CN114456378A - Polyimide for liquid crystal aligning agent and liquid crystal alignment film prepared from polyimide - Google Patents
Polyimide for liquid crystal aligning agent and liquid crystal alignment film prepared from polyimide Download PDFInfo
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- CN114456378A CN114456378A CN202011238978.3A CN202011238978A CN114456378A CN 114456378 A CN114456378 A CN 114456378A CN 202011238978 A CN202011238978 A CN 202011238978A CN 114456378 A CN114456378 A CN 114456378A
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- liquid crystal
- polyimide
- aligning agent
- crystal aligning
- alignment film
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 97
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 52
- 229920001721 polyimide Polymers 0.000 title claims abstract description 39
- 239000004642 Polyimide Substances 0.000 title claims abstract description 35
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 46
- 239000000758 substrate Substances 0.000 claims description 32
- 239000010408 film Substances 0.000 claims description 30
- 229920005575 poly(amic acid) Polymers 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 22
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 14
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 13
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 150000004984 aromatic diamines Chemical class 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 6
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 5
- ZSQIQUAKDNTQOI-UHFFFAOYSA-N 4-[1-(4-aminophenyl)cyclohexyl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)CCCCC1 ZSQIQUAKDNTQOI-UHFFFAOYSA-N 0.000 claims description 5
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 5
- 230000010287 polarization Effects 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 3
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 claims description 3
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical group O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- KBRVQAUYZUFKAJ-UHFFFAOYSA-N 1-trimethoxysilylpropan-2-amine Chemical compound CO[Si](OC)(OC)CC(C)N KBRVQAUYZUFKAJ-UHFFFAOYSA-N 0.000 claims description 2
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 150000001448 anilines Chemical class 0.000 claims description 2
- 238000000137 annealing Methods 0.000 claims description 2
- BYURCDANQKFTAN-UHFFFAOYSA-N n'-(3-dimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[SiH](OC)CCCNCCN BYURCDANQKFTAN-UHFFFAOYSA-N 0.000 claims description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- -1 silane compound Chemical class 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000011521 glass Substances 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 206010047571 Visual impairment Diseases 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000000565 sealant Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007644 letterpress printing Methods 0.000 description 2
- 231100000862 numbness Toxicity 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007699 photoisomerization reaction Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- SBHHKGFHJWTZJN-UHFFFAOYSA-N 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1(C)C(C(O)=O)C(C)(C(O)=O)C1C(O)=O SBHHKGFHJWTZJN-UHFFFAOYSA-N 0.000 description 1
- KWFFEQXPFFDJER-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)propoxy]aniline Chemical compound C1=CC(N)=CC=C1OCCCOC1=CC=C(N)C=C1 KWFFEQXPFFDJER-UHFFFAOYSA-N 0.000 description 1
- JXYITCJMBRETQX-UHFFFAOYSA-N 4-ethynylaniline Chemical compound NC1=CC=C(C#C)C=C1 JXYITCJMBRETQX-UHFFFAOYSA-N 0.000 description 1
- QZHXKQKKEBXYRG-UHFFFAOYSA-N 4-n-(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C(N)C=C1 QZHXKQKKEBXYRG-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
Classifications
-
- 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
- C08G73/1042—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
- C08G73/1003—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
- C09K19/542—Macromolecular compounds
-
- 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
- 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
Abstract
The invention discloses polyimide for a liquid crystal aligning agent, and belongs to the technical field of liquid crystal display. The structure of the polyimide is shown as formula (1):
Description
Technical Field
The invention relates to the technical field of liquid crystal display, in particular to polyimide for a liquid crystal aligning agent and a liquid crystal aligning film prepared from the polyimide.
Background
Thin film transistor liquid crystal display devices (TFT-LCDs) have been widely used in various aspects of people's work and life because of their display advantages such as high resolution, high brightness, light weight, low power consumption, and flat panel. The TFT-LCD includes a liquid crystal layer interposed between two substrates and a color filter substrate, a pixel electrode and a common electrode that apply an electric field to the liquid crystal layer, an alignment film that controls the alignment of liquid crystal molecules of the liquid crystal layer, a thin film transistor that switches an electric signal supplied to the pixel electrode, and the like. The alignment film, which is one of the structures of the TFT-LCD, functions to uniformly align liquid crystal molecules on a substrate in one direction and to make the liquid crystal molecules have a certain tilt angle (pretilt angle) with respect to the plane of the substrate. Therefore, the liquid crystal alignment film is very relevant to the display quality of the liquid crystal display device, and the function thereof is important in accordance with the high quality of the TFT-LCD.
The liquid crystal alignment film is formed by coating, drying and film-forming a liquid crystal alignment agent and then performing alignment treatment. The liquid crystal aligning agent used at present refers to an organic solution of polyamic acid or soluble polyimide. The alignment treatment method, which is widely used industrially, is a rubbing method of rubbing cotton cloth or nylon in a single direction along the surface of a liquid crystal alignment film to generate grooves on the surface of the liquid crystal alignment film or to orderly align molecules on the surface of the alignment film in the rubbing direction, thereby inducing the alignment of the liquid crystal molecules on the surface of the alignment film. However, the rubbing method has the following problems: the surface is likely to be scratched or chipped, and is likely to cause static electricity, in-plane treatment unevenness, and the like, thereby causing display failure.
As an alternative method to rubbing alignment, a photo-alignment method is known in which a surface of a liquid crystal alignment film is irradiated with polarized ultraviolet light to align liquid crystals, that is, a photo-alignment method. The photo-alignment method has uniform alignment as compared with the rubbing method, and since it is non-contact alignment, it does not damage the film and can reduce display defects due to dust or static electricity. The photo-orientation treatment can be divided into three methods according to the mechanism, namely a photo-decomposition method, a photo-isomerization method and a photo-crosslinking method, and the photo-isomerization method and the photo-crosslinking method are popular at present because of poor stability in the later period. TFT-LCDs are classified into TN (twisted nematic) mode, STN (super twisted) mode, IPS (in-plane switching), FFS (fringe field switching), VA (vertical alignment) mode, etc. according to the state of liquid crystal change before and after application of an applied electric field and the driving method, among which the IPS (in-plane switching) and FFS (fringe field switching) mode display modes are widely used in high-end display areas such as mobile phones, televisions, and computer displays because of their advantages such as high contrast and wide viewing field, and the above-mentioned photo-alignment processing method is helpful to improve the contrast and viewing angle of the IPS and FFS modes compared to the conventional rubbing alignment process. However, photo-alignment treatment has a problem that the anchoring ability of liquid crystal is weak as compared with rubbing alignment, and after a long-term ac driving, an afterimage due to small anisotropy is generated.
The IPS and FFS type liquid crystal display devices generate dc bias charges during driving, and the charges accumulated during switching the screen cannot be quickly dissipated with the dc bias charges accumulated on the surface, which causes the electric field intensity received by the liquid crystal to be inconsistent with the applied electric field intensity, thereby generating an afterimage due to the dc charge accumulation.
Disclosure of Invention
In view of the above problems in the prior art, the present applicant provides a polyimide for a liquid crystal aligning agent and a liquid crystal alignment film prepared therefrom. The orientation agent has high-efficiency orientation control, excellent electrical property and image retention property.
The technical scheme of the invention is as follows:
a polyimide for a liquid crystal aligning agent, the polyimide having a structure represented by formula (1):
in formula (1), X, which may be the same or different at each occurrence, is represented by any one of the following groups:
y represents any one of the following groups:
n and m are the number of repeating units of the repeating unit in the polymer, and are respectively independent natural numbers of 0-100.
Preferably, n and m are respectively and independently a natural number of 30-50.
A method for preparing polyimide for a liquid crystal aligning agent, comprising the steps of:
(1) dissolving 1, 1-bis (4-aminophenyl) cyclohexane and aromatic diamine in an aprotic polar solvent, then adding one or two aliphatic tetracarboxylic acid dianhydrides, a molecular weight regulator and the aprotic polar solvent, and stirring and reacting for 6-8 hours at 40-80 ℃ to obtain an initial polyamic acid solution;
(2) and (2) adding a diluent and an additive into the polyamic acid solution obtained in the step (1), and stirring at room temperature for 1-2 hours to form a uniform solution, thereby obtaining the polyimide liquid crystal aligning agent.
Preferably, the structural formula of the 1, 1-bis (4-aminophenyl) cyclohexane is shown as the formula (2):
the aromatic diamine is selected from one or more of the following structures:
the aliphatic tetracarboxylic dianhydride is cyclobutane tetracarboxylic dianhydride or a derivative thereof.
In a preferred embodiment, the aprotic polar solvent is at least one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and γ -butyrolactone; the molecular weight regulator is at least one of phthalic anhydride, phthalic anhydride derivatives, aniline and aniline derivatives; the diluent is at least one of N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide, gamma-butyrolactone and ethylene glycol monobutyl ether; the additive is epoxy and/or silane compounds, and the addition amount of the additive is 0.1-5% of the solid content of the polyimide liquid crystal aligning agent;
preferably, the epoxy compound is one or more of ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, N ' -tetracyclooxypropyl-m-xylylenediamine, N ' -tetracyclooxypropyl-4, 4 ' -diaminodiphenylmethane, or 3- (N, N-diglycidyl) aminopropyltrimethoxysilane;
the silane compound is one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane or N-bis (ethylene oxide) -3-aminopropyltriethoxysilane.
The molar ratio of the aromatic diamine to the aliphatic tetracarboxylic dianhydride in the step (1) is 1: 098-1; the polyimide liquid crystal aligning agent obtained in the step (2) has a solid content of 1-15%, a viscosity of 20-50 mPa · s, a weight average molecular weight of 1000-200000, a number average molecular weight of 1000-100000, and a polydispersity of 1-20.
A liquid crystal alignment film prepared from the obtained liquid crystal alignment agent comprises the following steps:
(1) coating the polyimide liquid crystal aligning agent on a substrate, and obtaining a polyimide film after pre-curing and main curing treatment;
(2) irradiating the polyimide film by using linearly polarized ultraviolet light, and then annealing to obtain the polyimide liquid crystal alignment film;
in the preferable scheme, the pre-curing temperature in the step (1) is 50-100 ℃, and the time is 1-3 min; the main curing temperature is 200-250 ℃, and the time is 30-60 min; the wavelength of the linear polarization ultraviolet light in the step (2) is 150 nm-365 nm.
The polyimide orientation film is applied to a thin film transistor liquid crystal display.
The photo-alignment polyimide alignment film prepared by the invention can be used for preparing TFT-LCD displays, and is particularly suitable for IPS and FFS modes.
The alignment property of the alignment film of the present invention was evaluated by the following procedure:
two 3cm × 4cm glass substrates with a thickness of 0.7mm were prepared, wherein the lower substrate was provided with comb-shaped ITO electrodes with a thickness of 50nm and a pitch of adjacent comb-shaped electrodes of 3 μm, and pixel electrodes were arranged to intersect with the common electrode. The upper glass substrate is not provided with an electrode, the prepared liquid crystal aligning agent is coated on the two substrates in modes of spin coating or letterpress printing and the like, and the polyimide coating with the film thickness of 50-100 nm is obtained through pre-curing (hot plate, 80 ℃ and 3 minutes) and main curing (circulating oven, 230 ℃ and 60 minutes).
Irradiating upper and lower glass substrates with polyimide coating with ultraviolet linearly polarized light with wavelength of 254nm and light dose of 400mj/cm for photo-orientation treatment2Then heating the glass substrates in a thermal circulation oven at 230 ℃ for 60min, spraying spacer particles with the diameter of 4 mu m on one substrate of the oriented upper and lower glass substrates, printing sealant at the position 5mm away from the short side of the glass on the other substrate, directly printing the sealant on the film surface of an orientation agent by the sealant, leaving a liquid crystal filling port with the diameter of 5mm, then pasting the upper and lower substrates together in a mode that the orientation film surface is opposite, the polarization axis of the photo-orientation treatment is parallel and the superposition width of the upper and lower substrates is 3cm, fixing the pasted two substrates by a clamp, curing for 1 hour at the temperature of 150 ℃ to prepare a liquid crystal empty box, injecting IPS negative liquid crystal into the empty box in a decompression mode, and sealing the liquid crystal filling port. The corresponding liquid crystal display element is obtained. Illuminating a backlight source, attaching the upper substrate and the lower substrate to the polaroid, and visually observing the orientation state of the liquid crystal; testing of the pretilt angle on a RETS-100 (tsukau electronics limited) device; the RDC and VHR tests were performed on a liquid crystal electro-optic tester (Instec).
The beneficial technical effects of the invention are as follows:
the TFT-LCD device prepared by the light-operated oriented polyimide oriented film provided by the invention has the characteristics of uniform orientation, pretilt angle less than 0.1%, RDC less than 0.5V, VHR more than 99.5% and the like, so that accumulated charges in a liquid crystal box can be quickly released, and a display device with excellent afterimage performance can be obtained.
Detailed Description
The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention. The abbreviations of the compounds used in examples and comparative examples and the methods for measuring the respective properties are as follows:
NMP: n-methyl-2-pyrrolidone
BC ethylene glycol monobutyl ether
Gamma-butyrolactone of GBL
TAPC 1, 1-bis (4-aminophenyl) cyclohexane
a-1:1, 3-bis (4-aminophenoxy) ethane
a-2:1, 3-bis (4-aminophenoxy) propane
a-3-P-phenylenediamine
a-4: 4, 4' -diaminodiphenylamine
b-1:1,2,3, 4-Cyclobutanetetracarboxylic dianhydride
b-2:1, 3-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride
b-3:2,3, 5-tricarboxycyclopentylacetic acid dianhydride
< example 1>
13.309g (50mmol) of TAPC, 12.206g (50mmol) of a-1 and 131.478g of NMP are sequentially added to a 500mL three-necked round-bottomed flask under nitrogen atmosphere, and stirred to dissolve all components, and then 9.8g (50mmol) of b-1, 11.089g (49.5mmol) of b-2, 0.01g of phthalic anhydride and 131.478g of NMP are added to the system and stirred at 40 ℃ for 8 hours to obtain a polyamic acid polymer having a solid content of 15%.
354.2172g of NMP, 176.3352g of GBL, 88.1676g of BC and 0.05g of ethylene glycol diglycidyl ether were added to the above polyamic acid solution, stirred at room temperature for 2 hours, and then filtered through a 0.2 μm filter to obtain a liquid crystal aligning agent PI-1 of example 1 having a viscosity of 31.5 mPas. The concentration of the polymer in the liquid crystal aligning agent was 5%, and the solvent ratio was NMP to GBL to BC was 7 to 2 to 1.
The structural formula of the PI prepared in the embodiment is as follows:
GPC measurement results: the weight average molecular weight is 46510.5, the number average molecular weight is 22147.86, the polydispersity is 2.1, n is 50, and m is 50.
< example 2>
13.309g (50mmol) of TAPC, 12.206g (50mmol) of a-1 and 126.99g of NMP are sequentially added to a 500mL three-necked round-bottomed flask under nitrogen atmosphere, and stirred to dissolve all components, and then 19.306g (98.5mmol) of b-1, 0.01g of aniline and 126.99g of NMP are added to the system, and stirred at 60 ℃ for 8 hours to obtain a polyamic acid polymer having a solid content of 15%.
100g of the polyamic acid solution was put in a 500mL three-necked flask, 114.5g of NMP, 85.5g of BC, 0.03g of polypropylene glycol diglycidyl ether, and 0.04g of 3-aminopropyltrimethoxysilane were added thereto, and the mixture was stirred at room temperature for 2 hours, followed by filtration through a 0.2 μm filter to obtain a liquid crystal aligning agent PI-2 of example 2 having a viscosity of 28.7 mPas. The concentration of the polymer in the liquid crystal aligning agent is 5%, and the solvent ratio is NMP, BC is 7: 3.
the structural formula of the PI prepared in the embodiment is as follows:
GPC measurement results: the weight average molecular weight is 45112.11, the number average molecular weight is 18796.67, the polydispersity is 2.4, n1 is 50, and m1 is 50.
< example 3>
13.309g (50mmol) of TAPC, 5.4035g (50mmol) of a-3 and 107.72g of NMP are sequentially added to a 500mL three-necked round-bottomed flask under nitrogen protection, stirred to be completely dissolved, and then 19.306g (98.5mmol) of b-1, 0.02g of 4-phenylacetylene phthalic anhydride and 107.72g of NMP are added to the system, and stirred at 40 ℃ for 6 hours to obtain a polyamic acid polymer having a solid content of 15%.
100g of the polyamic acid solution was put in a 500mL three-necked flask, 114.5g of NMP, 85.5g of BC, 0.05g of propylene glycol diglycidyl ether, and 0.7g of 3-aminopropyltriethoxysilane were added thereto, and the mixture was stirred at room temperature for 1 hour, followed by filtration through a 0.2 μm filter to obtain the liquid crystal aligning agent PI-3 of example 3, which had a viscosity of 34.3 mPas. The concentration of the polymer in the liquid crystal aligning agent is 5%, and the solvent ratio is NMP, BC is 7: 3.
the structural formula of the PI prepared in the embodiment is as follows:
GPC measurement results: the weight average molecular weight is 38311.05, the number average molecular weight is 15324.8, the polydispersity is 2.5, n2 is 50, and m2 is 50.
< example 4>
13.309g (50mmol) of TAPC, 9.9555g (50mmol) of a-4 and 120.62g of NMP are sequentially added to a 500mL three-necked round-bottomed flask under nitrogen atmosphere, and stirred to be completely dissolved, and then 19.306g (98.5mmol) of b-1, 0.04g of aniline and 120.62g of NMP are added to the system, and stirred at 80 ℃ for 8 hours to obtain a polyamic acid polymer having a solid content of 15%.
100g of the polyamic acid solution was put in a 500mL three-necked flask, 114.5g of NMP and 85.5g of 85.5gBC were added to the solution, and 3-aminopropyltrimethoxysilane was added thereto, and the mixture was stirred at room temperature for 2 hours and then filtered through a 0.2 μm filter to obtain a liquid crystal aligning agent PI-4 of example 4 having a viscosity of 33.1 mPas. The concentration of the polymer in the liquid crystal aligning agent is 5%, and the solvent ratio is NMP, BC is 7: 3.
the structural formula of the PI prepared in the embodiment is as follows:
GPC measurement results: the weight average molecular weight is 38311.05, the number average molecular weight is 15324.8, the polydispersity is 5, n3 is 50, and m3 is 50.
< example 5>
13.309g (50mmol) of TAPC, 12.907g (50mmol) of a-2 and 129.53g of NMP are sequentially added to a 500mL three-necked round-bottomed flask under nitrogen protection, stirred to be completely dissolved, and then 19.502g (99.5mmol) of b-1, 0.08g of 4-ethynylaniline and 129.53g of NMP are added to the system, and stirred at 60 ℃ for 8 hours to obtain a polyamic acid polymer having a solid content of 15%.
100g of the polyamic acid solution was put in a 500mL three-necked flask, 114.5g of NMP, 85.5g of BC, 0.5g of 1, 6-hexanediol diglycidyl ether, and 0.04g of 3-aminopropyltrimethoxysilane were added thereto, and the mixture was stirred at room temperature for 2 hours, followed by filtration through a 0.2 μm filter to obtain the liquid crystal aligning agent PI-5 of example 5 having a viscosity of 30.1 mPas. The concentration of the polymer in the liquid crystal aligning agent is 5%, and the solvent ratio is NMP, BC is 7: 3.
the structural formula of the PI prepared in the embodiment is as follows:
GPC measurement results: the weight average molecular weight is 45809, the number average molecular weight is 14270.71, the polydispersity is 3.21, n4 is 50, and m4 is 50.
< example 6>
13.309g (50mmol) of TAPC and 65.059g of NMP were put into a 500mL three-necked round-bottomed flask under nitrogen atmosphere and stirred to dissolve all components, and 9.653g (49.25mmol) of b-1, 0.04g of aniline and 65.059g of NMP were added to the system and stirred at 40 ℃ for 8 hours to obtain a polyamic acid polymer having a solid content of 15%.
100g of the polyamic acid solution was put in a 500mL three-necked flask, added with 114.5g of NMP, 85.5g of BC and 0.3g N-phenyl-3-aminopropyltrimethoxysilane, stirred at room temperature for 2 hours, and then filtered through a 0.2 μm filter to obtain the liquid crystal aligning agent PI-6 of example 6 having a viscosity of 24.6 mPas. The concentration of the polymer in the liquid crystal aligning agent is 5%, and the solvent ratio is NMP, BC is 7: 3.
the structural formula of the PI prepared in the embodiment is as follows:
GPC measurement results: the weight average molecular weight is 18973.31, the number average molecular weight is 3579.87, the polydispersity is 5.3, and n5 is 43.
< example 7>
13.309g (50mmol) of TAPC and 69.13g of NMP were put into a 500mL three-necked round-bottomed flask under nitrogen atmosphere and stirred to dissolve all components, and 11.089g (49.5mmol) of b-3, 0.04g of aniline and 69.13g of NMP were added to the system and stirred at 40 ℃ for 8 hours to obtain a polyamic acid polymer having a solid content of 15%.
100g of the polyamic acid solution was put in a 3L three-necked flask, and 954.5g of NMP, 445.5g of BC, and 0.3g of 3-aminopropyltriethoxysilane were added thereto, and the mixture was stirred at room temperature for 2 hours, followed by filtration through a 0.2 μm filter to obtain liquid crystal aligning agent PI-7 of example 7 having a viscosity of 25.3 mPas. The concentration of the polymer in the liquid crystal aligning agent is 1%, and the solvent ratio is NMP, BC is 7: 3.
the structural formula of the PI prepared in the embodiment is as follows:
GPC measurement results: the weight average molecular weight is 21000, the number average molecular weight is 5499.92, the polydispersity is 4.1, and n6 is 46.
< comparative example 1>
5.4035g (50mmol) of a-3 and 42.80g of NMP were put into a 500mL three-necked round-bottomed flask under nitrogen atmosphere and stirred to dissolve the whole, then 9.702g (49.5mmol) of b-1, 0.04g of aniline and 42.80g of NMP were added to the system and stirred at 40 ℃ for 8 hours to obtain a polyamic acid polymer having a solid content of 15%.
100g of the polyamic acid solution was taken in a 500mL three-necked flask, and 0.06g of 3-aminopropyltrimethoxysilane was added thereto, and the mixture was stirred at room temperature for 2 hours, followed by filtration through a 0.2 μm filter to obtain the liquid crystal aligning agent of comparative example 1 having a viscosity of 22.8 mPas. The concentration of the polymer in the liquid crystal aligning agent is 15%, and the solvent ratio is NMP, BC is 7: 3.
the structural formula of the PI prepared in the comparative example is as follows:
GPC measurement results: the weight average molecular weight is 10466.87, the number average molecular weight is 1661.41, the polydispersity is 6.3, and m5 is 41.
< comparative example 2>
9.9555g (50mmol) of a-4 and 59.94g of NMP were put into a 500mL three-necked round-bottomed flask under nitrogen atmosphere and stirred to dissolve all the components, then 11.2015g (50mmol) of b-2, 0.04g of aniline and 59.94g of NMP were added to the system and stirred at 40 ℃ for 7 hours to obtain a polyamic acid polymer having a solid content of 15%.
100g of the above polyamic acid solution was taken in a 500mL three-necked flask, 114.5g of NMP, 85.5g of BC and 0.5g of 3-aminopropyltrimethoxysilane were added, stirred at room temperature for 2 hours, and then filtered through a 0.2 μm filter to obtain the liquid crystal aligning agent of comparative example 2 having a viscosity of 20.4 mPas. The concentration of the polymer in the liquid crystal aligning agent is 5%, and the solvent ratio is NMP, BC is 7: 3.
the structural formula of the PI prepared in the comparative example is as follows:
GPC measurement results: the weight average molecular weight is 15887.48, the number average molecular weight is 2444.23, the polydispersity is 6.5, and m6 is 46.
< comparative example 3>
12.907g (50mmol) of a-2 and 64.34g of NMP were put into a 500mL three-necked round-bottomed flask under nitrogen atmosphere and stirred to dissolve the whole, and then 9.8g (50mmol) of b-1, 0.04g of aniline and 64.34g of NMP were added to the system and stirred at 40 ℃ for 6 hours to obtain a polyamic acid polymer having a solid content of 15%.
100g of the polyamic acid solution was taken in a 500mL three-necked flask, 114.5g of NMP, 85.5g of BC and 0.5g of 3-aminopropyltrimethoxysilane were added, stirred at room temperature for 2 hours, and then filtered through a 0.2 μm filter to obtain the liquid crystal aligning agent of comparative example 3 having a viscosity of 20.3 mPas. The concentration of the polymer in the liquid crystal aligning agent is 5%, and the solvent ratio is NMP, BC is 7: 3.
the structural formula of the PI prepared in the comparative example is as follows:
GPC measurement results: the weight average molecular weight is 17610.45, the number average molecular weight is 1600.95, the polydispersity is 11, and m7 is 38.
And (3) verifying the performance of the orientation agent:
two 3cm × 4cm glass substrates with a thickness of 0.7mm were prepared, wherein the lower substrate was provided with comb-shaped ITO electrodes with a thickness of 50nm and a pitch of adjacent comb-shaped electrodes of 3 μm, and pixel electrodes were arranged to intersect with the common electrode. The upper glass substrate does not have electrodes, the prepared liquid crystal aligning agent is coated on the two substrates in a spin coating or letterpress printing mode and the like, and a polyimide coating with the film thickness of 50-100 nm is obtained through pre-curing (hot plate, 80 ℃,3 minutes) and main curing (circulating oven, 230 ℃, 60 minutes).
Irradiating upper and lower glass substrates with polyimide coatings with ultraviolet linearly polarized light for photoalignment treatment, wherein the wavelength of the irradiated ultraviolet polarized light is 254nm, the light dose is 400mj/cm2, heating in a thermal cycle oven at 230 ℃ for 60min, spraying spacer particles with the diameter of 4 μm on one substrate, printing sealant on the other substrate at the position 5mm away from the short side of the glass, directly printing the sealant on the film surface of the aligning agent, leaving a liquid crystal inlet with the diameter of 5mm, bonding the upper and lower substrates together in a manner that the alignment film is opposite, the polarization axis of the photoalignment treatment is parallel, and the superposition width of the upper and lower substrates is 3cm, fixing the bonded two substrates by a clamp, curing at 150 ℃ for 1 hour to prepare a liquid crystal empty box, injecting negative IPS liquid crystal into the empty box in a decompression manner, the liquid crystal injection port is sealed. The corresponding liquid crystal display element is obtained. Lightening a backlight source, attaching the upper substrate and the lower substrate to the polaroid, and visually observing the orientation state of the liquid crystal; testing of the pretilt angle on a RETS-100 (tsukamur electronics limited) device; the RDC and VHR tests were performed on a liquid crystal electro-optic tester (Instec). The results of the comparative tests on the above liquid crystal aligning agents are shown in the following table:
table 1 evaluation results of liquid crystal display elements in examples and comparative examples
| Examples | Orientation state | Pretilt angle (°) | RDC(V) | VHR(％) |
| Example 1 | Uniformity | 0.01 | 0.21 | 99.85 |
| Example 2 | Uniformity | 0.03 | 0.38 | 99.56 |
| Example 3 | Uniformity | 0.04 | 0.24 | 99.74 |
| Example 4 | Uniformity | 0.03 | 0.27 | 99.71 |
| Example 5 | Uniformity | 0.05 | 0.32 | 99.69 |
| Example 6 | Uniformity | 0.07 | 0.45 | 99.53 |
| Example 7 | Uniformity | 0.08 | 0.48 | 99.51 |
| Comparative example 1 | Weak spots of numbness | 0.3 | 0.63 | 98.71 |
| Comparative example 2 | Weak spots of numbness | 0.54 | 0.58 | 99.05 |
| Comparative example 3 | Pocking mark | 0.68 | 0.72 | 97.47 |
As can be seen from the above, the liquid crystal aligning agent of the present invention has advantages of uniform alignment, strong liquid crystal aligning ability, and fast charge dissipation, and can eliminate afterimages due to weak aligning ability (i.e., small anisotropy) of the aligning agent, suppress afterimages due to slow dc bias charge dissipation, and provide IPS-type and FFS-type driving liquid crystal display devices having excellent afterimage characteristics and excellent display effects.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A polyimide for a liquid crystal aligning agent, characterized in that the structure of the polyimide is represented by formula (1):
in formula (1), X, which may be the same or different at each occurrence, is represented by any one of the following groups:
y represents any one of the following groups:
n and m are the number of repeating units of the repeating unit in the polymer, and are respectively independent natural numbers of 0-100.
2. The polyimide for a liquid crystal aligning agent according to claim 1, wherein n and m are each independently a natural number of 30 to 50.
3. A method for preparing polyimide for a liquid crystal aligning agent according to claim 1, comprising the steps of:
(1) dissolving 1, 1-bis (4-aminophenyl) cyclohexane and aromatic diamine in an aprotic polar solvent, then adding one or two aliphatic tetracarboxylic acid dianhydrides, a molecular weight regulator and the aprotic polar solvent, and stirring and reacting for 6-8 hours at 40-80 ℃ to obtain an initial polyamic acid solution;
(2) and (2) adding a diluent and an additive into the polyamic acid solution obtained in the step (1), and stirring at room temperature for 1-2 hours to form a uniform solution, thereby obtaining the polyimide liquid crystal aligning agent.
4. The method according to claim 3, wherein the structural formula of the 1, 1-bis (4-aminophenyl) cyclohexane is represented by the formula (2):
the aromatic diamine is selected from one or more of the following structures:
the aliphatic tetracarboxylic dianhydride is cyclobutane tetracarboxylic dianhydride or a derivative thereof.
5. The production method according to claim 3, wherein the aprotic polar solvent is at least one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, and γ -butyrolactone; the molecular weight regulator is at least one of phthalic anhydride, phthalic anhydride derivatives, aniline and aniline derivatives; the diluent is at least one of N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide, gamma-butyrolactone and ethylene glycol monobutyl ether; the additive is epoxy and/or silane compounds, and the addition amount of the additive is 0.1-5% of the solid content of the polyimide liquid crystal aligning agent.
6. The method according to claim 5, wherein the epoxy compound is one or more of ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, N, N, N ', N ' -tetracyclooxypropyl-m-xylylenediamine, N, N, N ', N ' -tetracyclooxypropyl-4, 4 ' -diaminodiphenylmethane, and 3- (N, N-diglycidyl) aminopropyltrimethoxysilane;
the silane compound is one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane or N-bis (ethylene oxide) -3-aminopropyltriethoxysilane.
7. The method according to claim 3, wherein the molar ratio of the aromatic diamine to the aliphatic tetracarboxylic dianhydride in the step (1) is 1: 0.98-1; the polyimide liquid crystal aligning agent obtained in the step (2) has a solid content of 1-15%, a viscosity of 20-50 mPa · s, a weight average molecular weight of 1000-200000, a number average molecular weight of 1000-100000, and a polydispersity of 1-20.
8. A liquid crystal alignment film produced from the liquid crystal aligning agent obtained in claim 3, characterized in that the production method of the liquid crystal alignment film comprises the steps of:
(1) coating the polyimide liquid crystal aligning agent on a substrate, and obtaining a polyimide film after pre-curing and main curing treatment;
(2) and irradiating the polyimide film by adopting linear polarization ultraviolet light, and then annealing to obtain the polyimide liquid crystal alignment film.
9. The liquid crystal alignment film according to claim 8, wherein the pre-curing temperature in step (1) is 50 to 100 ℃ for 1 to 3 min; the main curing temperature is 200-250 ℃, and the time is 30-60 min; the wavelength of the linear polarization ultraviolet light in the step (2) is 150 nm-365 nm.
10. Use of the polyimide alignment film according to any one of claims 8 to 9 in a thin film transistor liquid crystal display.
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