CN101153996A - Liquid crystal aligning agent and liquid crystal display element - Google Patents
Liquid crystal aligning agent and liquid crystal display element Download PDFInfo
- Publication number
- CN101153996A CN101153996A CNA2007101518817A CN200710151881A CN101153996A CN 101153996 A CN101153996 A CN 101153996A CN A2007101518817 A CNA2007101518817 A CN A2007101518817A CN 200710151881 A CN200710151881 A CN 200710151881A CN 101153996 A CN101153996 A CN 101153996A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- hydrogen atom
- group
- aligning agent
- dicarboxylic anhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
- 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
- C08L79/02—Polyamines
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
Abstract
The invention provides a liquid crystal aligning film maintaining the voltage retention rate and reducing the accumulated charges with a good printing performance. The liquid crystal aligning agent has the compound containing the following formula (I), in which R1-R8 is respectively independent hydrogen atom, alkyl, or alkoxy group, R9-R12 is respectively independent hydrogen atom, aromatic group or aliphatic group. A is hydrogen atom or aliphatic group, n is an integer from 1 to 100.
Description
Technical field
The present invention relates to aligning agent for liquid crystal and liquid crystal display cells.More particularly, relate to and to form electrical property good and the aligning agent for liquid crystal of the liquid crystal orientation film that printing is good and the liquid crystal display cells that contains this liquid crystal orientation film.
Background technology
At present, as liquid crystal display cells, known TN type liquid crystal display cells with so-called TN (Twisted Nematic) type liquid crystal cell, it is being provided with the liquid crystal orientation film that formation is formed by polyamic acid, polyimide etc. on the substrate surface of nesa coating, substrate as used for liquid crystal display element, 2 these substrates are oppositely arranged, form nematic crystal layer betwixt in the crack with positive dielectric anisotropy, constitute the box of sandwich construction, the major axis of liquid crystal molecule is turned round continuously to another piece substrate from a substrate and is turn 90 degrees.And, also developed and compared the STN that contrast is higher, its view angle dependency is littler (Super Twisted Nematic) type liquid crystal display cells and vertical alignment-type liquid crystal display device with TN type liquid crystal display cells.This STN type liquid crystal display cells will be in nematic crystal fusion use as liquid crystal as the liquid crystal of the chirality agent of optically active substance, it utilizes by the major axis that makes liquid crystal molecule and be in the birefringence effect that the state of turning round the above amplitude of turnback continuously produces between substrate.By contrast, as described in non-patent literature 1 and patent documentation 1, proposed on ITO, to form the vertical alignment-type liquid crystal display device that is called the MVA type that projection is controlled the liquid crystal aligning direction.Not only visual angle, contrast etc. are good for MVA type liquid crystal display cells, and can also not carry out grinding process etc. in the process that forms liquid crystal orientation film, thereby also are good aspect manufacturing process.As the liquid crystal orientation film that is applicable to TN, STN, MVA type, need the performances such as image retention elimination time weak point of liquid crystal display cells.In addition, as forming the used alignment agent of this liquid crystal orientation film, require in hectographic printing, to have superior printing characteristics.
[non-patent literature 1] " liquid crystal " Vol.3No.2,117 (1999)
[patent documentation 1] Japanese kokai publication hei 11-258605 communique
Summary of the invention
The present invention makes in view of the above problems, its objective is to provide can be formed in to make the liquid crystal orientation film of accumulating the electric charge minimizing and the liquid crystal display cells that has the aligning agent for liquid crystal of superior printing characteristics and adopt this liquid crystal orientation film when keeping voltage retention again.
Other purposes of the present invention and advantage can be found out by the following description.
According to the present invention, above-mentioned purpose of the present invention and advantage, the first, reach by a kind of aligning agent for liquid crystal, it is characterized in that containing the compound (below, be also referred to as specific compound) of following formula (I) expression,
(in the formula, R
1～R
8Be hydrogen atom, alkyl or alkoxy independently of one another, R
9～R
12Be hydrogen atom, aromatic group or aliphatic group independently of one another, A is hydrogen atom or aliphatic group, and n is 1～100 integer).
Following compound is preferred compound in the above-mentioned formula (I), R
1～R
8Independently of one another for hydrogen atom, carbon number are that 1～6 alkyl or carbon number are 1～6 alkoxy, R
9～R
12Be hydrogen atom, A is a hydrogen atom, and n is 1～100 integer.
Following compound is other preferred compounds in the above-mentioned formula (I), R
1～R
8Independently of one another for hydrogen atom, carbon number are that 1～6 alkyl or carbon number are 1～6 alkoxy, R
9And R
11Be aromatic group, R
10And R
12Be hydrogen atom or aliphatic group, A is hydrogen atom or aliphatic group, and n is 1～100 integer.
In addition, following compound is preferred compound in the above-mentioned formula (I), R
1～R
8Independently of one another for hydrogen atom, carbon number are that 1～6 alkyl or carbon number are 1～6 alkoxy, R
9And R
11Be aromatic group, R
10And R
12For hydrogen or contain the aliphatic group of epoxy radicals, A is hydrogen atom or the aliphatic group that contains epoxy radicals, and n is 1～100 integer.
According to the present invention, above-mentioned purpose of the present invention and advantage, the second, reach by a kind of aligning agent for liquid crystal, it is characterized in that containing by R in the above-mentioned formula (I)
1～R
8Independently of one another for hydrogen atom, carbon number are that 1～6 alkyl or carbon number are 1～6 alkoxy, R
9～R
12Be hydrogen atom, A is a hydrogen atom, and n is the above-mentioned preferred compound of 1～100 integer and the polyamic acid polymer of tetrabasic carboxylic acid dicarboxylic anhydride reaction gained (below be also referred to as specific polyamic acid polymer).
In addition, aligning agent for liquid crystal of the present invention can also contain at least a in above-mentioned specific compound and the above-mentioned specific polyamic acid polymer and from the polyamic acid of the repetitive that comprises following formula (I-1) expression with comprise at least a polymkeric substance of selecting the group that the polyimide of the repetitive of (I-2) expression constitutes.
(wherein, P
1Be the organic group of 4 valencys, and Q
1Organic group for divalent),
(wherein, P
2Be the organic group of 4 valencys, and Q
2Organic group for divalent).
Description of drawings
The box that has the ITO electrode that Fig. 1 makes for the print test evaluation.
Embodiment
Below, the present invention is carried out more specific description.
Aligning agent for liquid crystal of the present invention is preferably with at least a of specific compound and specific polyamic acid polymer and be selected from polyamic acid and at least a polymkeric substance of polyimide is dissolved in the organic solvent and constitutes.
[specific compound]
In the formula (I), R
1～R
8Be hydrogen atom, alkyl or alkoxy independently of one another.Alkyl, the preferred carbon number of alkoxy are that 1～6 alkyl, carbon number are 1～6 alkoxy.As alkyl contained in this alkyl and the alkoxy, can enumerate for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, 2-methyl-propyl group, 3-methyl-propyl group, n-pentyl, n-hexyl.R
9～R
12Be hydrogen atom, aromatic group or aliphatic group independently of one another.Preferred hydrogen atom, phenyl, naphthyl, carbon number are 1～4 aliphatic group or the aliphatic group that contains epoxy radicals, can enumerate methyl, ethyl, propyl group, butyl, glycidyl particularly.A is preferably hydrogen atom or carbon number is 1～4 aliphatic group or the aliphatic group that contains epoxy radicals, can enumerate methyl, ethyl, propyl group, butyl, glycidyl particularly.And n is 1～100 integer.
Wherein preferred especially R
1～R
8Be hydrogen, R
9～R
12Be hydrogen atom, methyl, ethyl, phenyl, glycidyl independently of one another, A is hydrogen atom or glycidyl.
As specific compound, can enumerate following compound.
In the above-mentioned specific compound, work as R
9～R
12When being hydrogen atom, make itself and acid dianhydride reaction can make specific polyamic acid polymer.When synthetic this specific polyamic acid polymer,, for example preferably can enumerate 1,2 as acid dianhydride, 3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c] furans-1, the 3-diketone, cis-3,7-dibutyl ring suffering-1,5-diene-1,2,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 3,5,6-three carbonyls-2-carboxyl norbornane-2:3, the 5:6-dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c] furans-1, the 3-diketone, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-and 3-methyl-3-cyclohexene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8,10-tetraketone, pyromellitic acid dicarboxylic anhydride etc.These acid dianhydrides can be used singly or two or more kinds in combination.
In addition, at this moment, except above-mentioned specific compound with two amine structures, can also other diamine compounds of coupling.As preferred other diamine compounds, can enumerate for example p-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfide, 2,2 '-dimethyl-4,4 '-benzidine, 1, the 5-diaminonaphthalene, 2, the 7-diamino-fluorene, 9,9-dimethyl-2, the 7-diamino-fluorene, 4,4 '-diamino-diphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 4,4 '-(right-the phenylene isopropylidene) diphenylamine, 4,4 '-(-the phenylene isopropylidene) diphenylamine, 1, the 4-cyclohexane diamine, 4,4 '-methylene two (cyclohexylamine), 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, 3,6-diamido carbazole, N-methyl-3,6-diamido carbazole, N-ethyl-3,6-diamido carbazole, N-phenyl-3,6-diamido carbazole, N, N '-two (4-aminophenyl)-benzidine, N, N '-two (4-aminophenyl)-N, N '-dimethyl-benzidine etc.These other diamine compounds can be used singly or two or more kinds in combination.
[polyamic acid]
＜tetrabasic carboxylic acid dicarboxylic anhydride 〉
In the present invention, as the above-mentioned polyamic acid beyond the above-mentioned specific polyamic acid polymer synthetic in used tetrabasic carboxylic acid dicarboxylic anhydride, preferred ester ring type tetrabasic carboxylic acid dicarboxylic anhydride.As ester ring type tetrabasic carboxylic acid dicarboxylic anhydride, for example, can enumerate 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-two chloro-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-cyclopentane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,4,5-cyclohexane tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-dicyclohexyl tetrabasic carboxylic acid dicarboxylic anhydride, cis-3,7-dibutyl ring suffering-1,5-diene-1,2,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 3,5,6-three carbonyls-2-carboxyl norbornane-2:3, the 5:6-dicarboxylic anhydride, 2,3,4,5-tetrahydrofuran tetrabasic carboxylic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 5-(2,5-dioxo tetrahydrofuran methylene)-and 3-methyl-3-cyclohexene-1,2-dicarboxylic acid dicarboxylic anhydride, dicyclo [2.2.2]-Xin-7-alkene-2,3,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8,10-tetraketone, following formula (II) and the compound of (III) representing,
(in the formula, R
1And R
3Expression has the divalent organic group of aromatic rings, R
2And R
4Expression hydrogen atom or alkyl, the R of a plurality of existence
2And R
4Separately can be identical, also can be different).
In addition, can also enumerate aliphatics tetrabasic carboxylic acid dicarboxylic anhydrides such as BTCA dicarboxylic anhydride; The pyromellitic acid dicarboxylic anhydride, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic acid dicarboxylic anhydride, 2,3,6,7-naphthalene tetracarboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl ether tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-tetraphenyl silane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-furans tetrabasic carboxylic acid dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenylsulfide dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dicarboxylic anhydride, 3,3 ', 4,4 '-perfluor isopropylidene, two phthalic acid dicarboxylic anhydrides, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dicarboxylic anhydride, 2,2 ', 3,3 '-biphenyltetracarboxyacid acid dicarboxylic anhydride, two (phthalic acid) phosphniline oxide dicarboxylic anhydride, right-phenylene-two (triphenyl phthalic acid) dicarboxylic anhydride, between-phenylene-two (triphenyl phthalic acid) dicarboxylic anhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl ether dicarboxylic anhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl methane dicarboxylic anhydride, ethylene glycol-two (dehydration trimellitate), propylene glycol-two (dehydration trimellitate), 1,4-butylene glycol-two (dehydration trimellitate), 1,6-hexanediol-two (dehydration trimellitate), 1,8-ethohexadiol-two (dehydration trimellitate), 2,2-two (4-hydroxyphenyl) propane-two (dehydration trimellitate), aromatic tetracarboxylic acid's dicarboxylic anhydrides such as compound of following formula (1)～(4) expression.They can a kind be used singly or two or more kinds in combination.
In the above-mentioned tetrabasic carboxylic acid dicarboxylic anhydride, from making the angle of the good liquid crystal aligning of its performance, preferred 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-cyclopentane tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 5-(2,5-dioxo tetrahydrofuran methylene)-and 3-methyl-3-cyclohexene-1,2-dicarboxylic acid dicarboxylic anhydride, cis-3,7-dibutyl ring suffering-1,5-diene-1,2,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 3,5,6-three carbonyls-2-carboxyl norbornane-2:3, the 5:6-dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c] furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c] furans-1, the 3-diketone, dicyclo [2.2.2]-Xin-7-alkene-2,3,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8, the ester ring type tetrabasic carboxylic acid dicarboxylic anhydrides such as compound of following formula (8) expression in the compound of ester ring type tetrabasic carboxylic acid dicarboxylic anhydride such as the compound of following formula (5)～(7) expression in the compound of 10-tetraketone, above-mentioned formula (II) expression and above-mentioned formula (III) expression.As particularly preferred, can enumerate 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, cis-3,7-dibutyl ring suffering-1,5-diene-1,2,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 3,5,6-three carbonyls-2-carboxyl norbornane-2:3, the 5:6-dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c] furans-1, the 3-diketone, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-and 3-methyl-3-cyclohexene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8, the compound of 10-tetraketone and following formula (5) expression.
As preferred tetrabasic carboxylic acid dicarboxylic anhydride in other tetrabasic carboxylic acid dicarboxylic anhydrides beyond the ester ring type tetrabasic carboxylic acid dicarboxylic anhydride, can enumerate for example BTCA dicarboxylic anhydride, pyromellitic acid dicarboxylic anhydride, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydride, 2,2 ', 3,3 '-biphenyltetracarboxyacid acid dicarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic acid dicarboxylic anhydride etc.
In these tetrabasic carboxylic acid dicarboxylic anhydrides, preferred ester ring type tetrabasic carboxylic acid dicarboxylic anhydride is 50 moles more than the % with respect to whole tetrabasic carboxylic acid dicarboxylic anhydrides.
＜diamines 〉
As the above-mentioned polyamic acid beyond the specific polyamic acid polymer synthetic in used diamines, for example, can enumerate p-phenylenediamine, between-phenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ethane, 4,4 '-diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone, 2,2 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene formailide, 4,4 '-diaminodiphenyl ether, 1, the 5-diaminonaphthalene, 3,3-dimethyl-4,4 '-benzidine, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 3,4 '-diamino-diphenyl ether, 3,3 '-diamido benzophenone, 3,4 '-diamido benzophenone, 4,4 '-diamido benzophenone, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 2,2-two [4-(4-amino-benzene oxygen) phenyl] sulfone, 1,4-two (4-amino-benzene oxygen) benzene, 1,3-two (4-amino-benzene oxygen) benzene, 1,3-two (3-amino-benzene oxygen) benzene, 9,9-two (4-aminophenyl)-10-hydrogen anthracene, 2, the 7-diamino-fluorene, 9,9-dimethyl-2, the 7-diamino-fluorene, 9,9-two (4-aminophenyl) fluorenes, 4,4 '-methylene-two (2-chloroaniline), 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamido-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 1,4,4 '-(right-the phenylene isopropylidene) diphenylamine, 4,4 '-(-the phenylene isopropylidene) diphenylamine, 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamido-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-aromatic diamines such as octafluoro biphenyl;
1,1-m-xylene diamine, 1,3-propane diamine, butanediamine, pentanediamine, hexane diamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, 4,4-diamido heptamethylene diamine, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene bicyclopentadiene diamines, six hydrogen-4,7-methanoindene dimethylene diamines, three ring [6.2.1.0
2,7]-undecylene two methanediamines, 4,4 '-methylene two (cyclohexylamine), 1,3-two (amino methyl) cyclohexane, 1, aliphatics and ester ring type diamines such as 4-two (amino methyl) cyclohexane;
2, the 3-diamino-pyridine, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 5,6-diamido-2,3-dicyano pyrazine, 5,6-diamido-2, the 4-dihydroxy-pyrimidine, 2,4-diamido-6-dimethylamino-1,3, the 5-triazine, 1,4-two (3-aminopropyl) piperazine, 2,4-diamido-6-isopropoxy-1,3, the 5-triazine, 2,4-diamido-6-methoxyl-1,3,5-triazines, 2,4-diamido-6-phenyl-1,3, the 5-triazine, 2,4-diamido-6-methyl-s-triazine, 2, the 4-diaminostilbene, 3, the 5-triazine, 4,6-diamido-2-vinyl-s-triazine, 2,4-diamido-5-phenyl thiazole, 2, the 6-diaminopurine, 5,6-diaminostilbene, 3-dimethyl uracil, 3, the 5-diaminostilbene, 2, the 4-triazole, 6,9-diamido-2-ethoxy acridine lactate, 3,8-diamido-6-phenylphenanthridineand, 1,4-diamido piperazine, 3, the 6-proflavin, two (4-aminophenyl) phenyl amine, 3,6-diamido carbazole, N-methyl-3,6-diamido carbazole, N-ethyl-3,6-diamido carbazole, N-phenyl-3,6-diamido carbazole, N, N '-two (4-aminophenyl)-benzidine, N, N '-two (4-aminophenyl)-N has the diamines of the nitrogen-atoms beyond 2 primary amino radicals and this primary amino radical in N '-dimethyl-benzidine equimolecular; The diamido organosiloxane of following formula (IV) expression etc.These diamines can be used in combination separately or more than 2 kinds.
(in the formula, R
5The expression carbon number is 1～12 alkyl, the R of a plurality of existence
5Can be the same or different separately, p is 1～3 integer, and q is 1～20 integer).
Wherein, preferred p-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfide, 2,2 '-dimethyl-4,4 '-benzidine, 1, the 5-diaminonaphthalene, 2, the 7-diamino-fluorene, 9,9-dimethyl-2, the 7-diamino-fluorene, 4,4 '-diaminodiphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 4,4 '-(right-the phenylene diisopropylidene) diphenylamine, 4,4 '-(-the phenylene diisopropylidene) diphenylamine, 1, the 4-cyclohexane diamine, 4,4 '-methylene two (cyclohexylamine), 1,3-two (amino methyl) cyclohexane, 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, 3,6-diamido carbazole, N-methyl-3,6-diamido carbazole, N-ethyl-3,6-diamido carbazole, N-phenyl-3,6-diamido carbazole, N, N '-two (4-aminophenyl)-benzidine etc.
When making aligning agent for liquid crystal of the present invention have tilt angle performance performance, preferred above-mentioned formula (I-1) and (I-2) in Q
1, Q
2Part or all be at least a group of following formula (Q-1) and following formula (Q-2) expression.That is, adopt the diamines (below be also referred to as " specific diamines ") of group with following formula (Q-1) or following formula (Q-2) expression.They can a kind be used singly or two or more kinds in combination.
(in the formula, X be singly-bound ,-O-,-CO-,-COO-,-OCO-,-NHCO-,-CONH-,-S-or arlydene, R
6Be that carbon number is that 10～20 alkyl, carbon number are that 4～40 1 valency organic group with ester ring type skeleton or carbon number are 1 valency organic group of 6～20 contain fluorine atoms).
(in the formula, X be singly-bound ,-O-,-CO-,-COO-,-OCO-,-NHCO-,-CONH-,-S-or arlydene, R
7Be that carbon number is 4～40 the divalent organic group with ester ring type skeleton).
In the above-mentioned formula (Q-1), as R
6The carbon number of expression is 10～20 alkyl, can enumerate for example positive decyl, dodecyl, n-pentadecane base, n-hexadecyl, n-octadecane base, n-eicosane base etc.In addition, as the R of above-mentioned formula (Q-1)
6With the R in the above-mentioned formula (Q-2)
7The carbon number of expression is 4～40 the organic group with ester ring type skeleton, can enumerate the group of the ester ring type skeleton that for example has cycloalkanes such as deriving from cyclo-butane, cyclopentane, cyclohexane, cyclodecane; Group with steroid backbone such as cholesterol, cholestanols; Has the group of endocyclic skeletons such as norborene, diamantane etc.Wherein, the group that especially preferably has steroid backbone.Organic group with above-mentioned ester ring type skeleton can also be by halogen atom, preferred fluorine atom or fluoro-alkyl, the group that preferred trifluoromethyl replaces.
In addition, as the R of above-mentioned formula (Q-1)
6The carbon number of expression is the group of 6～20 contain fluorine atoms, can enumerate carbon numbers such as n-hexyl, n-octyl, positive decyl for example and be the straight chained alkyl more than 6; Carbon numbers such as cyclohexyl, ring octyl group are the ester ring type alkyl more than 6; Carbon number such as phenyl, xenyl is the group that the hydrogen atom of the organic groups such as aromatic hydrocarbyl more than 6 is partly or entirely replaced by fluoro-alkyls such as fluorine atom or trifluoromethyls.
In addition, X in above-mentioned formula (Q-1) and the above-mentioned formula (Q-2) be singly-bound ,-O-,-CO-,-COO-,-OCO-,-NHCO-,-CONH-,-S-or arlydene, as arlydene, can enumerate for example phenylene, methylene phenyl, biphenylene, naphthylene etc.Wherein, be preferably especially-O-,-COO-,-group that OCO-represents.Object lesson as the diamines of group with above-mentioned formula (Q-1) expression, preferably can enumerate dodecyloxy-2,4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, hexadecane oxygen base-2,4-diaminobenzene, octadecane oxygen base-2, the compound of 4-diaminobenzene, following formula (9)～(13) expression.
In addition, as the object lesson of the diamines of group, preferably can enumerate the diamines of following formula (14)～(16) expression with above-mentioned formula (Q-2) expression.
Wherein, as particularly preferred, can enumerate the compound that above-mentioned formula (9), (11), (13), (14) are represented separately.
Specific diamines is with respect to the usage rate of whole diamines amounts, difference for the situation of TN type, STN type liquid crystal display cells, is preferably 0～5 mole of % along with the size of the tilt angle that will make its performance, for the situation of vertical alignment-type liquid crystal display device, be preferably 5～100 moles of %.
Synthesizing of＜polyamic acid 〉
Supply with the tetrabasic carboxylic acid dicarboxylic anhydride of polyamic acid (comprising specific polyamic acid polymer) synthetic reaction and the usage rate of diamines, preferably with respect to the amino of 1 equivalent diamines, the anhydride group that makes the tetrabasic carboxylic acid dicarboxylic anhydride is the ratio of 0.2～2 equivalent, more preferably is the ratio of 0.3～1.2 equivalent.
The synthetic reaction of polyamic acid in organic solvent, is preferable over-20 ℃～150 ℃, more preferably carries out under 0～100 ℃ temperature conditions.
Here, as organic solvent, as long as can dissolve synthetic polyamic acid, then it is had no particular limits, can illustration for example 1-Methyl-2-Pyrrolidone, N,N-dimethylacetamide, N, dinethylformamide, 3-butoxy-N, N-dimethyl propylene acid amides, 3-methoxyl N, N-dimethyl propylene acid amides, the own oxygen base-N of 3-, aprotic polar solvents such as amide solvent, dimethyl sulfoxide (DMSO), gamma-butyrolacton, tetramethylurea, HMPA such as N-dimethyl propylene acid amides; Between phenol solvent such as sylvan, xylenols, phenol, halogenated phenol.In addition, to be preferably the total amount (β) that makes tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound usually be the amount of 0.1～30 weight % with respect to the total amount (alpha+beta) of reaction solution to the consumption of organic solvent (α).
In addition, in the scope that the polyamic acid that does not make generation is separated out, the poor solvent alcohols of all right coupling polyamic acid, ketone, ester class, ethers, halogenated hydrocarbon, hydro carbons etc. in the above-mentioned organic solvent.Object lesson as this poor solvent, can enumerate for example methyl alcohol, ethanol, isopropyl alcohol, cyclohexanol, 4-hydroxy-4-methyl-2 pentanone, ethylene glycol, propylene glycol, 1, the 4-butylene glycol, triethylene glycol, glycol monoethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, diethy-aceto oxalate, diethyl malonate, ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, the ethylene glycol positive propyl ether, glycol isopropyl ether, the ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic acid esters, the diethylene glycol monoethyl ether acetic acid esters, tetrahydrofuran, methylene chloride, 1, the 2-ethylene dichloride, 1, the 4-dichloroetane, trichloroethanes, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, dimethylbenzene, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether etc.
As mentioned above, obtained dissolving the reaction solution of polyamic acid.Then, this reaction solution is put in a large amount of poor solvents, obtained precipitate, by this precipitate of drying under reduced pressure or with evaporator the reaction solution decompression is distillated and to obtain polyamic acid.Can get polyamic acid.And, this polyamic acid is dissolved in the organic solvent once more, with poor solvent it is separated out then, by carrying out once or this operation several times, can make with extra care polyamic acid.
＜dehydration closed-loop reaction 〉
The polyimide that constitutes aligning agent for liquid crystal of the present invention can synthesize by part or all dehydration closed-loop with above-mentioned polyamic acid.The ratio (below, be also referred to as " imidizate rate ") that has the repetitive of imide ring among the present invention in the used whole repetitives of polyimide is 40 moles more than the %, is preferably 50 moles more than the %.By using the imidizate rate is 40 moles of polymkeric substance more than the %, can obtain to form the aligning agent for liquid crystal of short liquid crystal orientation film of image retention elimination time.The imidizate rate can be obtained according to following method.
[the imidizate rate assay method of imide amination polymer]
Imide amination polymer at room temperature behind the drying under reduced pressure, is dissolved in the deuterated dimethyl sulfoxide, is primary standard substance with the tetramethylsilane, at room temperature carries out
1H-NMR measures.Try to achieve with the following (ii) formula of expression.
Imidizate rate (%)=(1-A
1/ A
2* α) * 100------is (ii)
A
1: the peak area (10ppm) that derives from the proton of NH base
A
2: the peak area that derives from other proton
α: 1 proton of NH base in the precursor (polyamic acid) of relative polymkeric substance, the number ratio of other proton
The dehydration closed-loop of polyamic acid can (i) by the method for heating polyamic acid, perhaps (ii) by polyamic acid is dissolved in the organic solvent, in this solution, adds the method for dewatering agent and dehydration closed-loop catalyzer and heating as required and carry out.
Temperature of reaction in the method for the heating polyamic acid of above-mentioned (i) is preferably 50～200 ℃, more preferably 60～170 ℃.When 50 ℃ of temperature of reaction less thaies, then the dehydration closed-loop reaction can not be carried out fully, if temperature of reaction surpasses 200 ℃, the situation of the molecular weight and molecular weight of gained imide amination polymer then can occur.
On the other hand, in the above-mentioned method of in polyamic acid solution, adding dewatering agent and dehydration closed-loop catalyzer (ii),, can use for example acid anhydrides such as acetic anhydride, propionic andydride, trifluoroacetic anhydride as dewatering agent.The consumption of dewatering agent is decided according to required imidizate rate, preferably with respect to the repetitive of 1 mole of polyamic acid, is 0.01～20 mole.In addition, as the dehydration closed-loop catalyzer, can use for example tertiary amines such as pyridine, collidine, lutidines, triethylamine.But, be not limited to these.The dehydration closed-loop catalyst consumption with respect to 1 mole of used dewatering agent, is preferably 0.01～10 mole.Above-mentioned dewatering agent, dehydration closed-loop catalyst consumption are many more, then can make the imidizate rate high more.In addition, as the organic solvent that uses in the dehydration closed-loop reaction, can enumerate as polyamic acid and synthesize middle solvent for use and illustrative organic solvent.And the temperature of reaction of dehydration closed-loop reaction is preferably 0～180 ℃, more preferably 10～150 ℃.In addition, by the reaction solution that so obtains is carried out the operation same with the polyamic acid process for purification, can make with extra care the gained particular polymers.
＜end modified type polymkeric substance 〉
Polyamic acid and polyimide used among the present invention can also be the end modified type polymkeric substance that has carried out molecular-weight adjusting.By using this end modified type polymkeric substance, can under the prerequisite of not damaging effect of the present invention, improve the coating characteristic of aligning agent for liquid crystal etc.This end modified type polymkeric substance can be by when polyamic acid synthetic, adds monobasic acid anhydrides, monoamine compound, monoisocyanates compound etc. and synthesize in reaction system.Wherein, as the monobasic acid anhydrides, can enumerate for example maleic anhydride, phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinic anhydride, n-tetradecane base succinic anhydride, n-hexadecyl succinic anhydride etc.In addition, as monoamine compound, can enumerate for example aniline, cyclohexylamine, n-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine, n-tridecane amine, n-tetradecane amine, n-pentadecane amine, n-hexadecane amine, n-heptadecane amine, n-octadecane amine, n-eicosane amine etc.In addition, as the monoisocyanates compound, can enumerate for example phenyl isocyanate, isocyanic acid naphthyl ester etc.
[solution viscosity]
Be used in the polymkeric substance of alignment agent of the present invention, under the situation of solution 10%, preferred 20～800mPas viscosity, more preferably 30～500mPas viscosity.
In addition, use specific solvent, cooperate the solution that is diluted to specific solids content concn, under 25 ℃, measure the solution viscosities (mPas) of polymkeric substance with E type rotational viscosimeter.
[aligning agent for liquid crystal]
Aligning agent for liquid crystal of the present invention normally is contained in the organic solvent by other composition dissolving with specific compound or the preferred above-mentioned polymkeric substance of specific polyamic acid polymer and any interpolation and constitutes.
Aligning agent for liquid crystal of the present invention is considered the fusible angle of substrate surface from improving in the scope of not damaging the purpose rerum natura, can also be contained compound, the epoxy compounds of functional silanes.As this epoxy compounds, can enumerate for example ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-four glycidyl group-2, the 4-hexanediol, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1,3-two (N, N-diglycidyl amino methyl) cyclohexane, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, 3-(N-allyl-N-glycidyl) TSL 8330,3-(N, the N-diglycidyl) TSL 8330, N, N-diglycidyl-benzylamino, N, N-diglycidyl-amino methyl cyclohexane etc.And, as containing epoxy compounds, preferably can enumerate ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-four glycidyl group-2, the 4-hexanediol, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1,3-two (N, N-diglycidyl amino methyl) cyclohexane, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzylamino, N, N-diglycidyl-amino methyl cyclohexane etc.These contain the proportioning of epoxy compounds, with respect to 100 parts by weight polymer, are preferably below 40 weight portions, more preferably 0.1～30 weight portion.
As this compound that contains functional silanes, can enumerate for example 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-carbethoxyl group-3-TSL 8330, N-carbethoxyl group-3-aminopropyltriethoxywerene werene, N-tri-ethoxy silylpropyl diethylenetriamine, N-trimethoxy silane base propyl group diethylenetriamine, 10-trimethoxy silane-1,4,7-three azepine decane, 10-triethoxysilicane alkyl-1,4,7-three azepine decane, 9-trimethoxy silane base-3,6-diaza nonyl acetic acid esters, 9-triethoxysilicane alkyl-3,6-diaza nonyl acetic acid esters, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, N-two (oxyethylene group)-3-TSL 8330, N-two (oxyethylene group)-3-aminopropyltriethoxywerene werene etc.As the proportioning that contains the functional silanes compound,, be preferably below 4 weight portions with respect to 100 parts by weight polymer.
As the organic solvent that constitutes aligning agent for liquid crystal of the present invention, for example, can enumerate 1-Methyl-2-Pyrrolidone, gamma-butyrolacton, butyrolactam, N, dinethylformamide, N, the N-dimethyl acetamide, 4-hydroxy-4-methyl-2 pentanone, glycol monoethyl ether, butyl lactate, butyl acetate, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, the ethylene glycol positive propyl ether, glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic acid esters, the diethylene glycol monoethyl ether acetic acid esters, 3-butoxy-N, N-dimethyl propylene acid amides, 3-methoxyl-N, N-dimethyl propylene acid amides, the own oxygen base-N of 3-, N-dimethyl propylene acid amides, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether etc.Wherein, 3-butoxy-N, N-dimethyl propylene acid amides, 3-methoxyl-N, N-dimethyl propylene acid amides, the own oxygen base-N of 3-, N-dimethyl propylene acid amides is preferred especially owing to show good printing.
Solids content concn is considered viscosity, volatility etc. and is selected in the aligning agent for liquid crystal of the present invention, is preferably the scope of 1～10 weight %.In other words, aligning agent for liquid crystal of the present invention is coated on substrate surface, formation is filmed as liquid crystal orientation film, and when solids content concn less than 1 weight %, the thickness that will cause this to film is too small, thereby can not obtain good liquid crystal orientation film; When solids content concn surpasses 10 weight %, will cause coating thickness blocked up, thereby can not obtain good liquid crystal orientation film, and the viscosity of aligning agent for liquid crystal increases, coating characteristic variation.
In addition, particularly preferred solids content concn scope is according to the method that is adopted when the coating of substrates aligning agent for liquid crystal and difference.For example, when being spin-coating method, the scope of preferred especially 1.5～4.5 weight %.When adopting print process, special preferable solids content concentration is the scope of 3～9 weight %, like this, can make solution viscosity drop on the scope of 12～50mPas.When adopting ink-jet method, special preferable solids content concentration is the scope of 1～5 weight %, can make solution viscosity drop on the scope of 3～15mPas like this.
Temperature when modulating aligning agent for liquid crystal of the present invention is preferably 0 ℃-200 ℃, more preferably 20 ℃-60 ℃.
＜liquid crystal display cells 〉
With the liquid crystal display cells that aligning agent for liquid crystal of the present invention makes, can be by for example following method manufacturing.
(1) by hectographic printing method, spin-coating method or ink jet printing method, aligning agent for liquid crystal of the present invention is coated on the substrate one side that is provided with the nesa coating that forms pattern, then, film by the formation of heating applicator surface.Here, as substrate, can use for example glass such as float glass, soda-lime glass; Plastics system transparency carriers such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, ester ring type polyolefin.Simultaneously go up set nesa coating as substrate, can use tin oxide (SnO
2) system NESA film (U.S. PPG register of company trade mark), indium oxide-tin oxide (In
2O
3-SnO
2) the ITO film etc. of system.The formation of these electrically conducting transparent film figures is adopted photoetch method or is used the method for mask in advance.When the coating of aligning agent for liquid crystal, for the cohesive of further improving substrate surface and nesa coating and filming, can also be on this surface of substrate coating in advance contain functional silanes compound, contain the compound of functionality titanium etc.Behind the coated with liquid crystal alignment agent, the purpose for the sagging grade of alignment agent liquid that prevents to apply preferably preheats (prebake).The prebake temperature is preferably 30～200 ℃, and more preferably 40～150 ℃, preferred especially 40～100 ℃.Then, remove fully and desolvate,, carry out roasting (afterwards curing) operation in order to make the purpose of polyamic acid hot-imide.This roasting (afterwards curing) temperature is preferably 80～300 ℃, more preferably 120～250 ℃.In addition, contain the aligning agent for liquid crystal of the present invention of polyamic acid, by removing organic solvent after the coating, formation is filmed as alignment films, can also make its dehydration closed-loop by further heating, forms filming of further imidizate.The thickness of filming that forms is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
(2) formed film coated surface is carried out grinding process with the certain orientation friction with being tied with the roller of fibrous cloth such as nylon, regenerated fiber, cotton for example.Like this, be formed in produced on filming liquid crystal molecular orientation can liquid crystal orientation film.In addition; to the liquid crystal orientation film that forms by aligning agent for liquid crystal of the present invention; the processing of carrying out the part irradiation ultraviolet radiation shown in Japanese kokai publication hei 6-222366 communique for example or the Japanese kokai publication hei 6-281937 communique and tilt angle being changed; perhaps carrying out the liquid crystal orientation film upper surface after implementing grinding process shown in the Japanese kokai publication hei 5-107544 communique divides ground to form diaphragm; after carrying out grinding process with the direction different with previous grinding process; remove diaphragm; the processing that the liquid crystal aligning of liquid crystal orientation film can be changed can improve the visual field characteristic of liquid crystal display cells like this.
(3) make 2 substrates that as above form liquid crystal orientation film, 2 substrates are staggered relatively by gap (box gap), make the vertical mutually or antiparallel of polishing direction of liquid crystal orientation film separately, fitted with sealant in 2 substrate periphery positions, in the box gap that is partitioned into by substrate surface and sealant, annotate the topping up crystalline substance, the sealing filling orifice constitutes liquid crystal cell.Then,, promptly constitute on the another side of each substrate of liquid crystal cell at the outside surface of liquid crystal cell, the applying polaroid, it is consistent or vertical to make its polarization direction and this substrate simultaneously go up the polishing direction of formed liquid crystal orientation film, makes liquid crystal display cells.
Here, as sealant, for example can use epoxy resin as the salic ball of hardening agent and separator etc.
As liquid crystal, can enumerate nematic crystal and dish shape type liquid crystal, wherein preferred nematic crystal can use for example schiff base class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, cyclohexylbenzene class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cube alkanes liquid crystal etc.In addition, can also add cholesteryl liquid crystal such as for example cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate in these liquid crystal and the chirality agent of selling with trade name " C-15 ", " CB-15 " (メ Le Network corporate system) etc. and using.And, can also use oxygen base benzylidene-in the last of the ten Heavenly stems to ferroelectric liquid crystals such as amino-2-methyl butyl cinnamates.
In addition, as the polaroid of fitting on the liquid crystal cell outside surface, can enumerate polyvinyl alcohol (PVA) is extended that the polarizing coating that is referred to as the H film that orientation absorbs the iodine gained simultaneously is clipped in the acetate fiber diaphragm and the polaroid that polaroid of making or H film self are made.
[embodiment]
Below, by embodiment the present invention is carried out more specific description, but the present invention is not limited to these embodiment.
[printing evaluation]
Formed the glass substrate of 127mm (D) * 127mm (the W) * 1.1mm (H) of ITO film on whole of a prefabricated side, is after the millipore filter of 0.2 μ m filters with the aligning agent for liquid crystal that obtains in the above-mentioned experiment by the aperture, being coated with application printing machine (Japan's description printing (strain) is made, オ Application グ ス ト ロ one マ one S-40L) with liquid crystal orientation film is coated on the transparency electrode face of this glass substrate.Carry out drying by the heating plate driving fit formula pre-dryers that is set at 80 ℃, 200 ℃ of following roastings 60 minutes, on the glass substrate that has the ITO film, form liquid crystal orientation film again.According to irregular the carry out visual assessment of following benchmark to the gained alignment films.
Zero: a bit all do not observe irregular.
△: observe that some are irregular.
*: observe irregular significantly.
[voltage retention]
In 167 milliseconds time span, under 60 ℃, apply the voltage of 5V to liquid crystal display cells, the voltage application time is 60 microseconds, measures then from voltage and removes voltage retention after 167 milliseconds.Determinator adopts the VHR-1 of (strain) bundle Yang テ Network ニ カ system.
[print experiment]
Make the box that has the ITO electrode as shown in Figure 1.At room temperature apply 24 hours 6.0V DC voltage, apply 24 hours 0.5V DC voltage to electrode B to electrode A.After discharging stress, apply 0.1～5.0V DC voltage with the amplification of each 0.1V to electrode A, B.Luminance difference by each voltage bottom electrode A, B is judged the print characteristic.When luminance difference was big, it is poor that the print characteristic is judged as.
Zero: do not find luminance difference fully.
△: have certain luminance difference.
＜specific compound synthetic 1
Used Raney nickel in this reaction since with atmosphere in oxygen and water vapor reaction and inactivation easily.Therefore, used solvent and reagent re-use after removing impurity by distillation and recrystallization processing in advance in the reaction.Polyreaction is carried out under nitrogen environment.
Polyreaction is carried out according to literature method (T.Kanbara, J.Polym.Sci.Part-A, Polym.Chem., 38,4194 (2000)).In the four neck flasks of taking a breath with nitrogen in inside, add 4,4 '-DCBP (1mmol), benzidine (1mmol) and toluene 15ml are after stirring a few minutes, at room temperature add tert-butoxy sodium 288mg (3mmol), two (1, the 5-cyclo-octadiene) nickel (0) (Ni (cod)
2) 28mg (0.1mmol) and 1,1 '-two (diphenylphosphine) ferrocene (DPPF) 166mg (0.3mmol).This reactant liquor is heated to 60 ℃ while stirring under nitrogen environment, makes the reaction beginning.Reaction is after 24 hours down at 60 ℃ to make it, and adding minute quantity benzidine (0.05mmol) makes polymer ends seal with benzidine, thereby polymerization is stopped.After being cooled to room temperature, reaction solution is injected in the mixed solution of 200ml ammoniacal liquor and methyl alcohol, leaches the sediment of gained, the sediment that reclaims is further washed with methyl alcohol and ether, obtain specific compound A-1.
The Synthetic 2 of＜specific compound 〉
Specific compound A-2 comprises multiple structure as implied above.
THF solution with specific compound A-1 in three-neck flask mixes with excess of ammonia base sodium.Make this vlil after 2 hours, cooled reaction solution drips excessive epoxy bromopropane.Be heated to 80 ℃, continue to stir 6 hours.Filtering reacting solution, filtrate carry out the separatory washing with chloroform/10% aqueous hydrochloric acid solution, saturated aqueous common salt successively.With the organic layer anhydrous magnesium sulfate drying, distillation removes and desolvates.Residue is precipitated with methyl alcohol again, obtain specific compound A-2.
Polyimide synthesis example 1
Will be as 2 of tetrabasic carboxylic acid dicarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride 112g (0.50 mole) and 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c] furans-1,3-diketone 157g (0.50 mole) is as the p-phenylenediamine 96g (0.89 mole) of diamine compound, 3,3 '-(tetramethyl disiloxane-1,3-two bases) two (propylamine) 25g (0.10 mole) and 3,6-two (4-aminobenzoic acyl-oxygen base) cholestane 13g (0.02 mole), n-octadecane base amine 8.1g (0.03 mole) as monoamine is dissolved in the 960gN-N-methyl-2-2-pyrrolidone N-, and it was reacted 6 hours down at 60 ℃.The polyamic acid solution branch that obtains is taken a morsel, add NMP, under the solution of solids content concn 10%, measure viscosity, be 60mPas.Then, in the gained polyamic acid solution, add 2700g N-N-methyl-2-2-pyrrolidone N-, 396g pyridine and 409g acetic anhydride, 110 ℃ of following dehydration closed-loops 4 hours.After the imidization reaction, solvent in system carries out solvent exchange (in this operation with new gamma-butyrolacton, outside system, remove the pyridine, the acetic anhydride that use in the imidization reaction), the solution viscosity of (gamma-butyrolacton solution) is imide amination polymer (it is as " polyimide (a-1) ") solution of 70mPas, imidizate rate about 95% when obtaining about 2000g solids content concn 15wt%, solids content concn 10%.
Polyimide synthesis example 2
Will be as 2 of tetrabasic carboxylic acid dicarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride 224g (1.0 moles), p-phenylenediamine 108g (1.0 moles) and 3 as diamine compound, 5-diaminobenzoic acid cholestane base ester 7.8g (0.015 mole) is dissolved in the 3039g N-N-methyl-2-2-pyrrolidone N-, it was reacted 6 hours down at 60 ℃, obtain the polyamic acid solution that solution viscosity is about 260mPas.Then, in the gained polyamic acid solution, add 2700g N-N-methyl-2-2-pyrrolidone N-, 396g pyridine and 306g acetic anhydride, 110 ℃ of following dehydration closed-loops 4 hours.After the imidization reaction, solvent in system carries out solvent exchange (in this operation with new gamma-butyrolacton, outside system, remove the pyridine, the acetic anhydride that use in the imidization reaction), the solution viscosity of (gamma-butyrolacton solution) is imide amination polymer (it is as " imide amination polymer (a-2) ") solution of 250mPas, imidizate rate about 51% when obtaining the about 9.0wt% of about 3000g solids content concn, solids content concn 10%.
Polyamic acid synthesis example 1
Will be as 1 of tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride 196g (1.0 moles), as 2 of diamine compound, 2 '-dimethyl-4,4 '-benzidine 212g (1.0 moles) is dissolved in 370g N-N-methyl-2-2-pyrrolidone N-, the 3300g gamma-butyrolacton, it was reacted 3 hours down at 40 ℃, obtain polyamic acid (it is as " polyamic acid (b-1) ") the about 3700g of solution of solution viscosity 160mPas.
Polyamic acid synthesis example 2
Will be as 1 of tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride 95g (0.50 mole), pyromellitic acid dicarboxylic anhydride 109g (0.50 mole), as 2 of diamine compound, 7-diamino-fluorene 196g (1.0 moles) is dissolved in 230g N-N-methyl-2-2-pyrrolidone N-, the 2060g gamma-butyrolacton, it was reacted 3 hours down at 40 ℃, append the 1350g gamma-butyrolacton, the solution viscosity that obtains under the solids content concn 10% is polyamic acid (it is as " polyamic acid (b-2) ") the about 3600g of solution of 125mPas.
Embodiment 1
With the polyamic acid (b-1) that makes in the polyimide (a-1) that makes in the polyimide synthesis example 1 and the polyamic acid synthesis example 1 with polyimide: polyamic acid=20: 80 (weight ratio) is dissolved in gamma-butyrolacton/N-N-methyl-2-2-pyrrolidone N-/butyl cellosolve mixed solvent (weight ratio 71/17/12), in this solution, add 2 weight portion N with respect to 100 parts by weight polymer respectively, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, add 10 weight portion specific compound A-1 with respect to the above-mentioned polymkeric substance of 100 weight portions, make solution that solids content concn is 3.5 weight % and the solution of 6.0 weight %.After each solution fully stirred, be that the filter of 1 μ m filters, modulate aligning agent for liquid crystal of the present invention with the aperture.
Adopting spin coater is that to be coated on thickness be (rotating speed: 2500rpm on the ITO film system nesa coating set on the one side of glass substrate of 1mm for the solution of 3.5 weight % with solids content concn in the above-mentioned aligning agent for liquid crystal, the coating time: 1 minute), drying is 1 hour under 200 ℃, and forming dry film thickness is the overlay film of 0.08 μ m.The sander of the roller that twines Artificial Fibers cloth is equipped with in employing, is that 400rpm, operator's console translational speed are 3cm/ second at the roller rotating speed, and fine hair is clamp-oned under the condition that length is 0.4mm, and this overlay film is carried out grinding process.With above-mentioned liquid crystal orientation film coated substrate in ultrapure water with ultrasonic cleansing after 1 minute, in 100 ℃ clean baking box dry 10 minutes.Then, on each outer rim of the above-mentioned liquid crystal orientation film coated substrate of a pair of transparency electrode/transparent electrode substrate with liquid crystal orientation film, it is the epoxy adhesive of the alumina balls of 5.5 μ m that coating has added diameter, then, the liquid crystal aligning face is relatively overlapped and pressing, bonding agent is solidified.Then, (メ Le Network society system MLC-6221), is sealed liquid crystal injecting port with the acrylic compounds Photocurable adhesive then, and the polaroid of fitting on the two sides in the substrate outside is made the TN liquid crystal display cells to fill nematic crystal by liquid crystal injecting port between substrate.The voltage retention of gained liquid crystal display cells and the evaluation of print are carried out according to above-described method.
In addition, adopting solids content concn is the solution of 6.0 weight %, carries out the printing evaluation according to above-described method.
Embodiment 2～4
Except polyimide, polyamic acid, specific compound use the material shown in the table 1, carry out according to flow process similarly to Example 1.
Embodiment 5
The polyimide (a-2) that makes in the polyimide synthesis example 2 is dissolved in N-N-methyl-2-2-pyrrolidone N-/butyl cellosolve mixed solvent (weight ratio 50/50), add 2 weight portion N with respect to 100 parts by weight polymer, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane adds 10 weight portion specific compound A-1 with respect to 100 parts by weight polymer, makes solution that solids content concn is 3.5 weight % and the solution of 6.0 weight %.After each solution fully stirred, be that the filter of 1 μ m filters, modulate aligning agent for liquid crystal of the present invention with the aperture.The evaluation method of the method for making of liquid crystal display cells, the evaluation method of liquid crystal display cells and alignment agent printing is carried out according to the method identical with embodiment 1.
Embodiment 6
Except specific compound uses the material shown in the table 1, carry out according to flow process similarly to Example 5.
Comparative example 1～2
Except polyimide, polyamic acid use the material shown in the table 1, and do not add beyond the specific compound, carry out according to flow process similarly to Example 1.
Comparative example 3
Except not adding specific compound, carry out according to flow process similarly to Example 5.
Comparative example 4～5
Except polyimide, polyamic acid use the material shown in the table 1, and use the compound (compounds X) of following structure to replace carrying out according to flow process similarly to Example 1 beyond the specific compound.Compounds X is synthetic according to the method described in TOHKEMY 2000-44683 number.
Compounds X
Comparative example 6
Except adding compounds X replacement specific compound, carry out according to flow process similarly to Example 5.
Comparative example 7～8
Except polyimide, polyamic acid use the material shown in the table 1, and use the compound (compound Y) of following structure to replace carrying out according to flow process similarly to Example 1 beyond the specific compound.Compound Y is synthetic according to the method described in the WO 2002/100949.Its molecular weight Mn=15000, Mw=30000.
Comparative example 9
Except adding compound Y replacement specific compound, carry out according to flow process similarly to Example 5.
Table 1
| Polyimide | Polyamic acid | Specific compound | Voltage retention | Printing | ||
| Embodiment 1 | a-1 | b-1 | Specific compound A-1 | ＞99％ | ○ | ○ |
| Embodiment 2 | a-1 | b-1 | Specific compound A-2 | ＞99％ | ○ | ○ |
| Embodiment 3 | a-1 | b-2 | Specific compound A-1 | ＞99％ | ○ | ○ |
| Embodiment 4 | a-1 | b-2 | Specific compound A-2 | ＞99％ | ○ | ○ |
| Embodiment 5 | a-2 | - | Specific compound A-1 | ＞99％ | ○ | ○ |
| Embodiment 6 | a-2 | - | Specific compound A-2 | ＞99％ | ○ | ○ |
| Comparative example 1 | a-1 | b-1 | Do not have | ＞99％ | △ | ○ |
| Comparative example 2 | a-1 | b-2 | Do not have | ＞99％ | △ | ○ |
| Comparative example 3 | a-2 | - | Do not have | ＞99％ | △ | ○ |
| Comparative example 4 | a-1 | b-1 | Compounds X | 98％ | △ | ○ |
| Comparative example 5 | a-1 | b-2 | Compounds X | 98％ | △ | ○ |
| Comparative example 6 | a-2 | - | Compounds X | 98％ | △ | ○ |
| Comparative example 7 | a-1 | b-1 | Compound Y | 98％ | ○ | × |
| Comparative example 8 | a-1 | b-2 | Compound Y | 98％ | ○ | × |
| Comparative example 9 | a-2 | - | Compound Y | 98％ | ○ | × |
Claims (7)
1. an aligning agent for liquid crystal is characterized in that containing the compound that following formula (I) is represented,
In the formula, R
1～R
8Be hydrogen atom, alkyl or alkoxy independently of one another, R
9～R
12Be hydrogen atom, aromatic group or aliphatic group independently of one another, A is hydrogen atom or aliphatic group, and n is 1～100 integer.
2. the described aligning agent for liquid crystal of claim 1, in its Chinese style (I), R
1～R
8Independently of one another for hydrogen atom, carbon number are that 1～6 alkyl or carbon number are 1～6 alkoxy, R
9～R
12Be hydrogen atom, A is a hydrogen atom, and n is 1～100 integer.
3. the described aligning agent for liquid crystal of claim 1, the R in its Chinese style (I)
1～R
8Independently of one another for hydrogen atom, carbon number are that 1～6 alkyl or carbon number are 1～6 alkoxy, R
9And R
11Be aromatic group, R
10And R
12Be hydrogen atom or aliphatic group, A is hydrogen atom or aliphatic group, and n is 1～100 integer.
4. the described aligning agent for liquid crystal of claim 1, the R in its Chinese style (I)
1～R
8Independently of one another for hydrogen atom, carbon number are that 1～6 alkyl or carbon number are 1～6 alkoxy, R
9And R
11Be aromatic group, R
10And R
12For hydrogen atom or contain the aliphatic group of epoxy radicals, A is hydrogen atom or the aliphatic group that contains epoxy radicals, and n is 1～100 integer.
5. an aligning agent for liquid crystal is characterized in that containing the polyamic acid polymer by described compound of claim 2 and tetrabasic carboxylic acid dicarboxylic anhydride reaction gained.
6. each described aligning agent for liquid crystal of claim 1～5, it also contains at least a polymkeric substance of selecting from the group that the polyimide of the polyamic acid of the repetitive that comprises following formula (I-1) expression and the repetitive that comprises following formula (I-2) expression constitutes
Wherein, P
1Be the organic group of 4 valencys, and Q
1Be the organic group of divalent,
Wherein, P
2Be the organic group of 4 valencys, and Q
2Organic group for divalent.
7. a liquid crystal display cells is characterized in that having the liquid crystal orientation film that makes with each described aligning agent for liquid crystal of claim 1～6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006260858 | 2006-09-26 | ||
| JP2006260858 | 2006-09-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101153996A true CN101153996A (en) | 2008-04-02 |
| CN100549786C CN100549786C (en) | 2009-10-14 |
Family
ID=39255733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007101518817A Active CN100549786C (en) | 2006-09-26 | 2007-09-25 | Aligning agent for liquid crystal and liquid crystal display cells |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20080028318A (en) |
| CN (1) | CN100549786C (en) |
| TW (1) | TWI354843B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI499588B (en) * | 2010-06-10 | 2015-09-11 | Nissan Chemical Ind Ltd | Liquid crystal alignment film and a liquid crystal display element to the processing agent, with the liquid crystal |
| CN111868620A (en) * | 2018-03-19 | 2020-10-30 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5360356B2 (en) * | 2008-05-26 | 2013-12-04 | Ｊｓｒ株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| JP5668922B2 (en) * | 2010-03-01 | 2015-02-12 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
-
2007
- 2007-09-21 KR KR1020070096544A patent/KR20080028318A/en not_active Application Discontinuation
- 2007-09-25 CN CNB2007101518817A patent/CN100549786C/en active Active
- 2007-09-26 TW TW096135644A patent/TWI354843B/en active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI499588B (en) * | 2010-06-10 | 2015-09-11 | Nissan Chemical Ind Ltd | Liquid crystal alignment film and a liquid crystal display element to the processing agent, with the liquid crystal |
| CN111868620A (en) * | 2018-03-19 | 2020-10-30 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| CN111868620B (en) * | 2018-03-19 | 2023-11-03 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100549786C (en) | 2009-10-14 |
| TW200821716A (en) | 2008-05-16 |
| KR20080028318A (en) | 2008-03-31 |
| TWI354843B (en) | 2011-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101676363B (en) | Liquid crystal aligning agent, liquid crystal display element and compound | |
| CN101042504B (en) | Liquid crystal aligning agent and film and liquid crystal display device | |
| CN101452153B (en) | Liquid crystal oriented agent and liquid crystal display element | |
| CN101210184B (en) | Upright tropism type crystal tropism agent and upright tropism type crystal display element | |
| CN101241272B (en) | Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display element | |
| CN101382703A (en) | Liquid crystal aligning agent and liquid crystal display element | |
| CN101178519A (en) | Liquid crystal aligning agent and liquid crystal display device | |
| CN101539687B (en) | Liquid crystal alignment agent and liquid crystal display element | |
| CN101114085A (en) | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device | |
| CN100468173C (en) | Liquid crystal aligning agent and lateral field style liquid crystal display element | |
| CN101539688A (en) | Liquid crystal alignment agent and liquid crystal display element | |
| CN101109873A (en) | Liquid crystal aligning agent,liquid crystal aligning film and liquid crystal display device | |
| CN101144943B (en) | Liquid crystal orientating agent and liquid crystal displaying element | |
| CN101261403A (en) | Liquid crystal oriented agent and liquid crystal display element | |
| CN100549786C (en) | Aligning agent for liquid crystal and liquid crystal display cells | |
| CN101692144B (en) | Liquid crystal aligning agent and liquid crystal display device | |
| CN101458425A (en) | Liquid crystal oriented agent and liquid crystal display element | |
| CN101458427B (en) | Liquid crystal oriented agent and liquid crystal display element | |
| CN100549785C (en) | Aligning agent for liquid crystal and liquid crystal display cells | |
| CN101144942A (en) | Liquid crystal orientating agent, liquid crystal orientating film and liquid crystal displaying element | |
| CN101487955B (en) | Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display element | |
| CN101520575B (en) | Vertical orientation type liquid crystal orientating agent and vertical orientation type liquid crystal display element | |
| CN101246283B (en) | Liquid crystal aligning agent and liquid crystal display element | |
| CN101256316A (en) | Lquid crystal aligning agent and luid crystal display element | |
| CN101256314B (en) | Liquid crystal aligning agent and liquid crystal display element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |