CN104560061A - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element Download PDF

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CN104560061A
CN104560061A CN201410696304.6A CN201410696304A CN104560061A CN 104560061 A CN104560061 A CN 104560061A CN 201410696304 A CN201410696304 A CN 201410696304A CN 104560061 A CN104560061 A CN 104560061A
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liquid crystal
group
compound
aligning agent
methyl
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CN104560061B (en
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宫本佳和
樫下幸志
秋池利之
德久博昭
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JSR Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

Abstract

The present invention is providing a liquid crystal alignment agent, which could prepare a liquid crystal display element capable of fast response with superior voltage retention rate, afterimage characteristics and light resistance, and excellent in coating uniformity, a liquid crystal alignment film and a liquid crystal display element. The liquid crystal alignment agent contains polymer [A], which is at least one selected from a group including polyamic acid, polyimide, methacrylic polymer, polysiloxane and polyamic acid ester. Furthermore, the polymer is having a group represented by the following formula (1), wherein R3 is preferred a group represented by the following formula (2).

Description

Liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device
The present invention is the denomination of invention of application on March 16th, 2012 is the divisional application of No. 201210080143.9 application for a patent for invention of " liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device ".
Technical field
The present invention relates to liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device.
Background technology
In recent years, liquid crystal display device due to have power consumption little, easily realize the advantage such as miniaturization and flattening, be therefore applicable to the purposes of the wide region of the large-screen lc display unit from the small-scale liquid crystal device of mobile telephone etc. to LCD TV etc.
According to the change of orientation (arrangement) state of liquid crystal molecule, the drive pattern of liquid crystal indicator there will be a known TN (twisted-nematic), STN (surpassing to row distortion), IPS (in face switch type), VA (vertical orientated) etc.In addition, visual angle is improved in order to be split by orientation in VA pattern, employing has MVA (multi-domain vertical alignment) mode, PVA (image is vertical orientated) mode, in order to improve high-speed response, panel aperture opening ratio and give liquid crystal with tilt angle further, studying and adopting light vertical orientation mode, PSA (polymkeric substance continues to aim at) mode etc.In any one drive pattern in them, the state of orientation of liquid crystal molecule is all directly controlled by liquid crystal orientation film, and liquid crystal orientation film is in the manifesting and be responsible for sizable effect in control of functional performance of liquid crystal display device.
Described liquid crystal indicator can expect the dynamic menu display device as mobile telephone, LCD TV etc., therefore as the characteristic required by liquid crystal display device, should not only show dynamic menu glibly but also suppress ghost as far as possible, require the further high speed realizing the time of response of electrooptics effect.Tackle in this requirement, report in the polymer lateral chain used in liquid crystal orientation film to give and can bring the structure of dielectric anisotropy thus the technology (with reference to Japanese Unexamined Patent Application Publication 2007-521361 publication and Japanese Unexamined Patent Application Publication 2007-521506 publication) of seeking improvement.But, except the high speed of electrooptics time of response, be not documented in the electrical characteristic such as voltage retention important in practical aspect, ghost characteristic completely in this patent documentation.
Consider such situation, expect to develop a kind of liquid crystal aligning agent, it can produce the high-speed response and the liquid crystal display device of all excellent performances such as voltage retention that realize liquid crystal cell.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Application Publication 2007-521361 publication
Patent documentation 2: Japanese Unexamined Patent Application Publication 2007-521506 publication
Summary of the invention
The problem that invention will solve
The present invention is based on above such situation and carry out, its object is to provide a kind of liquid crystal aligning agent, it can be produced can high-speed response and the liquid crystal display device of voltage retention, ghost characteristic and excellent in light-resistance, and uniform applicability is also excellent.
For the scheme of dealing with problems
The invention of developing to solve above-mentioned problem is a kind of liquid crystal aligning agent, the at least a kind of polymkeric substance (hereinafter also referred to " [A] polymkeric substance ") selected in the group that it contains [A] is made up of polyamic acid, polyimide, (methyl) acrylate copolymer, polysiloxane and poly amic acid ester, and above-mentioned polymkeric substance has the group represented by following formula (1).
(in formula (1), R 1for alkylidene group, the-(C of methylene radical, carbonatoms 2 ~ 30 bh 2bo) c-, phenylene or cyclohexylidene.B is the integer of 0 ~ 20.C is the integer of 0 ~ 10.And part or all hydrogen atom of these groups can be substituted.
R 2for comprising the concatenating group of carbon-to-carbon double bond, carbon-to-carbon triple bond, ehter bond, ester bond or amido linkage.
R 3for having the group of at least two single ring architectures.
A is the integer of 0 or 1.)
This liquid crystal aligning agent contains [A] polymkeric substance of the group with the ad hoc structure that above-mentioned formula (1) represents, thus can realize high-speed response.In addition, the at least a kind of polymkeric substance selected in the group be made up of polyamic acid, polyimide, (methyl) acrylate copolymer, polysiloxane and poly amic acid ester that polymer backbone conformation is different by suitable selection, thus liquid crystal display device can be given with desired characteristic (voltage retention, ghost characteristic, uniform applicability, photostabilization).
Above-mentioned R 3the group preferably represented by following formula (2).
(in formula (2), R 4and R 6be phenylene, biphenylene, naphthyl, cyclohexylidene, two cyclohexylidene, cyclohexylidene phenylene or heterocycle independently of one another.And part or all hydrogen atom of these groups can be substituted.
R 5for comprising the concatenating group of methylene radical, the alkylidene group of carbonatoms 2 ~ 10, carbon-to-carbon double bond, carbon-to-carbon triple bond, ehter bond, ester bond or heterocycle.And part or all hydrogen atom of above-mentioned concatenating group can be substituted.
R 7for hydrogen atom, cyano group, fluorine atom, trifluoromethyl, alkoxy carbonyl, alkyl, alkoxyl group, trifluoromethoxy or alkyl-carbonyl oxygen base.
B is 0 or 1.C is the integer of 1 ~ 9.Wherein, R 7for when multiple, multiple R 7can identical also can be different.)
The structure represented by above-mentioned formula (2) by importing as the side chain of [A] polymkeric substance, thus can improve the response speed of the liquid crystal aligning element of acquisition more.
Be suitable in the present invention comprising the liquid crystal orientation film formed by this liquid crystal aligning agent and the liquid crystal display device possessing this liquid crystal orientation film.As described above according to this liquid crystal aligning agent, owing to producing: can high-speed response and the liquid crystal display device of all excellent performances such as voltage retention, ghost characteristic, uniform applicability, photostabilization, therefore this liquid crystal display device also can be suitable for being applicable to the drive pattern such as TN, STN, IPS, FFS, Ht-VA (VA-IPS), VA (comprising the modes such as MVA, PVA, light are vertical orientated, PSA).
The effect of invention
Can provide a kind of liquid crystal aligning agent according to the present invention, it can be produced can high-speed response and the liquid crystal display device of all excellent performances such as voltage retention, ghost characteristic, photostabilization, and uniform applicability is also excellent.Therefore, this liquid crystal display device can be suitable for being applicable to the drive pattern such as TN, STN, IPS, FFS, Ht-VA (VA-IPS), VA (comprising the modes such as MVA, PVA, light are vertical orientated, PSA).
Embodiment
< liquid crystal aligning agent >
Liquid crystal aligning agent of the present invention contains [A] polymkeric substance.In addition, this liquid crystal aligning agent can contain other optional member in the scope not damaging effect of the present invention.Each composition is below described in detail in detail.
< [A] polymkeric substance >
[A] polymkeric substance contains at least a kind of polymkeric substance selected in the group be made up of polyamic acid, polyimide, (methyl) acrylate copolymer, polysiloxane and poly amic acid ester, and above-mentioned polymkeric substance has the group represented by above-mentioned formula (1).This liquid crystal aligning agent passes through [A] polymkeric substance containing the group with the ad hoc structure represented by above-mentioned formula (1), thus can realize high-speed response.In addition, at least a kind of polymkeric substance in the group be made up of polyamic acid, polyimide, (methyl) acrylate copolymer, polysiloxane and poly amic acid ester that polymer backbone conformation is different by suitable selection, thus liquid crystal display device can be given with desired characteristic (voltage retention, ghost characteristic, uniform applicability, photostabilization).Below, the group represented by above-mentioned formula (1), each polymkeric substance are sequentially described in detail in detail.
[group represented by formula (1)]
In above-mentioned formula (1), R 1for alkylidene group, the-(C of methylene radical, carbonatoms 2 ~ 30 bh 2bo) c-, phenylene or cyclohexylidene.B is the integer of 0 ~ 20.C is the integer of 0 ~ 10.And part or all hydrogen atom of these groups can be substituted.R 2for comprising the concatenating group of carbon-to-carbon double bond, carbon-to-carbon triple bond, ehter bond, ester bond or amido linkage.R 3for having the group of at least two single ring architectures.A is the integer of 0 or 1.
As by above-mentioned R 2the concatenating group represented, is preferably ether, ester group, amide group.
As above-mentioned R 1the alkylidene group of represented carbonatoms 2 ~ 30, such as, list: ethylidene, propylidene, butylidene, pentylidene, hexylidene, octylene, nonamethylene, sub-decyl, sub-undecyl, sub-dodecyl, sub-tetradecyl, sub-hexadecyl, sub-octadecyl, sub-nonadecyl, sub-eicosyl, sub-heneicosyl, sub-docosyl, sub-tricosyl, sub-tetracosyl, sub-pentacosyl, sub-ceryl, sub-heptacosyl, sub-octacosyl, sub-nonacosyl, sub-triacontyl etc.
As above-mentioned R 3the represented group at least with two single ring architectures, the group preferably represented by above-mentioned formula (2).The structure represented by above-mentioned formula (2) by importing as the side chain of [A] polymkeric substance, thus can improve the response speed of obtained liquid crystal aligning element more.
In above-mentioned formula (2), R 4and R 6be phenylene, biphenylene, naphthyl, cyclohexylidene, two cyclohexylidene, cyclohexylidene phenylene or heterocycle independently of one another.And part or all hydrogen atom of these groups can be substituted.R 5for comprising the concatenating group of methylene radical, the alkylidene group of carbonatoms 2 ~ 10, carbon-to-carbon double bond, carbon-to-carbon triple bond, ehter bond, ester bond or heterocycle.And part or all of the hydrogen atom of above-mentioned concatenating group can be substituted.R 7for hydrogen atom, cyano group, fluorine atom, trifluoromethyl, alkoxy carbonyl, alkyl, alkoxyl group, trifluoromethoxy or alkyl-carbonyl oxygen base.B is 0 or 1.C is the integer of 1 ~ 9.Wherein, R 7for when multiple, multiple R 7can identical also can be different.Again, the condensed ring such as above-mentioned naphthyl is covered by monocycle in this manual.
As above-mentioned R 4and R 6represented heterocycle, such as, list pyridine ring, pyridazine ring, pyrimidine ring etc.As comprising above-mentioned R 5the alkylidene group of the carbonatoms 2 ~ 10 in the concatenating group of the alkylidene group of represented carbonatoms 2 ~ 10, such as, list ethylidene, propylidene, butylidene, pentylidene, hexylidene, octylene etc.As above-mentioned R 5represented heterocycle, such as, list pyridine ring, pyridazine ring, pyrimidine ring etc.As R 7represented alkoxy carbonyl, such as, list methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl etc.As R 7represented alkyl, such as, list the alkyl etc. of the straight or branched of the carbonatomss 1 ~ 20 such as methyl, ethyl, propyl group, normal-butyl, isobutyl-.As R 7represented alkoxyl group, such as, list methoxyl group, oxyethyl group, propoxy-etc.As R 7represented alkyl-carbonyl oxygen base, such as, list methoxycarbonyl oxygen base, ethoxy carbonyl oxygen base, propoxycarbonyl oxygen base etc.
From the viewpoint of the high-speed response of liquid crystal display device employing this liquid crystal aligning agent, as above-mentioned R 7, be preferably alkyl, be more preferably the alkyl of the straight-chain of carbonatoms 1 ~ 20.In addition, above-mentioned R 4~ R 6in at least one group preferably there is fluorine atom.
As the group represented by above-mentioned formula (2), such as, list the group etc. represented by following formula.
In above-mentioned formula (2-1) ~ (2-123), R 8for alkyl or the alkoxyl group of carbonatoms 1 ~ 20.X is hydrogen atom or fluorine atom independently of one another.
As above-mentioned R 8, be preferably the alkyl of carbonatoms 1 ~ 20, be more preferably the alkyl of carbonatoms 1 ~ 10.
As the group represented by above-mentioned formula (2), from the viewpoint of the high-speed response of liquid crystal display device employing this liquid crystal aligning agent, be preferably by above-mentioned formula (2-1), formula (2-4), formula (2-6), formula (2-41), formula (2-50) ~ (2-60), formula (2-64), the group that formula (2-65) ~ (2-123) represents, be more preferably such as formula (2-41), formula (2-50) ~ (2-58), formula (2-65) ~ (2-123) has fluorine atom like that and has the group of alkyl at end, the base represented by formula (2-72) and the group represented by formula (2-90).
[polyamic acid]
Polyamic acid as [A] polymkeric substance obtains by making tetracarboxylic dianhydride and diamine compound carry out reacting.Need a part for above-mentioned diamine compound to be made the diamine compound comprising the group represented by above-mentioned formula (1).
As tetracarboxylic dianhydride, such as, list aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc.These tetracarboxylic dianhydrides can be used alone or combine two or more and use.
As aliphatics tetracarboxylic dianhydride, such as, list butane tetracarboxylic acid dianhydride etc.
As ester ring type tetracarboxylic dianhydride, such as list: 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 3-oxabicyclo [3.2.1] octane-2, 4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxotetrahydro-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride, 3, 5, 6-tri-carboxyl-2-carboxymethyl norcamphane-2:3, 5:6-dianhydride, 2, 4, 6, 8-tetracarboxylic dicyclo [3.3.0] octane-2:4, 6:8-dianhydride, 4, 9-dioxa three ring [5.3.1.0 2,6] undecane-3,5,8,10-tetraketone etc.
As aromatic tetracarboxylic acid's dianhydride, such as, list the tetracarboxylic dianhydride also listing outside pyromellitic acid dianhydride etc. and record in No. 2010-97188, Japanese Patent Application.
Among these tetracarboxylic dianhydrides, be preferably ester ring type tetracarboxylic dianhydride, be more preferably 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride.
As diamine compound, such as, list aliphatie diamine, ester ring type diamines, diamino organo-siloxane, aromatic diamine etc.These diamine compounds can be used alone or combine two or more and use.
As aliphatie diamine, such as, list m-xylene diamine, 1,3-propylene diamine, tetramethylene-diamine, five methylene diamine, hexamethylene-diamine etc.
As ester ring type diamines, such as, list Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-methylene-bis (hexahydroaniline), 1,3-two (amino methyl) hexanaphthenes etc.
As diamino organo-siloxane, outside listing such as 1,3-two (3-aminopropyl)-tetramethyl disiloxanes etc., also list the diamines recorded in No. 2009-97188, Japanese Patent Application.
As aromatic diamine, such as, list: Ursol D, 4,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diamino-2,2 '-bis-(trifluoromethyl) biphenyl, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two (4-aminophenyl) fluorenes of 9,9-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two (4-aminophenyl) HFC-236fa of 2,2-, 4,4 '-(to phenyl two isopropylidene) two (aniline), 4,4 '-(phenyl two isopropylidene) two (aniline), Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N '-bis-(4-aminophenyl)-p-diaminodiphenyl, N, N '-bis-(4-aminophenyl)-N, N '-dimethyl p-diaminodiphenyl, Isosorbide-5-Nitrae-bis--(4-aminophenyl)-piperazine, 3,5-diaminobenzoic acid, dodecyloxy-2,4-diaminobenzene, tetradecyloxyaniline-2,4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, n-Hexadecane oxygen base-2,4-diaminobenzene, octadecane oxygen base-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, tetradecyloxyaniline-2,5-diaminobenzene, pentadecane oxygen base-2,5-diaminobenzene, n-Hexadecane oxygen base-2,5-diaminobenzene, octadecane oxygen base-2,5-diaminobenzene, cholestane oxygen base-3,5-diaminobenzene, cholestene oxygen base-3,5-diaminobenzene, cholestane oxygen base-2,4-diaminobenzene, cholestene oxygen base-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestane ester, 3,5-diaminobenzoic acid cholestene ester, 3,5-diaminobenzoic acid lanostane ester, two (the 4-aminobenzoic acyl-oxygen base) cholestane of 3,6-, two (4-amino-benzene oxygen) cholestane of 3,6-, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 4-(4 '-trifluoromethylbenzoyl oxygen base) cyclohexyl-3,5-diaminobenzoic acid ester, two (4-((aminophenyl) methyl) the phenyl)-4-butyl cyclohexane of 1,1-, two (4-((aminophenyl) methyl) the phenyl)-4-heptylcyclohexane of 1,1-, two (4-((amino-benzene oxygen) methyl) the phenyl)-4-heptylcyclohexane of 1,1-, two (4-((aminophenyl) methyl) phenyl)-4-(the 4-heptyl cyclohexyl) hexanaphthene of 1,1-, 2,4-diamino-N, N-diallyl aniline, 4-amino-benzylamine, 3-amino-benzylamine, the compound represented by following formula (3), the compound etc. represented by following formula (4).
In above-mentioned formula (3), R 9, R 9" and R 9" ' be singly-bound ,-O-, *-COO-or-OCO-independently of one another.Wherein, R 9* be the position be combined with diamino-phenyl.In addition, R 9" and R 9" ' * be the position being incorporated into phenylene side.R 9' be alkane two base of carbonatoms 1 ~ 3.D is 0 or 1.E is the integer of 0 ~ 2.F is 0 or 1.R 10for the alkyl of straight-chain, branched or ring-type.2 amino preferred combination in diamino-phenyl in 2,4 or 3,5.
In above-mentioned formula (4), R 9, d and e is same with above-mentioned formula (3) defines.R 1~ R 3and a is same with above-mentioned formula (1) defines.2 amino preferred combination in diamino-phenyl in 2,4 or 3,5.G is the integer of 1 ~ 5.
About above-mentioned R 1~ R 3, directly can be suitable for the explanation of the definition of each group in above-mentioned [group represented by formula (1)] and the explanation of preferred group.
As above-mentioned g, from the viewpoint of the high-speed response of liquid crystal display device employing this liquid crystal aligning agent, be preferably 1 ~ 3, be more preferably 2 or 3.
As the diamines represented by above-mentioned formula (4), such as, list the diamines etc. represented by following formula.
Among these diamines, when selecting polyamic acid as [A] polymkeric substance, import in polymkeric substance from the viewpoint of the group that will be represented by above-mentioned formula (1), the diamines with the group represented by formula (1) of the compound at least needing use to be represented by above-mentioned formula (4) etc. is as 1 in diamines.Again, as share other the situation of diamines, the compound represented by above-mentioned formula (3) is preferably used.
Supply in the tetracarboxylic dianhydride of the building-up reactions of polyamic acid and the usage ratio of diamine compound, relative to amino 1 equivalent contained in diamine compound, the anhydride group of tetracarboxylic dianhydride is preferably 0.2 equivalent ~ 2 equivalent, is more preferably 0.3 equivalent ~ 1.2 equivalent.
Building-up reactions is preferably carried out in organic solvent.As temperature of reaction, be preferably-20 DEG C ~ 150 DEG C, be more preferably 0 DEG C ~ 100 DEG C.As the reaction times, be preferably 0.5 hour ~ 24 hours, be more preferably 2 hours ~ 12 hours.
As organic solvent, if the organic solvent of the polyamic acid synthesized by solubilized is then not particularly limited, such as list: METHYLPYRROLIDONE (NMP), N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, N, N-methylimidazole alkane ketone, dimethyl sulfoxide (DMSO), gamma-butyrolactone, 4-methyl urea, HMPA, meta-cresol, xylenol, phenol, halogenated phenol, diethylene glycol ethyl methyl ether etc.
As the consumption of organic solvent, relative to total amount 100 mass parts of tetracarboxylic dianhydride and diamine compound, be preferably 0.1 mass parts ~ 50 mass parts, be more preferably 5 mass parts ~ 40 mass parts.
The polyamic acid solution obtained after reaction directly can be supplied in the preparation of liquid crystal aligning agent, also can for the preparation of liquid crystal aligning agent on the basis of to isolate separately in reaction soln contained polyamic acid, also can for the preparation of liquid crystal aligning agent on the basis of refining independent isolated polyamic acid.As the independent separation method of polyamic acid, such as, list: the method for precipitate drying under reduced pressure will obtained by making reaction soln inject a large amount of poor solvents, the method etc. reaction soln underpressure distillation removed by vaporizer.As the process for purification of polyamic acid, list: again independent isolated polyamic acid is dissolved in organic solvent and the method separated out by poor solvent, for 1 time or repeatedly carry out the method for the operation underpressure distillation such as organic solvent removed with vaporizer.
[polyimide]
Polyimide carries out dehydration closed-loop and imidization by the amido acid structure had above-mentioned polyamic acid thus manufactures.The complete imide compound that polyimide can carry out dehydration closed-loop for the whole amido acid structure had the polyamic acid as its precursor and obtain, also can for only carrying out dehydration closed-loop, amido acid structure and imide ring structure to a part for amido acid structure and the part imide compound of depositing.
As the synthetic method of polyimide, such as list: the heating means (hereinafter also referred to " method (i) ") of (i) polyamic acid, (ii) polyamic acid is dissolved in organic solvent, in this solution, add dewatering agent and dehydration closed-loop catalyzer, carry out the method that method (hereinafter also referred to " method (ii) ") heated etc. is reacted based on the dehydration closed-loop of polyamic acid as required.
As the temperature of reaction in method (i), be preferably 50 DEG C ~ 200 DEG C, be more preferably 60 DEG C ~ 170 DEG C.When temperature of reaction is less than 50 DEG C, insufficiently carry out dehydration closed-loop reaction, the molecular weight of the polyimide then obtained when temperature of reaction is more than 200 DEG C reduces sometimes.As the reaction times, be preferably 0.5 hour ~ 48 hours, be more preferably 2 hours ~ 20 hours.
The polyimide obtained in method (i) can directly for the preparation of liquid crystal aligning agent, also can for the preparation of liquid crystal aligning agent on the basis of isolating separately polyimide, or on the basis of refining independent isolated polyimide or also can for the preparation of liquid crystal aligning agent on the basis of having refined the polyimide obtained.
As the dewatering agent in method (ii), such as, list the acid anhydrides such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride.
As the consumption of dewatering agent, be suitable for selecting according to desired imide rate, but be preferably 0.01 mole ~ 20 moles relative to 1 mole, the amido acid structure of polyamic acid.
As the dehydration closed-loop catalyzer in method (ii), such as, list pyridine, trimethylpyridine, lutidine, triethylamine etc.
As the consumption of dehydration closed-loop catalyzer, be preferably 0.01 mole ~ 10 moles relative to the dewatering agent contained 1 mole.Again, imide rate can be higher more at most for the content of above-mentioned dewatering agent and dehydration closed-loop agent.
As the organic solvent used in method (ii), such as, list: the organic solvent etc. same with the illustrative organic solvent as the organic solvent used in the synthesis of polyamic acid.
As the temperature of reaction in method (ii), be preferably 0 DEG C ~ 180 DEG C, be more preferably 10 DEG C ~ 150 DEG C.As the reaction times, be preferably 0.5 hour ~ 20 hours, be more preferably 1 hour ~ 8 hours.By making reaction conditions be above-mentioned scope, dehydration closed-loop sufficient reacting can be made to carry out, the molecular weight of obtained polyimide can be made in addition to be appropriate molecular weight.
The reaction soln containing polyimide can be obtained in method (ii).Can directly by the preparation of this reaction soln for liquid crystal aligning agent, also the preparation of basis for liquid crystal aligning agent of dewatering agent and dehydration closed-loop catalyzer can eliminated from reaction soln, also can for the preparation of liquid crystal aligning agent on the basis of isolating separately polyimide, or also can for the preparation of liquid crystal aligning agent on the basis of refining independent isolated polyimide.As the method removing dewatering agent and dehydration closed-loop catalyzer from reaction soln, such as, list the method etc. of solvent exchange.As independent separation method and the process for purification of polyimide, such as, list: with as the independent separation method of polyamic acid and process for purification and the same method etc. of illustrative method.
[(methyl) acrylate copolymer]
As (methyl) acrylate copolymer of [A] polymkeric substance if (methyl) acrylate copolymer comprising the group represented by above-mentioned formula (1) does not then need to be particularly limited to, by known ethene unsaturated polymerizable compound being obtained with known method.Such as by making, a () is containing the ethene unsaturated compound of epoxy group(ing), (hereinafter also referred to ", (a) unsaturated compound ") and, (b1) ethene unsaturated carboxylic acid and/or the unsaturated polybasic acid anhydride of polymerizability, (hereinafter also referred to ", (b1) unsaturated compound ") and except, (a) unsaturated compound and, (b1) polymerizable unsaturated compound beyond unsaturated compound, (hereinafter also referred to ", (b2) unsaturated compound ") multipolymer carry out being polymerized and obtaining.
As (a) unsaturated compound, such as list: (methyl) glycidyl acrylate, α-ethylacrylate glycidyl ester, α-n-propyl glycidyl acrylate, α-n-butyl acryloyloxy ethyl acid glycidyl ester, (methyl) vinylformic acid 3,4-epoxy butyl ester, α-ethylacrylate 3,4-epoxy butyl ester, (methyl) vinylformic acid 6,7-epoxy heptyl ester, α-ethylacrylate 6,7-epoxy heptyl ester etc.
As (b1) unsaturated compound, such as, list: the unsaturated carboxylic acid classes such as (methyl) vinylformic acid, β-crotonic acid, α-ethylacrylate, α-n-propyl vinylformic acid, α-n-butyl, toxilic acid, fumaric acid, citraconic acid, methylfumaric acid, methylene-succinic acid; The unsaturated polybasic acid anhydride classes etc. such as maleic anhydride, itaconic anhydride, citraconic anhydride, cis-1,2,3,4-Tetra Hydro Phthalic Anhydride.
As (b2) unsaturated compound, such as list: (methyl) acrylate with the group represented by above-mentioned formula (1), (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate etc. have the ester class of (methyl) dihydroxypropyl;
(methyl) alkyl acrylate classes such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate;
(methyl) vinylformic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid 2-methyl cyclohexyl, (methyl) vinylformic acid three ring [5.2.1.0 2,6] last of the ten Heavenly stems-8-base ester, (methyl) vinylformic acid 2-bicyclopentane oxygen base ethyl ester, (methyl) isobornyl acrylate, (methyl) CALCIUM ACRYLATE ring type ester class such as (methyl) vinylformic acid cholestane ester;
(methyl) benzyl acrylate classes such as (methyl) phenyl acrylate, (methyl) benzyl acrylate;
The unsaturated dicarboxylic acid diester classes such as ethyl maleate, DEF, diethyl itaconate;
The unsaturated dicarbonyl imides derivatives such as N-phenylmaleimide, N-benzyl maleimide, N-N-cyclohexylmaleimide, N-succinimido-3-maleimidobenzoate, N-succinimido-4-maleimidobutyric acid ester, N-succinimido-6-maleimidocaproic acid ester, N-succinimido-3-maleimidoproprionic acid ester, N-(9-acridyl) maleimide;
The vinyl cyanide based compounds such as (methyl) vinyl cyanide, α-chloro-acrylonitrile, vinylidene dicyanide;
The unsaturated acyl amine compound such as (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide;
Vinylbenzene, alpha-methyl styrene, a vinyl toluene, p-methylstyrene, Vinyl toluene, to aromatic ethenyl compounds such as methoxy styrenes;
The indene derivative classes such as indenes, 1-methyl indenes;
1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene equiconjugate diolefinic compounds, and vinylchlorid, vinylidene chloride, vinyl-acetic ester etc.
(methyl) glycidyl acrylate is preferably as (a) unsaturated compound, be preferably (methyl) vinylformic acid as (b1) unsaturated compound, be preferably (methyl) vinylformic acid cholestane ester as (b2) unsaturated compound.Such as, when being synthesized (methyl) acrylate copolymer as [A] polymkeric substance by radical polymerization, import in polymkeric substance from the viewpoint of the group that will be represented by above-mentioned formula (1), at least need use to have the unsaturated compound of the group represented by above-mentioned formula (1) as 1 in unsaturated compound.On the other hand, such as, also can utilize the epoxy group(ing) in the polymkeric substance without the group represented by above-mentioned formula (1), import by always known high molecular weight reactive the group represented by above-mentioned formula (1).
As the synthetic method of (methyl) acrylate copolymer, be such as easy by each unsaturated compound of the incompatible synthesis of radical polymerization under the existence of suitable solvent and polymerization starter.As organic solvent, such as, list: the organic solvent etc. same with the illustrative organic solvent as the organic solvent used in the synthesis of polyamic acid.
As polymerization starter, such as, list:
2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two-(2,4-methyl pentane nitrile), 2,2 '-azo is two-azo-compound such as (4-methoxyl group-2,4-methyl pentane nitrile), benzoyl peroxide, lauroyl peroxide, tert-Butyl peroxypivalate, 1, the organo-peroxides such as 1 '-bis--(tert-butyl hydroperoxide) hexanaphthene, hydrogen peroxide, comprises the redox type initiator etc. of these superoxide and reductive agent.These polymerization starters can be used alone or mix two or more and use.
[polysiloxane]
As the polysiloxane of [A] polymkeric substance if the polysiloxane comprising the group represented by above-mentioned formula (1) is so not particularly limited, but such as by following and synthesize: by least 1 silane compound (hereinafter also referred to " raw silicon hydride compounds ") in the group that be made up of alkoxysilane compound containing trialkylsilyl group in molecular structure and halogenated silane compounds, be preferably hydrolyzed or hydrolytic condensation under the existence of water and catalyzer in suitable organic solvent.
As raw silicon hydride compounds, such as, list:
Tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane, four sec-butoxy silane, four tert-butoxy silane, tetrachloro silicane etc.;
Methyltrimethoxy silane, Union carbide A-162, octadecyltriethoxy silane, methyl three positive propoxy silane, methyl three isopropoxy silane, methyl three n-butoxy silane, methyl three sec-butoxy silane, methyl three tert-butoxy silane, methyl triple phenoxyl silane, METHYL TRICHLORO SILANE, ethyl trimethoxy silane, ethyl triethoxysilane, ethyl three positive propoxy silane, ethyl three isopropoxy silane, ethyl three n-butoxy silane, ethyl three sec-butoxy silane, ethyl three tert-butoxy silane, ethyl trichlorosilane, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl-trichloro-silicane etc.,
Dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyldichlorosilane(DMCS) etc.;
Trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane etc.;
There is the silane etc. of the group represented by above-mentioned formula (1).
Among these raw silicon hydride compounds, preferred tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, Union carbide A-162, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, octadecyltriethoxy silane, there is the silane of the group represented by above-mentioned formula (1).When selecting polysiloxane as [A] polymkeric substance, import in polymkeric substance from the viewpoint of the group that will be represented by above-mentioned formula (1), at least need use to have the silane of the group represented by above-mentioned formula (1) as 1 in raw silicon hydride compounds.
When synthesizing polysiloxane, optionally spendable organic solvent, such as, list alkylol cpd, ketone compound, amide compound, ester cpds or other aprotic compound.They can be used alone and also may be combined with two or more use.
As temperature of reaction during synthesis polysiloxane, be preferably 0 DEG C ~ 100 DEG C, be more preferably 15 DEG C ~ 80 DEG C.As the reaction times, be preferably 0.5 hour ~ 24 hours, be more preferably 1 hour ~ 8 hours.
[poly amic acid ester]
Poly amic acid ester is the polymkeric substance obtained by making above-mentioned polyamic acid and Organohalogen compounds, alcohols or phenols carry out reacting.
Again, when [A] polymkeric substance is at least a kind of polymkeric substance selected in the group be made up of polyamic acid, polyimide, (methyl) acrylate copolymer, polysiloxane and poly amic acid ester, at [A] polymeric oxidizer when multiple polymers, if at least a kind of polymkeric substance has the group represented by above-mentioned formula (1), the high-speed response as the effect desired by the application can be realized.
Being not particularly limited through the vinylbenzene weight-average molecular weight (Mw) obtained that converts based on gel permeation chromatography of [A] polymkeric substance, but when polyamic acid, polyimide or poly amic acid ester, be preferably 1000 ~ 500000, be more preferably 2000 ~ 300000.When (methyl) acrylate copolymer, be preferably 1000 ~ 1000000, be more preferably 2000 ~ 500000.When polysiloxane, be preferably 1000 ~ 200000, be more preferably 2000 ~ 100000.By being in such molecular weight ranges, thus good orientation and the stability of liquid crystal display device can be guaranteed.
Other optional member of < >
Only otherwise damage effect of the present invention, so this liquid crystal aligning agent can containing other optional member of such as solidifying agent, curing catalysts, curing catalyst, epoxy compounds, tensio-active agent etc.Again, these other optional members each composition that can be used alone also can mix two or more and use.In addition, the use level of other optional member can be suitable for according to its object determining.Each composition is below described in detail in detail.
[solidifying agent, curing catalysts and curing catalyst]
Solidifying agent and curing catalysts can be contained in this liquid crystal aligning agent for making the crosslinking reaction of [A] polymkeric substance more strong object.For promoting the object of the curing reaction that solidifying agent is undertaken, curing catalyst can be contained in this liquid crystal aligning agent.
As solidifying agent, can use: have normally used solidifying agent in the solidification of the solidified nature compound of epoxy group(ing) or containing have epoxy group(ing) compound solidification compound solidification in normally used solidifying agent.As such solidifying agent, such as, list polyamine, polybasic acid anhydride etc.
As polybasic acid anhydride, such as, list acid anhydrides and other the polybasic acid anhydride of cyclohexanetricarboxylic acid.As cyclohexanetricarboxylic acid's acid anhydride, such as, list hexanaphthene-1,3,4-tricarboxylic acid-3,4-acid anhydride, hexanaphthene-1,3,5-tricarboxylic acid-3,5-acid anhydride, hexanaphthene-1,2,3-tricarboxylic acid-2,3-acid anhydride etc.As other polybasic acid anhydride, such as, list 4-methyl tetrahydrophthalic anhydride, methylnadic anhydride, dodecenylsuccinic anhydride, succinyl oxide, maleic anhydride, Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride etc.
As curing catalysts, such as, list antimony hexafluoride compound, phosphorus hexafluoride compound, praseodynium aluminium etc.These catalyzer can carry out catalysis to the cationoid polymerisation of epoxy group(ing) under the effect of heating.
As curing catalyst, such as list: imidazolium compounds, quaternary phosphonium compound, quaternary ammonium compound, 1, 8-diazabicyclo [5.4.0] 11 carbon-7-alkene, the Diazabicycloalkenes such as its organic acid salt, zinc octoate, stannous octoate, the organometallic compounds such as aluminium acetylacetonate coordination compound, boron trifluoride, the boron compounds such as triphenyl borate, zinc chloride, the metal halide compounds such as tin chloride, Dyhard RU 100, the high-melting-point decentralized potentiality curing catalysts such as amine add-on type promotor such as the affixture of amine and epoxy resin, the microcapsule-type potentiality curing catalyst the surface-coated of quaternary alkylphosphonium salt etc. obtained by polymkeric substance, amine salt type potentiality curing catalyst, lewis acid, the hot cationic polymerization type potentiality curing catalyst etc. of Bronsted hydrochlorate contour temperature dissociative type.
[epoxy compounds]
From the viewpoint of improving the liquid crystal orientation film that formed for the cementability of substrate surface, epoxy compounds can be contained in this liquid crystal aligning agent.
As epoxy compounds, preferred: ethylene glycol diglycidyl base ether, polyethylene glycol diglycidyl base ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexylene glycol diglycidyl ether, glycerine diglycidyl ether, 2, 2-bis-bromo neopentyl glycol diglycidyl ether, 1, 3, 5, 6-four glycidyl group-2, 4-hexylene glycol, N, N, N ', N '-four glycidyl group m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethyl cyclohexane.
[tensio-active agent]
As tensio-active agent, such as, list nonionogenic tenside, anion surfactant, cats product, amphoterics, (gathering) silicone surfactant, polyalkylene oxide tensio-active agent, fluorochemical surfactant etc.
The preparation method > of < liquid crystal aligning agent
This liquid crystal aligning agent contains [A] polymkeric substance as required composition as described above, can contain other optional member as required, but preferably be prepared as the composition of the solution shape that each component dissolves obtains in organic solvent.
As can be used for the organic solvent preparing this liquid crystal aligning agent, preferably dissolve [A] polymkeric substance and other optional member and the organic solvent do not reacted with them.As organic solvent, such as list in the synthesis as above-mentioned polyamic acid use and in above-mentioned illustrative organic solvent etc.In addition, the poor solvent and illustrative poor solvent that use in the synthesis as polyamic acid can also be share.Again, these organic solvents can be used alone also can use two or more.
The preferred solvent that can be used for preparing this liquid crystal aligning agent is: under preferred solid component concentration described later, not make in this liquid crystal aligning agent contained each one-tenth analyze and make the surface tension of liquid crystal aligning agent be the solvent of the scope of 25mN/m ~ 40mN/m.
As the solid component concentration of this liquid crystal aligning agent, the ratio shared in the gross weight of liquid crystal aligning agent of the weight of the whole compositions except solvent namely, in liquid crystal aligning agent, by considering that viscosity, volatility etc. are selected, is preferably the scope of 1 quality % ~ 10 quality %.This liquid crystal aligning agent is coated substrate surface and forms the film as liquid crystal orientation film, when solid component concentration is more than 1 quality %, the thickness of this film can be made not easily to become too small and obtain good liquid crystal orientation film.On the other hand, when solid component concentration is below 10 quality %, the thickness of film can be suppressed to become excessive and obtain good liquid crystal orientation film.In addition, can prevent the viscosity of liquid crystal aligning agent from increasing and making coating characteristics be good.As the scope of preferred solid component concentration, such as, when based on when rotational method being 1.5 quality % ~ 4.5 quality %.When based on print process, be 3 quality % ~ 9 quality %.When based on ink jet method, be 1 quality % ~ 5 quality %.
< liquid crystal display device >
The type of drive of liquid crystal display device of the present invention is not particularly limited, and this technology can be applicable to the known various mode such as TN, STN, IPS, FFS, Ht-VA (VA-IPS), VA (comprising VA-MVA mode, VA-PVA mode etc.); Possesses the above-mentioned liquid crystal orientation film formed by above-mentioned liquid crystal aligning agent.As described above according to this liquid crystal aligning agent, can produce can high-speed response and the liquid crystal display device of all excellent performances such as voltage retention, ghost characteristic, uniform applicability, photostabilization.Generally speaking, liquid crystal display device possesses a pair substrate being sequentially laminated with transparency electrode and liquid crystal orientation film on surface, and this pair substrate subtend is disposed in inner side, is filled in by liquid crystal between this pair substrate, is sealed by periphery with sealing agent.
The manufacture method > of < liquid crystal display device
Liquid crystal display device of the present invention can manufacture like that such as below.The liquid crystal orientation film that this liquid crystal display device possesses, by being coated with this liquid crystal aligning agent on substrate, then heating coated face and being formed on substrate.As substrate, such as, can use: the glass such as float glass, soda glass; The transparency carrier formed by plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, ester ring type polyolefine.Operate as described above and prepare the substrate that 2 are formed with liquid crystal orientation film, between these 2 substrates, configuring liquid crystal, thus manufacturing liquid crystal cell.As the manufacture method of liquid crystal cell, such as, list following method etc.
First method is: be that 2 substrate subtends configure across gap (box gap) by the mode of subtend according to each liquid crystal orientation film, sealing agent is used to be fitted by the periphery of 2 substrates, to by after the thick interior injection filling liquid crystal of the box of substrate surface and sealing agent zoning, seal filling orifice, thus can liquid crystal cell be manufactured.
As second method, list the technology being called ODF (under liquid crystal drop) mode.The position of the regulation on a substrate among 2 substrates forming liquid crystal orientation film is coated with the sealing material of such as ultraviolet light curable, liquid crystal has been dripped further on liquid crystal aligning face, then the mode being subtend according to liquid crystal orientation film is fitted another substrate, then in whole irradiating ultraviolet light of substrate by sealant cures, thus can liquid crystal cell be manufactured.
When based on any one method, all preferably: next liquid crystal cell is heated to the temperature that used liquid crystal takes isotropic phase, is then slowly cooled to room temperature, thus remove inject time flow orientation.And, at the outer surface laminating Polarizer of liquid crystal cell, thus this liquid crystal display device can be obtained.
As above-mentioned sealing agent, such as, list and contain as the alumina balls of spacer and the epoxy resin etc. of solidifying agent.
As above-mentioned liquid crystal, such as, nematic liquid crystal, smectic liquid crystal etc. can be used.When TN type liquid crystal cell or STN type liquid crystal cell, preferably form the liquid crystal with positive dielectric anisotropy of nematic liquid crystal.As such liquid crystal, such as, can use: biphenyls liquid crystal, Santosol 360 class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cubane-like liquid crystal etc.Also the cholesteric liquid crystals such as such as cholesterly chloride, cholesteryl nonanoate, cholesteryl carbonate can be added further in above-mentioned liquid crystal in addition, with such chiral agent that trade(brand)name C-15, CB-15 (Merck Ltd.) sell, to oxygen base benzylidene-to Ferroelectric liquid Crystals such as amino-2-methyl butyl laurate etc. thus use in the last of the ten Heavenly stems.
On the other hand, when vertical alignment-type liquid crystal box, preferably form the liquid crystal with negative dielectric anisotropy of nematic liquid crystal.As such liquid crystal, such as, can use dicyanobenzenes class liquid crystal, pyridazine class liquid crystal, Schiff bases liquid crystal, azoxy class liquid crystal, biphenyls liquid crystal, Santosol 360 class liquid crystal etc.
The Polarizer used in the outside of liquid crystal cell is not particularly limited; but list: make PVA (PVOH) FILM stretch orientation absorb iodine and the light polarizing film being referred to as " H film " obtained clips via rhodia protective membrane and the Polarizer obtained, or the Polarizer etc. formed by H film itself.
Embodiment
Below, more specifically the present invention is described by embodiment, but the present invention is not limited to these embodiments.
The weight-average molecular weight (Mw) of [A] polymkeric substance obtained below in an example is the polystyrene conversion value measured by the GPC of following specification.
Chromatographic column: East ソ commercial firm, TSKgelGRCXLII
Solvent: tetrahydrofuran (THF)
Temperature: 40 DEG C
Pressure: 68kgf/cm 2
[synthesis example 1]
Compound 1,2 and 3 has been synthesized according to following reaction scheme.
To have prolong 500mL there-necked flask in add 4-cyano group-4 '-xenol 12.6g (0.0645 mole), the bromo-1-decanol 17.0g of 10-(0.0717 mole), salt of wormwood 28.4g and N, dinethylformamide 350mL, 160 DEG C of heated and stirred 5 hours.After utilizing TLC to confirm the end of reaction, reaction soln is cooled to room temperature.Reaction soln is devoted water 1000mL, carried out mix and blend.By separated out white solid filtering separation, wash further with water.At 80 DEG C, obtained solid is carried out vacuum-drying, thus obtain 20.6g above-claimed cpd 1.Then obtained 20g (0.0569 mole) compound 1 is dissolved in the dehydration tetrahydrofuran (THF) (THF) of 150mL, add triethylamine 7.49g (0.0740 mole), then slowly add the THF by being dissolved in 150mL ice-cold lower cost 30 minutes and obtain 3,5-dinitrobenzoyl chloride 14.4g (0.0625 mole), thereafter, at room temperature stir 3 hours.After reaction terminating, by filtering triethylamine hydrochloride removal and adding chloroform 400mL by underpressure distillation by after THF removal.This solution is washed, with magnesium sulfate by after organic layer drying, by underpressure distillation, chloroform is removed.Thereafter implement recrystallize with ethanol, carry out vacuum-drying at 80 DEG C thus obtain 23.8g above-claimed cpd 2.Under nitrogen gas stream, the 5%Pd/C of the above-claimed cpd 2 of 20g (0.0367 mole) and 1g (be 5wt.% relative to compound 2) is added in ethanol 500mL, with the addition of 28% ammoniacal liquor 4.2g (being 2 times moles relative to compound 2) further.While this solution is held in 15 ± 5 DEG C slowly add hydrazine hydrate (80% purity) 21g after, stir about reacts for 20 hours.Thereafter, reaction solution is carried out heat filtering while drip in pure water, at room temperature carry out after agitator treating filtering and obtaining white ~ faint yellow solid.It is carried out vacuum-drying at 35 DEG C and obtain 16.8g above-claimed cpd 3.
[synthesis example 2]
Compound 4 has been synthesized according to following reaction scheme.
The compound 1 that 20g (0.0569 mole) is obtained by the operation same with synthesis example 1 is dissolved in the THF of 300mL, after adding triethylamine 7.49g (0.0740 mole), within 30 minutes, slowly add methacrylic chloride 6.53g (0.0625 mole) in ice-cold lower cost, at room temperature stir 3 hours thereafter.After reaction terminating, by filtering triethylamine hydrochloride removal and adding chloroform 400mL by underpressure distillation by after THF removal.This solution is washed, with magnesium sulfate by after organic layer drying, by underpressure distillation, chloroform is removed.Thereafter implement recrystallize with ethanol, carry out vacuum-drying at 80 DEG C thus obtain 17.7g above-claimed cpd 4.
[synthesis example 3]
Compound 5 and 6 has been synthesized according to following reaction scheme.
To have prolong 500mL there-necked flask in add 4-cyano group-4 '-xenol 12.6g (0.0645 mole), 11-bromo-1-undecylene 16.7g (0.0717 mole), salt of wormwood 28.4g and N, dinethylformamide 350mL, 160 DEG C of heated and stirred 5 hours.After utilizing TLC to confirm the end of reaction, reaction soln is cooled to room temperature.Reaction soln is devoted in water 1000mL, carried out mix and blend.By separated out white solid filtering separation, wash further with water.At 80 DEG C, obtained solid is carried out vacuum-drying, thus obtain 19.8g above-claimed cpd 5.To have return line and nitrogen ingress pipe 100mL there-necked flask in load the aqueous isopropanol 40 μ L of 8.69g (0.0250 mole) compound 6,15g Trimethoxy silane and 0.2M six hydration Platinic chloride, carry out degassed, then react under 10 hours reflux under a nitrogen.Make the short column (short colume) that reaction mixture passes through in silica gel, then refined by silica column, remove solvent further, thus obtain 3.5g above-claimed cpd 6.
[synthesis example 4]
Compound 7 ~ 11 has been synthesized according to following route.
To have prolong 500mL there-necked flask in add 4-[difluoro (4-pentylcyclohexyl) methoxyl group]-2,3-difluorophenol 12.5g, 11-bromoundecane acid methyl esters 10g, salt of wormwood 14.2g, N, dinethylformamide 200mL, 160 DEG C of heated and stirred 5 hours.After utilizing TLC to confirm the end of reaction, reaction soln is cooled to room temperature.Reaction soln is devoted water 500mL, carried out mix and blend.By separated out white solid filtering separation, wash further with water.At 80 DEG C, obtained solid is carried out vacuum-drying, thus obtain 14.8g compound 7.
To in the there-necked flask of 200mL having prolong, add 10g compound 7,1.6g mono-hydronium(ion) Lithium Oxide 98min, 30mL methyl alcohol, 15mL water, 80 DEG C of heated and stirred 4 hours.After utilizing TLC to confirm the end of reaction, reaction soln is cooled to room temperature.Under the state stirring reaction soln, dilute hydrochloric acid is slowly dripped in reaction soln.Solid filtering will be separated out, by the sequential purge of water, ethanol.At 80 DEG C, obtained solid is carried out vacuum-drying, thus obtain 6g compound 8.
To in the there-necked flask of 100mL having prolong, mixing 5g compound 8,5mL thionyl chloride, reacted 1 hour 80 DEG C of heated and stirred.Undertaken reducing pressure by flow type lift pump and after eliminating unreacted thionyl chloride, mix with tetrahydrofuran (THF) 50mL, made solution (1).Then in the 200ml there-necked flask having a dropping funnel, mix ethylene glycol 8.9g, tetrahydrofuran (THF) 20mL, triethylamine 2.2g, stir in ice bath.After having dripped solution (1) wherein, at room temperature stirring reaction 3 hours.Add ethyl acetate 300mL after reaction, utilize separatory to refine and wash.Thereafter, organic layer concentrated and obtain solid.In ethanol/distilled water, obtained solid is carried out recrystallize, separated out solid is carried out filter, dry, thus obtain 4.3g compound 9.
In the 100mL there-necked flask having dropping funnel, in ice bath, 4.0g compound 9,35mL tetrahydrofuran (THF), 1.0g triethylamine are stirred.After slowly dripping 3,5 dinitrobenzoylchloride 1.8g wherein, at room temperature stirring reaction 3 hours.After reaction, add ethyl acetate 300mL, utilize separatory to refine and wash.Thereafter, organic layer concentrated and obtain solid.With ethanol, obtained solid is carried out recrystallize, separated out solid is carried out filter, dry, thus obtain 4.8g compound 10.
In the 100mL there-necked flask having a dropping funnel, mix 4g compound 10,7g zinc, 1.1g ammonium chloride, carry out vacuum outgas, nitrogen replacement.Then, add tetrahydrofuran (THF) 10mL, ethanol 10mL and be uniformly mixed in ice bath.Then distilled water 5mL has slowly been dripped.Again, the solvent for reacting has carried out nitrogen bubble in advance.In dropping, utilize ice bath to carry out cooling and stir, at room temperature reacted 4 hours thereafter.Then, reacting liquid filtering is eliminated catalyzer.Then, add ethyl acetate 300mL, utilize distilled water to carry out separatory and refine.Then organic layer concentrated and remove solvent thus obtain solid.Utilize ethanol to carry out recrystallize, solid carried out filter, drying under reduced pressure, carry out filtering and it carried out vacuum-drying at 35 DEG C, thus obtaining 2.4g compound 11.
[synthesis example 5]
Compound 12 ~ 14 has been synthesized according to following route.
To have prolong 500mL there-necked flask in mixing 3,5-dinitrofluorobenzene 18.6g, 11-bromine undecyl alcohol 24.4g, triethylamine 20g, tetrahydrofuran (THF) 100mL, at 100 DEG C, reacted 30 hours in a nitrogen atmosphere.After reaction, add ethyl acetate 200mL, carried out 4 separatory with distilled water 50mL and refined.Then organic layer concentrated and remove solvent thus obtain filemot liquid.Add ethanol on a small quantity wherein and cool below 0 DEG C thus separate out solid.Then, separated out solid is carried out filter, dry thus obtain 30g compound 12.
To have prolong 300mL there-necked flask in mix 8.3g compound 12,2,3-bis-fluoro-4-(4-pentylcyclohexyl) phenol of 6g, 6g salt of wormwood, 100mL dimethyl formamide, at 80 DEG C, reacted 5 hours.Confirm reaction terminating, add ethyl acetate 200mL, carried out 4 separatory with distilled water 50mL and refined.Then organic layer concentrated and remove solvent thus obtain filemot liquid.Add ethanol on a small quantity wherein and cool below 0 DEG C thus separate out solid.Then, separated out solid is carried out filter, dry thus obtain 10g compound 13.
In the 200mL there-necked flask having a dropping funnel, mix 9.8g compound 13,20g zinc, 3.4g ammonium chloride, carry out vacuum outgas, nitrogen replacement.Then, add tetrahydrofuran (THF) 30mL, ethanol 30mL and be uniformly mixed in ice bath.Then distilled water 10mL has slowly been dripped.Again, the solvent for reacting has carried out nitrogen bubble in advance.In dropping, utilize ice bath to carry out cooling and stir, at room temperature reaction 6 hours thereafter.Then, reacting liquid filtering is eliminated catalyzer.Then, add ethyl acetate 300mL, utilize distilled water to carry out separatory washing.Then organic layer concentrated and remove solvent thus obtain solid.Utilize ethanol to carry out recrystallize, solid carried out filter, drying under reduced pressure thus obtain 5g compound 14.
[synthesis example 6]
Compound 15 ~ 17 has been synthesized according to following route.
Mixing 3 ', 4 ', 5 '-three fluoro-4-xenol 4.48g, 2-[2-(2-chloroethoxy) oxyethyl group] ethanol 3.38g, salt of wormwood 8.3g, dimethyl formamide 100mL, reacted 24 hours in a nitrogen atmosphere at 85 DEG C.Then, add ethyl acetate 200mL, utilize distilled water to carry out separatory and refine.Organic layer is concentrated and removes solvent thus obtain 6g compound 15 (flaxen liquid).
The DNF of mixing 5g compound 15,2.9g, 50mL tetrahydrofuran (THF), 1.9g triethylamine and reacted 10 hours at 80 DEG C.Add ethyl acetate 200mL, utilize distilled water to carry out separatory and refine.Organic layer is concentrated and removes solvent thus obtain 4.8g compound 16.
In the 100mL there-necked flask having a dropping funnel, mix 4g compound 16,10g zinc, 1.6g ammonium chloride, carry out vacuum outgas, nitrogen replacement.Then, under nitrogen flowing, add tetrahydrofuran (THF) 10ml, ethanol 10ml and be uniformly mixed in ice bath.Then, distilled water 5ml has slowly been dripped.Again, the solvent for reacting has carried out nitrogen bubble in advance.In dropping, utilize ice bath to carry out cooling and stir, at room temperature reaction 2 hours thereafter.Then, reacting liquid filtering is eliminated catalyzer.Then, add ethyl acetate 300ml, utilize distilled water to carry out separatory and refine.Then organic layer concentrated and remove solvent thus obtain solid.Utilize ethanol to carry out recrystallize, solid carried out filter, drying under reduced pressure, filter thus and be dried thus obtain 3.3g compound 17.
[synthesis example 7]
Compound 18 and 19 has been synthesized according to following route.
Mixing 4-[difluoro (4-pentylcyclohexyl) methoxyl group]-2,3-difluorophenol 50g, 11-bromine undecyl alcohol 38g, salt of wormwood 60g, dimethyl formamide 100mL, reacted 24 hours in a nitrogen atmosphere at 85 DEG C.Then, add ethyl acetate 200mL, utilize distilled water to carry out separatory and refine.Organic layer is concentrated and removes solvent thus obtain 38.7g compound 18.
10g compound 18 is dissolved in tetrahydrofuran (THF) 20mL, after adding triethylamine 3.9g, within 15 minutes, slowly adds in ice-cold lower cost: acrylate chloride 2.6g is dissolved in the solution obtained in tetrahydrofuran (THF) 10mL, at room temperature stir 2 hours thereafter.After reaction terminating, removing triethylamine hydrochloride by filtering, after removing solvent by underpressure distillation, adding chloroform 400mL.This solution is washed, with magnesium sulfate by after organic layer drying, by underpressure distillation, chloroform is removed.Thereafter implement recrystallize with ethanol, carry out vacuum-drying at 80 DEG C thus obtain 11g compound 19.
The synthesis > of < [A] polymkeric substance
[synthesis of polyamic acid]
[synthesis example 8]
The diamines 66.0g of 1,2,3,4-tetramethylene tetracarboxylic dianhydride 26.08g, diamines (G-1) 7.90g represented by following formula and above-claimed cpd 3 is dissolved in NMP400g, at room temperature reacts 6 hours.Then, reaction mixture is injected excessive methyl alcohol, reaction product is precipitated.Use methanol wash throw out, under reduced pressure 40 DEG C of dryings 15 hours, thus obtain 78.5g polyamic acid (PA-1).
[synthesis example 9]
Except use 96.6g compound 11 comes, except alternative compounds 3, to operate in the same manner as synthesis example 8, thus obtain 100.1g polyamic acid (PA-2).
[synthesis of polyimide]
[synthesis example 10]
Using as tetracarboxylic dianhydride's 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride 13.45g, as 3 of diamine compound, the diamines 14.81g of 5-diaminobenzoic acid 3.72g, diamines (G-2) 3.02g represented by following formula and compound 3 is dissolved in NMP 140g, has reacted 4 hours at 60 DEG C.The viscosity measuring this polymer fluid is 2200mPas.Being flow in excessive methyl alcohol by reaction soln makes reaction product precipitate.Thereafter, by methanol wash, under reduced pressure obtain polyamic acid 40 DEG C of dryings 24 hours.Whole polyamic acids obtained is dissolved in the NMP of 465g again, add pyridine 7.12g and diacetyl oxide 9.19g and 110 DEG C of dehydration closed-loops 4 hours, operate as described above and carry out precipitating, wash, drying under reduced pressure, obtain the polyimide (PI-1) of 21.5g imide rate 68%.
[synthesis example 11]
Using as tetracarboxylic dianhydride 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride 10.89g, be dissolved in NMP as above-mentioned diamines (G-2) 7.33g of diamine compound and the diamines 16.78g of compound 3, reacted 4 hours at 60 DEG C.The viscosity measuring this polymer fluid is 1,250mPas.Being flow in excessive methyl alcohol by reaction soln makes reaction product precipitate.Thereafter, by methanol wash, under reduced pressure obtain polyamic acid 40 DEG C of dryings 24 hours.Whole polyamic acids obtained is dissolved in NMP465g again, add pyridine 3.84g and diacetyl oxide 4.96g, and 110 DEG C of dehydration closed-loops 4 hours, operate as described above and carry out precipitating, wash, drying under reduced pressure, obtain the polyimide (PI-2) of 23.1g imide rate 49%.
[synthesis example 12]
Using as tetracarboxylic dianhydride's 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride 15.17g, as above-mentioned diamines (G-1) 3.60g of diamine compound, the diamines 6.68g and 4 of compound 3,4 '-diaminodiphenyl-methane 9.55g is dissolved in NMP 140g, has reacted 4 hours at 60 DEG C.The viscosity measuring this polymer fluid is 2700mPas.Being flow in excessive methyl alcohol by reaction soln makes reaction product precipitate.Thereafter, by methanol wash, under reduced pressure obtain polyamic acid 40 DEG C of dryings 24 hours.Whole polyamic acids obtained is dissolved in NMP465g again, add pyridine 10.70g and diacetyl oxide 13.82g and 110 DEG C of dehydration closed-loops 4 hours, operate as described above and carry out precipitating, wash, drying under reduced pressure, obtain the polyimide (PI-3) of 22.4g imide rate 76%.
[synthesis example 13]
Except use 7.69g compound 14 comes, except alternative compounds 3, to operate in the same manner as synthesis example 10, thus obtain the polyimide (PI-4) of 22.9g imide rate 76%.
[synthesis example 14]
Except use 6.36g compound 17 comes, except alternative compounds 3, to operate in the same manner as synthesis example 10, thus obtain the polyimide (PI-5) of 21.9g imide rate 76%.
[synthesis of methacrylate polymer]
[synthesis example 15]
Methacrylic acid cholestane ester has been synthesized according to following reaction scheme.
Beta-cholestanol 80g is dissolved in the THF of 800mL, after adding triethylamine 27.2g, slowly adds methacrylic chloride 35.6g, at room temperature stirred 3 hours.After reaction terminating, by filtering triethylamine hydrochloride removal and adding chloroform 400mL by underpressure distillation by after THF removal.This solution is washed, with magnesium sulfate by after organic layer drying, by underpressure distillation, chloroform is removed.Thereafter, implement the recrystallize based on ethanol, obtain the methacrylic acid cholestane ester 54g (yield rate: 57.4%) of the white solid shown in above-mentioned reaction formula.The above-mentioned methacrylic acid cholestane ester 15.16g (0.033 mole) of monomer, glycidyl methacrylate 12.8g (0.09 mole), methacrylic acid 7.2g (0.084 mole) and 45.85g (0.109 mole) above-claimed cpd 4 is loaded as in the four-hole boiling flask having installed stirring rod, three-way tap, thermometer, with the addition of as the diethylene glycol ethyl methyl ether 52.8g of solvent, as 2 of polymerization starter, two (2, the 4-methyl pentane nitrile) 2.24g and the α-methylstyrenedimer 0.96g as chain-transfer agent of 2 '-azo.By stream of nitrogen gas, about 10 minutes bubblings carried out to it and after having carried out intrasystem nitrogen replacement, obtain methacrylate polymer (PM-1) 70 DEG C of reactions 5 hours in a nitrogen atmosphere.Carried out the molecular weight determination of methacrylate polymer (PM-1) by GPC, result is Mw=96000, Mw/Mn=7.87, does not find to result from the peak of residual monomer.Again, being assumed to loading complete monomer conversion is in a polymer solution methacrylate polymer (PM-1), directly dilutes and is used in preparation liquid crystal aligning agent of the present invention.
[synthesis example 16]
Except loading 10.0g (0.0219 mole) methacrylic acid cholestane ester, 15.0g (0.1055 mole) glycidyl methacrylate, 9.0g (0.1045 mole) methacrylic acid and 19.3g (0.046 mole) compound 4, be used as the diethylene glycol ethyl methyl ether 43.0g of solvent, as 2 of polymerization starter, 2 '-azo two (2, 4-methyl pentane nitrile) 1.83g and as beyond the α-methylstyrenedimer 0.78g of chain-transfer agent, operate in the same manner as synthesis example 15, thus obtain methacrylate polymer (PM-2).Carried out the molecular weight determination of methacrylate polymer (PM-2) by GPC, result is Mw=125000, Mw/Mn=9.54, does not find to result from the peak of residual monomer.Again, in this polymers soln, being assumed to loading complete monomer conversion is methacrylate polymer (PM-2), directly dilutes, is used in making of liquid crystal aligning agent of the present invention.
[synthesis example 17]
Except use 25.6g (0.046 mole) compound 19 comes, except alternative compounds 4, operate and obtain methacrylate polymer (PM-3) in the same manner as synthesis example 16.Carried out the molecular weight determination of methacrylate polymer (PM-3) by GPC, result is Mw=131000, Mw/Mn=9.43, does not find to result from the peak of residual monomer.Again, in this polymers soln, being assumed to loading complete monomer conversion is methacrylate polymer (PM-3), directly dilutes, is used in making of liquid crystal aligning agent of the present invention.
[synthesis of polysiloxane]
[synthesis example 18]
To in the reaction vessel having agitator, thermometer, dropping funnel and reflux condensing tube, drop into oxalic acid 12.4g and ethanol 22.2g, stir and prepared the ethanolic soln of oxalic acid.Then after in a nitrogen atmosphere this solution being heated to 70 DEG C, dripped wherein as raw material and silane compound, the mixture that comprises 11.1g tetraethoxysilane and 10.6g compound 6.After dropping terminates, after the temperature of 70 DEG C is maintained 6 hours, be cooled to 25 DEG C, then add ethylene glycol butyl ether 40.0g and prepared the solution containing organopolysiloxane (PS-1).The Mw of organopolysiloxane (PS-1) contained in this solution is 9000.
[synthesis example 19]
To in the reaction vessel having agitator, thermometer, dropping funnel and reflux condensing tube, drop into oxalic acid 13.9g and ethanol 19.5g, stir and prepared the ethanolic soln of oxalic acid.Then after in a nitrogen atmosphere this solution being heated to 70 DEG C, dripped wherein as raw material and silane compound, the mixture that comprises 15.1g tetraethoxysilane and 3.95g compound 6.After dropping terminates, after the temperature of 70 DEG C is maintained 6 hours, be cooled to 25 DEG C, then add ethylene glycol butyl ether 40.0g and prepared the solution containing organopolysiloxane (PS-2).The Mw of organopolysiloxane (PS-2) contained in this solution is 12000.
[synthesis example 20]
To in the reaction vessel having agitator, thermometer, dropping funnel and reflux condensing tube, drop into oxalic acid 10.2g and ethanol 26.3g, stir and prepared the ethanolic soln of oxalic acid.Then after in a nitrogen atmosphere this solution being heated to 70 DEG C, dripped wherein as raw material and silane compound, comprise tetraethoxysilane 5.54g, mixture that compound 6 is 12.49g and octadecyltriethoxy silane 2.5g.After dropping terminates, after the temperature of 70 DEG C is maintained 6 hours, be cooled to 25 DEG C, then add ethylene glycol butyl ether 40.0g and prepared the solution containing organopolysiloxane (PS-3).The Mw of organopolysiloxane (PS-3) contained in this solution is 6000.
[synthesis example 21]
Using as tetracarboxylic dianhydride's 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride 19.88g, is dissolved in NMP 140g as Ursol D 6.83g, the diaminodiphenyl-methane 3.58g of diamine compound and above-mentioned diamines (G-1) 4.72g, has reacted 4 hours at 60 DEG C.The viscosity measuring this polymer fluid is 2100mPas.Then, reaction soln is flow in excessive methyl alcohol reaction product is precipitated.Thereafter, by methanol wash, under reduced pressure obtain polyamic acid 32.8g 40 DEG C of dryings 24 hours.Obtained polyamic acid 30g is dissolved in NMP400g, add pyridine 12.0g and diacetyl oxide 15.5g and 110 DEG C of dehydration closed-loops 4 hours, operate as described above, carry out precipitating, wash, drying under reduced pressure, obtain the polyimide (PI-6) of 25g imide rate 79%.
[synthesis example 22]
To having installed stirring rod, three-way tap, the methacrylic acid cholestane ester 15.16g (0.0332 mole) of monomer is loaded as in the four-hole boiling flask of thermometer, glycidyl methacrylate 12.8g (0.09 mole), methacrylic acid 7.2g (0.0836 mole), vinylbenzene 7.2g (0.0691 mole) and N-N-cyclohexylmaleimide 7.2g (0.0402 mole), with the addition of the diethylene glycol ethyl methyl ether 52.8g as solvent further, as 2 of polymerization starter, 2 '-azo two (2, 4-methyl pentane nitrile) 2.24g and the α-methylstyrenedimer 0.96g as chain-transfer agent.By stream of nitrogen gas, about 10 minutes bubblings carried out to it and after having carried out intrasystem nitrogen replacement, react 5 hours at 70 DEG C thus obtain the methacrylate polymer (PM-4) that there is tilt angle and manifest composition in a nitrogen atmosphere.Carried out the molecular weight determination of methacrylate polymer (PM-4) by GPC, result is Mw=96000, Mw/Mn=7.87, does not find to result from the peak of residual monomer.Again, in this polymers soln, being assumed to loading complete monomer conversion is methacrylate polymer (PM-4), directly dilutes, is used in making of liquid crystal aligning agent of the present invention.
[synthesis example 23]
To in the reaction vessel having agitator, thermometer, dropping funnel and reflux condensing tube, drop into oxalic acid 10.2g and ethanol 26.3g, stir and prepared the ethanolic soln of oxalic acid.Then after in a nitrogen atmosphere this solution being heated to 70 DEG C, dripped wherein as raw material and silane compound, the mixture that comprises tetraethoxysilane 11.1g and octadecyltriethoxy silane 2.5g.After dropping terminates, be cooled to 25 DEG C after the temperature of 70 DEG C is maintained 6 hours, then add ethylene glycol butyl ether 40.0g, prepare the solution containing organopolysiloxane (PS-4) thus.The Mw of organopolysiloxane (PS-4) contained in this solution is 6,900.
The preparation > of < liquid crystal aligning agent
[embodiment 1]
Be NMP according to solvent composition in above-mentioned polyamic acid (PA-1): the mode of ethylene glycol butyl ether=50:50 (mass ratio) adds NMP and ethylene glycol butyl ether, thus the solution that to make solution that solid component concentration is 3.5 quality % (use made by liquid crystal cell) and solid component concentration be 7.0% (uniform applicability evaluation with).After these solution of abundant stirring, use the metre filter in 0.2 μm, aperture respectively, thus prepare liquid crystal aligning agent (S-1).
[embodiment 2]
Except the above-mentioned polyamic acid of use (PA-2) comes, except alternative above-mentioned polyamic acid (PA-1), to operate similarly to Example 1, thus prepared liquid crystal aligning agent (S-2).
[embodiment 3]
Be NMP according to solvent composition in above-mentioned polyimide (PI-1): the mode of ethylene glycol butyl ether=50:50 (mass ratio) adds NMP and ethylene glycol butyl ether, thus the solution that to make solution that solid component concentration is 3.5 quality % (use made by liquid crystal cell) and solid component concentration be 7.0% (uniform applicability evaluation with).After these solution of abundant stirring, use the metre filter in 0.2 μm, aperture respectively, thus prepare liquid crystal aligning agent (S-3).
[embodiment 4]
Be NMP according to solvent composition in above-mentioned polyimide (PI-2): the mode of ethylene glycol butyl ether=50:50 (mass ratio) adds NMP and ethylene glycol butyl ether, thus the solution that to make solution that solid component concentration is 3.5 quality % (use made by liquid crystal cell) and solid component concentration be 7.0% (uniform applicability evaluation with).After these solution of abundant stirring, use the metre filter in 0.2 μm, aperture respectively, thus prepare liquid crystal aligning agent (S-4).
[embodiment 5]
Be NMP according to solvent composition in above-mentioned polyimide (PI-3): the mode of ethylene glycol butyl ether=70:30 (mass ratio) adds NMP and ethylene glycol butyl ether, thus the solution that to make solution that solid component concentration is 3.5 quality % (use made by liquid crystal cell) and solid component concentration be 7.0% (uniform applicability evaluation with).After these solution of abundant stirring, use the metre filter in 0.2 μm, aperture respectively, thus prepare liquid crystal aligning agent (S-5).
[embodiment 6]
Except the above-mentioned polyimide of use (PI-4) comes, except alternative above-mentioned polyimide (PI-1), to operate similarly to Example 3, thus prepared liquid crystal aligning agent (S-6).
[embodiment 7]
Except the above-mentioned polyimide of use (PI-5) comes, except alternative above-mentioned polyimide (PI-1), to operate similarly to Example 3, thus prepared liquid crystal aligning agent (S-7).
[embodiment 8]
Diethylene glycol methyl ethyl ether is added further, the solution that to make solution that solid component concentration is 3.5 quality % (use made by liquid crystal cell) and solid component concentration be 7.0% (uniform applicability evaluation with) in above-mentioned methacrylate polymer (PM-1) solution.After these solution of abundant stirring, use the metre filter in 0.2 μm, aperture respectively, prepared liquid crystal aligning agent (S-8).
[embodiment 9]
Diethylene glycol methyl ethyl ether is added further, the solution that to make solution that solid component concentration is 3.5 quality % (use made by liquid crystal cell) and solid component concentration be 7.0% (uniform applicability evaluation with) in above-mentioned methacrylate polymer (PM-2) solution.After these solution of abundant stirring, use the metre filter in 0.2 μm, aperture respectively, prepared liquid crystal aligning agent (S-9).
[embodiment 10]
Except the above-mentioned methacrylate polymer of use (PM-3) comes, except alternative above-mentioned methacrylate polymer (PM-1), to operate similarly to Example 8, thus prepared liquid crystal aligning agent (S-10).
[embodiment 11]
Ethylene glycol butyl ether is added in the solution containing above-mentioned organopolysiloxane (PS-1), thus the solution that to make the solution of solid component concentration 5 % by weight (use made by liquid crystal cell) and solid component concentration be 10.0% (uniform applicability evaluation with).After these solution of abundant stirring, use the metre filter in 1 μm, aperture respectively, thus prepared liquid crystal aligning agent (S-11).
[embodiment 12]
Ethylene glycol butyl ether is added in the solution containing above-mentioned organopolysiloxane (PS-2), thus the solution that to make the solution of solid component concentration 5 % by weight (use made by liquid crystal cell) and solid component concentration be 10.0% (uniform applicability evaluation with).After these solution of abundant stirring, use the metre filter in 1 μm, aperture respectively, thus prepared liquid crystal aligning agent (S-12).
[embodiment 13]
Ethylene glycol butyl ether is added in the solution containing above-mentioned organopolysiloxane (PS-3), thus the solution that to make the solution of solid component concentration 5 % by weight (use made by liquid crystal cell) and solid component concentration be 10.0% (uniform applicability evaluation with).After these solution of abundant stirring, use the metre filter in 1 μm, aperture respectively, thus prepared liquid crystal aligning agent (S-13).
[comparative example 1]
Be NMP according to solvent composition in above-mentioned polyimide (PI-6): the mode of ethylene glycol butyl ether=50:50 (mass ratio) adds NMP and ethylene glycol butyl ether respectively, thus the solution that to make solution that solid component concentration is 3.5 quality % (use made by liquid crystal cell) and solid component concentration be 7.0% (uniform applicability evaluation with).After these solution of abundant stirring, use the metre filter in 0.2 μm, aperture respectively, thus prepare liquid crystal aligning agent (CS-1).
[comparative example 2]
Diethylene glycol methyl ethyl ether is added further, the solution that to make solution that solid component concentration is 3.5 quality % (use made by liquid crystal cell) and solid component concentration be 7.0% (uniform applicability evaluation with) in above-mentioned methacrylate polymer (PM-4) solution.After these solution of abundant stirring, use the metre filter in 0.2 μm, aperture respectively, thus obtain liquid crystal aligning agent (CS-2).
[comparative example 3]
Ethylene glycol butyl ether is added in the solution containing above-mentioned organopolysiloxane (PS-4), thus the solution that to make the solution of solid component concentration 5 % by weight (use made by liquid crystal cell) and solid component concentration be 10.0% (uniform applicability evaluation with).After these solution of abundant stirring, use the metre filter in 1 μm, aperture respectively, thus prepared liquid crystal aligning agent (CS-3).
The manufacture > of < liquid crystal display device
Turner is used to be coated on the transparent electrical pole-face with the glass substrate of the transparency electrode formed by ito film by prepared each liquid crystal aligning agent, after having carried out 1 minute prebake conditions with the hot plates of 80 DEG C, in the baking oven being replaced into nitrogen, remove solvent 200 DEG C of heating 1 hour, thus define the film (liquid crystal orientation film) of thickness 0.08 μm.Repeat this operation, make the substrate that a pair (2) have liquid crystal orientation film.After being incorporated with the epoxy resin adhesive of the alumina balls of diameter 3.5 μm by the periphery coating with the face of liquid crystal orientation film of 1 substrate of silk screen printing among aforesaid substrate, make the liquid crystal orientation film of a pair substrate in the face of crimping to ground overlap, 150 DEG C of heating 1 hour by caking agent thermofixation.Then, after filling negative type liquid crystal (Merck system, MLC-6608) from liquid crystal injecting port to the gap of substrate, seal liquid crystal injecting port with epoxies caking agent, further in order to remove flow orientation during Liquid crystal pour, it is slowly cooled to room temperature 150 DEG C of heating after 10 minutes.Further, to fit Polarizer according to the mode that the polarization direction of 2 Polarizers is mutually orthogonal on the two sides, outside of substrate, thus manufactured liquid crystal display device.
< evaluates >
Following evaluation has been carried out to the liquid crystal display device manufactured.Show the result in table 1.
[response speed (msec.)]
The device comprising polarizing microscope, photodetector and pulses generation machine is utilized to determine response speed (time of the beginning of liquid crystal response).Liquid crystal response speed refers to herein, and never execute alive state to when being applied with the voltage of 5V of maximum 1 second to made liquid crystal display device, transmissivity is changed to the time (msec.) required for 90% from 10%.
[voltage retention (%)]
After the voltage of 5V being applied to the liquid crystal display device by above-mentioned manufacture with the application time of 60 microseconds, the span of 167 milliseconds, determine the voltage retention (%) after 167 milliseconds from applying to remove.The VHR-1 of determinator Shi Yong East Yang テ Network ニ カ.
[ghost characteristic (mV)]
The liquid crystal display device produced for operating as described above, in the liquid crystal cell apply the voltage of the direct current 17V of 20 hours under the envrionment temperature of 100 DEG C, cutting off after volts DS soon remain under voltage (remanant DC voltages (mV)) obtained by flickering elimination method (flicker minimizing method).
[uniform applicability]
6 inches of Silicon Wafers scatter the interlaminar resin parting (Plot aquation length of schooling, ミ Network ロ パ ー Le EX-0041-AC4) of diameter about 4.1 μm, the hot plate being set as 120 DEG C carries out 10 minutes heat treated, has prepared the Silicon Wafer with set spacer.Form about foregoing liquid crystal alignment agent in addition, liquid crystal orientation film printing press (Japan's description printing system) is used to coat on the above-mentioned Silicon Wafer with set spacer by the liquid crystal aligning agent (solid component concentration is 7.0% ~ 10.0%) being prepared as printing, the hot plate of 80 DEG C carries out 1 minute prebake conditions and eliminates solvent, then carry out toasting after 10 minutes on the hot plate of 200 DEG C, thus define average film thickness film.The evaluation of uniform applicability has been carried out with this film of microscopic examination of multiplying power 20 times.Presence or absence according to the depression of printing in uneven and set spacer portions carrys out implementation evaluation, the printing of not observing completely is uneven is " A " (being judged as excellent) with the situation of the depression of set spacer portions, slightly observe coating defective, but can be judged as roughly not being coated with underproof situation for " B " (being judged as good), printing uneven is " C " (being judged as defective) with the situation about being observed repeatedly of either party in the depression of set spacer portions.
[photostabilization]
Operating as described above and measuring with carbon arc is that the Ageing machine of light source irradiates the voltage retention after 3000 hours, the situation being less than 0.5% with the variable quantity of the measured value comparison with voltage conservation rate of pre-irradiation is " A " (being judged as excellent), more than 0.5% and be less than 1% situation be " B " (be judged as good), more than 1% and be less than 3% situation be " C " (being judged as good slightly), the situation more than 3% is " D " (being judged as defective).
Table 1
According to the result of table 1, possess and use the liquid crystal aligning agent of embodiment 1 ~ 13 and the liquid crystal display device of liquid crystal orientation film that formed demonstrates good liquid crystal response speed.The liquid crystal display device possessing the liquid crystal orientation film formed by this liquid crystal aligning agent containing polyimide or polysiloxane demonstrates high voltage retention.In addition, this liquid crystal aligning agent containing polyamic acid or methacrylate polymer demonstrates excellent uniform applicability.Further, the liquid crystal display device possessing the liquid crystal orientation film formed by this liquid crystal aligning agent containing polysiloxane or polyamic acid demonstrates excellent ghost characteristic.The liquid crystal display device possessing the liquid crystal orientation film formed by this liquid crystal aligning agent containing polysiloxane demonstrates excellent photostabilization.Therefore, this liquid crystal aligning agent can realize the high-speed response of liquid crystal display device and by suitable selective polymer backbone structure, desired characteristic (voltage retention, ghost characteristic, uniform applicability, photostabilization) can be made more excellent.
Utilizability in industry
Can provide a kind of liquid crystal aligning agent according to the present invention, it can be produced can high-speed response and the liquid crystal display device of all excellent performances such as voltage retention, ghost characteristic, photostabilization, and uniform applicability is also excellent.Therefore, this liquid crystal display device can be suitable for being applicable to the drive pattern such as TN, STN, IPS, FFS, Ht-VA (VA-IPS), VA (comprising the modes such as MVA, PVA, light are vertical orientated, PSA).

Claims (4)

1. a liquid crystal aligning agent, at least a kind of polymkeric substance that it contains [A] selects from the group that the polyamic acid, polyimide and the poly amic acid ester that are obtained as a part for raw material by the diamines represented by following formula (4) form,
In formula (4), R 1for alkylidene group, the-(C of methylene radical, carbonatoms 2 ~ 30 bh 2bo) c-, phenylene or cyclohexylidene, b is the integer of 0 ~ 20, and c is the integer of 0 ~ 10, and part or all hydrogen atom of these groups can be substituted,
R 2for comprising the concatenating group of carbon-to-carbon double bond, carbon-to-carbon triple bond, ehter bond, ester bond or amido linkage,
R 3for having the group of at least two single ring architectures,
A is the integer of 0 or 1,
R 9for singly-bound ,-O-, *-COO-or-OCO-, wherein R 9* be the position be combined with diamino-phenyl, d be 0 or 1, e be the integer of 0 ~ 2, g is 2 or 3.
2. liquid crystal aligning agent according to claim 1, wherein, above-mentioned R 3for the group represented by following formula (2),
In formula (2), R 4and R 6be phenylene, biphenylene, naphthyl, cyclohexylidene, two cyclohexylidene, cyclohexylidene phenylene or heterocycle independently of one another, and part or all hydrogen atom of these groups can be substituted,
R 5for comprising the concatenating group of methylene radical, the alkylidene group of carbonatoms 2 ~ 10, carbon-to-carbon double bond, carbon-to-carbon triple bond, ehter bond, ester bond or heterocycle, and part or all hydrogen atom of above-mentioned concatenating group can be substituted,
R 7for hydrogen atom, cyano group, fluorine atom, trifluoromethyl, alkoxy carbonyl, alkyl, alkoxyl group, trifluoromethoxy or alkyl-carbonyl oxygen base,
B be 0 or 1, c be the integer of 1 ~ 9, wherein, R 7for when multiple, multiple R 7can identical also can be different.
3. a liquid crystal orientation film, it is formed by the liquid crystal aligning agent described in claim 1 or 2.
4. a liquid crystal display device, it possesses liquid crystal orientation film according to claim 3.
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CN108070388A (en) * 2017-12-05 2018-05-25 中节能万润股份有限公司 A kind of aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display element
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