CN114958393B - Polyamic acid liquid crystal orientation agent with nitrogen-containing aromatic ring structure, liquid crystal orientation film and preparation method thereof - Google Patents

Polyamic acid liquid crystal orientation agent with nitrogen-containing aromatic ring structure, liquid crystal orientation film and preparation method thereof Download PDF

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CN114958393B
CN114958393B CN202210680158.2A CN202210680158A CN114958393B CN 114958393 B CN114958393 B CN 114958393B CN 202210680158 A CN202210680158 A CN 202210680158A CN 114958393 B CN114958393 B CN 114958393B
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liquid crystal
nitrogen
aromatic ring
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diamine
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CN114958393A (en
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苏江华
王胜林
黎厚明
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Changsha Dalton Electronic Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties

Abstract

The invention belongs to the technical field of liquid crystal aligning agents. The invention provides a polyamide acid liquid crystal orientation agent with a nitrogen-containing aromatic ring structure and a preparation method thereof, wherein basic organic diamine, diamine with a large side chain structure, diamine with a nitrogen-containing aromatic ring structure and a polar aprotic solvent are mixed under inert atmosphere; and (3) reacting the mixed solution with dianhydride monomer, and mixing the reaction product with a polar aprotic solvent and a leveling agent to obtain the polyamide acid liquid crystal aligning agent with the nitrogen-containing aromatic ring structure. The invention also provides a liquid crystal alignment film containing the liquid crystal alignment agent and a preparation method thereof. The basic organic diamine is used as the basis for synthesizing the liquid crystal aligning agent, so that the electrical property of the liquid crystal box is improved; diamine with a large side chain structure provides alignment performance for the liquid crystal alignment agent, so that the liquid crystal box has a certain pretilt angle; the diamine with the nitrogen-containing aromatic ring structure is used for modifying the liquid crystal aligning agent, so that the aligning agent material has the capability of resisting UV irradiation, and the applicability of the special scene is optimized.

Description

Polyamic acid liquid crystal orientation agent with nitrogen-containing aromatic ring structure, liquid crystal orientation film and preparation method thereof
Technical Field
The invention relates to the technical field of liquid crystal aligning agents, in particular to a polyamide acid liquid crystal aligning agent with a nitrogen-containing aromatic ring structure, a liquid crystal aligning film and a preparation method thereof.
Background
In order to obtain good display effect, a thin film transistor liquid crystal display (TFT-LCD) needs to have good and stable alignment of liquid crystal molecules, so that a liquid crystal alignment agent has become a key issue in the development of the thin film transistor liquid crystal display. Polyimide has been the most widely used liquid crystal alignment material in industry so far.
In recent years, the application of the liquid crystal display element is becoming more and more widespread, and in addition to the main application of the existing liquid crystal display element, that is, the common displays of liquid crystal televisions, notebook computers and the like, new intelligent scenes such as vehicle-mounted display, rail transit, outdoor scene display and the like are becoming more and more popular. In particular, the requirements for exposure to high-intensity ultraviolet and solar light irradiation, long-time driving, and other severe environments tend to be more stringent as the applications thereof are diversified. Therefore, the performance requirements of the lcd are increasing, and the reliability requirements of the picture quality are also increasing.
The liquid crystal display element has the following problems when exposed to ultraviolet radiation for a long time: the prior transparent polymer film such as polyethylene, polypropylene, polyester and other films mainly comprises ultraviolet absorber or stabilizer such as hindered amine stabilizer (HALS) and the like. However, the conventional UV stabilizer has poor heat resistance stability, and cannot meet the application requirements of a high-temperature treatment (more than or equal to 200 ℃) procedure in the preparation process of the liquid crystal alignment film, so that the conventional UV stabilizer cannot be applied to the UV resistance application of the liquid crystal alignment film. Other high temperature resistant UV stabilizers tend to be darker in color and the addition to the liquid crystal alignment film matrix tends to destroy the optical properties of the film.
Therefore, how to maintain high heat resistance and high transparency of a liquid crystal alignment film while imparting good UV irradiation resistance is a problem that needs to be solved by researchers at present.
Disclosure of Invention
The invention aims to provide a polyamide acid liquid crystal aligning agent with a nitrogen-containing aromatic ring structure, a preparation method thereof and a liquid crystal aligning film prepared from the polyamide acid liquid crystal aligning agent with the nitrogen-containing aromatic ring structure.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a polyamide acid liquid crystal aligning agent with a nitrogen-containing aromatic ring structure, which comprises the following steps:
1) Mixing basic organic diamine, diamine with a large side chain structure, diamine with a nitrogen-containing aromatic ring structure and a polar aprotic solvent in an inert atmosphere to obtain a solution;
2) And (3) reacting the solution with dianhydride monomer, and mixing the reaction product with polar aprotic solvent and leveling agent to obtain the polyamide acid liquid crystal aligning agent with the nitrogen-containing aromatic ring structure.
Preferably, the inert atmosphere in the step 1) is a nitrogen atmosphere or an argon atmosphere;
the molar ratio of the total mole number of the basic organic diamine, the diamine with a large side chain structure and the diamine with a nitrogen-containing aromatic ring structure to the dianhydride monomer is 90-110: 90-110;
the molar ratio of the basic organic diamine, the diamine with a large side chain structure to the diamine with a nitrogen-containing aromatic ring structure is 0.01-100: 0.01 to 50:1 to 100.
Preferably, the basic organic diamine has the structural formula:
wherein A is-C n H 2n -, -O-, -NH-; -S-or-SO 2 -；-C n H 2n -wherein n is any integer from 0 to 20; r is independently-H or-CH 3 ；
The structural formula of the diamine with the large side chain structure is as follows:
wherein X is alkyl chain-C n H 2n+1 Y is alkyl chain-C n H 2n And n in X and Y is any integer from 1 to 50.
Preferably, the structural formula of the diamine with the nitrogen-containing aromatic ring structure is as follows:
wherein R1 and R2 are minus-NH 2 The other residues, R1 is a main structure of a nitrogen-containing aromatic ring, and comprises a functional group A and a functional group B, wherein the functional groups A and B are adjacent;
a comprises one or more of pyridine ring, imidazole ring, pyrazine ring, triazine ring and quinoxaline ring, B comprises-OH and/or-COOH, A and B are independently any integer from 1 to 4;
the structural formula of the dianhydride monomer is as follows:
preferably, the polar aprotic solvent of step 1) and step 2) comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, m-cresol and tetrahydrofuran;
the leveling agent in the step 2) comprises one or more of ethyl acetate, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diacetone alcohol and ethylene glycol butyl ether acetate;
the mass ratio of the total mass of the polar aprotic solvent in the step 1) to the polar aprotic solvent in the step 2) to the leveling agent in the step 2) is 1-2: 1 to 2; the mass ratio of the polar aprotic solvent in the step 1) to the polar aprotic solvent in the step 2) is 80-120: 180-260 parts;
in step 2), the molar mass ratio of dianhydride monomer to polar aprotic solvent is 0.1mol: 180-260 g.
Preferably, the solid content of the reaction product in the step 2) is 10-50%, and the solid content of the polyamide acid liquid crystal aligning agent with the nitrogen-containing aromatic ring structure is 1-10%.
Preferably, the mixing time in the step 1) is 20-40 min; the temperature of the reaction in the step 2) is between-15 and 100 ℃ and the time is between 0.5 and 48 hours.
The invention also provides the polyamide acid liquid crystal aligning agent with the nitrogen-containing aromatic ring structure, which is prepared by the preparation method, and has the structural formula:
wherein n is more than or equal to 1, A is dianhydride residue, B is basic organic diamine residue, C is diamine residue with large side chain structure, and D is diamine residue with nitrogen-containing aromatic ring structure.
The invention also provides a method for preparing the liquid crystal alignment film by using the polyamide acid liquid crystal alignment agent with the nitrogen-containing aromatic ring structure, which comprises the steps of coating the polyamide acid liquid crystal alignment agent with the nitrogen-containing aromatic ring structure on an ITO glass substrate, and then sequentially carrying out drying, imidization and friction to obtain the liquid crystal alignment film coated on the ITO glass substrate;
the drying temperature is 60-120 ℃ and the drying time is 10-20 min; the imidization treatment is carried out at 200-250 ℃ for 30-90 min.
The invention also provides the liquid crystal orientation film prepared by the preparation method.
The beneficial effects of the invention include the following points:
1) The basic organic diamine is used as the basis for synthesizing the polyamide acid liquid crystal aligning agent with the nitrogen-containing aromatic ring structure, so that the electrical property of the liquid crystal box is improved; the diamine with the large side chain structure provides alignment performance for the polyamide acid liquid crystal alignment agent with the nitrogen-containing aromatic ring structure, and the polyamide acid liquid crystal alignment agent with the nitrogen-containing aromatic ring structure can align liquid crystal after friction, so that the liquid crystal box has a certain pretilt angle.
2) According to the invention, the polyamide acid liquid crystal aligning agent with the nitrogen-containing aromatic ring structure is modified by using the diamine with the nitrogen-containing aromatic ring structure, so that the aligning agent material can effectively absorb UV, has the capability of resisting UV irradiation, and optimizes the applicability of special scenes.
3) The polyamide acid liquid crystal aligning agent with the nitrogen-containing aromatic ring structure has the capability of keeping stable UV irradiation resistance under the long-time UV condition, and has the advantages of high Voltage Holding Ratio (VHR), high heat resistance and the like.
Detailed Description
The invention provides a preparation method of a polyamide acid liquid crystal aligning agent with a nitrogen-containing aromatic ring structure, which comprises the following steps:
1) Mixing basic organic diamine, diamine with a large side chain structure, diamine with a nitrogen-containing aromatic ring structure and a polar aprotic solvent in an inert atmosphere to obtain a solution;
2) And (3) reacting the solution with dianhydride monomer, and mixing the reaction product with polar aprotic solvent and leveling agent to obtain the polyamide acid liquid crystal aligning agent with the nitrogen-containing aromatic ring structure.
The inert atmosphere in step 1) of the present invention is preferably a nitrogen atmosphere or an argon atmosphere.
In the invention, the molar ratio of the total mole number of the basic organic diamine, the diamine with a large side chain structure and the diamine with a nitrogen-containing aromatic ring structure to the dianhydride monomer is preferably 90-110: 90 to 110, more preferably 95 to 105:95 to 105, more preferably 100:100;
the molar ratio of the basic organic diamine, the diamine with a large side chain structure and the diamine with a nitrogen-containing aromatic ring structure is preferably 0.01-100: 0.01 to 50:1 to 100, more preferably 2 to 80: 1-40: 5 to 80, more preferably 10 to 50: 5-30: 20 to 50.
The structural formula of the basic organic diamine is as follows:
wherein A is-C n H 2n -, -O-, -NH-; -S-or-SO 2 -；-C n H 2n -wherein n is any integer from 0 to 20, preferably from 5 to 15, more preferably from 8 to 12; r is independently-H or-CH 3 。
The structural formula of the basic organic diamine is preferably:
the structural formula of the diamine with a large side chain structure is as follows:
wherein X is alkyl chain-C n H 2n+1 Y is alkyl chain-C n H 2n -, n in X and Y is any one of 1 to 50An integer is preferably any one of 3 to 40, and more preferably any one of 8 to 20.
The structural formula of the diamine monomer with a large side chain structure is preferably as follows:
the structural formula of the diamine with the nitrogen-containing aromatic ring structure is as follows:
wherein R1 and R2 are minus-NH 2 The other residues, R1 is a main structure of a nitrogen-containing aromatic ring, and comprises a functional group A and a functional group B, wherein the functional groups A and B are adjacent;
a comprises one or more of a pyridine ring, an imidazole ring, a pyrazine ring, a triazine ring and a quinoxaline ring, and B comprises-OH and/or-COOH, preferably comprises-OH and-COOH; a and B are independently preferably an integer of 1 to 4, more preferably an integer of 2 to 3.
The structural formula of the dianhydride monomer is as follows:
the polar aprotic solvent of step 1) and step 2) of the present invention preferably comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone (NMP), m-cresol and tetrahydrofuran;
the leveling agent in the step 2) preferably comprises one or more of ethyl acetate, ethylene glycol monobutyl ether (BCS), diethylene glycol diethyl ether, diacetone alcohol and ethylene glycol butyl ether acetate.
In the present invention, the mass ratio of the total mass of the polar aprotic solvent of step 1) and the polar aprotic solvent of step 2) to the leveling agent of step 2) is preferably 1 to 2:1 to 2, more preferably 1:1; the mass ratio of the polar aprotic solvent of step 1) to the polar aprotic solvent of step 2) is preferably 80 to 120:180 to 260, more preferably 90 to 110:200 to 250, more preferably 95 to 105: 220-240.
In step 2) of the present invention, the molar mass ratio of the dianhydride monomer to the polar aprotic solvent is preferably 0.1mol:180 to 260g, more preferably 0.1mol:200 to 240g, more preferably 0.1mol: 210-230 g.
The solid content of the reaction product of step 2) of the present invention is preferably 10 to 50%, more preferably 20 to 40%, still more preferably 30%; the solid content of the polyamide acid liquid crystal aligning agent having a nitrogen-containing aromatic ring structure is preferably 1 to 10%, more preferably 3 to 8%, and even more preferably 5 to 6%.
The mixing time in step 1) of the present invention is preferably 20 to 40min, more preferably 25 to 35min, and even more preferably 30min; the temperature of the reaction in step 2) is preferably-15 to 100 ℃, more preferably 10 to 50 ℃, still more preferably 20 to 35 ℃; the reaction time is preferably 0.5 to 48 hours, more preferably 2 to 24 hours, and still more preferably 3 to 12 hours.
The invention also provides the polyamide acid liquid crystal aligning agent with the nitrogen-containing aromatic ring structure, which is prepared by the preparation method, and has the structural formula:
wherein n is not less than 1, n is preferably any integer of 10 to 500, more preferably any integer of 50 to 400, and even more preferably any integer of 100 to 300; a is dianhydride residue, B is basic organic diamine residue, C is diamine residue with large side chain structure, and D is diamine residue with nitrogen-containing aromatic ring structure.
The invention also provides a method for preparing the liquid crystal alignment film by using the polyamide acid liquid crystal alignment agent with the nitrogen-containing aromatic ring structure, which comprises the steps of coating the polyamide acid liquid crystal alignment agent with the nitrogen-containing aromatic ring structure on an ITO glass substrate, and then sequentially carrying out drying, imidization and friction to obtain the liquid crystal alignment film coated on the ITO glass substrate.
The drying temperature of the invention is preferably 60-120 ℃, more preferably 70-110 ℃, and even more preferably 80-100 ℃; the drying time is preferably 10 to 20 minutes, more preferably 12 to 18 minutes, and still more preferably 14 to 16 minutes; the temperature of the imidization treatment is preferably 200 to 250 ℃, more preferably 210 to 240 ℃, still more preferably 220 to 230 ℃; the imidization treatment time is preferably 30 to 90 minutes, more preferably 40 to 80 minutes, and still more preferably 50 to 70 minutes.
The thickness of the coating according to the present invention is preferably 50 to 200nm, more preferably 80 to 150nm, still more preferably 100 to 120nm; the angle of friction is preferably 0 to 50 °, more preferably 0 to 45 °, and even more preferably 0 ° or 45 °.
The invention also provides the liquid crystal orientation film prepared by the preparation method.
In the invention, two liquid crystal orientation films coated on an ITO glass substrate are bonded into a box, liquid crystal is filled in, and the box is sealed by photo-curing glue to obtain a liquid crystal box; in the process of bonding into a box, the friction surfaces of the glass substrates of the two liquid crystal alignment films are opposite and the friction directions are opposite; the thermosetting adhesive is used for bonding, and the thermosetting adhesive contains spacer particles having a particle diameter of preferably 3 to 20. Mu.m, more preferably 4 to 15. Mu.m, still more preferably 5 to 10. Mu.m.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
The dianhydride monomers used in the examples and comparative examples have the following structural formulas:
DA-1:1,2,3, 4-cyclobutane tetracarboxylic dianhydride (CBDA) DA-2: pyromellitic anhydride (PMDA)
The basic organic diamines used in the examples and comparative examples have the following structural formulas:
DN-1: para-phenylenediamine
The structural formulae of the diamine having a large side chain structure used in examples and comparative examples are as follows:
DN-2:2, 4-diaminophenyloctadecane ether
DN-3:4,4' - (1, 3-propanediol) diphenylamine
DN-4: dihydrocholesterol-3, 5-diaminobenzoate
The structural formula of the diamine containing nitrogen aromatic ring used in the examples is as follows: DN-5: 5-amino-2- [4' - (2, 5) p-aminophenol) ] benzimidazole
DN-6:2, 5-bis (4' -aminobenzoic acid) pyridine
DN-7:2, 3-bis [2,3' - (amino, hydroxy) benzene]Quinoxaline
Example 1
Under the environment of 25 ℃ and nitrogen atmosphere, 0.06mol of DN-1, 0.01mol of DN-2, 0.03mol of DN-5 and 86.4g of NMP are added in sequence, and the mixture is stirred for 30min, thus obtaining a completely dissolved uniform solution. And adding 0.1mol of DA-1, stirring and reacting for 3 hours, wherein the solid content of the reaction product is 30%. The reaction product was diluted with 203.7g of NMP and 290.1g of BCS to obtain a transparent and viscous polyamide acid liquid crystal aligning agent with a nitrogen-containing aromatic ring structure, the solid content of which was 6%.
The polyamide acid liquid crystal orientation agent with the nitrogen-containing aromatic ring structure is uniformly spin-coated on a clean ITO glass substrate (the coating thickness is 120 nm), the ITO glass substrate is pre-baked for 15min at 80 ℃, imidized for 60min at 230 ℃, and then a polyimide film on the ITO glass substrate is rubbed by a rubbing machine, wherein the rubbing angle is 45 degrees, so that the liquid crystal orientation film coated on the ITO glass substrate is obtained.
Two ITO glass substrates coated with liquid crystal alignment films are bonded into a box by using thermosetting glue containing spacer particles (with the particle size of 4 um) in a mode that friction surfaces of the substrates are opposite and the friction directions are opposite, liquid crystal is filled in, and then the liquid crystal box is obtained by sealing with the thermosetting glue.
Example 2
Under the environment of 25 ℃ and nitrogen atmosphere, 0.06mol of DN-1, 0.01mol of DN-3, 0.03mol of DN-5 and 83.7g of NMP are added in sequence, and the mixture is stirred for 30min, thus obtaining a completely dissolved uniform solution. And adding 0.1mol of DA-1, stirring and reacting for 3 hours, wherein the solid content of the reaction product is 30%. The reaction product was diluted with 197.2g of NMP and 280.9g of BCS to obtain a transparent and viscous polyamide acid liquid crystal aligning agent with a nitrogen-containing aromatic ring structure, the solid content of which was 6%.
The polyamide acid liquid crystal aligning agent having a nitrogen-containing aromatic ring structure of example 2 was prepared into a liquid crystal alignment film and a liquid crystal cell by the method of example 1, wherein the rubbing angle was 0 °, and the other conditions were the same as in example 1.
Example 3
Under the environment of 25 ℃ and nitrogen atmosphere, 0.05mol of DN-1, 0.02mol of DN-4, 0.03mol of DN-5 and 99.5g of NMP are added in sequence, and the mixture is stirred for 30min to obtain a completely dissolved uniform solution. And adding 0.1mol of DA-1, stirring and reacting for 3 hours, wherein the solid content of the reaction product is 30%. The reaction product was diluted with 234.5g NMP and 334.0g BCS to obtain a transparent and viscous polyamide acid liquid crystal aligning agent with a nitrogen-containing aromatic ring structure, the solid content of which was 6%.
The polyamide acid liquid crystal aligning agent having a nitrogen-containing aromatic ring structure of example 3 was prepared into a liquid crystal alignment film and a liquid crystal cell by the method of example 1, wherein the rubbing angle was 0 °, and the other conditions were the same as in example 1.
Example 4
Under the environment of 25 ℃ and nitrogen atmosphere, 0.06mol of DN-1, 0.01mol of DN-2, 0.03mol of DN-6 and 94.1g of NMP are added in sequence, and the mixture is stirred for 30min to obtain a completely dissolved uniform solution. And adding 0.1mol of DA-1, stirring and reacting for 3 hours, wherein the solid content of the reaction product is 30%. The reaction product was diluted with 221.7g NMP and 315.8g BCS to obtain a transparent viscous polyamide acid liquid crystal aligning agent with a nitrogen-containing aromatic ring structure, the solid content of which was 6%.
The nitrogen-containing aromatic ring structure polyamic acid liquid crystal aligning agent of example 4 was prepared into a liquid crystal alignment film and a liquid crystal cell by the method of example 1.
Example 5
Under the environment of 25 ℃ and nitrogen atmosphere, 0.06mol of DN-1, 0.01mol of DN-3, 0.03mol of DN-6 and 91.3g of NMP are added in sequence, and the mixture is stirred for 30min to obtain a completely dissolved uniform solution. And adding 0.1mol of DA-1, stirring and reacting for 3 hours, wherein the solid content of the reaction product is 30%. The reaction product was diluted with 215.2g NMP and 306.5g BCS to obtain a transparent viscous polyamide acid liquid crystal aligning agent with a nitrogen-containing aromatic ring structure, the solid content of which was 6%.
The polyamide acid liquid crystal aligning agent having a nitrogen-containing aromatic ring structure of example 5 was prepared into a liquid crystal alignment film and a liquid crystal cell by the method of example 1, wherein the rubbing angle was 0 °, and the other conditions were the same as in example 1.
Example 6
Under the condition of 25 ℃ and nitrogen atmosphere, 0.05mol of DN-1, 0.02mol of DN-4, 0.03mol of DN-6 and 107.1g of NMP are added in sequence, and the mixture is stirred for 30min, thus obtaining a completely dissolved uniform solution. And adding 0.1mol of DA-1, stirring and reacting for 3 hours, wherein the solid content of the reaction product is 30%. The reaction product was diluted with 252.5g of NMP and 359.6g of BCS to obtain a transparent and viscous polyamide acid liquid crystal aligning agent with a nitrogen-containing aromatic ring structure, the solid content of which was 6%.
The polyamide acid liquid crystal aligning agent having a nitrogen-containing aromatic ring structure of example 6 was prepared into a liquid crystal alignment film and a liquid crystal cell by the method of example 1, wherein the rubbing angle was 0 °, and the other conditions were the same as in example 1.
Example 7
Under the environment of 25 ℃ and nitrogen atmosphere, 0.06mol of DN-1, 0.01mol of DN-2, 0.03mol of DN-7 and 93.7g of NMP are added in sequence, and the mixture is stirred for 30min, thus obtaining a completely dissolved uniform solution. And adding 0.1mol of DA-1, stirring and reacting for 3 hours, wherein the solid content of the reaction product is 30%. The reaction product was diluted with 220.9g NMP and 314.6g BCS to obtain a transparent viscous polyamide acid liquid crystal aligning agent with a nitrogen-containing aromatic ring structure, the solid content of which was 6%.
The nitrogen-containing aromatic ring structure polyamic acid liquid crystal aligning agent of example 7 was prepared into a liquid crystal alignment film and a liquid crystal cell by the method of example 1.
Example 8
Under the environment of 25 ℃ and nitrogen atmosphere, 0.06mol of DN-1, 0.01mol of DN-3, 0.03mol of DN-7 and 91.0g of NMP are added in sequence, and the mixture is stirred for 30min to obtain a completely dissolved uniform solution. And adding 0.1mol of DA-1, stirring and reacting for 3 hours, wherein the solid content of the reaction product is 30%. The reaction product was diluted with 214.4g of NMP and 305.4g of BCS to obtain a transparent and viscous polyamide acid liquid crystal aligning agent with a nitrogen-containing aromatic ring structure, the solid content of which was 6%.
The polyamide acid liquid crystal aligning agent having the structure of containing nitrogen aromatic ring of example 8 was prepared into a liquid crystal alignment film and a liquid crystal cell by the method of example 1, wherein the rubbing angle was 0 °, and other conditions were the same as those of example 1.
Example 9
Under the environment of 25 ℃ and nitrogen atmosphere, 0.05mol of DN-1, 0.02mol of DN-4, 0.03mol of DN-7 and 106.8g of NMP are added in sequence, and the mixture is stirred for 30min, thus obtaining a completely dissolved uniform solution. And adding 0.1mol of DA-1, stirring and reacting for 3 hours, wherein the solid content of the reaction product is 30%. The reaction product was diluted with 251.7g of NMP and 358.5g of BCS to obtain a transparent and viscous polyamide acid liquid crystal aligning agent with a nitrogen-containing aromatic ring structure, the solid content of which was 6%.
The polyamide acid liquid crystal aligning agent having a nitrogen-containing aromatic ring structure of example 9 was prepared into a liquid crystal alignment film and a liquid crystal cell by the method of example 1, wherein the rubbing angle was 0 °, and the other conditions were the same as in example 1.
Example 10
Under the condition of 30 ℃ and argon atmosphere, 0.05mol of DN-1, 0.02mol of DN-3, 0.03mol of DN-5 and 110g of N, N-dimethylformamide are added in sequence, and stirring is carried out for 35min, thus obtaining a completely dissolved uniform solution. Then 0.1mol of DA-2 is added, and the mixture is stirred and reacted for 10 hours at 15 ℃, wherein the solid content of the reaction product is 26 percent. The reaction product was diluted with 220g of N, N-dimethylformamide and 330g of ethylene glycol butyl ether acetate to obtain a transparent and viscous polyamide acid liquid crystal aligning agent having a nitrogen-containing aromatic ring structure, the solid content of the polyamide acid liquid crystal aligning agent having a nitrogen-containing aromatic ring structure was 7%.
The nitrogen-containing aromatic ring structure polyamic acid liquid crystal aligning agent of example 10 was prepared into a liquid crystal alignment film and a liquid crystal cell by the method of example 1.
Comparative example 1
Under the condition of 25 ℃ and nitrogen atmosphere, 0.09mol of DN-1, 0.01mol of DN-2 and 77.2g of NMP are added in sequence, and the mixture is stirred for 30min, thus obtaining a completely dissolved uniform solution. And adding 0.1mol of DA-1, stirring and reacting for 3 hours, wherein the solid content of the reaction product is 30%. The reaction product was diluted with 181.9g of NMP and 259.1g of BCS to obtain a transparent and viscous polyamide acid liquid crystal aligning agent with a nitrogen-containing aromatic ring structure, the solid content of which was 6%.
The nitrogen-containing aromatic ring structure polyamic acid liquid crystal aligning agent of comparative example 1 was prepared into a liquid crystal alignment film and a liquid crystal cell by the method of example 1.
Comparative example 2
Under the condition of 25 ℃ and nitrogen atmosphere, 0.09mol of DN-1, 0.01mol of DN-3 and 74.4g of NMP are added in sequence, and the mixture is stirred for 30min, thus obtaining a completely dissolved uniform solution. And adding 0.1mol of DA-1, stirring and reacting for 3 hours, wherein the solid content of the reaction product is 30%. The reaction product was diluted with 175.5g NMP and 249.9g BCS to give a transparent viscous polyamide acid liquid crystal aligning agent having a nitrogen-containing aromatic ring structure, the solid content of which was 6%.
The polyamide acid liquid crystal aligning agent having the nitrogen-containing aromatic ring structure of comparative example 2 was prepared into a liquid crystal alignment film and a liquid crystal cell by the method of example 1, wherein the rubbing angle was 0 °, and other conditions were the same as in example 1.
Comparative example 3
Under the condition of 25 ℃ and nitrogen atmosphere, 0.08mol of DN-1, 0.02mol of DN-4 and 90.3g of NMP are added in sequence, and the mixture is stirred for 30min, thus obtaining a completely dissolved uniform solution. And adding 0.1mol of DA-1, stirring and reacting for 3 hours, wherein the solid content of the reaction product is 30%. The reaction product was diluted with 212.7g NMP and 303.0g BCS to obtain a transparent viscous polyamide acid liquid crystal aligning agent with a nitrogen-containing aromatic ring structure, the solid content of which was 6%.
The polyamide acid liquid crystal aligning agent having the nitrogen-containing aromatic ring structure of comparative example 3 was prepared into a liquid crystal alignment film and a liquid crystal cell by the method of example 1, wherein the rubbing angle was 0 °, and other conditions were the same as in example 1.
The electro-optical properties of the liquid crystal cells of examples 1 to 10 and comparative examples 1 to 3 of the present invention were measured using different UV aging times, respectively. In general, liquid crystal material designs generally contain more polar components and low molecular weight substances, and under long-term UV conditions, the liquid crystal absorbs UV energy to cause the liquid crystal box to separate out a large amount of ions and to be degraded along with the low molecular weight substances, and the presence of the two impurities can reduce the VHR (voltage holding rate) of the liquid crystal box and increase Ion Density, so that even the problems of liquid crystal bubbles and chromatic aberration are generated, the chromatic aberration in the box can be characterized by delta Eab values, and the larger the numerical value is, the larger the chromatic aberration is.
The pretilt angle test conditions of the liquid crystal boxes of the examples and comparative examples of the present invention were: test equipment: shintech Optitro-STD (3 STN 11), test wavelength: 591.4nm, test mode: TN/VA/IPS mode. Pretilt angles and alignment effects of the liquid crystal cells of examples and comparative examples of the present invention are shown in table 1.
The UV aging conditions of the liquid crystal cells of the examples and comparative examples of the present invention were: ageing equipment: 10W fish eye UV LED lamp, illumination intensity: 325mW/cm 2 Wavelength: UVA band 320-390 nm, deterioration time: and 0-168 h.
The electrical performance test conditions of the liquid crystal cells of the examples and comparative examples under UV aging conditions were: test equipment: 6254c, vhr measurement conditions: the voltage was 5V, the pulse width was 60 us/frame, the period 1667ms, and the measured temperature was 23℃at 90 ℃. The VHR values for the liquid crystal cells of the examples and comparative examples of the invention at different UV aging times are shown in table 2.
The liquid crystal cell grades of the inventive and comparative examples at different UV aging times are shown in table 3.
The ΔEab measurement conditions and calculation methods of the liquid crystal boxes of the examples and the comparative examples of the present invention under UV aging conditions are: test equipment: colorimeter, instrument model: CA310, calculation method: ΔEab=
[(△L*) 2 +(△a*) 2 +(△b*) 2 ] 1/2 Wherein L, a, b are chromaticity values, Δl, Δa, Δb are differences before and after UV aging, respectively. Color difference values of the liquid crystal cells of examples and comparative examples of the present invention at different UV aging times are shown in table 4.
Table 1 pretilt angle and alignment effects of the liquid crystal cells of examples and comparative examples
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Table 2 VHR values for the liquid crystal cells of examples and comparative examples at different UV aging times
Table 3 liquid crystal cell grades for the examples and comparative examples at different UV aging times
Table 4 color difference values of the liquid crystal cells of examples and comparative examples at different UV aging times
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From examples and comparative examples, the liquid crystal cell of the present invention has a high voltage holding ratio under long-term UV conditions, and is less likely to cause liquid crystal bubbles and color difference problems.
The reason that the polyamide acid liquid crystal box with the nitrogen-containing aromatic ring structure has better UV resistance is that: in the molecular structure of the nitrogen-containing aromatic ring, the nitrogen atoms and the ortho-hydroxyl (-OH) or ortho-carboxyl (-COOH) on the benzene ring form stable intramolecular hydrogen bonds, after being irradiated by ultraviolet rays, the hydrogen bonds are broken, electron cloud density is transferred from oxygen atoms to the nitrogen atoms on the aromatic ring, so that the nitrogen atoms are alkaline, protons are transferred to the nitrogen atoms to form unstable tautomers, and then the energy is released in a low heat energy, fluorescence or phosphorescence form, so that the stable intramolecular hydrogen bond ground state is restored again.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (8)

1. The preparation method of the polyamide acid liquid crystal aligning agent with the nitrogen-containing aromatic ring structure is characterized by comprising the following steps:
1) Mixing basic organic diamine, diamine with a large side chain structure, diamine with a nitrogen-containing aromatic ring structure and a polar aprotic solvent in an inert atmosphere to obtain a solution;
2) Reacting the solution with dianhydride monomer, mixing the reaction product with polar aprotic solvent and leveling agent to obtain polyamide acid liquid crystal aligning agent with nitrogen-containing aromatic ring structure;
the structural formula of the basic organic diamine is as follows:
wherein A is-C n H 2n -, -O-, -NH-; -S-or-SO 2 -；-C n H 2n -wherein n is any integer from 0 to 20; r is independently-H or-CH 3 ；
The structural formula of the diamine with the large side chain structure is as follows:
wherein X is alkyl chain-C n H 2n+1 Y is alkyl chain-C n H 2n -, n in X and Y is any integer from 1 to 50A number;
the structural formula of the diamine with the nitrogen-containing aromatic ring structure is as follows:
wherein R1 and R2 are minus-NH 2 The other residues, R1 is a main structure of a nitrogen-containing aromatic ring, and comprises a functional group A and a functional group B, wherein the functional groups A and B are adjacent;
a comprises one or more of pyridine ring, imidazole ring, pyrazine ring, triazine ring and quinoxaline ring, B comprises-OH and/or-COOH, A and B are independently any integer from 1 to 4;
the structural formula of the dianhydride monomer is as follows:
2. the method of claim 1, wherein the inert atmosphere of step 1) is a nitrogen atmosphere or an argon atmosphere;
the molar ratio of the total mole number of the basic organic diamine, the diamine with a large side chain structure and the diamine with a nitrogen-containing aromatic ring structure to the dianhydride monomer is 90-110: 90-110;
the molar ratio of the basic organic diamine, the diamine with a large side chain structure to the diamine with a nitrogen-containing aromatic ring structure is 0.01-100: 0.01 to 50:1 to 100.
3. The preparation method according to claim 2, wherein the polar aprotic solvent of step 1) and step 2) contains one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, m-cresol and tetrahydrofuran;
the leveling agent in the step 2) comprises one or more of ethyl acetate, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diacetone alcohol and ethylene glycol butyl ether acetate;
the mass ratio of the total mass of the polar aprotic solvent in the step 1) to the polar aprotic solvent in the step 2) to the leveling agent in the step 2) is 1-2: 1 to 2; the mass ratio of the polar aprotic solvent in the step 1) to the polar aprotic solvent in the step 2) is 80-120: 180-260 parts;
in step 2), the molar mass ratio of dianhydride monomer to polar aprotic solvent is 0.1mol: 180-260 g.
4. The method according to claim 2 or 3, wherein the solid content of the reaction product in step 2) is 10 to 50%, and the solid content of the nitrogen-containing aromatic ring-structured polyamic acid liquid crystal aligning agent is 1 to 10%.
5. The method according to claim 4, wherein the mixing time in step 1) is 20 to 40 minutes; the temperature of the reaction in the step 2) is between-15 and 100 ℃ and the time is between 0.5 and 48 hours.
6. The nitrogen-containing aromatic ring structure polyamic acid liquid crystal aligning agent according to any one of claims 1 to 5, wherein the structural formula of the nitrogen-containing aromatic ring structure polyamic acid liquid crystal aligning agent is:
wherein n is more than or equal to 1, A is dianhydride residue, B is basic organic diamine residue, C is diamine residue with large side chain structure, and D is diamine residue with nitrogen-containing aromatic ring structure.
7. The method for preparing a liquid crystal alignment film by using the polyamide acid liquid crystal alignment agent with the nitrogen-containing aromatic ring structure according to claim 6, which is characterized in that the polyamide acid liquid crystal alignment agent with the nitrogen-containing aromatic ring structure is coated on an ITO glass substrate, and then is subjected to drying, imidization and friction in sequence, so that the liquid crystal alignment film coated on the ITO glass substrate is obtained;
the drying temperature is 60-120 ℃ and the drying time is 10-20 min; the imidization treatment is carried out at 200-250 ℃ for 30-90 min.
8. The liquid crystal alignment film produced by the production method of claim 7.
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