CN106318407A - Liquid crystal alignment agent, liquid crystal alignment film, preparation method of liquid crystal alignment film and liquid crystal display element - Google Patents
Liquid crystal alignment agent, liquid crystal alignment film, preparation method of liquid crystal alignment film and liquid crystal display element Download PDFInfo
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- CN106318407A CN106318407A CN201610682416.5A CN201610682416A CN106318407A CN 106318407 A CN106318407 A CN 106318407A CN 201610682416 A CN201610682416 A CN 201610682416A CN 106318407 A CN106318407 A CN 106318407A
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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
-
- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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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
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
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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
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
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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
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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
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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
- G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
- G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
Abstract
The invention discloses a liquid crystal alignment agent, a liquid crystal alignment film, a preparation method of the liquid crystal alignment film and a liquid crystal display element, and belongs to the technical field of liquid crystal display. The liquid crystal alignment agent is prepared from a polymer A obtained through a reaction of a mixture, and a solvent B, wherein the mixture contains a tetracarboxylic acid dianhydride component a and a diamine component b, and the diamine component b at least comprises a diamine compound b-1 shown in the formula I. The invention further provides the liquid crystal alignment film prepared from the liquid crystal alignment agent, the preparation method of the liquid crystal alignment agent and the liquid crystal display element. The liquid crystal alignment agent is formed by polymerizing diamine monomers containing tert-butylphenol fragments and other tetracarboxylic acid dianhydride monomers. When applied to a photo-alignment exposure process, the liquid crystal alignment film can enlarge a working window and has the dual advantages that exposure in an exposure zone is thorough and a non-exposure zone has excellent ultraviolet resistance; thus, the display effect of a liquid crystal displayer can be improved, and the service life of the liquid crystal displayer can be prolonged.
Description
Technical field
The present invention relates to a kind of aligning agent for liquid crystal, liquid crystal orientation film and preparation method thereof and liquid crystal display cells, belong to
Technical field of liquid crystal display.
Background technology
Liquid crystal display is dependent on controlling the ordered state of liquid crystal molecule and realizes display, meeting in usual liquid crystal display cells
Liquid crystal orientation film is set to control the initial alignment state of liquid crystal molecule.As liquid crystal orientation film, mainly by the property such as high temperature resistant
Exsertile polyimide material, current industrial most popular method for alignment, is to use the fibrages such as cotton, nylon, polyester
The cloth become, carries out friction orientation in one direction.But friction orientation is easily generated dust, chip, easily takes liquid crystal simultaneously
Scar is produced to film, along with the requirement that display image quality and advanced lines are produced line yields is more and more higher, friction-type orientation skill
Art can not meet requirements above the most gradually, and the most also at the orientation technology that exploitation is new, wherein the development of light orientation technology is
For rapidly.
So-called light orientation technology, it is simply that use up and irradiate a kind of skill replacing the mode of tradition cloth friction to realize orientation
Art.During implementing this technology, the light generally using deep ultraviolet goes to irradiate, and general polyimides is organic as one
Thing, being irradiated by the light of deep ultraviolet can be by certain infringement, if controlling bad light exposure, can cause producing non-exposed areas not
Good impact, affects display effect, and therefore the exposure manufacture process process window of light orientation technology is narrower at present.It addition, liquid crystal display
Inevitably being radiated by ultraviolet light during work, as core material, the ultra-violet resistance of liquid crystal orientation film also determines liquid
The reliability of LCD and life-span.
Therefore, develop the polyimide material with outstanding ultra-violet resistance energy, to improving light orientation exposure manufacture process work
Make window, raising liquid crystal display reliability and life-span most important.
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 tert-butyl benzene
The diamine monomer of phenol fragment is polymerized with other tetracarboxylic dianhydride's monomer；Owing to diamine monomer containing tert-butyl phenol sheet
Section, the material ultra-violet resistance after polymerization can be more prominent, and therefore, the liquid crystal orientation film of the present invention is orientated at the light carrying out the present invention
During exposure manufacture process, it is possible to increase its operation window, have the exposure of exposure area thoroughly, non-exposed areas there is outstanding resistance to ultraviolet
The two-fold advantage of performance, it is thus possible to improve display effect and the service life of liquid crystal display.
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 an a tetracarboxylic dianhydride component a and diamidogen component b, and described two
Amine component b at least includes that the diamine compound b-1 represented by Formulas I, described diamine compound b-1 have a following structural formula:
Wherein, X represents
Singly-bound,In one.
Compared with prior art, the aligning agent for liquid crystal of the present invention by the diamine monomer containing tert-butyl phenol fragment with other four
Carboxylic acid dianhydride monomer is polymerized；Owing to diamine monomer containing tert-butyl phenol fragment, the material ultra-violet resistance energy after polymerization
More prominent.Therefore, the liquid crystal orientation film of the present invention is when the exposure manufacture process that the light carrying out the present invention is orientated, it is possible to increase its working window
Mouthful, have the two-fold advantage that exposure is thorough, non-exposed areas has outstanding ultra-violet resistance energy of exposure area, it is thus possible to improve
The display effect of liquid crystal display and service life.On the basis of technique scheme, the present invention can also do following improvement.
Further, one or both the mixture during described polymer A is 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 carries out polyreaction at a temperature of 0-100 DEG C
1-24 hour, obtain polyamic acid solution, it is also possible under reduced pressure evaporate solvent and obtain polyamic acid solid, or by reactant
System pours in substantial amounts of poor solvent, and precipitate is dried to obtain polyamic acid solid.
Further, described solvent B is METHYLPYRROLIDONE, 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,
The mixture of one or more in diethylene glycol monomethyl ether ethyl ester.Wherein, the weight ratio of described polymer A and described solvent B is
1:5-80。
Further, described tetracarboxylic dianhydride component a is 1,2,3,4-Tetramethylene. tetracarboxylic dianhydrides, 1,2,3,4-Pentamethylene. four
Carboxylic acid dianhydride, 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride, equal benzene tertacarbonic acid's dianhydride, 1,2,4,5-cyclopentanetetracarboxylic's dianhydride,
The mixture of one or more in 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl sulfone tetracarboxylic dianhydride.
Further, described diamine compound b-1, Formulas I-1 can be exemplified as to the mixture of one or more in I-4.
Use and above-mentioned further provide the benefit that: if aligning agent for liquid crystal does not uses diamine compound b-1, liquid crystal take
The ultra-violet resistance of the liquid crystal orientation film prepared to agent can be poor, affects the liquid crystal display life-span, if being used in light orientation process, then
Exposure manufacture process operation window is narrow.
Further, described diamidogen component b also include diamine compound b-2, described diamine compound b-2 be p-phenylenediamine,
M-diaminobenzene., 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, p-aminophenyl ethamine, 4,4 '-MDA, 4,4 '-diamino
Base diphenylethane, 4,4 '-diaminodiphenyl ether, 1,4-bis-(4-amino-benzene oxygen) benzene, 4,4 '-diaminobenzophenone, 1,2-
Double (4-amino-benzene oxygen) propane of double (4-amino-benzene oxygen) ethane, 1,3-, double (4-amino-benzene oxygen) butane of 1,4-, 1,5-are double
Double (4-amino-benzene oxygen) hexane of (4-amino-benzene oxygen) pentane, 1,6-, N, N '-two (4-aminophenyl) piperazine, the double [4-of 2,2-
(4-amino-benzene oxygen) phenyl] propane, 2,4-diamino dodecane epoxide benzene, 2,4-diaminourea octadecane epoxide benzene, 2,2-be double
[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-double (4-aminophenyl) HFC-236fa, 4-(4-heptyl cyclohexyl) benzene
Base-3,5-diaminobenzoic acid ester, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene Methanamide, 1-(4-
(4-pentylcyclohexyl cyclohexyl) phenoxy group)-2,4-diaminobenzene, 1-(4-(4-heptyl cyclohexyl) phenoxy group)-2,4-diamino
The mixture of one or more in base benzene, 3,5-diaminobenzoic acid.
Further, the mol ratio of described tetracarboxylic dianhydride component a and described diamidogen component b is 100:20-200.
Further, the mol ratio of described tetracarboxylic dianhydride component a and described diamidogen component b is 100:80-120.
Further, the mol ratio of described tetracarboxylic dianhydride component a and described diamine compound b-1 is 100:0.001-10.
Further, the mol ratio of described tetracarboxylic dianhydride component a and described diamine compound b-1 is 100:0.05-3.
Solvent for polyreaction can be identical or different with the solvent B in aligning agent for liquid crystal, and for polyreaction
Solvent be not particularly limited, as long as reactant can be dissolved.Solvent include but not limited to METHYLPYRROLIDONE,
DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, gamma-butyrolacton.Wherein, described mixture and the mol ratio of described solvent
For 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 addition of C according to the aligning agent for liquid crystal of the present invention.This adds
Adding agent C is a kind of epoxy compounds or a kind of silane compound with functional groups.The effect of this addition of C is to carry
Adhesive force between high liquid crystal orientation film and substrate, this addition of C individually a kind of use also can mix multiple use.
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 chemical combination
The weight ratio of thing 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
The weight ratio of A and the described silane compound with functional groups is 100:0-2.
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 be by under agitation mixing system in 20-100 DEG C by polymer A and addition of C in solvent B
?.
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
Containing tert-butyl phenol fragment, the material ultra-violet resistance after polymerization can be more prominent, and therefore, the liquid crystal orientation film of the present invention is being carried out
During the exposure manufacture process of the light orientation of the present invention, it is possible to increase its operation window, have the exposure of exposure area thoroughly and non-exposed area
Territory has the two-fold advantage of outstanding ultra-violet resistance energy, it is thus possible to improve display effect and the service life of liquid crystal display.Body
In presently implemented example, utilizing the Δ VHR (%)≤5% of liquid crystal display cells prepared by this alignment agent, ultra-violet resistance can be outstanding.
The three of the purpose of the present invention, are to provide the light orientation preparation method of above-mentioned liquid crystal orientation film.The liquid crystal of the present invention takes
To the light orientation side preparation method of film, just it is exposed owing to terminating the most non-after bake in front baking, it is possible to ensure liquid crystal orientation film
Exposition uniformity, improves the liquid crystal orientation film anchorage force to liquid crystal, simultaneously as the ultra-violet resistance of aligning agent for liquid crystal itself, it is possible to
Ensure to occur without the situation of overexposure.
The technical scheme is that the light orientation preparation method of a kind of liquid crystal orientation film,
Comprise the steps:
(1) use aligning agent for liquid crystal as above, substrate is formed precoated shet；
(2) step (1) gained precoated shet is carried out front baking, single exposure, after bake, re-expose, i.e. form described liquid crystal
Alignment films；
Or step (1) gained precoated shet is carried out front baking, single exposure, re-expose, after bake, i.e. form described liquid crystal and take
To film；
Or step (1) gained precoated shet is carried out front baking, high intensity exposure, an after bake, i.e. form described liquid crystal aligning
Film.
The light orientation side preparation method of the liquid crystal orientation film of the present invention, just exposes owing to terminating the most non-after bake in front baking
Light, it is possible to ensure the exposition uniformity of liquid crystal orientation film, improves the liquid crystal orientation film anchorage force to liquid crystal, simultaneously as liquid crystal takes
Ultra-violet resistance to agent itself, it is possible to ensure to occur without the situation of overexposure.
On the basis of technique scheme, the present invention can also do following improvement.
Further, described in step (2), the temperature of front baking is 50-120 DEG C, and the time is 2-7mins.
Further, single exposure described in step (2), the light of re-expose are polarized light, and wavelength is different, is selected from
Single 254nm, or single 313nm, or dual wavelength 254nm, 313nm, exposure light intensity is 1-10mW/cm2, the accumulative light quantity of exposure is
10-1000mj/cm2。
Further, described in step (2), the temperature range of after bake is 180-250 DEG C, and time range is 30-90mins.
Further, described in step (2), the light of a high intensity exposure is polarized light, is selected from single 254nm, or single
313nm, or dual wavelength 254nm, 313nm, the accumulative light quantity of exposure is 20-2000mj/cm2。
Substrate described in above-mentioned steps (1) is a kind of transparent material with ordinary electrode.This transparent material comprise but not
It is confined to soda-lime glass, hard glass, alkali-free glass, quartz glass, polyethylene terephthalate, polybutene p-phthalic acid
Ester, polyether sulfone, Merlon.This ordinary electrode can comprise the transparent conductive material of a kind of picture ITO, IZO or ITZO.
The purpose of front baking described in above-mentioned steps (2) is to remove the most of solvent in precoated shet.The behaviour that this front baking processes
Being 30-200 DEG C as temperature, preferably 50-120 DEG C, the time that this front baking processes is 1-10 minute, preferably 2-7 minute.
The purpose of after bake described in above-mentioned steps (2) is to improve the imines rate of precoated shet.The operation temperature that this after bake processes
Degree is 80-300 DEG C, preferably 180-250 DEG C；The time that this after bake processes is 5-200 minute, preferably 30-90 minute；This is pre-
Coating thickness after after bake processes is 0.01-0.5 μm, preferably 0.05-0.2 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 four 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 containing tert-butyl phenol fragment, the material ultra-violet resistance after polymerization can be more prominent, and therefore, the liquid crystal orientation film of the present invention is entering
During the exposure manufacture process that the light of the row present invention is orientated, it is possible to increase its operation window, the service life of liquid crystal display can be improved simultaneously.
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 IPS 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 by the diamine monomer containing tert-butyl phenol fragment and its
Its tetracarboxylic dianhydride's monomer is polymerized；Material ultra-violet resistance owing to diamine monomer contains tert-butyl phenol fragment, after polymerization
Can be more prominent, therefore, the liquid crystal orientation film of the present invention is when the exposure manufacture process that the light carrying out the present invention is orientated, it is possible to increase its work
Window, has the two-fold advantage that exposure is thorough, non-exposed areas has outstanding ultra-violet resistance energy of exposure area, it is thus possible to carry
The display effect of high liquid crystal display and service life.
The most compared with prior art, the liquid crystal orientation film of the present invention have the exposure of exposure area thoroughly, non-exposed areas
There is the two-fold advantage of outstanding ultra-violet resistance energy.
3. the light orientation side preparation method of the liquid crystal orientation film of the present invention, just exposes owing to terminating the most non-after bake in front baking
Light, it is possible to ensure the exposition uniformity of liquid crystal orientation film, improves the liquid crystal orientation film anchorage force to liquid crystal, simultaneously as liquid crystal takes
Ultra-violet resistance to agent itself, it is possible to ensure to occur without the situation of overexposure.
The most compared with prior art, the display effect of the liquid crystal display of the present invention more preferably, service life longer.
5. 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 IPS 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
2,4-DNP (110.5g, 600 mMs), Carbon Dioxide is put in the three neck round bottom flask of 1000mL
Potassium (82.9g, 600 mMs) and 400g DMF, gained redness suspension is stirred at room temperature 10 minutes,
Subsequently this solution is warming up to 60 DEG C, under stirring, will containing 2,6-di-t-butyl-4-bromophenol (171.1g, 600 mMs) and
In the solution instillation system of 300g DMF, system heat release.After all solution all add, at 60-65 DEG C
Insulated and stirred 2 hours.Reaction, after having detected through gas chromatogram (GC), stops stirring then sucking filtration.Gained black filtrate is used
Dilute hydrochloric acid is acidified to acidity, adds 3L water subsequently, and system separates out solid, and gained suspension sucking filtration will obtain a kind of yellow filter
Cake, is mixed and stirred for yellow filter cake and 200g ethanol/water 30 minutes, through sucking filtration and drying, is obtained by the yield with 65%
The solid chemical compound (b-1-1a) of a kind of yellow, tests GC-MS, m/z=460 after silication.
(2) synthesis of compound b-1-1
Put into the compound b-1-1a (38.8g, 100 mMs) of acquisition in 1L autoclave, (3.9g contains the palladium carbon of 5%
Water, solid content is 30%) and 400g oxolane, autoclave is sealed, 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 100g 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's1H-NMR data (500MHz, CHCl3-d1, δ, ppm) are: 1.33 (18H, 6 × CH3),
5.38(1H,OH),5.75(1H,CH-Ph),6.12(1H,CH-Ph),6.33(4H,2×NH2),6.75(1H,CH-Ph),7.13
(2H,2×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
2 are put into, 6-di-tert-butyl hydroquinone (44.4g, 200 mMs), three in the three neck round bottom flask of 1000mL
Ethamine (20.2g, 200 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 be containing 3, and 5-dinitrobenzoyl chloride (46.1g, 200 mmoles
You) and the solution instillation system of 100g oxolane in, system heat release, control rate of addition with keep in temperature be less than 20 DEG C.?
After all solution all add, insulated and stirred 2 hours at 15-20 DEG C.Reaction, after having detected through gas chromatogram (GC), stops
Stir then sucking filtration, filtrate is poured in 2L water under stirring, gained suspension sucking filtration will be obtained a kind of yellow filter cake, by yellow
Filter cake and 120g ethanol/water are mixed and stirred for 30 minutes, through sucking filtration and drying, will obtain a kind of yellow with the yield of 80%
Solid chemical compound b-1-2a.
(2) synthesis of compound (b-1-2)
Putting into the compound b-1-2a (41.6g, 100 mMs) of acquisition in 1L autoclave, (4.2g contains the palladium carbon of 5%
Water, solid content is 30%) and 400g oxolane, autoclave is sealed, 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 93%
Solid chemical compound b-1-2.
This compound b-1-2's1H-NMR data (500MHz, CHCl3-d1, δ, ppm) are: 1.36 (18H, 6 × CH3),
5.42(1H,OH),6.08(1H,CH-Ph),6.33(4H,2×NH2),6.66(2H,2×CH-Ph),7.28(2H,2×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, input 2 in the three neck round bottom flask of 1000mL, 5-di-tert-butyl hydroquinone (133.4g,
600 mMs), Anhydrous potassium carbonate (82.9g, 600 mMs) and 400g DMF, gained redness suspension
Be stirred at room temperature 10 minutes, subsequently this solution be warming up to 60 DEG C, under stirring, will containing DNFB (121.5g,
600 mMs) and the solution instillation system of 300g DMF in, system heat release.All add at all solution
After, insulated and stirred 2 hours at 60-65 DEG C.Reaction, after having detected through gas chromatogram (GC), stops stirring then sucking filtration
Except inorganic salt and by-product.Gained black filtrate is acidified to acidity with dilute hydrochloric acid, adds 3L water subsequently, and it is solid that system separates out thickness
Body, sucking filtration, by gained sticky solid ethyl acetate, toluene Mixed Solvent recrystallization, through sucking filtration and drying, by with 35%
Yield obtains the solid chemical compound b-1-3a of a kind of yellow.
(2) synthesis of compound b-1-3
Put into the compound b-1-3a (38.8g, 100 mMs) of acquisition in 1L autoclave, (3.9g contains the palladium carbon of 5%
Water, solid content is 30%), 400g oxolane, autoclave is sealed, 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 100g ethanol and stirs 30 minutes, through sucking filtration and drying, will obtain a kind of yellow with the yield of 89%
Solid chemical compound b-1-3.
As it is shown in figure 1, this compound b-1-31H-NMR data (500MHz, CHCl3-d1, δ, ppm) are: 1.28-
1.38(18H,6×CH3),3.62(4H,2×NH2),4.68(1H,OH),6.05(1H,CH-Ph),6.22(1H,CH-Ph),
6.50 (1H, CH-Ph), 6.63 (1H, CH-Ph), 6.68 (1H, CH-Ph).
(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 (1.6g, 5 mMs) (hereinafter referred to as b-1-1), p-phenylenediamine (5.4g, 50 mMs) (hereinafter referred to as b-2-1), 1,2-is double
(4-amino-benzene oxygen) ethane (12.2g, 50 mMs) (hereinafter referred to as b-2-2), p-aminophenyl ethamine (19.7g, 145 mmoles
You) (hereinafter referred to as b-2-3) and the METHYLPYRROLIDONE (hereinafter referred to as NMP) of 600g, by gained suspension stir until
Obtain the solution of a yellow.Then by the 1,2,3,4-Tetramethylene. tetracarboxylic dianhydride of 49.0g (250 mMs) (hereinafter referred to as
A-1) and 100g NMP add system.Exothermic heat of reaction, is stirred at room temperature 4 hours, obtains the polyamic acid polymer A-1-in NMP
1。
Synthesis example A-1-2 to A-1-20 and compare synthesis example A-2-1 to A-2-5
Synthesis example A-1-2 to A-1-20 and compare synthesis example A-2-1 to A-2-5 can be by identical with synthesis example A-1-1
Prepared by method, difference is: kind and the consumption of monomer used change, and concrete outcome sees below Tables 1 and 2, here
Repeat no more.
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: p-phenylenediamine
Double (4-amino-benzene oxygen) ethane of b-2-2:1,2-
B-2-3: p-aminophenyl ethamine
B-2-4:3,5-diaminobenzoic acid
B-2-5:2,4-diamino dodecane epoxide benzene
B-2-6:1-(4-(4-heptyl cyclohexyl) phenoxy group)-2,4-diaminobenzene
B-2-7:1-(4-(4-pentylcyclohexyl cyclohexyl) phenoxy group)-2,4-diaminobenzene
B-2-8:4,4 '-diaminourea diphenylethane
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, the aligning agent for liquid crystal of embodiment 1 is coated in a piece of first glass substrate with ITO electrode
On, to form precoated shet.Through front baking (hot plate, 80 DEG C, 5 minutes), single exposure (254nm, 5mW/cm2、800mj/cm2), after
Dry (circulation baking oven, 230 DEG C, 30 minutes) and re-expose (313nm, 5mW/cm2、600mj/cm2), will obtain that there is ITO electrode
Form the first glass substrate of the liquid crystal orientation film of embodiment 1 above.
By the mode of spin coating, the aligning agent for liquid crystal of embodiment 1 is coated in a piece of second glass base without ITO electrode
On plate, to form precoated shet.After also passing through above-mentioned front baking, single exposure, after bake and re-expose, obtain forming embodiment above
Second glass substrate of the liquid crystal orientation film of 1.
A kind of ultra-violet curing glue is coated on the first glass substrate and the most a piece of periphery of the second glass substrate, by 3.5 μ
The introns of m are sprinkled upon on another plate base.Then by this two panels glass substrate being that antiparallel mode is carried out with differently-oriented directivity
Laminating (5kg, 30min), then solidifies ultra-violet curing glue with ultra violet lamp.Then liquid crystal is injected, then utilize ultraviolet
Photo-hardening glue seals liquid crystal injecting port, and makes ultraviolet light photopolymerization glue harden with ultraviolet light, then outside two panels glass substrate
Polarizer is sticked in side, can obtain the IPS type liquid crystal display cells of embodiment 1.
The liquid crystal display cells of embodiment 1 is evaluated, the results are shown in Table 3.
Embodiment 2 to embodiment 33
Embodiment 2 to the embodiment 33 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
Changing, additionally orientation process also changes, and is shown in Table 3.The liquid crystal display cells of embodiment 2 to embodiment 33 is evaluated and
The results are shown in Table 3.
Comparing embodiment 1 to comparing embodiment 7
Comparing embodiment 1 to the comparing embodiment 7 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 additionally orientation process also changes, and is shown in Table 4.Liquid crystal display to comparing embodiment 1 to comparing embodiment 7
Element is evaluated and the results are shown in Table 4.
Evaluation methodology
Ultra-violet resistance energy
The ultra-violet resistance 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 under the irradiation of 254nm DUV, exposure rate
For 4200mj/cm2, then the VHR measured now by identical method (is designated as VHR2).Then the change of VHR is calculated by public formula V
Change value (is designated as Δ VHR (%)), and the lowest Δ VHR (%) means the best heat stability.
Formula V
The evaluation criterion of Δ VHR (%) is as follows:
◎: Δ VHR (%)≤5%, ultra-violet resistance can be outstanding,
Zero: 5% ＜ Δ VHR (%)≤10%, ultra-violet resistance can be good
△: 10% ＜ Δ VHR (%)≤20%, ultra-violet resistance can be general
X:20% ＜ Δ VHR (%), ultra-violet resistance can be poor
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
In table, * A:254nm, 5mW/cm2、800mj/cm2；* B:313nm, 5mW/cm2、800mj/cm2；* C:254nm,
10mW/cm2、1000mj/cm2；* D: dual wavelength (254nm, 313nm), 10mW/cm2、800mj/cm2；* E: dual wavelength (254nm,
313nm)、10mW/cm2、1800mj/cm2。
As can be seen here, compared with prior art, the aligning agent for liquid crystal of the present invention is by the diamidogen containing tert-butyl phenol fragment
Monomer is polymerized with other tetracarboxylic dianhydride's monomer；Owing to diamine monomer containing tert-butyl phenol fragment, the material after polymerization
Material ultra-violet resistance can be more prominent.Therefore, the liquid crystal orientation film of the present invention carry out the present invention light be orientated exposure manufacture process time, by
Just it is exposed in terminating the most non-after bake in front baking, it is possible to ensure the exposition uniformity of liquid crystal orientation film, improves liquid crystal orientation film
Anchorage force to liquid crystal, simultaneously as the ultra-violet resistance of aligning agent for liquid crystal itself, it is possible to ensure to occur without the situation of overexposure, can
Increase its operation window, have the exposure of exposure area thoroughly, non-exposed areas have outstanding ultra-violet resistance can dual excellent
Point, it is thus possible to improve display effect and the service life of liquid crystal display.And method is simple, wide market, it is suitable for rule
Modelling 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 mix
Thing comprises an a tetracarboxylic dianhydride component a and diamidogen component b, and described diamidogen component b at least includes the diamidogen represented by Formulas I
Compound b-1, described diamine compound b-1 have a following structural formula:
Wherein, X represents
Singly-bound ,-O-,-S-、In one.
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, polyamides
One or both mixture in imines.
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-pyrrolidine
Ketone, gamma-butyrolacton, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, glycol monoethyl ether, ethylene glycol monoethyl ether, second two
The mixture of one or more in alcohol monobutyl ether, ethylene glycol methyl ether, glycol dimethyl ether, diethylene glycol monomethyl ether ethyl ester.Its
In, the weight ratio of described polymer A and described solvent B is 1:5-80.
A kind of aligning agent for liquid crystal the most according to claim 1, it is characterised in that described tetracarboxylic dianhydride 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, equal benzene
Tetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic's dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl sulfone
The mixture of one or more in 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 two aminations
Compound b-2, described diamine compound b-2 be p-phenylenediamine, m-diaminobenzene., 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, to amino
Phenethylamine, 4,4 '-MDA, 4,4 '-diaminourea diphenylethane, 4,4 '-diaminodiphenyl ether, 1,4-bis-(4-ammonia
Phenoxyl) benzene, 4,4 '-diaminobenzophenone, double (4-amino-benzene oxygen) ethane of 1,2-, 1,3-be double (4-amino-benzene oxygen)
Double (4-amino-benzene oxygen) butane of propane, 1,4-, double (4-amino-benzene oxygen) pentane of 1,5-, 1,6-double (4-amino-benzene oxygen) are own
Alkane, N, N '-two (4-aminophenyl) piperazine, 2,2-double [4-(4-amino-benzene oxygen) phenyl] propane, 2,4-diamino dodecane
Double [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of epoxide benzene, 2,4-diaminourea octadecane epoxide benzene, 2,2-, the double (4-of 2,2-
Aminophenyl) HFC-236fa, 4-(4-heptyl cyclohexyl) phenyl-3,5-diaminobenzoic acid ester, 2,2 '-dimethyl-4,4 '-two
Aminobphenyl, 4,4 '-diaminobenzene Methanamide, 1-(4-(4-pentylcyclohexyl cyclohexyl) phenoxy group)-2,4-diaminobenzene, 1-
The mixture of one or more in (4-(4-heptyl cyclohexyl) phenoxy group)-2,4-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 component a and described
The mol ratio of diamidogen component b is 100:20-200；Described tetracarboxylic dianhydride component a and the mol ratio of described diamine compound b-1
For 100:0.001-10.
7. 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 1-6.
8. the light orientation preparation method of a liquid crystal orientation film as claimed in claim 7, it is characterised in that comprise the steps:
(1) use aligning agent for liquid crystal as above, substrate is formed precoated shet；
(2) step (1) gained precoated shet is carried out front baking, single exposure, after bake, re-expose, i.e. form described liquid crystal aligning
Film；
Or step (1) gained precoated shet is carried out front baking, single exposure, re-expose, after bake, i.e. form described liquid crystal aligning
Film；
Or step (1) gained precoated shet is carried out front baking, high intensity exposure, an after bake, i.e. form described liquid crystal orientation film.
The light orientation preparation method of liquid crystal orientation film the most according to claim 8, it is characterised in that described in step (2)
The temperature of front baking is 50-120 DEG C, and the time is 2-7mins；Described single exposure, the light of re-expose are polarized light, and wavelength is the most not
Identical, it is selected from single 254nm, or single 313nm, or dual wavelength 254nm, 313nm, exposure light intensity is 1-10mW/cm2, expose
It is 10-1000mj/cm that light adds up light quantity2；The temperature range of described after bake is 180-250 DEG C, and time range is 30-90mins；
The light of described high intensity exposure is polarized light, is selected from single 254nm, or single 313nm, or dual wavelength 254nm,
313nm, the accumulative light quantity of exposure is 20-2000mj/cm2。
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 1-6.
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| TW105129722A TWI570184B (en) | 2016-08-17 | 2016-09-13 | A?liquid crystal alignment film and a liquid crystal display element having the liquid crystal alignment film and a liquid crystal alignment film formed by the liquid crystal alignment agent and the method of the forming. |
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| CN109651631A (en) * | 2018-01-18 | 2019-04-19 | 深圳瑞华泰薄膜科技股份有限公司 | A kind of Kapton of low dielectric loss |
| CN111575023A (en) * | 2020-06-12 | 2020-08-25 | 江苏三月科技股份有限公司 | Novel compound additive, liquid crystal aligning agent prepared from novel compound additive and liquid crystal aligning film |
| CN114524938A (en) * | 2021-10-28 | 2022-05-24 | 江苏三月科技股份有限公司 | Polymer, photosensitive resin composition, cured film prepared from same and electronic element |
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| CN114456378B (en) * | 2020-11-09 | 2024-02-27 | 江苏三月科技股份有限公司 | Polyimide for liquid crystal alignment agent and liquid crystal alignment film prepared from polyimide |
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| CN101838537A (en) * | 2009-03-18 | 2010-09-22 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal orientation film, liquid crystal display device, polyamic acid, imide amination polymer and compound |
| CN102206495A (en) * | 2010-03-30 | 2011-10-05 | 智索株式会社 | Liquid crystal aligning agent, liquid crystal alignment layer and liquid crystal display device |
| JP2015090427A (en) * | 2013-11-06 | 2015-05-11 | Dic株式会社 | Manufacturing method of liquid crystal alignment film and liquid crystal display element using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109651631A (en) * | 2018-01-18 | 2019-04-19 | 深圳瑞华泰薄膜科技股份有限公司 | A kind of Kapton of low dielectric loss |
| CN111575023A (en) * | 2020-06-12 | 2020-08-25 | 江苏三月科技股份有限公司 | Novel compound additive, liquid crystal aligning agent prepared from novel compound additive and liquid crystal aligning film |
| CN111575023B (en) * | 2020-06-12 | 2022-03-01 | 江苏三月科技股份有限公司 | Compound additive, liquid crystal aligning agent prepared from compound additive and liquid crystal aligning film |
| CN114524938A (en) * | 2021-10-28 | 2022-05-24 | 江苏三月科技股份有限公司 | Polymer, photosensitive resin composition, cured film prepared from same and electronic element |
| CN114524938B (en) * | 2021-10-28 | 2024-02-09 | 江苏三月科技股份有限公司 | Polymer, photosensitive resin composition, cured film prepared from polymer and photosensitive resin composition, and electronic element |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI570184B (en) | 2017-02-11 |
| TW201807065A (en) | 2018-03-01 |
| WO2018032588A1 (en) | 2018-02-22 |
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