CN101458427B - Liquid crystal oriented agent and liquid crystal display element - Google Patents

Liquid crystal oriented agent and liquid crystal display element Download PDF

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CN101458427B
CN101458427B CN2008101857562A CN200810185756A CN101458427B CN 101458427 B CN101458427 B CN 101458427B CN 2008101857562 A CN2008101857562 A CN 2008101857562A CN 200810185756 A CN200810185756 A CN 200810185756A CN 101458427 B CN101458427 B CN 101458427B
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liquid crystal
compound
polyamic acid
tetracarboxylic dianhydride
aligning agent
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CN101458427A (en
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秋池利之
清水成夫
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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 a liquid crystal orientation agent and liquid crystal displaying element, wherein the liquid crystal orientation agent can form the liquid crystal orientation membrane capable of reducing the residual DC with good electrostatic leakage performance. The liquid crystal orientation agent comprises at least one polymer selected from the groups constituted by polyamic acid formed by reacting tetraearboxylic dianhydride with diamide containing the compound represented by the below formula (1) and polyimide formed by dehydration and loop-closing of the polyamic acid, in formula (1), R is hydrogen atom or one-valence 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, relate to the aligning agent for liquid crystal of the liquid crystal orientation film that can form electric property and excellent heat resistance and can carry out high-quality demonstration, and can suppress the demonstration deterioration that thermal stress causes, the liquid crystal display cells that can drive for a long time.
Background technology
At present, as liquid crystal display cells, TN type liquid crystal display cells with so-called TN type (twisted-nematic) liquid crystal cell is widely known by the people, it forms liquid crystal orientation film being provided with on the substrate surface of nesa coating, as the substrate of used for liquid crystal display element, two these substrates are oppositely arranged, form nematic crystal layer betwixt in the crack with positive dielectric anisotropy, constitute the box of sandwich construction, the major axis of liquid crystal molecule is turned round continuously to another piece substrate from a substrate and is turn 90 degrees.In addition, also developed compare with TN type liquid crystal display cells can reach the STN of high-contrast (supertwist is to row) type liquid crystal display cells more, IPS (switching face in) type liquid crystal display cells that view angle dependency is little, change IPS type electrode structure and the aperture opening ratio that improves the display element peristome with good OCB (optical compensation curved) the type liquid crystal display cells of FFS (fringing field conversion) type liquid crystal display cells, VA (vertical orientated) type liquid crystal display cells and the video pictures high-speed response of little while of view angle dependency of raising brightness etc.
Material as the liquid crystal orientation film in these liquid crystal display cells, resin materials such as known polyamic acid, polyimide, polyamide, polyester, the liquid crystal orientation film of making by polyamic acid or polyimide particularly, its thermotolerance, physical strength, good with the compatibility of liquid crystal etc., and be used to (referring to for example patent documentation 1～3) in most liquid crystal display cells.
Liquid crystal display cells with the liquid crystal orientation film that is formed by these resin materials is in order to realize that the user according to liquid crystal orientation film, and requires high-caliber characteristic to the high quality images demonstration of liquid crystal display cells requirement in recent years.Particularly, requirement to the image retention characteristic becomes harsh in low voltage drive type liquid crystal display cells for the purpose that reaches low power consumption, and the performance of the liquid crystal orientation film that uses in the liquid crystal display cells in the past can not satisfy the requirement as the liquid crystal orientation film of low voltage drive type liquid crystal display cells gradually.That is to say that if the liquid crystal orientation film in the past is directly used in the low voltage drive type liquid crystal display cells, then problem can often take place in the image retention aspect.For this reason, it is good to seek a kind of image retention characteristic, i.e. the lower liquid crystal orientation film of residual DC voltage.
In addition, in recent years, follow the increase of the size of substrate, the manufacturing process of liquid crystal display cells has obtained bigger progress.Particularly, the technology such as (ODF) of mode under large substrate transportation techniques and the liquid crystal drop receives publicity, and may become major technique in the future.Substrate is fixing in these operations, is to adopt to have utilized powerful static, just is called as the method for " electrostatic clamp ", stays on the substrate and is not removed but have this static, thereby cause and show underproof problem.In order to address this problem, the most effectively introduce Destaticizing device, but need a large amount of expenses for this reason, therefore it is defective to wish that liquid crystal orientation film by the covered substrate surface reduces the demonstration that static causes.That is to say, seek a kind of liquid crystal orientation film that improves leakage with voltage.
But the aligning agent for liquid crystal that can form the liquid crystal orientation film that satisfies above-mentioned requirements still is unknown.
[patent documentation 1] Japanese kokai publication hei 9-197411 communique
[patent documentation 2] TOHKEMY 2003-149648 communique
[patent documentation 3] TOHKEMY 2003-107486 communique
[patent documentation 4] Japanese kokai publication hei 6-222366 communique
[patent documentation 5] Japanese kokai publication hei 6-281937 communique
[patent documentation 6] Japanese kokai publication hei 5-107544 communique
Summary of the invention
The present invention In view of the foregoing makes, and its objective is provides a kind of aligning agent for liquid crystal that forms the liquid crystal orientation film that reduces residual DC and electrostatic leakage function admirable.
Another object of the present invention provides can carry out high-quality demonstration, even and the liquid crystal display cells that display performance can deterioration yet when driving for a long time.
A further object of the present invention provides the polymkeric substance that can be made into the aligning agent for liquid crystal with above-mentioned advantage and as the compound of its raw material.
Other purposes of the present invention and advantage, by the following description as can be seen.
According to the present invention, above-mentioned purpose of the present invention, first, reach by a kind of aligning agent for liquid crystal, it comprises at least a polymkeric substance that is selected from the following substances group, this material group is by tetracarboxylic dianhydride and the polyamic acid of the diamine reactant gained of the compound that contains following formula (1) expression and the polyimide that this polyamic acid dehydration closed-loop is formed are constituted
Figure G2008101857562D00031
In the formula (1), R is the organic group of hydrogen atom or 1 valency.
Above-mentioned purpose of the present invention, the second, to reach by a kind of liquid crystal display cells, it comprises the liquid crystal orientation film that is formed by above-mentioned aligning agent for liquid crystal.
Above-mentioned purpose of the present invention, the 3rd, by the polyamic acid that the tetracarboxylic dianhydride is made with the diamine reactant of the compound that comprises above-mentioned formula (1) expression or make this polyamic acid dehydration closed-loop and the polyimide that obtains is reached.
Above-mentioned purpose of the present invention, the 4th, reach by the compound of above-mentioned formula (1) expression.
It is good that aligning agent for liquid crystal of the present invention can form electric property, even and apply long thermal stress, liquid crystal aligning can be also can deterioration liquid crystal orientation film.By the liquid crystal orientation film that aligning agent for liquid crystal of the present invention forms, can perform well in the various liquid crystal display cells such as TN type, STN type, IPS type, FFS type, VA type, OCB type, strong dielectricity, anti-strong dielectricity.
Liquid crystal display cells of the present invention with this liquid crystal orientation film can carry out high-quality demonstration, even under long-time situation about driving, its display performance can deterioration yet.Therefore, liquid crystal display cells of the present invention can be effectively applied to various devices, for example is used for the display device of clock and watch, portable game machine, word processor, subnotebook PC, automobile navigation instrument, video camera, portable information terminal, digital camera, mobile phone, various watch-dog, liquid crystal TV set etc.
Embodiment
Below the present invention is described in detail.
Aligning agent for liquid crystal of the present invention comprises at least a polymkeric substance of selecting from the following substances group, polyamic acid that makes and the polyimide that this polyamic acid dehydration closed-loop is formed constitute this material group with the diamine reactant of the compound that comprises above-mentioned formula (1) expression by the tetracarboxylic dianhydride.
＜polyamic acid 〉
The polyamic acid that can contain in the aligning agent for liquid crystal of the present invention can make by making the tetracarboxylic dianhydride and the diamine reactant of the compound that contains above-mentioned formula (1) expression.
[tetracarboxylic dianhydride]
As used tetracarboxylic dianhydride in the contained polyamic acid of aligning agent for liquid crystal of the present invention synthetic, can exemplify ester ring type tetracarboxylic dianhydride, aliphatics tetracarboxylic dianhydride and aromatic tetracarboxylic acid's dianhydride.
As above-mentioned ester ring type tetracarboxylic dianhydride's object lesson, for example can enumerate 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-two chloro-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, cis-3,7-dibutyl ring suffering-1,5-diene-1,2,5, the 6-tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, 5-(2,5-dioxo tetrahydrochysene-3-furyl)-and 3-methyl-3-cyclohexene-1, the 2-dicarboxylic anhydride, 3,5,6-three carbonyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 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)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 5-(2,5-dioxo tetrahydrofurfuryl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic anhydride, dicyclo [2.2.2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), the following formula (T-I) or (T-II) compound etc. of expression
In the formula, R 1And R 3For having the divalent organic group of aromatic rings, R 2And R 4Be hydrogen atom or alkyl, a plurality of R of existence 2And R 4Separately can be identical, also can be different.
As above-mentioned aliphatics tetracarboxylic dianhydride's object lesson, can enumerate for example butane tetracarboxylic acid dianhydride etc.
Object lesson as above-mentioned aromatic tetracarboxylic acid's dianhydride, can enumerate for example pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride, 3,3 ', 4,4 '-tetraphenyl silane tetracarboxylic dianhydride, 1,2,3,4-furans tetracarboxylic dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenylsulfide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dianhydride, 3,3 ', 4,4 '-perfluor isopropylidene, two O-phthalic acid dianhydrides, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, two (phthalic acid) phosphniline oxide dianhydride, to phenylene-two (triphenyl phthalic acid) dianhydride, metaphenylene-two (triphenyl phthalic acid) dianhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl ether dianhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl methane dianhydride, 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 that following formula (T-1)～(T-4) is represented separately etc.
These tetracarboxylic dianhydrides can use in a kind of independent or two or more mixing.
As operable tetracarboxylic dianhydride in polyamic acid contained in the aligning agent for liquid crystal of the present invention synthetic, be preferably and be selected from least a in the material group that constitutes by ester ring type tetracarboxylic dianhydride and pyromellitic acid dianhydride, wherein, from making the angle of the good liquid crystal aligning of its performance, more preferably contain and be selected from by 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic anhydride, 5-(2,5-dioxo tetrahydrofurfuryl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic anhydride, cis-3,7-dibutyl ring suffering-1,5-diene-1,2,5, the 6-tetracarboxylic dianhydride, 3,5,6-three carbonyls-2-carboxyl norbornane-2:3,5:6-dianhydride, 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)-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, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), the compound that following formula (T-5)～(T-7) in the compound of above-mentioned formula (T-I) expression is represented separately, the compound of following formula (T-8) expression in the compound of above-mentioned formula (T-II) expression, and at least a tetracarboxylic dianhydride in the material group of pyromellitic acid dianhydride formation.
Figure G2008101857562D00091
Used tetracarboxylic dianhydride in the polyamic acid that aligning agent for liquid crystal of the present invention is contained synthetic, preferably contain 50 moles more than the %, more preferably 80 moles of at least a tetracarboxylic dianhydrides that are selected from more than the % in the material group that constitutes by ester ring type tetracarboxylic dianhydride and pyromellitic acid dianhydride with respect to whole tetracarboxylic dianhydrides.And then, preferably contain 50 moles more than the %, more preferably 80 moles of at least a tetracarboxylic dianhydrides that are selected from the ester ring type tetracarboxylic dianhydride more than the % with respect to whole tetracarboxylic dianhydrides.
[diamines]
Employed diamines contains the compound of above-mentioned formula (1) expression in the polyamic acid that aligning agent for liquid crystal of the present invention is contained synthetic.As the 1 valency organic group of R in the above-mentioned formula (1), can enumerate carbon number for example and be 1～40 alkyl, carbon number and be 1～40 fluoroalkyl, carbon number and be 3～40 ester ring type group etc.
As above-mentioned carbon number is 1～40 alkyl, can enumerate the alkyl of for example following formula (R-1) expression.
-(CH 2) a-CH 3 (R-1)
In the formula (R-1), a is 1～19 integer, is preferably 11～17 integer.
As above-mentioned carbon number is 1～40 fluoroalkyl, can enumerate for example following formula (R-2) or (R-3) fluoroalkyl of expression.
-(CH 2) b-CF 3 (R-2)
-(CH 2) c-C 2F 5 (R-3)
C in b in the formula (R-2) and the formula (R-3) is respectively 1～19 integer independently, is preferably 3～9 integer.
As above-mentioned carbon number is 3～40 ester ring type group, is preferably the carbon number with steroid backbone and is 17～40 ester ring type group, is preferably 3-cholestane base or 3-cholesteryl especially.
In the above-mentioned formula (1), respectively with the bonding position of two amino of two phenyl bondings, from the viewpoint of dissolubility and polymerism, position between preferably laying respectively at.
The compound of above-mentioned formula (1) expression of preferably using as the present invention can be enumerated the compound of any one expression of for example following formula (1-1)～(1-6),
Figure G2008101857562D00111
A in the formula, b and c with above-mentioned formula (R-1), (R-2) and (R-3) are identical meanings respectively.
The compound of above-mentioned formula (1) expression can synthesize by vitochemical common method.
Such as, the compound that the middle R of above-mentioned formula (1) is a hydrogen atom can synthesize by the following method, promptly, make the alkali metal salt reaction of the cyanic acid of the isocyanic acid nitrobenzophenone cyanic acid of 2 equivalents and 1 equivalent, synthetic 1,3-two (nitrobenzophenone)-s-triazine-2,4, the 6-triketone, then, reduction has the nitro of this intermediate.
In addition, the compound that the middle R of above-mentioned formula (1) is 1 valency organic group can synthesize by the following method, promptly, make with above-mentioned with quadrat method synthetic 1,3-two (nitrobenzophenone)-s-triazine-2,4,6-triketone and compound R-X are (wherein, R be with above-mentioned formula (1) in 1 identical valency organic group, X is the chlorine atom, bromine atoms or iodine atom) or R-OH (wherein, R be with above-mentioned formula (1) in 1 identical valency organic group) reaction, obtain 5 of 5 replacements of s-triazine ring to be replaced 1 by 1 valency organic group, 3-two (nitrobenzophenone)-s-triazine-2,4, the 6-triketone, with it as intermediate, then, reduction has the nitro of this intermediate.
The reduction reaction of above-mentioned nitro can be undertaken by known reduction reaction, for example uses the suitable methods such as method of the method for palladium carbon and hydrazine monohydrate, the method for using zinc and ammonium chloride, use tin chloride.
As the diamines of synthesizing polyamides acid usefulness, can use the compound of expression in the above-mentioned formula (1) separately, also the compound of above-mentioned formula (1) expression can be mixed use with other diamines.
As operable other diamines among the present invention, can enumerate for example p-phenylenediamine (PPD), m-phenylene diamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ethane, 4,4 '-diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene formailide, 4,4 '-diaminodiphenyl ether, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 3,4 '-diamino-diphenyl ether, 3,3 '-diamido benzophenone, 3,4 '-diamido benzophenone, 4,4 '-diamido benzophenone, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 2,2-two [4-(4-amino-benzene oxygen) phenyl] sulfone, 1,4-two (4-amino-benzene oxygen) benzene, 1,3-two (4-amino-benzene oxygen) benzene, 1,3-two (3-amino-benzene oxygen) benzene, 9,9-two (4-aminophenyl)-10-hydrogen anthracene, 2, the 7-diamino-fluorene, 9,9-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, 4,4 '-(to the phenylene isopropylidene) diphenylamine, 4,4 '-(metaphenylene 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, aromatic diamines such as two (4-aminophenyl) biphenylamine;
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, three ring [6.2.1.0 2,7] undecylene two methanediamines, 4,4 '-methylene two (cyclohexylamine), 1, aliphatics or ester ring type diamines such as 3-two (amino methyl) cyclohexane;
2, the 3-diamino-pyridine, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 5,6-diamido-2,3-dicyano pyrazine, 5,6-diamido-2, the 4-dihydroxy-pyrimidine, 2,4-diamido-6-dimethylamino-1,3,5-triazines, 1,4-two (3-aminopropyl) piperazine, 2,4-diamido-6-isopropoxy-1,3,5-triazines, 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, 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, the 6-diaminostilbene, the 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, 1-(3, the 5-diamino-phenyl)-3-decyl succinamide, 1-(3, the 5-diamino-phenyl)-3-octadecyl succinamide, the compound of following formula (D-I) expression
Figure G2008101857562D00131
(in the formula (D-I), R 5For being selected from the 1 valency organic group with nitrogen atom ring texture of the material group that constitutes by pyridine, pyrimidine, triazine, piperidines and piperazine, X 1Organic group for divalent), the compound of following formula (D-II) expression
(in the formula (D-II), X 2Respectively do for oneself and be selected from the divalent organic group with nitrogen atom ring texture of the material group that constitutes by pyridine, pyrimidine, triazine, piperidines and piperazine, R 6Be the organic group of divalent, a plurality of X of existence 2Separately can be identical, also can be different) have the diamines of the nitrogen-atoms beyond 2 primary amino radicals and this primary amino radical in the equimolecular;
The single-substituted diamines of following formula (D-III) expression
(in the formula (D-III), R 7For be selected from by-O-,-COO-,-OCO-,-NHCO-,-CONH-and-the divalent organic group of the material group that CO-constitutes, R 8To be selected from by 1 valency organic group of skeleton in steroid backbone, trifluoromethyl and the fluorine-based material group that constitutes or group or carbon number be 6～30 alkyl in order to have); The diamido organosiloxanes such as compound of following formula (D-IV) expression
Figure G2008101857562D00143
(in the formula (D-IV), R 9Represent that separately carbon number is 1～12 alkyl, a plurality of R of existence 9Separately can be identical, also can be different, respectively do for oneself 1～3 integer of p, q is 1～20 integer); The compound that following formula (D-1)～(D-5) is represented separately etc.
Figure G2008101857562D00151
Y in the formula (D-4) is 2～12 integer, and the z in the formula (D-5) is 1～5 integer.
These diamines can separately or be used in combination.
Wherein, preferred p-phenylenediamine (PPD), 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfide, 1, the 5-diaminonaphthalene, 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 '-(to the phenylene diisopropylidene) diphenylamine, 4,4 '-(metaphenylene 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, the compound that above-mentioned formula (D-1)～(D-5) is represented separately, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, the compound of following formula (D-6) expression in the compound of above-mentioned formula (D-I) expression, the compound of following formula (D-7) expression in the compound of above-mentioned formula (D-II) expression;
Figure G2008101857562D00161
Dodecyloxy-2 in the compound of above-mentioned formula (D-III) expression, 4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, hexadecane oxygen base-2,4-diaminobenzene, octadecane oxygen base-2,5-diaminobenzene, dodecyloxy-2,5-diaminobenzene, pentadecane oxygen base-2,5-diaminobenzene, hexadecane oxygen base-2,5-diaminobenzene, octadecane oxygen base-2, the compound that 5-diaminobenzene, following formula (D-8)～(D-16) are represented separately.
Figure G2008101857562D00171
Figure G2008101857562D00181
Used diamines in the polyamic acid that aligning agent for liquid crystal of the present invention is contained synthetic with respect to whole diamines, preferably contains 1 mole more than the %, more preferably the compound of above above-mentioned formula (1) expression of 5-50 mole %.And used diamines among the present invention except that the compound of above-mentioned formula (1) expression, preferably also contains at least a in the compound that is selected from above-mentioned formula (D-III) expression.At this moment, the compound of above-mentioned formula (D-III) expression preferably contains 0.5 mole more than the % with respect to whole diamines, more preferably contains more than 1 mole.
[synthesizing of polyamic acid]
Polyamic acid contained in the aligning agent for liquid crystal of the present invention can make by making the tetracarboxylic dianhydride and the diamine reactant of the compound that contains above-mentioned formula (A) expression.
Supply with the tetracarboxylic dianhydride of polyamic acid synthetic reaction and the usage rate of diamines, preferably with respect to 1 equivalent amino of diamines, the anhydride group that makes the tetracarboxylic dianhydride 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 preferably in organic solvent, is preferable over-20 ℃～150 ℃, more preferably under 0～100 ℃ temperature conditions, preferably carries out 1～48 hour, more preferably carries out 2～12 hours.Here, as organic solvent, as long as can dissolve the polyamic acid of generation, 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-, non-protonic solvents such as amide compound, dimethyl sulfoxide (DMSO), gamma-butyrolacton, tetramethylurea, HMPA such as N-dimethyl propylene acid amides; Between phenolic compound such as sylvan, xylenols, phenol, halogenated phenol etc.The consumption of organic solvent (α), being preferably the total amount (β) that makes tetracarboxylic dianhydride and diamines usually is the amount of 0.1～30 weight % with respect to the total amount (alpha+beta) of reaction solution.
In the above-mentioned organic solvent, in the scope that the polyamic acid that does not make generation is separated out, the alcohols of the poor solvent of all right coupling 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, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, isoamyl oxide etc.
When with organic solvent and poor solvent coupling, the consumption of poor solvent can suitably be set in and not make in the scope that the polyamic acid that generated separates out, and preferably the total amount with respect to solvent is below the 80 weight %, more preferably below the 50 weight %.
As mentioned above, obtained dissolving the reaction solution of polyamic acid.This reaction solution can be supplied with to former state the preparation of aligning agent for liquid crystal, also polyamic acid contained in the reaction solution can be separated the back and supply with the preparation of aligning agent for liquid crystal, resupply the preparation of aligning agent for liquid crystal after perhaps also isolated polyamic acid can being made with extra care.The separation of polyamic acid can obtain precipitate by above-mentioned reaction solution is put in a large amount of poor solvents, and the method for this precipitate of drying under reduced pressure is perhaps carried out reaction solution with the method for evaporator decompression distillation again.In addition,, make its method of separating out with poor solvent then, or, can make with extra care polyamic acid with the operation of evaporator decompression distillation by carrying out that this polyamic acid is dissolved in the organic solvent once more.
＜polyimide 〉
The polyimide that can contain in the aligning agent for liquid crystal of the present invention can be by making aforesaid polyamic acid dehydration closed-loop.
As the tetracarboxylic dianhydride who uses in above-mentioned polyimide synthetic, can enumerate and above-mentioned polyamic acid synthetic in the identical compound of tetracarboxylic dianhydride that uses.
The synthetic middle tetracarboxylic dianhydride who uses of the polyimide that contains in the aligning agent for liquid crystal of the present invention is preferably and contains at least a tetracarboxylic dianhydride who is selected from the ester ring type tetracarboxylic dianhydride, more preferably contains to be selected from 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, 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-dicarboxylic anhydride, 4,9-two oxatricyclo [5.3.1.0 2,6] undecane-3,5,8, at least a tetracarboxylic dianhydride of the material group that the 10-tetraketone constitutes.
The synthetic middle tetracarboxylic dianhydride who uses of the polyimide that contains in the aligning agent for liquid crystal of the present invention preferably with respect to whole tetracarboxylic dianhydrides, is contained 50 moles of at least a tetracarboxylic dianhydrides that are selected from the ester ring type tetracarboxylic dianhydride more than the %.
The diamines that uses during as the polyimide that contains in the aligning agent for liquid crystal of the present invention synthetic, can enumerate and above-mentioned polyamic acid synthetic in the identical diamines of diamine compound that uses.
Contained polyimide in the aligning agent for liquid crystal of the present invention, it can be the complete imidizate thing of the amic acid structure fully dehydrating closed loop that had of polyamic acid raw material, also can be only a part of amic acid structure dehydration closed-loop, amic acid structure and imide ring structure and the part imidizate thing of depositing.
Contained polyimide in the aligning agent for liquid crystal of the present invention, its imidizate rate is preferably 80 moles more than the %, more preferably 85 moles more than the %.
Above-mentioned imidizate rate is meant the total quantity with respect to amic acid structure number in the polyimide thing and imide ring structure number, the value that the shared ratio of imide ring number of structures is represented with percent.At this moment, the part of imide ring can also be different imide ring.The imidizate rate can be a primary standard substance with the tetramethylsilane by polyimide being dissolved in the suitable deuterated solvent (for example deuterated dimethyl sulfoxide), at room temperature measures 1H-NMR, by measurement result according to the following equation (i) obtain.
Imidizate rate (%)=(1-A 1/ A 2* α) * 100 (i)
(in the formula (i), A 1Be near the peak area that comes from NH matrix that occurs the chemical shift 10ppm, A 2For coming from the peak area of other protons, α is 1 NH matrix in the precursor (polyamic acid) with respect to polyimide, the individual percentage of other protons).
The dehydration closed-loop of polyamic acid preferred (i) is by the method for heating polyamic acid, and perhaps (ii) by polyamic acid is dissolved in the organic solvent, the method that adds dewatering agent and dehydration closed-loop catalyzer and heating as required in this solution is carried out.
Temperature of reaction in the method for the heating polyamic acid of above-mentioned (i) is preferably 50～200 ℃, more preferably 60～170 ℃.Reaction time is preferably 1～120 hour, more preferably 2～48 hours.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 polyimide 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, and preferably the amic acid structure with respect to 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, trimethylpyridine, 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.As used organic solvent in the dehydration closed-loop reaction, can enumerate as polyamic acid and synthesize middle solvent for use and illustrative organic solvent.The temperature of reaction of dehydration closed-loop reaction is preferably 0～180 ℃, more preferably 10～150 ℃.Reaction time is preferably 1～24 hour, more preferably 2～8 hours.
Said method (ii) in, obtain containing the reaction solution of polyimide as mentioned above.This reaction solution can be supplied with to former state the preparation of aligning agent for liquid crystal, also can from reaction solution, remove dewatering agent and dehydration closed-loop catalyzer and supply with the preparation of aligning agent for liquid crystal afterwards, polyimide can also be separated the back and supply with the preparation of aligning agent for liquid crystal, resupply the preparation of aligning agent for liquid crystal after perhaps also the polyimide that separates can being made with extra care.Remove dewatering agent and dehydration closed-loop catalyzer from reaction solution, can adopt for example method such as solvent exchange.The separation of polyimide, refining can be taked to carry out as the separating of polyamic acid, operation that process for purification is same with above-mentioned.
The polymkeric substance of-end modified type-
Polyamic acid or polyimide contained in the aligning agent for liquid crystal of the present invention can also be the end modified type polymkeric substance that has carried out molecular-weight adjusting.By using the polymkeric substance of end modified type, can under the prerequisite of not damaging effect of the present invention, further improve the coating performance of aligning agent for liquid crystal etc.This end modified type polymkeric substance can be by when polyamic acid synthetic, adds molecular weight regulator and prepare in polymerization reaction system.As molecular weight regulator, can enumerate for example monobasic acid anhydrides, monoamine compound, monoisocyanates compound etc.
As above-mentioned 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.As above-mentioned 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.As above-mentioned monoisocyanates compound, can enumerate for example phenyl isocyanate, isocyanic acid naphthyl ester etc.
The usage rate of molecular weight regulator with respect to 100 weight portion diamines, is preferably below 20 weight portions, more preferably below 5 weight portions.
-solution viscosity-
Polyamic acid that as above makes or polyimide preferably when being made into concentration when being the solution of 10 weight %, have the solution viscosity of 20～800mPas, more preferably have the solution viscosity of 30～500mPas.
The solution viscosity of above-mentioned polymkeric substance (mPas) is the polymer solution to 10 weight % of the good solvent preparation of adopting this polymkeric substance, with the values of E type rotational viscosimeter mensuration under 25 ℃.
＜other adjuvant 〉
Liquid crystal orientation film of the present invention contains the essential composition of at least a conduct that is selected from the material group that polyimide that aforesaid polyamic acid and dehydration closed-loop thereof form constitutes, and can also contain other compositions as required.As this other compositions, can enumerate for example other polymkeric substance, bonding agent etc.
Above-mentioned other polymkeric substance can use in order to improve solution property and electric property.This other polymkeric substance are polyimide polymkeric substance in addition that the polyamic acid of the diamine reactant gained of tetracarboxylic dianhydride and the compound that contains above-mentioned formula (1) expression gets with making this polyamic acid dehydration closed-loop, for example, can enumerate the polyamic acid (hereinafter referred to as " other polyamic acids ") that does not contain tetracarboxylic dianhydride and the diamine reactant gained of the compound that does not contain above-mentioned formula (1) expression, the polyimide (hereinafter referred to as " other polyimide ") that makes this polyamic acid dehydration closed-loop and get, poly amic acid ester, polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly-(styrene-phenyl maleimide) derivant, poly-(methyl) acrylate etc.Wherein, preferably other polyamic acids or other polyimide.
The usage rate of other polymkeric substance, with respect to the total amount of polymkeric substance (be meant the polyamic acid of above-mentioned tetracarboxylic dianhydride and the diamine reactant gained of the compound that contains above-mentioned formula (1) expression and make this polyamic acid dehydration closed-loop and polyimide and the total amount of other polymkeric substance, down together), be preferably below the 99 weight %, more preferably below the 90 weight %.
Above-mentioned bonding agent can use for the liquid crystal orientation film that improves gained and the fusible purpose of substrate surface.As this bonding agent, can enumerate the compound (hereinafter referred to as " epoxy compounds ") that has at least 1 epoxy radicals in the molecule for example, functional silanes compound etc.
As above-mentioned epoxy compounds, can enumerate for example ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-four glycidyl group-2, the 4-hexanediol, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1,3-two (N, N-diglycidyl amino methyl) cyclohexane, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, 3-(N-allyl-N-glycidyl) TSL 8330,3-(N, N-diglycidyl) TSL 8330 etc.
The usage rate of aforesaid epoxy compounds with respect to the total amount of 100 parts by weight polymer, is preferably below 40 weight portions, more preferably 0.1～30 weight portion.
As above-mentioned functional silanes compound, 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.
The usage rate of aforesaid functional silanes compound, the total amount with respect to 100 parts by weight polymer is preferably below 40 weight portions.
＜aligning agent for liquid crystal 〉
Aligning agent for liquid crystal of the present invention be will be selected from least a and optional as required other adjuvant preferred dissolutions that cooperate of the material group that constitutes of aforesaid polyamic acid and polyimide be contained in the organic solvent and constitute.
As the operable organic solvent of aligning agent for liquid crystal of the present invention, can enumerate for example N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolacton, butyrolactam, N, dinethylformamide, N,N-dimethylacetamide, 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, isoamyl propionate, isoamyl isobutyrate, isoamyl oxide etc.They can use separately, also can two or more mixing use.
Solid component concentration in the aligning agent for liquid crystal of the present invention (the total weight of the composition beyond desolventizing in the aligning agent for liquid crystal accounts for the ratio of aligning agent for liquid crystal general assembly (TW)) is considered viscosity, volatility etc. and is suitably selected, is preferably the scope of 1～10 weight %.That is to say, with the aligning agent for liquid crystal of the present invention substrate surface that is coated on as described below, preferably by adding thermosetting as the filming of liquid crystal orientation film, when solid component concentration less than 1 weight %, the thickness that will cause this to film is too small and can not obtain good liquid crystal orientation film; On the other hand, when solid component concentration surpasses 10 weight %, will cause coating thickness blocked up and can not obtain good liquid crystal orientation film, and the viscosity of aligning agent for liquid crystal increase, and causes applying degradation.
Particularly preferred solid component concentration scope, the method that is adopted when aligning agent for liquid crystal is coated on substrate and difference.For example, when adopting spin-coating method, preferred especially solid component concentration is the scope of 1.5～4.5 weight %.When adopting print process, especially preferably making 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, especially preferably making solid component concentration is the scope of 1～5 weight %, like this, can make solution viscosity drop on the scope of 3～15mPas.
Temperature when preparing aligning agent for liquid crystal of the present invention is preferably 0 ℃～200 ℃, more preferably 20 ℃～60 ℃.
＜liquid crystal display cells 〉
Liquid crystal display cells of the present invention has the liquid crystal orientation film that is formed by aforesaid aligning agent for liquid crystal of the present invention.
Liquid crystal display cells of the present invention can pass through for example following operation manufacturing.
(1) by methods such as rolling method, spin-coating method, offset printing method, ink-jet methods, 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; Polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly-plastics system transparency carriers such as (alicyclic hydrocarbon).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, forming the acquisition of the nesa coating of pattern, for example can adopt after forming patternless nesa coating to form method of patterning by photoengraving or employing has the mask of required pattern when nesa coating forms method etc.When the coating of aligning agent for liquid crystal, for the cohesive of further improving substrate surface and nesa coating and filming, can also will form on the face of filming in substrate surface, apply the pre-treatment of functional silanes compound, functionality titanium compound etc. in advance.
Heating after the aligning agent for liquid crystal coating preferably preheats (prebake) operation and roasting (afterwards curing) operation successively.The heating-up temperature of prebake is preferably 30～300 ℃, more preferably 40～200 ℃, is preferably 50～150 ℃ especially.Be preferably 0.1～10 minute the heat time heating time of prebake, more preferably 1～5 minute.After to cure operation be that purpose is carried out to remove solvent of containing in the aligning agent for liquid crystal of the present invention etc. fully.The temperature of curing after this is preferably 80～300 ℃, more preferably 120～250 ℃.After heat time heating time of curing be preferably 5～300 minutes, more preferably 30～120 minutes.
Aligning agent for liquid crystal of the present invention is removed organic solvent after by coating like this, formation is filmed as alignment films, when the polymkeric substance that contains in the aligning agent for liquid crystal of the present invention is polyamic acid or has the imide ring structure simultaneously and during the polyimide of amic acid structure, can also be after the formation of filming, further make its dehydration closed-loop, to form filming of further imidizate by heating.
Here the thickness of filming of Xing Chenging is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
(2) then, adopt the roller that is tied with fibrous cloth such as nylon, regenerated fiber, cotton for example that the coated surface that as above forms is carried out grinding process with the certain orientation friction.Like this, making films goes up generation liquid crystal molecular orientation energy, makes liquid crystal orientation film.In addition, for the situation of VA type liquid crystal display cells, also have and not carry out grinding process.
In addition; to the liquid crystal orientation film that forms by aligning agent for liquid crystal of the present invention; carry out the processing that the regional tilt angle of a liquid crystal orientation film part is changed to a part of irradiation ultraviolet radiation of liquid crystal orientation film shown in patent documentation 4 (Japanese kokai publication hei 6-222366 communique) for example or the patent documentation 5 (Japanese kokai publication hei 6-281937 communique); perhaps carry out shown in the patent documentation 6 (Japanese kokai publication hei 5-107544 communique) after forming diaphragm on the part surface of liquid crystal orientation film; carry out the processing of removing diaphragm after the grinding process with the direction different with previous grinding process; make each zone of liquid crystal orientation film have different liquid crystal aligning energy, can improve the visual field performance of gained liquid crystal display cells like this.
(3) it is staggered relatively a pair of substrate that as above forms liquid crystal orientation film to be passed through gap (box gap), make the vertical or antiparallel of polishing direction of the liquid crystal orientation film of two substrates, fitted with sealant in two 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, the polaroid of fitting on the outside surface of liquid crystal cell makes the polishing direction of the liquid crystal orientation film that forms on its polarization direction and each substrate consistent or vertical, so just can make liquid crystal display cells.Here, as sealant, can use epoxy resin that for example contains as the alumina balls 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 for example cholesteryl liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate in these liquid crystal; Chirality agent with trade name " C-15 ", " CB-15 " (メ Le Network corporate system) sale; To oxygen base benzylidene-to ferroelectric liquid crystals such as amino-2-methyl butyl cinnamate etc. and using in the last of the ten Heavenly stems.
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 " 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.
As above the liquid crystal display cells of the present invention of Zhi Zuoing is compared with previously known liquid crystal display cells, even have the advantage that display performance when driving for a long time can deterioration yet.
[embodiment]
Below, by embodiment the present invention is carried out more specific description, but the present invention is not limited to these embodiment.Following polymer solution viscosity all is to adopt E type viscosity meter 25 ℃ of values of measuring down.
The synthesis example of the compound of＜above-mentioned formula (1) expression 〉
Embodiment 1 (synthesizing of compound (1-2-1))
According to following proposal 1 synthetic compound (1-2-1).
Figure G2008101857562D00301
Scheme 1
In the three-neck flask of the 2L with nitrogen ingress pipe, thermometer and tap funnel, add the 38g potassium cyanate, in tap funnel, add 224g 3-nitrobenzophenone isocyanates, fully carry out drying.Then, add the abundant dried N of 1L and 500mL respectively in flask and tap funnel, dinethylformamide carries out dropping liquid after flask is heated to 75 ℃, and then reacts continuing to stir under 30 minutes the condition.After reaction is finished, under reduced pressure remove N, dinethylformamide adds 1L ethyl acetate and 3L water in residue, carry out separatory.In water layer, add concentrated hydrochloric acid, reclaim the sediment of separating out, carry out crystallization again, thus, obtain the white crystals of 191g compound (1-1a) by ethanol.
Then, the 74g in the three-neck flask of 2000mL in the compound (1-1a) of the above-mentioned acquisition of adding adds 2.2g potassium hydroxide, 73g bromination n-octadecane again, and 1000mLN, and dinethylformamide is reacting under 5 hours the condition of stirring down at 50 ℃.After reaction is finished, in reaction mixture, add ethyl acetate and saturated sodium hydrate aqueous solution, shake, remove water layer.The flushing organic layer after carrying out drying, concentrate with magnesium sulphate, carries out crystallization again with the mixed solution of ethanol and tetrahydrofuran, thus, and the yellow crystal of acquisition 41g compound (1-2-1b).
Then, the 23.9g in the three-neck flask of the 1000mL with thermometer in the compound (1-2-1b) of the above-mentioned acquisition of adding, and then add 86g tin chloride dihydrate and 400mL ethanol, reacting under 1 hour the condition of stirring down at 70 ℃.After reaction is finished, adding sodium bicarbonate aqueous solution in reaction mixture neutralizes, adding ethyl acetate then filters, the organic layer of water flushing afterwards, after carrying out drying, concentrate with magnesium sulphate, make with extra care with silicagel column, and carry out crystallization again with ethanol, thus, obtain the white crystals of 5.1g compound (1-2-1).
Embodiment 2
Synthetic compound as scheme 2 (1-2-2).
Synthesizing of compound (1-2-2b)
In the three-neck flask of the 1L with thermometer, tap funnel and nitrogen ingress pipe, add compound (1-1a), 21.0g triphenylphosphine, 11.7g cholestanol and 400mL tetrahydrofuran synthetic among the 11.1g embodiment 1.Then, 34mL 2.2M diethyl azodiformate/toluene solution is dissolved in the 100mL tetrahydrofuran, with 30 minutes with this solution dropping liquid at room temperature, continue then at room temperature to stir 2 hours.After reaction is finished, add ethyl acetate, carry out twice separatory with saturated sodium bicarbonate aqueous solution and clean, water carries out three separatory and cleans, and carries out drying with magnesium sulphate.Then, after drying is solidified, use methyl alcohol: the mixed solvent of tetrahydrofuran=8: 2 carries out crystallization again, obtains the white crystals of 13.1g compound (1-2-2b) thus.
Synthesizing of compound (1-2-2)
In the pyriform bottle of the 500mL with nitrogen ingress pipe and recirculatory pipe, add 13.1g compound (1-2-2b), add 38g tin chloride dihydrate and 200mL ethanol, react under 1 hour the condition of stirring down at 70 ℃.After reaction is finished, adding sodium bicarbonate aqueous solution in reaction mixture neutralizes, adding ethyl acetate then filters, the organic layer of water flushing afterwards, after carrying out drying, concentrate with magnesium sulphate, use ethanol: the mixed solvent of tetrahydrofuran=10: 1 carries out crystallization again, thus, obtains the white crystals of 4.0g compound (1-2-2).
Figure G2008101857562D00321
Scheme 2
Embodiment 3
Synthetic compound as scheme 3 (1-1-1).
In the pyriform bottle of the 1L with nitrogen ingress pipe and recirculatory pipe, add 37.1g compound (1-1a), 0.5g palladium carbon, 350mL ethanol, 150mL tetrahydrofuran and 12.3mL hydrazine monohydrate, at room temperature stirred 1 hour, then, reacted 2 hours down at 70 ℃.After reaction finishes, that the filtered fluid that filters gained is concentrated, dry.Use tetrahydrofuran: the ratio of methyl alcohol=5: 1 is carried out crystallization again to the gained solid, obtains 16g compound (1-1-1) thus.
Figure G2008101857562D00331
Scheme 3
The synthesis example of＜polyimide 〉
Embodiment 4
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 2.24g (0.01 mole) and as the p-phenylenediamine (PPD) 0.97g (0.009 mole) of diamine compound, and the 0.56g (0.001 mole) of the compound (1-2-1) of gained is dissolved in the 15.12gN-N-methyl-2-2-pyrrolidone N-in the foregoing description 1, it was reacted 6 hours down at 60 ℃, obtain containing the solution of 20 weight % polyamic acids.The solution viscosity of this polyamic acid solution is 5000mPas.
Then, in the gained polyamic acid solution, append 35.10g N-N-methyl-2-2-pyrrolidone N-, add 0.79g pyridine and 10.2g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by the solvent in the system is carried out solvent exchange (in this operation the pyridine and the acetic anhydride that use in the dehydration closed-loop reaction being removed to system) with new N-N-methyl-2-2-pyrrolidone N-, obtain 19.00g and contain the solution that 19 weight % imidizate rates are 49% polyimide (A-1).This solution that takes a morsel adds the N-N-methyl-2-2-pyrrolidone N-, is made into the solution that polymer concentration is 6.0 weight %, and the solution viscosity of mensuration is 22mPas.
Embodiment 5
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 5.1g and as the p-phenylenediamine (PPD) 2.1g of diamine compound, and the 5.1g of the compound (1-2-2) of gained is dissolved in the 42g N-N-methyl-2-2-pyrrolidone N-in the foregoing description 2, it was reacted 6 hours down at 60 ℃, obtain containing the solution of 20 weight % polyamic acids.The solution viscosity of this polyamic acid solution is 4800mPas.
Then, in the gained polyamic acid solution, append 98g N-N-methyl-2-2-pyrrolidone N-, add 1.8g pyridine and 2.3g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by the solvent in the system is carried out solvent exchange (in this operation the pyridine and the acetic anhydride that use in the dehydration closed-loop reaction being removed to system) with new N-N-methyl-2-2-pyrrolidone N-, obtain 140g and contain the solution that 19 weight % imidizate rates are 50% polyimide (A-2).This solution that takes a morsel adds the N-N-methyl-2-2-pyrrolidone N-, is made into the solution that polymer concentration is 6.0 weight %, and the solution viscosity of mensuration is 21mPas.
Embodiment 6
Will be as tetracarboxylic dianhydride's cyclo-butane tetracarboxylic dianhydride 4.0g with as 2 of diamine compound, 2 '-dimethylbenzidine 4.4g, and the 1.6g of the compound (1-1-1) of gained is dissolved in 9.0g N-N-methyl-2-2-pyrrolidone N-and the 81g gamma-butyrolacton in the foregoing description 3, it was at room temperature reacted 6 hours, obtain containing the solution (as (PA-1)) of 10 weight % polyamic acids.The solution viscosity of this polyamic acid solution is 168mPas.
Synthesis example 1
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 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), p-phenylenediamine (PPD) 96g (0.89 mole) as diamine compound, two aminopropyl tetramethyl disiloxane 25g (0.10 mole) and 3,6-two (4-aminobenzoic acyl-oxygen base) cholestane 13g (0.020 mole), and be dissolved in the 960g N-N-methyl-2-2-pyrrolidone N-as the N-octadecylamine 8.1g (0.030 mole) of monoamine, make it 60 ℃ of reactions 6 hours down.The take a morsel polyamic acid solution of gained adds NMP, and the measured in solution viscosity with solid component concentration 10% is 60mPas.Then, in the polyamic acid solution of gained, add the 2700gN-N-methyl-2-2-pyrrolidone N-, add 396g pyridine and 409g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the imidization reaction, by the solvent in the system being carried out solvent exchange (pyridine and the acetic anhydride that use in imidization reaction are removed to system) with new gamma-butyrolacton in this operation, obtaining about 2000g solid component concentration is that 15wt%, solid component concentration are that 6.0% o'clock (gamma-butyrolacton solution) solution viscosity is that 16mPas, imidizate rate are about 95% imide amination polymer (with it as " imide amination polymer (B-2) ").
Compare synthesis example 1
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 224g (1.0 moles) and as the p-phenylenediamine (PPD) 99g (0.90 mole) of diamine compound, and the compound 53g (0.10 mole) of expression in the above-mentioned formula (D-10) is dissolved in the 1510g N-N-methyl-2-2-pyrrolidone N-, it was reacted 6 hours down at 60 ℃, obtain containing the polymer solution of 20 weight % polyamic acids.The solution viscosity of this polyamic acid solution is 2560mPas.
Then, in the gained polyamic acid solution, append 3500g N-N-methyl-2-2-pyrrolidone N-, add 79g pyridine and 102g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by the solvent in the system is carried out solvent exchange (in this operation the pyridine and the acetic anhydride that use in the dehydration closed-loop reaction being removed to system) with new N-N-methyl-2-2-pyrrolidone N-, obtain about 2000g and contain the solution that 20 weight % imidizate rates are about 53% polyimide (B-1).This solution that takes a morsel adds the N-N-methyl-2-2-pyrrolidone N-, is made into the solution that polymer concentration is 6.0 weight %, and the solution viscosity of mensuration is 16mPas.
The preparation of＜aligning agent for liquid crystal and evaluation 〉
Embodiment 7
(I) preparation of aligning agent for liquid crystal
In the solution that contains polyimide (A-1) synthetic in the foregoing description 4, add N-N-methyl-2-2-pyrrolidone N-and butyl cellosolve as polymkeric substance, making solvent composition is the N-N-methyl-2-2-pyrrolidone N-: butyl cellosolve=50: 50 (weight ratio), solid component concentration are the solution of 4 weight %, the use aperture is that the filtrator of 1 μ m filters this solution, makes aligning agent for liquid crystal thus.
(II) evaluation of aligning agent for liquid crystal
(1) manufacturing of liquid crystal display cells
Adopt spin coater that the aligning agent for liquid crystal of above-mentioned preparation is coated on the simultaneously last ITO film system nesa coating that is provided with of glass substrate that thickness is 1mm, in prebake conditions on 80 ℃ the heating plate after 1 minute, heated 60 minutes down in 200 ℃, forming thickness is film (liquid crystal orientation film) of 0.08 μ m.Repeat these operations, make a pair of (two) have liquid crystal orientation film on nesa coating substrate.
On each outer rim of the face with liquid crystal orientation film of above-mentioned a pair of substrate, coating relatively overlaps the liquid crystal aligning face and pressing after having added the epoxy adhesive of alumina balls that diameter is 5.5 μ m, and bonding agent solidified.Then, by liquid crystal injecting port between substrate, fill negative type liquid crystal (メ Le Network society system, MLC-6608) after, with the acrylic compounds Photocurable adhesive liquid crystal injecting port is sealed, the polaroid of fitting on the two sides, the outside of substrate produces liquid crystal display cells.
To this liquid crystal display cells, by the following method vertical orientated property, residual DC voltage and voltage leak are estimated.
(2) evaluation of vertical orientated property
To the liquid crystal display cells of above manufacturing, the employing polarizing microscope is observed under the cross Nicol prism and is applied at voltage, has or not abnormal area when removing, no abnormal zone, its liquid crystal aligning is evaluated as " well ".
(3) evaluation of residual DC voltage
Under 60 ℃ environment temperature, the liquid crystal display cells of as above making is applied the DC voltage of 20 hours 5.0V, remove this voltage application after, under room temperature environment, place cooling after 15 minutes, adopt the flicker null method to obtain residual voltage in the liquid crystal cell.At this moment, residual voltage is 300mV when following, and residual DC voltage is chosen as " well ".
(4) evaluation of leakage with voltage
To the liquid crystal display cells of above-mentioned manufacturing apply 1 second 10V voltage after, circuit is made as open state leaves standstill, measure from the variation in time of the transmitted intensity of liquid crystal cell projection.At this moment, be reduced to 10% situation of the transmitted intensity of initial (when voltage applies) within 10 minutes, its leakage with voltage is evaluated as " well ", not being evaluated as of reduction " defective " within 10 minutes.
Above-mentioned all evaluation results are shown in table 1.The aligning agent for liquid crystal of confirming present embodiment shows good vertical orientated property and low-residual dc voltage, and leakage with voltage is good.
Embodiment 8
(I) preparation of aligning agent for liquid crystal
In the solution that contains polyimide (A-1) synthetic in the foregoing description 4, add N-N-methyl-2-2-pyrrolidone N-and butyl cellosolve as polymkeric substance, the polyimide (A-1) that adds again with respect to 100 weight portions is the N as epoxide of 10 weight portions, N, N ', N '-four glycidyl group-m-xylene diamine, making solvent composition is the N-N-methyl-2-2-pyrrolidone N-: butyl cellosolve=50: 50 (weight ratio), solid component concentration are the solution of 4 weight %, the use aperture is that the filtrator of 1 μ m filters this solution, makes aligning agent for liquid crystal thus.
(II) evaluation of aligning agent for liquid crystal
As aligning agent for liquid crystal, except the aligning agent for liquid crystal that uses above-mentioned preparation, liquid crystal display cells is made in operation similarly to Example 3, estimates.
Evaluation result is shown in table 1
Comparative example 1
As polymer solution, except use contains the solution of the polyimide (B-1) that above-mentioned relatively synthesis example 1 makes, operation similarly to Example 7, the preparation aligning agent for liquid crystal is estimated.
Evaluation result is shown in table 1
Comparative example 2
As polymer solution, except use contains the solution of the polyimide (B-1) that above-mentioned relatively synthesis example 1 makes, operation similarly to Example 8, the preparation aligning agent for liquid crystal is estimated.
Evaluation result is shown in table 1
Table 1
Figure G2008101857562D00381
Embodiment 9
Except using polyimide (A-2) to replace carrying out similarly to Example 8 the polyimide (A-1).Vertical orientated property, residual DC voltage, leakage with voltage are all good.
Embodiment 10
(I) preparation of aligning agent for liquid crystal
To convert by solid constituent as polyimide (B-2) synthetic in polyamic acid (PA-1) synthetic in the foregoing description 6 of polymkeric substance and the synthesis example 1, be adjusted into 8: 2, in this solution, add gamma-butyrolacton, N-N-methyl-2-2-pyrrolidone N-and butyl cellosolve, making solvent composition is gamma-butyrolacton: the N-N-methyl-2-2-pyrrolidone N-: butyl cellosolve=40: 40: 20 (weight ratio), solid component concentration are the solution of 4 weight %, the use aperture is that the filtrator of 1 μ m filters this solution, makes aligning agent for liquid crystal thus.
(II) evaluation of aligning agent for liquid crystal
(1) manufacturing of liquid crystal display cells
Adopt spin coater that the aligning agent for liquid crystal of above-mentioned preparation is coated on the simultaneously last ITO film system nesa coating that is provided with of glass substrate that thickness is 1mm, in prebake conditions on 80 ℃ the heating plate after 1 minute, heated 60 minutes down in 200 ℃, forming thickness is film (liquid crystal orientation film) of 0.08 μ m.Repeat these operations, make a pair of (two) have liquid crystal orientation film on nesa coating substrate.The sander of the roller that twines Artificial Fibers cloth is equipped with in employing, is that 500rpm, 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, this is filmed carry out grinding process, forms liquid crystal orientation film.Then, use ultrasonic washing after 1 minute in ultrapure water, drying is 10 minutes in 100 ℃ cleaning oven.Then, on each outer rim with liquid crystal orientation film of this a pair of substrate, coating relatively overlaps the liquid crystal aligning face and pressing after having added the epoxy adhesive of alumina balls that diameter is 5.5 μ m, and bonding agent is solidified.Then, by liquid crystal injecting port between a pair of substrate, fill nematic crystal (メ Le Network society system, MLC-6221) after, with the acrylic compounds Photocurable adhesive liquid crystal injecting port is sealed, produce liquid crystal display cells of the present invention.
Under 70 ℃ environment temperature, apply 500 hours overlapping 30Hz of 6.0V alternating current (peak-peak), the square waves of 3.0V to the liquid crystal display cells of gained, the visual observations element does not find that the demonstration of liquid crystal display cells is defective.
In addition, under 60 ℃ environment temperature, the liquid crystal display cells of as above making is applied the DC voltage of 20 hours 5.0V, remove this voltage application after, decay adopted the flicker null method to obtain residual voltage in the liquid crystal cell after 15 minutes under room temperature environment.At this moment, residual voltage is below the 300mV, and residual DC voltage is " well ".
Have again, to the liquid crystal display cells of above-mentioned manufacturing apply 1 second 10V voltage after, circuit is made as open state leaves standstill, measure from the variation in time of the transmitted intensity of liquid crystal cell projection.At this moment, within 10 minutes, be reduced to initial (when voltage applies) transmitted intensity 10%, leakage with voltage is " well ".
The aligning agent for liquid crystal of confirming present embodiment shows good vertical orientated property and low-residual dc voltage, and leakage with voltage is good.

Claims (7)

1. aligning agent for liquid crystal, it is characterized in that comprising at least a polymkeric substance that is selected from the following substances group, this material group is by tetracarboxylic dianhydride and the polyamic acid of the diamine reactant gained of the compound that contains following formula (1) expression and the polyimide that this polyamic acid dehydration closed-loop is formed are constituted
Figure FSB00000587323400011
In the formula (1), R is that hydrogen atom, carbon number are that 1～40 alkyl, carbon number are that 1～40 fluoroalkyl or carbon number are 3～40 ester ring type group.
2. the described aligning agent for liquid crystal of claim 1, the R in the above-mentioned formula (1) are that carbon number with steroid backbone is 17～40 ester ring type group.
3. claim 1 or 2 described aligning agent for liquid crystal, wherein, the tetracarboxylic dianhydride comprises at least a tetracarboxylic dianhydride who is selected from the material group that is made of ester ring type tetracarboxylic dianhydride and pyromellitic acid dianhydride.
4. liquid crystal display cells, it comprises the liquid crystal orientation film that is formed by each described aligning agent for liquid crystal in the claim 1～3.
5. polyamic acid, it is made with the diamine reactant of the compound that comprises following formula (1) expression by the tetracarboxylic dianhydride,
Figure FSB00000587323400012
In the formula (1), R is that hydrogen atom, carbon number are that 1～40 alkyl, carbon number are that 1～40 fluoroalkyl or carbon number are 3～40 ester ring type group.
6. polyimide, it is made by the polyamic acid dehydration closed-loop that the tetracarboxylic dianhydride is made with the diamine reactant of the compound that comprises following formula (1) expression,
Figure FSB00000587323400021
In the formula (1), R is that hydrogen atom, carbon number are that 1～40 alkyl, carbon number are that 1～40 fluoroalkyl or carbon number are 3～40 ester ring type group.
7. the compound of a following formula (1) expression,
Figure FSB00000587323400022
In the formula (1), R is that hydrogen atom, carbon number are that 1～40 alkyl, carbon number are that 1～40 fluoroalkyl or carbon number are 3～40 ester ring type group.
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