CN114456378B - Polyimide for liquid crystal alignment agent and liquid crystal alignment film prepared from polyimide - Google Patents
Polyimide for liquid crystal alignment agent and liquid crystal alignment film prepared from polyimide Download PDFInfo
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- CN114456378B CN114456378B CN202011238978.3A CN202011238978A CN114456378B CN 114456378 B CN114456378 B CN 114456378B CN 202011238978 A CN202011238978 A CN 202011238978A CN 114456378 B CN114456378 B CN 114456378B
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- aligning agent
- crystal alignment
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 96
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 51
- 229920001721 polyimide Polymers 0.000 title claims abstract description 29
- 239000004642 Polyimide Substances 0.000 title abstract description 25
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 46
- 239000010408 film Substances 0.000 claims description 31
- 239000000758 substrate Substances 0.000 claims description 31
- 229920005575 poly(amic acid) Polymers 0.000 claims description 24
- 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
- 238000000034 method Methods 0.000 claims description 14
- 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 150000004984 aromatic diamines Chemical class 0.000 claims description 5
- 125000006158 tetracarboxylic acid group Chemical group 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 4
- 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
- 239000003085 diluting agent Substances 0.000 claims description 4
- 230000008569 process Effects 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
- 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
- 230000001678 irradiating effect Effects 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
- 229910000077 silane Inorganic materials 0.000 claims description 3
- -1 silane compound Chemical class 0.000 claims description 3
- 238000003756 stirring Methods 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
- 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
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000012528 membrane Substances 0.000 description 9
- 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 5
- 238000007639 printing Methods 0.000 description 5
- 206010047571 Visual impairment Diseases 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical group O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 2
- 241000204066 Tsukamurella Species 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
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000007789 sealing 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
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-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
- 239000004952 Polyamide 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
- 150000001448 anilines Chemical class 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
- 239000004744 fabric Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000007644 letterpress printing Methods 0.000 description 1
- 238000000691 measurement method Methods 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
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000007699 photoisomerization reaction Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 150000004756 silanes Chemical class 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/542—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Engineering & Computer Science (AREA)
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- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Liquid Crystal (AREA)
Abstract
The invention discloses polyimide for a liquid crystal aligning agent, and belongs to the technical field of liquid crystal display. The polyimide has a structure shown in a formula (1):
Description
Technical Field
The invention relates to the technical field of liquid crystal display, in particular to polyimide used 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 of high resolution, high brightness, light weight, low power consumption, and planarization. The TFT-LCD includes a liquid crystal layer interposed between two substrates and a color filter substrate, a pixel electrode and a common electrode for applying an electric field to the liquid crystal layer, an alignment film for controlling the orientation of liquid crystal molecules of the liquid crystal layer, a thin film transistor for switching an electric signal supplied to the pixel electrode, and the like. The alignment film is one of the TFT-LCD structures, and functions to uniformly align liquid crystal molecules on a substrate in one direction and to have a certain tilt angle (pretilt angle) with respect to the substrate plane. Therefore, the liquid crystal alignment film is important for improving the quality of the TFT-LCD due to its function, which is related to the display quality of the liquid crystal display device.
The liquid crystal alignment film is formed by coating and drying a liquid crystal alignment agent to form a film 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 is widely used in industry, i.e., rubbing with cotton cloth or nylon along the surface of the liquid crystal alignment film in a single direction to generate grooves on the surface of the liquid crystal alignment film or to arrange molecules on the surface of the alignment film in order along the rubbing direction, thereby inducing the alignment of the liquid crystal molecules on the surface of the alignment film. However, the friction method has the following problems: the surface is liable to be scratched and chipped, static electricity is liable to be caused, in-plane treatment is not uniform, and the like, thereby causing poor display.
As an alternative to rubbing alignment, there is known a photo-alignment method in which a liquid crystal alignment film surface is irradiated with polarized ultraviolet light to align the liquid crystal. The photo-alignment method is uniform in alignment compared with the rubbing method, and does not damage the film because of non-contact alignment, so that display defects due to dust or static electricity can be reduced. The photo-alignment treatment can be divided into three methods according to the mechanism, namely, photodecomposition, photoisomerization and photocrosslinking, which are currently popular methods of photodecomposition due to poor stability in the later stage. The TFT-LCD is classified into TN (twisted nematic) mode, STN (super twisted nematic) mode, IPS (in-plane switching) mode, FFS (fringe field switching) mode, VA (vertical alignment) mode, etc. according to the state of change of the liquid crystal before and after the application of an external electric field and the driving mode, wherein IPS (in-plane switching) mode and FFS (fringe field switching) mode display modes are widely used in high-end display areas such as mobile phones, televisions, and computer displays due to their advantages of high contrast ratio, wide field of view, etc., and the above-mentioned photo-alignment processing method is helpful for improving contrast ratio and viewing angle of IPS and FFS two display modes compared with the existing rubbing alignment process. However, the photoalignment treatment has a problem of weak anchoring ability of liquid crystal compared with rubbing alignment, and an afterimage due to small anisotropy is generated after long-time ac driving.
Direct-current bias charges are generated in the driving process of the IPS and FFS type liquid crystal display elements, the direct-current bias charges accumulate along with the surface of the direct-current bias charges, and the charges accumulated during picture switching cannot be rapidly dissipated, so that the intensity of an electric field received by liquid crystals is inconsistent with the intensity of an applied electric field, and afterimages generated by the accumulation of the direct-current charges appear.
Disclosure of Invention
In view of the above problems of the prior art, the applicant of the present invention 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 performance and residual image characteristics.
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 is represented, identically or differently, for each occurrence, as any one of the following groups:
y represents any one of the following groups:
n and m represent the number of repeating units of the repeating units in the polymer, and are each independently a natural number of 0 to 100.
Preferably, n and m are each independently a natural number of 30 to 50.
A method for preparing polyimide for a liquid crystal aligning agent, the method comprising the steps of:
(1) 1, 1-bis (4-aminophenyl) cyclohexane and aromatic diamine are dissolved in an aprotic polar solvent, then one or two aliphatic tetracarboxylic dianhydride, a molecular weight regulator and the aprotic polar solvent are added, and the mixture is stirred and reacted for 6 to 8 hours at the temperature of between 40 and 80 ℃ to obtain an initial polyamic acid solution;
(2) And (3) adding a diluent and an additive into the polyamic acid solution in the step (1), and stirring for 1-2 hours at room temperature to form a uniform solution, thus obtaining the polyimide liquid crystal aligning agent.
In a preferred scheme, the structural formula of the 1, 1-bis (4-aminophenyl) cyclohexane is shown as a 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.
Preferably, the aprotic polar solvent is at least one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and gamma-butyrolactone; the molecular weight regulator is at least one of phthalic anhydride, phthalic anhydride derivative, aniline and aniline derivative; 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, N, N ', N ' -tetraepoxypropyl-m-xylene diamine, N, N, N ', N ' -tetraepoxypropyl-4, 4' -diaminodiphenylmethane or 3- (N, N-diglycidyl) aminopropyl trimethoxysilane;
the silane compound is one or more of 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, 2-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, N- (2-aminoethyl) -3-aminopropyl trimethoxy silane, N- (2-aminoethyl) -3-aminopropyl dimethoxy silane, N-phenyl-3-aminopropyl trimethoxy silane or N-bis (ethylene oxide) -3-aminopropyl triethoxy silane.
In the step (1), the molar ratio of the aromatic diamine to the aliphatic tetracarboxylic dianhydride is 1:098-1; the polyimide liquid crystal aligning agent obtained in the step (2) has the solid content of 1-15%, the viscosity of 20-50 mPa.s, the weight average molecular weight of 1000-200000, the number average molecular weight of 1000-100000 and the polydispersity of 1-20.
The preparation method of the liquid crystal alignment film prepared by 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;
preferably, 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 linearly polarized ultraviolet light in the step (2) is 150 nm-365 nm.
The polyimide alignment film is applied to a thin film transistor liquid crystal display.
The photo-oriented polyimide orientation film prepared by the invention can be used for preparing TFT-LCD displays, and is especially suitable for IPS and FFS modes.
The evaluation of the orientation properties of the orientation film of the present invention can be performed according to the following steps:
two glass substrates of 3cm×4cm and 0.7mm in thickness were prepared, wherein the lower substrate was provided with comb-tooth-shaped ITO electrodes having a thickness of 50nm, the adjacent comb-shaped electrodes were spaced apart by 3 μm, and the pixel electrodes were arranged to intersect with the common electrode. The upper glass substrate is provided with no electrode, the prepared liquid crystal aligning agent is coated on the two substrates in a spin coating or letterpress printing mode, and the polyimide coating with the film thickness of 50-100 nm is obtained after pre-curing (hot plate, 80 ℃ for 3 min) and main curing (circulating oven, 230 ℃ for 60 min).
The upper and lower glass substrates with polyimide coating are irradiated with ultraviolet polarized light with wavelength of 254nm and light dose of 400mj/cm for photo-orientation treatment 2 Heating the upper and lower glass substrates subjected to orientation treatment in a thermal circulation oven at 230 ℃ for 60min, spraying spacer particles with the diameter of 4 mu m on one substrate, printing sealant on the other substrate at a position 5mm away from the short side of the glass, directly printing sealant on the surface of an orientation agent film, leaving a liquid crystal filling opening with the diameter of 5mm, adhering the upper and lower substrates together in a mode that the orientation films face to face, the polarization axes of the photo-orientation treatment are parallel, and the overlapping width of the upper and lower substrates is 3cm, fixing the adhered two substrates by using a clamp, curing at the temperature of 150 ℃ for 1 hour 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 opening. The corresponding liquid crystal display element is manufactured. The backlight source is lightened, the upper substrate and the lower substrate are attached with polaroids, and the alignment state of the liquid crystal is visually checked; performing a pretilt angle test on a RETS-100 (tsukamurella electronic equipment limited) device; RDC and VHR tests were performed on a liquid crystal optoelectric tester (Intec).
The beneficial technical effects of the invention are as follows:
the TFT-LCD device prepared by the photo-alignment polyimide alignment film provided by the invention has the characteristics of uniform alignment, pretilt angle less than 0.1 percent, RDC less than 0.5V, VHR more than 99.5 percent and the like, so that accumulated charges in a liquid crystal box can be rapidly released, and a display device with excellent afterimage performance is obtained.
Detailed Description
The principles and features of the present invention are described below in connection with examples, which are set forth only to illustrate the present invention and not to limit the scope of the invention. The abbreviations of the compounds used in the examples and comparative examples and the measurement methods of the respective properties are as follows:
NMP: n-methyl-2-pyrrolidone
BC ethylene glycol monobutyl ether
GBL gamma-butyrolactone
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-cyclobutane tetracarboxylic dianhydride
b-2:1, 3-dimethyl-1, 2,3, 4-cyclobutane tetracarboxylic dianhydride
b-3:2,3, 5-tricarboxycyclopentanyl acetic acid dianhydride
Example 1 ]
Under the protection of nitrogen, 13.309g (50 mmol) of TAPC, 12.206g (50 mmol) of a-1 and 131.478g of NMP were sequentially added to a 500mL three-necked round bottom flask, stirred to dissolve all, and then 9.8g (50 mmol) of b-1, 11.089g (49.5 mmol) of b-2, 0.01g of phthalic anhydride and 131.478g 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%.
To the polyamic acid solution were added 354.2172g of NMP, 176.3352g of GBL, 88.1676g of BC and 0.05g of ethylene glycol diglycidyl ether, and stirred at room temperature for 2 hours, and then filtered through a 0.2 μm filter to obtain the 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 is 5%, and the solvent ratio is NMP GBL: BC=7:2:1.
The structural formula of PI prepared in this example is:
GPC test results: weight average molecular weight= 46510.5, number average molecular weight= 22147.86, polydispersity=2.1, n=50, m=50.
Example 2 ]
13.309g (50 mmol) of TAPC, 12.206g (50 mmol) of a-1 and 126.99g of NMP were sequentially added to a 500mL three-necked round bottom flask under nitrogen protection, stirred to dissolve all, then 19.306g (98.5 mmol) of b-1, 0.01g of aniline and 126.99g of NMP were 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 placed 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-aminopropyl trimethoxysilane were added, and the mixture was stirred at room temperature for 2 hours, and then filtered through a 0.2 μm filter membrane to give 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%, the solvent ratio is NMP: bc=7: 3.
the structural formula of PI prepared in this example is:
GPC test results: weight average molecular weight= 45112.11, number average molecular weight= 18796.67, polydispersity=2.4, n1=50, m1=50.
Example 3 ]
Under the protection of nitrogen, 13.309g (50 mmol) of TAPC, 5.4035g (50 mmol) of a-3 and 107.72g of NMP are sequentially added into a 500mL three-neck round bottom flask, stirred to be fully dissolved, then 19.306g (98.5 mmol) of b-1, 0.02g of 4-phenylacetylene phthalic anhydride and 107.72g of NMP are added into the system, and stirred at 40 ℃ for 6 hours to obtain the polyamide acid polymer with the solid content of 15%.
100g of the polyamic acid solution was placed 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-aminopropyl triethoxysilane were added, and the mixture was stirred at room temperature for 1 hour, and then filtered through a 0.2 μm filter membrane to give a liquid crystal aligning agent PI-3 of example 3 having a viscosity of 34.3 mPas. The concentration of the polymer in the liquid crystal aligning agent is 5%, the solvent ratio is NMP: bc=7: 3.
the structural formula of PI prepared in this example is:
GPC test results: weight average molecular weight= 38311.05, number average molecular weight= 15324.8, polydispersity=2.5, n2=50, m2=50.
Example 4 ]
13.309g (50 mmol) of TAPC, 9.9555g (50 mmol) of a-4 and 120.62g of NMP were sequentially added to a 500mL three-necked round bottom flask under nitrogen protection, stirred to dissolve all, then 19.306g (98.5 mmol) of b-1, 0.04g of aniline and 120.62g of NMP were 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 placed in a 500mL three-necked flask, 114.5g of NMP and 85.5g of gBC and 0.5g of 3-aminopropyl trimethoxysilane were added, and the mixture was stirred at room temperature for 2 hours, followed by filtration through a 0.2 μm filter membrane 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%, the solvent ratio is NMP: bc=7: 3.
the structural formula of PI prepared in this example is:
GPC test results: weight average molecular weight= 38311.05, number average molecular weight= 15324.8, polydispersity=5, n3=50, m3=50.
Example 5 ]
13.309g (50 mmol) of TAPC, 12.907g (50 mmol) of a-2 and 129.53g of NMP were sequentially added to a 500mL three-necked round bottom flask under nitrogen protection, stirred to dissolve all, then 19.502g (99.5 mmol) of b-1, 0.08g of 4-ethynylaniline and 129.53g of NMP were 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 placed 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-aminopropyl trimethoxysilane were added, and the mixture was stirred at room temperature for 2 hours, and then filtered through a 0.2 μm filter membrane to obtain a 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%, the solvent ratio is NMP: bc=7: 3.
the structural formula of PI prepared in this example is:
GPC test results: weight average molecular weight= 45809, number average molecular weight= 14270.71, polydispersity=3.21, n4=50, m4=50.
Example 6 ]
13.309g (50 mmol) of TAPC and 65.059g of NMP were added to a 500mL three-necked round bottom flask under nitrogen atmosphere, and stirred to dissolve all, then 9.653g (49.25 mmol) 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, 114.5g of NMP, 85.5g of BC and 0.3. 0.3g N-phenyl-3-aminopropyl trimethoxysilane were added, and the mixture was stirred at room temperature for 2 hours, and then filtered through a 0.2 μm filter membrane to obtain a 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%, the solvent ratio is NMP: bc=7: 3.
the structural formula of PI prepared in this example is:
GPC test results: weight average molecular weight= 18973.31, number average molecular weight= 3579.87, polydispersity=5.3, n5=43.
Example 7 ]
13.309g (50 mmol) of TAPC and 69.13g of NMP were added to a 500mL three-necked round bottom flask under nitrogen atmosphere, and stirred to dissolve all, then 11.089g (49.5 mmol) 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 placed in a 3L three-necked flask, 954.5g of NMP, 445.5g of BC and 0.3g of 3-aminopropyl triethoxysilane were added, and the mixture was stirred at room temperature for 2 hours, followed by filtration through a 0.2 μm filter membrane to obtain a 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=7: 3.
the structural formula of PI prepared in this example is:
GPC test results: weight average molecular weight=21000, number average molecular weight= 5499.92, polydispersity=4.1, n6=46.
Comparative example 1 ]
A500 mL three-necked round bottom flask was charged with 5.4035g (50 mmol) of a-3 and 42.80g of NMP under nitrogen atmosphere, stirred to dissolve all, and 9.702g (49.5 mmol) 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 placed in a 500mL three-necked flask, and 0.06g of 3-aminopropyl trimethoxysilane was added thereto, followed by stirring at room temperature for 2 hours, and then filtration through a 0.2 μm filter membrane to obtain a 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%, the solvent ratio is NMP: bc=7: 3.
the structural formula of PI prepared in this comparative example is:
GPC test results: weight average molecular weight= 10466.87, number average molecular weight= 1661.41, polydispersity=6.3, m5=41.
Comparative example 2 ]
A500 mL three-necked round bottom flask was charged with 9.9555g (50 mmol) of a-4 and 59.94g of NMP under nitrogen atmosphere, stirred to dissolve all, and 11.2015g (50 mmol) 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 polyamic acid solution was put in a 500mL three-necked flask, 114.5g of NMP, 85.5g of BC and 0.5g of 3-aminopropyl trimethoxysilane were added, and the mixture was stirred at room temperature for 2 hours, and then filtered through a 0.2 μm filter membrane to obtain a liquid crystal aligning agent of comparative example 2, the viscosity of which was 20.4 mPas. The concentration of the polymer in the liquid crystal aligning agent is 5%, the solvent ratio is NMP: bc=7: 3.
the structural formula of PI prepared in this comparative example is:
GPC test results: weight average molecular weight= 15887.48, number average molecular weight= 2444.23, polydispersity=6.5, m6=46.
Comparative example 3 ]
A500 mL three-necked round bottom flask was charged with 12.907g (50 mmol) of a-2 and 64.34g of NMP under nitrogen atmosphere, stirred to dissolve all, and then 9.8g (50 mmol) 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 put in a 500mL three-necked flask, 114.5g of NMP, 85.5g of BC and 0.5g of 3-aminopropyl trimethoxysilane were added, and the mixture was stirred at room temperature for 2 hours, and then filtered through a 0.2 μm filter membrane to obtain a liquid crystal aligning agent of comparative example 3, the viscosity of which was 20.3 mPas. The concentration of the polymer in the liquid crystal aligning agent is 5%, the solvent ratio is NMP: bc=7: 3.
the structural formula of PI prepared in this comparative example is:
GPC test results: weight average molecular weight= 17610.45, number average molecular weight= 1600.95, polydispersity=11, m7=38.
And (3) verifying the performance of the orientation agent:
two glass substrates of 3cm×4cm and 0.7mm in thickness were prepared, wherein the lower substrate was provided with comb-tooth-shaped ITO electrodes having a thickness of 50nm, the adjacent comb-shaped electrodes were spaced apart by 3 μm, and the pixel electrodes were arranged to intersect with the common electrode. The upper glass substrate is electrodeless, the prepared liquid crystal aligning agent is coated on the two substrates by spin coating or relief printing, and the polyimide coating with the film thickness of 50-100 nm is obtained after pre-curing (hot plate, 80 ℃ for 3 minutes) and main curing (circulating oven, 230 ℃ for 60 minutes).
Irradiating upper and lower glass substrates with polyimide coating with ultraviolet polarized light with wavelength of 254nm and light dose of 400mj/cm2, heating in a 230 deg.C heat circulation oven for 60min, spraying spacer particles with diameter of 4 μm on one of the upper and lower glass substrates, printing sealant on the other substrate at a position 5mm away from short side of glass, directly printing sealant on the surface of the alignment agent film, leaving liquid crystal filling port with diameter of 5mm, bonding the upper and lower substrates together with alignment film face to face, photo-alignment treatment polarization axis parallel and upper and lower substrates overlapping width of 3cm, fixing the two substrates with clamp, curing at 150deg.C for 1 hr to obtain liquid crystal empty box, injecting IPS negative liquid crystal into the empty box by decompression, and sealing the liquid crystal filling port. The corresponding liquid crystal display element is manufactured. The backlight source is lightened, the upper substrate and the lower substrate are attached with polaroids, and the alignment state of the liquid crystal is visually checked; performing a pretilt angle test on a RETS-100 (tsukamurella electronic equipment limited) device; RDC and VHR tests were performed on a liquid crystal optoelectric tester (Intec). The results of the comparative test of the above liquid crystal aligning agent 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 of | 0.01 | 0.21 | 99.85 |
| Example 2 | Uniformity of | 0.03 | 0.38 | 99.56 |
| Example 3 | Uniformity of | 0.04 | 0.24 | 99.74 |
| Example 4 | Uniformity of | 0.03 | 0.27 | 99.71 |
| Example 5 | Uniformity of | 0.05 | 0.32 | 99.69 |
| Example 6 | Uniformity of | 0.07 | 0.45 | 99.53 |
| Example 7 | Uniformity of | 0.08 | 0.48 | 99.51 |
| Comparative example 1 | Weak pit | 0.3 | 0.63 | 98.71 |
| Comparative example 2 | Weak pit | 0.54 | 0.58 | 99.05 |
| Comparative example 3 | Pitting point | 0.68 | 0.72 | 97.47 |
As is clear from the above, compared with the prior art, the liquid crystal aligning agent of the present invention has the advantages of uniform alignment, strong liquid crystal alignment ability, and fast charge dissipation, and can eliminate the ghost caused by the weak alignment ability (i.e., small anisotropy) of the aligning agent, suppress the ghost caused by slow dissipation of dc bias charge, and obtain IPS-mode and FFS-mode driving type liquid crystal display elements having excellent afterimage characteristics and excellent display effects.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (8)
1. A liquid crystal aligning agent characterized by comprising a structure represented by formula (1):
in formula (1), X is represented, identically or differently, for each occurrence, as any one of the following groups:
y represents any one of the following groups:
n and m represent the number of repeating units of the repeating units in the polymer, and n and m are each independently a natural number of 30 to 50.
2. A method for preparing the liquid crystal aligning agent according to claim 1, comprising the steps of:
(1) 1, 1-bis (4-aminophenyl) cyclohexane and aromatic diamine are dissolved in an aprotic polar solvent, then one or two aliphatic tetracarboxylic dianhydride, a molecular weight regulator and the aprotic polar solvent are added, and the mixture is stirred and reacted for 6 to 8 hours at the temperature of between 40 and 80 ℃ to obtain an initial polyamic acid solution;
(2) And (2) adding a diluent and an additive into the polyamic acid solution in the step (1), and stirring for 1-2 hours at room temperature to form a uniform solution, thus obtaining the liquid crystal aligning agent.
3. The production method according to claim 2, 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, 4-phenylacetylene phthalic anhydride and aniline; 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 compound, and the addition amount of the additive is 0.1-5% of the solid content of the liquid crystal aligning agent.
4. The process according to claim 3, wherein the epoxy compound is 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, one or more of N, N ' -tetraepoxypropyl-m-xylylenediamine, N ' -tetraepoxypropyl-4, 4' -diaminodiphenylmethane, or 3- (N, N-diglycidyl) aminopropyl trimethoxysilane;
the silane compound is one or more of 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, 2-aminopropyl trimethoxy silane, N- (2-aminoethyl) -3-aminopropyl dimethoxy silane, N-phenyl-3-aminopropyl trimethoxy silane or N-bis (ethylene oxide) -3-aminopropyl triethoxy silane.
5. The process according to claim 2, wherein the molar ratio of aromatic diamine to aliphatic tetracarboxylic dianhydride in step (1) is 50:98.5 or 50:99.5; the solid content of the liquid crystal aligning agent obtained in the step (2) is 1-15%, the viscosity is 20-50 mPa.s, the weight average molecular weight is 1000-200000, the number average molecular weight is 1000-100000, and the polydispersity is 1-20.
6. A liquid crystal alignment film prepared by the liquid crystal alignment agent of claim 1, wherein the preparation method of the liquid crystal alignment film comprises the steps of:
(1) Coating the 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 using linearly polarized ultraviolet light, and then annealing to obtain the liquid crystal alignment film.
7. The liquid crystal alignment film according to claim 6, wherein the pre-curing temperature in step (1) is 50 to 100 ℃ for 1 to 3 minutes; the main curing temperature is 200-250 ℃ and the time is 30-60 min; the wavelength of the linearly polarized ultraviolet light in the step (2) is 150 nm-365 nm.
8. Use of the liquid crystal alignment film according to any one of claims 6 to 7 in a thin film transistor liquid crystal display.
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| CN114456378A (en) | 2022-05-10 |
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Address after: B312-194, No. 2 Fengwei Road, Huizhi Enterprise Center, Xishan Economic and Technological Development Zone, Xishan District, Wuxi City, Jiangsu Province, 214101 Applicant after: Jiangsu March Technology Co.,Ltd. Address before: 214112 No.210 Xinzhou Road, Wuxi City, Jiangsu Province Applicant before: Jiangsu March Technology Co.,Ltd. |
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