CN118562129A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element using same - Google Patents
Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element using same Download PDFInfo
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- CN118562129A CN118562129A CN202410732781.7A CN202410732781A CN118562129A CN 118562129 A CN118562129 A CN 118562129A CN 202410732781 A CN202410732781 A CN 202410732781A CN 118562129 A CN118562129 A CN 118562129A
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- liquid crystal
- aligning agent
- crystal aligning
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- 239000010409 thin film Substances 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention relates to a liquid crystal aligning agent, a liquid crystal aligning film and a liquid crystal display element applied by the same, and belongs to the technical field of liquid crystal display. The liquid crystal aligning agent at least comprises one polyimide precursor and an imidization product of the polyimide precursor. The polyimide precursor has a structural unit represented by the following formula: ; wherein R 1、R2 is independently selected from one of hydroxyl and 1-5 carbon element alkoxy, A is a divalent organic group, and B is a tetravalent organic group. The liquid crystal alignment film is prepared from the liquid crystal alignment agent. The liquid crystal display element comprises the liquid crystal alignment film. The liquid crystal aligning agent has strong adhesive force with sealing glue, excellent high-temperature afterimage resistance and long-term flicker inhibition.
Description
Technical Field
The invention relates to a liquid crystal aligning agent, a liquid crystal aligning film and a liquid crystal display element applied by the same, and belongs to the technical field of liquid crystal display.
Background
Liquid Crystal Displays (LCDs) are widely used in various display fields such as televisions, computers, mobile phones, etc., because they have remarkable advantages of low driving voltage, low power consumption, light weight, small size, and no harmful rays.
Polyimide resins are widely used in LCD cases for their excellent oxidation resistance, corrosion resistance, and simple synthesis methods, and are mainly used as liquid crystal alignment films for aligning liquid crystal molecules in LCDs. The liquid crystal display element is divided into TN (twisted nematic), STN (super twisted nematic), IPS/FFS (in-plane switching/fringe field switching), VA (vertical alignment) and other types according to the internal structure and driving mode, and the working principle of the liquid crystal display is that an external electric field is applied to liquid crystal, so that liquid crystal polar molecules are twisted under the action of the external electric field, the arrangement state of the liquid crystal molecules is changed, the incident polarized light is changed in direction, and the polarizer is matched to control the passing of light or not, thereby achieving the aim of display.
In recent years, with the development of LCD panels and the increase of display quality requirements, LCD panels are being advanced in the directions of higher performance, larger area, energy saving, narrower frames, etc., and the use rate of liquid crystal display elements is being increased, for example, in-vehicle liquid crystal dashboards, in-vehicle entertainment displays, and public control dashboards, and accordingly, various display problems of LCDs are becoming serious.
In the aspect of saving energy consumption, the low-frequency and broadband driving of the LCD panel becomes a development direction, the alternating current driving period is prolonged under the low-frequency condition, the feed-through voltage of the LCD driving, the raw materials in the LCD box and Direct Current (DC) charges in the preparation process are more easily accumulated to form DC bias, particularly, under the high-temperature condition, the overflow rate of impurity ions and impurities in the box is obviously accelerated, the DC bias is increased, so that the problems of Flicker, afterimage and the like caused by the asymmetry of positive and negative voltages under the alternating current driving seriously affect the display quality of the LCD panel.
In terms of large-area and appearance design, narrow-frame products become the development direction of the LCD, the sealant and the PI film (polyimide orientation film) are required to be in a full-coverage mode under the narrow frames, the width of the sealant is gradually narrowed, the problem of box opening caused by poor sealing is easy to occur, and the problems of poor display and the like caused by the fact that external impurities and water vapor can enter the LCD are easy to occur.
Disclosure of Invention
The invention provides a liquid crystal aligning agent, a liquid crystal aligning film and a corresponding liquid crystal display element, which are strong in sealing adhesive force, excellent in high-temperature afterimage resistance and capable of inhibiting long-term flicker.
The technical scheme for solving the technical problems is as follows: a liquid crystal aligning agent comprising at least one of a polyimide precursor having a structural unit represented by the following formula 1 and an imidization product of the polyimide precursor:
Formula 1;
R 1、R2 in the formula 1 is independently selected from one of hydroxyl or alkoxy with 1-5 carbon atoms;
wherein A is a divalent organic group comprising at least one of the structures represented by the following formula A-1, "-" represents a bonding position;
A-1；
R 3、R4 is independently selected from one of alkylene and single bond of C 1-5, Z 1、Z2 is independently selected from any one of-O-, -NH-, and C 1 is selected from one of C-1:
C-1；
R 5 is selected from one of O, S, N;
B in the formula 1 is a tetravalent organic group, and B comprises any one of the following groups B-1 and B-2:
。
Further, each of said R 3、R4 is independently selected from the group consisting of alkylene of C 2-3.
Further, the structural unit A-1 has any one of the following structural formulas A-1-1 to A-1-6:
。
further, the structures A-1-1 to A-1-6 are derived from diamine monomers represented by the following formulae DA (A-1-1) to DA (A-1-6), respectively:
。
Further, the divalent organic group A in formula 1 may further include other structures other than the A-1 structure, which are one or more of the following formulas:
。
Further, the tetravalent organic group B in the formula 1 can also comprise other structures besides B-1 and B-2, and the other structures are one or more of the following formulas:
。
further, the A-1 structural unit accounts for 10 to 90 percent of the total mole number of the A structural unit.
Further, the liquid crystal aligning agent also comprises a solvent, wherein the solvent is one or more of N-methyl-2-pyrrolidone, gamma-butyrolactone, N-dimethylacetamide, N-dimethylformamide, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol methylethyl ether, ethylene glycol dimethyl ether and diethylene glycol monomethyl ether ethyl ester.
The invention also discloses a liquid crystal alignment film which is prepared from the liquid crystal alignment agent.
The invention also discloses a liquid crystal display element, which comprises the liquid crystal alignment film.
The beneficial effects of the invention are as follows:
The liquid crystal alignment film prepared by the liquid crystal alignment agent has the advantages of strong adhesion with sealing glue, excellent high-temperature afterimage resistance and long-term flicker inhibition. The liquid crystal alignment agent contains a specific structural unit of A-1, a specific conjugated group in the molecule and a spatial distribution arrangement mode of an A-1 structure and other monomer molecules after film formation, so that the liquid crystal alignment film has the advantage of high release rate of DC bias charge, and can inhibit flickering and high-temperature afterimage problems caused by DC bias; on the other hand, the specific molecular structure of A-1 can improve Van der Waals force with liquid crystal molecules and inhibit high-temperature residual image problem caused by the reduction of anchoring force due to the elastic deformation of the surface of the PI film under high-temperature conditions; in addition, double bonds in the A-1 molecular structural unit are easy to form covalent bonds with acrylic ester or bridging agent in the sealant at high temperature, so that the adhesion between the PI film and the sealant is improved.
Drawings
FIG. 1 is a 1 H-NMR chart of compound a-3;
FIG. 2 is a 1 H-NMR chart of FIG. 1 with a chemical shift of 2.9-3.7;
FIG. 3 is a 1 H-NMR chart of FIG. 1 with a chemical shift of 6.4-9.4;
FIG. 4 is a DSC melting point profile of Compound a-3;
FIG. 5 is a 1 H-NMR spectrum of diamine compound DA (A-1-1);
FIG. 6 is a 1 H-NMR chart of FIG. 5 with a chemical shift of 1.5-5.5;
FIG. 7 is a 1 H-NMR chart of FIG. 5 with a chemical shift of 6-9;
FIG. 8 is a DSC melting point chart of diamine compound DA (A-1-1);
FIG. 9 is a schematic diagram showing the A, B, C, D pixel positions on a liquid crystal display element in the evaluation of the high temperature residual image resistance of the liquid crystal display element.
Detailed Description
The following detailed description of the present invention will provide further details in order to make the above-mentioned objects, features and advantages of the present invention more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, whereby the invention is not limited to the specific embodiments disclosed below.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
< Liquid Crystal alignment agent >
A liquid crystal aligning agent comprising at least one of a polyimide precursor having a structural unit represented by the following formula 1 and an imidization product of the polyimide precursor:
Formula 1;
R 1、R2 in the formula 1 is independently selected from one of hydroxyl or alkoxy with 1-5 carbon atoms;
wherein A is a divalent organic group comprising at least one of the structures represented by the following formula A-1, "-" represents a bonding position;
A-1；
R 3、R4 is independently selected from one of alkylene and single bond of C 1-5, Z 1、Z2 is independently selected from any one of-O-, -NH-, and C 1 is selected from one of C-1:
C-1；
R 5 is selected from one of O, S, N;
B in the formula 1 is a tetravalent organic group, and B comprises any one of the following groups B-1 and B-2:
。
Further, each of said R 3、R4 is independently selected from the group consisting of alkylene of C 2-3.
Further, the structural unit A-1 has any one of the following structural formulas A-1-1 to A-1-6:
。
further, the structures A-1-1 to A-1-6 are derived from diamine monomers represented by the following formulae DA (A-1-1) to DA (A-1-6), respectively:
。
Further, the divalent group A in formula 1 may further include other structures other than the A-1 structure, which are one or more of the following formulae:
。
Further, the tetravalent organic group B in the formula 1 can also comprise other structures besides B-1 and B-2, and the other structures are one or more of the following formulas:
。
further, the A-1 structural unit accounts for 10 to 90 percent of the total mole number of the A structural unit.
Further, the liquid crystal aligning agent also comprises a solvent, wherein the solvent is one or more of N-methyl-2-pyrrolidone, gamma-butyrolactone, N-dimethylacetamide, N-dimethylformamide, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol methylethyl ether, ethylene glycol dimethyl ether and diethylene glycol monomethyl ether ethyl ester.
A liquid crystal alignment film made of the liquid crystal alignment agent of the present invention.
A liquid crystal display element comprising the liquid crystal alignment film of the present invention.
The concentration of the final liquid crystal aligning agent of the present invention is preferably 2 to 10%, more preferably 3 to 7%, and the concentration of the liquid crystal aligning agent directly affects the thickness of the liquid crystal alignment film, and the concentration of the liquid crystal aligning agent can be freely adjusted according to the required film thickness.
(1) Synthesis of polyimide precursor-polyamic acid
Providing diamine with a structure A and tetracarboxylic dianhydride with a structure B in the formula 1, carrying out stirring polymerization reaction in the presence of an organic solvent to obtain a polymer solution, then adding the polymer solution into the solvent to dilute the polymer solution to prepare the liquid crystal aligning agent, or adding the polymer solution into a poor solvent to obtain a purified polymer solid through precipitation, filtration and drying, and then adding a diluting solvent into the purified polymer solid to prepare the liquid crystal aligning agent.
The polymerization reaction is carried out in a solvent to accelerate the reaction rate, and the organic solvent used in the reaction is not particularly limited, and the diamine and dianhydride monomers are dissolved, and aprotic polar solvents are preferable, and one or a mixture of several of N-methyl-2-pyrrolidone, γ -butyrolactone, N-dimethylacetamide and N, N-dimethylformamide are exemplified; the concentration of the polymerization reaction is preferably 5 to 30%, more preferably 10 to 20%.
The stirring speed and the temperature of the polymerization reaction are not particularly limited, and the stirring speed may be 100 to 1000rpm, the reaction temperature may be 0 to 180 ℃, and preferably 20 to 100 ℃.
The solvent used for the purification and precipitation of the polymer solid in the present invention is not particularly limited as long as the solvent used can precipitate the polymer solid, and examples thereof include one or more of methanol, ethanol, water, propanol, isopropanol, butanol, ethyl acetate, ethylene carboxylic acid and a halogen-containing solvent. The solvent used for diluting the polymerization reaction liquid or the polymer solid of the present invention may be exemplified by one or more of N-methyl-2-pyrrolidone, N-ethyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide, gamma-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol methylethyl ether, ethylene glycol dimethyl ether, and diethylene glycol methyl ether acetate. The first 5 solvents (N-methyl-2-pyrrolidone, N-ethyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide, and γ -butyrolactone) mentioned above are benign solvents, and mainly play a role in dissolving the polymer, and the latter 6 solvents (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol methylethyl ether, ethylene glycol dimethyl ether, and diethylene glycol methyl ether acetate) are poor solvents, and mainly play a role in reducing the surface tension of the solution and increasing the leveling effect of the alignment agent.
(2) Synthesis of polyimide precursor-polyamic acid ester
The polyamic acid ester can be esterified by dianhydride compound and alcohol compound to obtain tetracarboxylic diester compound intermediate, and then the intermediate and diamine compound are polymerized under the condition of catalyst to obtain polyamic acid ester polymer. Then adding the polymer into poor solvent to separate out, filtering and drying to obtain polyamic acid ester solid, dissolving the polyamic acid ester solid in organic solvent, and filtering to remove mechanical impurities to obtain the liquid crystal aligning agent.
The synthesis of the polyamic acid ester can also be obtained by esterifying the polyamic acid solution, specifically, the polyamic acid ester solution can be obtained by dehydrating and esterifying the polyamic acid solution and an esterifying agent, then the solution is added into a poor solvent to be separated out, the esterifying agent is removed by filtration and drying to obtain polyamic acid ester solid, and then the polyamic acid ester solid is dissolved in an organic solvent, and mechanical impurities are removed by filtration to obtain the liquid crystal aligning agent. The esterifying agent is exemplified by one of N, N-dimethylformamide dimethyl acetal, N-dimethylformamide diethyl acetal, N-dimethylformamide dipropyl acetal, N-dimethylformamide dibutyl acetal, and N, N-dimethylformamide dipentyl acetal, and the amount of the esterifying agent is 1 to 8 times, more preferably 2 to 5 times, the molar equivalent of the polyamic acid dianhydride used. The temperature for the esterification reaction is preferably 10 to 150 ℃, more preferably 20 to 60 ℃. The reaction time of the polyamic acid ester is preferably 0.5 to 20 hours, more preferably 3 to 8 hours, and the concentration of the esterification reaction is preferably 2 to 15%, more preferably 5 to 10%.
The poor solvent used for the solute precipitation and extraction and the solvent used for the dissolution of the polyamic acid ester solid in the two polyamic acid ester preparation methods can be the same as the solvent used for the precipitation of the polyamic acid solution and the dissolution of the polyamic acid solid, so that the description thereof is omitted here.
(3) Synthesis of polyimide
Polyimide can be obtained by dehydrating imidization of the synthesized polyamic acid. The polyimide may be a partially imidized product obtained by dehydrating and imidizing a part of the polyamic acid that is a precursor thereof to form a polyimide and the polyamic acid coexist, or may be a completely imidized product obtained by dehydrating and imidizing the entire polyamic acid. The imidization ratio of the polyimide is preferably 20 to 95%, more preferably 40 to 70%. The imidization ratio refers to the number of imide ring structures relative to the sum of the amic acid structures and the number of imide ring structures. Here, a part of the imide ring may be an isopolyimide ring.
The polyimide may be prepared through chemical imidization process, which is to dehydrate polyamide acid in the presence of dehydrating agent and catalyst to close ring at low temperature.
The type of the dehydrating agent in the chemical imidization may be one or a mixture of more of acetic anhydride, propionic anhydride or trifluoroacetic anhydride, the catalyst may be one or a mixture of more of pyridine, 4-methylpyridine, trimethylamine or triethylamine, the reaction materials of the dehydrating agent and the catalyst are not particularly limited in the invention, the ratio of the dehydrating agent to the catalyst may be adjusted according to the imidization degree, and the temperature for the chemical imidization reaction is 20 to 70 ℃, preferably 30 to 50 ℃; the reaction time is 1 to 20 hours, more preferably 3 to 10 hours; the dehydrating agent and the catalyst remaining in the solution after the polyimide reaction are preferably removed by a precipitation method. The precipitation method is to add polyimide reaction liquid into poor solvent to precipitate polyimide solid, and remove imidization dehydrating agent and catalyst by filtering and drying. The poor solvent used for precipitation may be the same as the solvent used for precipitation of the polyamic acid solid described above, and thus, the description thereof will not be repeated, and the obtained polyimide solid is redissolved to obtain a polyimide solution.
The solvent used for dissolving the polyimide solid is not particularly limited, and can be completely the same as the solvent used for dissolving the polyamic acid solid, so that the description is omitted herein, and the prepared solution is filtered to remove mechanical impurities to obtain the liquid crystal aligning agent.
Further, the liquid crystal aligning agent of the present invention may further comprise a molecular weight regulator, which is mainly aimed at regulating the molecular weight of the polymer so that the polymerization degree of the polymer is controlled in a proper interval to facilitate the dissolution of the polymer and the feasibility of the PI film line coating, wherein the molecular weight regulator refers to monoamine compounds, monoanhydride compounds or monoisocyanate compounds; specifically, monoamine compounds refer to butylamine, pentylamine, aniline, p-aminostyrene, p-aminophenylethane and the like; the monoanhydride compound is phthalic anhydride, ortho-cyclohexanedicarboxylic anhydride, maleic anhydride, itaconic anhydride, nadidac anhydride, n-dodecyl succinic anhydride, etc.; the monoisocyanate-based compound means phenyl isocyanate, naphthalene isocyanate, etc., and the amount of the molecular weight regulator is not particularly limited in the present invention, as long as the prepared liquid crystal aligning agent is excellent in dissolution effect and coating effect.
Further, the liquid crystal aligning agent can also comprise additives, wherein the additives are silane compounds and epoxy compounds, the silane additives can improve the adhesive force between the PI film and the substrate, and the presence of the epoxy compounds can improve the uniformity and the stability of the liquid crystal aligning film.
The silane compounds include, but are not limited to, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, N-bis (ethylene oxide) -3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, diethoxy (3-glycidoxypropyl) methylsilane, 2-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane. The addition amount of the silane compound additive is 0.1-15% of the total weight of the polymer, and more preferably 0.5-5%.
The epoxy compounds include, but are not limited to, polypropylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, N '-tetraepoxypropyl-m-xylylenediamine, N, N', N '-tetraepoxypropyl-4, 4' -diaminodiphenylmethane, 3- (N, N-diglycidyl) aminopropyl trimethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether. The epoxy additive is added in an amount of 0.1 to 15% by weight, more preferably 0.5 to 5% by weight, based on the total weight of the polymer.
< Liquid Crystal alignment film >
The liquid crystal alignment film of the present invention is preferably produced by applying the liquid crystal alignment agent of the present invention to a substrate, pre-curing the liquid crystal alignment film, subjecting the liquid crystal alignment film to alignment treatment, and then washing the surface of the alignment film with water or an organic solvent or subjecting the surface to secondary curing treatment to obtain the liquid crystal alignment film of the present invention.
The substrate used for coating the liquid crystal aligning agent of the present invention is not particularly limited as long as it has high transparency, and in addition to a glass substrate, polypropylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, N '-tetraepoxypropyl-m-xylylenediamine, N', N '-tetraepoxypropyl-4, 4' -diaminodiphenyl methane or 3- (N, N-diglycidyl) aminopropyl trimethoxy silane plate, silicon nitride substrate, transparent polyimide substrate, polyester substrate, etc., are preferably coated on glass substrate containing ITO electrode, wherein the ITO is indium tin oxide for providing electric field to control movement deflection of liquid crystal, and polarizer is matched to achieve display purpose.
The method of applying the liquid crystal aligning agent of the present invention is not particularly limited, and in the production of the application method, relief printing, screen printing, ink-jet method, dipping method, slit coating method, spin coating method, etc., any of them may be used as needed in the production.
The main purpose of the pre-curing of the liquid crystal aligning agent is to remove the solvent in the liquid crystal aligning agent, and the pre-curing temperature is generally 60-140 ℃ and the pre-curing time is 1-10 min. The main purpose of the main curing is to imidize the polyamic acid component in the film formed by the pre-curing into polyimide, or to improve the imidization rate of the oriented film with the polyimide component, so as to improve the stability of the film.
The thickness of the liquid crystal alignment film of the present invention is not particularly limited, and is usually 30 to 200nm, preferably 50 to 120nm, and too thick film tends to affect the alignment effect of the liquid crystal alignment film, whereas too thin film tends to cause a decrease in the stability of the liquid crystal at a later stage, and a suitable liquid crystal alignment film thickness can be selected as required.
The orientation treatment of the film includes rubbing orientation and photo-orientation treatment methods, and the present invention is preferably photo-orientation treatment because the rubbing orientation method is prone to dust and electrostatic breakdown, but the present invention is not limited thereto, and the wavelength of polarized light at the time of the photo-orientation treatment is preferably 100 to 400nm, more preferably 200 to 365nm, and the light dose required for the film photo-orientation treatment is preferably 10 to 2000mj/cm 2, more preferably 100 to 1000mj/cm 2.
After the alignment treatment is completed, the solvent used in the cleaning process is not particularly limited in the invention, and one or more of water, methanol, ethanol and methyl lactate can be used as a mixed solution.
The above-mentioned orientation film obtained after the photo-orientation treatment may be further subjected to post-baking treatment for the purpose of removing small molecular compounds generated in the photo-orientation treatment or removing a solvent used in the cleaning process and promoting the re-orientation of molecular chains on the film surface.
The post-baking temperature for the liquid crystal alignment film of the present invention is preferably 150 to 300 ℃, more preferably 180 to 250 ℃, and the baking time is preferably 5 to 120 minutes, more preferably 10 to 60 minutes. The higher the temperature is, the more the reorientation of the film surface molecules is promoted, but the higher the temperature is, the breakage of the film surface molecules is caused, and the baking temperature and time can be appropriately selected according to the characteristics of the film surface molecules.
< Liquid Crystal display element >
The liquid crystal used in the liquid crystal display device of the present invention is not particularly limited, and for example, nematic liquid crystal, smectic liquid crystal or cholesteric liquid crystal may be used, and the type of liquid crystal having positive or negative dielectric anisotropy may be selected depending on the mode of the liquid crystal display device, and the type of the liquid crystal display device produced by the liquid crystal aligning agent and the liquid crystal aligning film of the present invention is not particularly limited, and may be TN type (twisted nematic), STN type (super twisted nematic), VA type (vertical alignment), IPS/FFS (in-plane switching/fringe field switching) or the like.
The preparation method of the IPS or FFS type liquid crystal display element comprises the following steps: preparing two substrates, wherein one substrate is provided with an IPS or FFS type ITO electrode, the other substrate is provided with no ITO electrode or ITO or other conductive materials used for shielding electromagnetic interference, coating the liquid crystal aligning agent on the two substrates, baking for 5min by a hot plate at 90 ℃ and baking for 25min by a baking oven at 230 ℃, respectively carrying out illumination treatment on the two substrates by ultraviolet polarized light with 254nm wavelength in a certain direction, and then putting the two substrates into the baking oven for further heat drying treatment, wherein the secondary curing temperature is 230 ℃ and the time is 30min.
And dispersing spacer particles with the diameter of 4 mu m on one of the two substrates after the post-baking treatment (if the substrate is provided with a thick supporting material, the spacer particles are not required to be dispersed), coating sealant on the other substrate, sticking the substrates in a mode that the alignment films face to face and the alignment directions of the upper substrate and the lower substrate are antiparallel, solidifying the sealant to obtain a liquid crystal empty box, injecting liquid crystal into the liquid crystal empty box in a vacuum crystal filling mode, and sealing a liquid crystal liquid inlet to obtain the IPS type or FFS type liquid crystal display element.
In the polarization alignment treatment, the incident angle of the light is not particularly limited in the present invention, and the incident light may be perpendicular to the substrate or may form a certain inclination angle with the substrate.
< Synthetic example of diamine Compound >
Synthesis example 1:
a process for producing the diamine compound DA (A-1-1) represented by the structural unit A-1-1 is shown in the following synthetic scheme:
；
(1) Synthesis of Compound a-3
A500 mL three-neck round bottom flask is charged with a-1 (39.88 g,240 mmol), triethylamine (22.26 g,220 mmol) and 200g of solvent toluene, the temperature is raised to 50 ℃, a mixed solution of a-2 (19.30 g,100 mmol) and 100g of solvent toluene is slowly added dropwise into the system, the dropwise addition is completed within one hour, the system is subjected to heat preservation for 5 hours at 50 ℃, TLC tracks the raw material furan dicarboxyl chloride to be free, the reaction is stopped, the reaction solution is washed with water to be neutral, the upper organic phase is desolventized, 45g of tetrahydrofuran and 90g of methanol are added into the obtained solid, the obtained solid is stirred for 1 hour, and 34g of yellow solid a-3 is obtained after filtration and drying, and the yield is 76%.
1 The H-NMR (as shown in FIGS. 1-3) test determines that the structure is the target compound a-3, and the melting point (as shown in FIG. 4) is 232.90-238.59 ℃.
；
In fig. 1 to 3, δ=2.979 to 3.350ppm is c, d 8H, δ= 7.122ppm is f 2H, δ=7.523 to 8.185ppm is a, b 8H, and δ=8.575 to 8.605ppm is e 2H, thereby the compound a-3 is a target structure.
(2) Synthesis of Compound DA (A-1-1)
The above-mentioned compound a-3 (45 g,100 mmol), 5% palladium on carbon (2.25 g, water content, solid content 44.1%) and 450g solvent tetrahydrofuran were put into a 1L autoclave, the autoclave was sealed, after 3 to 5 times of replacement with hydrogen, the hydrogen was pressurized to 1.0 to 1.5MPa, the reaction was carried out at 50℃for 12 hours under stirring, after the completion of the reaction, the catalyst palladium on carbon was filtered with a filter membrane having a pore diameter of 0.2 μm, the filtrate was desolventized, the obtained solid was stirred in 120g of ethanol for 0.5 hours, and 32g of yellow solid compound DA (A-1-1) was obtained by filtration and drying, the yield was 82%.
1 The structure of the target compound DA (A-1-1) was determined by H-NMR (FIG. 5-FIG. 7) test, and the melting point (FIG. 8) was 159.35-170.85 ℃.
；
In fig. 5 to 7, δ=2.646 to 3.412ppm is c, d 8H, δ=7.117 ppm is f 2H, δ=6.480 to 6.902ppm is a, b 8H, δ=8.569 to 8.598ppm is e 2H, and δ= 4.877ppm is g 2H, whereby the compound DA (a-1-1) is seen as a target structure.
Diamine compounds DA (A-1-2) to DA (A-1-6) represented by the formulas A-1-2 to A-1-6 can be synthesized according to the process route of synthesis example 1, and the corresponding parent compounds can be amidated or esterified, and then the target diamine compounds DA (A-1-2) to DA (A-1-6) are synthesized through catalytic hydrogenation reaction, wherein the structural formulas of DA (A-1-2) to DA (A-1-6) are as follows, and the high-resolution mass spectrum results and the element analysis results of the corresponding target compounds are shown in the following table 1.
。
TABLE 1 Mass Spectrometry and elemental analysis data for target diamine Compounds DA (A-1-2) to DA (A-1-6)
< Example >
The present invention will be explained in further detail by way of specific examples, which are not intended to limit the present invention, and the abbreviations of the compounds used in the present examples and comparative examples and the measurement methods of the respective characteristics are as follows:
NMP: n-methyl-2-pyrrolidone;
BC: ethylene glycol monobutyl ether;
DA（A-1-1）：；
DA（A-1-2)：；
DA（A-1-3)：；
DA（A-1-4)：；
DA（A-1-5)：；
DA（A-1-6)：；
DA (A-2): p-phenylenediamine;
DA (A-3): 4,4' -diaminodiphenyl ether;
DA (A-4): 2, 4-diaminododecyloxybenzene;
DA (A-5): 4,4' -diaminodiphenylmethane;
DA (A-6): 1, 2-bis (4-aminophenoxy) ethane;
DAH (B-1): 1,2,3, 4-cyclobutane tetracarboxylic dianhydride;
DAH (B-2): 1, 3-dimethyl-1, 2,3, 4-cyclobutane tetracarboxylic dianhydride;
DAH (B-3): 2,3, 5-tricarboxycyclopentaacetic acid dianhydride;
DAH (B-4): 3,3', 4' -biphenyltetracarboxylic dianhydride.
Determination of the imidization ratio & gt
The method for measuring the imidization rate in the polyimide solution is as follows: adding the imidized solid powder into deuterated dimethyl sulfoxide solvent to prepare a solution with the mass concentration of 5%, carrying out ultrasonic total dissolution, adding the solution into a nuclear magnetic sample tube, and measuring the hydrogen spectrum of the nuclear magnetic by using a nuclear magnetic instrument (JNM-ECZ 400, JEOL DATUM). The product value of the proton is used to calculate the imidization rate by taking the proton of the structure which does not change before and after imidization as a reference proton and using the product value of the proton and the product value of the carboxylic acid proton in the vicinity of 11 to 14 ppm.
Imidization ratio= (1-a/b) 100%
The formula a is the ratio of the product value of carboxylic protons to the reference protons in the H1-NMR under test, and b is the ratio of the number of carboxylic protons to the number of reference protons when no imidization has occurred.
Example 1:
A500 mL three-necked round bottom flask was purged and then charged with the compound DA (A-1-1) (7.85 g,20 mmol), DA (A-2) (2.70 g,25 mmol), DA (A-4) (1.46 g,5 mmol) and NMP (81.55 g) at room temperature, the reaction system was warmed to 40℃and kept for 0.5 hour to dissolve all the materials, DAH (B-1) (6.86 g,35 mmol), DAH (B-2) (3.36 g,215 mmol) and NMP (81.55 g) were then charged into the flask and reacted at 80℃for 10 hours, and the reaction system was cooled to room temperature to give a polyamide acid polymer PA-1 having a concentration of 12%.
Dilution: 100g of PA-1 polyamic acid solution was added with 71.6g of NMP and 68.4g of BC, stirred at room temperature for 2 hours, and then filtered through a 0.2 μm filter membrane to obtain a liquid crystal aligning agent LCA-1 of example 1. The concentration of the polymer in the liquid crystal aligning agent is 5.0%, and the solvent ratio is NMP: BC=70:30.
Examples 2 to 12:
The liquid crystal aligning agents corresponding to examples 2 to 12 were (LCA-2) to (LCA-12), respectively, and were prepared in the same manner as in example 1, except that the types and the material ratios of the monomers used were changed, the initial concentrations of the polymerization reaction were 12.0%, the concentrations of the liquid crystal aligning agents obtained after dilution were 5.0%, and the solvent ratios of the aligning agents were NMP: BC=70:30. The types and the material ratios of the specific monomers are shown in Table 2 below.
TABLE 2 types and amounts of monomers used for liquid Crystal alignment agent of examples
Example 13:
Synthesis of polyamic acid ester: a500 mL three-necked round bottom flask was charged with the polyamic acid solution PA-1 (100 g) prepared in example 1 and 140g of NMP, the reaction concentration was diluted to 5%, then 4 times of dianhydride molar equivalent of N, N-dimethyldiethyl acetal was added to the system, the reaction was stirred at 50℃for 5 hours, the esterification reaction was carried out, the obtained reaction solution was then dropped into 2000mL of methanol with stirring, the esterifying agent N, N-dimethyldiethyl acetal was removed, the white precipitate was filtered off, the filter cake was rinsed with methanol, then dried to obtain 11.5g of a white solid, 10g of the solid was dissolved in 133g of NMP and 57g of BC solvent, then 200g of the liquid crystal aligning agent LCA-2 corresponding to example 2 was added to the system, the mixture was stirred at room temperature for 3 hours, and the liquid crystal aligning agent (LCA-13) corresponding to example 13 was obtained by filtration.
Example 14:
Synthesis of SPI (soluble polyimide): a500 mL three-necked round bottom flask was charged with the polyamic acid solution PA-1 (100 g) prepared in example 1 and 140g of NMP as a solvent, the reaction concentration was diluted to 5%, then acetic anhydride 3 times as much as molar equivalent of dianhydride and pyridine 2.5 times as much as molar equivalent of dianhydride were added to the system, and the reaction was stirred at 30℃for 5 hours to effect chemical imidization. Then, the obtained reaction solution was dropped into 2000mL of methanol with stirring, acetic anhydride and pyridine were removed, white precipitate was filtered off, the filter cake was rinsed with methanol, and further dried to obtain a white solid powder, the imidization rate of the solid powder was 65% as measured by nuclear magnetic resonance hydrogen spectroscopy, 12g of the solid was taken and added into 88g of solvent NMP, and the polyimide solution SPI-1 was obtained with stirring and total dissolution, at a concentration of 12%.
Dilution: 100g of SPI-1 solution is taken, 71.6g of NMP solvent and 68.4g of BC solvent are added, the mixture is stirred uniformly, and the liquid crystal aligning agent LCA-14 corresponding to the example 14 is obtained through filtration.
Example 15:
30g of liquid crystal aligning agent LCA-1 and 20g of liquid crystal aligning agent LCA-13 are stirred uniformly in a 100mL three-necked flask, and the liquid crystal aligning agent LCA-15 corresponding to the embodiment is obtained through filtration.
Example 16:
20g of liquid crystal aligning agent LCA-14 and 80g of liquid crystal aligning agent LCA-4 are stirred uniformly in a 100mL three-port bottle, and the liquid crystal aligning agent LCA-16 corresponding to the embodiment is obtained through filtration.
Comparative examples 1 to 6:
The liquid crystal aligning agents (LCA-17) to (LCA-22) corresponding to comparative examples 1 to 6 were prepared in the same manner as in example 1, the concentration of the polymer in the obtained liquid crystal aligning agents was 5%, the solvent ratio was NMP: BC=70:30, and the specific results are shown in Table 3 below, except that the types and the amount ratios of the monomers used were changed.
TABLE 3 types and amounts of monomers used for each of the liquid crystal aligning agents of comparative examples 1 to 6
Specific characterization of seal adhesion, high temperature image retention and long term flicker of liquid crystal display elements:
an IPS type liquid crystal display cell was prepared as follows: two glass substrates having a length and width of 3cm×4cm and a thickness of 0.7mm 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 number of the pixel electrodes is 4, and the pixel electrodes can be driven independently. The upper glass substrate was free of electrodes, and the liquid crystal alignment agent prepared in example 1 was coated on both substrates, and was pre-cured (hot plate, 85 ℃ C., 3 minutes), and main cured (circulation oven, 230 ℃ C., 60 minutes), to obtain a polyimide coating with a film thickness of 700A.
Irradiating upper and lower glass substrates with polyimide coating with ultraviolet polarized light with wavelength of 254nm and light dose of 450mj/cm 2, heating in a 230 deg.C heat circulation oven for 30min, spraying spacer particles with diameter of 4 μm on one of the upper and lower glass substrates, printing square sealant on the other substrate at a position 5mm away from the periphery 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 in such a way that the alignment film faces, the polarization axis of the photo alignment treatment is parallel and the overlapping width of the upper and lower substrates is 3cm, fixing the two substrates with a clamp, curing at 150 deg.C for 1 hr to obtain liquid crystal empty box, injecting IPS negative liquid crystal into the empty box in a decompression way, and sealing the liquid crystal filling port. A liquid crystal display element corresponding to example 1 was produced.
The liquid crystal display elements of examples 2 to 16 and comparative examples 1 to 6 were prepared in the same manner as described above, except that the applied liquid crystal aligning agent was changed to the liquid crystal aligning agents LCA-2 to LCA-16 of examples 2 to 16 and the liquid crystal aligning agents LCA-17 to LCA-22 of comparative examples 1 to 6.
A. evaluation of seal adhesion force of liquid Crystal display element
Placing the prepared liquid crystal display element in a 1L high-pressure reaction kettle, adding 500ml of deionized water into the high-pressure reaction kettle, dripping 10ml of red ink into the high-pressure reaction kettle, sealing the reaction kettle, heating to 130 ℃, keeping the pressure at 0.3MPa for 10 hours, cooling, taking out the liquid crystal display element, observing the liquid crystal display element, and powering up and driving.
The evaluation criteria for seal adhesion were as follows:
and (2) the following steps: the liquid crystal display element is not immersed in red ink, and the driving display is normal.
X: the liquid crystal display element is immersed in red ink, and the driving cannot display.
B. evaluation of high temperature residual image resistance of liquid crystal display element
And setting the manufactured liquid crystal unit between two orthogonal polaroids, and lighting the backlight source under the condition of no voltage application, so as to adjust the configuration angle of the liquid crystal unit in a mode of minimum brightness of transmitted light. Then, the liquid crystal cell was driven by applying an AC voltage having a frequency of 30Hz to the liquid crystal cell, and a V-T curve of the liquid crystal cell (apparatus: PWW-V-T type V-T test System, manufactured by Asahi Denka Co., ltd.) was measured, and an AC driving voltage V23 having a relative transmittance of 23% and an AC driving voltage V100 having a relative transmittance of 100% were calculated. As shown in fig. 9: the liquid crystal display element was placed over a high temperature backlight having a luminance of 10000 lumens, a temperature set at 70 ℃, A, B pixels were driven at V 100 for 24 hours, then simultaneously the pixels A, B, C, D were switched to V 23 for driving, and the time Ts required from the application of the voltage V 23 to visual observation of no difference in luminance between A, B and C, D pixels was calculated.
The evaluation criteria for high temperature resistance residual image are as follows:
Excellent: and Ts is less than or equal to 30s, and the high-resistance Wen Can image characteristic is excellent.
Generally: the Ts is more than or equal to 30s after 3min, and the anti-high Wen Can has common image characteristics.
The difference is: ts is more than 3min, and the image characteristic of the high-resistance Wen Can is poor.
C. Evaluation of long-term flicker characteristics of liquid Crystal display element
The liquid crystal display elements of examples and comparative examples of the present invention were subjected to a long-term flicker (flicker) test, the test instrument being CA-410 (manufacturer: kenicamantadine, japan).
The testing method comprises the following steps: the driving voltage was V 23, the frequency was 15Hz, the measurement duration was 24 hours, and the Flicker value F was recorded.
The long term Flicker inhibition characteristic evaluation criteria are as follows:
and (2) the following steps: f is less than or equal to-50 DB, and has excellent long-term flicker inhibition property.
Delta: -50DB < F is less than or equal to-30 DB DEG, and the long-term flicker suppression characteristic is general;
X: pt > -20DB DEG, poor long-term flicker suppression characteristics;
The liquid crystal aligning agents LCA-1 to LCA-22 corresponding to examples 1 to 16 and comparative examples 1 to 6 of the present invention were tested and evaluated for DC charge relaxation property and pretilt angle property as described above.
Evaluation results:
the liquid crystal aligning agents, liquid crystal alignment films and corresponding liquid crystal display elements prepared in examples 1 to 16 and comparative examples 1 to 6 were evaluated in the following table 4.
Table 4 evaluation results of liquid crystal display elements in examples and comparative examples
Compared with the prior art, the liquid crystal alignment agent provided by the invention introduces a unit containing an A-1 specific structure in the synthesis process, the prepared liquid crystal alignment film has the advantage of strong adhesion with sealing glue, and the prepared liquid crystal display element has the advantages of excellent high-temperature residual image resistance and outstanding long-term flicker inhibition property. The implementation method is simple and suitable for large-scale popularization.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. A liquid crystal aligning agent comprising at least one of a polyimide precursor and an imidization product of the polyimide precursor, characterized in that the polyimide precursor has a structural unit represented by the following formula 1:
Formula 1;
R 1、R2 in the formula 1 is independently selected from one of hydroxyl or alkoxy with 1-5 carbon atoms;
wherein A is a divalent organic group comprising at least one of the structures represented by the following formula A-1, "-" represents a bonding position;
A-1；
R 3、R4 is independently selected from one of alkylene and single bond of C 1-5, Z 1、Z2 is independently selected from any one of-O-, -NH-, and C 1 is selected from one of C-1:
C-1；
R 5 is selected from one of O, S, N;
B in the formula 1 is a tetravalent organic group, and B comprises any one of the following groups B-1 and B-2:
。
2. A liquid crystal aligning agent according to claim 1 wherein R 3、R4 is independently selected from the group consisting of C 2-3 alkylene.
3. The liquid crystal aligning agent according to claim 1, wherein the structural unit A-1 has any one of the following structural formulas A-1-1 to A-1-6:
。
4. A liquid crystal aligning agent according to claim 3, wherein the structures a-1-1 to a-1-6 are derived from diamine monomers represented by the following formulas DA (a-1-1) to DA (a-1-6), respectively:
。
5. The liquid crystal aligning agent according to claim 1, wherein the divalent organic group A in the formula 1 may further comprise other structures than the structure A-1, and the other structures are one or more of the following formulas:
。
6. the liquid crystal aligning agent according to claim 1, wherein the tetravalent organic group B in formula 1 may further comprise other structures than B-1 and B-2 structures, and the other structures are one or more of the following formulas:
。
7. The liquid crystal aligning agent according to claim 1, wherein the A-1 structural unit accounts for 10 to 90% of the total mole number of the A structural unit.
8. The liquid crystal aligning agent according to any one of claims 1 to 6, further comprising a solvent, wherein the solvent is one or more of N-methyl-2-pyrrolidone, γ -butyrolactone, N-dimethylacetamide, N-dimethylformamide, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol methylethyl ether, ethylene glycol dimethyl ether, and diethylene glycol monomethyl ether ethyl ester.
9. A liquid crystal alignment film, characterized in that the liquid crystal alignment film is made of the liquid crystal alignment agent according to any one of claims 1 to 8.
10. A liquid crystal display element comprising the liquid crystal alignment film according to claim 8.
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