CN1807551A - Liquid crystal oriental agent and liquid crystal displaying componnet - Google Patents
Liquid crystal oriental agent and liquid crystal displaying componnet Download PDFInfo
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- CN1807551A CN1807551A CNA200610001143XA CN200610001143A CN1807551A CN 1807551 A CN1807551 A CN 1807551A CN A200610001143X A CNA200610001143X A CN A200610001143XA CN 200610001143 A CN200610001143 A CN 200610001143A CN 1807551 A CN1807551 A CN 1807551A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- 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 provides a liquid crystal aligning agent capable of forming a liquid crystal alignment layer which can stably develop a high pretilt angle and of having superior printing characteristics, even with respect to a substrate having a large surface level difference. The liquid crystal aligning agent contains a polyamic acid, obtained by using phenylenediamine having a steroid skeleton, such as cholestanyloxy methyldiaminobenzene as diamine, or imidized polymers of the polyamic acid.
Description
Technical field
The present invention relates to liquid crystal aligning agent and liquid crystal display device.
Background technology
So far, known liquid crystal display device with TN (twisted-nematic (Twisted Nematic)) type or STN (supertwist is to row (Super Twisted Nematic)) type liquid crystal cell, this liquid crystal cell by nesa coating between 2 substrates that formed the liquid crystal orientation film that polyamic acid or polyimide constitute on the surface, formation has the nematic liquid crystal layer of positive dielectric anisotropy, constitute sandwich structure, the major axis of above-mentioned liquid crystal molecule twist continuously between the substrate 90 degree or more than.Driving so-called TFT LCD panel that this TN type liquid crystal display device the carries out work cathode tube before substituting by TFT popularizes widely.Liquid crystal aligning in these liquid crystal display device usually by given through grinding process etc. liquid crystal molecular orientation can liquid crystal orientation film realize.In addition, as the liquid crystal display device beyond above-mentioned, known liquid crystal display device with vertical orientated (Vertical Alignment) type liquid crystal cell, this liquid crystal cell makes the liquid crystal molecule with negative dielectric anisotropic vertical orientated between substrate.In this liquid crystal display device, the control of the orientation of liquid crystal realizes by the liquid crystal orientation film that is formed by the liquid crystal aligning agent that contains polymkeric substance such as polyamic acid, polyimide usually.
In recent years, for the purpose of the picture that reaches the more bright-coloured grace of acquisition, liquid crystal display device constantly carries out high apertureization, high-accuracyization.For example, in TN type liquid crystal display device, must have and stably to show tilt angle than bigger in the past liquid crystal orientation film.
In addition, the good vertical alignment-type liquid crystal display device majority of angle of visibility is used for watch-dog purposes, TV purposes, and it must have can stablize the liquid crystal orientation film that shows about 90 degree tilt angles.Liquid crystal orientation film is coated liquid crystal aligning agent on the substrate and is cured by printing press usually and forms, but, then have in the image that the liquid crystal display device of this liquid crystal orientation film shows and also have the mottled situation that occurs if the liquid crystal orientation film media thickness that forms is inhomogeneous.Therefore need the good liquid crystal aligning agent of coating.
Tilt angle can be by introducing in polymkeric substance as having 1-octadecane oxygen base-2 on the disclosed side chain in the patent documentation 1, the substituent monomer of the such large volume of 4-diaminobenzene (below, be called the monomer that shows tilt angle) and show.Tilt angle depends on monomeric introducing amount greatly, even and under the situation of identical introducing amount, if side-chain structure changes, then Biao Xian tilt angle also can change.
1-octadecane oxygen base-2, the tilt angle expressive ability of 4-diaminobenzene is very little, if will stably show the high tilt angle of 90 degree, then monomeric introducing amount must be quite a lot of.Like this, the liquid crystal aligning agent printing that forms with resulting polymers is not fine, and there is the problem that can not show the graceful graph picture in the liquid crystal display device that has with the liquid crystal orientation film of its formation.
In addition, disclose in the patent documentation 2 and comprise 4-(4-(4-n-amyl group cyclohexyl) cyclohexyl-2,6-difluorophenyl) oxygen base difluoromethyl-1, the 3-phenylenediamine is at 6 kinds of interior diamines, and put down in writing under the situation of introducing with respect to 90 moles of % of diamines total amount, can show high tilt angle.But the liquid crystal aligning agent printing that contains the polymkeric substance that useful this diamines obtains is not fine, and there is the problem that can not show the graceful graph picture in the liquid crystal display device that has with the liquid crystal orientation film of its formation.
On the other hand, in the patent documentation 3 disclosed 3,5-diaminobenzoic acid cholesteryl ester, lithocholic acid octadecyl (3,5-diaminobenzoic acid ester) has higher tilt angle expressive ability, the polymkeric substance of enough molecular weight can be obtained having with it, superior printing characteristics can be shown with the liquid crystal aligning agent of this polymer manufacture.Therefore, the liquid crystal display device with the liquid crystal orientation film that forms with this liquid crystal aligning agent can show graceful image.
The flat 6-136122 communique of [patent documentation 1] TOHKEMY
[patent documentation 2] TOHKEMY 2003-96034 communique
[patent documentation 3] JP speciallys permit communique No. 2893671
Summary of the invention
But liquid crystal display device needs more accurate more graceful demonstration, and must can be adapted to animation.
Therefore, the stage difference that forms on the substrate is greater than one-level, and existing liquid crystal aligning agent printing becomes gradually and can not meet the demands.
The present invention is based on above-mentioned situation.
First purpose of the present invention provides a kind of liquid crystal aligning agent, and it can form the liquid crystal orientation film that can stably show high tilt angle, and the bigger substrate of stage difference is also had superior printing characteristics.
Second purpose of the present invention provides a kind of liquid crystal display device that can show the graceful graph picture.
Other purpose of the present invention and advantage can be found out by the following description.
According to the present invention, above-mentioned purpose of the present invention and advantage, first, reach by a kind of liquid crystal aligning agent, it is characterized in that containing a kind of polymkeric substance, this polymkeric substance (being limited to the represented polymkeric substance with organic group of formula (III)) has at least a repeating unit that is selected among the group that repeating unit that following formula (I) and following formula (II) represent separately forms
Wherein, R
1And R
3Independently of each other for remove the divalent organic group of 2 amino, R by diamines
2And R
4For removed 4 valency organic groups of 4 carboxyls by tetracarboxylic acid, m, n are positive integer independently of each other, still, and R
1And R
3At least one is the organic group of following formula (III) expression,
Wherein, C is 1 a valency organic group with steroid backbone, and A is that methylene radical or carbonatoms are 2～4 alkylidene group, and it can also have the halogen atom substituting group, and B is singly-bound or ehter bond group.
In addition, according to the present invention, above-mentioned purpose of the present invention and advantage, the second, reach by a kind of liquid crystal aligning element with the liquid crystal orientation film that forms by above-mentioned liquid crystal aligning agent.
Liquid crystal aligning agent printing of the present invention is good, can form the liquid crystal orientation film that stably shows high tilt angle.
Use the liquid crystal display device of liquid crystal aligning agent of the present invention, except applicable to the vertical alignment-type liquid crystal display device, can also be applicable to the liquid crystal display device of IPS (In-Plane Switching) type, TN type, STN type, strong dielectricity and anti-strong dielectricity etc. according to selection to used liquid crystal.
And the liquid crystal display device with liquid crystal orientation film of the present invention can be used for various devices effectively, for example is used for display unit such as desk-top computer, wrist-watch, table clock, coefficient display screen, word processor, Personal Computer, liquid crystal TV set.
Embodiment
Below, the present invention is described in detail.Liquid crystal aligning agent of the present invention contains the repeating unit of above-mentioned formula (I) expression and/or the repeating unit of above-mentioned formula (II) expression.The repeating unit of above-mentioned formula (I) expression can make by making the reaction in organic solvent of tetracarboxylic acid dicarboxylic anhydride and diamine compound, polymerization.In addition, by the polymkeric substance dehydration closed-loop imidization of the repeating unit with formula (I) expression that will so obtain, can obtain the repeating unit of above-mentioned formula (II) expression by the repeating unit of above-mentioned formula (I) expression.
R in the repeating unit of above-mentioned formula (I) expression
1With the R in the repeating unit of representing in the above-mentioned formula (II)
3For remove the divalent organic group of 2 amino, R by diamines
1, R
3In at least one is the organic group of above-mentioned formula (III) expression.
As the organic group that C in the above-mentioned formula (III) represents, can enumerate the structure of following formula (III-1)～(III-4) expression particularly with steroid backbone.
In the formula (III-4), R
0It is 1～20 alkyl or alicyclic ring shape skeleton and the optional 1 valency organic group that can be replaced by halogen atom that expression has carbonatoms.
Have that the diamine compound of the organic group with steroid backbone of above-mentioned formula (III) expression is following to be represented with " specific diamine compound ".
As the object lesson of specific diamines, for example, can enumerate 1-cholestene oxygen ylmethyl-2, the 4-diaminobenzene, 2-cholestene oxygen base ethyl-2, the 4-diaminobenzene, 3-cholestene oxygen base propyl group-2, the 4-diaminobenzene, 4-cholestene oxygen Ji Dingji-2, the 4-diaminobenzene, 1-cholestene oxygen ylmethyl-3, the 5-diaminobenzene, 2-cholestene oxygen base ethyl-3, the 5-diaminobenzene, 3-cholestene oxygen base propyl group-3, the 5-diaminobenzene, 4-cholestene oxygen Ji Dingji-3, the 5-diaminobenzene, 1-(1-cholestene Oxy-1,1-difluoromethyl)-2, the 4-diaminobenzene, 1-(2-cholestene Oxy-1,1,2,2-tetrafluoro ethyl)-2, the 4-diaminobenzene, 1-(3-cholestene Oxy-1,1,2,2,3,3-hexafluoro propyl group)-2, the 4-diaminobenzene, 1-(4-cholestene Oxy-1,1,2,2,3,3,4,4-octafluoro butyl)-2, the 4-diaminobenzene, 1-(1-cholestene Oxy-1,1-difluoromethyl)-3, the 5-diaminobenzene, 1-(2-cholestene Oxy-1,1,2,2-tetrafluoro ethyl)-3, the 5-diaminobenzene, 1-(3-cholestene Oxy-1,1,2,2,3,3-hexafluoro propyl group)-3, the 5-diaminobenzene, 1-(4-cholestene Oxy-1,1,2,2,3,3,4,4-octafluoro butyl)-3, the 5-diaminobenzene;
1-cholestane oxygen ylmethyl-2,4-diaminobenzene, 2-cholestane oxygen base ethyl-2,4-diaminobenzene, 3-cholestane oxygen base propyl group-2,4-diaminobenzene, 4-cholestane oxygen Ji Dingji-2,4-diaminobenzene, 1-cholestane oxygen ylmethyl-3,5-diaminobenzene, 2-cholestane oxygen base ethyl-3,5-diaminobenzene, 3-cholestane oxygen base propyl group-3,5-diaminobenzene, 4-cholestane oxygen Ji Dingji-3, the 5-diaminobenzene,
1-(1-cholestane Oxy-1,1-difluoromethyl)-2, the 4-diaminobenzene, 1-(2-cholestane Oxy-1,1,2,2-tetrafluoro ethyl)-2, the 4-diaminobenzene, 1-(3-cholestane Oxy-1,1,2,2,3,3-hexafluoro propyl group)-2, the 4-diaminobenzene, 1-(4-cholestane Oxy-1,1,2,2,3,3,4,4-octafluoro butyl)-2, the 4-diaminobenzene, 1-(1-cholestane Oxy-1,1-difluoromethyl)-3, the 5-diaminobenzene, 1-(2-cholestane Oxy-1,1,2,2-tetrafluoro ethyl)-3, the 5-diaminobenzene, 1-(3-cholestane Oxy-1,1,2,2,3,3-hexafluoro propyl group)-3, the 5-diaminobenzene, 1-(4-cholestane Oxy-1,1,2,2,3,3,4,4-octafluoro butyl)-3, the 5-diaminobenzene;
3-(2,4-diaminobenzene ylmethoxy)-4, (2-(2 for 4-dimethyl cholestane, 3-, the 4-diamino-phenyl) oxyethyl group)-4,4-dimethyl cholestane, 3-(3-(2, the 4-diamino-phenyl) propoxy-)-4, (4-(2 for 4-dimethyl cholestane, 3-, the 4-diamino-phenyl) butoxy)-4,4-dimethyl cholestane,
3-(3,5-diaminobenzene ylmethoxy)-4, (2-(3 for 4-dimethyl cholestane, 3-, the 5-diamino-phenyl) oxyethyl group)-4,4-dimethyl cholestane, 3-(3-(3, the 5-diamino-phenyl) propoxy-)-4, (4-(3 for 4-dimethyl cholestane, 3-, the 5-diamino-phenyl) butoxy)-4,4-dimethyl cholestane,
3-(1-(2, the 4-diamino-phenyl)-1,1-difluoro-methoxy)-4,4-dimethyl cholestane, (2-(2 for 3-, the 4-diamino-phenyl)-1,1,2,2-tetrafluoro methoxyl group)-4,4-dimethyl cholestane, 3-(3-(2, the 4-diamino-phenyl)-1,1,2,2,3,3-hexafluoro methoxyl group)-4,4-dimethyl cholestane, (4-(2 for 3-, the 4-diamino-phenyl)-1,1,2,2,3,3,4,4-octafluoro methoxyl group)-4,4-dimethyl cholestane, 3-(1-(3, the 5-diamino-phenyl)-1,1-difluoro-methoxy)-4,4-dimethyl cholestane, (2-(3 for 3-, the 5-diamino-phenyl)-1,1,2,2-tetrafluoro methoxyl group)-4,4-dimethyl cholestane, 3-(3-(3, the 5-diamino-phenyl)-1,1,2,2,3,3-hexafluoro methoxyl group)-4,4-dimethyl cholestane, (4-(3 for 3-, the 5-diamino-phenyl)-1,1,2,2,3,3,4,4-octafluoro methoxyl group)-4,4-dimethyl cholestane;
3-(2, the 4-diamino-phenyl) methoxyl group cholane-24-acid cetyl ester, (2-(2 for 3-, the 4-diamino-phenyl) cholane-24-acid cetyl ester oxyethyl group), (3-(2 for 3-, the 4-diamino-phenyl) cholane-24-acid cetyl ester propoxy-), (4-(2 for 3-, the 4-diamino-phenyl) cholane-24-acid cetyl ester butoxy), 3-(3, the 5-diamino-phenyl) methoxyl group cholane-24-acid cetyl ester, (2-(3 for 3-, the 5-diamino-phenyl) cholane-24-acid cetyl ester oxyethyl group), (3-(3 for 3-, the 5-diamino-phenyl) cholane-24-acid cetyl ester propoxy-), 3-(4-(3, the 5-diamino-phenyl) butoxy) cholane-24-acid cetyl ester;
3-(1-(3, the 5-diamino-phenyl)-1,1-difluoro-methoxy) cholane-24-acid cetyl ester, (2-(3 for 3-, the 5-diamino-phenyl)-1,1,2,2-tetrafluoro oxyethyl group) cholane-24-acid cetyl ester, (3-(3 for 3-, the 5-diamino-phenyl)-1,1,2,2,3,3-hexafluoro propoxy-) cholane-24-acid cetyl ester, 3-(4-(3, the 5-diamino-phenyl)-1,1,2,2,3,3,4,4-octafluoro butoxy) cholane-24-acid cetyl ester, 3-(3,5-diaminobenzene ylmethoxy) cholane-24-acid stearyl, 3-(2-(3, the 5-diamino-phenyl) oxyethyl group) cholane-24-acid stearyl, (3-(3 for 3-, the 5-diamino-phenyl) cholane-24-acid stearyl propoxy-), 3-(4-(3, the 5-diamino-phenyl) butoxy) cholane-24-acid stearyl;
3-((3, the 5-diamino-phenyl)-1,1-difluoro-methoxy) cholane-24-acid stearyl, 3-(2-(3, the 5-diamino-phenyl)-1,1,2,2-tetrafluoro oxyethyl group) cholane-24-acid stearyl, 3-(3-(3, the 5-diamino-phenyl)-1,1,2,2,3,3-hexafluoro propoxy-) cholane-24-acid stearyl, 3-(4-(3, the 5-diamino-phenyl)-1,1,2,2,3,3,4,4-octafluoro butoxy) cholane-24-acid stearyl.
Wherein, preferred 1-cholestene oxygen ylmethyl-2, the 4-diaminobenzene, 1-cholestene oxygen ylmethyl-3, the 5-diaminobenzene, 1-(1-cholestene Oxy-1, the 1-difluoromethyl)-2, the 4-diaminobenzene, 1-(1-cholestene Oxy-1, the 1-difluoromethyl)-3, the 5-diaminobenzene, 1-(1-cholestane Oxy-1, the 1-difluoromethyl)-2, the 4-diaminobenzene, 1-(1-cholestane Oxy-1, the 1-difluoromethyl)-3, the 5-diaminobenzene, 3-(2,4-diaminobenzene ylmethoxy)-4,4-dimethyl cholestane, 3-(1-(2, the 4-diamino-phenyl)-1,1-difluoro-methoxy)-4,4-dimethyl cholestane, 3-(3,5-diaminobenzene ylmethoxy)-4,4-dimethyl cholestane, 3-(1-(3, the 5-diamino-phenyl)-1, the 1-difluoro-methoxy)-4,4-dimethyl cholestane, 3-((2, the 4-diamino-phenyl) methoxyl group) cholane-24-acid cetyl ester, 3-(1-(2, the 4-diamino-phenyl)-1, the 1-difluoro-methoxy) cholane-24-acid cetyl ester, 3-((3, the 5-diamino-phenyl) cholane-24-acid cetyl ester methoxyl group), 3-(1-(3, the 5-diamino-phenyl)-1,1-difluoro-methoxy) cholane-24-acid cetyl ester;
3-(2,4-diaminobenzene ylmethoxy) cholane-24-acid stearyl, (1-(2 for 3-, the 4-diamino-phenyl)-1, the 1-difluoro-methoxy) cholane-24-acid stearyl, 3-(3,5-diaminobenzene ylmethoxy) cholane-24-acid stearyl, (1-(3 for 3-, the 5-diamino-phenyl)-1, cholane-24-acid stearyl 1-difluoro-methoxy).
In addition, as the repeating unit of above-mentioned in order to obtain (I) expression and the diamine compound that uses, in the scope of not damaging effect of the present invention, other diamine compound beyond can also the coupling specific diamine compound.Here, the ratio that specific diamine compound accounts for whole diamine compounds of supply response is preferably 0.1～100 mole of %, particularly preferred ratio, in TN type and STN type liquid crystal display device, be 0.5～30 mole of %, in vertical alignment-type liquid crystal display device 10～80 moles of %, 10～50 moles of % more preferably.
But other diamine compound as coupling, 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, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene formylaniline, 4,4 '-diamino-diphenyl ether, 1, the 5-diaminonaphthalene, 3,3-dimethyl-4,4 '-benzidine, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethylammonium indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethylammonium indane, 3,4 '-diamino-diphenyl ether, 3,3 '-diamino benzophenone, 3,4 '-diamino benzophenone, 4,4 '-diamino 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 radical-two (2-chloroaniline), 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 1,4,4 '-(right-the phenylene isopropylidene) pentanoic, 4,4 '-(-the phenylene isopropylidene) pentanoic, 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-diamino-2,2 '-dimethyl diphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-aromatic diamines such as octafluoro biphenyl;
1,1-m-xylene diamine, 1,3-propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, 4,4-diamino heptamethylene diamine, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene Dicyclopentadiene (DCPD) diamines, six hydrogen-4,7-methanoindene dimethylene diamines, three ring [6.2.1.02,7]-undecylenes, two methanediamines, 4,4 '-methylene radical two aliphatics and alicyclic diamines such as (hexahydroaniline);
2, the 3-diamino-pyridine, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 5,6-diamino-2,3-dicyano pyrazine, 5,6-diamino-2,4-dihydroxy-pyrimidine, 2,4-diamino-6-dimethylamino-1,3, the 5-triazine, 1,4-two (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3, the 5-triazine, 2,4-diamino-6-methoxyl group-1,3, the 5-triazine, 2,4-diamino-6-phenyl-1,3, the 5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diaminostilbene, 3, the 5-triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenyl thiazole, 2,6-diaminopurine, 5, the 6-diaminostilbene, the 3-dimethyl uracil, 3,5-diaminostilbene, 2, the 4-triazole, 6,9-diamino-2-oxyethyl group acridine lactate, 3,8-diamino-6-phenylphenanthridineand, 1,4-diamino piperazine, 3, the 6-proflavin, two (4-aminophenyl) aniline and following formula (VI) and (VII) have the diamines of the nitrogen-atoms beyond 2 primary aminos and this primary amino in the compound equimolecular of expression
(in the formula, R
5Expression is selected from the 1 valency organic group with nitrogen atom ring texture of pyridine, pyrimidine, triazine, piperidines and piperazine, and X represents the divalent organic group),
(in the formula, X represents to be selected from the divalent organic group with nitrogen atom ring texture of pyridine, pyrimidine, triazine, piperidines and piperazine, R
6Expression divalent organic group, a plurality of X of existence can be the same or different);
Single-substituted two amines of following formula (VIII) expression; The diamino organo-siloxane of following formula (IX) expression;
(in the formula, R
7Expression is selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-the divalent organic group of CO-, R
8It is 6～30 alkyl that expression has 1 valency organic group of the steroid backbone of being selected from, trifluoromethyl and fluorin radical or carbonatoms),
(in the formula, R
9The expression carbonatoms is 1～12 alkyl, a plurality of R of existence
9Separately can be identical, also can be different, p is 1～3 integer, q is 1～20 integer);
The compound of following formula (2)～(6) expression etc.
(in the formula, y is 2～12 integer, and z is 1～5 integer).These diamine compounds can be separately or 2 kinds or above being used in combination.
Wherein, preferred p-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfide, 1, the 5-diaminonaphthalene, 2, the 7-diamino-fluorene, 4,4 '-diaminodiphenyl oxide, 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) pentanoic, 4,4 '-(-the phenylene diisopropylidene) pentanoic, 1, the 4-cyclohexane diamine, 4,4 '-methylene radical two (hexahydroaniline), 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-diamino-2,2 '-dimethyl diphenyl, the compound of above-mentioned formula (2)～(6) expression, 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 (7) expression in the compound of above-mentioned formula (VI) expression, the compound of following formula (8) expression in the compound of above-mentioned formula (VII) expression, the compound of following formula (19) expression in the compound of following formula (9)～(18) expression in the compound of above-mentioned formula (VIII) expression and the compound of above-mentioned formula (IX) expression.
(tetracarboxylic acid dicarboxylic anhydride)
R in the repeating unit of R2 in the repeating unit of above-mentioned formula (I) expression and above-mentioned formula (II) expression
4For remove 4 valency organic groups of 4 carboxyls by tetracarboxylic acid.As the object lesson of the tetracarboxylic acid dicarboxylic anhydride that uses in order to obtain above-mentioned formula (I) and above-mentioned formula (II), can enumerate the BTCA dicarboxylic anhydride, 1,2,3,4-tetramethylene tetracarboxylic acid dicarboxylic anhydride, 1,2-dimethyl-1,2,3,4-tetramethylene tetracarboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic acid dicarboxylic anhydride, 1,3-two chloro-1,2,3,4-tetramethylene tetracarboxylic acid dicarboxylic anhydride, 1,2,3,4-tetramethyl--1,2,3,4-tetramethylene tetracarboxylic acid dicarboxylic anhydride, 1,2,3,4-pentamethylene tetracarboxylic acid dicarboxylic anhydride, 1,2,4,5-hexanaphthene tetracarboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 3,5,6-three carboxyls norbornane-2-acetic acid dicarboxylic anhydride, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-eat and mutter-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 5-(2,5-dioxo tetrahydrofuran (THF) methylene radical)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic acid dicarboxylic anhydride, dicyclo [2,2,2]-and Xin-7-alkene-2,3,5,6-tetracarboxylic acid dicarboxylic anhydride, following formula (X) and aliphatics and the alicyclic tetracarboxylic acid dicarboxylic anhydrides such as compound (XI) represented
(in the formula, R
10And R
12Expression has the divalent organic group of aromatic nucleus, R
11And R
13Expression hydrogen atom or alkyl, the R of a plurality of existence
11And R
13Separately can be identical, also can be different);
The pyromellitic acid dicarboxylic anhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic 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 tetracarboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-ditan tetracarboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-tetraphenyl silane tetracarboxylic acid dicarboxylic anhydride, 1,2,3,4-furans tetracarboxylic acid dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenylsulfide dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) sulfobenzide 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, two (phthalic acid) phosphniline oxide compound dicarboxylic anhydride, right-phenylene-two (triphenyl phthalic acid) dicarboxylic anhydride, between-phenylene-two (triphenyl phthalic acid) dicarboxylic anhydride, two (triphenyl phthalic acids)-4,4 '-phenyl ether dicarboxylic anhydride, two (triphenyl phthalic acids)-4,4 '-ditan dicarboxylic anhydride, ethylene glycol-two (dehydration trimellitate), propylene glycol-two (dehydration trimellitate), 1,4-butyleneglycol-two (dehydration trimellitate), 1,6-hexylene glycol-two (dehydration trimellitate), 1,8-ethohexadiol-two (dehydration trimellitate), 2,2-two (4-hydroxyphenyl) propane-two (dehydration trimellitate), 2,3,4,5-pyridine tetracarboxylic acid dicarboxylic anhydride, 2,6-two (3,4-dicarboxyl phenyl) pyridine, aromatic tetracarboxylic acid's dicarboxylic anhydrides such as compound of following formula (20)～(23) expression.
They can a kind of independent or 2 kinds or above being used in combination.
Wherein, from showing the angle of good liquid crystal aligning, preferred BTCA dicarboxylic anhydride, 1,2,3,4-tetramethylene tetracarboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic acid dicarboxylic anhydride, 1,2,3,4-pentamethylene tetracarboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 5-(2,5-dioxo tetrahydrofuran (THF) methylene radical)-and 3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic 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)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, dicyclo [2,2,2]-Xin-7-alkene-2,3,5,6-tetracarboxylic acid dicarboxylic anhydride, the pyromellitic acid dicarboxylic anhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic acid dicarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic acid dicarboxylic anhydride, the compound of following formula (27) expression in the compound of following formula (24)～(26) expression in the compound of above-mentioned formula (X) expression and the compound of above-mentioned formula (XI) expression is as particularly preferred, can enumerate 1,2,3,4-tetramethylene tetracarboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 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, the compound of pyromellitic acid dicarboxylic anhydride and following formula (24) expression.
(synthesizing of polyamic acid)
Supply contains the tetracarboxylic acid dicarboxylic anhydride in the building-up reactions of polyamic acid of the above-mentioned formula of the present invention (I) repeating unit and the usage rate of diamine compound, with respect to contained amino in the 1 equivalent diamine compound, the anhydride group that preferably makes the tetracarboxylic acid dicarboxylic anhydride is 0.2～2 normal ratio, more preferably is 0.3～1.2 normal ratio.
The building-up reactions of polyamic acid is preferable over-20～150 ℃, more preferably carries out under 0～100 ℃ temperature condition in organic solvent.Here, as organic solvent,, then it is had no particular limits so long as can dissolve the synthetic polyamic acid.Can illustration for example N-N-methyl-2-2-pyrrolidone N-, N,N-dimethylacetamide, N, aprotic polar solvents such as dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA; Between phenol solvent such as sylvan, xylenol, phenol, halogenated phenol.In addition, to be preferably the total amount (b) that makes tetracarboxylic acid dicarboxylic anhydride and diamine compound be the amount of 0.1～30 weight % with respect to the total amount (a+b) of reaction soln to the consumption of organic solvent (a).
In addition, in the scope that the polyamic acid that does not make generation is separated out, poor solvent alcohols, ketone, ester class, ethers, halogenated hydrocarbon and the hydro carbons etc. of all right coupling polyamic acid in the above-mentioned organic solvent.Object lesson as this poor solvent, can enumerate for example methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, 1, the 4-butyleneglycol, triglycol, ethylene glycol monomethyl ether, ethyl lactate, n-Butyl lactate, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, ritalin, vinyl acetic monomer, N-BUTYL ACETATE, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, oxalic acid diethyl ester, 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, diglyme, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic ester, the diethylene glycol monoethyl ether acetic ester, tetrahydrofuran (THF), methylene dichloride, 1, the 2-ethylene dichloride, 1, the 4-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene, hexane, heptane, octane, benzene, toluene, dimethylbenzene etc.
As mentioned above, obtained dissolving the reaction soln of polyamic acid.Then, this reaction soln is put in a large amount of poor solvents, obtained precipitate.Can get polyamic acid by this precipitate of drying under reduced pressure.And, once more this polyamic acid is dissolved in the organic solvent, separate out with poor solvent then, by carrying out once or this operation several times, can make with extra care polyamic acid.
(imide amination polymer)
The imide amination polymer that contains the above-mentioned formula of the present invention (II) repeating unit can be by preparing above-mentioned polyamic acid dehydration closed-loop.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, the method that adds dewatering agent and dehydration closed-loop catalyzer and heating as required in this solution is carried out.
Temperature of reaction is preferably 50～200 ℃, more preferably 60～170 ℃ in the method for above-mentioned (i) heating polyamic acid.When 50 ℃ of temperature of reaction less thaies, the dehydration closed-loop reaction is difficult to carry out fully, if temperature of reaction surpasses 200 ℃, the situation of the molecular weight and molecular weight of gained imide amination polymer can occur.
On the other hand, in the above-mentioned method that in polyamic acid solution, adds dewatering agent and dehydration closed-loop catalyzer (ii),, can use for example acid anhydrides such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride as dewatering agent.The consumption of dewatering agent with respect to 1 mole of polyamic acid repeating unit, is preferably 0.01～20 mole.In addition, as the dehydration closed-loop catalyzer, can use for example tertiary amines such as pyridine, collidine, lutidine, 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.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 soln that so obtains is carried out the operation same with the polyamic acid process for purification, can make with extra care imide amination polymer.
Preferred imidization rate is 1～100% in the imide amination polymer when constituting liquid crystal aligning agent of the present invention, more preferably 10～98%.Here, so-called " imidization rate " is meant the sum with respect to repeating unit in the polymkeric substance, the value that the ratio of the repeating unit quantity of formation imide ring is represented with %.At this moment, the part of imide ring can also be different imide ring.The imide rate can be controlled by the reaction conditions of regulating above-mentioned dehydration closed-loop reaction.
[end modified type polymkeric substance]
The polyamic acid and the imide amination polymer that constitute liquid crystal aligning agent of 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 situation of not damaging effect of the present invention, improve the coating characteristics of liquid crystal aligning agent 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.Here, as the monobasic acid anhydrides, can enumerate for example maleic anhydride, Tetra hydro Phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinyl oxide, n-tetradecane base succinyl oxide, n-hexadecyl succinyl oxide etc.In addition, as monoamine compound, can enumerate for example aniline, cyclo-hexylamine, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine, n-tridecane amine, n-tetradecane amine, Pentadecane amine, n-hexadecane amine, n-heptadecane amine, Octadecane amine, NSC 62789 amine etc.In addition, as the monoisocyanates compound, can enumerate for example phenylcarbimide, isocyanic acid naphthyl ester etc.
In addition, liquid crystal aligning agent of the present invention can also make by for example method of polyimide block and polyamic acid block being carried out copolymerization shown in the TOHKEMY 2002-204250 communique.At this moment preferred imidization rate is 10～100% in the polyimide block, more preferably 30～98%.
(the logarithm viscosity of polymkeric substance)
Constitute the polyamic acid and the imide amination polymer of liquid crystal aligning agent of the present invention, its logarithm viscosity (η 1n) value is generally 0.05～10dl/g, is preferably 0.1～5dl/g.
Logarithm viscosity of the present invention (η 1n) value is by using the N-N-methyl-2-2-pyrrolidone N-as solvent, is that the solution of 0.5g/100ml carries out viscosimetric analysis to concentration under 30 ℃, the value of being tried to achieve by following formula (i).
(liquid crystal aligning agent)
Liquid crystal aligning agent of the present invention is to be dissolved in organic solvent by polyamic acid that will constitute and imide amination polymer to constitute.
Temperature when preparing liquid crystal aligning agent of the present invention is preferably 0 ℃～200 ℃, more preferably 20 ℃～60 ℃.
As the organic solvent that constitutes liquid crystal aligning agent of the present invention, can enumerate as the solvent that uses in the polyamic acid building-up reactions and illustrative solvent.In addition, can also suitably select as solvent that can coupling when the polyamic acid building-up reactions and illustrative poor solvent carries out coupling.
The concentration of solids component consideration viscosity, volatility etc. are selected in the liquid crystal aligning agent of the present invention, but are preferably 1～10 weight %.That is to say that liquid crystal aligning agent of the present invention is coated substrate surface, form that when solid component concentration less than 1 weight %, then this thickness of filming is too small and can not obtain good liquid crystal orientation film as the filming of liquid crystal orientation film.When solid component concentration surpassed 10 weight %, then coating thickness was blocked up and can not obtain good liquid crystal orientation film, and the viscosity of liquid crystal aligning agent increases, the coating characteristics variation.
From improving, can also contain compound with functional silanes or compound in the liquid crystal aligning agent of the present invention with epoxy group(ing) to the fusible angle of substrate surface.As this compound with 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-ethoxycarbonyl-3-TSL 8330, N-ethoxycarbonyl-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 ester, 9-triethoxysilicane alkyl-3,6-diaza nonyl acetic ester, 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.
In addition, as compound with epoxy group(ing), preferably 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 diglycidylether, 1,3,5,6-four glycidyl group-2, the 4-hexylene glycol, N, N, N ', N '-four glycidyl group-m-benzene dimethylamine, 1,3-two (N, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane etc.The mixture ratio that these have the compound of functional silanes and have the compound of epoxy group(ing) with respect to 100 parts by weight polymer, is preferably 60 weight parts or following, more preferably 0.1～50 weight part.
＜liquid crystal display device 〉
Liquid crystal display device of the present invention can be by for example following method manufacturing.
(1) by for example methods such as roller coating machine method, spin coater method, print process, ink jet method, liquid crystal aligning agent of the present invention is coated on the substrate one side that is provided with the nesa coating that forms pattern, then,, coated face 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.Simultaneously go up set nesa coating as substrate, can use stannic oxide (SnO
2) system NESA film (U.S. PPG register of company trade mark), Indium sesquioxide-stannic oxide (In
2O
3-SnO
2) the ITO film etc. of system.The pattern of these nesa coatings forms the method that adopts photoetch method and use mask in advance.Can use metals such as Al or Ag in the reflecting electrode, perhaps contain the alloy of these metals etc.As long as have enough reflectivity, then it had no particular limits.When the coating of liquid crystal aligning agent, for the binding property of further improving substrate surface and nesa coating and reflecting electrode and filming, can also be on this surface of substrate coating in advance contain functional silanes compound, contain the compound of functionality titanium etc.Heating temperature behind the coating of liquid crystalline alignment agent is preferably 80～300 ℃, more preferably 120～250 ℃.The liquid crystal aligning agent of the present invention that contains polyamic acid, by removing organic solvent after the coating, formation is filmed as alignment films, or carries out dehydration closed-loop by further heating, can also form filming of further imidization.The thickness of filming that forms is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
(2) formed coated surface such as TOHKEMY 2002-327058 communique are shown on the substrate form structure, form the vertical liquid crystal tropism film thereon with photoresist.
(3) make 2 substrates that as above form the vertical liquid crystal tropism film, 2 substrates are staggered relatively by gap (box gap), fitted with sealing agent in 2 substrate periphery positions, in the box gap that is partitioned into by substrate surface and sealing agent, inject filling liquid crystal, the sealing filling orifice constitutes liquid crystal cell.Then,, promptly constitute this side preparation polaroid of transparency carrier of liquid crystal cell, make liquid crystal display device at the outside surface of liquid crystal cell.
Here, as sealing agent, for example can use Resins, epoxy as the salic ball of solidifying agent and separator etc.
As liquid crystal, can enumerate nematic liquid crystal and dish shape type liquid crystal.Wherein preferred nematic liquid crystal can use for example schiff base class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, phenylcyclohexane class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexane class liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cube alkanes liquid crystal etc.In addition, also can 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(brand)name " C-15 ", " CB-15 " (メ Le Network corporate system) etc. and using.And, can also use the strong dielectricity liquid crystal of oxygen base Ben Yajiaji-p-amino-2-methyl butyl laurate etc. in the last of the ten Heavenly stems.
In addition, as the polaroid of fitting on the liquid crystal cell outside surface, can enumerate polyvinyl alcohol 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 cellulose acetate protective membrane and the polaroid that polaroid of making or H film self are made.
[embodiment]
By the following examples the present invention is carried out more specific description, but the present invention is not limited to these embodiment.Printing in embodiment and the comparative example, vertical orientated property are estimated by following method.
[the printing test of LCD alignment agent]
LCD alignment agent of the present invention is coated on the transparency electrode face of substrate with liquid crystal orientation film printing press (Japanese photographic printer (strain) manufacturing), it is that 200nm, width are the 20 μ m transparency electrodes of the ITO film of 100 μ m at interval that described substrate has with striated formation thickness, behind baking formation liquid crystal orientation film, the peripheral position of this liquid crystal orientation film, the microscope that the central part multiplying power is 20 times are observed, the situation of no crawling is judged to be " well ", has the situation of crawling to be judged to be " bad ".
When under crossed nicols, voltage being closed with exchange 12V (peak-peak) under liquid crystal display device observe, with polarized light microscope observing whether abnormal area is arranged, will not have the situation of abnormal area to be judged to be " well ".
Synthesis example 1
Will be as 2 of tetracarboxylic acid dicarboxylic anhydride, 3,1.0 moles of 5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydrides are as 0.8 mole of p-phenylenediamine, the 1-cholestane oxygen ylmethyl-2 of diamine compound, the 4-diaminobenzene is dissolved in the 4500g N-N-methyl-2-2-pyrrolidone N-for 0.2 mole, reacts 6 hours down at 60 ℃.Then, reaction soln is injected in the big excessive methyl alcohol, makes the reaction product precipitation, then, use methanol wash, in 40 ℃ of dryings 15 hours, obtaining 400g logarithm viscosity was the polyamic acid of 0.50dl/g by under reduced pressure.
30g gained polyamic acid is dissolved in the 570g N-N-methyl-2-2-pyrrolidone N-, adds 5.7g pyridine and 7.4g acetic anhydride,, similarly precipitate, wash, reduce pressure with above-mentioned 110 ℃ of following dehydration closed-loops 4 hours.Obtain 19.0g imidization rate and be 52%, logarithm viscosity is the polyimide (it is called as " polyimide (PI-1) ") of 0.41dl/g.
Synthesis example 2
In synthesis example 1, except using 1-cholestane Oxy-1,1-difluoromethyl-2,4-diaminobenzene replace 1-cholestane oxygen ylmethyl-2, beyond the 4-diaminobenzene, similarly operate with synthesis example 1, and obtaining 390g logarithm viscosity is the polyamic acid of 0.37dl/g.Except using 30g gained polyamic acid, similarly carry out imidization with synthesis example 1, obtain 18.9g imidization rate and be 49%, logarithm viscosity is the polyimide (it is called as " polyimide (PI-2) ") of 0.32dl/g.
Synthesis example 3
In synthesis example 1, except using 3,5-diaminobenzoic acid cholestane base ester replaces 1-cholestane oxygen ylmethyl-2, beyond the 4-diaminobenzene, similarly operates with synthesis example 1, and obtaining 390g logarithm viscosity is the polyamic acid of 0.40dl/g.Except using 30g gained polyamic acid, similarly carry out imidization with synthesis example 1, obtain 18.9g imidization rate and be 55%, logarithm viscosity is the polyimide (it is called as " polyimide (PI-3) ") of 0.30dl/g.
Synthesis example 4
In synthesis example 1, except using 0.2 mole of 1-octadecane oxygen base-2, the 4-diaminobenzene replaces 0.2 mole of 1-cholestane oxygen ylmethyl-2, beyond the 4-diaminobenzene, similarly operates with synthesis example 1, and obtaining 372g logarithm viscosity is the polyamic acid of 0.17dl/g.Except using 30g gained polyamic acid, similarly carry out imidization with synthesis example 1, obtain 18.9g imidization rate and be 51%, logarithm viscosity is the polyimide (it is called as " polyimide (PI-4) ") of 0.35dl/g.
Embodiment 1
(printing test)
The part imide amination polymer (PI-1) that makes in the synthesis example 1 is dissolved in N-N-methyl-2-2-pyrrolidone N-/gamma-butyrolactone/ethylene glycol monobutyl ether mixed solvent (weight ratio 70/10/20), make the solution that solid component concentration is 5 weight %, after fully stirring, is the filter filtration of 1 μ m with this solution with the aperture, prepares LCD alignment agent of the present invention.Use liquid crystal orientation film printing press (Japanese photographic printer (strain) manufacturing) above-mentioned LCD alignment agent to be coated on the ITO film system nesa coating that is arranged on the glass substrate one side, under 80 ℃, carrying out 1 minute predrying on the hot-plate, then in dustless baking oven in 200 ℃ dry 1 hour down, forming dry film thickness is the liquid crystal orientation film of 500_.This liquid crystal orientation film is not observed crawling, and therefore, the printing of the LCD alignment agent of preparation is judged as " well " among the embodiment 1.
(test of vertical orientated property)
The part imide amination polymer (PI-1) that makes in the synthesis example 1 is dissolved in N-N-methyl-2-2-pyrrolidone N-/gamma-butyrolactone/ethylene glycol monobutyl ether mixed solvent (weight ratio 70/10/20), make the solution that solid component concentration is 3.5 weight %, after fully stirring, with this solution is the filter filtration of 1 μ m with the aperture, use spin coater to coat then to be arranged on the ITO film system nesa coating on the glass substrate one side, under 80 ℃, carrying out 1 minute predrying on the hot-plate, then in dustless baking oven in 200 ℃ dry 1 hour down, make and have the transparent electrode substrate that dry film thickness is the liquid crystal orientation film of 500_.Then, on each outer rim with the above-mentioned coating of liquid crystalline alignment films substrate of a pair of transparency electrode/transparent electrode substrate with liquid crystal orientation film, it is the epoxy resin binder of the alumina balls of 3.5 μ m that coating adds diameter, then, the liquid crystal aligning face is relatively overlapped and carry out pressing, tackiness agent is solidified.Then, between substrate, fill negative type liquid crystal (メ Le Network society system by liquid crystal injecting port, MLC-6608), with the acrylic acid or the like Photocurable adhesive liquid crystal injecting port is sealed then, the polaroid of fitting on the two sides in the substrate outside is made liquid crystal display device, and the vertical orientated property of gained liquid crystal display device is estimated, do not produce abnormal area, be judged as " well ".
Embodiment 2
In embodiment 1, polymkeric substance (PI-2) replace polymeric (PI-1) that in use synthesis example 2, makes, operation similarly to Example 1, the agent of preparation LCD alignment, and operation are similarly to Example 1 estimated printing energy, vertical orientated property.The results are shown in table 1.
Comparative example 1～2
In embodiment 1, except replacing the polymkeric substance (PI-1) with making polymkeric substance (PI-3) and polymkeric substance (PI-4) in synthesis example 3 and the synthesis example 4 respectively, operation similarly to Example 1, the agent of preparation LCD alignment, and operation similarly to Example 1, printing energy, vertical orientated property are estimated.The results are shown in table 1.
| Polymkeric substance | Printing | Vertical orientated property | |
| Embodiment 1 | PI-1 | Well | Well |
| Embodiment 2 | PI-2 | Well | Well |
| Comparative example 1 | PI-3 | Bad | Well |
| Comparative example 2 | PI-4 | Bad | Bad |
Claims (2)
1. liquid crystal aligning agent, it is characterized in that containing a kind of polymkeric substance, this polymkeric substance (being limited to the represented polymkeric substance with organic group of formula (III)) has at least a repeating unit that is selected among the group that repeating unit that following formula (I) and following formula (II) represent separately forms
Wherein, R
1And R
3Independently of each other for remove the divalent organic group of 2 amino, R by diamines
2And R
4For removed 4 valency organic groups of 4 carboxyls by tetracarboxylic acid, m, n are positive integer independently of each other, still, and R
1And R
3At least one is the organic group of following formula (III) expression,
Wherein, C is 1 a valency organic group with steroid backbone, and A is that carbonatoms is 1～4 alkylidene group, and it can also have the halogen atom substituting group, and B is singly-bound or ehter bond group.
2. a liquid crystal aligning element is characterized in that having the liquid crystal orientation film that is formed by the described liquid crystal aligning agent of claim 1.
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| CN101836155B (en) * | 2007-10-26 | 2012-01-25 | Jsr株式会社 | Liquid crystal aligning agent, method for forming liquid crystal alignment film and liquid crystal display device |
| CN101359130B (en) * | 2007-08-01 | 2012-02-29 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device |
| CN103374354A (en) * | 2012-04-24 | 2013-10-30 | 奇美实业股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
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| TWI468441B (en) * | 2013-07-23 | 2015-01-11 | Chi Mei Corp | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device having thereof |
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| CN108165281A (en) * | 2017-12-29 | 2018-06-15 | 常州市尚科新材料有限公司 | Aligning agent for liquid crystal and its preparation method and application |
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| JP5158314B2 (en) * | 2007-02-02 | 2013-03-06 | Ｊｓｒ株式会社 | Liquid crystal aligning agent and liquid crystal display element |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3257325B2 (en) * | 1995-01-31 | 2002-02-18 | ジェイエスアール株式会社 | Method for producing polyimide copolymer, thin film forming agent, and method for producing liquid crystal alignment film |
| JP3289271B2 (en) * | 1995-02-13 | 2002-06-04 | 日産化学工業株式会社 | Liquid crystal alignment agent and liquid crystal device using the same |
| JP3849138B2 (en) * | 2002-02-18 | 2006-11-22 | Ｊｓｒ株式会社 | Liquid crystal aligning agent, method for forming liquid crystal aligning film, and liquid crystal display element |
| TWI291475B (en) * | 2002-09-11 | 2007-12-21 | Eternal Chemical Co Ltd | Aromatic diamine derivatives, the preparations thereof, and alignment film materials containing same for liquid crystal display cell |
-
2006
- 2006-01-12 TW TW095101142A patent/TWI386434B/en active
- 2006-01-13 CN CNA200610001143XA patent/CN1807551A/en active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI386434B (en) | 2013-02-21 |
| KR20060084376A (en) | 2006-07-24 |
| TW200630413A (en) | 2006-09-01 |
| KR101319806B1 (en) | 2013-10-17 |
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