CN101165572A - Liquid crystal orientation agent and liquid crystal displaying element - Google Patents

Liquid crystal orientation agent and liquid crystal displaying element Download PDF

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CN101165572A
CN101165572A CNA2007101636264A CN200710163626A CN101165572A CN 101165572 A CN101165572 A CN 101165572A CN A2007101636264 A CNA2007101636264 A CN A2007101636264A CN 200710163626 A CN200710163626 A CN 200710163626A CN 101165572 A CN101165572 A CN 101165572A
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liquid crystal
aligning agent
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dicarboxylic anhydride
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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
    • 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

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Abstract

The present invention relates to an aligning agent for liquid crystal, a liquid crystal alignment film and a liquid crystal display device. And an aligning agent for liquid crystal capable of forming the liquid crystal alignment film difficult to form grinding damage. Said aligning agent for liquid crystal contains the compound represented by the following formula (I), (referring to the figure) wherein, R1 and R2 are univalent organic groups having five member to eight member nitrogen heterocyclic ring, and m is an integer from 1 to 3, and R3 is the hydrogen atom or the univalent organic group.

Description

Aligning agent for liquid crystal and liquid crystal display cells
Technical field
The present invention relates to aligning agent for liquid crystal and liquid crystal display cells.More particularly, it is good and can be formed in the aligning agent for liquid crystal of the damage that is difficult to produce grinding process on the liquid crystal orientation film surface and brings (below be also referred to as " polishing damage ") to relate to electrical property, liquid crystal aligning, and has the liquid crystal display cells that uses the liquid crystal orientation film that this aligning agent for liquid crystal obtains.
Background technology
In the past, known TN type liquid crystal display cells with TN (Twisted Nematic) type liquid crystal cell, its by nesa coating between 2 substrates that formed liquid crystal orientation film on the surface, formation has the nematic crystal layer of positive dielectric anisotropy, constitute the box of sandwich construction, the major axis of above-mentioned liquid crystal molecule is turned round continuously to another piece substrate from a substrate and is turn 90 degrees.The orientation of liquid crystal in the liquid crystal display cells such as this TN type liquid crystal display cells is realized by the liquid crystal orientation film of giving its liquid crystal molecular orientation energy by grinding process usually.Here, as the material of the liquid crystal orientation film that constitutes liquid crystal display cells, resins such as present known polyimide, polyamide and polyester.Polyimide particularly, because its thermotolerance, good with aspects such as the compatibility of liquid crystal, physical strengths, and be used in most liquid crystal display cells.Wherein disclose in the patent documentation 1 in the liquid crystal aligning membrane material that uses polyimide resin, improved the example of anti-grinding process performance.
In patent documentation 1, the method for adding the epoxy compound of nitrogen atom in polyimide and polyamic acid resin is disclosed.Present inventors study in order to make the liquid crystal orientation film material list reveal better anti-grinding process performance.
[patent documentation 1] Japanese kokai publication hei 10-333153 communique
Summary of the invention
Present inventors contain the compound structure of 2 nitrogen-atoms and set about studying in the disclosed molecule from patent documentation 1, found that, by specific nitrogen-containing compound is added in polyimide and the polyamic acid resin, can further improve anti-grinding process performance, thereby finish the present invention.Improving the mechanism of anti-grinding process performance, is the reason that has improved the film density and the film hardness of alignment films owing to the specific nitrogen-containing compound of interpolation by inference.
That is, the present invention is as described below.
The present invention is 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,
Figure S2007101636264D00021
(in the formula, R 1And R 2For having any monovalent organic radical group of 5～8 member heterocyclic ring containing nitrogens, m is 1～3 integer, R 3Organic group for hydrogen atom or 1 valency).
Preferably contain in the above-mentioned formula (I) m and be 2 and R 3Aligning agent for liquid crystal for the specific compound of hydrogen atom.
And, more preferably contain the aligning agent for liquid crystal of the specific compound of following formula (II) expression as specific compound,
(in the formula, A and B are the organic group of divalent independently of each other, R 4～R 7Organic group for hydrogen atom or 1 valency).
More preferably containing middle A of formula (II) and B is-CH independently of each other 2-,-CH 2CH 2-or-CH 2CH 2CH 2The aligning agent for liquid crystal of-any one specific compound.
And, also preferably contain R in the formula (II) 4And R 5In any one and R 6And R 7In any one be to contain 1 amino valency organic group and A and B to be-CH 2CH 2-the aligning agent for liquid crystal of specific compound.
And, also preferably contain R in the formula (II) 4～R 7In at least one is to contain 1 valency organic group of epoxy radicals and A and B to be-CH 2CH 2-the aligning agent for liquid crystal of specific compound.
In addition, the present invention also provides a kind of aligning agent for liquid crystal, it is characterized in that containing by R 4And R 5In any one and R 6And R 7In any one be the polyamic acid polymer that the specific compound and the tetrabasic carboxylic acid dicarboxylic anhydride that contain the above-mentioned formula (II) of 1 amino valency organic group reacts gained.
Thereby, according to the present invention, a kind of aligning agent for liquid crystal preferably is provided, it is characterized in that containing at least a in above-mentioned specific compound and the above-mentioned polyamic acid polymer and be selected from the polyamic acid of the repetitive that comprises following formula (I-1) expression and comprise at least a polymkeric substance of polyimide of the repetitive of following formula (I-2) expression.
Figure S2007101636264D00031
(wherein, P 1Be the organic group of 4 valencys, and Q 1Organic group for divalent),
Figure S2007101636264D00032
(wherein, P 2Be the organic group of 4 valencys, and Q 2Organic group for divalent).
P in the preferred above-mentioned formula (I-1) 1With the P in the above-mentioned formula (I-2) 2For deriving from 2,3, the group of 5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride.
According to the present invention, can provide that a kind of electrical property and liquid crystal aligning are good, liquid crystal orientation film is difficult to produce the aligning agent for liquid crystal of polishing damage, this liquid crystal orientation film and liquid crystal display cells on surperficial.
Embodiment
Below, the present invention is carried out specific description.
Aligning agent for liquid crystal of the present invention constitutes by specific compound and/or specific polyamic acid polymer and the preferred at least a polymkeric substance that is selected from polyamic acid and polyimide in addition are dissolved in the organic solvent.
[specific compound]
In the above-mentioned formula (I), R 1And R 2For having any monovalent organic radical group of 5～8 member heterocyclic ring containing nitrogens.These heterocycles can also form condensed ring by the condensation aromatic rings.Particularly, can enumerate:
Figure S2007101636264D00041
In addition, the organic group of all right bonding 1 valency on each aromatic rings of said structure.
Wherein, preferred:
Figure S2007101636264D00042
In the above-mentioned formula (I), m is 1～3 integer, and preferred m is 2.In addition, R 3Organic group for hydrogen atom or 1 valency.As the organic group of 1 valency, preferred alkyl, alkoxy, more preferably carbon number is that 1～6 alkyl, carbon number are 1～6 alkoxy.As alkyl contained in 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 3Most preferably be hydrogen atom.
In the above-mentioned formula (II), R 4～R 7Organic group for hydrogen or 1 valency.As the organic group of 1 valency, preferred alkyl, alkoxy, phenyl, phenoxy group, more preferably carbon number is that 1～6 alkyl, carbon number are 1～6 alkoxy.As alkyl contained in 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.In addition, can also have substituting group on phenyl, its aromatic rings of phenoxy group.As its substituting group, preferably contain 1 valency organic group of amino and epoxy radicals.As R 4～R 7Object lesson, can enumerate following structure:
Figure S2007101636264D00051
In the above-mentioned specific compound, work as R 4And R 5In any one and R 8And R 9In any one be when containing 1 amino valency organic group, to make itself and anhydride reaction can make polyamic acid.When synthesizing this polyamic acid,, it is had no particular limits as acid anhydrides, as preferably, 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-2:3,5:6-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-furans)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic acid anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dicarboxylic anhydride, 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 be used singly or two or more kinds in combination.
In addition, as diamine compound, except 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 diisopropylidene) diphenylamine, 4,4 '-(-the phenylene diisopropylidene) diphenylamine, 1, the 4-cyclohexane diamine, 4,4 '-methylene two (cyclo-hexylamine), 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 diamines can be used singly or two or more kinds in combination.
[polyamic acid and polyimide]
＜tetrabasic carboxylic acid dicarboxylic anhydride 〉
As the polyamic acid of the repetitive that comprises above-mentioned formula (I-1) expression synthetic in used tetrabasic carboxylic acid dicarboxylic anhydride, preferred ester ring type tetrabasic carboxylic acid dicarboxylic anhydride, aliphatics tetrabasic carboxylic acid dicarboxylic anhydride and aromatic tetracarboxylic acid's dicarboxylic anhydride.As the object lesson of 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-furans)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic acid anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dicarboxylic anhydride, 4,9-two oxatricyclo [5.3.1.0 2,6] undecane-3,5,8,10-tetraketone, following formula (III) and the compound of (IV) representing,
Figure S2007101636264D00081
(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.
Figure S2007101636264D00091
In the above-mentioned tetrabasic carboxylic acid dicarboxylic anhydride, from making its angle that can show good liquid crystal aligning, 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-furans)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic acid anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dicarboxylic anhydride, 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 (III) expression and above-mentioned formula (IV) 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-furans)-and 3-methyl-3-cyclohexene-1, the 2-dicarboxylic acid anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dicarboxylic anhydride, 4,9-two oxatricyclo [5.3.1.0 2,6] undecane-3,5,8, the compound of 10-tetraketone and following formula (5) expression.
In addition, as preferred tetrabasic carboxylic acid dicarboxylic anhydride in other tetrabasic carboxylic acid dicarboxylic anhydride 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 accounts for 50 moles more than the % with respect to whole tetrabasic carboxylic acid dicarboxylic anhydrides.
＜diamines 〉
As the polyamic acid of the repetitive that comprises above-mentioned formula (I-1) expression 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, 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, 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 aliphatics and ester ring type diamines such as (cyclohexylamine);
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)-biphenylamine, 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 (V) expression etc.These diamines can be used in combination separately or more than 2 kinds.
Figure S2007101636264D00131
(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), 1,4-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.
The polyimide that comprises the repetitive of above-mentioned formula (I-2) expression can make by the polyamic acid dehydration closed-loop that makes the repetitive that comprises above-mentioned formula (I-1) expression.
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 the group contain following formula (Q-1) or following formula (Q-2) expression.They can a kind be used singly or two or more kinds in combination.
Figure S2007101636264D00141
(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).
Figure S2007101636264D00151
(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, perhaps fluoro-alkyl, the preferably group of trifluoromethyl replacement.
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 part or all group that is replaced by fluoro-alkyls such as fluorine atom or trifluoromethyls of hydrogen atom in 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.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.
Figure S2007101636264D00161
In addition, as the object lesson of the diamine compound of group, preferably can enumerate the diamines of following formula (14)～(16) expression with above-mentioned formula (Q-2) expression.
Figure S2007101636264D00171
Wherein, as particularly preferred, can enumerate the compound of above-mentioned formula (9), (11), (13), (14) 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 %.
Synthesizing of＜polyamic acid 〉
Supply with the tetrabasic carboxylic acid dicarboxylic anhydride of polyamic acid synthetic reaction and the usage rate of diamines, preferably with respect to the amino of 1 equivalent diamine compound, 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 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, diisobutyl ketone, 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,, or reaction solution decompression is distillated, can get polyamic acid by evaporator by this precipitate of drying under reduced pressure.And, this polyamic acid is dissolved in the organic solvent once more, with poor solvent it is separated out then, or distillate with evaporator decompression, 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.To have the ratio (below, be also referred to as " imidizate rate ") of the repetitive of imide ring in whole repetitives be 40 moles more than the % for used polyimide among the present invention, more 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 by 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
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 with the polyamic acid process for purification in same operation, can make with extra care the gained polyimide.
＜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%, the polymkeric substance of preferred 20～800mPas viscosity, the more preferably polymkeric substance of 30～500mPas viscosity.
In addition, the solution viscosity of polymkeric substance (mPas) uses specified solvent, for the solution that is diluted to the regulation solids content concn, measures down at 25 ℃ with E type rotational viscosimeter.
[aligning agent for liquid crystal]
Aligning agent for liquid crystal of the present invention is usually by making in above-mentioned specific compound and the specific polyamic acid polymer at least one, preferred above-mentioned polymkeric substance, and other composition dissolving of adding arbitrarily is contained in the organic solvent 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 the solvent that uses in the synthetic reaction as polyamic acid and illustrative solvent.In addition, also can suitably select as solvent that can coupling when the synthetic reaction of polyamic acid and illustrative poor solvent.
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, diisobutyl ketone (DIBK), isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, 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 etc.They can use separately, also can use mixing more than 2 kinds.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 %.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 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, the scope of particularly preferred solids content concn, employed method is different during because of coated with liquid crystal alignment agent on substrate.For example, use the occasion of spin-coating method, the scope of preferred especially 1.5～4.5 weight %.Use the occasion of print process, solids content concn is the scope of 3～9 weight %, and thus, special preferred solution viscosity is the scope of 12～50mPas.Use the occasion of spraying process, solids content concn is the scope of 1～5 weight %, and thus, special preferred solution viscosity is the scope of 3～15mPas.
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 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 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, N, N '-diglycidyl-benzylamine, N, N '-diglycidyl-amino methyl cyclohexane, 3-(N-allyl-N-glycidyl) TSL 8330,3-(N, N-diglycidyl) TSL 8330 etc.Among them, 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-benzylamine, N, N '-diglycidyl-amino methyl cyclohexane etc.The proportioning that these contain the functional silanes compound and contain epoxy compounds with respect to 100 parts by weight polymer, is preferably below 40 weight portions, more preferably 0.1～30 weight portion.
＜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,, applicator surface films by being added thermosetting.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, sagging etc. for the liquid of the alignment agent that prevents to apply, preferably implement to preheat (prebake).The temperature of prebake is preferably 30～200 ℃, more preferably 40～150 ℃, is preferably 40～100 ℃ especially.Then, solvent is removed fully,, implemented roasting (afterwards curing) operation to be purpose with the polyamic acid hot-imide.This roasting (afterwards curing) temperature is preferably 80～300 ℃, more preferably 120～250 ℃.The aligning agent for liquid crystal of the present invention that contains 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 field-of-view characteristics 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 the peripheral position of 2 substrates, 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, at the outside surface of liquid crystal cell, promptly constitute the polaroid of fitting on the another side of each substrate of liquid crystal cell, 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.
[rub resistance of liquid crystal orientation film]
On quartz base plate, form liquid crystal orientation film, the sander of the roller that twines Artificial Fibers cloth is equipped with in employing, clamp-oning length at fine hair is 0.8mm, the roller rotating speed is that 400rpm, operator's console translational speed are that 3cm/ second, polishing number of times are to carry out grinding process under 2 times the condition, formed liquid crystal orientation film is cleaned in isopropyl alcohol, range estimation is confirmed to have or not alignment films to come off or produces polishing from substrate to damage, do not come off and/or the damage of polishing takes place, be designated as " zero ", its generation is arranged, be designated as " * ".
[orientation of liquid crystal]
Have or not abnormal area when open cutting off (applying releasings), no abnormal be judged to be when regional " well " by polarized light microscope observing liquid crystal display cells voltage.
[voltage retention of liquid crystal display cells]
In 16.7 milliseconds time span, under 60 ℃, liquid crystal display cells is applied the voltage of 5V, the voltage application time is 60 microseconds, measures then from voltage and removes voltage retention after 16.7 milliseconds.Determinator adopts the (VHR-1 of strain) East Yang テ Network ニ カ system.
Synthesizing of＜specific compound 〉
Synthesis example 1 (aminating reaction)
Following reaction is by document J.Org.Chem.65, and the method for 1158 (2000) middle records is carried out.
Figure S2007101636264D00261
With 10,11-dihydro-5H-dibenzo [b, f] azepine  4.3g (22mmol), 4,4-two bromo biphenyl 3.12g (10mmol), three (dibenzalacetone) two palladium 91.6mg (0.1mmol), 2-(di-t-butyl phosphine) biphenyl 119mg (0.4mmol), tert-butoxy sodium 2.98g (31mmol) join in the three-neck flask that Di Muluo (ジ system ロ one ト) reflux condenser is housed.Bleed after the drying with vacuum pump, system is filled be nitrogen environment.Add the 20ml dehydrated toluene with syringe.80 ℃ of following heated and stirred 15 hours, reaction is finished.Reaction solution is cooled to room temperature, with 1N-HCl aqueous solution separatory washing 2 times, again with saturated aqueous common salt separatory washing 1 time.Distillation removes and desolvates, and carries out silicagel column again and makes with extra care, and obtains 3.24g compound 1.
Synthesis example 2 (bromination)
Join in the three-neck flask 3g (5.55mmol) compound 1,20ml acetic acid and mixing.On one side with the cooling of reaction solution ice bath, on one side the slow acetum 10ml of dripping bromine 4.27g (26.7mmol).Dripping the back stirred 6 hours.Reaction solution is injected in the 500ml water filtering-depositing.Gained solid and 500ml water are mixed together, filter.With the solid drying that leaches, obtain 3.33g compound 2.
Synthesis example 3
Figure S2007101636264D00272
Following being reflected under the nitrogen environment carried out.
3g (3.5mmol) compound 2,3-aminophenyl boric acid 2.1g (15.4mmol), tetrakis triphenylphosphine palladium 0.534g (0.46mmol), toluene 20ml are mixed in three-neck flask.In this solution, add 2 equivalent 2M-aqueous sodium carbonates.This solution was stirred 12 hours down at 100 ℃.Cooled reaction solution is with the washing of saturated aqueous common salt separatory.Distillation removes and desolvates, and makes with extra care by silicagel column, obtains 1.9g (2.1mmol) target compound 3 (specific compound A-1).
Synthesis example 4
Figure S2007101636264D00281
With 1.5g (1.66mmol) compound 3,2.46g (26.6mmol) epichlorokydrin in the mixed solution of 10mlTHF, 1.5ml water 80 ℃ of following heated and stirred 4 hours.After temperature of reaction is reduced to 60 ℃, drip the NaOH aqueous solution of 1g 50%.After the heated and stirred 4 hours, unreacted epichlorokydrin is removed in decompression distillation.Residue is carried out the separatory washing in toluene, distillation removes and desolvates, and obtains 1.6g target compound 4 (specific compound A-2).
Synthesis example 5
Following being reflected under the nitrogen environment carried out.
Figure S2007101636264D00291
With 3g (3.5mmol) compound 2,2.14g (15.4mmol) right-nitrophenol, 62.9mg (0.28mmol) palladium, 5.94g (28mmol) potassium phosphate, 125mg (0.42mmol) 2-(di-t-butyl phosphine) biphenyl, 20ml toluene mix in the three-neck flask that the Di Muluo reflux condenser is housed, with reaction solution 100 ℃ of following heated and stirred 12 hours.Reaction solution with the washing of saturated aqueous common salt separatory, is made with extra care by silicagel column again, obtained 2.7g target compound 5.
Synthesis example 6
Figure S2007101636264D00292
2.0g (1.84mmol) compound 5,4.81g (73.6mmol) zinc, 0.787g (14.7mmol) ammonium chloride, 20ml ethanol, 2.5ml water are mixed in the three-neck flask that the Di Muluo reflux condenser is housed.With reaction solution 100 ℃ of following heated and stirred 5 hours.Leach the zinc in the reaction solution, filtrate is splashed in the 250ml water.The powder that filtration is separated out, and dry, obtain 1.3g target compound 6 (specific compound B-1).
Synthesis example 7
Figure S2007101636264D00301
Adopt 1.0g (1.03mmol) compound 6, similarly operate, obtain 0.95g target compound 7 (specific compound B-2) with synthesis example 4.
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 960g N-N-methyl-2-2-pyrrolidone N-, and it was reacted 6 hours down at 60 ℃.The take a morsel polyamic acid solution of gained adds NMP, measures viscosity in solids content concn is 10% solution, is 60mPas.Then, in the polyamic acid solution that obtains, append 2700g N-N-methyl-2-2-pyrrolidone N-, add 396g pyridine and 409g acetic anhydride, make it 110 ℃ of following dehydration closed-loops 4 hours.After the imidization reaction, with new gamma-butyrolacton the solvent in the system is carried out solvent exchange (in this operation, outside system, remove the pyridine, the acetic anhydride that use in the imidization reaction), obtain about 2000g solids content concn 15wt%, the solution viscosity 70mPas of (gamma-butyrolacton solution) during solids content concn 10%, the imidizate rate is about 95% imide amination polymer (it is as " polyimide (a-1) ") solution.
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 of the about 260mPas of solution viscosity.Then, in the polyamic acid solution that obtains, append 2700g N-N-methyl-2-2-pyrrolidone N-, add 396g pyridine and 306g acetic anhydride, make it 110 ℃ of following dehydration closed-loops 4 hours.After the imidization reaction, with new gamma-butyrolacton the solvent in the system is carried out solvent exchange (in this operation, outside system, remove the pyridine, the acetic anhydride that use in the imidization reaction), obtain the about 9.0wt% of about 3000g solids content concn, the solution viscosity 250mPas of (gamma-butyrolacton solution) during solids content concn 10%, the imidizate rate is about 51% imide amination polymer (it is as " imide amination polymer (a-2) ") solution.
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, obtain about 3700g at 40 ℃ of down reactions 3 hours, the polyamic acid of the solution viscosity 160mPas during solids content concn 10% (it is as " polyamic acid (b-1) ") solution.
Polyamic acid synthesis example 2
Will be as 1 of tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,4-cyclohexane 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, after reacting 3 hours under 40 ℃, append the 1350g gamma-butyrolacton, the polyamic acid of the solution viscosity 125mPas when obtaining about 3600g solids content concn 10% (it is as " polyamic acid (b-2) ") solution.
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 35/60/5), add 10 weight portion specific compound A-1 with respect to 100 parts by weight polymer, 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 that 3cm/ second, fine hair are clamp-oned under the condition that length is 0.4mm at the roller rotating speed, and this overlay film is carried out grinding process.Above-mentioned liquid crystal orientation film coated substrate is carried out 1 minute ultrasonic washing in ultrapure water, in 100 ℃ cleaning 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, makes liquid crystal display cells to fill nematic crystal by liquid crystal injecting port between substrate.The evaluation of gained liquid crystal display cells voltage retention and the evaluation of liquid crystal aligning are carried out according to above-described method.The aligning agent for liquid crystal of the present invention that adopts spin coater as above to modulate is coated on the quartz base plate that thickness is 1.5mm, similarly forms during with the making liquid crystal display cells and films, and the evaluation of rub resistance is carried out according to above-described method.
Embodiment 2～7
Except polyimide, polyamic acid, specific compound use material as shown in table 1, carry out according to flow process similarly to Example 1.
Embodiment 8
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 90/10), add 10 weight portion specific compound A-1 with respect to 100 parts by weight polymer, 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.Adopt this alignment agent, make liquid crystal display cells according to the method described in the embodiment 1.
The evaluation of gained liquid crystal display cells voltage retention and the evaluation of liquid crystal aligning are carried out according to above-described method.The aligning agent for liquid crystal of the present invention that adopts spin coater as above to modulate is coated on the quartz base plate that thickness is 1.5mm, similarly forms during with the making liquid crystal display cells and films, and carries out the rub resistance evaluation according to above-described method.
Embodiment 9～12
Except specific compound uses the material shown in the table 1, carry out according to flow process similarly to Example 8.
Comparative example 1～2
Except polyimide, polyamic acid use material as shown in 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 8.
Comparative example 4～6
Polyimide, polyamic acid use material as shown in table 1, as specific compound, use N, N, and N ', N '-four glycidyl group-m-xylene diamine (compounds X) in addition, carries out according to flow process similarly to Example 1.N, N, N ', N '-four glycidyl group-m-xylene diamine uses the product of buying from ガ ス KCC of Mitsubishi.
Table 1
Polyimide Polyamic acid Specific compound Voltage retention Orientation Rub resistance
Embodiment 1 a-1 b-1 Specific compound A-1 ＞99％ Well ○
Embodiment 2 a-1 b-1 Specific compound A-2 ＞99％ Well ○
Embodiment 3 a-1 b-1 Specific compound B-1 ＞99％ Well ○
Embodiment 4 a-1 b-1 Specific compound B-2 ＞99％ Well ○
Embodiment 5 a-1 b-2 Specific compound A-1 ＞99％ Well ○
Embodiment 6 a-1 b-2 Specific compound A-2 ＞99％ Well ○
Embodiment 7 a-1 b-2 Specific compound B-1 ＞99％ Well ○
Embodiment 8 a-2 b-2 Specific compound B-1 ＞99％ Well ○
Embodiment 9 a-2 - Specific compound A-1 ＞99％ Well ○
Embodiment 10 a-2 - Specific compound A-2 ＞99％ Well ○
Embodiment 11 a-2 - Specific compound B-1 ＞99％ Well ○
Embodiment 12 a-2 - Specific compound B-2 ＞99％ Well ○
Comparative example 1 a-1 b-1 Do not have ＞99％ Well ×
Comparative example 2 a-1 b-2 Do not have ＞99％ Well ×
Comparative example 3 a-2 - Do not have ＞99％ Well ×
Comparative example 4 a-1 b-1 Compounds X 98％ Part is bad ×
Comparative example 5 a-1 b-2 Compounds X 98％ Part is bad ×
Comparative example 6 a-2 - Compounds X 98％ Part is bad ×

Claims (10)

1. an aligning agent for liquid crystal is characterized in that containing the compound that following formula (I) is represented,
Figure S2007101636264C00011
In the formula, R 1And R 2For having any monovalent organic radical group of 5～8 member heterocyclic ring containing nitrogens, m is 1～3 integer, R 3Organic group for hydrogen atom or 1 valency.
2. m is 2 and R in the described aligning agent for liquid crystal of claim 1, wherein above-mentioned formula (I) 3Be hydrogen atom.
3. claim 1 or 2 described aligning agent for liquid crystal, the compound of wherein above-mentioned formula (I) expression is the compound of following formula (II) expression,
Figure S2007101636264C00012
In the formula, A and B are the organic group of divalent independently of each other, R 4～R 7Organic group for hydrogen atom or 1 valency.
4. the described aligning agent for liquid crystal of claim 3, wherein A and B be independently of each other singly-bound ,-CH 2-,-CH 2CH 2-or-CH 2CH 2CH 2-in any one.
5. claim 3 or 4 described aligning agent for liquid crystal, wherein R 4And R 5In any one and R 6And R 7In any one be to contain 1 amino valency organic group, and A and B are-CH 2CH 2-.
6. claim 3 or 4 described aligning agent for liquid crystal, wherein R 4～R 7In at least one is the 1 valency organic group that contains epoxy radicals, and A and B are-CH 2CH 2-.
7. each described aligning agent for liquid crystal of claim 1～6, it contains by R 4And R 5In any one and R 6And R 7In any one be the polyamic acid polymer that the compound and the tetrabasic carboxylic acid dicarboxylic anhydride that contain the above-mentioned formula (II) of 1 amino valency organic group reacts gained.
8. aligning agent for liquid crystal, it is characterized in that containing at least a in each described compound of claim 1～6 and the described polyamic acid polymer of claim 7, and contain at least a polymkeric substance of from following group, selecting, this group comprises the polyamic acid of the repetitive that comprises following formula (I-1) expression and comprises the polyimide of the repetitive of formula (I-2) expression
Figure S2007101636264C00021
Wherein, P 1Be the organic group of 4 valencys, and Q 1Be the organic group of divalent,
Figure S2007101636264C00022
Wherein, P 2Be the organic group of 4 valencys, and Q 2Organic group for divalent.
9. the described aligning agent for liquid crystal of claim 8, the P in the wherein above-mentioned formula (I-1) 1With the P in the above-mentioned formula (I-2) 2Derive from 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride.
10. a liquid crystal display cells is characterized in that having the liquid crystal orientation film that adopts each described aligning agent for liquid crystal of claim 1～9 to make.
CNA2007101636264A 2006-10-19 2007-10-15 Liquid crystal orientation agent and liquid crystal displaying element Pending CN101165572A (en)

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CN103805212A (en) * 2012-11-07 2014-05-21 Jsr株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display device
CN103805212B (en) * 2012-11-07 2016-08-24 Jsr株式会社 Crystal aligning agent, liquid crystal orienting film and liquid crystal display cells

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