CN100549785C - Aligning agent for liquid crystal and liquid crystal display cells - Google Patents

Aligning agent for liquid crystal and liquid crystal display cells Download PDF

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CN100549785C
CN100549785C CNB2007101513103A CN200710151310A CN100549785C CN 100549785 C CN100549785 C CN 100549785C CN B2007101513103 A CNB2007101513103 A CN B2007101513103A CN 200710151310 A CN200710151310 A CN 200710151310A CN 100549785 C CN100549785 C CN 100549785C
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CN101153995A (en
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安田博幸
林英治
西川通则
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JSR Corp
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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
    • 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

Abstract

The invention provides when keeping voltage retention, to make again and accumulate the aligning agent for liquid crystal that electric charge reduces and has superior printing characteristics.This aligning agent for liquid crystal contains the compound of following general formula (1) expression, (in the formula, R 1～R 3Be hydrogen atom, alkyl or alkoxy independently of one another, R 4～R 7Independently of one another for the aliphatic group of the aromatic group of hydrogen atom, 1 valency, 1 valency or contain 1 valency aliphatic group of epoxy radicals, A 1And A 2Be the aliphatic group of hydrogen atom, 1 valency or the 1 valency aliphatic group that contains epoxy radicals independently of one another, n is 1～100 integer), perhaps contain by the compound of following general formula (1 ') expression and the polyamic acid of tetrabasic carboxylic acid dicarboxylic anhydride reaction gained, in the formula, R 1～R 3, A 1And A 2And it is identical in n and the above-mentioned general formula (1).

Description

Aligning agent for liquid crystal and liquid crystal display cells
Technical field
The present invention relates to form the used aligning agent for liquid crystal and the liquid crystal display cells of liquid crystal orientation film of 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 adopts it.
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 forms the liquid crystal orientation film that comprises polyamic acid, polyimide etc. being provided with on the substrate surface of nesa coating, substrate as used for liquid crystal display element, 2 these substrates are oppositely arranged, form the layer of nematic crystal 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 nesa coating, to form the vertical alignment-type liquid crystal display device that is called MVA (Multi-Domain Vertical Alignment) mode that projection is controlled the liquid crystal aligning direction.The liquid crystal display cells of MVA mode not only visual angle, contrast etc. is good, and can also not carry out grinding process etc. in the process that forms liquid crystal orientation film, thereby also is good aspect manufacturing process.As the liquid crystal orientation film that is applicable to TN, STN, MVA mode, 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
[patent documentation 2] Japanese kokai publication hei 6-222366 communique
[patent documentation 3] Japanese kokai publication hei 6-281937 communique
[patent documentation 4] Japanese kokai publication hei 5-107544 communique
[non-patent literature 2] K.Hasegawa, Polymer Journal.Vol.31, No.2,206 (1999)
[patent documentation 5] TOHKEMY 2000-44683 communique
[patent documentation 6] international pamphlet that discloses No. 2002/100949
Summary of the invention
The present invention In view of the foregoing makes, and its objective is to be provided to make again when keeping voltage retention to accumulate the aligning agent for liquid crystal that electric charge reduces and has superior printing characteristics, and the liquid crystal display cells that adopts it is provided.
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, the first, reach by a kind of aligning agent for liquid crystal (hereinafter referred to as " first aligning agent for liquid crystal "), it is characterized in that containing the compound of following general formula (1) expression,
(in the formula, R 1～R 3Be hydrogen atom, alkyl or alkoxy independently of one another, R 4～R 7Independently of one another for the aliphatic group of the aromatic group of hydrogen atom, 1 valency, 1 valency or contain 1 valency aliphatic group of epoxy radicals, A 1And A 2Be the aliphatic group of hydrogen atom, 1 valency or the 1 valency aliphatic group that contains epoxy radicals independently of one another, n is 1～100 integer).
Above-mentioned purpose of the present invention, the second, reach by a kind of aligning agent for liquid crystal (hereinafter referred to as " second aligning agent for liquid crystal "), it is characterized in that containing by the compound of following general formula (1 ') expression and the polyamic acid of tetrabasic carboxylic acid dicarboxylic anhydride reaction gained,
(in the formula, R 1～R 3, A 1And A 2And it is identical in n and the above-mentioned general formula (1)).
Above-mentioned problem of the present invention, the 3rd, to reach by a kind of liquid crystal display cells, it has the liquid crystal orientation film that is formed by above-mentioned any aligning agent for liquid crystal.
Description of drawings
Fig. 1 tests the mode chart of the box of making for the print of embodiment and comparative example.
Embodiment
First aligning agent for liquid crystal of the present invention contains the compound of above-mentioned formula (1) expression.
In above-mentioned formula (1), R 1～R 3Be hydrogen atom, alkyl or alkoxy independently of one another.
As abovementioned alkyl, preferred carbon number is 1～6 alkyl, as its concrete example, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, 2-methyl-propyl group, 3-methyl-propyl group, n-pentyl, n-hexyl etc.
As above-mentioned alkoxy, preferred carbon number is 1～6 alkoxy, as its concrete example, can enumerate methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, 2-methyl-propoxyl group, 3-methyl-propoxyl group, n-pentyloxy, just own oxygen base etc.
R in above-mentioned formula (1) 4～R 7Independently of one another for the aliphatic group of the aromatic group of hydrogen atom, 1 valency, 1 valency or contain 1 valency aliphatic group of epoxy radicals.
As the aromatic group of above-mentioned 1 valency, can enumerate for example phenyl, xenyl, terphenyl, naphthyl, phenanthryl, pyrenyl, perylene base, anthryl, fluorenyl etc., wherein preferred phenyl, xenyl, terphenyl, naphthyl or fluorenyl.
As the aliphatic group of above-mentioned 1 valency, preferred carbon number is 1～4 1 valency aliphatic group, can enumerate methyl, ethyl, propyl group, butyl etc. particularly.
As above-mentioned 1 valency aliphatic group with epoxy radicals, preferred total carbon atom number is 2～4 group, for example can enumerate glycidyl, 1-methyl glycidyl etc.
A in the above-mentioned formula (1) 1And A 2Be the aliphatic group of hydrogen atom, 1 valency or the 1 valency aliphatic group that contains epoxy radicals independently of one another.As A 1And A 2The aliphatic group of preferred 1 valency or contain 1 valency aliphatic group of epoxy radicals, with above as R 4～R 7The aliphatic group of preferred 1 valency and to contain 1 valency aliphatic group of epoxy radicals described identical.
N is 1～100 integer in the above-mentioned formula (1), is preferably 1～50.
In the above-mentioned formula (1), R 1～R 7And A 1And A 2Its preferred separately group is made up arbitrarily.
In the compound of above-mentioned formula (1) expression,, can enumerate following (A) to (D) compound as preferred.
(A) be R in above-mentioned formula (1) 1～R 3Independently of one another for hydrogen atom, carbon number are that 1～6 alkyl or carbon number are 1～6 alkoxy, R 4～R 7Be hydrogen atom, A 1And A 2Compound for hydrogen atom.
(B) be R in above-mentioned formula (1) 1～R 3Independently of one another for hydrogen atom, carbon number are that 1～6 alkyl or carbon number are 1～6 alkoxy, R 4～R 7For having 1 valency aliphatic group of epoxy radicals, A 1And A 2Be hydrogen atom or compound independently of one another with 1 valency aliphatic group of epoxy radicals.
(C) be R in above-mentioned formula (1) 1～R 3Independently of one another for hydrogen atom, carbon number are that 1～6 alkyl or carbon number are 1～6 alkoxy, R 4And R 6Be the aromatic group of 1 valency, R 5And R 7Be the aliphatic group of hydrogen atom or 1 valency, A 1And A 2Be the compound of the aliphatic group of hydrogen atom or 1 valency independently of one another.
(D) be R in above-mentioned formula (1) 1～R 3Independently of one another for hydrogen atom, carbon number are that 1～6 alkyl or carbon number are 1～6 alkoxy, R 4And R 6Be the aromatic group of 1 valency, R 5And R 7Be hydrogen atom or 1 valency aliphatic group, A with epoxy radicals 1And A 2Be hydrogen atom or compound independently of one another with 1 valency aliphatic group of epoxy radicals.In the case, preferably get rid of R 5, R 7, A 1And A 2Be the compound of hydrogen atom.
As the preferred object lesson of compound of above-mentioned formula (1) expression, can enumerate the compound that following structural formula is for example represented.
Figure C20071015131000101
Figure C20071015131000111
(among the said structure formula group, n is 1～100, preferred 1～50 integer).
Second aligning agent for liquid crystal of the present invention contains the polyamic acid by the compound of above-mentioned formula (1 ') expression and tetrabasic carboxylic acid dicarboxylic anhydride reaction gained.As the compound of above-mentioned formula (1 ') expression, R in the preferred above-mentioned formula (1 ') 1～R 3Independently of one another for hydrogen atom, carbon number are that 1～6 alkyl or carbon number are 1～6 alkoxy, A 1And A 2Be hydrogen atom, n is 1～50 compound.
As the preferred object lesson of compound of above-mentioned formula (1 ') expression, can enumerate the compound that following structural formula is for example represented.
Figure C20071015131000131
(among the said structure formula group, n is 1～100, preferred 1～50 integer).
Operable tetrabasic carboxylic acid dicarboxylic anhydride during as compound of representing by above-mentioned formula (1 ') and the acid of tetrabasic carboxylic acid dicarboxylic anhydride reaction synthesizing polyamides 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)-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)-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 anhydrides can only use a kind, also can will be used in combination more than 2 kinds.
At the compound by above-mentioned formula (1 ') expression during with the acid of tetrabasic carboxylic acid dicarboxylic anhydride reaction synthesizing polyamides, can also with other diamines of the compound while coupling of above-mentioned formula (1 ') expression.As operable preferred other diamines herein, 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 diisopropylidene) diphenylamine, 4,4 '-(-the phenylene diisopropylidene) 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 diamines can only use a kind, perhaps will be used in combination more than 2 kinds.
When with other diamines and during the compound coupling simultaneously of above-mentioned formula (1 ') expression, the consumption of diamines as other with respect to the compound of above-mentioned formula (1 ') expression and the total amount of other diamines, is preferably below the 50 weight %.
By compound and the acid of tetrabasic carboxylic acid dicarboxylic anhydride synthesizing polyamides of above-mentioned formula (1 ') expression, can be by similarly carrying out with the aftermentioned method of the synthetic method of the polyamic acid of choosing one of adding ingredient as aligning agent for liquid crystal of the present invention wantonly.
Aligning agent for liquid crystal of the present invention contain the compound of above-mentioned formula (1) expression or by the polyamic acid of the compound of above-mentioned formula (1 ') expression and tetrabasic carboxylic acid dicarboxylic anhydride reaction gained as must composition, but in addition, can also contain and have select the group that the polyimide of the repetitive of following formula (I-2) expression constitutes at least a, tackifier etc. from the polyamic acid of repetitive with following formula (I-1) expression.
Figure C20071015131000151
(in the formula, P 1Be the organic group of 4 valencys, and Q 1Organic group for divalent),
Figure C20071015131000152
(in the formula, P 2Be the organic group of 4 valencys, and Q 2Organic group for divalent).
Polyamic acid with repetitive of above-mentioned formula (I-1) expression can be synthetic by the reaction of tetrabasic carboxylic acid dicarboxylic anhydride and diamines, and the polyimide with repetitive of above-mentioned formula (I-2) expression can have P in the above-mentioned formula (I-1) by making 1Be P 2, Q 1Be Q 2Repetitive the polyamic acid dehydration closed-loop and make.
As the polyamic acid of repetitive with above-mentioned formula (I-1) expression synthetic in used tetrabasic carboxylic acid dicarboxylic anhydride, can enumerate for example ester ring type tetrabasic carboxylic acid dicarboxylic anhydride, aliphatics tetrabasic carboxylic acid dicarboxylic anhydride, aromatic tetracarboxylic acid's dicarboxylic anhydride etc.
As above-mentioned 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)-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)-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)-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)-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)-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-8-ethyl-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, 5-(2,5-dioxo tetrahydrofuran methylene)-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 (I) or the compound of (II) representing,
Figure C20071015131000171
(in the formula, R 8And R 10Expression has the divalent organic group of aromatic rings, R 9And R 11Expression hydrogen atom or alkyl, the R of a plurality of existence 9And R 11Separately can be identical, also can be different).
As above-mentioned aliphatics tetrabasic carboxylic acid dicarboxylic anhydride, can enumerate for example BTCA dicarboxylic anhydride etc.
As above-mentioned aromatic tetracarboxylic acid's dicarboxylic anhydride, can enumerate for example 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), the compound of following formula (2)～(5) expression etc.
These tetrabasic carboxylic acid dicarboxylic anhydrides can only use a kind, also can will be used in combination more than 2 kinds.
In the above-mentioned tetrabasic carboxylic acid dicarboxylic anhydride, as ester ring type 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)-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)-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-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 compound of following formula (6)～(8) expression in the compound of 10-tetraketone, above-mentioned formula (I) expression etc.,
Figure C20071015131000201
The compound of following formula (9) expression in the compound of perhaps above-mentioned formula (II) expression.
Figure C20071015131000202
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)-naphthalene [1,2-c] furans-1, the 3-diketone, 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)-and 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)-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 above-mentioned formula (6) expression, preferred especially 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride.
In addition, as preferred in aliphatics tetrabasic carboxylic acid dicarboxylic anhydride and the aromatic tetracarboxylic acid's dicarboxylic anhydride, can enumerate 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.
When two or more tetrabasic carboxylic acid dicarboxylic anhydrides being mixed when using, preferred ester ring type tetrabasic carboxylic acid dicarboxylic anhydride is 50 moles more than the % with respect to whole tetrabasic carboxylic acid dicarboxylic anhydrides.
As the polyamic acid of repetitive with above-mentioned formula (I-1) expression synthetic in used diamines, can enumerate have in for example aromatic diamine, aliphatics or ester ring type diamines, the molecule 2 primary amino radicals and this primary amino radical contained beyond the diamines, diamido organosiloxane etc. of nitrogen-atoms.
As above-mentioned aromatic diamine, can enumerate for example 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, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-two trifluoromethyls-4,4 '-benzidine, 3,3 '-two trifluoromethyls-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-2,7-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]-octafluoro biphenyl etc.
As above-mentioned aliphatics or ester ring type diamines, for example can enumerate 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) etc.
As the diamines that has the contained nitrogen-atoms in addition of 2 primary amino radicals and this primary amino radical in the molecule, for example can enumerate 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-2,4-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, the 5-triazine, 2,4-diamido-6-phenyl-1,3, the 5-triazine, 2,4-diamido-6-methyl-s-triazine, 2,4-diaminostilbene, 3, the 5-triazine, 4,6-diamido-2-vinyl-s-triazine, 2,4-diamido-5-phenyl thiazole, 2, the 6-diaminopurine, 5, the 6-diaminostilbene, the 3-dimethyl uracil, 3,5-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, N '-dimethyl-benzidine etc.
In addition,, can enumerate the compound of following formula (10) expression etc. as above-mentioned diamido organosiloxane,
Figure C20071015131000231
(in the formula, R 12The expression carbon number is 1～12 alkyl, the R of a plurality of existence 12Can be the same or different separately, p is 1～3 integer, and q is 1～20 integer).
These diamines can only use a kind, also can will be used in combination more than 2 kinds.
In these diamines, 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), 1,4-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.
When making aligning agent for liquid crystal of the present invention have tilt angle performance performance, part or all the diamines (hereinafter referred to as " specific diamines ") that preferably has the polyamic acid of repetitive of above-mentioned formula (I-1) expression used diamines in synthetic for structure with the expression of following formula (Q-1) or following formula (Q-2)
Figure C20071015131000232
(in the formula, X be singly-bound ,-O-,-CO-,-COO-,-OCO-,-NHCO-,-CONH-,-S-or arlydene, R 13Be 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).
Figure C20071015131000241
(in the formula, X be singly-bound ,-O-,-CO-,-COO-,-OCO-,-NHCO-,-CONH-,-S-or arlydene, R 14Be that carbon number is 4～40 the divalent organic group with ester ring type skeleton).Like this, can make group Q in the above-mentioned formula (I-1) 1With group Q 2Part or all be the above-mentioned formula (Q-1) or (Q-2) group of structure of expression, thereby help the performance of its performance tilt angle.
In the above-mentioned formula (Q-1), as R 13The 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) 13With the R in the above-mentioned formula (Q-2) 14The 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 bridge ester ring type 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) 13The 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 part or all group that is replaced by fluoro-alkyls such as fluorine atom or trifluoromethyls of the hydrogen atom of the organic groups such as aromatic hydrocarbyl more than 6.
In addition, the 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 phenylene, methylene phenyl, biphenylene, naphthylene etc.
Object lesson as the diamines of structure with above-mentioned formula (Q-1) expression, can enumerate for example 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 (11)～(15) expression etc.
Figure C20071015131000251
As the object lesson of the diamines of structure, can enumerate the compound of for example following formula (16)～(18) expression etc. with above-mentioned formula (Q-2) expression.
Figure C20071015131000261
These specific diamines can only use a kind, perhaps will be used in combination more than 2 kinds.
In these specific diamines, the compound of preferred above-mentioned formula (11), (13), (15) or (16) expression.
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 %.
Have the 1 equivalent amino of diamines of polyamic acid synthetic reaction of the repetitive of above-mentioned formula (I-1) expression with respect to supply, the anhydride group of tetrabasic carboxylic acid dicarboxylic anhydride is preferably the ratio of 0.2～2 equivalent, more preferably the ratio of 0.3～1.2 equivalent.
The synthetic reaction of polyamic acid in organic solvent, is preferable over-20 ℃～150 ℃, more preferably under 0～100 ℃ temperature conditions, preferably carries out 10 minutes～50 hours, more preferably carries out 30 minutes～30 hours.
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.
It is the amount of 0.1～30 weight % with respect to the total amount (alpha+beta) of reaction solution that the consumption of organic solvent (α) is preferably the total amount (β) that makes tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound usually.
In the scope that the polyamic acid that does not make generation is separated out, the part of aforesaid organic solvent can also substitute with the poor solvent alcohols of polyamic acid, ketone, ester class, ethers, halogenated hydrocarbon, hydro carbons etc.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.
Here the consumption of operable poor solvent all is being preferably below the 50 weight % in the solvent, more preferably below the 40 weight %.
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.Again, the operation of be dissolved in this polyamic acid in the organic solvent once more, separating out with poor solvent then or carry out once or for several times, can make with extra care polyamic acid thus with the operation that the evaporator decompression distillates.
Polyimide with repetitive of above-mentioned formula (I-2) expression can be by having P in the above-mentioned formula (I-1) 1Be P 2, Q 1Be Q 2Repetitive the polyamic acid dehydration closed-loop and make.
When dehydration closed-loop, can make amic acid structure fully dehydrating closed loop form imide ring, also can only make a part of dehydration closed-loop formation amic acid structure of amic acid structure and the polymkeric substance of imide ring structure coexistence.
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.Reaction time is preferably 10 minutes～and 5 hours, more preferably 30 minutes～3 hours.
On the other hand, in the above-mentioned situation of in polyamic acid solution, adding the method for dewatering agent and dehydration closed-loop catalyzer (ii),, can use for example acid anhydrides such as acetic anhydride, propionic andydride, trifluoro-acetic anhydride as dewatering agent.The consumption of dewatering agent is decided according to required imidizate rate, but 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 ℃.Reaction time is preferably 30 minutes～and 10 hours, more preferably 1 hour～7 hours.
By the reaction solution that so obtains being carried out the same operation with the polyamic acid process for purification, can make with extra care the polyimide of gained.
The polyimide that the present invention uses, the ratio (following, also be referred to as imidizate rate) that has the repetitive of imide ring in whole repetitives are 40 moles more than the %, preferred 50 moles more than the %.Because of having adopted the imidizate rate is 40 moles of polymkeric substance more than the %, can access the aligning agent for liquid crystal that can form short liquid crystal orientation film of image retention cancellation 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: relative other the number ratio of proton of 1 proton of NH base in the precursor (polyamic acid) of polymkeric substance
Having the polyamic acid of repetitive of above-mentioned formula (I-1) expression or the polyimide with repetitive of above-mentioned formula (I-2) expression can also be the end modified type polymkeric substance that has carried out molecular-weight adjusting.By using this end modified type polyamic acid or polyimide, 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 polyamic acid or polyimide can be by when polyamic acid synthetic, add 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.
The as above polyamic acid of the repetitive with above-mentioned formula (I-1) expression of gained or have the polyimide of the repetitive of above-mentioned formula (I-2) expression, when the solution that is 10%, the viscosity that preferably has 20～800mPas more preferably has the viscosity of 30～500mPas.
Again, the solution viscosity of polymkeric substance (mPas) is adopting specified solvent to be diluted in the solution of regulation solid component concentration, adopts E type rotational viscosimeter to carry out the mensuration of viscosity under 25 ℃.
Aligning agent for liquid crystal of the present invention is when the polyamic acid of the repetitive that contains above-mentioned formula (I-1) expression or when having the polyimide of repetitive of above-mentioned formula (I-2) expression, their usage rate, for first aligning agent for liquid crystal, compound with respect to the above-mentioned formula of 1 weight portion (1) expression, be preferably below 1000 weight portions, more preferably 10～500 weight portions.In addition, for above-mentioned second aligning agent for liquid crystal, by the compound of above-mentioned formula (1 ') expression and the polyamic acid of tetrabasic carboxylic acid dicarboxylic anhydride reaction gained, be preferably below 100 weight portions, more preferably 5～80 weight portions with respect to 1 weight portion.
Aligning agent for liquid crystal of the present invention makes above-mentioned particular polymers be dissolved in the organic solvent usually and constitutes.
Temperature when modulating aligning agent for liquid crystal of the present invention is preferably 0 ℃～200 ℃, more preferably 20 ℃～60 ℃.
As the organic solvent that constitutes aligning agent for liquid crystal of the present invention, can enumerate as the illustrated solvent of the solvent that uses in the polyamic acid synthetic reaction.In addition, can also suitably select as can coupling when the polyamic acid synthetic reaction and illustrative poor solvent carries out coupling.
Solid component concentration 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 %.That is to say, aligning agent for liquid crystal of the present invention is coated on substrate surface, formation is filmed as liquid crystal orientation film, and when solid component concentration less than 1 weight %, the thickness that will cause this to film is too small, thereby is difficult to obtain good liquid crystal orientation film; When solid component concentration surpasses 10 weight %, will cause coating thickness blocked up, thereby be difficult to obtain good liquid crystal orientation film, and the viscosity of aligning agent for liquid crystal increases, the easy variation of coating characteristic.
In addition, particularly preferred solid component concentration 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, preferred especially solid component 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, preferred especially solid component concentration is the scope of 1～5 weight %, can make solution viscosity drop on the scope of 3～15mPas like this.
As the organic solvent that constitutes aligning agent for liquid crystal of the present invention, 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, isoamyl ether etc.These can be used alone, or two or more kinds in combination.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.
Aligning agent for liquid crystal of the present invention is in the scope of not damaging the purpose rerum natura, from improving the fusible angle of substrate surface is considered, compound, the epoxy compounds (still, except the compound of above-mentioned formula (1) or (1 ') expression) that can also contain functional silanes.
Contain the compound of functional silanes as these, 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 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-xylylenediamine, 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, 3-(N-allyl-N-glycidyl) TSL 8330,3-(N, N-diglycidyl) TSL 8330 etc.
The usage rate of aforesaid tackifier, for first aligning agent for liquid crystal, the compound with respect to the above-mentioned formula of 100 weight portions (1) expression is preferably below 40 weight portions, more preferably 0.1～30 weight portion.In addition, for second aligning agent for liquid crystal, by the compound of above-mentioned general formula (1 ') expression and the polyamic acid of tetrabasic carboxylic acid dicarboxylic anhydride reaction gained, be preferably below 30 weight portions, more preferably 0.1～25 weight portion with respect to 100 weight portions.
Liquid crystal display cells of the present invention 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 pattern of these nesa coatings adopts photoetch method or uses 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 30～300 ℃, and more preferably 40～200 ℃, preferred especially 50～150 ℃.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 ℃.Like this, 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 (registered trademark), 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; carry out shown in patent documentation 2 (Japanese kokai publication hei 6-222366 communique) for example or the patent documentation 3 (Japanese kokai publication hei 6-281937 communique); part irradiation ultraviolet radiation and processing that tilt angle is changed; perhaps carry out shown in the patent documentation 4 (Japanese kokai publication hei 5-107544 communique); liquid crystal orientation film upper surface after implementing grinding process 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 thus.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 " (manufacturing of メ Le Network company) etc. and using.And, can also use oxygen base benzylidene-right-ferroelectric liquid crystals such as amino-2-methyl butyl cinnamate in the last of the ten Heavenly stems.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.
In following embodiment and comparative example, aligning agent for liquid crystal and carry out according to following method by the evaluation of its liquid crystal orientation film that makes.
[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 that strain) East Yang テ Network ニ カ makes.
[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 removing voltage, apply 0.1～5.0V DC voltage with the amplification of each 0.1V, carry out print performance evaluation then to electrode A, B.That does not find print is designated as zero, and the more weak △ that is designated as takes place in print, stronger being designated as of print generation *.
[printing evaluation]
Preparation has formed the glass substrate of 127mm (D) * 127mm (the W) * 1.1mm (H) of ITO film on whole an of side, is after the millipore filter of 0.2 μ m filters with the aligning agent for liquid crystal that makes in each embodiment or each comparative example with 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.Remove by the heating plate driving fit formula pre-dryers that is set at 80 ℃ and to desolvate, 200 ℃ of following roastings 60 minutes, on the glass substrate that has the ITO film, form liquid crystal orientation film again.To the irregular visual assessment that carries out of gained alignment films, do not find irregular being designated as " zero ", find irregular be designated as " * ".
Synthesis example 1
Synthesis example 1 is carried out according to non-patent literature 2 (K.Hasegawa, Polymer Journal.Vol.31, No.2,206 (1999)).
Under nitrogen environment, with 4,4 '-'-dibromobiphenyl 6.24g (20mmol), p-phenylenediamine (PPD) 2.16g (20mmol) join in the three-neck flask of 300ml, add 80ml toluene and make its dissolving.At room temperature add tert-butoxy sodium 5.8g (60mmol), three (dibenzalacetone) two palladium (Pd 2(dba) 3) 0.46g (0.5mmol), 2,2 '-two (diphenylphosphine)-1,1 '-dinaphthyl (BINAP) 0.93g (1.5mmol).Reaction solution was made its reaction in 16 hours in 100 ℃ of stirrings under nitrogen.Make reaction solution roll back room temperature then, adopt separating funnel, wash with the ammoniacal liquor of 2 liter of 25 weight % and the mixed solution of methyl alcohol (ammonia hydroxide/methanol=1/4 (volume ratio)).Organic solvent layer with after the sodium sulphate dehydration, is concentrated with Rotary Evaporators, the gained crude product is made with extra care by silica gel column chromatography, obtain the compd A-1 of the following formula of 2.1g (A-1) expression.
Figure C20071015131000361
(in the formula, m is a number of repeat unit).
By carrying out repeatedly same operation, guarantee compd A-1 in the capacity of following experimental example use.
Synthesis example 2
In three-neck flask, compd A-1 synthetic in the above-mentioned synthesis example 1 of 10g is dissolved in the 50mL dimethyl sulfoxide (DMSO).In this solution, mix excessive wet chemical.After this potpourri cooled off in ice bath, drip epoxy bromopropane DMSO solution (concentration be 1 mole/L) to excessive.Return after dropping finishes and drop to room temperature, continue stirring 48 hours.Reaction mixture is filtered, and filtrate is carried out the separatory washing with chloroform/saturated aqueous common salt.Then, distillation removes desolvates, and by precipitating with methyl alcohol, obtains the potpourri A-2 of the compound that following formula represents again.
Figure C20071015131000371
(in the formula, m ' and m " be respectively number of repeat unit).
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 solid component concentration 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 16mPas, imidizate rate about 95% when obtaining about 2000g solid component concentration 15wt%, solid component concentration 6.0%.
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 72mPas, imidizate rate about 51% when obtaining the about 9.0wt% of about 3000g solid component concentration, solid component concentration 5.0%.
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 solid component concentration 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), add 2 weight portion N with respect to 100 parts by weight polymer, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, add the compd A-1 that makes in the above-mentioned synthesis example 1 of 10 weight portions as the compound of above-mentioned formula (1) expression with respect to 100 parts by weight polymer, make solution that solid component concentration 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 the solution of 3.5 weight % is coated on (rotating speed: 2500rpm on the nesa coating that thickness is ITO film system set on the one side of glass substrate of 1mm with solid component concentration 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, reserve liquid crystal injecting port, then, the liquid crystal aligning face is relatively overlapped and pressing, bonding agent is solidified.Then, (メ Le Network company makes, and MLC-6221), with the acrylic compounds Photocurable adhesive liquid crystal injecting port is sealed then, makes 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 solid component concentration is the solution of 6.0 weight %, carries out the printing evaluation according to above-described method.
Embodiment 2～4
Except the material shown in compound, polyimide and the polyamic acid use table 1 of above-mentioned formula (1) expression, 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, add the compd A-1 that makes in the above-mentioned synthesis example 1 of 10 weight portions as the compound of above-mentioned formula (1) expression with respect to 100 parts by weight polymer, make solution that solid component concentration 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 using the compound of the material shown in the table 1, carry out according to flow process similarly to Example 5 as above-mentioned formula (1) expression.
Comparative example 1～2
Except polyimide, polyamic acid use the material shown in the table 1, and do not add beyond the compound of above-mentioned formula (1) expression, carry out according to flow process similarly to Example 1.
Comparative example 3
Except the compound that does not add above-mentioned formula (1) expression, carry out according to flow process similarly to Example 5.
Comparative example 4～5
In embodiment 1, polyimide, polyamic acid use the material shown in the table 1, and use the represented compound of following structure (hereinafter referred to as " compounds X ") to replace the compound of above-mentioned formula (1) expression, in addition, carry out according to flow process similarly to Example 1.In addition, compounds X is synthetic according to the method described in the patent documentation 5 (TOHKEMY 2000-44683 communique).
Figure C20071015131000411
Comparative example 6
In embodiment 5, except the use compounds X replaces the compound of above-mentioned formula (1) expression, carry out according to flow process similarly to Example 5.
Comparative example 7～8
In embodiment 1, polyimide, polyamic acid use the material shown in the table 1, and use polymkeric substance (being called " polymkeric substance Y ") to replace the compound of above-mentioned formula (1) expression with repetitive that following structure represents, in addition, carry out according to flow process similarly to Example 1.Polymkeric substance Y is synthetic according to the method described in the patent documentation 6 (the international pamphlet that discloses No. 2002/100949).Its number-average molecular weight Mn is 15000, and weight-average molecular weight Mw is 30000.
Comparative example 9
In embodiment 5, except use polymkeric substance Y replaces the compound of above-mentioned formula (1) expression, carry out according to flow process similarly to Example 5.
The above results whole one is listed in table 1.In addition, in the table 1, this composition in this hurdle is not used in "-" expression.In addition, the expression of "＞99% " in voltage retention hurdle measured value surpasses 99%.
Table 1
The compound of formula (1) Polyimide Polyamic acid Other compounds Voltage retention Print Printing
Embodiment 1 A-1 a-1 b-1 - ＞99％ ○ ○
Embodiment 2 A-2 a-1 b-1 - ＞99％ ○ ○
Embodiment 3 A-1 a-1 b-2 - ＞99％ ○ ○
Embodiment 4 A-2 a-1 b-2 - ＞99％ ○ ○
Embodiment 5 A-1 a-2 - - ＞99％ ○ ○
Embodiment 6 A-2 a-2 - - ＞99％ ○ ○
Comparative example 1 - a-1 b-1 - ＞99％ △ ○
Comparative example 2 - a-1 b-2 - ＞99％ △ ○
Comparative example 3 - a-2 - - ＞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 Polymkeric substance Y 98％ ○ ×
Comparative example 8 - a-1 b-2 Polymkeric substance Y 98％ ○ ×
Comparative example 9 - a-2 - Polymkeric substance Y 98％ ○ ×

Claims (8)

1. aligning agent for liquid crystal, it is characterized in that containing the compound of following general formula (1) expression, and from the polyamic acid of the repetitive that comprises following formula (I-1) expression with comprise select the group that the polyimide of the repetitive of following formula (I-2) expression constitutes at least a
Figure C2007101513100002C1
In the formula, R 1～R 3Be hydrogen atom, alkyl or alkoxy independently of one another, R 4～R 7Independently of one another for the aliphatic group of the aromatic group of hydrogen atom, 1 valency, 1 valency or contain 1 valency aliphatic group of epoxy radicals, A 1And A 2Be the aliphatic group of hydrogen atom, 1 valency or the 1 valency aliphatic group that contains epoxy radicals independently of one another, n is 1～100 integer,
Figure C2007101513100002C2
In the formula, P 1Be the organic group of 4 valencys, and Q 1Be the organic group of divalent,
Figure C2007101513100002C3
In the formula, P 2Be the organic group of 4 valencys, and Q 2Organic group for divalent.
2. the described aligning agent for liquid crystal of claim 1, in its formula of (1), R 1～R 3Independently of one another for hydrogen atom, carbon number are that 1～6 alkyl or carbon number are 1～6 alkoxy, A 1And A 2Be hydrogen atom.
3. the described aligning agent for liquid crystal of claim 1, in its formula of (1), R 1～R 3Independently of one another for hydrogen atom, carbon number are that 1～6 alkyl or carbon number are 1～6 alkoxy, R 4～R 7For containing 1 valency aliphatic group of epoxy radicals, A 1And A 2Be hydrogen atom or the 1 valency aliphatic group that contains epoxy radicals independently of one another.
4. the described aligning agent for liquid crystal of claim 1, in its formula of (1), R 1～R 3Independently of one another for hydrogen atom, carbon number are that 1～6 alkyl or carbon number are 1～6 alkoxy, R 4And R 6Be the aromatic group of 1 valency, R 5And R 7Be the aliphatic group of hydrogen atom or 1 valency, A 1And A 2Be the aliphatic group of hydrogen atom or 1 valency independently of one another.
5. the described aligning agent for liquid crystal of claim 1, in its formula of (1), R 1～R 3Independently of one another for hydrogen atom, carbon number are that 1～6 alkyl or carbon number are 1～6 alkoxy, R 4And R 6Be the aromatic group of 1 valency, R 5And R 7For hydrogen atom or contain 1 valency aliphatic group of epoxy radicals, A 1And A 2Be hydrogen atom or the 1 valency aliphatic group that contains epoxy radicals independently of one another.
6. the described aligning agent for liquid crystal of claim 1, the polyimide that it contains the polyamic acid of the repetitive that comprises above-mentioned formula (I-1) expression and comprises the repetitive of above-mentioned formula (I-2) expression, and these polyamic acids and polyimide are by comprising 2,3, the tetrabasic carboxylic acid dicarboxylic anhydride of 5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride and diamines synthesize.
7. an aligning agent for liquid crystal is characterized in that containing by the compound of following general formula (1 ') expression and the polyamic acid of tetrabasic carboxylic acid dicarboxylic anhydride reaction gained,
Figure C2007101513100003C1
In the formula, R 1～R 3, A 1And A 2And it is identical in n and the above-mentioned general formula (1).
8. a liquid crystal display cells is characterized in that having the liquid crystal orientation film that is formed by each described aligning agent for liquid crystal of claim 1～7.
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