CN117866199A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element thereof - Google Patents
Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element thereof Download PDFInfo
- Publication number
- CN117866199A CN117866199A CN202410268519.1A CN202410268519A CN117866199A CN 117866199 A CN117866199 A CN 117866199A CN 202410268519 A CN202410268519 A CN 202410268519A CN 117866199 A CN117866199 A CN 117866199A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- aligning agent
- crystal aligning
- tetracarboxylic dianhydride
- bis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 164
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 60
- -1 diamine compound Chemical class 0.000 claims abstract description 43
- 229920000642 polymer Polymers 0.000 claims abstract description 36
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 35
- 150000004985 diamines Chemical class 0.000 claims abstract description 30
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 125000001584 benzyloxycarbonyl group Chemical group C(=O)(OCC1=CC=CC=C1)* 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000000962 organic group Chemical group 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims description 31
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 26
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
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- 229940018564 m-phenylenediamine Drugs 0.000 claims description 5
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Landscapes
- Liquid Crystal (AREA)
Abstract
The invention relates to the technical field of liquid crystal display, in particular to a liquid crystal aligning agent, a liquid crystal aligning film and a liquid crystal display element thereof, wherein the liquid crystal aligning agent comprises a polymer obtained by reacting a tetracarboxylic dianhydride component a and a diamine component b, the diamine component b comprises a diamine compound b-1, and the diamine compound b-1 is at least one of the following compounds:the method comprises the steps of carrying out a first treatment on the surface of the n=an integer of 1 to 5; x is X 1 、X 2 Are independently selected from hydrogen atoms, C 1‑5 Alkyl, C 1‑5 Any one of alkoxy groups; r represents a monovalent organic group which can be removed by heat and replaced with a hydrogen atom, and is benzyloxycarbonyl or t-butoxycarbonyl. The liquid crystal aligning agent of the inventionThe liquid crystal display element has the advantages of fast afterimage disappearance, high contrast ratio and good stability.
Description
Technical Field
The invention relates to a liquid crystal aligning agent, a liquid crystal aligning film and a liquid crystal display element thereof, and belongs to the technical field of liquid crystal display.
Background
Liquid crystal display elements are classified into various modes according to the electrode structure and physical properties of liquid crystal molecules used. Liquid crystal display devices known heretofore are classified into various liquid crystal display elements of Twisted Nematic (TN) type, super Twisted Nematic (Super Twisted Nematic, STN) type, vertical alignment (VerticalAlignment, VA) type, in-Plane Switching (IPS) type, fringe field Switching (Fringe Field Switching, FFS) type, and the like.
The liquid crystal display element is a planar ultrathin display device, and the working principle is that an external electric field is applied to liquid crystal, 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 then the polarizer is matched for use to control the passing of the light, so that the aim of display is achieved. The liquid crystal alignment film aligns liquid crystal molecules in a liquid crystal display element, and polyimide is a preferred material for the liquid crystal alignment film because of its excellent heat resistance, mechanical strength, corrosion resistance, and affinity with liquid crystal.
With the recent expansion of the application range of LCDs, there are many cases where an afterimage phenomenon appears, in which the afterimage appears macroscopically when the LCD displays the same picture for a long time and then switches pictures, the original picture remains in the next picture.
The afterimage is formed inside the TFT-LCD display, and originates from the fact that liquid crystal molecules are easily polarized under static charge conditions. Individual liquid crystal molecules have their unique optical properties. When a fixed picture is displayed for a long time, parasitic charges in the liquid crystal are accumulated continuously to polarize, and finally the optical characteristics of the liquid crystal in terms of crystals are affected, so that the liquid crystal is prevented from returning to the original state under the control of an electric field when the picture is changed.
In practice, such image retention is caused for a number of reasons, such as the picture itself, the time at which the display is stationary, and the temperature of the display screen. In general, it can be divided into two main aspects, one being the influence of various material characteristic parameters and the other being the influence of various parameters and control conditions in the process.
Meanwhile, the influence of contrast on visual effect is very critical, and in general, the larger the contrast is, the clearer the image display effect is; and the contrast is small, so that the whole picture is gray. The high contrast is helpful for the definition, detail representation and gray level representation of the image. The contrast ratio of the LCD display screen refers to the measurement of different brightness levels between the brightest white and the darkest black in the bright and dark areas of a display picture, the larger the difference range is, the larger the contrast ratio is, the smaller the difference range is, the smaller the contrast ratio is, and the good contrast ratio can more easily display vivid and rich pictures.
In addition, conventional liquid crystal displays often suffer from a number of problems including display instability, distortion, damage, etc., for some extreme environmental conditions, such as ultra-high temperature, high humidity. These problems affect not only the display effect but also the stability and reliability of the whole system.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a liquid crystal aligning agent, a liquid crystal aligning film and a liquid crystal display element thereof, and the liquid crystal display element prepared by using the liquid crystal aligning agent has the advantages of quick afterimage disappearance, high contrast and good stability.
The technical scheme for solving the technical problems is as follows: a liquid crystal aligning agent comprising a polymer obtained by reacting a tetracarboxylic dianhydride component a with a diamine component b, wherein the diamine component b comprises a diamine compound b-1, and the diamine compound b-1 is at least one selected from compounds represented by the general formula (1):
a general formula (1);
in the general formula (1), n=an integer of 1 to 5;
in the general formula (1), X 1 、X 2 Are independently selected from hydrogen atoms, C 1-5 Alkyl, C 1-5 Any one of alkoxy groups;
in the general formula (1), R represents a monovalent organic group which can be removed by heat and replaced with a hydrogen atom, and is a benzyloxycarbonyl group (Cbz) or a t-butyloxycarbonyl group (Boc).
Further, the polymer comprises at least one of polyamide acid obtained by one-step reaction of a tetracarboxylic dianhydride component a and a diamine component b as raw materials or polyimide obtained by multi-step reaction of the tetracarboxylic dianhydride component a and the diamine component b as raw materials.
Further, the diamine compound b-1 is selected from at least one of structures shown in the following formulas 1-1 to 1-4:
。
further, the tetracarboxylic dianhydride component a is one or a combination of several of 3,3', 4' -biphenyl sulfone tetracarboxylic dianhydride, pyromellitic dianhydride, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 1, 3-dimethyl-1, 2,3, 4-cyclobutane tetracarboxylic dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic dianhydride and 2,3, 5-tricarboxyl cyclopentyl acetic dianhydride.
Further, the diamine component b includes a diamine compound b-2, the diamine compound b-2 is p-phenylenediamine, m-phenylenediamine, 1, 5-diaminonaphthalene, 1, 8-diaminonaphthalene, p-aminophenylamine, 4' -diaminodiphenylmethane, 4' -diaminodiphenylethane, 4' -diaminobenzamide, 4' -diaminodiphenylamine, 1, 3-bis (4-aminophenylethyl) urea, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis (4-aminophenyl) hexafluoropropane 4- (4-heptylcyclohexyl) phenyl-3, 5-diaminobenzoate, 2' -dimethyl-4, 4' -diaminobiphenyl, 4' -diaminodiphenyl ether, 1, 4-bis (4-aminophenoxy) benzene, 4' -diaminobenzophenone, 1, 2-bis (4-aminophenoxy) ethane, 1, 3-bis (4-aminophenoxy) propane, 1, 4-bis (4-aminophenoxy) butane, 1, 5-bis (4-aminophenoxy) pentane, 1, 6-bis (4-aminophenoxy) hexane, N, N ' -bis (4-aminophenyl) piperazine, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2, 4-diaminododecyloxybenzene, 2, 4-diaminooctadecyloxybenzene, one or a combination of more than one of 1- (4- (4-amyl cyclohexyl) phenoxy) -2, 4-diaminobenzene, 1- (4- (4-heptyl cyclohexyl) phenoxy) -2, 4-diaminobenzene and 3, 5-diaminobenzoic acid.
Further, the molar ratio of the tetracarboxylic dianhydride component a to the diamine component b is 100: (10-200); in the diamine component b, the diamine compound b-1 accounts for 0.1 to 100 percent of the mole percentage.
Further, the liquid crystal aligning agent also comprises a solvent component, wherein the solvent component is one or a combination of a plurality of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, gamma-butyrolactone, N-dimethylformamide, N-dimethylacetamide, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol methylethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol diethyl ether and diacetone alcohol.
Further, the polymer is dissolved in the solvent component to prepare the liquid crystal aligning agent, and the weight ratio of the polymer in the liquid crystal aligning agent is 3-20%.
The invention also discloses a liquid crystal alignment film, which comprises 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 contains the liquid crystal alignment agent, the diamine component b used for preparing the liquid crystal alignment agent contains the diamine compound b-1 with a specific structure, and the liquid crystal display element prepared by using the liquid crystal alignment film has the advantages of quick afterimage disappearance, high contrast and good stability.
The diamine compound b-1 monomer used in the liquid crystal aligning agent has better electron conduction capability, accelerates the dissipation of direct current bias charges in an LCD box, and reduces the afterimage and Flicker problems of an LCD panel caused by the accumulation of the direct current bias charges. In addition, the thermal leaving groups Cbz and Boc are high Wen Liqu, so that the anchoring groups can be promoted to move towards the PI surface, and the diamine compound b-1 monomer structure can strengthen the alignment force of the PI film on liquid crystal, weaken the alternating current afterimage level of the LCD panel caused by insufficient anchoring force, and further improve the contrast ratio of the LCD panel.
The preparation method of the liquid crystal aligning agent is simple, has wide market prospect and is suitable for large-scale application and popularization.
Drawings
FIG. 1 shows the structure of 1-1b compound 1 H-NMR spectrum;
FIG. 2 shows the structure of 1-1 compound 1 H-NMR spectrum.
Detailed Description
The following describes the present invention in detail. 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, so that the invention is not limited to the specific embodiments disclosed.
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 is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
A liquid crystal aligning agent comprising a polymer obtained by reacting a tetracarboxylic dianhydride component a with a diamine component b, wherein the diamine component b comprises a diamine compound b-1, and the diamine compound b-1 is at least one selected from compounds represented by the general formula (1):
a general formula (1);
in the general formula (1), n=an integer of 1 to 5;
in the general formula (1), X 1 、X 2 Are independently selected from hydrogen atoms, C 1-5 Alkyl, C 1-5 Any one of alkoxy groups;
in the general formula (1), R represents a monovalent organic group which can be removed by heat and replaced with a hydrogen atom, and is a benzyloxycarbonyl group (Cbz) or a t-butyloxycarbonyl group (Boc).
Specifically, the polymer comprises at least one of polyamide acid obtained by taking a tetracarboxylic dianhydride component a and a diamine component b as raw materials and performing one-step reaction or polyimide obtained by taking the tetracarboxylic dianhydride component a and the diamine component b as raw materials and performing multi-step reaction.
Specifically, the diamine compound b-1 is selected from at least one of structures shown in the following formulas 1-1 to 1-4:
。
specifically, the tetracarboxylic dianhydride component a is one or a combination of more than one of 3,3', 4' -biphenyl sulfone tetracarboxylic dianhydride, pyromellitic dianhydride, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 1, 3-dimethyl-1, 2,3, 4-cyclobutane tetracarboxylic dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic dianhydride and 2,3, 5-tricarboxyl cyclopentyl acetic dianhydride.
Specifically, the diamine component b comprises a diamine compound b-2, the diamine compound b-2 is p-phenylenediamine, m-phenylenediamine, 1, 5-diaminonaphthalene, 1, 8-diaminonaphthalene, p-aminophenylamine, 4' -diaminodiphenylmethane, 4' -diaminodiphenylethane, 4' -diaminobenzamide, 4' -diaminodiphenylamine, 1, 3-bis (4-aminophenylethyl) urea, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis (4-aminophenyl) hexafluoropropane 4- (4-heptylcyclohexyl) phenyl-3, 5-diaminobenzoate, 2' -dimethyl-4, 4' -diaminobiphenyl, 4' -diaminodiphenyl ether, 1, 4-bis (4-aminophenoxy) benzene, 4' -diaminobenzophenone, 1, 2-bis (4-aminophenoxy) ethane, 1, 3-bis (4-aminophenoxy) propane, 1, 4-bis (4-aminophenoxy) butane, 1, 5-bis (4-aminophenoxy) pentane, 1, 6-bis (4-aminophenoxy) hexane, N, N ' -bis (4-aminophenyl) piperazine, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2, 4-diaminododecyloxybenzene, 2, 4-diaminooctadecyloxybenzene, one or a combination of more than one of 1- (4- (4-amyl cyclohexyl) phenoxy) -2, 4-diaminobenzene, 1- (4- (4-heptyl cyclohexyl) phenoxy) -2, 4-diaminobenzene and 3, 5-diaminobenzoic acid.
Specifically, the molar ratio of the tetracarboxylic dianhydride component a to the diamine component b is 100: (10-200);
more preferably, the molar ratio of the tetracarboxylic dianhydride component a to the diamine component b is 100: (100-120).
Specifically, in the diamine component b, the mole percentage of the diamine compound b-1 is 0.1-100%;
more preferably, the diamine component b comprises 1 to 60 mole percent of the diamine compound b-1.
Specifically, the liquid crystal aligning agent further comprises a solvent component, wherein the solvent component is one or a combination of a plurality of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, gamma-butyrolactone, N-dimethylformamide, N-dimethylacetamide, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol methylethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol diethyl ether and diacetone alcohol.
Specifically, the polymer is polyamide acid, and the preparation method comprises the following steps: the mixture comprising the tetracarboxylic dianhydride component a and the diamine component b is dissolved in a solvent and polymerized at a temperature of 0-200 ℃ for 1-24 hours to obtain a polyamic acid solution, and then the solvent can be distilled off under reduced pressure to obtain polyamic acid solid, or the reaction system is poured into a large amount of solvent, and the precipitate is dried to obtain polyamic acid solid. The solvent used for the precipitation operation is not particularly limited as long as the solvent used can precipitate the polyamic acid, and examples thereof include one or more of methanol, propanol, isopropanol, butanol, ethanol, water, ethyl acetate, ethylene carboxylic acid, and a halogen-containing solvent.
Specifically, the solvent used for the polymerization reaction and the solvent component in the liquid crystal aligning agent may be the same or different, and the solvent used for the polymerization reaction is not particularly limited as long as the reactants can be dissolved. The solvent for the polymerization reaction includes, but is not limited to, any one or a combination of several of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide and gamma-butyrolactone. Wherein the reaction mixture obtained by mixing the tetracarboxylic dianhydride component a and the diamine component b and the reaction solution composed of the solvent account for 2 to 50% by weight of the reaction solution, and more preferably 10 to 20% by weight of the reaction solution.
Specifically, the polymer (polyamide acid) is dissolved in the solvent component to prepare the liquid crystal aligning agent, and the weight ratio of the polymer in the liquid crystal aligning agent is 3-20%. When the weight ratio of the polyamic acid solids in the liquid crystal aligning agent is less than 3%, the film thickness of the coating film becomes too small to obtain a good liquid crystal alignment film, whereas when the weight ratio of the polyamic acid solids in the liquid crystal aligning agent exceeds 20%, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment film.
Specifically, the liquid crystal aligning agent of the invention can also comprise a solvent which reduces the surface tension of the solution and increases the leveling effect of the aligning agent, wherein the solvent comprises one or more of 1, 2-dichloroethane, acetone, methyl ethyl ketone, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, tetrahydrofuran, dichloromethane, chlorobenzene, methyl isobutyl ketone, cyclobutanone, methyl acetate, ethyl acetate, diethyl ether, ethylene glycol monobutyl ether, ethylene glycol methylethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol dimethyl ether, and the solvent accounts for 0-70 percent of the total weight of the solvent component, preferably 10-60 percent of the total weight of the solvent.
Specifically, the polyimide can be prepared by, but not limited to, the following two imidization methods: thermal imidization or chemical imidization.
The thermal imidization method refers to directly heating polyimide solid to be dehydrated into a ring, and the heating temperature is preferably 150-300 ℃.
The chemical imidization method comprises the following steps: the polyamide acid is dehydrated and closed to prepare polyimide at a lower temperature in the presence of a dehydrating agent and a catalyst.
The solvent for imidization may be the same as that in the liquid crystal aligning agent.
Specifically, the weight ratio of the polyamic acid to the imidization solvent is 1: (2-25); imidization rate of the polyamic acid is 10% -100%; the imidization reaction temperature is 0 to 110 ℃, more preferably 30 to 80 ℃; the reaction time is 1 to 100 hours, more preferably 3 to 9 hours; the dehydrating agent can be an anhydride compound such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride; the molar ratio of the raw material tetracarboxylic dianhydride and the dehydrating agent used in the polyamic acid is 1: (0.1-10), more preferably 1: (1-5); the catalyst can be selected from pyridine, 4-methylpyridine, trimethylamine or triethylamine; the molar ratio of the dehydrating agent to the catalyst is 1: (0.1-5), more preferably 1: (2-4).
Specifically, the liquid crystal aligning agent may further include a molecular weight regulator, where the molecular weight regulator includes one or more of n-pentylamine, n-hexylamine, n-heptylamine, aniline, n-butylamine, phenyl isocyanate, naphthalene isocyanate, maleic anhydride, phthalic anhydride, succinic anhydride, and the molar ratio of the molecular weight regulator to the tetracarboxylic dianhydride component a is (0.001-15): 100. preferably, the molar ratio of molecular weight regulator to tetracarboxylic dianhydride component a is (0.4 to 6): 100, the molecular weight of the polymer is regulated by adding a molecular weight regulator in the synthesis process of the polymer, so that the feasibility of the subsequent coating process is ensured.
Specifically, the liquid crystal aligning agent can also comprise an additive, wherein the additive comprises an epoxy additive and/or a silane compound additive with a functional group, the addition amount of the epoxy additive is 0.01-15% of the total weight of polyamide acid or polyimide in the liquid crystal aligning agent, preferably, the addition amount of the epoxy additive is 0.5-10% of the total weight of polymer, the addition amount of the silane compound additive with the functional group is 0.01-10% of the total weight of polymer, preferably, the addition amount of the silane compound additive with the functional group is 0.5-5% of the total weight of polymer.
The epoxy additive is one or a combination of more of polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, glycerol diglycidyl ether, N, N, N ', N ' -tetraepoxypropyl-4, 4' -diaminodiphenyl methane or 3- (N, N-diglycidyl) aminopropyl trimethoxy silane.
The silane compound additive with functional groups is one or a combination of several of N- (2-amino ethyl) -3-amino propyl methyl dimethoxy silane, 3-amino propyl triethoxy silane, 2-amino propyl trimethoxy silane, 3-amino propyl triethoxy silane, N- (2-amino ethyl) -3-amino propyl trimethoxy silane, N-phenyl-3-amino propyl trimethoxy silane or N-bis (ethylene oxide) -3-amino propyl triethoxy silane. The additive has the effect of increasing the stability of the liquid crystal alignment film or improving the adhesion between the liquid crystal alignment film and the substrate, and the liquid crystal alignment agent can be prepared by mixing the polymer and the additive in a solvent at 10-100 ℃ with stirring, more preferably at 30-70 ℃.
A liquid crystal alignment film comprising the liquid crystal alignment agent of the present invention.
The liquid crystal alignment film contains the liquid crystal alignment agent, and diamine component b used for preparing the liquid crystal alignment agent contains diamine compound b-1 with a specific structure, so that the prepared liquid crystal display element has the advantages of fast afterimage disappearance, high contrast and good stability. In the embodiment, the liquid crystal display element prepared by the alignment agent has the following characteristics: ts is less than or equal to 5s, and the liquid crystal display element has excellent anti-afterimage performance; contrast evaluation: the contrast ratio is more than or equal to 2000, and the contrast ratio of the liquid crystal display element is excellent; stability performance evaluation: the delta Flicker is less than or equal to 5DB, and the stability of the liquid crystal display element is excellent.
The alignment method of the liquid crystal alignment film is not particularly limited, and a photo alignment method or a rubbing alignment method may be used, but is not limited thereto. Wherein, photo-alignment refers to exposing the film surface with polarized light to form a photo-aligned liquid crystal alignment film; the rubbing alignment means that a cloth made of nylon, rayon, cotton or other fibers is wound around a drum, and the alignment film is rubbed in a certain direction to form a rubbing alignment film.
A liquid crystal display element comprising the liquid crystal alignment film of the present invention.
The preparation method of the liquid crystal display element comprises the following steps: two substrates were prepared, each of which was coated with a liquid crystal alignment film prepared by the liquid crystal alignment agent of the present invention, and a liquid crystal cell was prepared by filling the liquid crystal between the two substrates.
The liquid crystal display element produced using the liquid crystal aligning agent of the present invention is suitable for various types of liquid crystal display elements, and may be a Twisted Nematic (TN) type or super Twisted Nematic (Super Twisted Nematic, STN) type, a vertical alignment (Vertical Alignment, VA) type, an In-Plane Switching (IPS) type, a fringe field Switching (Fringe FieldS witching, FFS) type, or the like. Among the above liquid crystal display elements, IPS and FFS type liquid crystal display elements are preferable.
Synthesis of (a) compound: synthesis of diamine compound
Synthesis example 1
The compound represented by the structural formula (1-1) can be synthesized according to the following synthetic route:
；
(1) Synthesis of 1-1b Compounds
Into a 1L three-necked round bottom flask, 1-1a (23.63 g,100 mmol), bis (4-nitrophenyl) carbonate (15.21 g,50 mmol), triethylamine 15.18g, N-dimethylaminopyridine 1.83g and tetrahydrofuran 400g were charged and reacted at room temperature for 12 hours. After the reaction is finished, pouring the reaction system into 3L of water to separate out solid precipitate, filtering to obtain solid precipitate, adding 60g of ethanol to pulp, filtering and drying to obtain 21g of solid. Melting point: 192.38 (. Degree.C.) testing of the product using high resolution liquid phase Mass Spectrometry, molecular formula C 27 H 36 N 4 O 4 ，[M+1]Theoretical 499.28, test 499.26. Of compounds of the formula 1-1b 1 The H-NMR spectrum is shown in FIG. 1, and it can be seen from FIG. 1: δ=1.466, 18H: boc methyl hydrogen sum; δ= 2.577, δ= 3.175,8H: methylene hydrogen totalAnd; δ= 5.826, δ= 9.234,4H: sum of amino hydrogens; δ=7.071, δ= 7.373,8H: the sum of unsubstituted hydrogens of the benzene ring; by passing through 1 H-NMR and mass spectrometry data confirm the target product 1-1b compound.
(2) Synthesis of Compound of formula 1-1
Triphenylphosphine (13.11 g,50 mmol), solid particulate iodine (12.69 g,50 mmol) and 600g dichloroethane were put into a 1L three-neck round bottom flask, stirred at room temperature for 4 hours, then 1-1b compound (24.93 g,50 mmol) and triethylamine (15.18 g,150 mmol) were added to the system, stirred at room temperature, heated and refluxed for 12 hours, cooled to room temperature, filtered, and the filtrate was dried, recrystallized with a mixture of 100g tetrahydrofuran and methanol (the mass ratio of tetrahydrofuran to methanol was 1:1), filtered and dried to obtain 20g solid. Testing the product using high resolution liquid phase mass spectrometry, molecular formula C 27 H 36 N 4 O 4 ，[M+1]Theoretical 481.27, test 481.26. Elemental analysis (C) 27 H 36 N 4 O 4 ) Theoretical C, 67.48, H, 7.55, N, 11.66, O, 13.32, measured C, 67.50, H, 7.53, N, 11.64, O, 13.34.Td value: 197.93 (. Degree. C.), melting point: 134.520 (. Degree.C.).
Of compounds of formula 1-1 1 The H-NMR spectrum is shown in FIG. 2, and it can be seen from FIG. 2: δ=1.510, 18H: boc methyl hydrogen sum; δ=2.687, δ= 3.275,8H: the sum of methylene hydrogens; δ= 6.520,2H: sum of amino hydrogens; δ= 7.068, δ= 7.271,8H: the sum of unsubstituted hydrogens of the benzene ring; by passing through 1 H-NMR and elemental analysis data gave: the product obtained by the route of this synthesis example is a compound of formula 1-1.
Synthesis examples 2 to 4
Compounds of formulas 1-2, 1-3, and 1-4 were prepared by the same method as in Synthesis example 1, except that: 1-1a is replaced by 1-1a, and the following compounds are respectively replaced by 1-1 a:
。
the results of elemental analysis of the compounds of formulas 1-2, 1-3 and 1-4 are shown in Table 1 below, and the results of high resolution mass spectrometry and elemental analysis of the target compounds corresponding to synthesis examples 2-4 are shown in Table 1.
Table 1 Mass Spectrometry and elemental analysis data for each target Compound in Synthesis examples 2-4
Preparation of (II) Polymer
Polymer preparation example 1
A500 mL three-necked round-bottomed flask was charged with a diamine compound represented by the formula 1-1 (24.03 g,50 mmol) (hereinafter abbreviated as 1-1), m-phenylenediamine (2.16 g,20 mmol) (hereinafter abbreviated as 2-1), 4' -diaminodiphenylethane (6.37 g,30 mmol) (hereinafter abbreviated as 2-2) and 147.8g of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) under a nitrogen atmosphere, and the resulting suspension was stirred until a yellow solution was obtained. 1,2,3, 4-cyclobutane tetracarboxylic dianhydride (19.61 g,100 mmol) (hereinafter referred to as a-1) and 147.8g of NMP were then added to the system. Stirring at high temperature for 4 hours gave a polyamic acid polymer having a concentration of 15% dissolved in NMP.
Polymer preparation examples 2 to 20 and polymer comparative preparation examples 1 to 10 were prepared by the same method as in Polymer preparation example 1, in which the concentrations were 15% each, and the solvents were NMP, except that: the types and amounts of the monomers used may vary, and are shown in tables 2 and 3, and are not repeated here.
In tables 2 and 3:
a-1:1,2,3, 4-cyclobutane tetracarboxylic dianhydride;
a-2:1, 3-dimethyl-1, 2,3, 4-cyclobutane tetracarboxylic dianhydride;
a-3:2,3, 5-tricarboxycyclopentylacetic acid dianhydride;
1-1: compounds represented by the formula 1-1
；
1-2: compounds represented by the formula 1-2
；
1-3: compounds represented by formulas 1-3
；
1-4: compounds represented by formulas 1-4
；
2-1: m-phenylenediamine;
2-2:4,4' -diaminodiphenylethane;
2-3:4,4' -diaminodiphenyl ether;
2-4：；
2-5：。
TABLE 2 Polymer preparation examples 1 to 20 monomer types and amounts
TABLE 3 comparison of the monomers used in the preparation of the polymers and the amounts thereof
(III) liquid Crystal alignment agent, liquid Crystal alignment film, and examples and comparative examples of liquid Crystal display element
Example 1
a. Liquid crystal aligning agent
100 parts by weight of a polymer (Polymer preparation 1), 86 parts by weight of NMP and 114 parts by weight of ethylene glycol monobutyl ether were charged into a three-necked round-bottomed flask under nitrogen atmosphere, the system was stirred at room temperature for 60 minutes, and the solution was filtered through a 0.2 μm filter to form the liquid crystal aligning agent of example 1 in a concentration of 5% in NMP: BC=60:40 (mass ratio).
b. Liquid crystal alignment film and liquid crystal display element
The present invention is explained only with IPS and FFS type liquid crystal display elements in the embodiments of the present invention, but the present invention is not limited thereto.
The liquid crystal aligning agent of example 1 was coated on a sheet of the first glass substrate having an IPS (in-plane switching) or FFS (fringe field switching) ITO electrode by spin coating to form a pre-coat layer. Through pre-curing (hot plate, 85 ℃ C., 10 minutes), main curing (circulating oven, 225 ℃ C., 50 minutes), exposure (254 nm polarized light, 5 mW/cm) 2 、500mj/cm 2 ) A first glass substrate having the liquid crystal alignment film of example 1 formed on the ITO electrode was obtained.
The liquid crystal aligning agent of example 1 was coated on a second glass substrate having no ITO electrode by spin coating to form a pre-coating layer. The second glass substrate on which the liquid crystal alignment film of example 1 was formed was also obtained after the above-mentioned pre-curing, main curing, and blasting.
A sealant was applied to the periphery of the first glass substrate leaving a liquid crystal inlet, and 3.5 μm spacers were sprayed on the other substrate. Then, the two glass substrates were bonded (5 kg,30 min) in an antiparallel manner to the alignment direction, then the sealant was cured, then the liquid crystal was injected, then the liquid crystal injection port was sealed with an ultraviolet curing adhesive, and the ultraviolet curing adhesive was cured with ultraviolet light, and polarizing plates were attached to the outer sides of the two glass substrates, respectively, to obtain the IPS or FFS type liquid crystal display element of example 1. The liquid crystal display element of example 1 was evaluated, and the results are shown in table 4.
Examples 2 to 20
Examples 2 to 20 of the liquid crystal aligning agent, the liquid crystal aligning film and the liquid crystal display element can be prepared by the same procedure as example 1 except that: the polymers used were replaced with the polymers corresponding to polymer preparation examples 2 to 20, the concentrations of the prepared liquid crystal aligning agents were 5%, the solvent ratios were NMP: bc=60:40, and the liquid crystal display elements of examples 2 to 20 were evaluated and the results are shown in table 4.
Comparative examples 1 to 10
Comparative examples 1 to 10 of the liquid crystal aligning agent, the liquid crystal aligning film and the liquid crystal display element can be prepared by the same procedure as in example 1, except that the polymer used was replaced with the polymer corresponding to the polymer comparative preparation examples 1 to 10, the concentrations of the corresponding liquid crystal aligning agents were all 5%, and the solvent ratios were NMP: bc=60:40, and the evaluation results of the liquid crystal display elements corresponding to comparative examples 1 to 10 are shown in table 4.
The relevant evaluation method is as follows:
(1) Characterization of image sticking Properties
And the manufactured liquid crystal unit is arranged between two orthogonal polaroids, the backlight source is lightened under the condition of no voltage application, and the configuration angle of the LCD box is adjusted in a mode of minimum transmitted light brightness. Then, the LCD cell was driven by applying an AC voltage having a frequency of 30Hz to the cell, and the V-T curve of the cell was measured (apparatus: PWW-V-T type V-T test System, manufactured by Asahi Denka Co., ltd.) to calculate an AC drive voltage having a relative transmittance of 23%. Then, an ac voltage of 23% relative transmittance was applied to the liquid crystal cell, a dc voltage of 3V was applied to the liquid crystal cell, the dc voltage was removed after 120 minutes of driving, the liquid crystal cell was driven with only the original ac voltage, and the time Ts required for the liquid crystal cell to decrease the relative transmittance to 30% or less from the removal of the dc voltage was calculated.
The afterimage evaluation results are as follows:
and (V) Ts is less than or equal to 5s, and the liquid crystal display element has excellent anti-afterimage performance.
Delta is that 10s is more than or equal to Ts > 5s, and the anti-afterimage performance is general.
X is that Ts is more than 10s, and the anti-afterimage performance is poor.
(2) Characterization of contrast stability
The manufactured liquid crystal display element (liquid crystal cell to which the polarizing plate was not attached) was driven at a saturated ac voltage for 30 hours, and then the contrast was measured. The instrument was a luminance meter (device model: 3298F, manufacturer: YOKOGAWA), and the liquid crystal display element was tested under a polarizing microscope equipped with a crossed nicols (cross nicol), and the minimum luminance tested was regarded as blackness. A30 Hz square wave voltage was applied to the liquid crystal element, the voltage value was slowly increased from 0VPP to 30VPP, and the maximum brightness was tested as whiteness. Contrast is defined as the ratio of whiteness to jetness.
The results of the contrast evaluation of the liquid crystal display element were as follows:
and (2) the following steps: the contrast ratio is more than or equal to 2000, and the contrast ratio of the liquid crystal display element is excellent.
O: the contrast ratio is 1600-2000, and the contrast ratio of the liquid crystal display element is good.
Delta: the contrast ratio is less than or equal to 1000 and less than 1600, and the contrast ratio of the liquid crystal display element is common.
X: the contrast ratio is less than 1000, and the contrast ratio of the liquid crystal display element is poor.
(3) Characterization of stability
The fabricated liquid crystal display element was driven at a 30hz 3.5vpp square wave voltage, placed over a backlight source with a brightness of 10000lux, tested for its Flicker value, and then the device was left to be driven and aged for 120 hours in a double 85% (temperature 85 ℃, humidity 85% rh) experimental box, and tested again for its Flicker value. (device model: CA-410, manufacturer: kenicamantadine), the difference ΔFlicker= |Flicker before aging-Flicker after aging was calculated for the two Flicker tests.
The stability evaluation results were as follows:
and (2) the following steps: the delta Flicker is less than or equal to 5DB, and the stability of the liquid crystal display element is excellent.
O: the delta Flicker is more than 5DB and less than or equal to 10DB, and the contrast ratio of the liquid crystal display element is good.
Delta: 10DB < DeltaFlicker is less than or equal to 20DB, and the contrast ratio of the liquid crystal display element is common.
X: Δflicker > 20DB, and the contrast ratio of the liquid crystal display element is poor.
Table 4 evaluation results of liquid crystal display elements of examples and comparative examples
As can be seen from Table 4, compared with the prior art, the liquid crystal aligning agent of the present invention contains diamine compound b-1 of specific structure in the diamine monomer, so that the liquid crystal display element containing the liquid crystal aligning agent of the present invention has the advantages of fast afterimage disappearance, high contrast ratio and good stability, and the implementation method of the present invention is simple, has wide market prospect, and is suitable for large-scale application and popularization.
The technical features of the above-described embodiments may be arbitrarily combined, and in order to simplify the description, all possible combinations of the technical features in the above-described embodiments are not exhaustive, 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.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims.
Claims (10)
1. A liquid crystal aligning agent, characterized in that the liquid crystal aligning agent comprises a polymer obtained by reacting a tetracarboxylic dianhydride component a and a diamine component b, wherein the diamine component b comprises a diamine compound b-1, and the diamine compound b-1 is at least selected from one of compounds shown in a general formula (1):
a general formula (1);
in the general formula (1), n=an integer of 1 to 5;
in the general formula (1), X 1 、X 2 Are independently selected from hydrogen atoms, C 1-5 Alkyl, C 1-5 Any one of alkoxy groups;
in the general formula (1), R represents a monovalent organic group which can be removed by heat and replaced with a hydrogen atom, and is a benzyloxycarbonyl group or a t-butoxycarbonyl group.
2. The liquid crystal aligning agent according to claim 1, wherein the polymer comprises at least one of polyamide acid obtained by one-step reaction of tetracarboxylic dianhydride component a and diamine component b as raw materials or polyimide obtained by multi-step reaction of tetracarboxylic dianhydride component a and diamine component b as raw materials.
3. The liquid crystal aligning agent according to claim 1, wherein the diamine compound b-1 is at least one selected from the structures represented by the following formulas 1-1 to 1-4:
。
4. the liquid crystal aligning agent according to claim 1, wherein the tetracarboxylic dianhydride component a is one or a combination of several of 3,3', 4' -biphenyl sulfone tetracarboxylic dianhydride, pyromellitic dianhydride, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 1, 3-dimethyl-1, 2,3, 4-cyclobutane tetracarboxylic dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic dianhydride and 2,3, 5-tricarboxyl cyclopentyl acetic dianhydride.
5. A liquid crystal aligning agent according to claim 1, wherein the diamine component b comprises a diamine compound b-2, the diamine compound b-2 is p-phenylenediamine, m-phenylenediamine, 1, 5-diaminonaphthalene, 1, 8-diaminonaphthalene, p-aminophenylamine, 4' -diaminodiphenylmethane, 4' -diaminodiphenylethane, 4' -diaminobenzamide, 4' -diaminodiphenylamine, 1, 3-bis (4-aminophenylethyl) urea, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis (4-aminophenyl) hexafluoropropane 4- (4-heptylcyclohexyl) phenyl-3, 5-diaminobenzoate, 2' -dimethyl-4, 4' -diaminobiphenyl, 4' -diaminodiphenyl ether, 1, 4-bis (4-aminophenoxy) benzene, 4' -diaminobenzophenone, 1, 2-bis (4-aminophenoxy) ethane, 1, 3-bis (4-aminophenoxy) propane, 1, 4-bis (4-aminophenoxy) butane, 1, 5-bis (4-aminophenoxy) pentane, 1, 6-bis (4-aminophenoxy) hexane, N, N ' -bis (4-aminophenyl) piperazine, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2, 4-diaminododecyloxybenzene, 2, 4-diaminooctadecyloxybenzene, one or a combination of more than one of 1- (4- (4-amyl cyclohexyl) phenoxy) -2, 4-diaminobenzene, 1- (4- (4-heptyl cyclohexyl) phenoxy) -2, 4-diaminobenzene and 3, 5-diaminobenzoic acid.
6. A liquid crystal aligning agent according to claim 1 wherein the molar ratio of the tetracarboxylic dianhydride component a to the diamine component b is 100: (10-200); in the diamine component b, the diamine compound b-1 accounts for 0.1 to 100 percent of the mole percentage.
7. The liquid crystal aligning agent according to any one of claims 1 to 6, further comprising a solvent component, wherein the solvent component is one or a combination of several of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ -butyrolactone, N-dimethylformamide, N-dimethylacetamide, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol methylethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol diethyl ether, diacetone alcohol.
8. The liquid crystal aligning agent according to claim 7, wherein the polymer is dissolved in the solvent component to prepare the liquid crystal aligning agent, and the weight ratio of the polymer in the liquid crystal aligning agent is 3-20%.
9. A liquid crystal alignment film comprising 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 9.
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