丁醚乙酸酯中的一种或多种；
优选的，所述流平剂在所述液晶取向剂中的添加量为0-80wt％。
本发明还提供一种上述液晶取向剂的制备方法，包括：将包括所述二胺单体、所述二酐单体、所述哌嗪单体以及所述溶剂在内的原料混合后反应；
可选的，所述反应的温度条件为-15℃-100℃，优选为0℃-80℃，更优选为20℃-60℃；
可选的，所述反应的时间为0.5-48小时，优选为1-24小时，更优选为2-12小时；
优选的，所述混合及反应在保护气氛环境中进行；优选的，所述保护气氛为氩气或氮气；
优选的，反应后的体系的固含量为10-50％，更优选为12-40％，进一步优选为15-30％；
优选的，所述制备方法还包括：在反应后的体系中添加流平剂；
优选的，所述制备方法还包括：在反应后的体系中进一步添加所述溶剂以对反应体系进行稀释；
优选的，稀释后的反应体系的固含量为1-10％。
本发明还提供一种液晶取向膜的制备方法，包括：将上述液晶取向剂经成膜、固化后，制得所述液晶取向膜。
本发明一些实施例中，所述成膜包括：将所述液晶取向剂涂布于基板上并通过烘烤去除溶剂；
优选的，所述烘烤的温度为60～120℃，烘烤时间为10～20min；
优选的，所述固化包括：将成膜后的基板在200～250℃的温度条件下进行亚胺化处理；优选的，亚胺化处理的时间为30～90min；
优选的，所述制备方法还包括：对固化后的薄膜进行摩擦处理。
本发明还提供一种液晶取向膜，采用上述液晶取向膜的制备方法制得。
本发明还提供一种液晶盒，包括相对设置的第一基板和第二基板以及设于所述第一基板和所述第二基板之间的液晶材料；所述第一基板与所述液晶材料接触的一侧以及所述第二基板与所述液晶材料接触的一侧均设有上述液晶取向膜；
优选的，所述第一基板和所述第二基板之间通过粘合胶密封连接；优选的，所述粘合胶包括光固化胶和/或热固化胶；
优选的，所述粘合胶内混有间隔粒子；优选的，所述间隔粒子的粒径为1～20μm，更优选为3～20μm。
间隔粒子的作用在于在所述第一基板和所述第二基板之间形成一定间隙，以容纳液晶材料。
本发明一些实施例中，所述第一基板和所述第二基板均为ITO玻璃基板。
本发明的有益效果：
本发明通过在液晶取向剂中添加哌嗪单体，能够降低液晶取向剂材料的体阻值与面阻值，有效提升取向剂材料释放残余电荷的能力，进而提高电子产品的可靠性及稳定性。采用本发明液晶取向剂的液晶盒具有高电压保持率(VHR)、低残留电压(RDC)等优点。
本发明的液晶取向剂可以应用于TN型(扭转向列型)、VA型(垂直取向型)等多种类型的液晶显示器中。
具体实施方式
如本文所用之术语：
“由……制备”与“包含”同义。本文中所用的术语“包含”、“包括”、“具有”、“含有”或其任何其它变形，意在覆盖非排它性的包括。例如，包含所列要素的组合物、步骤、方法、制品或装置不必仅限于那些要素，而是可以包括未明确列出的其它要素或此种组合物、步骤、方法、制品或装置所固有的要素。
连接词“由……组成”排除任何未指出的要素、步骤或组分。如果用于权利要求中，此短语将使权利要求为封闭式，使其不包含除那些描述的材料以外的材料，但与其相关的常规杂质除外。当短语“由……组成”出现在权利要求主体的子句中而不是紧接在主题之后时，其仅限定在该子句中描述的要素；其它要素并不被排除在作为整体的所述权利要求之外。
当量、浓度、或者其它值或参数以范围、优选范围、或一系列上限优选值和下限优选值限定的范围表示时，这应当被理解为具体公开了由任何范围上限或优选值与任何范围下限或优选值的任一配对所形成的所有范围，而不论该范围是否单独公开了。例如，当公开了范围“1～5”时，所描述的范围应被解释为包括范围“1～4”、“1～3”、“1～2”、“1～2和4～5”、“1～3和5”等。当数值范围在本文中被描述时，除非另外说明，否则该范围意图包括其端值和在该范围内的所有整数和分数。
在这些实施例中，除非另有指明，所述的份和百分比均按质量计。
“重量份”指表示多个组分的质量比例关系的基本计量单位，1份可表示任意的单位质量，如可以表示为1g，也可表示2.689g等。假如我们说A组分的重量份为a份，B组分的重量份为b份，则表示A组分的质量和B组 分的质量之比a：b。或者，表示A组分的质量为aK，B组分的质量为bK(K为任意数，表示倍数因子)。不可误解的是，与重量份数不同的是，所有组分的重量份之和并不受限于100份之限制。
“和/或”用于表示所说明的情况的一者或两者均可能发生，例如，A和/或B包括(A和B)和(A或B)。
下面将结合具体实施例对本发明的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限制本发明的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
本发明实施例及对比例所用单体如下：
DA-1：CBDA，结构式为：
Figure PCTCN2021125583-appb-000009
DA-2：3,3-(1,4哌嗪二基)二酸酐，结构式为：
Figure PCTCN2021125583-appb-000010
DA-3：3,3-(1,4哌嗪二基)二苯酐，结构式为：
Figure PCTCN2021125583-appb-000011
DN-1：对苯二胺，结构式为：
Figure PCTCN2021125583-appb-000012
DN-2：2,4-二氨基苯十八烷醚，结构式为：
Figure PCTCN2021125583-appb-000013
DN-3：二氢胆固醇3,5二氨基苯甲酸酯，结构式为：
Figure PCTCN2021125583-appb-000014
DN-4：1,4-双(4-氨基苯基)哌嗪，结构式为：
Figure PCTCN2021125583-appb-000015
DN-5：1,4-双(3-甲基-5氨基环己基)哌嗪，结构式为：
Figure PCTCN2021125583-appb-000016
实施例1
(一)聚酰胺酸液晶取向剂的制备
在室温环境，氮气氛围下，依次加入DN-1 6.48克(0.06mol)、DN-2 3.76克(0.01mol)、DN-4 8.04克(0.03mol)及NMP 88.4克，室温搅拌30分钟，确认完全溶解。再加入DA-1 19.6克(0.1mol)，室温搅拌反应3小时，反应固含量30％。反应结束后分别用NMP 208.3克及BC 296.7克稀释后得到透明黏稠聚酰胺酸溶液，固含量为6％，溶剂比例NMP/BC＝50/50。
(二)液晶取向膜及液晶盒的制备
按上述制备方法制得的聚酰胺酸液晶取向剂溶液均匀旋涂于洁净的ITO玻璃上，然后依次将该ITO玻璃基板放在温度60～120℃预烘10～20min，再在温度200～250℃亚胺化处理30～90min，然后用摩擦机摩擦该ITO玻璃基板上的聚酰亚胺薄膜，摩擦角度为45°，即得涂覆在ITO玻璃基板上的液晶取向膜。将两片上述制得的涂覆有液晶取向膜的ITO玻璃基板用含有4μm的间隔粒子的热固化胶使两片基板摩擦面相对且摩擦方向相反粘结成盒，灌入液晶，随后用光固化胶封口，获得液晶盒。
实施例2
(一)聚酰胺酸液晶取向剂的制备
在室温环境，氮气氛围下，依次加入DN-1 9.72克(0.09mol)、DN-2 3.76(0.01mol)及NMP 83.2克，室温搅拌30分钟，确认完全溶解。再依次加入DA-1 13.72克(0.07mol)及DA-3 8.46克(0.03mol)，室温搅拌反应3小时， 反应固含量30％。反应结束后分别用NMP 196.1克及BC 279.3克稀释后得到透明黏稠聚酰胺酸溶液，固含量为6％，溶剂比例NMP/BC＝50/50。
(二)液晶取向膜及液晶盒的制备
按上述制备方法制得的聚酰胺酸液晶取向剂溶液均匀旋涂于洁净的ITO玻璃上，然后依次将该ITO玻璃基板放在温度60～120℃预烘10～20min，再在温度200～250℃亚胺化处理30～90min，然后用摩擦机摩擦该ITO玻璃基板上的聚酰亚胺薄膜，摩擦角度为45°，即得涂覆在ITO玻璃基板上的液晶取向膜。将两片上述制得的涂覆有液晶取向膜的ITO玻璃基板用含有4μm的间隔粒子的热固化胶使两片基板摩擦面相对且摩擦方向正交粘结成盒，灌入液晶，随后用光固化胶封口，获得液晶盒。
实施例3
(一)聚酰胺酸液晶取向剂的制备
在室温环境，氮气氛围下，依次加入DN-1 5.4克(0.05mol)、DN-3 10.44克(0.02mol)、DN-4 8.04克(0.03mol)及NMP 101.4克，室温搅拌30分钟，确认完全溶解。再加入DA-1 19.6克(0.1mol)，室温搅拌反应3小时，反应固含量30％。反应结束后分别用NMP 239.1克及BC 340.6克稀释后得到透明黏稠聚酰胺酸溶液，固含量为6％，溶剂比例NMP/BC＝50/50。
(二)液晶取向膜及液晶盒的制备
按上述制备方法制得的聚酰胺酸液晶取向剂溶液均匀旋涂于洁净的ITO玻璃上，然后依次将该ITO玻璃基板放在温度60～120℃预烘10～20min，再在温度200～250℃亚胺化处理30～90min，然后用摩擦机摩擦该ITO玻璃基板上的聚酰亚胺薄膜，摩擦角度为0°，即得涂覆在ITO玻璃基板上的液晶取向膜。将两片上述制得的涂覆有液晶取向膜的ITO玻璃基板用含有4μm的间隔粒子的热固化胶使两片基板摩擦面相对且摩擦方向相反粘结成盒，灌入液晶，随后用光固化胶封口，获得液晶盒。
实施例4
(一)聚酰胺酸液晶取向剂的制备
在室温环境，氮气氛围下，依次加入DN-1 8.64克(0.08mol)、DN-3 10.44克(0.02mol)及NMP 96.3克，室温搅拌30分钟，确认完全溶解。再依次加入DA-1 13.72克(0.07mol)及DA-3 8.46克(0.03mol)，室温搅拌反应3小时，反应固含量30％。反应结束后分别用NMP 226.9克及BC 323.2克稀释后得到透明黏稠聚酰胺酸溶液，固含量为6％，溶剂比例NMP/BC＝50/50。
(二)液晶取向膜及液晶盒的制备
按上述制备方法制得的聚酰胺酸液晶取向剂溶液均匀旋涂于洁净的ITO玻璃上，然后依次将该ITO玻璃基板放在温度60～120℃预烘10～20min，再在温度200～250℃亚胺化处理30～90min，然后用摩擦机摩擦该ITO玻璃基板上的聚酰亚胺薄膜，摩擦角度为0°，即得涂覆在ITO玻璃基板上的液晶取向膜。将两片上述制得的涂覆有液晶取向膜的ITO玻璃基板用含有4μm的间隔粒子的热固化胶使两片基板摩擦面相对且摩擦方向相反粘结成盒，灌入液晶，随后用光固化胶封口，获得液晶盒。
实施例5
(一)聚酰胺酸液晶取向剂的制备
在室温环境，氮气氛围下，依次加入DN-1 6.48克(0.06mol)、DN-2 3.76克(0.01mol)、DN-5 9.24克(0.03mol)及NMP 91.2克，室温搅拌30分钟，确认完全溶解。再加入DA-1 19.6克(0.1mol)，室温搅拌反应3小时，反应固含量30％。反应结束后分别用NMP 214.9克及BC 306.1克稀释后得到透明黏稠聚酰胺酸溶液，固含量为6％，溶剂比例NMP/BC＝50/50。
(二)液晶取向膜及液晶盒的制备
按上述制备方法制得的聚酰胺酸液晶取向剂溶液均匀旋涂于洁净的 ITO玻璃上，然后依次将该ITO玻璃基板放在温度60～120℃预烘10～20min，再在温度200～250℃亚胺化处理30～90min，然后用摩擦机摩擦该ITO玻璃基板上的聚酰亚胺薄膜，摩擦角度为45°，即得涂覆在ITO玻璃基板上的液晶取向膜。将两片上述制得的涂覆有液晶取向膜的ITO玻璃基板用含有4μm的间隔粒子的热固化胶使两片基板摩擦面相对且摩擦方向相反粘结成盒，灌入液晶，随后用光固化胶封口，获得液晶盒。
实施例6
(一)聚酰胺酸液晶取向剂的制备
在室温环境，氮气氛围下，依次加入DN-1 9.72克(0.09mol)、DN-2 3.76(0.01mol)及NMP 89.9克，室温搅拌30分钟，确认完全溶解。再依次加入DA-1 13.72克(0.07mol)及DA-3 11.34克(0.03mol)，室温搅拌反应3小时，反应固含量30％。反应结束后分别用NMP 212.0克及BC 301.9克稀释后得到透明黏稠聚酰胺酸溶液，固含量为6％，溶剂比例NMP/BC＝50/50。
(二)液晶取向膜及液晶盒的制备
按上述制备方法制得的聚酰胺酸液晶取向剂溶液均匀旋涂于洁净的ITO玻璃上，然后依次将该ITO玻璃基板放在温度60～120℃预烘10～20min，再在温度200～250℃亚胺化处理30～90min，然后用摩擦机摩擦该ITO玻璃基板上的聚酰亚胺薄膜，摩擦角度为45°，即得涂覆在ITO玻璃基板上的液晶取向膜。将两片上述制得的涂覆有液晶取向膜的ITO玻璃基板用含有4μm的间隔粒子的热固化胶使两片基板摩擦面相对且摩擦方向正交粘结成盒，灌入液晶，随后用光固化胶封口，获得液晶盒。
实施例7
(一)聚酰胺酸液晶取向剂的制备
在室温环境，氮气氛围下，依次加入DN-1 5.4克(0.05mol)、DN-3 10.44 克(0.02mol)、DN-5 9.24克(0.03mol)及NMP 104.3克，室温搅拌30分钟，确认完全溶解。再加入DA-1 19.6克(0.1mol)，室温搅拌反应3小时，反应固含量30％。反应结束后分别用NMP 245.7克及BC 350.0克稀释后得到透明黏稠聚酰胺酸溶液，固含量为6％，溶剂比例NMP/BC＝50/50。
(二)液晶取向膜及液晶盒的制备
按上述制备方法制得的聚酰胺酸液晶取向剂溶液均匀旋涂于洁净的ITO玻璃上，然后依次将该ITO玻璃基板放在温度60～120℃预烘10～20min，再在温度200～250℃亚胺化处理30～90min，然后用摩擦机摩擦该ITO玻璃基板上的聚酰亚胺薄膜，摩擦角度为0°，即得涂覆在ITO玻璃基板上的液晶取向膜。将两片上述制得的涂覆有液晶取向膜的ITO玻璃基板用含有4μm的间隔粒子的热固化胶使两片基板摩擦面相对且摩擦方向相反粘结成盒，灌入液晶，随后用光固化胶封口，获得液晶盒。
实施例8
(一)聚酰胺酸液晶取向剂的制备
在室温环境，氮气氛围下，依次加入DN-1 8.64克(0.08mol)、DN-3 10.44克(0.02mol)及NMP103.0克，室温搅拌30分钟，确认完全溶解。再依次加入DA-1 13.72克(0.07mol)及DA-3 11.34克(0.03mol)，室温搅拌反应3小时，反应固含量30％。反应结束后分别用NMP 242.8克及BC 345.8克稀释后得到透明黏稠聚酰胺酸溶液，固含量为6％，溶剂比例NMP/BC＝50/50。
(二)液晶取向膜及液晶盒的制备
按上述制备方法制得的聚酰胺酸液晶取向剂溶液均匀旋涂于洁净的ITO玻璃上，然后依次将该ITO玻璃基板放在温度60～120℃预烘10～20min，再在温度200～250℃亚胺化处理30～90min，然后用摩擦机摩擦该ITO玻璃基板上的聚酰亚胺薄膜，摩擦角度为0°，即得涂覆在ITO玻璃基板上的液晶取向膜。将两片上述制得的涂覆有液晶取向膜的ITO玻璃基板 用含有4μm的间隔粒子的热固化胶使两片基板摩擦面相对且摩擦方向相反粘结成盒，灌入液晶，随后用光固化胶封口，获得液晶盒。
对比例1
(一)聚酰胺酸液晶取向剂的制备
在室温环境，氮气氛围下，依次加入DN-1 9.72克(0.09mol)、DN-2 3.76克(0.01mol)及NMP 77.2克，室温搅拌30分钟，确认完全溶解。再加入DA-1 19.6克(0.1mol)，室温搅拌反应3小时，反应固含量30％。反应结束后分别用NMP 181.9克及BC 259.1克稀释后得到透明黏稠聚酰胺酸溶液，固含量为6％，溶剂比例NMP/BC＝50/50。
(二)液晶取向膜及液晶盒的制备
按上述制备方法制得的聚酰胺酸液晶取向剂溶液均匀旋涂于洁净的ITO玻璃上，然后依次将该ITO玻璃基板放在温度60～120℃预烘10～20min，再在温度200～250℃亚胺化处理30～90min，然后用摩擦机摩擦该ITO玻璃基板上的聚酰亚胺薄膜，摩擦角度为45°，即得涂覆在ITO玻璃基板上的液晶取向膜。将两片上述制得的涂覆有液晶取向膜的ITO玻璃基板用含有4μm的间隔粒子的热固化胶使两片基板摩擦面相对且摩擦方向正交粘结成盒，灌入液晶，随后用光固化胶封口，获得液晶盒。
对比例2
(一)聚酰胺酸液晶取向剂的制备
在室温环境，氮气氛围下，依次加入DN-1 8.64克(0.08mol)、DN-3 10.44克(0.02mol)及NMP 90.25克，室温搅拌30分钟，确认完全溶解。再加入DA-1 19.6克(0.1mol)，室温搅拌反应3小时，反应固含量30％。反应结束后分别用NMP 212.7克及BC 303.0克稀释后得到透明黏稠聚酰胺酸溶液，固含量为6％，溶剂比例NMP/BC＝50/50。
(二)液晶取向膜及液晶盒的制备
按上述制备方法制得的聚酰胺酸液晶取向剂溶液均匀旋涂于洁净的ITO玻璃上，然后依次将该ITO玻璃基板放在温度60～120℃预烘10～20min，再在温度200～250℃亚胺化处理30～90min，然后用摩擦机摩擦该ITO玻璃基板上的聚酰亚胺薄膜，摩擦角度为45°，即得涂覆在ITO玻璃基板上的液晶取向膜。将两片上述制得的涂覆有液晶取向膜的ITO玻璃基板用含有4μm的间隔粒子的热固化胶使两片基板摩擦面相对且摩擦方向正交粘结成盒，灌入液晶，随后用光固化胶封口，获得液晶盒。
液晶盒电性能测试条件：
测试设备：6254C；
VHR量测条件：电压5V、脉冲宽度为60μs/帧、周期1667ms、测量温度为60℃；
RDC量测条件：电压5V、充电时间为2400sec、测量时间为1200sec、测量温度为60℃。
液晶盒预倾角测试条件：
测试设备：Shintech Optitro-STD(3STN11)；
测试波长：591.4nm；
测试模式：TN/VA模式。
液晶取向膜体阻和面阻测试条件：
测试设备：静电计/高阻表(KEYSIGHT B2985A)，样品厚度5-50微米，有效面积30-60cm 2，测试参数：电压量测范围1μV-20V，0.01fA测量分辨率，2000读数/s。
表1对比例及实施例液晶盒电性能及液晶取向膜体积电阻率
Figure PCTCN2021125583-appb-000017
Figure PCTCN2021125583-appb-000018
从上表1可以看出，本申请实施例的液晶取向膜的体积电阻率及表面电阻率均低于对比例，本申请实施例的液晶盒的电压保持率(VHR)均高于对比例，残留电压(RDC)均低于对比例，说明本申请实施例制备的液晶取向膜具有电荷快速释放等优点，采用本申请液晶取向膜制备的液晶盒具有较高的可靠性及稳定性。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
此外，本领域的技术人员能够理解，尽管在此的一些实施例包括其它实施例中所包括的某些特征而不是其它特征，但是不同实施例的特征的组合意味着处于本发明的范围之内并且形成不同的实施例。例如，在上面的权利要求书中，所要求保护的实施例的任意之一都可以以任意的组合方式来使用。公开于该背景技术部分的信息仅仅旨在加深对本发明的总体背景 技术的理解，而不应当被视为承认或以任何形式暗示该信息构成已为本领域技术人员所公知的现有技术。

Claims (32)

  1. 一种液晶取向剂，其特征在于，包括：二胺单体、二酐单体、哌嗪单体以及溶剂，所述哌嗪单体的结构通式为：
    Figure PCTCN2021125583-appb-100001
    其中，R表示胺基基团或者酸酐基团；
    所述二胺单体包括第一二胺化合物和第二二胺化合物；
    所述第一二胺化合物包括结构通式为通式Ⅰ或通式Ⅱ所示的化合物中的至少一种：
    Figure PCTCN2021125583-appb-100002
    通式Ⅰ中，A表示化学键、烷基链C nH 2n，n＝1-20、-O-、-NH-、-S-或-SO 2-，R表示-H或者-CH 3；
    Figure PCTCN2021125583-appb-100003
    通式Ⅱ中，R表示-H或者-CH 3；
    所述第二二胺化合物包括结构通式为通式Ⅲ或通式Ⅳ所示的化合物中的至少一种：
    Figure PCTCN2021125583-appb-100004
    通式Ⅲ中，R表示烷基链C nH (2n+1)，n＝1-50；
    Figure PCTCN2021125583-appb-100005
    通式Ⅳ中，R表示烷基链C nH (2n+1)，n＝1-50。
  2. 如权利要求1所述的液晶取向剂，其特征在于，所述哌嗪单体与所述二胺单体的摩尔数之比为1～100：100。
  3. 如权利要求1所述的液晶取向剂，其特征在于，所述哌嗪单体包括下述结构式所示的化合物中的一种或多种：
    Figure PCTCN2021125583-appb-100006
  4. 如权利要求1所述的液晶取向剂，其特征在于，所述第一二胺化合物的摩尔数占所述二胺单体的总摩尔数的0.01-99.9％。
  5. 如权利要求4所述的液晶取向剂，其特征在于，所述第一二胺化合物 的摩尔数占所述二胺单体的总摩尔数的10-99.9％。
  6. 如权利要求5所述的液晶取向剂，其特征在于，所述第一二胺化合物的摩尔数占所述二胺单体的总摩尔数的50-99.9％。
  7. 如权利要求1所述的液晶取向剂，其特征在于，所述第一二胺化合物包括以下化合物中的一种或多种：
    Figure PCTCN2021125583-appb-100007
    所述第二二胺化合物包括以下化合物中的一种或多种：
    Figure PCTCN2021125583-appb-100008
  8. 如权利要求1所述的液晶取向剂，其特征在于，所述液晶取向剂的固 含量为1-10％。
  9. 如权利要求1所述的液晶取向剂，其特征在于，所述二胺单体和所述二酐单体的摩尔比为(80-100)：(80-100)。
  10. 如权利要求9所述的液晶取向剂，其特征在于，所述二胺单体和所述二酐单体的摩尔比为(90-100)：(90-100)。
  11. 如权利要求10所述的液晶取向剂，其特征在于，所述二胺单体和所述二酐单体的摩尔比为100：100。
  12. 如权利要求1所述的液晶取向剂，其特征在于，所述溶剂包括N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮、间甲酚及四氢呋喃中的一种或多种。
  13. 如权利要求1所述的液晶取向剂，其特征在于，所述液晶取向剂还包括流平剂，所述流平剂包括乙酸乙酯、乙二醇单丁醚、二乙二醇二乙醚、二丙酮醇、乙二醇丁醚乙酸酯中的一种或多种。
  14. 如权利要求13所述的液晶取向剂，其特征在于，所述流平剂在所述液晶取向剂中的添加量为0-80wt％。
  15. 权利要求1-14任一项所述的液晶取向剂的制备方法，其特征在于，包括：将包括所述二胺单体、所述二酐单体、所述哌嗪单体以及所述溶剂在内的原料混合后反应。
  16. 权利要求15所述的液晶取向剂的制备方法，其特征在于，所述反应的温度条件为-15℃-100℃，所述反应的时间为0.5-48小时。
  17. 权利要求16所述的液晶取向剂的制备方法，其特征在于，所述反应的温度条件为0℃-80℃，所述反应的时间为1-24小时。
  18. 权利要求17所述的液晶取向剂的制备方法，其特征在于，所述反应的温度条件为20℃-60℃，所述反应的时间为2-12小时。
  19. 权利要求15所述的液晶取向剂的制备方法，其特征在于，所述混合及反应在保护气氛环境中进行；所述保护气氛为氩气或氮气。
  20. 权利要求15所述的液晶取向剂的制备方法，其特征在于，反应后的体系的固含量为10-50％。
  21. 权利要求20所述的液晶取向剂的制备方法，其特征在于，反应后的体系的固含量为12-40％。
  22. 权利要求21所述的液晶取向剂的制备方法，其特征在于，反应后的体系的固含量为15-30％。
  23. 权利要求15所述的液晶取向剂的制备方法，其特征在于，所述制备方法还包括：在反应后的体系中添加流平剂。
  24. 权利要求15所述的液晶取向剂的制备方法，其特征在于，所述制备方法还包括：在反应后的体系中进一步添加所述溶剂以对反应体系进行稀释；稀释后的反应体系的固含量为1-10％。
  25. 一种液晶取向膜的制备方法，其特征在于，包括：将权利要求1-14任一项所述的液晶取向剂经成膜、固化后，制得所述液晶取向膜。
  26. 如权利要求25所述的液晶取向膜的制备方法，其特征在于，所述成膜包括：将所述液晶取向剂涂布于基板上并通过烘烤去除溶剂；
    所述烘烤的温度为60～120℃，烘烤时间为10～20min；
    所述固化包括：将成膜后的基板在200～250℃的温度条件下进行亚胺化处理；亚胺化处理的时间为30～90min。
  27. 如权利要求25所述的液晶取向膜的制备方法，其特征在于，所述制备方法还包括：对固化后的薄膜进行摩擦处理。
  28. 一种液晶取向膜，其特征在于，采用权利要求25-27任一项所述的液晶取向膜的制备方法制得。
  29. 一种液晶盒，其特征在于，包括相对设置的第一基板和第二基板以及设于所述第一基板和所述第二基板之间的液晶材料；所述第一基板与所述液晶材料接触的一侧以及所述第二基板与所述液晶材料接触的一侧均设有权利要求28所述的液晶取向膜。
  30. 根据权利要求29所述的液晶盒，其特征在于，所述第一基板和所述第二基板之间通过粘合胶密封连接。
  31. 根据权利要求30所述的液晶盒，其特征在于，所述粘合胶包括光固化胶和/或热固化胶。
  32. 根据权利要求30所述的液晶盒，其特征在于，所述粘合胶内混有间隔粒子；所述间隔粒子的粒径为1～20μm。
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