CN109370614A - A kind of aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display element - Google Patents
A kind of aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display element Download PDFInfo
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- CN109370614A CN109370614A CN201811390643.6A CN201811390643A CN109370614A CN 109370614 A CN109370614 A CN 109370614A CN 201811390643 A CN201811390643 A CN 201811390643A CN 109370614 A CN109370614 A CN 109370614A
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- liquid crystal
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
Abstract
The invention belongs to technical field of liquid crystal display, a kind of aligning agent for liquid crystal and liquid crystal orientation film and liquid crystal display element comprising this aligning agent for liquid crystal are disclosed, aligning agent for liquid crystal of the invention includes at least one of polyamic acid solution and polyimide solution, the polyamic acid solution and polyimide solution are made in a solvent by polymerization reaction by dianhydride compound and diamine compound, and above-mentioned diamine compound includes at least one of diamine compound group (wherein A as shown in formula 11Selected from one of oxygen atom, sulphur atom, NH group), liquid crystal orientation film containing aligning agent for liquid crystal of the present invention can dramatically increase the pre-tilt angle of liquid crystal, and there are excellent liquid crystal aligning uniformity, prepared liquid crystal display element and contrast with higher and because the image retention caused by direct current charge buildup disappears fast characteristic.
Description
Technical field
The invention belongs to technical field of liquid crystal display more particularly to a kind of aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal
Display element.
Background technique
Liquid crystal display (LCD) is the most electronic product of development vitality in display field, because it has driving electricity
Force down, be low in energy consumption, lightweight is small, without the remarkable advantages such as harm ray, be widely used in TV, computer, portable
Each display field such as phone.Liquid crystal display element is a kind of display equipment of planar ultra-thin, its working principle is to liquid crystal
Apply an extra electric field, liquid crystal polar molecule reverses under the action of extra electric field, changes the arrangement inside liquid crystal molecule
State makes incident polarised light change direction, then can control whether passing through of light with the use of polaroid, to reach display
Purpose.In order to which the direction for reversing liquid crystal when applying extra electric field is consistent, liquid crystal can be set in usual liquid crystal display element
Alignment films control the initial alignment state of liquid crystal molecule, variable condition of the liquid crystal cell according to liquid crystal before and after applying extra electric field
And it is divided into the liquid crystal displays members such as TN (twisted-nematic) type, STN (supertwist) type, IPS (in-plane switching), VA (the straight orientation of weight) type
Part.
In above-mentioned liquid crystal display element, in order to be orientated liquid crystal molecule with predetermined direction relative to substrate surface, need pair
Alignment layer surface carries out orientation process, and method for orientation treatment more popular at present is broadly divided into two kinds: one is be friction orientation
Mode, another kind are the modes of light orientation.Friction orientation mode generallys use the textile materials such as cotton or staple fibre to liquid crystal
Alignment layer surface carries out friction with certain orientation and assigns its liquid crystal aligning performance, but the method for friction orientation is carried out in technique
In be easy to produce electrostatic and dust, cause alignment layer surface to cause to show underproof problem because of Electrostatic Absorption dust, even
There is the phenomenon that partial electrostatic accumulation breakdown oriented layer causes liquid crystal cell short circuit, in addition electrostatic accumulation may further result in display picture
There is image retention；Light orientation refers to that the irradiation for carrying out polarized ultraviolet to orientation layer surface takes to assign liquid crystal orientation film to liquid crystal
To ability, photoisomerization type, photo-crosslinking type and photolysis type are broadly divided into according to the mechanism of light orientation, no matter which kind of light orientation class
There is relative friction orientation process mode liquid crystal aligning deficiency in type, prepared liquid crystal display element is caused to occur
Point is orientated the problems such as uneven, black state light leakage and contrast are insufficient, so needing to enhance alignment films to the anchoring energy of liquid crystal
Power, to make up the problem of light orientation deficiency.In addition no matter friction orientation processing or light orientation processing liquid crystal display element
Under alternating voltage driving, the accumulation of electrode both ends charge all will form, liquid crystal when liquid crystal display element OFF state is caused to restore just
Beginning state is not thorough, to lead to the problem of liquid crystal display element light leakage and contrast decline.
Summary of the invention
In order to overcome the deficiencies of the prior art, a kind of aligning agent for liquid crystal is disclosed, unlike the prior art, including is selected from down
Formula 1 indicate diamine compound and tetracid dianhydride carry out polymerization reaction and obtain polyamic acid and by the polyamic acid imidization and
At least one polymer of obtained polyimides.
Wherein, X1It is selected from :-O-,One of singly-bound；
Wherein, A1Selected from oxygen atom, sulphur atom andOne of group；
Wherein, R1、R2、R3It is independently selected from H atom, halogen, C1-20Alkyl and its derivative containing substituent group,
C2-20Alkenyl and derivative, C containing substituent group2-20Alkynes and derivative containing substituent group, contain 1-10 rouge
The alkyl compound of ring and its derivative containing substituent group, the aryl compound containing 1-10 aromatic ring and its contain substituent group
One of derivative, the compound containing 1-10 heterocycle and its derivative containing substituent group；
Polyamic acid composition contained by aligning agent for liquid crystal of the invention introduces contain phenyl benzo miaow in the synthesis process
The diamine monomer of oxazolyl group, phenylbenzothiazol group or phenyl benzoxazoles group, the phenylbenzimidazol in diamine monomer
Group, phenylbenzothiazol group or phenyl benzoxazoles group are polycyclic organic groups, are to have stronger rigid side switch
Group increases alignment films and acts on the anchoring of liquid crystal, and then improves the pre-tilt angle and orientation uniformity of liquid crystal.
In addition phenyl benzimidazole groups group, phenylbenzothiazol group or the phenyl benzene contained in diamine monomer of the invention
And oxazole group is tricyclic conjugated structure, the movement speed of charge can effectively be accelerated by forming the big pi bond of conjugation, reduce charge
Local accumulation, so liquid crystal orientation film of the invention with reduce the electrostatic dust in friction orientation processing procedure inhale symbol and film surface it is quiet
Electric breakdown phenomena broadens process window, improves the yield of product, can be quick just because of above-mentioned tricyclic conjugated structure
The direct current biasing charge at dispersive electrode both ends keeps prepared liquid crystal display element fast because of the image retention caused by direct current charge buildup
Speed disappears, and returns to original state liquid crystal when liquid crystal display element OFF state more thoroughly, thus normally black mode can be improved
The blackness of liquid crystal display element, and then improve the contrast of display panel.
Specifically, the diamine compound has structural formula shown in 1-1~1-10:
Further, further include other diamine compounds except diamine compound shown in formula 1: p-phenylenediamine, m-phenylene diamine (MPD),
1,5- diaminonaphthalene, 1,8- diaminonaphthalene, p-aminophenyl ethamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diamino hexichol second
Alkane, 4,4 '-diaminodiphenyl ethers, 1,4- bis- (4- amino-benzene oxygen) benzene, 4,4 '-diaminobenzophenones, bis- (the 4- amino of 1,2-
Phenoxy group) ethane, bis- (4- amino-benzene oxygen) propane of 1,3-, bis- (4- amino-benzene oxygen) butane of 1,4-, bis- (the 4- aminobenzenes of 1,5-
Oxygroup) pentane, 1,6- bis- (4- amino-benzene oxygen) hexanes, N, N '-two (4- aminophenyl) piperazine, bis- [4- (the 4- aminobenzenes of 2,2-
Oxygroup) phenyl] propane, 2,4- diamino dodecane oxygroup benzene, 2,4- diamino octadecane epoxide benzene, bis- [4- (the 4- amino of 2,2-
Phenoxy group) phenyl] hexafluoropropane, bis- (4- aminophenyl) hexafluoropropane of 2,2-, 4- (4- heptyl cyclohexyl) phenyl -3,5- diamino
Yl benzoic acid ester, 2,2 '-dimethyl -4,4 '-benzidine, 4,4 '-diaminobenzene formamides, 1- (4- (4- pentylcyclohexyl
Cyclohexyl) phenoxy group) -2,4- diaminobenzene, 1- (4- (4- heptyl cyclohexyl) phenoxy group) -2,4- diaminobenzene, 3,5- diamino
The mixture of one or more of yl benzoic acid.The diamine components b further includes diamine components b-2, the diamine components b-2
For p-phenylenediamine, m-phenylene diamine (MPD), 1,5- diaminonaphthalene, 1,8- diaminonaphthalene, p-aminophenyl ethamine, 4,4 '-diamino hexichol first
Alkane, 4,4 '-diamino-diphenylamines, 4,4 '-diaminodiphenyl ethers, 1,4- bis- (4- amino-benzene oxygen) benzene, 4,4 '-diamino hexichol
Bis- (4- amino-benzene oxygen) ethane of ketone, 1,2-, bis- (4- amino-benzene oxygen) propane of 1,3-, bis- (4- amino-benzene oxygen) fourths of 1,4-
Bis- (4- amino-benzene oxygen) pentanes of alkane, 1,5-, 1,6- bis- (4- amino-benzene oxygen) hexanes, N, N '-two (4- aminophenyl) piperazine,
2,2- bis- (4- (4- amino-benzene oxygen) phenyl) propane, 2,4- diamino dodecane oxygroup benzene, 2,4- diamino octadecane epoxide
Bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of benzene, 2,2-, bis- (4- aminophenyl) hexafluoropropane of 2,2-, 4- (4- heptyl
Cyclohexyl) phenyl -3,5- diaminobenzoic acid ester, 1,4 diamino -2,3- bis- (4- (4- heptyl cyclohexyl) phenoxy group) benzene, 1,4
The double n-dodecane oxygroup benzene of diamino -2,3-, 2,2 '-dimethyl -4,4 '-benzidine, 4,4 '-diaminobenzene formamides,
1- (4- (4- pentylcyclohexyl cyclohexyl) phenoxy group) -2,4- diaminobenzene, 1- (4- (4- pentylcyclohexyl cyclohexyl) benzene oxygen
Base) -2,4- diaminobenzene, 2,3- bis- (4- (4- heptyl cyclohexyl) phenoxy group) -1,4- diaminobenzenes, 3,5- diaminobenzoic acid
One of or a variety of mixtures.
Further, the molar ratio of the diamine compound and tetracarboxylic dianhydride are 100:20-200, more preferably 100:80-
100。
Further, it is 0.1-100% that diamine compound shown in formula 1, which accounts for entire diamine compound molar content, more excellent
It is selected as 10-95%.
Further, the tetracarboxylic dianhydride is 1,2,3,4- cyclobutane tetracarboxylic dianhydrides, 1,2,3,4- pentamethylene tetrabasic carboxylic acids
Dianhydride, 2,3,5- tricarboxylic cyclopentyl acetic acid dianhydride, equal benzene tertacarbonic acid's dianhydride, 1,3- dimethyl -1,2,3,4- cyclobutane tetracarboxylic acid
Acid dianhydride, 1,2,4,5- cyclopentanetetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydrides, 3,3 ', 4,4 '-biphenyl sulfone tetracarboxylic acids
One of acid dianhydride, 4- (2,5- dioxotetrahydro furans -3- base) -1,2,3,4- naphthane -1,2- dicarboxylic anhydride are a variety of
Mixture.
Further, the solvent is n-methyl-2-pyrrolidone, gamma-butyrolacton, n,N-dimethylacetamide, N, N- bis-
Methylformamide, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol methyl ether, glycol dimethyl ether,
One of diethylene glycol monomethyl ether ethyl ester or a variety of mixtures.
The beneficial effect of aligning agent for liquid crystal provided by the invention is:
1) aligning agent for liquid crystal of the invention is disliked by group containing phenyl benzimidazole groups, phenylbenzothiazol group or phenyl benzo
The diamine monomer of oxazolyl group is formed with other tetracarboxylic dianhydride's monomer polymerizations, due to the phenyl benzimidazole groups in diamine monomer
Group, phenylbenzothiazol group or phenyl benzoxazoles group are polycyclic organic groups, and are to have stronger rigid side
Key group increases alignment films and acts on the anchoring of liquid crystal, and then improves the pre-tilt angle and orientation uniformity of liquid crystal.
2) phenylbenzimidazol contained in diamine monomer used in aligning agent for liquid crystal aligning agent for liquid crystal of the invention
Group, phenylbenzothiazol group or phenyl benzoxazoles group are tricyclic conjugated structures, and forming the big pi bond of conjugation can add
The dispersion of fast electrode both ends direct current biasing charge, makes liquid crystal display element quickly disappear because of the image retention caused by direct current biasing charge
It loses.
3) the direct current biasing charge that can be gathered just because of above-mentioned tricyclic conjugated structure with rapid dispersion electrode both ends, makes
Liquid crystal returns to original state another plus thorough when liquid crystal display element OFF state, thus the liquid crystal display member of normally black mode can be improved
The blackness of part, and then improve the contrast of display panel.
4) the method for the present invention is simple, wide market, and scale application is suitble to promote.
It further, further include molecular weight regulator in the alignment agent, the molecular weight regulator refers to mono-acid anhydride
Close object, monoamine compound or monoisocyanates class compound；Specifically, mono-acid compound anhydride refers to maleic anhydride, adjacent benzene
Dicarboxylic acid anhydride, adjacent cyclohexyl dicarboxylic acid acid anhydride, maleic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinic acid
Acid anhydride etc.；Monoamine compound refers to aniline, n-butylamine, n-amylamine, n-hexylamine, positive heptyl amice or n-octyl amine etc.；Monoisocyanates class
Compound refers to phenyl isocyanate, naphthyl isocyanate etc., wherein the molar ratio of molecular weight regulator and tetracarboxylic dianhydride's component a
For (0.01~20): 100, preferably (0.5~5): 100.
Beneficial effect using above-mentioned further technical solution is, by using molecular weight regulator and tetracarboxylic dianhydride,
Diamine components are used together to synthesize the polymer of end band modification type group, can be in the skill for not influencing alignment agent and alignment films
Under the premise of art effect, the molecular weight of polymer is adjusted, to guarantee the feasibility of aligning agent for liquid crystal panel coating.
Further, it may also include additive in the aligning agent for liquid crystal, the additive is epoxy compounds, silanes
One of compound or a variety of mixtures.The epoxy compounds are including but not limited to ethylene glycol diepoxy propyl
Ether, polyethylene glycol bisglycidyl ethers, propylene glycol bisglycidyl ethers, polypropylene glycol bisglycidyl ethers, 1,6- hexylene glycol two
Glycidyl ethers, glycerine bisglycidyl ethers, N, N, N ' ,-four glycidyl of N '-m-xylenedimaine, N, N, N ', N '-four
Glycidyl -4,4 '-diaminodiphenylmethane or 3- (N, N- diepoxy propyl) TSL 8330.Epoxies adds
The additional amount for adding agent is 0.1~20%, more preferably the 3~10% of polymer A total weight.The silane compound include but
It is not limited to 3- TSL 8330,3-aminopropyltriethoxysilane, diethoxy (3- glycidyl oxygen
Base propyl) methyl-monosilane, 2- TSL 8330,3-aminopropyltriethoxysilane, N- (2- amino-ethyl)-
3- TSL 8330, N- (2- amino-ethyl) -3- aminopropyl first dimethoxysilane, N- phenyl -3- amino
Bis- (the ethylene oxide) -3-aminopropyltriethoxysilane of propyl trimethoxy silicane, N-.Silane compound additive adds
Enter 0.1~10%, more preferably 0.5~3% that amount is total polymer weight.
Beneficial effect using above-mentioned further technical solution is that the stabilization of liquid crystal orientation film can be improved in the presence of additive
Property or improve adhesive force between liquid crystal orientation film and substrate.
Under the premise of not influencing effect of the invention, aligning agent for liquid crystal of the invention can also include other polymers, institute
Stating other polymers can enumerate: be obtained using polymerization reaction is carried out with tetracarboxylic dianhydride without diamine components shown in formula 1
Polyamic acid and dehydration imidization cyclization and the polyimides, polyester, polyamide, cellulose derivative, the bunching that generate
Aldehyde, polystyrene derivative etc..The effect for adding the polymer is to improve solution properties or electrical characteristic.The polymer adds
Enter amount for 50% of polymer total amount in aligning agent for liquid crystal hereinafter, more preferable 0.1~40%.
The aligning agent for liquid crystal can be made by mixing polymer and additive under stiring in 10~100 DEG C in a solvent
, more preferably 25~60 DEG C.
The polyimides contained in aligning agent for liquid crystal of the present invention can be by carrying out dehydration imidization for the polyamic acid of synthesis
It obtains.Polyimides can be will as the whole of the polyamic acid of its presoma carry out dehydration imidization cyclization obtained from it is complete
Full imidization product is also possible to that a part of polyamic acid is only carried out dehydration imidization cyclization, forms polyimides and gather
The part imidizate product that amic acid coexists.The acid imide rate of polyimides is preferably 5%~70%, and more preferably 10%
~50%, most preferably 5%~30%.The acid imide rate refer to the number of structures of imide ring relative to amic acid structure with
For the summation of imide ring number of structures.Herein, a part of imide ring can be different imide ring.
The preparation method of above-mentioned polyimides can use but be not limited to following two imidization method, this two kinds of imines
Change method refers to hot imidization method or chemical imidization method.
Hot imidization method, which refers to, directly heats dehydration cyclization for polyimide solids, and heating temperature is preferably 150-300 DEG C.
Chemical imidization method includes the following steps: that polyamic acid in the presence of dehydrating agent and catalyst, passes through lower temperature
Degree dehydration ring closure prepares polyimides.
The solvent of imidization can be identical as the solvent in aligning agent for liquid crystal, and so it will not be repeated.
Wherein, the weight ratio of the polyamic acid and imidization solvent is 1:(2~50)；The Asia of the polyamic acid
Amination rate is 5~100%；The temperature of the imidization is 0~100 DEG C, more preferably 30~70 DEG C；Reaction time is 1
~50 hours, more preferably 2~8 hours；The dehydrating agent can choose an anhydride compound, such as acetic anhydride, propionic acid
Acid anhydride or trifluoro-acetic anhydride；The molar ratio of raw materials tetracid dianhydride and the dehydrating agent is preferably 1 in the polyamic acid:
(0.1~10), more preferably 1:(0.4~5)；The catalyst can be selected from pyridine, 4- picoline, trimethylamine or triethylamine；
The molar ratio of the dehydrating agent and catalyst is 1:(0.1~10), more preferably 1:(1~3).
The liquid crystal orientation film made of above-mentioned aligning agent for liquid crystal is also claimed in the present invention.
Liquid crystal orientation film of the invention contains aligning agent for liquid crystal of the invention, and diamines used in aligning agent for liquid crystal in the present invention
Diamine monomer containing phenyl benzimidazole groups group, phenylbenzothiazol group or phenyl benzoxazoles group in monomer, diamines
Phenyl benzimidazole groups group, phenylbenzothiazol group or phenyl benzoxazoles group in monomer are polycyclic organic groups,
It is stronger rigid side switch group, increases alignment films and the anchoring of liquid crystal is acted on, and then improve the pre-tilt angle and orientation of liquid crystal
Uniformity.Pre-tilt angle can (PAT-20, NORTH LCD ENGINEERING R&D CENTER be public with the measuring device of rotating crystal method
Department's manufacture), liquid crystal pretilt angle >=89.5 ° of the VA type liquid crystal display element containing this bright liquid crystal orientation film, the orientation of liquid crystal
Uniformity can use the state of orientation of polarized light microscope observing structure cell, and confirming liquid crystal display element of the invention through testing result is
Intact limit is uniformly directed.
The method for alignment of above-mentioned liquid crystal orientation film is not particularly limited, and can be used but is not limited to process for optical alignment or rub
The method for wiping orientation.Light orientation, which refers to, is exposed processing to film surface with polarised light, forms the liquid crystal orientation film of light orientation, rubs
It wipes orientation and refers to that the cloth being made into nylon, artificial silk, cotton class or other fibers is wrapped on roller, and rubbed with certain orientation
Alignment films are wiped, the alignment films of friction orientation are formed.
The liquid crystal display element comprising above-mentioned liquid crystal orientation film is also claimed in the present invention.
The phenyl benzimidazole groups group contained in alignment films in liquid crystal display element of the invention, phenylbenzothiazol base
Group or phenyl benzoxazoles group are tricyclic conjugated structures, and the mobile speed of charge can effectively be accelerated by forming the big pi bond of conjugation
Degree, reduces the local accumulation of charge, can accelerate the dispersion of electrode both ends direct current biasing charge, make liquid crystal display element because of direct current
Image retention quick disappearance caused by biascharge returns to original state liquid crystal another plus thoroughly,
The blackness of the liquid crystal display element of normally black mode thus can be improved, and then improve the contrast of display element.It is embodied in
In specific embodiment, the anti-image retention of liquid crystal display element prepared by the present invention is had excellent performance, and its contrast >=2000 (test
Device: PWW-V-T type V-T test macro, the manufacture of Dong Xu electricity Science and Technology Ltd.).
The preparation method of above-mentioned liquid crystal display element includes the following steps: to prepare two plate bases, be coated on every plate base
One layer of liquid crystal orientation film as obtained by aligning agent for liquid crystal of the invention, and liquid crystal is full of among two-layer substrate to be made one
Liquid crystal cell.
The liquid crystal display element made from the aligning agent for liquid crystal in the present invention is suitble to various types of liquid crystal display elements, can
Be TN type (stable twisted nematic), STN type (super-twisted nematic), VA type (vertical orientating type), 1PS type (in-plane switching) or
FFS type (fringing field switch type).
Specific embodiment
Principles and features of the present invention are described below in conjunction with example, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.
In following specific embodiment, only the aligning agent for liquid crystal is illustrated with the liquid crystal display element of VA type, but
The present invention is not limited thereto.
One, the synthesis example of diamine compound
Embodiment 1:
The synthesis of diamine compound representated by structural formula 1-1 is as shown in synthetic route 1:
Synthetic route 1
Specific operation process are as follows:
(1) synthesis of compound 1-1-a
In the three neck round bottom flask of 1000mL investment to 4- n-heptyl -2- amino aniline (41.27g, 200 mMs),
Triethylamine (24.29,240 mMs) and DMAC solvent 300ml are cooled to 0-10 DEG C and start that p-nitrophenyl first is added dropwise into system
The mixed liquor of acyl chlorides (37.11g, 200 mMs) and 200ml solvent DMAC, are added dropwise for 0.5 hour, are warming up to 60 DEG C of heat preservations
Reaction 10 hours, then reaction solution is poured into ice water, filter out precipitating, be washed with water, and filter cake is from dioxane/water (2:1)
Crystalline mixture obtains faint yellow solid 1-1-a, and product carries out high resolution mass spec test, and M/Z=355.17 is confirmed as mesh
Mark product 1-1-a.
(2) synthesis of compound 1-1-b
Compound 1-1-a (28.44g, 80 mMs), 240 gram 84% are put into the three neck round bottom flask of 1000mL
Polyphosphoric acids is warming up to 180 DEG C of reaction 5h, and 10g phosphorus pentoxide is then added into system and is warming up to 220 DEG C, reaction 5 is small
When, reaction solution is slowly added into 2L water, tan precipitate is filtered out, successively with water, 10% sodium bicarbonate aqueous solution and water
It is adequately washed, obtains yellow solid, crude product is recrystallized to give compound 1-1-b from DMF/ water (1:2).
(3) synthesis of compound 1-1-c
Put into 1L autoclave acquisition compound 1-1-b (13.5g, 40 mMs), 10% palladium carbon (1.3g, Gu
Content is 30%) to seal autoclave with 400g tetrahydrofuran, after hydrogen displacement 3-5 times, pressurized with hydrogen to 0.4-
0.6MPa reacts under stirring in 50-60 DEG C.After reaction, catalyst, filtrate desolventizing is removed by filtration, obtained solid adds
Enter 100g ethyl alcohol and stir 30 minutes, filtered and dried, obtain white solid, product tests high-resolution liquid chromatography mass spectrometric, [M/Z+
=308.21,1] it is confirmed as target product 1-1-c.
(4) synthesis of compound 1-1-d
Investment three is put into the three neck round bottom flask of 1000mL to compound 1- in the three neck round bottom flask of 1000mL
1-c (30.74g, 100 mMs), triethylamine (15.18g, 150 mMs) and DMAC solvent 300ml, are cooled to 0-10 DEG C and open
Begin the mixed liquor that 3,5- dinitrobenzoyl chloride (23.06g, 100 mMs) and 200ml solvent DMAC is added dropwise into system, and 0.5
Hour is added dropwise, and then system is warming up to 60 DEG C of insulation reactions 5 hours, then pours into ice water reaction solution, filters out precipitating,
It is washed with water, filter cake obtains target product 1-1-d faint yellow solid 40.5g, this object from the crystalline mixture of THF/ water (2:1)
Product yield 81%.
(5) synthesis of compound 1-1
Put into 1L autoclave acquisition compound 1-1-d (25.08g, 50 mMs), 10% palladium carbon (2.5g, Gu
Content is 30%) to seal autoclave with 400g tetrahydrofuran, after hydrogen displacement 3-5 times, pressurized with hydrogen to 0.4-
0.6MPa reacts under stirring in 50-60 DEG C.After reaction, catalyst is removed by filtration, filtrate crosses silicagel column, and it is de- to cross column liquid
Solvent, obtained solid are added 100gTHF and 50g ethyl alcohol recrystallization, are filtered and dried, obtain white solid 20.75g, this step is received
Rate is 94%.
The high resolution mass spec of compound 1-1, the source ESI, positive ion mode, theoretical value 441.25, test value 441.31.
Elemental analysis (C27H31N5O), theoretical value C:73.44, H:7.08, N:15.86, O:3.62 measured value C:73.42, H:7.09, N:
15.87,O:3.62。
Embodiment 2~3:
Compound representated by structural formula (1-2)-(1-3) can compound 4- positive heptan corresponding to respective parent respectively
Base -2- hydroxyanilines and 4- n-heptyl -2- sulfydryl base aniline are synthesized according to synthetic route 1, the high score of corresponding compound
Resolution mass spectral results and elemental analysis result see the table below 1.
Mass spectrum, the Elemental analysis data of each compound in 1 embodiment 2~3 of table
Embodiment 4:
The synthetic method of compound representated by structural formula (1-4) and the synthetic method of synthesis example 1 are almost the same, only will
Paranitrobenzoyl chloride replaces with 4- benzyloxy chlorobenzoyl chloride, is protected using benzyloxy to alkyl, then adds hydrogen by urging
Method be deprotected, concrete operation method can be synthesized according to following synthetic route 2:
Synthetic route 2
Specific operation process is as follows:
(1) synthesis of compound 1-4-a
In the three neck round bottom flask of 1000mL investment to 4- n-heptyl -2- amino aniline (41.27g, 200 mMs),
Triethylamine (24.29g, 240 mMs) and DMAC solvent 300ml are cooled to 0-10 DEG C and start that 4- benzyloxy is added dropwise into system
The mixed liquor of chlorobenzoyl chloride (49.34g, 200 mMs) and 200ml solvent DMAC, are added dropwise, are warming up to 60 DEG C for 0.5 hour
Insulation reaction 10 hours, then reaction solution is poured into ice water, filters out precipitating, be washed with water, filter cake from dioxane/water (2:
1) crystalline mixture, obtains faint yellow solid 1-4-a, and product carries out high resolution mass spec test, M/Z=416.27, confirmation
For target product 1-4-a.
(2) synthesis of compound 1-4-b
Compound 1-4-a (33.3g, 80 mMs), 240 gram 84% more are put into the three neck round bottom flask of 1000mL
Polyphosphoric acid is warming up to 180 DEG C of reaction 5h, and 10g phosphorus pentoxide is then added into system and is warming up to 220 DEG C, reacts 5 hours,
Reaction solution is slowly added into 2L water, tan precipitate is filtered out, successively with water, 10% sodium bicarbonate aqueous solution and water carry out
Adequately washing, obtains yellow solid, crude product is recrystallized to give compound 1-4-b from DMF/ water (1:2).
(3) synthesis of compound 1-4-c
Put into 1L autoclave acquisition compound 1-4-b (15.94g, 40 mMs), 10% palladium carbon (1.6g, Gu
Content is 30%) to seal autoclave with 400g tetrahydrofuran, after hydrogen displacement 3-5 times, pressurized with hydrogen to 0.4-
0.6MPa reacts under stirring in 50-60 DEG C.After reaction, catalyst, filtrate desolventizing is removed by filtration, obtained solid adds
Enter 100g ethyl alcohol and stir 30 minutes, filtered and dried, obtain white solid, product carries out high resolution mass spec test, m/z=
308.15 being confirmed as target product 1-4-c.
(4) synthesis of compound 1-4-d
Investment three is put into the three neck round bottom flask of 1000mL to compound 1- in the three neck round bottom flask of 1000mL
4-c (30.84g, 100 mMs), triethylamine (15.18g, 150 mMs) and DMAC solvent 300ml, are cooled to 0-10 DEG C and open
Begin the mixed liquor that 3,5- dinitrobenzoyl chloride (23.06g, 100 mMs) and 200ml solvent DMAC is added dropwise into system, and 0.5
Hour is added dropwise, and then system is warming up to 60 DEG C of insulation reactions 5 hours, then pours into ice water reaction solution, filters out precipitating,
It is washed with water, filter cake obtains target product 1-4-d faint yellow solid 45.73g, this object from the crystalline mixture of THF/ water (2:1)
Product yield 91%.
(5) synthesis of compound 1-4
Put into 1L autoclave acquisition compound 1-4-d (25.12g, 50 mMs), 10% palladium carbon (2.5g, Gu
Content is 30%) to seal autoclave with 400g tetrahydrofuran, after hydrogen displacement 3-5 times, pressurized with hydrogen to 0.4-
0.6MPa reacts under stirring in 50-60 DEG C.After reaction, catalyst is removed by filtration, filtrate crosses silicagel column, and it is de- to cross column liquid
Solvent, obtained solid are added 100gTHF and 50g ethyl alcohol recrystallization, are filtered and dried, obtain white solid 18.8g, this step yield
It is 85%.
The high resolution mass spec of compound 1-4, the source ESI, positive ion mode, theoretical value 442.23, test value 442.21.
Elemental analysis (C27H31N4O2), theoretical value C:73.28, H:6.83, N:12.66, O:7.23 measured value C:73.28, H:6.82, N:
12.67,O:7.23。
Embodiment 5~6:
Compound representated by structural formula (1-5)-(1-6) can compound 4- positive heptan corresponding to respective parent respectively
Base -2- hydroxyanilines and 4- n-heptyl -2- sulfydryl base aniline are synthesized according to synthetic route 2, the high score of corresponding compound
Resolution mass spectral results and elemental analysis result see the table below 2.
Mass spectrum, the Elemental analysis data of each compound in 2 embodiment 5-6 of table
Embodiment 7:
Compound representated by structural formula 1-7 can be synthesized according to following synthetic route 3:
Synthetic route 3
Specific operation process is as follows:
(1) synthesis of compound 1-7-a
Compound 1-4-c (51.40g, 167 mMs), potassium carbonate are put into the three neck round bottom flask of 1000mL
(34.55g, 250 mMs) and toluene solvant 300ml, are warming up to 90 DEG C and start that 2,4-dinitrofluorobenzene is added dropwise into system
The mixed liquor of (37.22g, 200 mMs) and 200ml solvent toluene, are added dropwise for 0.5 hour, temperature 90-100 in holding system
DEG C the reaction was continued 5 hours, and TLC tracks raw material 1-4-c fully reacting, and system is down to room temperature, with the originally washing of 1000ml*2
Wash reaction solution twice, upper organic phase is de- dry by solvent, and the ethyl alcohol that the THF and 150g of 150g is added in obtained solid is tied again
Crystalline substance is filtered, dries to obtain faint yellow solid 64.78g, this reaction yield is 82%.Product carries out high resolution mass spec analysis,
M/z=474.19 is confirmed as target product 1-7-a.
(2) synthesis of compound 1-7
Put into 1L autoclave acquisition compound 1-7-a (47.45g, 100 mMs), 10% palladium carbon (4.7g,
Solid content is 30%) to seal autoclave with 500g tetrahydrofuran, after hydrogen displacement 3-5 times, pressurized with hydrogen to 0.4-
0.6MPa reacts under stirring in 50-60 DEG C.After reaction, catalyst, filtrate desolventizing is removed by filtration, obtained solid adds
Enter 100g ethyl alcohol and stir 30 minutes, is filtered and dried, obtain white solid 38.14g, yield 92%.
The high resolution mass spec of compound 1-7, the source ESI, positive ion mode, theoretical value 414.24, test value 414.18.
Elemental analysis (C26H30N4O), theoretical value C:75.33, H:7.29, N:13.52, O:3.86 measured value C:75.33, H:7.29, N:
13.51,O:3.87。
Embodiment 8-10
Compound representated by structural formula (1-8)-(1-10) can respectively the compound corresponding to respective parent according to
Synthetic route 3 carries out etherificate and catalytic hydrogenation prepares target product, the high resolution mass spec result of corresponding compound and
Elemental analysis result see the table below 3:
Mass spectrum, the Elemental analysis data of each compound in 3 embodiment 8-10 of table
Two, the synthesis example of polymer
Embodiment 1:
The preparation of polymer P AA-1, specific operation process are as follows:
Under nitrogen atmosphere, the diamine compound representated by input structure formula (1-1) in the three neck round bottom flask of 500mL
N- methyl -2- the pyrrolidines of (22.08g, 50mmol), p-phenylenediamine (5.4g, 50mmol) (hereinafter referred to as a-1) and 133.39g
Ketone (hereinafter referred to as NMP), stirring while supplying nitrogen keeps it complete molten, then by 1,2,3, the 4- rings of 19.6g (100mmol)
System is added in the NMP of butane tetracarboxylic acid dianhydride (hereinafter referred to as b-1) and 133.39g.Exothermic heat of reaction is stirred at room temperature 4 hours, thus
Obtain the polyamic acid polymer PAA-1 that solid content is 15%.
Polymer P AA-2~PAA-20 and comparative example polymer P AA-21~PAA-28 can by with polymer P AA-1 phase
Same method preparation, the difference is that: the type and usage ratio of monomer used change, and concrete outcome see the table below 4 Hes
Table 5.
The structural formula and title of the monomer occurred in table 4 and table 5 are described below:
B-1:1,2,3,4- cyclobutane tetracarboxylic dianhydride；
B-2:2,3,5- tricarboxylic base cyclopentaneacetic acid dianhydride；
B-3: pyromellitic acid anhydride；
1-1:
1-5:
1-9:
1-10:
A-1: p-phenylenediamine
A-2:4,4 '-diaminodiphenyl ether
A-3:2,4- diamino octadecane epoxide benzene
A-4:
Table 4 synthesizes monomeric species used in each polymer and dosage
Monomeric species and dosage used in each polymer of 5 comparative example of table
Three, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display element
Embodiment 1:
A, the preparation of aligning agent for liquid crystal
Under nitrogen protection, the polymer (PAA-1) of 100 parts by weight, the NMP of 85 parts by weight are put into three neck round bottom flask
The ethylene glycol monobutyl ether (hereinafter referred to as S-2) of (hereinafter referred to as S-1) and 115 parts by weight, system stir 60 minutes at room temperature, so
The aligning agent for liquid crystal of embodiment 1 is formed with 0.2 μm of the membrane filtration solution afterwards.
B, liquid crystal orientation film and liquid crystal display element
Band ITO electricity of the mode for the aligning agent for liquid crystal spin coating that above embodiments 1 are obtained coated in two panels 3cm × 4cm
On the ito surface of the glass substrate of pole, by precuring (hot plate, 80 DEG C, 10 minutes), it is main solidification (circulation baking oven, 220 DEG C, 60 points
Clock), the polyimide coating of film thickness 100nm will be obtained.By the rubbing device of the rayon cloth of roller diameter 120mm, with roller
Wheel speed 700rpm, substrate travel speed 40mm/sec, intrusion 0.3mm condition to film surface carry out friction orientation processing, obtain
To the substrate comprising liquid crystal orientating membrane.The substrate for preparing 2 pieces of friction orientations, makes film surface in inside, frictional direction is on the contrary, centre
Two pieces of substrates are combined by the spacer particle of clamping 4um, and with sealing glue sticking peripheral part, sylphon is made.It is infused by decompression
Enter method and inject VA type liquid crystal in the sylphon, liquid crystal injecting port is sealed, the parallel VA type liquid crystal display cell of opposite direction has been made.
The liquid crystal display element of embodiment 1 is evaluated, the results are shown in Table 6.
Embodiment 2~20:
The embodiment 2~20 of aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display element can be by same as Example 1
Step preparation.The evaluation that carry out to the liquid crystal display element of embodiment 2~20 and it the results are shown in Table 6.
Comparative example 1 is to embodiment 8:
The comparative example 1~8 of aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display element can by with 1 phase of embodiment
Same step preparation, the difference is that the type and dosage of polymer used and solvent change, is shown in Table 6 in detail.Comparison
The evaluation and the results are shown in Table 6 that the liquid crystal display element of embodiment 1 to comparative example 8 carries out.
Evaluation method:
(1) characterization of liquid crystal pretilt angle
The upper and lower base plate of liquid crystal display element obtained in embodiment and comparative example is being sticked into polarization axis direction just
The polaroid of friendship, then with test device (PAT-20, NORTH LCD ENGINEERING the R&D CENTER based on rotating crystal method
Company's manufacture) test of liquid crystal pretilt angle is carried out to it.
The evaluation result of pre-tilt angle is as follows:
√: the pre-tilt angle of pre-tilt angle >=89.5 °, liquid crystal is high, and it is excellent that alignment agent is anchored performance.
89.5 ° of zero: 88.5 °≤pre-tilt angle <, liquid crystal pretilt angle is general, and it is general that alignment agent is anchored performance.
×: 88.5 ° of pre-tilt angle <, liquid crystal pretilt angular difference, it is poor that alignment agent is anchored performance.
(2) characterization of liquid crystal aligning uniformity
For the VA type liquid crystal display element of the manufacture, application/releasing is observed with 50 times of multiplying power using microscope
The presence or absence of the exceptions area of light and shade variation when 5V voltage.The case where not observing exceptions area, is considered as liquid crystal aligning " good ",
It will be observed that the case where exceptions area, is considered as liquid crystal aligning " bad ".
(3) characterization of liquid crystal display element image retention rate of disappearance
The liquid crystal cells made are set between the orthogonal polaroid of two panels, no-voltage lights back in the case where applying
Light source, with the arrangement angles of the brightness least way adjustment liquid crystal cells of transmitted light.Then frequency is applied to liquid crystal cells side
V-T curve (the equipment: PWW-V-T type V-T test macro, the eastern rising sun of the alternating voltage driving liquid crystal cell side measurement liquid crystal cell of 30Hz
Electric Science and Technology Ltd.'s manufacture), calculate the AC drive voltage that relative permeability is 23%.Then liquid crystal cell side is applied opposite
The alternating voltage that transmitance is 23%, side apply the DC voltage of 1V, and driving after sixty minutes removes DC voltage, are only handed over original
Galvanic electricity pressure driving liquid crystal cell, when calculating needed for since liquid crystal cell be down to 30% or less to relative permeability removing DC voltage
Between Ts.
The image retention husband's rate evaluation result that disappears is as follows:
√: Ts≤20min, image retention disappear fastly, the anti-image retention excellent performance of liquid crystal display element.
×: Ts > 20min, image retention disappear slowly, and the anti-image retention performance of liquid crystal display element is poor.
(4) liquid crystal display element contrast characterizes
To obtained liquid crystal display element, is driven 2 hours with being saturated alternating voltage, driving voltage is then removed, by liquid
Crystal display element pixel electrode and public electrode are shorted 0.5 hour, immediately followed by the contrast (dress of test liquid crystal display element
It sets: PWW-V-T type V-T test macro, the manufacture of Dong Xu electricity Science and Technology Ltd.).
The contrast evaluation of liquid crystal display element is as follows:
√: contrast >=2000, liquid crystal display element contrast are excellent.
Zero: 800≤contrast < 2000, liquid crystal display element contrast are good.
×: contrast < 800, liquid crystal display element poor contrast.
In table 6:
S-1:N- N-methyl-2-2-pyrrolidone N
S-2: ethylene glycol monobutyl ether
The evaluation result of the liquid crystal display element of 6 embodiment of table
It can be seen that compared with prior art, aligning agent for liquid crystal of the invention introduces in the synthesis process contains phenyl benzene
And the diamine monomer of imidazole group, phenylbenzothiazol group or phenyl benzoxazoles group, the phenyl benzo in diamine monomer
Imidazole group, phenylbenzothiazol group or phenyl benzoxazoles group are polycyclic organic groups, are to have stronger rigidity
Side switch group increases alignment films and acts on the anchoring of liquid crystal, and then improves the pre-tilt angle and orientation uniformity of liquid crystal.
In addition phenyl benzimidazole groups group, phenylbenzothiazol group or the phenyl benzene contained in diamine monomer of the invention
And oxazole group is tricyclic conjugated structure, the movement speed of charge can effectively be accelerated by forming the big pi bond of conjugation, reduce charge
Local accumulation, so liquid crystal orientation film of the invention with reduce the electrostatic dust in friction orientation processing procedure inhale symbol and film surface it is quiet
Electric breakdown phenomena broadens process window, improves the yield of product, can be quick just because of above-mentioned tricyclic conjugated structure
The direct current biasing charge at dispersive electrode both ends keeps prepared liquid crystal display element fast because of the image retention caused by direct current charge buildup
Speed disappears, and returns to original state liquid crystal when liquid crystal display element OFF state more thoroughly, thus normally black mode can be improved
The blackness of liquid crystal display element, and then improve the contrast of display panel.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of aligning agent for liquid crystal, which is characterized in that the diamine compound including indicating selected from following formula 1 is gathered with tetracid dianhydride
It closes reaction and obtains polyamic acid and by least one polymer of polyimides obtained from the polyamic acid imidization:
Wherein, X1It is selected from :-O-,One of singly-bound；
Wherein, A1Selected from oxygen atom, sulphur atom andOne of group；
Wherein, R1、R2、R3It is independently selected from H atom, halogen, C1-20Alkyl and its derivative containing substituent group, C2-20's
Alkenyl and derivative, C containing substituent group2-20Alkynes and derivative containing substituent group, containing 1-10 alicyclic ring
Alkyl compound and its derivative containing substituent group, the aryl compound containing 1-10 aromatic ring and its spreading out containing substituent group
One of biology, the compound containing 1-10 heterocycle and its derivative containing substituent group；
Wherein, R1、R2、R3When for non-hydrogen atom substituent group, the link position relative to phenyl ring is limited there is no specific, can use
For the hydrogen atom of any position on phenyl ring.
2. aligning agent for liquid crystal according to claim 1, which is characterized in that the diamine compound have as following formula 1-1~
Structural formula shown in formula 1-10 is any:
3. a kind of aligning agent for liquid crystal according to claim 1, which is characterized in that further include one kind or several selected from following solvent
Kind: n-methyl-2-pyrrolidone, gamma-butyrolacton, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, diglycol monotertiary second
Ether, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol methyl ether, glycol dimethyl ether, diglycol monotertiary
Methyl ether ethyl ester.
4. a kind of aligning agent for liquid crystal according to claim 1, which is characterized in that the tetracarboxylic dianhydride is 1,2,3,4- ring fourths
Alkane tetracarboxylic dianhydride, 1,3- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,2,3,4- pentamethylene tetracarboxylic dianhydride, 2,
3,5- tricarboxylic cyclopentyl acetic acid dianhydride, equal benzene tertacarbonic acid's dianhydride, 1,2,4,5- cyclopentanetetracarboxylic dianhydride, 3,3 ', 4,4 '-connection
The mixture of one or more of benzene tertacarbonic acid's dianhydride, 3,3 ', 4,4 '-biphenyl sulfone tetracarboxylic dianhydrides.
5. a kind of aligning agent for liquid crystal according to claim 1 or claim 2, which is characterized in that further include diamine compound shown in formula 1 with
Outer other diamine compounds: p-phenylenediamine, m-phenylene diamine (MPD), 4,4 '-diaminodiphenylmethane, 4,4 '-diamino diphenylethanes,
Bis- [4- (4- amino-benzene oxygen) phenyl] six of 2,4- diamino dodecane oxygroup benzene, 2,4- diamino octadecane epoxide benzene, 2,2-
Bis- (4- aminophenyl) hexafluoropropane of fluoro-propane, 2,2-, 4- (4- heptyl cyclohexyl) phenyl -3,5- diaminobenzoic acid ester, 2,
2 '-dimethyl -4,4 '-benzidine, 1,5- diaminonaphthalene, 1,8- diaminonaphthalene, p-aminophenyl ethamine, 4,4 '-diamino
Benzamide, 1- (4- (4- pentylcyclohexyl cyclohexyl) phenoxy group) -2,4- diaminobenzene, 1- (4- (4- heptyl cyclohexyl) benzene
Oxygroup) -2,4- diaminobenzene, 3,5- diaminobenzoic acid, 4,4 '-diaminodiphenyl ethers, 1,4- bis- (4- amino-benzene oxygen) benzene,
Bis- (4- amino-benzene oxygen) ethane of 4,4 '-diaminobenzophenones, 1,2-, bis- (4- amino-benzene oxygen) propane of 1,3-, 1,4- are bis-
Bis- (4- amino-benzene oxygen) pentanes of (4- amino-benzene oxygen) butane, 1,5-, 1,6- bis- (4- amino-benzene oxygen) hexanes, N, N '-two
The mixture of one or more of bis- [4- (4- amino-benzene oxygen) phenyl] propane of (4- aminophenyl) piperazine, 2,2-.
6. aligning agent for liquid crystal according to claim 1, which is characterized in that further include in the polyamic acid or polyimides
Molecular weight regulator, the molecular weight regulator refer to mono-acid compound anhydride, monoamine compound or monoisocyanates class
Close object.
7. aligning agent for liquid crystal according to claim 1, which is characterized in that further include additive, the additive is epoxy
One of class compound, silane compound or a variety of mixtures.
8. a kind of liquid crystal orientation film, which is characterized in that be made of the described in any item aligning agent for liquid crystal of claim 1-7.
9. a kind of liquid crystal display element, which is characterized in that including a kind of liquid crystal orientation film according to any one of claims 8.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111117666A (en) * | 2019-12-18 | 2020-05-08 | Tcl华星光电技术有限公司 | Alignment film, preparation method thereof and display panel |
| CN112029512A (en) * | 2019-06-04 | 2020-12-04 | Dic株式会社 | Liquid crystal composition and liquid crystal display element |
| CN112457867A (en) * | 2020-12-15 | 2021-03-09 | 深圳清荷科技有限公司 | Liquid crystal film material, liquid crystal aligning agent, liquid crystal aligning film and preparation method thereof, and liquid crystal display element |
| CN112877079A (en) * | 2020-12-03 | 2021-06-01 | 深圳清荷科技有限公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| TWI774321B (en) * | 2021-04-15 | 2022-08-11 | 李長榮化學工業股份有限公司 | Polyamic acid, polyimide, and element formed therefrom |
| CN114989433A (en) * | 2022-08-08 | 2022-09-02 | 烟台三月科技有限责任公司 | Resin, positive photosensitive resin composition and application |
| CN112029512B (en) * | 2019-06-04 | 2024-04-26 | Dic株式会社 | Liquid crystal composition and liquid crystal display element |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807551A (en) * | 2005-01-19 | 2006-07-26 | Jsr株式会社 | Liquid crystal oriental agent and liquid crystal displaying componnet |
| CN101200822A (en) * | 2007-11-30 | 2008-06-18 | 四川大学 | Polyimide fibre containing benzimidazole structure and preparation method thereof |
| CN101608122A (en) * | 2008-06-17 | 2009-12-23 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display device |
| JP2010054872A (en) * | 2008-08-29 | 2010-03-11 | Chisso Corp | Liquid crystal aligning agent, liquid crystal alignment layer, and liquid crystal display element |
| CN101984157A (en) * | 2010-12-03 | 2011-03-09 | 中国科学院长春应用化学研究所 | Polyimide fiber and preparation method thereof |
| CN102604091A (en) * | 2012-01-13 | 2012-07-25 | 东华大学 | Polyimide containing benzimidazole unit and preparation method thereof |
| CN103571500A (en) * | 2012-07-18 | 2014-02-12 | 奇美实业股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| CN104673328A (en) * | 2013-11-29 | 2015-06-03 | 达兴材料股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| CN105622938A (en) * | 2016-04-06 | 2016-06-01 | 京东方科技集团股份有限公司 | Polyimide, polyimide composition and preparation method thereof, alignment film and display device |
-
2018
- 2018-11-21 CN CN201811390643.6A patent/CN109370614A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807551A (en) * | 2005-01-19 | 2006-07-26 | Jsr株式会社 | Liquid crystal oriental agent and liquid crystal displaying componnet |
| CN101200822A (en) * | 2007-11-30 | 2008-06-18 | 四川大学 | Polyimide fibre containing benzimidazole structure and preparation method thereof |
| CN101608122A (en) * | 2008-06-17 | 2009-12-23 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display device |
| JP2010054872A (en) * | 2008-08-29 | 2010-03-11 | Chisso Corp | Liquid crystal aligning agent, liquid crystal alignment layer, and liquid crystal display element |
| CN101984157A (en) * | 2010-12-03 | 2011-03-09 | 中国科学院长春应用化学研究所 | Polyimide fiber and preparation method thereof |
| CN102604091A (en) * | 2012-01-13 | 2012-07-25 | 东华大学 | Polyimide containing benzimidazole unit and preparation method thereof |
| CN103571500A (en) * | 2012-07-18 | 2014-02-12 | 奇美实业股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| CN104673328A (en) * | 2013-11-29 | 2015-06-03 | 达兴材料股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| CN105622938A (en) * | 2016-04-06 | 2016-06-01 | 京东方科技集团股份有限公司 | Polyimide, polyimide composition and preparation method thereof, alignment film and display device |
Non-Patent Citations (1)
| Title |
|---|
| NOSOVA, GI等: "Synthesis and photoconductive properties of soluble polyimides bearing heterocyclic substituents on polymer main and side chains", 《POLYMER SCIENCE SERIES A》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112029512A (en) * | 2019-06-04 | 2020-12-04 | Dic株式会社 | Liquid crystal composition and liquid crystal display element |
| CN112029512B (en) * | 2019-06-04 | 2024-04-26 | Dic株式会社 | Liquid crystal composition and liquid crystal display element |
| CN111117666A (en) * | 2019-12-18 | 2020-05-08 | Tcl华星光电技术有限公司 | Alignment film, preparation method thereof and display panel |
| CN112877079A (en) * | 2020-12-03 | 2021-06-01 | 深圳清荷科技有限公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| CN112457867A (en) * | 2020-12-15 | 2021-03-09 | 深圳清荷科技有限公司 | Liquid crystal film material, liquid crystal aligning agent, liquid crystal aligning film and preparation method thereof, and liquid crystal display element |
| TWI774321B (en) * | 2021-04-15 | 2022-08-11 | 李長榮化學工業股份有限公司 | Polyamic acid, polyimide, and element formed therefrom |
| CN114989433A (en) * | 2022-08-08 | 2022-09-02 | 烟台三月科技有限责任公司 | Resin, positive photosensitive resin composition and application |
| CN114989433B (en) * | 2022-08-08 | 2022-10-28 | 烟台三月科技有限责任公司 | Resin, positive photosensitive resin composition and application |
| US11886115B1 (en) | 2022-08-08 | 2024-01-30 | Yantai Sunera Llc | Resin, positive photosensitive resin composition and use |
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Application publication date: 20190222 |