CN114058384A - Polyimide photo-alignment agent solution and preparation method thereof, photo-alignment film and liquid crystal box - Google Patents

Polyimide photo-alignment agent solution and preparation method thereof, photo-alignment film and liquid crystal box Download PDF

Info

Publication number
CN114058384A
CN114058384A CN202111425290.0A CN202111425290A CN114058384A CN 114058384 A CN114058384 A CN 114058384A CN 202111425290 A CN202111425290 A CN 202111425290A CN 114058384 A CN114058384 A CN 114058384A
Authority
CN
China
Prior art keywords
photo
polyimide
diamine monomer
alignment
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202111425290.0A
Other languages
Chinese (zh)
Inventor
苏江华
王胜林
黎厚明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Dalton Electronic Material Co ltd
Original Assignee
Shenzhen Dalton Electronic Material Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen Dalton Electronic Material Co ltd filed Critical Shenzhen Dalton Electronic Material Co ltd
Priority to CN202111425290.0A priority Critical patent/CN114058384A/en
Publication of CN114058384A publication Critical patent/CN114058384A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • C09K19/542—Macromolecular 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Liquid Crystal (AREA)

Abstract

The invention relates to the technical field of an alignment agent, in particular to a polyimide photo-alignment agent solution, a preparation method thereof, a photo-alignment film and a liquid crystal box. The preparation method comprises the steps of firstly preparing an upper layer photo-alignment layer polyimide solution and a lower layer characteristic polyamide acid solution, and mixing the obtained polyimide solution and the characteristic polyamide acid solution to obtain a polyimide photo-alignment agent solution. The invention provides a synthesis method of a double-layer liquid crystal photo-alignment agent with rapid alignment, stable pretilt angle, high voltage holding ratio, low residual direct current voltage and good residual image expression capability, and a method for preparing a liquid crystal alignment film by using the alignment agent.

Description

Polyimide photo-alignment agent solution and preparation method thereof, photo-alignment film and liquid crystal box
Technical Field
The invention relates to the technical field of an alignment agent, in particular to a polyimide photo-alignment agent solution, a preparation method thereof, a photo-alignment film and a liquid crystal box.
Background
In general, a liquid crystal display device includes a liquid crystal alignment film for controlling the alignment state of liquid crystal in the device. The display performance of the liquid crystal display device is mainly affected by the alignment property, the pretilt angle, the uniformity, the electrical property, and the like of the liquid crystal. The liquid crystal properties are not only greatly related to the used liquid crystal materials, but also are obviously related to the liquid crystal orientation film which is directly contacted with the liquid crystal materials.
Polyimides are generally made by polycondensation, i.e., the polycondensation of a dianhydride and a diamine in a high boiling solvent. The formation of the imide ring structure can be classified into: one-step and two-step processes. The one-step method is a method for obtaining polyimide by heating dianhydride and diamine in a high-boiling point solvent to 150-220 ℃, and simultaneously performing molecular chain growth and imidization. The two-step process generally includes generating a polyimide precursor, polyamic acid, with high molecular weight from dianhydride and diamine in a polar aprotic solvent, and cyclizing the polyamic acid at high temperature or under the action of a catalyst to form polyimide, and the current synthesis of polyimide is generally performed by a two-step process.
The IPS type TFT-LCD has advantages of wide viewing angle, high contrast, accurate color expression, etc., and is widely used in televisions, notebook computer displays, and high resolution displays. For the traditional IPS-LCD, a soluble resin of polyamic acid or polyimide is mainly used as a liquid crystal alignment agent, which is coated on a substrate, and after curing at high temperature, rubbing treatment is performed to obtain an alignment film. However, this alignment technique has some significant disadvantages, such as dust generation due to rubbing, static electricity generation, and low yield. In recent years, as the demand of consumers for display effect is increasing, the demand for high resolution and afterimage representation of liquid crystal displays is also increasing. The photo-alignment technology has been a research hotspot as a non-contact novel alignment method, and photo-alignment type polyimide alignment agents will also be the mainstream trend in the future.
At present, the traditional single-layer photo-alignment agent cannot simultaneously achieve the photoelectric property of the alignment film and the property of the alignment agent. In order to simultaneously achieve the characteristics of good alignment effect, high VHR, low RDC, stable pretilt angle and the like, two or more types of polyimide or polyamic acid with different structural characteristics are combined and matched to form a double-layer or multi-layer type alignment agent. However, the photo-alignment agents currently used in the market require a large amount of light area in the alignment stage, which results in a long time consumption in the alignment stage during the panel production process and seriously affects the productivity.
Disclosure of Invention
The invention aims to provide a polyimide photo-alignment agent solution, a preparation method thereof, a photo-alignment film and a liquid crystal box, so as to overcome the problems in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of polyimide photo-alignment agent solution, which comprises the following steps:
(1) preparation of polyimide solution of upper photo-alignment layer:
(1.1) under a protective atmosphere, mixing a basic diamine monomer, a fast photo-oriented diamine monomer, a polar aprotic solvent and a dianhydride monomer, and then reacting to obtain a reaction system;
(1.2) mixing the obtained reaction system with pyridine and acetic anhydride, and then carrying out imidization reaction to generate polyimide resin;
(1.3) dissolving the obtained polyimide resin in a polar aprotic solvent and a leveling agent to obtain a polyimide solution;
(2) preparation of bottom layer characteristic polyamic acid solution
(2.1) under a protective atmosphere, mixing a basic diamine monomer, a characteristic diamine monomer, a polar aprotic solvent and a dianhydride monomer, and then reacting to obtain a reaction system;
(2.2) mixing the obtained reaction system with a polar aprotic solvent and a leveling agent to obtain a characteristic polyamic acid solution;
the characteristic diamine monomer is
Figure BDA0003378101260000021
Wherein, R is5is-CnH2n-NH-, -O-or-SO2-, n is an integer of 1 to 5;
(3) mixing the obtained polyimide solution and the characteristic polyamic acid solution to obtain a polyimide photo-alignment agent solution;
the step (1) and the step (2) are not limited in sequence.
Preferably, in the step (1.1):
the protective atmosphere is nitrogen or argon;
the base diamine monomer is
Figure BDA0003378101260000031
And/or
Figure BDA0003378101260000032
Wherein, X groups are independently-H, methyl, ethyl or propyl;
the fast photo-oriented diamine monomer is
Figure BDA0003378101260000033
Wherein R is6And R7Independently is-CH2-、-CH2-CH2-、-CH2-CH2-CH2-, -NH-or-O-;
the polar aprotic solvent is one or more of N-methylpyrrolidone, 1, 4-butyrolactone, N-ethylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide;
the dianhydride monomer is one of the following structural formulas
Figure BDA0003378101260000041
The reaction temperature is 55-65 ℃, and the reaction time is 2-24 h;
the mole fraction of the basic diamine monomer in the total mole number of the basic diamine monomer and the rapid photo-orientation diamine monomer is 10-99%;
the molar ratio of the total moles of the basic diamine monomer and the fast photo-orientation diamine monomer to the dianhydride monomer is 1 (0.8-1.2);
the mass ratio of the total moles of the basic diamine monomer and the fast photo-orientation diamine monomer to the polar aprotic solvent is 1 mol: (130-150) g.
Preferably, in the step (1.2):
the temperature of the imidization reaction is 75-85 ℃, and the time is 1-12 h;
the mass ratio of the pyridine to the acetic anhydride to the polar aprotic solvent in the step (1.1) is (10-15): (15-20): (130-150).
Preferably, in the step (1.3):
the polar aprotic solvent is one or more of N-methylpyrrolidone, 1, 4-butyrolactone, N-ethylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide;
the flatting agent is one or more of ethylene glycol monobutyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether ethyl ester, butyl lactate, cyclopentanone and diisobutyl ketone;
the mass ratio of the polar aprotic solvent to the leveling agent to the polar aprotic solvent in the step (1.1) is (90-100): (55-70): (130-150);
the viscosity of the obtained polyimide solution is 5-100 cps.
Preferably, in the step (2.1):
the protective atmosphere is nitrogen or argon;
the base diamine monomer is
Figure BDA0003378101260000051
And/or
Figure BDA0003378101260000052
Wherein, X groups are independently-H, methyl, ethyl or propyl;
the polar aprotic solvent is one or more of N-methylpyrrolidone, 1, 4-butyrolactone, N-ethylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide;
the dianhydride monomer is one of the following structural formulas
Figure BDA0003378101260000061
The reaction temperature is 55-65 ℃, and the reaction time is 2-12 h;
the molar ratio of the total mole number of the basic diamine monomer and the characteristic diamine monomer to the mole number of the dianhydride monomer is 1 (0.8-1.2);
the mole fraction of the basic diamine monomer in the total mole number of the basic diamine monomer and the characteristic diamine monomer is 10-90%;
the mass ratio of the total mole number of the basic diamine monomer and the characteristic diamine monomer to the polar aprotic solvent is 1 mol: (130-150) g.
Preferably, in the step (2.2):
the polar aprotic solvent is one or more of N-methylpyrrolidone, 1, 4-butyrolactone, N-ethylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide;
the flatting agent is one or more of ethylene glycol monobutyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether ethyl ester, butyl lactate, cyclopentanone and diisobutyl ketone;
the mass ratio of the polar aprotic solvent to the leveling agent to the polar aprotic solvent in the step (2.1) is (190-200): (220-230): (130-150);
the viscosity of the obtained characteristic polyamic acid solution is 10-100 cps;
the mass ratio of the polyimide solution to the characteristic polyamide acid solution in the step (3) is (10-30): 70-90.
The invention also provides the polyimide photo-alignment agent solution obtained by the preparation method.
The present invention also provides a method of preparing a photo-alignment film coated on a substrate from the polyimide photo-alignment agent solution, comprising the steps of:
coating the polyimide photo-alignment agent solution on a substrate, and then sequentially baking and curing to obtain a liquid crystal photo-alignment film; the baking temperature is 60-120 ℃, and the baking time is 1-5 min; the curing temperature is 220-240 ℃, and the curing time is 20-40 min;
irradiating the obtained liquid crystal photo-alignment film with ultraviolet polarized light for alignment, and then baking to obtain a photo-alignment film; the baking temperature is 220-240 ℃, and the baking time is 20-40 min.
The invention also provides a photo-alignment film coated on a substrate obtained by the method.
The invention also provides a liquid crystal box prepared by the optical alignment film coated on the substrate.
The invention provides a synthesis method of a double-layer liquid crystal photo-alignment agent with rapid alignment, stable pretilt angle, high voltage holding ratio, low residual direct current voltage and good residual image expression capability, and a method for preparing a liquid crystal alignment film by using the alignment agent.
The layered structure of the polyimide photo-alignment film obtained by the invention is as follows:
the upper layer structural formula:
Figure BDA0003378101260000071
the structural formula of the lower layer is as follows:
Figure BDA0003378101260000072
wherein n, m is not less than 1, n is 1-500, preferably 30-300, and most preferably 50-100. m is 1 to 1000, preferably 100 to 500, and most preferably 300 to 500.
In the structural formula R1Is a residual radical of a dianhydride, R2Based on the remaining diamine radical, R3For fast photo-alignment of the remaining radicals, R4Are characteristic diamine residual groups. It can be understood that the base diamine is mainly a base structure for synthesizing the liquid crystal photo-alignment agent, so that it has better electrical properties, and the fast photo-alignment monomer is to reduce the energy required for photo-cracking and accelerate the photo-alignment rate. The characteristic diamine monomer is used for accelerating the charge-conducting rate of the photo-alignment agent and improving the residual image expression capability of the liquid crystal alignment agent.
Drawings
FIG. 1 is a result of transmittance test of example 1, example 3, example 5 and comparative example 1;
fig. 2 is a result of transmittance test of example 2, example 4, example 6 and comparative example 2.
Detailed Description
The invention provides a preparation method of polyimide photo-alignment agent solution.
In the present invention, the base diamine monomer has a structure of one of the following:
Figure BDA0003378101260000081
in the present invention, the fast photo-alignment diamine monomer has a structure of one of:
Figure BDA0003378101260000091
in the present invention, the characteristic diamine monomer has a structure of one of the following:
Figure BDA0003378101260000092
in step (1.1) of the present invention:
the reaction temperature is 55-65 ℃, and preferably 60-62 ℃; the reaction time is 2-24 h, preferably 2-12 h, and further preferably 2-6 h;
the mole fraction of the basic diamine monomer in the total mole number of the basic diamine monomer and the rapid photo-orientation diamine monomer is 10-99%, preferably 30-99%, further preferably 50-99%, and most preferably 70-99%;
the molar ratio of the total moles of the basic diamine monomer and the rapid photo-orientation diamine monomer to the dianhydride monomer is 1 (0.8-1.2), preferably 1 (0.9-0.95);
the mass ratio of the total moles of the basic diamine monomer and the fast photo-orientation diamine monomer to the polar aprotic solvent is 1 mol: (130-150) g, preferably 1 mol: (140-141.32) g.
In step (1.2) of the present invention:
the temperature of the imidization reaction is 75-85 ℃, and preferably 80-82 ℃; the time of the imidization reaction is 1-12 h, preferably 2-8 h, and most preferably 3-6 h;
the mass ratio of the pyridine to the acetic anhydride to the polar aprotic solvent in the step (1.1) is (10-15): (15-20): (130-150), preferably (12-13): (16-18): (135-140).
After the imidization reaction is finished, slowly dripping the solution into ethanol to precipitate polyimide resin; and drying at 75-80 ℃ to obtain the dry polyimide resin.
In step (1.3) of the present invention:
the mass ratio of the polar aprotic solvent to the leveling agent to the polar aprotic solvent in the step (1.1) is (90-100): (55-70): (130-150), preferably (95-98): (60-65): (135-145);
the viscosity of the polyimide solution at 25 ℃ is 5 to 100cps, preferably 10 to 60cps, and most preferably 20 to 50 cps.
In step (2.1) of the present invention:
the reaction temperature is 55-65 ℃, and preferably 60-62 ℃; the reaction time is 2-12 h, preferably 2-8 h, and most preferably 4-8 h;
the molar ratio of the total mole number of the basic diamine monomer and the characteristic diamine monomer to the mole number of the dianhydride monomer is 1 (0.8-1.2), and preferably 1 (0.9-0.95);
the mole fraction of the basic diamine monomer in the total mole number of the basic diamine monomer and the characteristic diamine monomer is 10-90%, preferably 30-80%, and further preferably 40-75%;
the mass ratio of the total mole number of the basic diamine monomer and the characteristic diamine monomer to the polar aprotic solvent is 1 mol: (130-150) g, preferably 1 mol: (140-143.36) g.
In step (2.2) of the present invention:
the mass ratio of the polar aprotic solvent to the leveling agent to the polar aprotic solvent in the step (2.1) is (190-200): (220-230): (130-150), preferably (195-198): (222-225): (135-140);
the viscosity of the obtained characteristic polyamic acid solution is 10 to 100cps, preferably 30 to 90cps, and most preferably 35 to 80 cps.
In the step (3), the mass ratio of the polyimide solution to the characteristic polyamic acid solution is (10-30): 70-90), preferably (15-22): 78-85.
The polyimide solution and the characteristic polyamic acid solution are mixed and then vibrated, and the vibration time is 4-48 hours, preferably 4-24 hours, and most preferably 6-12 hours.
The invention also provides the polyimide photo-alignment agent solution obtained by the preparation method.
The present invention also provides a method of preparing a photo-alignment film coated on a substrate from the polyimide photo-alignment agent solution, comprising the steps of:
coating the polyimide photo-alignment agent solution on a substrate, and then sequentially baking and curing to obtain a liquid crystal photo-alignment film; the baking temperature is 60-120 ℃, and preferably 80-100 ℃; the baking time is 1-5 min, preferably 2-3 min; the curing temperature is 220-240 ℃, preferably 225-230 ℃; the curing time is 20-40 min, preferably 30-35 min; the film thickness of the liquid crystal photo-alignment film is 600 angstrom;
irradiating the obtained liquid crystal photo-alignment film with ultraviolet polarized light for alignment, and then baking to obtain a photo-alignment film; the baking temperature is 220-240 ℃, preferably 225-230 ℃; the baking time is 20-40 min, preferably 25-30 min; the ultraviolet polarized light used is 254nm, 200mj/cm2In the 0 ° direction; the film thickness of the photo-alignment film was 600 angstroms.
The invention also provides a photo-alignment film coated on a substrate obtained by the method.
The invention also provides a liquid crystal box prepared by the optical alignment film coated on the substrate.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
The monomers used in the examples of the present application are as follows:
eg1 cyclobutanetetracarboxylic dianhydride
Figure BDA0003378101260000111
Eg2 para-xylylenediamine
Figure BDA0003378101260000121
Eg3:4, 4' -diaminodiphenylamine
Figure BDA0003378101260000122
Eg4:1, 3-bis (4-diamino) urea
Figure BDA0003378101260000123
Eg5:1, 3-bis (4-aminophenylethyl) urea
Figure BDA0003378101260000124
Eg6 p-aminobenzophenone
Figure BDA0003378101260000131
Comparative example 1
Preparation of polyimide solution for upper photo-alignment layer
Eg213.62g (0.1mol) and 132.88g of NMP (N-methylpyrrolidone) are added into a 500ml three-neck round bottom flask equipped with a mechanical stirring device, a thermometer and an argon protection device, stirring is continuously carried out at 60 ℃, Eg119.6g (0.1mol) is added after complete dissolution is confirmed, 13.44g of pyridine and 17.34g of acetic anhydride are added after reaction is carried out for 10h at the temperature of 60 ℃ under the condition of 20 wt%, polyimide resin is precipitated from the solution slowly ethanol after chemical imidization for 16h, vacuum baking is carried out at 80 ℃ for 24h to obtain dry polyimide resin 1, 10g of dry polyimide resin 1 is dissolved into 93.99g of NMP, 62.66gBC (ethylene glycol monobutyl ether) is added to dilute the solid content to 6 wt%, and the polyimide solution 1 is obtained after filtration by using a filter membrane with the aperture of 0.2um, and the NMP/BC is 60/40 and the viscosity is 25 cps.
Preparation of bottom layer characteristic polyamic acid solution
Eg212.26g (0.08mol) Eg33.98g (0.02mol) and 143.36g NMP were added to a 500ml three neck round bottom flask equipped with mechanical stirring, thermometer and argon protection, stirring was continued at 60 ℃ to confirm complete dissolution, Eg119.6g was added, 20 wt% was reacted at 60 ℃ for 6h, 193.53g NMP was added, 224.59gBC diluted the solids to 6 wt%, and filtered through a 0.2um pore size filter to give polyamic acid solution 1 with a viscosity of 40cps at NMP/BC 60/40.
Preparation of polyimide/polyamic acid photo-alignment agent solution
30g of the polyimide solution 1 prepared above was mixed with 70g of the polyamic acid solution 1, and the mixture was uniformly shaken to obtain a polyimide/polyamic acid photo-alignment agent solution 1 having a NMP/BC of 60/40 and a viscosity of 35 cps.
Optical orientation film and liquid crystal test box preparation
The polyimide/polyamic acid photo-alignment agent 1 is uniformly coated on an ITO glass substrate, baked for 2min at the temperature of 80 ℃, and then cured for 30min at the temperature of 230 ℃ to form a liquid crystal photo-alignment film with the film thickness of 600 angstroms. Then, the films were irradiated with ultraviolet polarized light in the 0 ℃ direction at 254nm, 100mj/cm2, 200mj/cm2, and 300mj/cm2, respectively, and then baked at 230 ℃ and post-cured for 30 minutes to form a 600. ANGSTROM-oriented film. And finally, assembling the liquid crystal box, and filling liquid crystal to obtain the complete liquid crystal test box 1.
Comparative example 2
Preparation of polyimide/polyamic acid photo-alignment agent solution
10g of the polyimide solution 1 prepared above was mixed with 90g of the polyamic acid solution 1, and the mixture was uniformly shaken to obtain a polyimide/polyamic acid photo-alignment agent solution 2 having a NMP/BC of 60/40 and a viscosity of 39 cps.
Preparation of orientation film and liquid crystal test box
The polyimide/polyamic acid photo-alignment agent 1 is uniformly coated on an ITO glass substrate, baked for 2min at the temperature of 80 ℃, and then cured for 30min at the temperature of 230 ℃ to form a liquid crystal photo-alignment film with the film thickness of 600 angstroms. Then, the films were irradiated with ultraviolet polarized light in the 0 ℃ direction at 254nm, 100mj/cm2, 200mj/cm2, and 300mj/cm2, respectively, and then baked at 230 ℃ and post-cured for 30 minutes to form a 600. ANGSTROM-oriented film. And finally, assembling the liquid crystal box, and filling liquid crystal to obtain the complete liquid crystal test box 2.
Example 1
Preparation of polyimide solution for upper photo-alignment layer
Eg210.89g (0.08mol), Eg44.84g (0.02mol) and 141.32g NMP are added into a 500ml three-neck round bottom flask equipped with a mechanical stirring device, a thermometer and an argon protection device, stirring is continuously carried out at 60 ℃, Eg119.6g is added after complete dissolution is confirmed, 13.44g pyridine and 17.34g acetic anhydride are added after reaction is carried out at 60 ℃ for 10h under the condition of 20 wt%, polyimide resin 2 is precipitated from the solution by slow ethanol after chemical imidization is carried out for 16h, vacuum baking is carried out at 80 ℃ for 24h to obtain dry polyimide resin 2, 10g dry polyimide resin 2 is taken and dissolved in 93.99g NMP, 62.66gBC is added to dilute the solution to 6 wt%, and the polyimide solution 2 is obtained after filtration by using a 0.2um pore filter membrane, wherein the NMP/BC is 60/40 and the viscosity is 27 cps.
Preparation of bottom layer characteristic polyamic acid solution
Eg212.26g (0.08mol) Eg33.98g (0.02mol) and 143.36g NMP were added to a 500ml three neck round bottom flask equipped with mechanical stirring, thermometer and argon protection, stirring was continued at 60 ℃ to confirm complete dissolution, Eg119.6g was added, 20 wt% was reacted at 60 ℃ for 6h, 193.53g NMP was added, 224.59gBC diluted the solids to 6 wt%, and filtered through a 0.2um pore size filter to give polyamic acid solution 1 with a viscosity of 40cps at NMP/BC 60/40.
Preparation of polyimide/polyamic acid photo-alignment agent solution
30g of the polyimide solution 2 prepared above was mixed with 70g of the polyamic acid solution 1, and the mixture was uniformly shaken to obtain a polyimide/polyamic acid photo-alignment agent solution 3 having a NMP/BC of 60/40 and a viscosity of 37 cps.
Optical orientation film and liquid crystal test box preparation
The polyimide/polyamic acid photo-alignment agent 2 is uniformly coated on an ITO glass substrate, baked for 2min at the temperature of 80 ℃, and then cured for 30min at the temperature of 230 ℃ to form a liquid crystal photo-alignment film with the film thickness of 600 angstroms. Then, the films were irradiated with ultraviolet polarized light in the 0 ℃ direction at 254nm, 100mj/cm2, 200mj/cm2, and 300mj/cm2, respectively, and then baked at 230 ℃ and post-cured for 30 minutes to form a 600. ANGSTROM-oriented film. And finally, assembling the liquid crystal box, and filling liquid crystal to obtain the complete liquid crystal test box 3.
Example 2
Preparation of polyimide/polyamic acid photo-alignment agent solution
10g of the polyimide solution 2 prepared above was mixed with 90g of the polyamic acid solution 1, and the mixture was uniformly shaken to obtain a polyimide/polyamic acid photo-alignment agent solution 3 having a NMP/BC of 60/40 and a viscosity of 40 cps.
Optical orientation film and liquid crystal test box preparation
The polyimide/polyamic acid photo-alignment agent 2 is uniformly coated on an ITO glass substrate, baked for 2min at the temperature of 80 ℃, and then cured for 30min at the temperature of 230 ℃ to form a liquid crystal photo-alignment film with the film thickness of 600 angstroms. Then, the films were irradiated with ultraviolet polarized light in the 0 ℃ direction at 254nm, 100mj/cm2, 200mj/cm2, and 300mj/cm2, respectively, and then baked at 230 ℃ and post-cured for 30 minutes to form a 600. ANGSTROM-oriented film. And finally, assembling the liquid crystal box, and filling liquid crystal to obtain the complete liquid crystal test box 4.
Example 3
Preparation of polyimide solution for upper photo-alignment layer
Eg210.89g (0.08mol), Eg55.96g (0.02mol) and 145.8g of NMP are added into a 500ml three-neck round-bottom flask equipped with a mechanical stirrer, a thermometer and an argon protection device, stirring is continuously carried out at 60 ℃, Eg119.6g is added after complete dissolution is confirmed, 13.44g of pyridine and 17.34g of acetic anhydride are added after reaction is carried out at 60 ℃ under the condition of 20 wt%, polyimide resin is precipitated by slowly dripping the solution into ethanol after chemical imidization is carried out for 16h, dried polyimide resin 3 is obtained after vacuum baking is carried out at 80 ℃ for 24h, 10g of dried polyimide resin 3 is dissolved into 93.99g of NMP, 62.66gBC is added to dilute the solution to 6 wt%, and the solution is filtered by using a 0.2um pore filter membrane to obtain the polyimide solution 3, wherein the NMP/BC is 60/40, and the viscosity is 29 cps.
Preparation of bottom layer characteristic polyamic acid solution
Eg212.26g (0.08mol) Eg33.98g (0.02mol) and 143.36g NMP were added to a 500ml three neck round bottom flask equipped with mechanical stirring, thermometer and argon protection, stirring was continued at 60 ℃ to confirm complete dissolution, Eg119.6g was added, 20 wt% was reacted at 60 ℃ for 6h, 193.53g NMP was added, 224.59gBC diluted the solids to 6 wt%, and filtered through a 0.2um pore size filter to give polyamic acid solution 1 with a viscosity of 40cps at NMP/BC 60/40.
Preparation of polyimide/polyamic acid photo-alignment agent solution
30g of the polyimide solution 3 prepared above was mixed with 70g of the polyamic acid solution 1, and the mixture was uniformly shaken to obtain a polyimide/polyamic acid photo-alignment agent solution 4 having a NMP/BC of 60/40 and a viscosity of 38 cps.
Optical orientation film and liquid crystal test box preparation
The polyimide/polyamic acid photo-alignment agent 3 is uniformly coated on an ITO glass substrate, baked for 2min at the temperature of 80 ℃, and then cured for 30min at the temperature of 230 ℃ to form a liquid crystal photo-alignment film with the film thickness of 600 angstroms. Then, the films were irradiated with ultraviolet polarized light of 254nm, 100mj/cm2, 200mj/cm2, and 300mj/cm2 at 0 ℃ for orientation, and then baked at 230 ℃ and post-cured for 30min to form a 600. ANGSTROM-oriented film. And finally, assembling the liquid crystal box, and filling liquid crystal to obtain the complete liquid crystal test box 4.
Example 4
Preparation of polyimide/polyamic acid photo-alignment agent solution
10g of the polyimide solution 3 prepared above was mixed with 90g of the polyamic acid solution 1, and the mixture was uniformly shaken to obtain a polyimide/polyamic acid photo-alignment agent solution 5 having a NMP/BC of 60/40 and a viscosity of 40 cps.
Optical orientation film and liquid crystal test box preparation
The polyimide/polyamic acid photo-alignment agent 5 is uniformly coated on an ITO glass substrate, baked for 2min at the temperature of 80 ℃, and then cured for 30min at the temperature of 230 ℃ to form a liquid crystal photo-alignment film with the film thickness of 600 angstroms. Then, the films were irradiated with ultraviolet polarized light of 254nm, 100mj/cm2, 200mj/cm2, and 300mj/cm2 at 0 ℃ for orientation, and then baked at 230 ℃ and post-cured for 30min to form a 600. ANGSTROM-oriented film. And finally, assembling the liquid crystal box, and filling liquid crystal to obtain the complete liquid crystal test box 5.
Example 5
Preparation of polyimide solution for upper photo-alignment layer
Eg210.89g (0.08mol), Eg64.80g (0.02mol) and 141.16g NMP are added into a 500ml three-neck round bottom flask equipped with a mechanical stirring device, a thermometer and an argon protection device, stirring is continuously carried out at 60 ℃, Eg119.6g is added after complete dissolution is confirmed, 13.44g pyridine and 17.34g acetic anhydride are added after reaction is carried out at 60 ℃ for 10h under the condition of 20 wt%, polyimide resin is precipitated from the solution slowly ethanol after chemical imidization is carried out for 16h, vacuum baking is carried out at 80 ℃ for 24h to obtain dry polyimide resin 4, 10g dry polyimide resin 4 is taken and dissolved in 93.99g NMP, 62.66gBC is added to dilute the solution to 6 wt%, and the polyimide solution 4 is obtained after filtration by using a 0.2um filter membrane, wherein the viscosity of NMP/BC is 60/40 cps.
Preparation of bottom layer characteristic polyamic acid solution
Eg212.26g (0.08mol) Eg33.98g (0.02mol) and 143.36g NMP were added to a 500ml three neck round bottom flask equipped with mechanical stirring, thermometer and argon protection, stirring was continued at 60 ℃ to confirm complete dissolution, Eg119.6g was added, 20 wt% was reacted at 60 ℃ for 6h, 193.53g NMP was added, 224.59gBC diluted the solids to 6 wt%, and filtered through a 0.2um pore size filter to give polyamic acid solution 1 with a viscosity of 40cps at NMP/BC 60/40.
Preparation of polyimide/polyamic acid photo-alignment agent solution
30g of the polyimide solution 4 prepared above was mixed with 70g of the polyamic acid solution 1, and the mixture was uniformly shaken to obtain a polyimide/polyamic acid photo-alignment agent solution 6 having a NMP/BC of 60/40 and a viscosity of 34 cps.
Optical orientation film and liquid crystal test box preparation
The polyimide/polyamic acid photo-alignment agent 6 is uniformly coated on an ITO glass substrate, baked for 2min at the temperature of 80 ℃, and then cured for 30min at the temperature of 230 ℃ to form a liquid crystal photo-alignment film with the film thickness of 600 angstroms. Then, the films were irradiated with ultraviolet polarized light in the 0 ℃ direction at 254nm, 100mj/cm2, 200mj/cm2, and 300mj/cm2, respectively, and then baked at 230 ℃ and post-cured for 30 minutes to form a 600. ANGSTROM-oriented film. And finally, assembling the liquid crystal box, and filling liquid crystal to obtain the complete liquid crystal test box 6.
Example 6
Preparation of polyimide/polyamic acid photo-alignment agent solution
10g of the polyimide solution 4 prepared above was mixed with 90g of the polyamic acid solution 1, and the mixture was uniformly shaken to obtain a polyimide/polyamic acid photo-alignment agent solution 7 having a NMP/BC of 60/40 and a viscosity of 34 cps.
Optical orientation film and liquid crystal test box preparation
The polyimide/polyamic acid photo-alignment agent 7 is uniformly coated on an ITO glass substrate, baked for 2min at the temperature of 80 ℃, and then cured for 30min at the temperature of 230 ℃ to form a liquid crystal photo-alignment film with the film thickness of 600 angstroms. Then, the films were irradiated with ultraviolet polarized light in the 0 ℃ direction at 254nm, 100mj/cm2, 200mj/cm2, and 300mj/cm2, respectively, and then baked at 230 ℃ and post-cured for 30 minutes to form a 600. ANGSTROM-oriented film. And finally, assembling the liquid crystal box, and filling liquid crystal to obtain the complete liquid crystal test box 7.
The liquid crystal test boxes prepared in each proportion and in the examples are subjected to orientation effect and photoelectric property tests under the following test conditions:
alignment effect determination conditions:
and (5) under a light table, visually observing the liquid crystal flushing mark state in the liquid crystal test box surface through a polaroid.
The grade was determined as in table 1 below:
table 1: orientation grade determination
Figure BDA0003378101260000181
Pretilt angle test conditions:
testing equipment: shintech Optitro-STD (3STN11)
And (3) testing wavelength: 591.4nm
And (3) a test mode: IPS mode
Electrical property test conditions:
testing equipment: 6254C
VHR measurement conditions: voltage 5V, pulse width 60 us/frame, period 1667ms, and measurement temperature 25 deg.C/60 deg.C
Ion sensitivity measurement conditions: voltage 5V, pulse width 60 us/frame, period 1667ms, and measurement temperature 25 deg.C/60 deg.C
Residual direct-current voltage test conditions:
testing equipment: 6254C RDC measurement conditions: voltage 5V, energization time 2400s, test time 1200 s. The liquid crystal cell test results are shown in tables 2 and 3 below, wherein "/" is no test
TABLE 2 liquid Crystal cell test results-1
Figure BDA0003378101260000191
Figure BDA0003378101260000201
TABLE 3 liquid Crystal cell test results-2
Figure BDA0003378101260000202
Figure BDA0003378101260000211
Transmittance tests are carried out on the liquid crystal test cells prepared in each comparative example and in the example, and the absorption capacity of the photoalignment film to light with a specific wavelength is judged by comparing the transmittance difference, so that the alignment rate of the photoalignment film is determined. The absorbance is inversely proportional to the transmittance data, i.e., the transmittance data can be tested to compare the intensity of light absorbed by the alignment film. The test conditions were as follows:
testing equipment: agilent Cary 300
Test wavelength of 200-
The transmittance test results of the photo-alignment films under different amounts of photo-deposition are shown in fig. 1 and 2. Wherein, fig. 1 is a result of transmittance test of example 1, example 3, example 5 and comparative example 1, and fig. 2 is a result of transmittance test of example 2, example 4, example 6 and comparative example 2.
The results of the test on the photo-alignment films were compared to each other, and it was found that:
the photo-alignment agent added with the rapid alignment structure monomer has an alignment effect obviously superior to that of a comparative example under the condition of the same photo-deposition amount, wherein the improvement effect of adding the Eg5 is the best.
The photo-alignment agent added with the fast alignment structure monomer has more stable performance than the comparative example along with the increase of the photo-deposition amount.
The transmittance of the photo-alignment agent added with the rapid alignment structure monomer under the condition of 250-300 nm is obviously lower than that of a comparative example, wherein the photo-alignment film added with the Eg5 has the best absorption effect on the waveband.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A method for preparing a polyimide photo-alignment agent solution, comprising the steps of:
(1) preparation of polyimide solution of upper photo-alignment layer:
(1.1) under a protective atmosphere, mixing a basic diamine monomer, a fast photo-oriented diamine monomer, a polar aprotic solvent and a dianhydride monomer, and then reacting to obtain a reaction system;
(1.2) mixing the obtained reaction system with pyridine and acetic anhydride, and then carrying out imidization reaction to generate polyimide resin;
(1.3) dissolving the obtained polyimide resin in a polar aprotic solvent and a leveling agent to obtain a polyimide solution;
(2) preparation of bottom layer characteristic polyamic acid solution
(2.1) under a protective atmosphere, mixing a basic diamine monomer, a characteristic diamine monomer, a polar aprotic solvent and a dianhydride monomer, and then reacting to obtain a reaction system;
(2.2) mixing the obtained reaction system with a polar aprotic solvent and a leveling agent to obtain a characteristic polyamic acid solution;
the characteristic diamine monomer is
Figure FDA0003378101250000011
Wherein, R is5is-CnH2n-NH-, -O-or-SO2-, n is an integer of 1 to 5;
(3) mixing the obtained polyimide solution and the characteristic polyamic acid solution to obtain a polyimide photo-alignment agent solution;
the step (1) and the step (2) are not limited in sequence.
2. The method according to claim 1, wherein in the step (1.1):
the protective atmosphere is nitrogen or argon;
the base diamine monomer is
Figure FDA0003378101250000012
And/or
Figure FDA0003378101250000021
Wherein, X groups are independently-H, methyl, ethyl or propyl;
the fast photo-oriented diamine monomer is
Figure FDA0003378101250000022
Wherein R is6And R7Independently is-CH2-、-CH2-CH2-、-CH2-CH2-CH2-, -NH-or-O-;
the polar aprotic solvent is one or more of N-methylpyrrolidone, 1, 4-butyrolactone, N-ethylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide;
the dianhydride monomer is one of the following structural formulas
Figure FDA0003378101250000023
The reaction temperature is 55-65 ℃, and the reaction time is 2-24 h;
the mole fraction of the basic diamine monomer in the total mole number of the basic diamine monomer and the rapid photo-orientation diamine monomer is 10-99%;
the molar ratio of the total moles of the basic diamine monomer and the fast photo-orientation diamine monomer to the dianhydride monomer is 1 (0.8-1.2);
the mass ratio of the total moles of the basic diamine monomer and the fast photo-orientation diamine monomer to the polar aprotic solvent is 1 mol: (130-150) g.
3. The method according to claim 1 or 2, wherein in the step (1.2):
the temperature of the imidization reaction is 75-85 ℃, and the time is 1-12 h;
the mass ratio of the pyridine to the acetic anhydride to the polar aprotic solvent in the step (1.1) is (10-15): (15-20): (130-150).
4. The production method according to claim 3, wherein in the step (1.3):
the polar aprotic solvent is one or more of N-methylpyrrolidone, 1, 4-butyrolactone, N-ethylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide;
the flatting agent is one or more of ethylene glycol monobutyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether ethyl ester, butyl lactate, cyclopentanone and diisobutyl ketone;
the mass ratio of the polar aprotic solvent to the leveling agent to the polar aprotic solvent in the step (1.1) is (90-100): (55-70): (130-150);
the viscosity of the obtained polyimide solution is 5-100 cps.
5. The production method according to claim 1 or 4, wherein in the step (2.1):
the protective atmosphere is nitrogen or argon;
the base diamine monomer is
Figure FDA0003378101250000031
And/or
Figure FDA0003378101250000041
Wherein, X groups are independently-H, methyl, ethyl or propyl;
the polar aprotic solvent is one or more of N-methylpyrrolidone, 1, 4-butyrolactone, N-ethylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide;
the dianhydride monomer is one of the following structural formulas
Figure FDA0003378101250000042
The reaction temperature is 55-65 ℃, and the reaction time is 2-12 h;
the molar ratio of the total mole number of the basic diamine monomer and the characteristic diamine monomer to the mole number of the dianhydride monomer is 1 (0.8-1.2);
the mole fraction of the basic diamine monomer in the total mole number of the basic diamine monomer and the characteristic diamine monomer is 10-90%;
the mass ratio of the total mole number of the basic diamine monomer and the characteristic diamine monomer to the polar aprotic solvent is 1 mol: (130-150) g.
6. The method according to claim 5, wherein in the step (2.2):
the polar aprotic solvent is one or more of N-methylpyrrolidone, 1, 4-butyrolactone, N-ethylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide;
the flatting agent is one or more of ethylene glycol monobutyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether ethyl ester, butyl lactate, cyclopentanone and diisobutyl ketone;
the mass ratio of the polar aprotic solvent to the leveling agent to the polar aprotic solvent in the step (2.1) is (190-200): (220-230): (130-150);
the viscosity of the obtained characteristic polyamic acid solution is 10-100 cps;
the mass ratio of the polyimide solution to the characteristic polyamide acid solution in the step (3) is (10-30): 70-90.
7. A polyimide photo-alignment agent solution obtained by the production method according to any one of claims 1 to 6.
8. A method for preparing a photo-alignment film coated on a substrate from the polyimide photo-alignment agent solution of claim 7, comprising the steps of:
coating the polyimide photo-alignment agent solution on a substrate, and then sequentially baking and curing to obtain a liquid crystal photo-alignment film; the baking temperature is 60-120 ℃, and the baking time is 1-5 min; the curing temperature is 220-240 ℃, and the curing time is 20-40 min;
irradiating the obtained liquid crystal photo-alignment film with ultraviolet polarized light for alignment, and then baking to obtain a photo-alignment film; the baking temperature is 220-240 ℃, and the baking time is 20-40 min.
9. A photoalignment film coated on a substrate obtained by the method of claim 8.
10. A liquid crystal cell prepared from the photo-alignment film coated on the substrate according to claim 9.
CN202111425290.0A 2021-11-26 2021-11-26 Polyimide photo-alignment agent solution and preparation method thereof, photo-alignment film and liquid crystal box Pending CN114058384A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111425290.0A CN114058384A (en) 2021-11-26 2021-11-26 Polyimide photo-alignment agent solution and preparation method thereof, photo-alignment film and liquid crystal box

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111425290.0A CN114058384A (en) 2021-11-26 2021-11-26 Polyimide photo-alignment agent solution and preparation method thereof, photo-alignment film and liquid crystal box

Publications (1)

Publication Number Publication Date
CN114058384A true CN114058384A (en) 2022-02-18

Family

ID=80276749

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111425290.0A Pending CN114058384A (en) 2021-11-26 2021-11-26 Polyimide photo-alignment agent solution and preparation method thereof, photo-alignment film and liquid crystal box

Country Status (1)

Country Link
CN (1) CN114058384A (en)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1922540A (en) * 2004-02-26 2007-02-28 日产化学工业株式会社 Liquid crystal aligning agent for photoalignment and liquid crystal display device utilizing the same
CN101589333A (en) * 2006-12-27 2009-11-25 日产化学工业株式会社 Liquid crystal orientating agent, the liquid crystal orientating membrane that has used this directing agent and liquid crystal display cells
CN102893207A (en) * 2010-03-15 2013-01-23 日产化学工业株式会社 Polyamic acid ester liquid crystal alignment agent, and liquid crystal alignment film using same
CN103666487A (en) * 2012-09-14 2014-03-26 Jsr株式会社 Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element
CN105765452A (en) * 2013-09-26 2016-07-13 日产化学工业株式会社 Liquid crystal aligning agent and liquid crystal display element using same
CN107615147A (en) * 2015-03-30 2018-01-19 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal represent element
CN108604028A (en) * 2015-11-30 2018-09-28 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
US20180298284A1 (en) * 2016-05-13 2018-10-18 Lg Chem, Ltd. Composition for liquid crystal alignment agent, manufacturing method of liquid crystal alignment film, liquid crystal alignment film using the same and liquid crystal display device
CN109970975A (en) * 2019-03-27 2019-07-05 北京波米科技有限公司 A kind of high voltage holding ratio type polyimides and its preparation method and application
WO2021106979A1 (en) * 2019-11-26 2021-06-03 日産化学株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
WO2021177080A1 (en) * 2020-03-06 2021-09-10 日産化学株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1922540A (en) * 2004-02-26 2007-02-28 日产化学工业株式会社 Liquid crystal aligning agent for photoalignment and liquid crystal display device utilizing the same
CN101589333A (en) * 2006-12-27 2009-11-25 日产化学工业株式会社 Liquid crystal orientating agent, the liquid crystal orientating membrane that has used this directing agent and liquid crystal display cells
CN102893207A (en) * 2010-03-15 2013-01-23 日产化学工业株式会社 Polyamic acid ester liquid crystal alignment agent, and liquid crystal alignment film using same
CN103666487A (en) * 2012-09-14 2014-03-26 Jsr株式会社 Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element
CN105765452A (en) * 2013-09-26 2016-07-13 日产化学工业株式会社 Liquid crystal aligning agent and liquid crystal display element using same
CN107615147A (en) * 2015-03-30 2018-01-19 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal represent element
CN108604028A (en) * 2015-11-30 2018-09-28 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
US20180298284A1 (en) * 2016-05-13 2018-10-18 Lg Chem, Ltd. Composition for liquid crystal alignment agent, manufacturing method of liquid crystal alignment film, liquid crystal alignment film using the same and liquid crystal display device
CN109970975A (en) * 2019-03-27 2019-07-05 北京波米科技有限公司 A kind of high voltage holding ratio type polyimides and its preparation method and application
WO2021106979A1 (en) * 2019-11-26 2021-06-03 日産化学株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
WO2021177080A1 (en) * 2020-03-06 2021-09-10 日産化学株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

Similar Documents

Publication Publication Date Title
TWI407211B (en) A liquid crystal alignment agent and a liquid crystal display device using the liquid crystal display device
CN100529917C (en) Liquid crystal tropism agent and LCD member
JP4605016B2 (en) Liquid crystal aligning agent for vertical alignment and liquid crystal display element
US20060246230A1 (en) Novel diaminobenzene derivative, polyimide precursor and polyimide obtained therefrom, and aligning agent for liquid crystal
WO2013041017A1 (en) Prepolymer, oriented film and preparation method thereof, and liquid crystal display device
CN110475838B (en) Polymer for liquid crystal aligning agent, liquid crystal aligning agent composition comprising same, liquid crystal aligning film using same, and liquid crystal display device
EP1507161B1 (en) Liquid crystal aligning agent, liquid crystal aligning films and liquid crystal display devices
WO2011074546A1 (en) Liquid crystal aligning agent and liquid crystal display element using same
CN112602013A (en) Liquid crystal aligning agent, method for producing same, liquid crystal alignment film, and liquid crystal display element
KR20160070777A (en) Composition, treatment agent for liquid crystal alignment, liquid crystal alignment film, and liquid crystal display element
WO2002005024A1 (en) Liquid crystal orientating agent and liquid crystal display element using the same
CN113544184B (en) Composition for film formation, cured film, liquid crystal alignment film, and retardation film
KR20160003120A (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
US6489431B1 (en) Polyimide precursors and polyimides
KR101973192B1 (en) Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film using the same
CN109970975B (en) High-voltage-holding-ratio polyimide and preparation method and application thereof
JP5833698B2 (en) Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element thereof
CN108070388B (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
CN114058384A (en) Polyimide photo-alignment agent solution and preparation method thereof, photo-alignment film and liquid crystal box
CN115960351A (en) Friction type polyimide liquid crystal aligning agent, liquid crystal alignment film and preparation method of liquid crystal box of liquid crystal alignment film
CN112225675B (en) Arylamine compound, liquid crystal aligning agent prepared from arylamine compound, liquid crystal aligning film and liquid crystal display element
TWI779250B (en) Cross-linking agent compound, liquid crystal alignment composition comprising the same, method of preparing liquid crystal alignment film, and liquid crystal alignment film, liquid crystal display using the same
CN114702403A (en) Semi-alicyclic ester bond-containing diamine monomer and preparation thereof, polyamic acid liquid crystal orientation agent, orientation film and preparation and application thereof, and liquid crystal box
JP5298398B2 (en) Liquid crystal aligning agent and liquid crystal display device using the same
US20090292103A1 (en) Polyamic acid and polyimide

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20220218