CN103718090B - Aligning agent for liquid crystal and use the liquid crystal display cells of this inorganic agent - Google Patents
Aligning agent for liquid crystal and use the liquid crystal display cells of this inorganic agent Download PDFInfo
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- CN103718090B CN103718090B CN201280036612.5A CN201280036612A CN103718090B CN 103718090 B CN103718090 B CN 103718090B CN 201280036612 A CN201280036612 A CN 201280036612A CN 103718090 B CN103718090 B CN 103718090B
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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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 present invention provides aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal display cells that the effect shortening the time needed for the after image caused by DC voltage disappears is high, make ultraviolet resistance raising, wearing character not lower.This aligning agent for liquid crystal contains at least one polymer selected from polyimide precursor and polyimides, and compound that following formula [1] represents (in formula, R1For hydrogen atom or vinyl, n represents the integer of 0～2).
Description
Technical field
The aligning agent for liquid crystal used when the present invention relates to make liquid crystal orientation film and the liquid crystal utilizing this inorganic agent
Display element.
Background technology
At present, the liquid crystal orientation film as liquid crystal display cells mainly uses so-called polyamide-based liquid crystal orientation film,
This film is by being coated with the solution of the polyimide precursor of polyamic acid etc. or soluble polyimide as main one-tenth on substrate
Point aligning agent for liquid crystal and burn till and obtain.Liquid crystal orientation film uses for the purpose of the state of orientation controlling liquid crystal.
Along with the high-precision refinement of liquid crystal display cells, from the viewpoint of reducing persistence of vision, it is desirable to the liquid crystal used
The material that in alignment films, the mitigation of the electric charge that employing DC voltage is accumulated is fast.In polyimide liquid crystal orientation film, as because of
DC voltage and the after image that produces disappear till time short liquid crystal orientation film, it is known that employ except polyamic acid or contain
Possibly together with the liquid crystal orientation film of aligning agent for liquid crystal of tertiary amine of ad hoc structure (referring for example to patent beyond the polyamic acid of imino group
Document 1), or employ the liquid crystal containing the soluble polyimide using the specific diamines with pyridine skeleton etc. in raw material
The liquid crystal orientation film (referring for example to patent document 2) etc. of alignment agent.
It addition, in aligning agent for liquid crystal, in addition to the electric charge of accumulation relaxes fast characteristic, from reducing the viewpoint that display is uneven
Consider, it is desirable to the material used is the most easy to wear in friction orientation processes.Outside these characteristics, further, liquid crystal in recent years
The manufacturing process of display element includes the operation by irradiating ultraviolet light such as ODF engineering or PSA process, therefore it is required that material tool
There is ultraviolet resistance.
Prior art literature
Patent document
Patent document 1: Japanese Patent Laid-Open 9-316200 publication
Patent document 2: Japanese Patent Laid-Open 10-104633 publication
Summary of the invention
Invent technical problem to be solved
In view of the foregoing, it is an object of the invention to provide the time shortened needed for the after image caused by DC voltage disappears
The additive that effect is high, ultraviolet resistance improves, wearing character does not lowers, the liquid crystal aligning adding this additive processes
Agent, and employ the liquid crystal display cells of this aligning agent for liquid crystal.
Solve the technical scheme that technical problem is used
The result that present inventor conscientiously studies to reach above-mentioned purpose is, it was found that except selected from polyimides
Outside the polymer of at least one of precursor and polyimides, it is the specific of novel substance before the application proposes possibly together with one part
The aligning agent for liquid crystal of material can reach above-mentioned purpose, thus completes the present invention.The present invention has techniques below main points.
1. aligning agent for liquid crystal, containing at least one polymer selected from polyimide precursor and polyimides, and under
The compound that formula [1] represents,
[changing 1]
In formula, R1For hydrogen atom or vinyl, n represents the integer of 0～2.
The aligning agent for liquid crystal that the most above-mentioned (1) is recorded, wherein, relative to 100 mass parts selected from polyimide precursor
And at least one polymer of polyimides, the compound represented by formula [1] containing 0.1～10 mass parts.
The aligning agent for liquid crystal that the most above-mentioned (1) or (2) are recorded, wherein, the R in formula [1]1For vinyl.
The aligning agent for liquid crystal recorded any one of the most above-mentioned (1)～(3), wherein, the compound represented by formula [1] is following
M1, M2, M3 or M4,
[changing 2]
The aligning agent for liquid crystal recorded any one of the most above-mentioned (1)～(4), wherein, the solid containing 0.5～10 mass % becomes
Point.
6. liquid crystal orientation film, is obtained by the aligning agent for liquid crystal recorded any one of above-mentioned (1)～(5).
7. liquid crystal display cells, has the liquid crystal orientation film that above-mentioned (6) are recorded.
8. the compound represented by following formula (2),
[changing 3]
In formula, n represents the integer of 0～2.
The effect of invention
According to the present invention, it is provided that the effect ultraviolet high, resistance to of the time needed for the after image disappearance that shortening is caused by DC voltage
The aligning agent for liquid crystal that photosensitiveness improves, wearing character does not lowers.
Further, since a part for the above-claimed cpd added in the aligning agent for liquid crystal of the present invention is in the present patent application
Front is noval chemical compound, and therefore the present invention also provides for above-mentioned noval chemical compound.
The mode carried out an invention
[additive]
The aligning agent for liquid crystal of the present invention adds (hereinafter referred to as the adding of the present invention of the compound represented by following formula [1]
Add agent).
[changing 4]
In formula, R1Representing hydrogen atom or vinyl, n is the integer of 0～2, the integer of preferably 1 or 2.
Although R1Represent hydrogen atom or vinyl, but from the viewpoint of the after image characteristic of the liquid crystal orientation film obtained, preferably
For vinyl.
The preferred concrete example of the additive of the present invention can enumerate following M1～M12.Wherein, preferably M1, M2, M3 or
M4。
[changing 5]
About the additive level of the present invention in aligning agent for liquid crystal, relative to 100 mass parts selected from polyimides
At least one polymer of precursor and polyimides, preferably 0.1～10 mass parts, more preferably 1～10 mass parts, particularly preferably
1～5 mass parts.
[synthetic method of additive]
The synthetic method of the additive of the present invention, is to synthesize with the combination of Synthetic Organic Chemistry technology, the most especially
Limit.Such as, available following method synthesis.
The additive represented with the formula [1] of the present invention, shown in synthetic reaction flow chart (A) described as follows, (B) etc.,
The reaction of compound (i) and organometallic reagent vinyl magnesium bromide, or the reducing agent such as compound (i) and sodium borohydride can be passed through
Reaction synthesize.
[changing 6]
The aldehyde compound represented by formula (i) in synthetic reaction flow chart (A), (B), it is possible to use commercially available compound,
Palladium catalyst can also be used to make the aniline compound of correspondence carry out cross-coupling reaction synthesis with halogenated aryl obtain.
The concrete method for optimizing of synthetic reaction flow chart (A) and synthetic reaction flow chart (B) is in respective conjunction described later
Become in example and be described.
[polyimide precursor and polyimides]
In the present invention, polyimide precursor refer to polyamic acid (Ployamic acid, also referred to as Polyamide acid) and
Poly amic acid ester.Polyamic acid is reacted acquisition by diamine component with tetracarboxylic dianhydride.Poly amic acid ester is by diamine component
Carry out in the presence of a base reacting with tetrabasic carboxylic acid diester diacid chloride or by tetrabasic carboxylic acid diester with diamines at suitable condensing agent and alkali
In the presence of carry out reaction obtain.The polyimides of the present invention can carry out dehydration closed-loop or to poly-by making this polyamic acid
Amic acid esters carries out heating so that its closed loop obtains.As being used for obtaining the polymer of liquid crystal orientation film, above-mentioned polyamic acid,
Any one in poly amic acid ester and polyimides is the most available.
The diamine component used in above-mentioned polyimide precursor manufacture is not particularly limited, and can enumerate ester ring type diamines, virtue
Fragrant race diamines, aromatic-aliphatic diamines, hetero ring type diamines, aliphatic diamine etc., respective concrete example enumerates as follows.
As the example of ester ring type Diamines, can enumerate Isosorbide-5-Nitrae-DACH, 1,3-DACH, 4,4 '-
Diamino-dicyclohexyl methane, 4,4 '-diaminourea-3,3 '-dimethyidicyclohexyl amine, IPD etc..
As the example of aromatic diamines, can enumerate o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, 2,4-diaminourea first
Benzene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diaminourea-2-methoxybenzene, 2,5-diaminourea paraxylene, 1,
3-diaminourea-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diaminourea-2,5-dichloro-benzenes, 4,4 '-diaminostilbene, 2-diphenyl
Ethane, 4,4 '-diaminourea-2,2 '-dimethyl bibenzyl, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane,
3,4 '-diaminodiphenyl-methane, 4,4 '-diaminourea-3,3 '-dimethyl diphenylmethane, 2,2 '-diaminourea, 4,4 '-two
Amino, 4,4 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diamino diphenyl sulfide, 4,4 '-two
Double (3-amino-benzene oxygen) benzene of ADP base sulfone, 3,3 '-diamino diphenyl sulfone, 4,4 '-diaminobenzophenone, 1,3-,
Double (4-amino-benzene oxygen) benzene of double (4-amino-benzene oxygen) benzene of 1,3-, 1,4-, double (4-amino-benzene oxygen) benzoic acid of 3,5-, 4,
Double [(4-amino-benzene oxygen) methyl] propane of 4 '-bis-(4-amino-benzene oxygen) bibenzyls, 2,2-, double [4-(the 4-aminobenzene oxygen of 2,2-
Base) phenyl] HFC-236fa, double [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, double [4-(3-amino-benzene oxygen) phenyl] sulfone,
Double [4-(4-amino-benzene oxygen) phenyl] sulfone, 1,1-double (4-aminophenyl) hexamethylene, α, α '-bis-(4-aminophenyl)-1,4-
Double (4-aminophenyl) fluorenes of diisopropyl benzene, 9,9-, double (3-aminophenyl) HFC-236fa of 2,2-, 2,2-are double (4-aminophenyl)
HFC-236fa, 4,4 '-diamino-diphenyl amine, 2,4-diamino-diphenyl amine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,
Double (the 4-ammonia of 5-diamino-anthraquinone, 1,3-diaminourea pyrene, 1,6-diaminourea pyrene, 1,8-diaminourea pyrene, 2,7 diamin of luorene, 1,3-
Base phenyl) tetramethyl disiloxane, benzidine, 2,2 '-dimethylbenzidine, double (4-aminophenyl) ethane of 1,2-, 1,3-be double
Double (4-aminophenyl) butane of (4-aminophenyl) propane, 1,4-, double (4-aminophenyl) pentane of 1,5-, double (the 4-amino of 1,6-
Phenyl) hexane, double (4-aminophenyl) heptane of 1,7-, double (4-aminophenyl) octane of 1,8-, double (4-aminophenyl) nonyl of 1,9-
Double (4-amino-benzene oxygen) propane of double (4-aminophenyl) decane of alkane, 1,10-, 1,3-, double (4-amino-benzene oxygen) butane of 1,4-,
Double (4-amino-benzene oxygen) hexane of double (4-amino-benzene oxygen) pentane of 1,5-, 1,6-, double (4-amino-benzene oxygen) heptane of 1,7-, 1,
Double (4-amino-benzene oxygen) nonane of double (4-amino-benzene oxygen) octane of 8-, 1,9-, double (4-amino-benzene oxygen) decane of 1,10-, two
(4-aminophenyl)-1,3-malonate, two (4-aminophenyl)-1,4-succinate, two (4-aminophenyl)-1,5-penta 2
Acid esters, two (4-aminophenyl)-1,6-adipate ester, two (4-aminophenyl)-1,7-pimelate, two (4-aminophenyls)-
1,8-suberate, two (4-aminophenyl)-1,9-azelate, two (4-aminophenyl)-1,10-sebacate, 1,3-are double
Double [4-(4-amino-benzene oxygen) phenoxy group] butane of [4-(4-amino-benzene oxygen) phenoxy group] propane, 1,4-, the double [4-(4-of 1,5-
Amino-benzene oxygen) phenoxy group] pentane, double [4-(4-amino-benzene oxygen) phenoxy group] hexane of 1,6-, double [4-(the 4-aminobenzene of 1,7-
Epoxide) phenoxy group] heptane, double [4-(4-amino-benzene oxygen) phenoxy group] octane of 1,8-, double [4-(4-amino-benzene oxygen) benzene of 1,9-
Epoxide] nonane, double [4-(4-amino-benzene oxygen) phenoxy group] decane of 1,10-etc..
As the example of aromatic-aliphatic diamines, 3-aminobenzene methyl amine, 4-aminobenzene methyl amine, 3-ammonia can be enumerated
Base-N-methylbenzylamine, 4-Amino-N-methyl benzyl amine, 3-aminophenethyl amine, 4-aminophenethyl amine, 3-amino-
N-methylphenethylamine, 4-Amino-N-methyl phenethyl amine, 3-(3-aminopropyl) aniline, 4-(3-aminopropyl) aniline, 3-
(3-dimethylaminopropyl) aniline, 4-(3-dimethylaminopropyl) aniline, 3-(4-aminobutyl) aniline, 4-(4-aminobutyl)
Aniline, 3-(4-methylamino butyl) aniline, 4-(4-methylamino butyl) aniline, 3-(5-Aminopentyl) aniline, 4-(5-ammonia
Base amyl group) aniline, 3-(5-methylamino-pentyl) aniline, 4-(5-methylamino-pentyl) aniline, 2-(6-amino naphthyl) methyl
Amine, 3-(6-amino naphthyl) methyl amine, 2-(6-amino naphthyl) ethylamine, 3-(6-amino naphthyl) ethylamine etc..
As the example of heterocyclic diamines, can enumerate DAP, 2,4-diamino-pyridine, 2,4-diaminourea-
1,3,5-triazine, 2,7 diaminodibenz of uran, 3,6-diaminocarbazole, 2,4-diaminourea-6-isopropyl-1,3,5-three
Double (4-aminophenyl)-1,3,4-diazole of piperazine, 2,5-etc..
As the example of aliphatic diamine class, can enumerate EDA, 1,3-diaminopropanes, Isosorbide-5-Nitrae-diaminourea
Butane, 1,5-1,5-DAP, 1,6-diamino hexane, 1,7-diaminoheptane, 1,8-diamino-octane, 1,9-diaminourea nonyl
Alkane, 1,10-diamino decane, 1,3-diaminourea-2,2-dimethylpropane, 1,6-diaminourea-2,5-dimethylhexane, 1,7-bis-
Amino-2,5-dimethyl heptane, 1,7-diaminourea-4,4-dimethyl heptane, 1,7-diaminourea-3-methyl heptane, 1,9-diamino
Double (3-aminopropan epoxide) ethane of base-5-methyl heptane, 1,12-diamino dodecane, 1,18-diaminourea octadecane, 1,2-etc..
Additionally, can together with above-mentioned diamines and be used on side chain have alkyl, containing fluoroalkyl, aromatic rings, aliphatic ring,
Heterocycle or the diamine compound (hereinafter referred to as other diamines) of big ring-type substituent being made up of them.As other diamines, tool
Body can illustrate the diamines represented with following formula [DA-1]～formula [DA-26].
[changing 7]
(in formula [DA1]～formula [DA5], R6For the alkyl of carbon number 1～22 or containing fluoroalkyl.)
[changing 8]
(in formula [DA6]～formula [DA9], S5Represent-COO-,-OCO-,-CONH-,-NHCO-,-CH2-,-O-,-CO-or-
NH-, R6Represent the alkyl of carbon number 1～22 or containing fluoroalkyl.)
[changing 9]
(in formula [DA10] and formula [DA11], S6Represent-O-,-OCH2-、-CH2O-、-COOCH2-or-CH2OCO-, R7For carbon
The alkyl of several 1～22, alkoxyl, containing fluoroalkyl or fluoroalkoxy.)
[changing 10]
(in formula [DA12]～formula [DA14], S7Represent-COO-,-OCO-,-CONH-,-NHCO-,-COOCH2-、-
CH2OCO-、-CH2O-、-OCH2-or-CH2-, R8Be the alkyl of carbon number 1～22, alkoxyl, containing fluoroalkyl or fluoroalkoxy.)
[changing 11]
(in formula [DA15] and formula [DA16], S8Represent-COO-,-OCO-,-CONH-,-NHCO-,-COOCH2-、-
CH2OCO-、-CH2O-、-OCH2-、-CH2-,-O-or-NH-, R9For fluorine-based, cyano group, trifluoromethyl, nitro, azo group, formyl
Base, acetyl group, acetoxyl group or hydroxyl.)
[changing 12]
(in formula [DA17]～formula [DA20], R10Be carbon number be the alkyl of 3～12, the cis-trans isomerization of Isosorbide-5-Nitrae-cyclohexylidene
The most trans.)
[changing 13]
[changing 14]
In addition, it is possible to and with diamines shown below.
[changing 15]
(in formula [DA31], m is the integer of 0～3, and in formula [DA34], n is the integer of 1～5.)
The voltage retention (also referred to as VHR) of liquid crystal display cells can be improved owing to introducing [DA-27] or [DA-28],
[DA-29]～[DA-34] is reduced the effect of the accumulated charge of liquid crystal display cells, the most preferably.
In addition it is also possible to enumerate the diaminourea siloxanes etc. represented with following formula [DA35].
[changing 16]
(in formula [DA35], m is the integer of 1～10.)
Other above-mentioned diamine compounds can keep spy according to liquid crystal aligning when making liquid crystal orientation film, voltage
The characteristics such as property, accumulated charge, are used alone, or mixing two or more.
Tetracarboxylic dianhydride for reacting with diamine component for obtaining the polyamic acid of the present invention is not particularly limited.Under
Face enumerates its object lesson.
As having the tetracarboxylic dianhydride of ester ring type structure or aliphatic structure, 1,2,3,4-cyclobutane tetracarboxylic acids can be enumerated
Acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetrabasic carboxylic acid two
Acid anhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 2,3,4,5-
Oxolane tetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic's dianhydride, 3,4-dicarboxyl-1-cyclohexyl butanedioic acid dianhydride, 3,
4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride, 1,2,3,4-butane tetracarboxylic acid dianhydride, two rings [3,3,0] octane-
2,4,6,8-tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride,
Cis-3,7-dibutyl ring octyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, three rings [4.2.1.02,5] nonane-3,4,7,8-four
Carboxylic acid-3,4:7,8-dianhydride, six rings [6.6.0.12,7.03,6.19,14.010,13] hexadecane-4,5,11,12-tetrabasic carboxylic acid-
4,5:11,12-dianhydride, 4-(2,5-dioxotetrahydro furans-3-base)-1,2,3,4-tetralin-1,2-dicarboxylic anhydride etc..
Further, if also using aromatic series four outside the above-mentioned tetracarboxylic dianhydride with ester ring type structure or aliphatic structure
Carboxylic acid dianhydride, then can improve liquid crystal aligning, and can reduce the accumulated charge of liquid crystal cell, the most preferably.As virtue
Fragrant race tetracarboxylic dianhydride, can enumerate pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl four
Carboxylic acid dianhydride, 2,3,3 ', 4-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4-benzophenone four
Carboxylic acid dianhydride, double (3,4-dicarboxyphenyi) ether dianhydride, double (3,4-dicarboxyphenyi) sulfone dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid two
Acid anhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride etc..
Tetracarboxylic dianhydride can be according to liquid crystal aligning when making liquid crystal orientation film, voltage retentivity, accumulated charge etc.
Characteristic, uses one or and with two or more.
[synthesis of polyamic acid]
When being obtained the polyamic acid of the present invention by the reaction of tetracarboxylic dianhydride and diamine component, known conjunction can be used
One-tenth method.Generally make the method that tetracarboxylic dianhydride and diamine component react in organic solvent.Tetracarboxylic dianhydride and diamines
Reaction be easier in organic solvent carry out, and be favourable at the aspect not generating accessory substance.
As the organic solvent of the reaction for tetracarboxylic dianhydride and diamines, as long as the polyamic acid that generates of solubilized
Solvent is not particularly limited.Enumerate its object lesson below.
N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrole can be enumerated
Pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolacton, isopropyl
Alcohol, methoxy amylalcohol, cinene, ethyl pentyl group ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl are different
Propyl group ketone, methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, butyl carbitol, second
Base carbitol, ethylene glycol, ethylene glycol acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propane diols, propane diols
Monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, DPGME, diethylene glycol, diethylene glycol list second
Acid esters, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, DPGME, DPG list second
Base ether, dipropylene glycol monoacetate list ethylether, DPG list propyl ether, dipropylene glycol monoacetate list propyl ether, 3-first
Base-3-methoxybutyl acetic acid esters, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl base
Ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, DIBK, methylcyclohexene, propyl ether, two hexyl ethers, twoAlkane,
N-hexane, normal heptane, normal octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate,
Methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate list ethylether, methyl pyruvate, ethyl pyruvate, 3-first
Epoxide methyl propionate, 3-ethoxy-propionic acid methyl ethyl ester, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-
Methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 3-methoxyl group-N,
N-dimethylpropionamide, 3-ethyoxyl-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide etc..These solvents
Can be used alone, it is also possible to be used in mixed way.Further, even the solvent of polyamic acid can not be dissolved, if poly-generate
In the range of amic acid does not separate out, may be combined in above-mentioned solvent and use.
Additionally, the moisture in organic solvent hinders polymerisation, and the polyamic acid of generation can be made to hydrolyze, the most organic
Solvent is preferably used the organic solvent as far as possible dehydrated.
Make tetracarboxylic dianhydride and diamine component that following method when reacting in organic solvent, can be enumerated: stirring makes diamine component
It is dispersed or dissolved in solution obtained by organic solvent, the most directly adds tetracarboxylic dianhydride or make tetracarboxylic dianhydride disperse or molten
The method that solution is added after organic solvent again；On the contrary tetracarboxylic dianhydride is being dispersed or dissolved in solution obtained by organic solvent
The method of middle interpolation diamine component；Alternately add tetracarboxylic dianhydride and the method etc. of diamine component, it is possible to use in these methods
Any one method.During it addition, tetracarboxylic dianhydride or diamine component are made up of multiple compounds, can be in the state being pre-mixed
Under make it react, it is possible to so that it reacts the most successively, then low-molecular weight hybrid reaction obtained by making to react respectively and obtain
HMW body.
Polymerization temperature now can select-20 DEG C～the arbitrary temp of 150 DEG C, preferably-5 DEG C～the scope of 100 DEG C.
Additionally, though reaction can be carried out with arbitrary concentration, if but concentration is too low, it is difficult to obtain the polymer of HMW, if dense
The viscosity spending high then reactant liquor becomes too high and is difficult to stir uniformly, and therefore tetracarboxylic dianhydride and diamine component are instead
The total concentration in solution is answered to be preferably 1～50 mass %, more preferably 5～30 mass %.Initial reaction stage can be entered in higher concentrations
OK, organic solvent is added afterwards.
In the polymerisation of polyamic acid, the ratio of the total mole number of tetracarboxylic dianhydride and the total mole number of diamine component is preferred
It is 0.8～1.2, more preferably 0.9～1.1.Identical with common polycondensation reaction, this mol ratio is closer to 1.0, the polyamides of generation
The molecular weight of amino acid is the biggest.
[synthesis of poly amic acid ester]
As the synthetic method of poly amic acid ester, can also can be by tetrabasic carboxylic acid two by tetrabasic carboxylic acid diester diacid chloride and diamine reactant
The reaction in the presence of suitable condensing agent with alkali of ester and diamines obtains the poly amic acid ester as one of polyimide precursor.Or
Person, the acid of prior polymeric polyamide, utilize high molecular weight reactive to make the carboxylic esterification in amic acid obtain.
Specifically, can make preferably at 0 DEG C～50 DEG C in-20 DEG C～150 DEG C in the presence of alkali and organic solvent
Tetrabasic carboxylic acid diester diacid chloride and diamine reactant 30 minutes～24 hours, preferably reaction synthesize for 1～4 hour.
Described alkali can use pyridine, triethylamine or 4-dimethylaminopyridine, in order to carry out with making stable reaction, preferably
Pyridine.From the amount easily removed and from the viewpoint of easily obtaining HMW body, the addition of alkali is relative to tetrabasic carboxylic acid diester two acyl
Chlorine is preferably 2～4 times moles.
When carrying out polycondensation reaction in the presence of condensing agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1-can be used
Ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy-1,3,5-triazine methyl
Morpholine, O-(BTA-1-base)-N, N, N ', N '-tetramethylurea (TMU) tetrafluoro boric acid ester, O-(BTA-1-base)-N, N, N ',
N '-tetramethylurea (TMU) hexafluorophosphoric acid ester, (2,3-dihydro-2-sulphur generation-3-benzoAzoles) phosphonic acid diphenyl ester, 4-(4,6-dimethoxy-1,
3,5-triazine-2-base) 4-methoxyl group morpholine chloride n hydrate etc..
Additionally, in the method using above-mentioned condensing agent, by interpolation lewis acid as additive, reaction can be made efficient
Ground is carried out.As lewis acid, the preferably lithium halide such as lithium chloride, lithium bromide.Lewis acidic addition is preferred relative to (C1)
It it is 0.1～1.0 times of mole.
As the solvent used in above-mentioned reaction, though be usable in being used during above-mentioned polymeric polyamide acid is molten
Agent, but consider from the dissolubility of monomer and polymer, preferably METHYLPYRROLIDONE or gamma-butyrolacton, can be by them
One or be use mixing two or more.Concentration during synthesis is from being not susceptible to the precipitation of polymer and being readily available high score
From the viewpoint of son amount body, preferably 1～30 mass %, more preferably 5～20 mass %.Additionally, in order to prevent tetrabasic carboxylic acid diester
Diacid chloride hydrolyzes, and for the solvent dehydration preferably as far as possible of the synthesis of poly amic acid ester, preferably prevents extraneous gas in blanket of nitrogen
Being mixed into of body.
In the present invention, though the tetrabasic carboxylic acid diester for reacting with diamine component to obtain poly amic acid ester does not has especially
Limit, but preferred aliphat tetrabasic carboxylic acid diester or aromatic tetracarboxylic acid's dialkyl, respective concrete example exemplified below.
As the object lesson of aliphatic tetrabasic carboxylic acid diester, can enumerate 1,2,3,4-cyclobutane tetrabasic carboxylic acid dialkyls, 1,
2-dimethyl-1,2,3,4-cyclobutane tetrabasic carboxylic acid dialkyl, 1,3-dimethyl-1,2,3,4-cyclobutane tetrabasic carboxylic acid dialkyl group
Ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetrabasic carboxylic acid dialkyl, 1,2,3,4-pentamethylene tetrabasic carboxylic acid dialkyl,
2,3,4,5-oxolane tetrabasic carboxylic acid dialkyl, 1,2,4,5-cyclopentanetetracarboxylic's dialkyl, 3,4-dicarboxyl-1-hexamethylene
Base dialkyl succinate, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dialkyl, 1,2,3,4-butane tetracarboxylic
Acid dialkyl ester, two rings [3,3,0] octane-2,4,6,8-tetrabasic carboxylic acid dialkyl, 3,3 ', 4,4 ' dicyclohexyl tetrabasic carboxylic acid dioxanes
Base ester, 2,3,5-tricarboxylic cyclopentyl dialkyl acetates, cis-3,7-dibutyl ring octyl-1,5-diene-1,2,5,6-tetrabasic carboxylic acid
Dialkyl, three rings [4.2.1.02,5] nonane-3,4,7,8-tetrabasic carboxylic acid-3,4:7,8-dialkyl, six rings [6.6.0.12,
7.03,6.19,14.010,13] hexadecane-4,5,11,12-tetrabasic carboxylic acid-4,5:11,12-dialkyl, 4-(2,5-dioxo
Oxolane-3-base)-1,2,3,4-tetralin-1,2-dicarboxylic acid dialkyl esters etc..
As the object lesson of aromatic tetracarboxylic acid's dialkyl, can enumerate Pyromellitic Acid dialkyl, 3,3 ', 4,
4 '-biphenyltetracarboxyacid acid dialkyl, 2,2 ', 3,3 '-biphenyltetracarboxyacid acid dialkyl, 2,3,3 ', 4-biphenyltetracarboxyacid acid dialkyl group
Ester, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dialkyl, 2,3,3 ', 4-benzophenone tetrabasic carboxylic acid dialkyl, double (3,4-dicarboxyl
Phenyl) ether dialkyl, double (3,4-dicarboxyphenyi) sulfone dialkyl, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl, 2,3,6,
7-naphthalene tetracarboxylic acid dialkyl etc..
[synthesis of polyimides]
The polyimides of the present invention is to make polyimides obtained by above-mentioned polyamic acid dehydration closed-loop, can be as being used for obtaining
The polymer of liquid crystal orientation film.In the polyimides of the present invention, the dehydration closed-loop rate (acid imide rate) of acid amides acidic group need not
One is set to 100%, arbitrarily can adjust according to purposes or purpose.
As the method making the polyimide precursor imidizates such as polyamic acid, can enumerate and directly heat the molten of polyamic acid
The hot-imide of liquid, in the solution of polyamic acid, add the catalysis imidizate of catalyst.
Temperature during polyamic acid hot-imide is made to be 100～400 DEG C in the solution, preferably 120～250 DEG C, preferably
Use the method carrying out imidizate while being expelled to outside system by the water generated by imidization reaction.
The catalysis imidizate of polyamic acid can pass through to add base catalyst and acid anhydrides in polyamic acid solution,
At-20～250 DEG C, more fortunately at 0～180 DEG C stirring and carry out.The amount of base catalyst is 0.5～30 mole of acid amides acidic group
Times, preferably 2～20 moles times, the amount of acid anhydrides is 1～50 mole times of acid amides acidic group, preferably 3～30 moles times.Urge as alkalescence
Agent, can enumerate pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc., and wherein pyridine has for making reaction carry out
The alkalescence of appropriateness, the most preferably.As acid anhydrides, acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc. can be enumerated, wherein, use
The purifying carrying out reacting after terminating it is prone to, the most preferably during acetic anhydride.The acid imide rate using catalysis imidizate can be led to
Cross adjustment catalytic amount and reaction temperature, reaction time control.
[recovery of polymer]
From polyamic acid, poly amic acid ester, polyimides reaction solution reclaim the polyamic acid of generation, polyamic acid
When ester, polyimides, reaction solution can be put into poor solvent and make it precipitate.As the poor solvent for precipitation, can
Enumerate methyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene, water etc..
Putting into the polymer precipitated in poor solvent can be after being recovered by filtration, under normal or reduced pressure, and air drying or add
Heated drying.If it addition, the polymer that precipitation reclaims being dissolved in organic solvent again and repeats 2～10 reprecipitations and return
The operation received, then can reduce the impurity in polymer.As poor solvent now, such as, can enumerate alcohols, ketone, hydro carbons
Deng, if using the poor solvent of more than 3 kinds in these solvents, then purification efficiency improves further, the most preferably.
Polyimide precursor or the molecules of polyimides such as polyamic acid contained in the aligning agent for liquid crystal of the present invention
Amount, in the case of operability when being formed in view of thus obtained painting film strength and film, the uniformity of film, profit
The weight average molecular weight measured by GPC (gel permeation chromatography) method is preferably 5000～1000000, more preferably 10000～150000.
<aligning agent for liquid crystal>
The aligning agent for liquid crystal of the present invention, refers to form the coating fluid that liquid crystal orientation film is used, and is by selected from upper
Obtained by the additive of at least one polymer and the present invention of stating polyimide precursor and polyimides is dissolved in organic solvent
Solution.Solid component concentration in the aligning agent for liquid crystal of the present invention can be according to the setting of the liquid crystal aligning film thickness formed
Suitably change, preferably 0.5～10 mass %, more preferably 1～8 mass %.Solid component concentration is then difficult to less than 0.5 mass %
Formed uniformly and do not have defective film, being deteriorated higher than the storage stability of 10 mass % solution the most sometimes.Solid herein becomes
Point, for the composition outside solvent in aligning agent for liquid crystal, i.e. refer to selected from least one of above-mentioned polyimide precursor and polyimides
Polymer, the additive of the present invention and following various additive.Specifically, the determination step of solid component content is, will
A small amount of aligning agent for liquid crystal is put in the most weighed aluminium vessel and weighs, and then heats 1 in 200 DEG C of baking ovens little
Time make solvent evaporate, afterwards aluminium vessel is weighed.Can calculate according to the numerical value obtained.
There is no particular limitation for the manufacture method of the aligning agent for liquid crystal of the present invention.Generally by polyimide solution or
The polyimide precursor solution such as polyamic acid mix with the solution of polyimides and manufacture.Before using the polyimides such as polyamic acid
In the case of body, polyamic acid reaction solution that polycondensation obtain be can be used directly, or in the case of having obtained polyamic acid,
The polyamic acid solution being again dissolved in organic solvent obtaining can be used.Polyamic acid solution can be dilute according to desired concn
Release use.
On the other hand, in the case of polyimides, the soluble polyimide reaction of imidizate gained be can be used directly
Solution, or in the case of having obtained polyimide powder, can use and again be dissolved in obtained in organic solvent
Polyimide solution.Polyimide solution can use according to desired concn dilution.
The organic solvent that the aligning agent for liquid crystal of the present invention is used, as long as solubilized is before above-mentioned polyimides
The organic solvent of at least one condensate (hereinafter also referred to resinous principle) of body and polyimides, is not particularly limited.Under
Face enumerates its object lesson.
Can enumerate N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, oneself is interior for N-methyl
Acid amides, 2-Pyrrolidone, N-ethyl pyrrolidone, NVP, dimethyl sulfoxide, tetramethylurea, pyridine, diformazan
Sulfone, pregnancy sulfoxide, gamma-butyrolacton, 3-methoxyl group-N, N-dimethylpropionamide, 3-ethyoxyl-N, N-dimethylpropionamide, 3-
Butoxy-N, N-dimethylpropionamide, 1,3-dimethyl-2-imidazolidinone, ethyl pentyl group ketone, methyl nonyl ketone, methyl ethyl ketone,
Methyl isoamyl ketone, methyl isopropyl Ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4-hydroxyl-
4-methyl-2 pentanone etc..These solvents can be used alone, it is also possible to is used in mixed way.
The aligning agent for liquid crystal of the present invention can comprise composition other than the above.Object lesson has, and improves coating of liquid crystalline
Film thickness uniformity during aligning agent or the solvent of surface smoothness or additive, raising liquid crystal orientation film and substrate closely sealed
The additive etc. of property.
As the concrete example of the solvent (poor solvent) of the above-mentioned uniformity that can improve thickness or surface smoothness, can enumerate
Following material.Such as can enumerate isopropanol, methoxy amylalcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, first
Base cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylcarbitol acetate, second two
Alcohol, ethylene glycol acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propane diols, Propylene glycol monoacetate, the third two
Alcohol monomethyl ether, propylene glycol t-butyl ether, DPGME, diethylene glycol, diethylene glycol monoacetate, diethylene glycol
Dimethyl ether, dipropylene glycol monoacetate monomethyl ether, DPGME, dihydroxypropane single-ethyl ether, DPG list
Acetic acid esters list ethylether, DPG list propyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxybutyl
Acetic acid esters, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, acetic acid
Pentyl ester, butyl butyrate, butyl ether, DIBK, methylcyclohexene, propyl ether, two hexyl ethers, 1-hexanol, n-hexane, pentane, just
Octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate list ethyl
Ether, methyl pyruvate, ethyl pyruvate, 3-methoxy methyl propionate, 3-ethoxy-propionic acid Methylethyl ester, 3-methoxypropionic acid
Ethyl ester, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 1-methoxyl group-2-
Propyl alcohol, 1-ethyoxyl-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, Propylene glycol monoacetate, propane diols two
Acetic acid esters, propane diols-1-monomethyl ether-2-acetic acid esters, propane diols-1-list ethylether-2-acetic acid esters, DPG, 2-(2-second
Epoxide propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate or isoamyl lactate etc. have low table
The solvent of surface tension.
These poor solvents can use a kind, or is used in mixed way multiple.When using solvent as above, preferably
5～80 mass % of solvent total amount contained in aligning agent for liquid crystal, more preferably 20～60 mass %.
As above-mentioned raising film thickness uniformity or the additive of surface smoothness, fluorine class surfactant, silica can be enumerated
Alkanes surfactant, nonionic surfactant etc..
More specifically, エ Off ト ッ プ EF301, EF303, EF352 (illuminating product Co., Ltd. (ト ケ system such as can be enumerated
プ ロ ダ クツ society) system), メ ガ Off ァ ッ Network F171, F173, R-30 (big Japanese ink Co., Ltd. (big Japan イ Application キ society)
System), Off ロ ラ De FC430, FC431 (Sumitomo 3M Co., Ltd. (Sumitomo ス リ エ system society) system), ア サ ヒ ガ De
AG710, サ Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd's (rising sun nitre
Sub-society) system) etc..The tree that the usage rate of these surfactants contains in the aligning agent for liquid crystal relative to 100 mass parts
Fat composition, preferably 0.01～2 mass parts, more preferably 0.01～1 mass parts.
As above-mentioned raising liquid crystal orientation film and the concrete example of the additive of the adaptation of substrate, can enumerate shown below
Compound containing functional silanes and the compound etc. containing epoxy radicals.
Such as, 3-TSL 8330, APTES, 2-aminopropyl three can be enumerated
Methoxy silane, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-
Amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-ureido-propyl trimethoxy silane, 3-ureido-propyl three ethoxy
Base silane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-3-aminopropyl triethoxysilicane
Alkane, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-
Trimethoxysilyl-1,4,7-three azepine decane, 10-triethoxysilyl-1,4,7-three azepine decane, 9-front three
Epoxide silicyl-3,6-diaza nonyl acetic acid esters, 9-triethoxysilyl-3,6-diaza nonyl acetic acid esters, N-
Benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-aminopropyl three
Double (the oxyethylene group)-3-aminopropyl trimethoxy silicon of methoxy silane, N-phenyl-APTES, N-
Double (the oxyethylene group)-APTES of alkane, N-, ethylene glycol diglycidylether, polyethylene glycol diglycidyl are sweet
Oil ether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol two
Glycidol ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol 2-glycidyl
Ether, 1,3,5,6-four glycidyl group-2,4-hexylene glycol, N, N, N ', N ' ,-four glycidyl group-m-xylene diamine, 1,3-
Double (N, N-diglycidyl amino methyl) hexamethylene, N, N, N ', N ' ,-four glycidyl group-4,4 '-diamino-diphenyl
Methane etc..
[liquid crystal orientation film]
The aligning agent for liquid crystal of the present invention, preferably filters before coating substrate, coats afterwards on substrate, through dry
Dry, burn till and make film, after the orientation process such as the rubbed process of this film coated surface or illumination, as the liquid crystal orientation film of the present invention
Use.
At this moment, as long as the high substrate of the substrate used transparency is then without particularly restriction, it is possible to use glass substrate, third
The plastic bases etc. such as olefin(e) acid substrate or polycarbonate substrate, from the angle making production technology simplify, are preferably used and are formed
Substrate for the ITO electrode etc. of liquid crystal drive.It addition, in reflection type liquid crystal display element, it is possible to use silicon wafers etc. are impermeable
Bright substrate, but it is only limitted to the substrate of one side, electrode now can also use the reflectorized materials such as aluminium.
As the coating process of aligning agent for liquid crystal, spin-coating method, print process, ink-jet method etc. can be enumerated, but from productivity
From the standpoint of, industrial circle is widely used flexographic printing process, and the method can be also suitably used for the aligning agent for liquid crystal of the present invention.
Although the drying process after coating of liquid crystalline aligning agent is not required in that, but after coating to before burning till
In the case of not fixing or burn till the most immediately after coating for every piece of substrate during this period of time, preferably comprise dry
Operation.This is dried and makes solvent evaporation reach the degree that film shape will not deform because of reasons such as the carryings of substrate, to being dried
There is no particular limitation for means.Specifically can enumerate following method so that it is 50～150 DEG C, on the hot plate of preferably 80～120 DEG C
Dry 0.5～30 minute, more preferably 1～5 minute.
The burning till of substrate being coated with aligning agent for liquid crystal can be carried out under the arbitrary temp in 100～350 DEG C, but
Preferably 150～300 DEG C, more preferably 180 DEG C～250 DEG C.The polyamic acid contained in aligning agent for liquid crystal acyl in sintering process
The conversion ratio that amino acid converts to acid imide is varied from, but polyamic acid is without 100% imidizate.Preferably with more brilliant than liquid crystal
In born of the same parents' manufacturing engineering, the temperature of high more than 10 DEG C of the heat treatment temperature of necessary sealant cures etc. is burnt till.
If the film after burning till is blocked up, then the consumption concerned power at liquid crystal display cells is unfavorable, if the thinnest, then has
Time liquid crystal display cells reliability reduce, the most preferably 10～200nm, more preferably 50～100nm.
The friction treatment of the coated surface on substrate formed as discussed above can use existing rubbing device.Rubbing at this moment
The material of wiper can enumerate cotton, artificial silk, nylon etc..
The liquid crystal display cells of the present invention is to be obtained band liquid crystal by said method by the aligning agent for liquid crystal of the present invention
After the substrate of alignment films, the liquid crystal display cells formed by known method manufacture liquid crystal cell.
If for an example manufacturing liquid crystal cell, usually using following method: will be formed with liquid crystal
A pair substrate folder of alignment films across preferably 1～30 μm, more preferably 2～10 septs of μm, according to make frictional direction become 0～
Requirement at any angle in 270 ° is arranged, and is fixed periphery with sealant, seals after injecting liquid crystal.To the method enclosing liquid crystal
Have no particular limits, can enumerate inject the vacuum method of liquid crystal after reducing pressure in prepared liquid crystal cell, drip liquid crystal
After carry out the method etc. of dripping that seals.
The after image characteristic of the liquid crystal display cells obtained by the aligning agent for liquid crystal of the use present invention and liquid crystal aligning
Well, the bad or adjoint ultraviolet light of display that the liquid crystal aligning membrane damage occurred during friction treatment, adjoint film are peeled off irradiates
Electrical characteristics lowly have and significantly alleviate, it is possible to as the liquid crystal display device that reliability is higher.
Embodiment
Embodiment shown below is detailed description further to the present invention, but the explanation of the present invention is not limited to this.
[synthesis of additive]
The synthesis example of additive in the present invention is shown.The each assay method and the analytical equipment that use are as described below.
<mensuration of NMR>
Compound is dissolved in deuterochloroform, uses 400MHz's1H NMR (Varian Associates, Inc. (US) 611 Hansen Way, Palo Alto, California 94303, U.S.A. (バ リ ア Application society)) surveys
Fixed.
The synthesis of (synthesis example 1) additive (M1)
Double (4-Fonnylphenyl) aniline 11.5g and oxolane is added in 500mL (L is for rising) four-hole boiling flask
230g, ice bath cools down.At temperature 0 DEG C, the tetrahydrofuran solution 60.1mL of the chlorovinyl magnesium of 1.46 moles/L of concentration of dripping,
It is stirred at room temperature 18 hours.Afterwards, add 15wt% aqueous ammonium chloride solution, be extracted with ethyl acetate.Organic layer adds
Anhydrous magnesium sulfate, removes solvent with rotary evaporator after filtration, obtains bronzing viscous liquid 13.2g.
The result measuring this bronzing liquid with NMR is as follows.From described results verification, the bronzing liquid of gained is
Following formula (M-1).
1H NMR (400MHz, CDCl3): δ 7.28-7.21 (m, 6H), 7.10-6.99 (m, 7H), 6.07 (ddd, 2H),
5.40-5.34 (m, 2H), 5.24-5.15 (m, 4H), 1.88 (d, 2H)
[changing 17]
The synthesis of (synthesis example 2) additive (M2)
4-(N, N-diphenyl amino) benzaldehyde 11.7g and oxolane 240g, ice is added in 500mL four-hole boiling flask
Bath cooling.At temperature 0 DEG C, the tetrahydrofuran solution 32.3mL of the chlorovinyl magnesium of 1.46 moles/L of concentration of dripping, in room temperature
Lower stirring 48 hours.Afterwards, add 15wt% aqueous ammonium chloride solution, be extracted with ethyl acetate.Anhydrous sulphur is added in organic layer
Acid magnesium, removes solvent with rotary evaporator after filtration, obtains bronzing viscous liquid 12.6g.
The result measuring this bronzing liquid with NMR is as follows.From described results verification, the bronzing liquid of gained is
Following formula (M2).
1H NMR (400MHz, CDCl3): δ 7.27-7.21 (m, 6H), 7.10-6.98 (m, 8H), 6.08 (ddd, 1H),
5.40-5.34 (m, 1H), 5.24-5.14 (m, 2H), 1.88 (d, 1H)
[changing 18]
The synthesis of (synthesis example 3) additive (M3)
Adding double (4-Fonnylphenyl) aniline 11.5g and methyl alcohol 220g in 500mL four-hole boiling flask, ice bath cools down.
At temperature 0 DEG C, add sodium borohydride 3.1g, be stirred at room temperature 24 hours.After ice bath cooling, add 10wt% ammonium chloride
The aqueous solution, is extracted with ethyl acetate.Organic layer adds water after carrying out separatory, in organic layer, add anhydrous magnesium sulfate.Filter
Remove solvent with rotary evaporator after magnesium sulfate, obtain white solid 11.6g.
The result measuring this white solid with NMR is as follows.From described results verification, the white solid of gained is following formula
(M3)。
1H NMR (400MHz, CDCl3): δ 7.27-7.22 (m, 6H), 7.10-7.05 (m, 6H), 7.05-6.99 (m, 1H),
4.64 (d, 4H), 1.60 (t, 2H)
[changing 19]
The synthesis of (synthesis example 4) additive (M4)
Adding double (4-Fonnylphenyl) aniline 13.0g and methyl alcohol 260g in 500mL four-hole boiling flask, ice bath cools down.
At temperature 0 DEG C, add sodium borohydride 2.0g, be stirred at room temperature 9 hours.After ice bath cooling, add 10wt% ammonium chloride
The aqueous solution, is extracted with ethyl acetate.Organic layer adds water after carrying out separatory, in organic layer, add anhydrous magnesium sulfate.Filter
Remove solvent with rotary evaporator after magnesium sulfate, obtain white solid 13.0g.
The result measuring this white solid with NMR is as follows.From described results verification, the white solid of gained is following formula
(M4)。
1H NMR (400MHz, CDCl3): δ 7.27-7.22 (m, 6H), 7.10-7.05 (m, 6H), 7.04-6.99 (m, 2H),
4.64 (d, 2H), 1.58 (t, 1H)
[changing 20]
[polyamic acid and the synthesis of polyimides]
The synthesis example of the resin in the present invention and resin solution is shown.The each assay method used and the following institute of analytical equipment
State.
The explanation of abbreviation used
<tetracarboxylic dianhydride>
CBDA:1,2,3,4-cyclobutane tetracarboxylic dianhydride
TDA:3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride
PMDA: pyromellitic acid anhydride
BODA: dicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride
TCA:2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride
<diamines>
DDM:4,4 '-diaminodiphenyl-methane
PDA: p-phenylenediamine
APC18:1,3-diaminourea-4-octadecane epoxide benzene
DADPA:4,4 '-diamino-diphenylamine
<organic solvent>
NMP:N-N-methyl-2-2-pyrrolidone N
γ-BL: butyrolactone
BCS: butyl cellosolve
<mensuration of molecular weight>
The molecular weight of polyimides measures this polyimides by using GPC (normal temperature gel permeation chromatography) device and obtains
, calculate number-average molecular weight and weight average molecular weight as polyethylene glycol, PEO scaled value.
GPC device: Showa Denko K. K ((strain) Shodex society) system (GPC-101)
Post: Showa Denko K. K's system (series connection of KD803, KD805)
Column temperature: 50 DEG C
Eluent: N, N'-dimethylformamide is (as additive, lithium bromide-hydrate (LiBr H2O) it is 30mmol/
L, phosphoric acid anhydrous crystal (o-phosphoric acid) are 30mmol/L, oxolane (THF) is 10mL/L)
Flow velocity: 1.0mL/ minute
Calibration curve making standard specimen: TOSOH Co., Ltd (ソ society) TSK processed standard PEO (molecule
Amount is about 900000,150000,100000,30000), and Polymer Laboratory company (Port リ マ ラ ボ ラ ト リ society) makes
Polyethylene glycol (molecular weight is about 12000,4000,1000).
<mensuration of acid imide rate>
The acid imide rate of polyimides calculates as follows: this polyimides is dissolved in d6-DMSO (dimethyl sulfoxide-d6),
With 400MHz's1H NMR (Varian Associates, Inc.'s system) is measured, the ratio of the integrated value of proton peak try to achieve non-imidizate and residual
The ratio of the acid amides acidic group deposited, thus calculate acid imide rate.
[the manufacture example of polymer solution]
(manufacturing example 1)
APC18 and NMP206g adding PDA11.7g, 4.5g in the four-hole boiling flask of 500mL dissolves, and adds
TDA35.3g.Under blanket of nitrogen, at room temperature reaction 11 hours, prepare polymer solution (P-1).
In polymer solution (P-1) 180g obtained add 270gNMP be diluted, add acetic anhydride 56.2g and
Pyridine 43.5g, at 40 DEG C, reaction carries out imidizate in 3 hours.After this reaction solution is cooled to room temperature, put into extremely
In 2000mL methyl alcohol, reclaim the solid matter of precipitation.Then, after this solid matter is cleaned for several times with methyl alcohol, the temperature of 100 DEG C
The lower drying under reduced pressure of degree, obtains white powder.The number-average molecular weight of this polyimides is 6500, and weight average molecular weight is 14400.This
Outward, acid imide rate is 80%.
In the eggplant-shape bottle of 1L, add 24g gained powder and γ-BL216g, stir 14 hours at 50 DEG C, obtain polymer
Solution (P-2).In the polymer solution (P-2) obtained, add BCS120g and γ-BL40g, be stirred at room temperature 18 hours,
Obtain polymer solution (P-3).
(manufacturing example 2)
In the four-hole boiling flask of 500mL, add DDM39.6g, NMP222g and γ-BL222g dissolve, add
CBDA19.6g and PMDA19.2g.Under blanket of nitrogen, at room temperature 5 hours prepared polymer solutions (P-4) of reaction.This polymer
Number-average molecular weight is 10900, and weight average molecular weight is 27300.
In the polymer solution (P-4) that 400g obtains, add γ-BL450g and BCS150g, be stirred at room temperature 2 little
Time, obtain polymer solution (P-5).
(manufacturing example 3)
By the polymer solution (P-3) obtained in 50g resin manufacture example 1 and being polymerized of obtaining in 400g resin manufacture example 2
Thing solution (P-5) is stirred at room temperature 20 hours, obtains polymer solution (P-6).
(manufacturing example 4) BODA/DADPA
In the four-hole boiling flask of 500mL, add DADPA39.9g and NMP356g dissolve, add BODA49.0g.Nitrogen
Under atmosphere, at 50 DEG C, react 24 hours prepared polymer solutions (P-7).The number-average molecular weight of this polymer is 13100, and weight average divides
Son amount is 31300.
In the polymer solution (P-7) that 300g obtains, add NMP500g and BCS200g, be stirred at room temperature 2 hours,
Obtain polymer solution (P-8).
(manufacturing example 5) TCA/PDA
In the four-hole boiling flask of 500mL, add PDA21.6g and NMP369g dissolve, add TCA43.5g.Blanket of nitrogen
Under, at 50 DEG C, react 24 hours prepared polymer solutions (P-9).The number-average molecular weight of this polymer is 12700, Weight-average molecular
Amount is 24300.
In the polymer solution (P-9) that 400g obtains, add NMP400g and BCS200g, be stirred at room temperature 2 hours,
Obtain polymer solution (P-10).
[aligning agent for liquid crystal]
(embodiment 1,3,5,7,9,10,11,12)
In 100mL eggplant-shape bottle, as shown in table 1 below, add 20.0g above-mentioned each polymer solution (P-3, P-6, P-8 or P-
10) and 0.06g compound (M1, M2, M3 or M4) stirring a hour, respectively obtain aligning agent for liquid crystal (C1, C3, C5,
C7、C9、C10、C11、C12)。
(embodiment 2,4)
In 100mL eggplant-shape bottle, as shown in table 1 below, add 20.0g above-mentioned polymer solution P-6 and 0.036g chemical combination
Thing (M1 or M3) also stirs one hour, respectively obtains aligning agent for liquid crystal (C2, C4).
(embodiment 6)
In 100mL eggplant-shape bottle, as shown in table 1 below, add 20.0g above-mentioned polymer solution P-3 and 0.12g compound
M2 also stirs one hour, obtains aligning agent for liquid crystal (C6).
(embodiment 8)
In 100mL eggplant-shape bottle, as shown in table 1 below, add 20.0g above-mentioned polymer solution P-3 and 0.012g chemical combination
Thing M2 also stirs one hour, obtains aligning agent for liquid crystal (C8).
(comparative example 1)
In 100mL eggplant-shape bottle, add the triphenylamine (hereinafter referred to as TPA) of 20.0g polymer solution P-3 and 0.06g
And stir one hour, obtain aligning agent for liquid crystal C13.
[table 1]
<making of liquid crystal cell>
(embodiment 13)
Aligning agent for liquid crystal C1 shown in table 1 is spun on the glass substrate of band transparency electrode, the heating of 80 DEG C
It is dried after 70 seconds on plate, the heating plate of 235 DEG C carries out 10 minutes burn till, forms the film that thickness is 100nm.Use roller
The rubbing device of footpath 120mm under conditions of roller rotating speed 1000rpm, roller gait of march 50mm/ second, intrusion 0.3mm with artificial
This coated surface is rubbed by silk cloth, obtains the substrate of band liquid crystal orientation film.
Prepare 2 substrates with above-mentioned liquid crystal orientation film, the most a piece of liquid crystal aligning face spreads between 6 μm
Parting, the most thereon printing and sealing agent, another plate base of fitting is so that liquid crystal aligning face is relative and frictional direction is orthogonal, so
After make sealant cures, prepare negative crystal box.Liquid crystal MLC-2003 (C080) (Merck is injected by decompression injection method in negative crystal box
Company (メ ルク society) system), seal inlet, obtain Twisted Nematic liquid crystal structure cell.
Assay method and the UV illuminating method of the characteristic of each liquid crystal cell made are as described below.
<mensuration of accumulated charge (RDC)>
To the Twisted Nematic liquid crystal structure cell manufactured by the method described in above-mentioned<making of liquid crystal cell>, at 23 DEG C
At a temperature of apply DC voltage with the interval of 0V～0.1V until 1.0V, measure the flicker amplitude level under each voltage, make school
Positive curve.After ground connection 5 minutes, apply alternating voltage 3.0V, DC voltage after 5.0V1 hour, only DC voltage be 0V it
After immediately measure flicker amplitude level, by compare ready-made calibration curve estimate RDC.(the estimating and measuring method of this RDC
It is referred to as flashing reference entry (Off リッカ reference entry))
Herein, the RDC value measured immediately after applying DC voltage 5.0V1 hour to this RDC value is reduced used by 50%
Time improves the time as RDC.During the structure cell made in evaluating embodiment 13, the RDC improvement time is 0.35 second.
<UV irradiation>
To the Twisted Nematic liquid crystal structure cell made by the method described in above-mentioned<making of liquid crystal cell>, use SEN
The light that the desk-top UV solidification equipment HCT3B28HEX-1 that special light sources company (セ Application special light sources society) makes is carried out 167 seconds irradiates.
Illumination now uses illumination photometer (CRC company (CRC society) UV Light MEASUREMODEL UV-M02) and UV-35 sensor
Being measured, recording illumination is 60.0mW/cm2。
<mensuration of voltage retention (VHR)>
The method using above-mentioned<UV irradiation>was carried out the voltage retention of the Twisted Nematic liquid crystal structure cell of process
It is determined as follows and carries out: at a temperature of 90 DEG C, this liquid crystal cell is applied voltage 60 microsecond of 4V, after measuring 16.67 milliseconds
Voltage, calculates voltage and can keep how many, and this is as voltage retention.Additionally, the mensuration of voltage retention uses special gram of Dongyang
The VHR-1 voltage retention determinator that Niker Co., Ltd. (テ Network ニ カ society) makes.
Being evaluated the structure cell made in embodiment 1, voltage retention is 47%.
(embodiment 14～16 and comparative example 2)
Use same method with embodiment 13, use the aligning agent for liquid crystal shown in table 2 and above-mentioned P-6 to prepare respectively
Polymer solution, makes Twisted Nematic liquid crystal structure cell.After above-mentioned each liquid crystal cell has been carried out RDC improvement time and UV process
The evaluation of VHR.Result is shown in Table 2.
[table 2]
(embodiment 17～24 and comparative example 3～4)
Use same method with above-described embodiment 13～16, make Twisted Nematic liquid crystal structure cell respectively.To above-mentioned each liquid
Jingjing born of the same parents have carried out RDC and have improved time and the evaluation of rub resistance.Result is shown in Table 3.
It addition, rub resistance makes following evaluation.
<evaluation of rub resistance>
The checking test of rub resistance is as follows: the condition changing 0.5mm with the amount of will be pressed into into rubs, with focal argon laser altogether
Microscope observes film surface.Evaluation is carried out as follows.
Zero: do not observe friction abrasive dust
×: observe friction abrasive dust
[table 3]
| Aligning agent for liquid crystal | RDC improves the time (minute) | (rub) | |
| Embodiment 17 | C5 | 7 | ○ |
| Embodiment 18 | C6 | 7 | ○ |
| Embodiment 19 | C7 | 7 | ○ |
| Embodiment 20 | C8 | 15 | ○ |
| Embodiment 21 | C9 | 9 | ○ |
| Embodiment 22 | C10 | 13 | ○ |
| Embodiment 23 | C11 | 1.0 | ○ |
| Embodiment 24 | C12 | 1.5 | ○ |
| Comparative example 3 | P-3 | 28 | ○ |
| Comparative example 4 | C13 | 13 | × |
The possibility utilized in industry
The aligning agent for liquid crystal of the present invention has the time needed for shortening the after image disappearance caused by DC voltage, carries
High ultraviolet resistance and do not lower the effect of wearing character, can perform well in TN element, STN element, TFT liquid crystal cell, spy
The formation of the liquid crystal orientation film not being vertically oriented in type liquid crystal cell etc..
Here quote the specification of Japanese patent application 2011-118371, power that on May 26th, 2011 files an application
The full content of profit claim and specification digest is as the announcement of description of the invention.
Claims (8)
1. aligning agent for liquid crystal, it is characterised in that containing at least one polymerization selected from polyimide precursor and polyimides
Thing, and the compound that following formula [1] represents,
[changing 1]
In formula, R1Representing hydrogen atom or vinyl, n represents the integer of 0～2.
2. aligning agent for liquid crystal as claimed in claim 1, it is characterised in that sub-selected from polyamides relative to 100 mass parts
At least one polymer of amine precursor and polyimides, the compound represented by formula [1] containing 0.1～10 mass parts.
3. aligning agent for liquid crystal as claimed in claim 1 or 2, it is characterised in that the R in formula [1]1For vinyl.
4. aligning agent for liquid crystal as claimed in claim 1, it is characterised in that the compound represented by formula [1] be following M1,
M2, M3 or M4,
[changing 2]
5. aligning agent for liquid crystal as claimed in claim 1, it is characterised in that containing the solid constituent of 0.5～10 mass %.
6. liquid crystal orientation film, it is characterised in that obtained by the aligning agent for liquid crystal according to any one of Claims 1 to 5.
7. liquid crystal display cells, it is characterised in that possess the liquid crystal orientation film described in claim 6.
8. the compound represented by following formula (2),
[changing 3]
In formula, n represents the integer of 0～2.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011118371 | 2011-05-26 | ||
| JP2011-118371 | 2011-05-26 | ||
| PCT/JP2012/063548 WO2012161329A1 (en) | 2011-05-26 | 2012-05-25 | Liquid crystal aligning agent and liquid crystal display element using same |
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| CN103718090B true CN103718090B (en) | 2016-08-17 |
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| JP (1) | JP6056754B2 (en) |
| KR (1) | KR101829501B1 (en) |
| CN (1) | CN103718090B (en) |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5571579A (en) * | 1992-07-24 | 1996-11-05 | Hitachi Chemical Company, Ltd | Alignment film for liquid crystal, liquid crystal-sandwiched panel, liquid crystal display module and material for liquid crystal alignment film |
| CN1359403A (en) * | 1999-06-30 | 2002-07-17 | 日产化学工业株式会社 | Diaminobenzene derivative, polyimide obtained thereform, and liquid-crystal alignment film |
| CN1720280A (en) * | 2002-12-11 | 2006-01-11 | 日产化学工业株式会社 | Novel diaminobenzene derivative, polyimide precursor and polyimide obtained therefrom, and aligning agent for liquid crystal |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1366107A4 (en) * | 2001-01-02 | 2004-05-12 | Univ Akron | Polyimide lcd alignment layers |
| JP2005321687A (en) | 2004-05-11 | 2005-11-17 | Konica Minolta Business Technologies Inc | Image forming apparatus and image forming method |
| JP2006151817A (en) * | 2004-10-25 | 2006-06-15 | Yamaguchi Univ | New diamino aromatic carbonyl compound |
| JP5451306B2 (en) * | 2009-10-23 | 2014-03-26 | 株式会社ジャパンディスプレイ | Liquid crystal display |
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2012
- 2012-05-25 WO PCT/JP2012/063548 patent/WO2012161329A1/en active Application Filing
- 2012-05-25 JP JP2013516465A patent/JP6056754B2/en active Active
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5571579A (en) * | 1992-07-24 | 1996-11-05 | Hitachi Chemical Company, Ltd | Alignment film for liquid crystal, liquid crystal-sandwiched panel, liquid crystal display module and material for liquid crystal alignment film |
| CN1359403A (en) * | 1999-06-30 | 2002-07-17 | 日产化学工业株式会社 | Diaminobenzene derivative, polyimide obtained thereform, and liquid-crystal alignment film |
| CN1720280A (en) * | 2002-12-11 | 2006-01-11 | 日产化学工业株式会社 | Novel diaminobenzene derivative, polyimide precursor and polyimide obtained therefrom, and aligning agent for liquid crystal |
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| TWI542620B (en) | 2016-07-21 |
| CN103718090A (en) | 2014-04-09 |
| KR20140028071A (en) | 2014-03-07 |
| JP6056754B2 (en) | 2017-01-11 |
| JPWO2012161329A1 (en) | 2014-07-31 |
| KR101829501B1 (en) | 2018-02-14 |
| WO2012161329A1 (en) | 2012-11-29 |
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