CN106190177A - A kind of aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells - Google Patents
A kind of aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells Download PDFInfo
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- CN106190177A CN106190177A CN201610565615.8A CN201610565615A CN106190177A CN 106190177 A CN106190177 A CN 106190177A CN 201610565615 A CN201610565615 A CN 201610565615A CN 106190177 A CN106190177 A CN 106190177A
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- liquid crystal
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- tetracarboxylic dianhydride
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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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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- 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
-
- 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 discloses a kind of aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells, belong to technical field of liquid crystal display.It includes polymer (A) and the solvent (B) obtained by mixture reaction, wherein mixture comprises tetracarboxylic dianhydride's component (a) and diamidogen component (b), and described diamidogen component (b) at least includes the diamine compound (b 1) represented by Formulas I.The invention also discloses the liquid crystal orientation film and liquid crystal display cells prepared by above-mentioned aligning agent for liquid crystal.The aligning agent for liquid crystal of the present invention is polymerized with other tetracarboxylic dianhydride's monomer by the diamine monomer containing amide-type；Owing to the relatively ether of the amide groups in diamine monomer and ester group are more stable, therefore, the liquid crystal orientation film of the present invention has the advantages such as outstanding heat stability, can improve the service life of liquid crystal display.
Description
Technical field
The present invention relates to a kind of aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells, belong to lcd technology
Field.
Background technology
Polyimides is widely used in electron trade as the material that heat stability is the highest, and such as polyimide film can quilt
As liquid crystal orientation film.The usual way of liquid crystal orientation film is at substrate by the polymer-coated containing polyamic acid or polyimides
Surface, is then passed through a hot processing procedure and an orientation processing procedure can be prepared by liquid crystal orientation film.
Improve constantly now with requirement long-life to liquid crystal display, correspondingly the heat stability to liquid crystal orientation film
Require also to become stricter.
The most how providing a kind of liquid crystal orientation film with outstanding heat stability is that pendulum is this field professional technique people
Problem demanding prompt solution in face of Yuan.
Owing to the C-N key bond energy in amide group is eager to excel, therefore than the C-O key in ehter bond and the C-O key in ester group
The liquid crystal orientation film made with the diamine compound containing amide group can improve the service life of liquid crystal display.
Summary of the invention
An object of the present invention, is to provide a kind of aligning agent for liquid crystal.The aligning agent for liquid crystal of the present invention is by containing amide-type
Diamine monomer be polymerized with other tetracarboxylic dianhydride's monomer；Due to the relatively ether of the amide groups in diamine monomer and ester group more
Stable, therefore, the liquid crystal orientation film of the present invention has the advantages such as outstanding heat stability, can improve the use longevity of liquid crystal display
Life.
The technical scheme is that a kind of aligning agent for liquid crystal, including by mixture reaction
The polymer (A) obtained and solvent (B), wherein mixture comprises tetracarboxylic dianhydride's component (a) and a diamidogen component
B (), described diamidogen component (b) at least includes the diamine compound (b-1) represented by Formulas I, and described diamine compound (b-1) has
Following structural formula:
Wherein, X represents
In one,
R1Represent singly-bound, the alkyl of carbon number 1-4 or the alkoxyl of carbon number 1-4,
R2Represent fluorine atom, chlorine atom or bromine atoms,
R3Represent alkyl or the alkoxyl of carbon number 1-8 of carbon number 1-8,
m1Represent the integer of 0-4,
M, n the most independently represent the integer of 0-2.
Compared with prior art, the aligning agent for liquid crystal of the present invention is by the diamine monomer containing amide-type and other tetrabasic carboxylic acid two
Anhydride monomer is polymerized；Owing to the relatively ether of the amide groups in diamine monomer and ester group are more stable, therefore, the liquid crystal of the present invention takes
There is to film the advantages such as outstanding heat stability, the service life of liquid crystal display can be improved.
On the basis of technique scheme, the present invention can also do following improvement.
Further, described polymer (A) is one or both the mixture in polyamic acid, polyimides.
Wherein, the preparation method of above-mentioned polyamic acid, conventional method can be used, comprise the steps: first will comprise four
The mixture of carboxylic acid dianhydride component (a) and diamidogen component (b) is dissolved in solvent, and is polymerized at a temperature of 0-100 DEG C
React 1-24 hour, the most under reduced pressure evaporate solvent and obtain polyamic acid, or reaction system is poured into substantial amounts of bad
In solvent, precipitate is dried to obtain polyamic acid.
Further, described solvent (B) is METHYLPYRROLIDONE, gamma-butyrolacton, N,N-dimethylacetamide, N, N-
Dimethylformamide, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol methyl ether, glycol dinitrate
The mixture of one or more in ether, diethylene glycol monomethyl ether ethyl ester.Wherein, described polymer (A) and the weight of described solvent (B)
Amount ratio is 1:5-80.
Further, described tetracarboxylic dianhydride's component (a) is 1,2,3,4-Tetramethylene. tetracarboxylic dianhydrides, 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 two
The mixture of one or more in acid anhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl sulfone tetracarboxylic dianhydride.
Further, described diamine compound (b-1), the mixture of one or more in Formulas I-1 to I-5:
Use and above-mentioned further provide the benefit that: if aligning agent for liquid crystal does not uses diamine compound (b-1), by liquid crystal
The long-time heat stability used of liquid crystal orientation film prepared by alignment agent can be poor.
Further, described diamidogen component (b) also include diamine compound (b-2), described diamine compound (b-2) be Isosorbide-5-Nitrae-
Diaminobenzene, 1,3-diaminobenzene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 4,4 '-MDA, 4,4 '-diamino
Double [4-(4-amino-benzene oxygen) benzene of yl diphenyl ether, 1,4-bis-(4-amino-benzene oxygen) benzene, 4,4 '-diaminobenzophenone, 2,2-
Base] propane, double [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, 2,2-double 4 (aminophenyl) HFC-236fa, 4-(4-
Heptyl cyclohexyl) phenyl-3,5-diaminobenzoic acid ester, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene
Methanamide, 1-(4-(4-heptyl cyclohexyl) phenoxy group)-2,4-diaminobenzene, 3, one or more in 5-diaminobenzoic acid
Mixture.
Further, the mol ratio of described tetracarboxylic dianhydride's component (a) and described diamidogen component (b) is 100:20-200.
Further, the mol ratio of described tetracarboxylic dianhydride's component (a) and described diamidogen component (b) is 100:80-120.
Further, the mol ratio of described tetracarboxylic dianhydride's component (a) and described diamine compound (b-1) is 100:5-90.
Further, the mol ratio of described tetracarboxylic dianhydride's component (a) and described diamine compound (b-1) is 100:20-
80。
Further, the mol ratio of described tetracarboxylic dianhydride's component (a) and described diamine compound (b-1) is 100:30-
70。
Further, the mol ratio of described diamidogen component (b) and described diamine compound (b-2) is 100:30-90.
Further, the mol ratio of described diamidogen component (b) and described diamine compound (b-2) is 100:40-80.
Further, the mol ratio of described diamidogen component (b) and described diamine compound (b-2) is 100:50-70.
Solvent for polyreaction can be identical or different with the solvent (B) in aligning agent for liquid crystal, and is used for being polymerized instead
The solvent answered is not particularly limited, as long as reactant can be dissolved.Solvent includes but not limited to N-methyl-2-pyrrolidine
Ketone, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, gamma-butyrolacton.Wherein, the rubbing of described mixture and described solvent
That ratio is 1:5-80.
It should be noted that the solvent of polyreaction can be used together appropriate poor solvent, wherein poor solvent will not be made
Polyamic acid is become to separate out.Poor solvent may be used alone or in combination, and includes but not limited to (1) alcohols: methanol, ethanol,
Isopropanol, Hexalin or ethylene glycol；(2) ketone: acetone, butanone, methylisobutylketone or cyclobutanone；(3) esters: acetic acid first
Ester, ethyl acetate or butyl acetate；(4) ethers: ether, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, second
Glycol ethyl methyl ether, glycol dimethyl ether or oxolane；(5) halogenated hydrocarbons: dichloromethane, chlorobenzene or 1,2-dichloroethanes.Wherein,
Described poor solvent accounts for the 0-60% of solvent gross weight.
On the basis of technique scheme, the present invention can also do following improvement.
Further, described poor solvent accounts for the 0-30% of solvent gross weight.
The above-mentioned preparation method preparing polyimides, can use conventional method, comprises the steps: at dehydrant and urges
In the presence of agent, the polyamic acid heating that method described above is obtained.
In the process, the amic acid functional group in polyamic acid can be transformed into imide group by imidization.
The solvent of imidization can be identical with the solvent (B) in aligning agent for liquid crystal, therefore repeats no more.
Wherein, the weight ratio of be set forth in polyamic acid and described imidization solvent is 1:5-30；Described amic acid
Imines rate is 30-100%；The temperature of described imidization is 0-100 DEG C, and the response time is 1-120 hour；Described dehydration
Agent can select an anhydrides compound, such as acetic anhydride, propionic andydride or trifluoro-acetic anhydride；Described polyamic acid and described de-
The mol ratio of water preparation is 1:1-10；Described catalyst is selected from pyridine, trimethylamine or triethylamine；Described dehydrant and described catalysis
The mol ratio of agent is 1:0.1-5.
On the basis of technique scheme, the present invention can also do following improvement.
Further, the imines rate of described amic acid is 55-100%.
Further, the temperature of described imidization is 20-60 DEG C, and the response time is 2-30 hour.
Under effect scope not affecting the present invention, this polyamic acid polymer and this polyimide compound are by dividing
End modified type polymer after son amount regulator regulation.By using the polymer of end modified type, this aligning agent for liquid crystal
Coating performance can increase.This end modified type polymer can be by adding one in the polyreaction prepare polyamic acid
Prepared by molecular weight regulator.This molecular weight regulator is including, but not limited to (1) unitary anhydride, such as maleic anhydride, adjacent benzene
Dicarboxylic acid anhydride or succinic anhydrides；(2) monoamine compound, such as aniline, n-butylamine, n-amylamine, n-hexylamine, positive heptyl amice or the most pungent
Amine；(3) monoisocyanates compounds, such as carbanil or naphthyl isocyanate.Wherein, described polyamic acid and described point
The mol ratio of son amount regulator is 1:0.1.
On the basis of technique scheme, the present invention can also do following improvement.
Further, the mol ratio of described polyamic acid and described molecular weight regulator is 1:0.05.
Under effect scope not affecting the present invention, comprise a kind of additive (C) according to the aligning agent for liquid crystal of the present invention.Should
Additive (C) is a kind of epoxy compounds or a kind of silane compound with functional groups.The work of this additive (C)
With being to improve the adhesive force between liquid crystal orientation film and substrate, this additive (C) individually a kind of use also can mix multiple making
With.
This epoxy compounds including but not limited to ethylene glycol bisthioglycolate glycidyl ethers, Polyethylene Glycol bisglycidyl ethers,
Propylene glycol bisglycidyl ethers, polypropylene glycol bisglycidyl ethers, 1,6-hexylene glycol bisglycidyl ethers, glycerol diepoxy third
Base ether, N, N, N ', N '-four glycidyl-m-xylenedimaine, N, N, N ', N '-four glycidyl-4,4 ' and-diaminourea hexichol
Methane or 3-(N, N-diepoxy propyl group) TSL 8330.Wherein, described polymer (A) and described epoxies
The weight ratio of compound is 100:0.1-15.
On the basis of technique scheme, the present invention can also do following improvement.
Further, the weight ratio of described polymer (A) and described epoxy compounds is 100:1-3.
This has the silane compound of functional groups including but not limited to 3-TSL 8330,3-
Aminopropyltriethoxywerene werene, 2-TSL 8330, APTES, N-(2-amino
Ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl first dimethoxysilane, N-phenyl-
3-TSL 8330 or double (the ethylene oxide)-APTES of N-.Wherein, described polymer
And the weight ratio of the described silane compound with functional groups is 100:0-2 (A).
On the basis of technique scheme, the present invention can also do following improvement.
Further, the weight ratio of described polymer (A) and the described silane compound with functional groups is 100:
0.02-0.2。
This aligning agent for liquid crystal can by by polymer (A) and additive (C) in solvent (B) in 20-100 DEG C under agitation
It is mixed to prepare.
The two of the purpose of the present invention, are to provide a kind of liquid crystal orientation film.
The technical scheme is that a kind of liquid crystal orientation film, by liquid crystal as above
Alignment agent is made.
The liquid crystal orientation film of the present invention, due to the aligning agent for liquid crystal containing the present invention, and in diamine monomer used by alignment agent
Amide groups relatively ether and ester group more stable, therefore, the liquid crystal orientation film of the present invention has the advantages such as outstanding heat stability.
Embodying in an embodiment, utilize the Δ VHR (%)≤5 of liquid crystal display cells prepared by this alignment agent, thermal stability is outstanding.
The preparation method of above-mentioned liquid crystal orientation film, for conventional method, such as roller rubbing method, rotation rubbing method, printing rubbing method,
Ink-jet methods etc., comprise the steps: that aligning agent for liquid crystal is coated in a substrate surface forms precoated shet；Then by this precoated shet
Through preliminary drying process, after bake inorganic agent orientation process to form a kind of alignment films.
Substrate mentioned above is a kind of transparent material with ordinary electrode.This transparent material is including but not limited to sodium
Lime glass, hard glass, alkali-free glass, quartz glass, polyethylene terephthalate, polybutylene terepthatlate, polyethers
Sulfone, Merlon.This ordinary electrode can comprise the transparent conductive material of a kind of picture ITO, IZO or ITZO.
The purpose of this preliminary drying is to remove the most of solvent in precoated shet.The operation temperature that this preliminary drying processes is 30-200
DEG C, preferably 40-150 DEG C, the time that this preliminary drying processes is 1-10 minute, preferably 2-5 minute.
The purpose of this after bake is to improve the imines rate of precoated shet.The operation temperature that this after bake processes is 80-300 DEG C, excellent
Elect 120-250 DEG C as；The time that this after bake processes is 5-200 minute, preferably 5-150 minute；This precoated shet processes through after bake
After thickness be 0.01-1.0 μm, preferably 0.05-0.5 μm.
This orientation process mode is not particularly limited, and can be made with nylon, artificial silk, cotton class or other fibers
Cloth is wrapped on cylinder, and operates in the way of certain orientation friction is orientated.
The three of the purpose of the present invention, are to provide a kind of liquid crystal display cells.
The technical scheme is that a kind of liquid crystal display cells, by liquid as above
Brilliant alignment agent is made.
The liquid crystal display cells of the present invention, due to the aligning agent for liquid crystal containing the present invention, and diamine monomer used by alignment agent
In amide groups relatively ether and ester group more stable, therefore, it is excellent that the liquid crystal orientation film of the present invention has outstanding heat stability etc.
Point, therefore can improve the service life of liquid crystal display.
The preparation method of above-mentioned liquid crystal display cells, comprises the steps: to prepare two plate bases, and every plate base all has one
Layer liquid crystal orientation film, and in the middle of two-layer substrate, it is full of liquid crystal to prepare a liquid crystal cell.
The liquid crystal display cells prepared with the aligning agent for liquid crystal in the present invention is suitable for various liquid crystal display cells, such as distorts
Nematic (TN), super-twist nematic (STN), vertical orientating type (VA), coplanar switch type (IPS) or fringe field switching type
(FFS).In above-mentioned liquid crystal display cells, preferably VA type liquid crystal display cells.
The invention has the beneficial effects as follows:
The most compared with prior art, the aligning agent for liquid crystal of the present invention is by the diamine monomer containing amide-type and other tetrabasic carboxylic acid
Dianhydride monomer is polymerized；Owing to the relatively ether of the amide groups in diamine monomer and ester group are more stable, therefore, the liquid crystal of the present invention
Alignment films has the advantages such as outstanding heat stability, can improve the service life of liquid crystal display.
The most compared with prior art, the liquid crystal orientation film of the present invention has the advantages such as outstanding heat stability.
The most compared with prior art, the service life of the liquid crystal display of the present invention is longer.
4. the inventive method is simple, wide market, is suitable for scale application.
Accompanying drawing explanation
Fig. 1 is the compound b-1-3 in the present invention1H-NMR spectrum.
Detailed description of the invention
Being described principle and the feature of the present invention below in conjunction with concrete accompanying drawing, example is served only for explaining this
Bright, it is not intended to limit the scope of the present invention.
Below in concrete example, only with the liquid crystal display cells of VA type, this aligning agent for liquid crystal is illustrated, but the present invention
It is not limited to this.
(1) synthesis example of compound
The synthesis example of diamine compound (b-1)
Synthesis example 1
Compound representated by structural formula (I-1) can synthesize according to following synthetic route 1:
(1) synthesis of compound (b-1-1a)
4 '-(4-pentylcyclohexyl)-4-Amino-biphenvl (32.2g, 100 millis are put in the three neck round bottom flask of 1000mL
Mole), triethylamine (10.1g, 100 mMs) and 400g oxolane, gained suspension be stirred at room temperature 10 minutes after
To a colourless solution, subsequently this solution is cooled to 0 DEG C, under stirring, will be containing 2-(2,4-dinitrophenyl) chloroacetic chloride
In (24.5g, 100 mMs) and the solution instillation system of 80g oxolane, system heat release, control rate of addition to keep interior
Temperature is less than 20 DEG C.After all solution all add, insulated and stirred 2 hours at 15-20 DEG C.React and examining through gas chromatogram (GC)
After survey completes, stop stirring then sucking filtration, filtrate is poured in 2L water under stirring, gained suspension sucking filtration will be obtained a kind of yellow
Color filter cake, is mixed and stirred for yellow filter cake and 200g ethanol 30 minutes, through sucking filtration and drying, is obtained by the yield with 85%
A kind of solid chemical compound (b-1-1a) of yellow.
(2) synthesis of compound (b-1-1)
Put in 1L autoclave the compound (b-1-1a) (53.0g, 100 mMs) of acquisition, 5% palladium carbon (5.3g,
Aqueous, solid content is 30%) and 400g oxolane, autoclave is sealed, after hydrogen exchange 3-5 time, pressurized with hydrogen is extremely
0.5-1.0MPa, in 40-45 DEG C of reaction under stirring.After reaction terminates, by a thin film, catalyst is removed, then remove molten
Agent, gained solid adds 300g ethanol and stirs 30 minutes, through sucking filtration and drying, will obtain a kind of yellow with the yield of 95%
Solid chemical compound (b-1-1).
This compound (b-1-1)1H-NMR data (500MHz, CHCl3-d1, δ, ppm) are: 0.88 (3H, CH3),
1.25-1.31(8H,4×CH2),1.43(1H,CH),1.52-1.86(8H,4×CH2-Cy),2.72(1H,CH-Cy),5.31
(1H,NH),3.55(2H,CH2),6.27(4H,2×NH2),5.65-6.73(3H,3×CH-Ph),7.36-7.87(8H,8×
CH-Ph)。
Synthesis example 2
Compound representated by structural formula (I-2) can synthesize according to following synthetic route 2:
(1) synthesis of compound (b-1-2a)
In the three neck round bottom flask of 1000mL put into 4-(4-pentylcyclohexyl) aniline (24.5g, 100 mMs), three
Ethamine (10.1g, 100 mMs) and 400g oxolane, gained suspension obtains a nothing after being stirred at room temperature 10 minutes
The solution of color, is cooled to 0 DEG C by this solution subsequently, under stirring, will containing 2-(2,4-dinitrophenyl) chloroacetic chloride (24.5g,
100 mMs) and the solution instillation system of 80g oxolane in, system heat release, control rate of addition with temperature in keeping less than 20
℃.After all solution all add, insulated and stirred 2 hours at 15-20 DEG C.Reaction is detecting through gas chromatogram (GC)
After, stop stirring then sucking filtration, filtrate is poured in 2L water under stirring, gained suspension sucking filtration will be obtained a kind of yellow filter
Cake, is mixed and stirred for yellow filter cake and 200g ethanol 30 minutes, through sucking filtration and drying, the yield with 83% is obtained one
The solid chemical compound (b-1-2a) of yellow.
(2) synthesis of compound (b-1-2)
The compound (b-1-2a) (45.4g, 100 mMs) of acquisition is put in 1L autoclave, the palladium carbon of 5% (4.5g,
Aqueous, solid content is 30%) and 400g oxolane, autoclave is sealed, after hydrogen exchange 3-5 time, pressurized with hydrogen is extremely
0.5-1.0MPa, in 40-45 DEG C of reaction under stirring.After reaction terminates, by a thin film, catalyst is removed, then remove molten
Agent, gained solid adds 300g ethanol and stirs 30 minutes, through sucking filtration and drying, will obtain a kind of yellow with the yield of 90%
Solid chemical compound (b-1-2).
This compound (b-1-2)1H-NMR data (500MHz, CHCl3-d1, δ, ppm) are: 0.88 (3H, CH3),
1.25-1.31(8H,4×CH2),1.43(1H,CH),1.52-1.86(8H,4×CH2-Cy),2.72(1H,CH-Cy),5.31
(1H,NH),3.55(2H,CH2),6.27(4H,2×NH2),5.65-6.73(3H,3×CH-Ph),7.28-7.60(4H,4×
CH-Ph).
Synthesis example 3
Compound representated by structural formula (I-3) can synthesize according to following synthetic route 3:
(1) synthesis of compound (b-1-3a)
Under nitrogen atmosphere, in the three neck round bottom flask of 1000mL, 4-(4-pentylcyclohexyl) phenylboric acid is put into
(27.4g, 100 mMs), the fluoro-aniline of the bromo-2-of 4-(19.1g, 100 mMs), 30% sodium hydrate aqueous solution (26.7g,
200 mMs) and 400g ethanol, gained suspension is stirred at room temperature 10 minutes and will obtain a colourless solution, will catalysis
Agent Pd (OAc)2(0.224g, 1 mM) adds system, system heat release, and Nei Wen can rise to 50-60 DEG C, is then heated to backflow
Insulated and stirred 2 hours.Reaction, after having detected through gas chromatogram (GC), stops stirring then sucking filtration, by filter cake and 200g second
Alcohol mixes and is kept stirring for 30 minutes, through sucking filtration and drying, will obtain the solid chemical compound of a kind of yellow with the yield of 93%
(b-1-3a)。
(2) synthesis of compound (b-1-3b)
Put in the three neck round bottom flask of 1000mL the compound (b-1-3a) (34.0g, 100 mMs) of gained, three
Ethamine (10.1g, 100 mMs) and 400g oxolane, gained suspension obtains a nothing after being stirred at room temperature 10 minutes
The solution of color, is cooled to 0 DEG C by this solution subsequently, under stirring, and will be containing 3.5-dinitrobenzoyl chloride (23.1g, 100 mmoles
You) and the solution instillation system of 80g oxolane in, system heat release, control rate of addition with keep in temperature be less than 20 DEG C.Institute
After having solution all to add, insulated and stirred 2 hours at 15-20 DEG C.Reaction, after having detected through gas chromatogram (GC), stops stirring
Mix then sucking filtration, filtrate is poured in 2L water under stirring, gained suspension sucking filtration will be obtained a kind of yellow filter cake, yellow is filtered
Cake and 200g ethanol are mixed and stirred for 30 minutes, through sucking filtration and drying, will obtain the solid of a kind of yellow with the yield of 80%
Compound (b-1-3b).
(3) synthesis of compound (b-1-3)
Put in 1L autoclave the compound (b-1-3b) (53.4g, 100 mMs) of acquisition, 5% palladium carbon (5.3g,
Aqueous, solid content is 30%), 400g oxolane, by autoclave seal, after hydrogen exchange 3-5 time, pressurized with hydrogen to 0.5-
1.0MPa, in 40-45 DEG C of reaction under stirring.After reaction terminates, by a thin film, catalyst is removed, then desolvation,
Gained solid adds 300g ethanol and stirs 30 minutes, through sucking filtration and drying, will obtain a kind of yellow with the yield of 94%
Solid chemical compound (b-1-3).
As it is shown in figure 1, this compound (b-1-3)1H-NMR data (500MHz, CHCl3-d1, δ, ppm) are: 0.88
(3H,CH3),1.25-1.31(8H,4×CH2),1.43(1H,CH),1.52-1.86(8H,4×CH2-Cy),2.72(1H,CH-
Cy),6.02(1H,CH-Ph),6.27(4H,2×NH2),6.45(2H,2×CH-Ph),7.36-7.37(4H,4×CH-Ph),
7.50(1H,CH-Ph),7.55(1H,CH-Ph),7.85(1H,CH-Ph),9.65(1H,NH)。
(2) synthesis example of polymer (A)
Synthesis example A-1-1
Under nitrogen atmosphere, two amine compounds representated by input structure formula (I-1) in the three neck round bottom flask of 1000mL
Thing (47.0g, 100 mMs) (hereinafter referred to as b-1-1), Isosorbide-5-Nitrae-diaminobenzene (16.2g, 150 mMs) (hereinafter referred to as b-2-
1) and the METHYLPYRROLIDONE (hereinafter referred to as NMP) of 600g, gained suspension is stirred until obtaining the molten of a yellow
Liquid.Then 1,2,3,4-Tetramethylene. tetracarboxylic dianhydride (hereinafter referred to as a-1) and the 100g NMP of 49.0g (250 mMs) are added
Enter system.Exothermic heat of reaction, is stirred at room temperature 4 hours, obtains the polyamic acid polymer (A-1-1) in NMP.
Synthesis example A-1-2 is to comparing synthesis example A-2-1 to A-2-4
Synthesis example A-1-2 can be prepared by the method identical with synthesis example A-1-1 to comparing synthesis example A-2-1 to A-2-4,
Difference is: kind and the consumption of monomer used change, and concrete outcome sees below Tables 1 and 2, repeats no more here.
In Tables 1 and 2:
A-1:1,2,3,4-Tetramethylene. tetracarboxylic dianhydride
A-2:2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride
A-3: pyromellitic acid anhydride
A-4:3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride
B-1-1: the compound represented by formula (I-1)
B-1-2: the compound represented by formula (I-2)
B-1-3: the compound represented by formula (I-3)
B-2-1:1,4-diaminobenzene
B-2-2:4,4 '-diaminodiphenyl methane
B-2-3:4,4 '-benzidine ether
B-2-4:1-(4-(4-heptyl cyclohexyl) phenoxy group)-2,4-diaminobenzene
Monomeric species and consumption used by each polymer of table 1 synthesis example
Table 2 compares monomeric species and consumption used by each polymer of synthesis example
(3) embodiment of aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells and comparative example
Embodiment 1
A, aligning agent for liquid crystal
Nitrogen atmosphere, puts into the polymer (A-1-1) of 100 weight portions, the NMP of 900 weight portions in three neck round bottom flask
The ethylene glycol monobutyl ether (hereinafter referred to as B-2) of (hereinafter referred to as B-1) and 800 weight portions, system stirs 30 minutes at room temperature, so
The aligning agent for liquid crystal of embodiment 1 is formed afterwards with this solution of membrane filtration of 0.3 μm.
B, liquid crystal orientation film and liquid crystal display cells
By the mode of spin coating, above-mentioned aligning agent for liquid crystal is coated in two panels and is respectively provided with on the glass substrate of ITO electrode formation
Precoated shet. two liquid crystal will be obtained through preliminary drying (hot plate, 100 DEG C, 5 minutes) and after bake (circulation baking oven, 220 DEG C, 30 minutes)
Alignment films, by rubbed for the two liquid crystal orientation film process (roller diameter 150mm, rotary speed: 500rpm, translational speed:
20mm/s, intrusion: 0.5mm).
After rubbed process, a kind of ultra-violet curing glue is coated on the periphery that this two panels glass substrate is the most a piece of, by 3.5
The introns of μm are sprinkled upon on another plate base.Then this two panels glass substrate is fitted (5kg, 30mIn), then shine with uviol lamp
Penetrate and solidify ultra-violet curing glue.Then liquid crystal injected and use hot plate (60 DEG C, 30mIn) maturation, the liquid of embodiment 1 can be obtained
Crystal display element.
The liquid crystal display cells of embodiment 1 is evaluated, the results are shown in Table 3.
Embodiment 2 to embodiment 20
Embodiment 2 to the embodiment 20 of aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells can by with embodiment 1
Prepared by identical step, difference is: polymer used (A), solvent (B) and the kind of additive (C) and consumption are
Change, be shown in Table 3.The liquid crystal display cells of embodiment 2 to embodiment 20 is evaluated and the results are shown in Table 3.
Comparing embodiment 1 to comparing embodiment 6
Comparing embodiment 1 to the comparing embodiment 6 of aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells can by with
Prepared by the step that embodiment 1 is identical, difference is: polymer used (A), solvent (B) and the kind of additive (C) and use
Amount changes, and is shown in Table 4.The liquid crystal display cells of comparing embodiment 1 to comparing embodiment 6 is evaluated and the results are shown in Table 4.
Evaluation methodology
A, heat stability
The heat stability of liquid crystal orientation film can be able to be evaluated (hereinafter referred to as by the voltage retention of liquid crystal display cells
VHR), furthermore, the detection method of voltage retention is as follows.
The condition of test VHR is: apply 5V voltage, after lasting 60ms, releases voltage, and measures from releasing voltage
VHR after 167ms (is designated as VHR1).Then this liquid crystal display cells is placed in 500h in baking oven (60 DEG C), is subsequently cooled to room
Temperature, then (it is designated as VHR with identical method measurement VHR now2).Then the changing value calculating VHR by public formula V (is designated as
Δ VHR (%)), the lowest Δ VHR (%) means the best heat stability.
Formula V
The evaluation criterion of Δ VHR (%) is as follows:
◎: Δ VHR (%)≤5%, heat stability is outstanding,
Zero: 5% ＜ Δ VHR (%)≤20%, good thermal stability,
Ⅹ: Δ VHR (%) ＞ 20%, poor heat stability.
B, vertical orientated property
During by no-voltage under polarizing microscope and additional alternating voltage 6V (peak to peak), observe liquid crystal from vertical direction
Display element.
Evaluation criterion is as follows:
Zero: there is no light leak,
Ⅹ: bad white displays occurs.
In table 3 and table 4:
B-1:N-N-methyl-2-2-pyrrolidone N,
B-2: ethylene glycol monobutyl ether,
C-1:N, N, N ', N '-four glycidyl-4,4 '-MDA,
C-2:3-aminopropyltriethoxywerene werene.
The evaluation result of the liquid crystal display cells of table 3 embodiment
The evaluation result of the liquid crystal display cells of table 4 comparing embodiment
As can be seen here, compared with prior art, the aligning agent for liquid crystal of the present invention by the diamine monomer containing amide-type and its
Its tetracarboxylic dianhydride's monomer is polymerized；Owing to the relatively ether of the amide groups in diamine monomer and ester group are more stable, therefore, this
Bright liquid crystal orientation film has the advantages such as outstanding heat stability, can improve the service life of liquid crystal display.And method is simple
Single, wide market, it is suitable for scale application.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (10)
1. an aligning agent for liquid crystal, it is characterised in that include polymer (A) and the solvent (B) obtained by mixture reaction, wherein
Mixture comprises tetracarboxylic dianhydride's component (a) and diamidogen component (b), and described diamidogen component (b) at least includes by Formulas I
The diamine compound (b-1) represented, described diamine compound (b-1) has a following structural formula:
Wherein, X represents
In one,
R1Represent singly-bound, the alkyl of carbon number 1-4 or the alkoxyl of carbon number 1-4,
R2Represent fluorine atom, chlorine atom or bromine atoms,
R3Represent alkyl or the alkoxyl of carbon number 1-8 of carbon number 1-8,
m1Represent the integer of 0-4,
M, n the most independently represent the integer of 0-2.
A kind of aligning agent for liquid crystal the most according to claim 1, it is characterised in that described polymer (A) is polyamic acid, gathers
One or both mixture in acid imide.
A kind of aligning agent for liquid crystal the most according to claim 1, it is characterised in that described solvent (B) is N-methyl-2-pyrroles
Alkanone, gamma-butyrolacton, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, glycol monoethyl ether, ethylene glycol monoethyl ether, second
The mixture of one or more in glycol monobutyl ether, ethylene glycol methyl ether, glycol dimethyl ether, diethylene glycol monomethyl ether ethyl ester.
A kind of aligning agent for liquid crystal the most according to claim 1, it is characterised in that described tetracarboxylic dianhydride's component (a) is 1,
2,3,4-Tetramethylene. tetracarboxylic dianhydride, 1,2,3,4-Pentamethylene. tetracarboxylic dianhydride, 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride, all
Benzene tertacarbonic acid's dianhydride, 1,2,4,5-cyclopentanetetracarboxylic's dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl
The mixture of one or more in sulfone tetracarboxylic dianhydride.
A kind of aligning agent for liquid crystal the most according to claim 1, it is characterised in that described diamidogen component (b) also includes diamidogen
Compound (b-2), described diamine compound (b-2) be Isosorbide-5-Nitrae-diaminobenzene, 1,3-diaminobenzene, 1,5-diaminonaphthalene, 1,8-
Diaminonaphthalene, 4,4 '-MDA, 4,4 '-diaminodiphenyl ether, 1,4-bis-(4-amino-benzene oxygen) benzene, 4,4 '-two
Double [4-(4-amino-benzene oxygen) phenyl] propane of aminobenzophenone, 2,2-, double [4-(4-amino-benzene oxygen) phenyl] six of 2,2-
Double 4 (aminophenyl) HFC-236fa of fluoro-propane, 2,2-, 4-(4-heptyl cyclohexyl) phenyl-3,5-diaminobenzoic acid ester, 2,
2 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene Methanamide, 1-(4-(4-heptyl cyclohexyl) phenoxy group)-2,4-
The mixture of one or more in diaminobenzene, 3,5-diaminobenzoic acid.
A kind of aligning agent for liquid crystal the most according to claim 1, it is characterised in that described tetracarboxylic dianhydride's component (a) and institute
The mol ratio stating diamidogen component (b) is 100:20-200.
A kind of aligning agent for liquid crystal the most according to claim 6, it is characterised in that described tetracarboxylic dianhydride's component (a) and institute
The mol ratio stating diamidogen component (b) is 100:80-120.
A kind of aligning agent for liquid crystal the most according to claim 1, it is characterised in that described tetracarboxylic dianhydride's component (a) and institute
The mol ratio stating diamine compound (b-1) is 100:5-90.
9. a liquid crystal orientation film, it is characterised in that be made up of the aligning agent for liquid crystal described in any one of claim 1-7.
10. a liquid crystal display cells, it is characterised in that be made up of the aligning agent for liquid crystal described in any one of claim 1-7.
Priority Applications (2)
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| PCT/CN2016/090864 WO2018010203A1 (en) | 2016-07-14 | 2016-07-21 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| TW105129723A TW201802142A (en) | 2016-07-14 | 2016-09-13 | A liquid crystal alignment film and a liquid crystal display element having the liquid crystal alignment film |
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| CN2016105553715 | 2016-07-14 | ||
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106905985A (en) * | 2017-03-29 | 2017-06-30 | 中节能万润股份有限公司 | A kind of aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells |
| CN107163952A (en) * | 2017-06-02 | 2017-09-15 | 合肥市惠科精密模具有限公司 | A kind of aligning agent for liquid crystal |
| WO2018010203A1 (en) * | 2016-07-14 | 2018-01-18 | 中节能万润股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| CN108070388A (en) * | 2017-12-05 | 2018-05-25 | 中节能万润股份有限公司 | A kind of aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display element |
| CN111077700A (en) * | 2019-12-20 | 2020-04-28 | 江苏三月光电科技有限公司 | Method for manufacturing liquid crystal display element |
| CN111592891A (en) * | 2020-06-12 | 2020-08-28 | 江苏三月科技股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment film prepared from same and liquid crystal display element |
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| CN103374354A (en) * | 2012-04-24 | 2013-10-30 | 奇美实业股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| 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 |
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| JP2857779B2 (en) * | 1988-12-19 | 1999-02-17 | セイコーエプソン株式会社 | Composition for liquid crystal alignment film and liquid crystal device |
| JPH03121132A (en) * | 1989-03-07 | 1991-05-23 | Japan Carlit Co Ltd:The | New polyimide |
| JPH04335615A (en) * | 1991-05-13 | 1992-11-24 | Fuji Photo Film Co Ltd | Liquid crystal display element |
| JP5771948B2 (en) * | 2010-10-28 | 2015-09-02 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element |
| CN106190177A (en) * | 2016-07-14 | 2016-12-07 | 中节能万润股份有限公司 | A kind of aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells |
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2016
- 2016-07-18 CN CN201610565615.8A patent/CN106190177A/en active Pending
- 2016-07-21 WO PCT/CN2016/090864 patent/WO2018010203A1/en active Application Filing
- 2016-09-13 TW TW105129723A patent/TW201802142A/en unknown
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|---|---|---|---|---|
| CN103374354A (en) * | 2012-04-24 | 2013-10-30 | 奇美实业股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| 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 |
| CN105087018A (en) * | 2014-07-21 | 2015-11-25 | 烟台德盈电子材料有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018010203A1 (en) * | 2016-07-14 | 2018-01-18 | 中节能万润股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| CN106905985A (en) * | 2017-03-29 | 2017-06-30 | 中节能万润股份有限公司 | A kind of aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells |
| CN106905985B (en) * | 2017-03-29 | 2019-03-26 | 中节能万润股份有限公司 | A kind of aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display element |
| CN107163952A (en) * | 2017-06-02 | 2017-09-15 | 合肥市惠科精密模具有限公司 | A kind of aligning agent for liquid crystal |
| CN108070388A (en) * | 2017-12-05 | 2018-05-25 | 中节能万润股份有限公司 | A kind of aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display element |
| CN108070388B (en) * | 2017-12-05 | 2021-04-23 | 中节能万润股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| CN111077700A (en) * | 2019-12-20 | 2020-04-28 | 江苏三月光电科技有限公司 | Method for manufacturing liquid crystal display element |
| CN111592891A (en) * | 2020-06-12 | 2020-08-28 | 江苏三月科技股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment film prepared from same and liquid crystal display element |
| CN111592891B (en) * | 2020-06-12 | 2022-03-01 | 江苏三月科技股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment film prepared from same and liquid crystal display element |
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| WO2018010203A1 (en) | 2018-01-18 |
| TW201802142A (en) | 2018-01-16 |
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