CN1236014C - Liquid crystal orientational agent and super torsional nematic liquid crystal display element - Google Patents
Liquid crystal orientational agent and super torsional nematic liquid crystal display element Download PDFInfo
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- CN1236014C CN1236014C CN 01141073 CN01141073A CN1236014C CN 1236014 C CN1236014 C CN 1236014C CN 01141073 CN01141073 CN 01141073 CN 01141073 A CN01141073 A CN 01141073A CN 1236014 C CN1236014 C CN 1236014C
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Abstract
This invention provides a liquid crystal aligning agent for an STN liquid crystal display element realizing a wide viewing angle and quick response speed. In the liquid crystal aligning agent containing a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride with a diamine and/or an imide polymer obtained by ring closure of the polyamic acid with dehydration, which is characterized by >= 15 mol% of the tetracarboxylic acid dianhydride being pyromellitic acid dianhydride, by >= 15 mol% of the diamine being 2,2-bis[4-(4-aminophenoxy)phenyl]propane and by retaining <= 4 DEG pretilt angle.
Description
Technical field
The present invention relates to liquid crystal aligning agent.More specifically relate to optimize liquid crystal aligning, realize the liquid crystal aligning agent that is applicable to STN type liquid crystal display device of wide angle and high-speed response.
Background technology
Up to now, between 2 substrates that are formed with liquid crystal orientation film by the nesa coating surface, formation has the nematic liquid crystal layer of positive dielectric anisotropy, as the layered struture unit, and the longitudinal axis with above-mentioned liquid crystal molecule from a side group plate towards the opposite side substrate continuously the TN type liquid crystal display device of TN (twisted nematic) the type liquid crystal cells that forms of distortion 90 degree be known.In addition, also there is STN (STN Super TN) the type liquid crystal display device that utilizes birefringence effect, wherein birefringence effect is because added the chirality agent, makes to be twisted together more than the longitudinal axis of this liquid crystal molecule is spent with 180 mutually between substrate and to produce when reaching continuous twisted state.
The liquid crystal aligning that can present this liquid crystal display device usually by liquid crystal orientation film through friction treatment.The liquid crystal aligning mould material of wherein previously known formation liquid crystal display device is a polyimide, polymeric amide and polyester etc.Polyimide particularly, because of its excellent thermotolerance, with the affinity of liquid crystal, and physical strength and in most of liquid crystal display device, using.
But, maximizing recently, lightweight, the display element aspect liquid crystal display device that performances such as low power consumptionization are higher has been realized surprising development, what follow with it is that performance requriements to liquid crystal orientation film becomes strict more.But, in the liquid crystal orientation film that forms by imide polymer of polyimide precursor-polyamic acid and structure that its dehydration closed-loop is obtained etc. as far as is known, using this liquid crystal orientation film to make under the situation of liquid crystal display device, though have for example excellent liquid crystal aligning ability and the stable advantage of tilt angle, it is narrow and small that but majority element also has the visual angle, the problem that response speed is slow.Particularly in the STN type liquid crystal display device that contains the above windup-degree of 180 degree, these problems become more remarkable.So in STN type liquid crystal display device, the tilt angle of having attempted being generally the 6-7 degree is reduced to for example below 4 degree, so that visual angle and response speed etc. is improved.The reason that can produce above-mentioned effect is to come the light leak of drop angle direction by reducing tilt angle, and the interaction between liquid crystal and the alignment films can become big.But for the liquid crystal orientation film of up to now STN type used for liquid crystal display element, too little can liquid crystal aligning to take place bad if reduce tilt angle, can not produce good liquid crystal display device.
Disclosure of an invention
The purpose of this invention is to provide realize wide visual angle and fast response, tilt angle is the following liquid crystal aligning agent that are particularly useful for STN type liquid crystal display device of 4 degree.
To understand other purpose of the present invention and advantage from the following description.
Above-mentioned purpose of the present invention and advantage can be reached by the liquid crystal aligning agent with following feature: according to the present invention, polyamic acid and/or this polyamic acid dehydration closed-loop that liquid crystal aligning agent contains tetracarboxylic dianhydride and diamine reaction gained obtain imide amination polymer, 15 moles is the pyromellitic acid acid anhydride more than the % among the tetracarboxylic dianhydride, 15 moles is 2 more than the % in the diamine, 2-two [4-(4-amino-benzene oxygen) phenyl] propane, and because the tilt angle that the liquid crystal orientation film that is obtained by this liquid crystal aligning agent presents is below 4 degree.
The preferred embodiment of invention
Below be about detailed description of the present invention.
Liquid crystal aligning agent of the present invention, usually contain the tetracarboxylic dianhydride of 15 moles of above pyromellitic acid acid anhydrides of % with organic solvent dissolution and contain 15 moles more than the % 2, the polyamic acid of the diamine reaction gained of 2-two [4 (4-amino-benzene oxygen) phenyl] propane and/or this polyamic acid dehydration closed-loop obtain that imide amination polymer (hereinafter this polyamic acid and imide amination polymer all being called " particular polymers ") constitutes.
＜polyamic acid 〉
The polyamic acid that the present invention uses is that the opening by tetracarboxylic dianhydride and diamine compound obtains.
＜tetracarboxylic dianhydride 〉
The present invention uses the tetracarboxylic dianhydride, contains 15 moles more than the % in whole tetracarboxylic dianhydrides, is preferably the pyromellitic acid dianhydride that contains 15-80 mole %.By containing 15 moles of above pyromellitic acid dianhydrides of %, can obtaining tilt angle is the liquid crystal orientation film of the following good liquid crystal aligning of 4 degree.
In the present invention, the tetracarboxylic anhydride as other preferably uses alicyclic tetracarboxylic dianhydride.By using alicyclic tetracarboxylic dianhydride, can also obtain the effect of the liquid crystal orientation film of 80-100% high voltage holding ratio.In whole tetracarboxylic dianhydrides better is to contain 85 moles below the %, is more preferably and contains 15-85 mole %, preferably contains the alicyclic tetracarboxylic dianhydride of 30-70 mole %.
As alicyclic tetracarboxylic dianhydride, for example have 1,2,3,4-ring butanetetra-carboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-ring butanetetra-carboxylic acid dianhydride, 1,3-dimethyl 1,2,3,4-ring butanetetra-carboxylic acid dianhydride, 1,3 ,-two chloro-1,2,3,4-ring butanetetra-carboxylic acid dianhydride, 1,2,3,4-tetramethyl--1,2,3,4-ring butanetetra-carboxylic acid dianhydride, 1,2,3,4-encircles penta tetracarboxylic dianhydride, 1,2,4,5-hexamethylene (alkane) tetracarboxylic dianhydride, 3,3 ', 4,4 '-two hexamethylene tetracarboxylic dianhydrides, 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, 3,5,6-three carboxyls norbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic dianhydride, two ring [2.2.2]-eight-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, suitable-3,7-dibutyl ring suffering-1,5-diene-1,2,5, the 6-tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5 (tetrahydrochysene-2,5-dioxan-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5 (tetrahydrochysene-2,5-dioxan-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-ethyl 5 (tetrahydrochysene-2,5-dioxan-3-furyl)-and naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-methyl 5 (tetrahydrochysene-2,5-dioxan-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-ethyl 5 (tetrahydrochysene-2,5-dioxan-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5 (tetrahydrochysene-2,5-dioxan-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-ethyl 5 (tetrahydrochysene-2,5-dioxan-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5, b-six hydrogen-5,8-dimethyl-5 (tetrahydrochysene-2,5-dioxan-3-furyl)-naphthalene-[1,2-c]-furans-1, the 3-diketone, 5-(2,5-dioxan tetrahydrofuran base)-3-methyl-3-tetrahydrobenzene-1,2-two acid dianhydrides and following formula (I) and (II) shown in compound etc.Above compound can use separately, also two or more compounds can be used in combination.
(in the formula, R
1And R
4Expression has the divalent organic group of aromatic ring, R
2And R
3Expression hydrogen atom or alkyl, each R of a plurality of existence
2And R
3Can be identical, also can be different.)
In the middle of these, have 1,2,3 preferably, 4-ring butanetetra-carboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-ring butanetetra-carboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-ring butanetetra-carboxylic acid dianhydride, 1,3-two chloro-1,2,3,4-ring butanetetra-carboxylic acid dianhydride, 1,2,3,4-tetramethyl--1,2,3,4-ring butanetetra-carboxylic acid dianhydride, 1,2,3,4-cyclopentyl tetracarboxylic dianhydride, 1,2,4,5-hexamethylene tetracarboxylic dianhydride, 3,3 ', 4,4 '-two hexamethylene tetracarboxylic dianhydrides, 2,3,5-tricarboxylic acid cyclopentyl acetic acid dianhydride, 3,5,6-tricarboxylic acid norbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic dianhydride, two ring [2.2.2]-eight-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, suitable-3,7-dibutyl ring suffering-1,5-diene-1,2,5, the 6-tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5 (tetrahydrochysene-2,5-oxane-3-furyl)-and naphtho-[1,2-c]-furans-1, the 3-diketone, 1,4,5,8-naphthalane tetracarboxylic dianhydride, 2,3,6,7-naphthalane tetracarboxylic dianhydride and 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride.Be more preferably 2,3,5-tricarboxylic acid cyclopentyl acetic acid dianhydride, 1,2,3,4-ring butanetetra-carboxylic acid dianhydride, 1,2-dimethyl 1,2,3,4-ring butanetetra-carboxylic acid dianhydride, 1,3-dimethyl 1,2,3,4-encircles butanetetra-carboxylic acid dianhydride and 1,2,4,5-hexanaphthene tetracarboxylic dianhydride.
In addition, in liquid crystal aligning agent of the present invention, can also be used in combination with other tetracarboxylic dianhydride.As this other tetracarboxylic dianhydride, adducible example has the butanetetra-carboxylic acid dianhydride that for example belongs to the aliphatics tetracarboxylic dianhydride; 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-two benzene sulfonyl tetracarboxylic dianhydrides, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride, 3,3 ', 4,4 '-tetraphenyl silane tetracarboxylic dianhydride, 1,2,3,4-furans tetracarboxylic dianhydride, 4,4 '-two (3,4-diacid phenoxy group) phenylbenzene sulphur dianhydride, 4,4 '-two (3,4-diacid phenoxy group) phenylbenzene sulphonyl dianhydride, 4,4 '-two (3,4-diacid phenoxy group) diphenyl propane dianhydride, 3,3 ', 4,4 '-perfluoro isopropylidene, two O-phthalic acid dianhydrides, 3,3 ', 4,4 '-phenylbenzene tetracarboxylic dianhydride, two (phthalic acid) phosphniline oxide compound dianhydride, to penylene-two (triphenyl phthalic acid) dianhydride, between penylene-two (triphenyl phthalic acid) dianhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl ether dianhydride, two (triphenyl phthalic acids)-4,4 '-ditan dianhydride, ethylene glycol bisthioglycolate (dehydration trimellitate), propylene glycol two (dehydration trimellitate), 1,4-butyleneglycol-two (dehydration trimellitate), 1,6-hexylene glycol-two (dehydration trimellitate), 1,8-ethohexadiol-two (dehydration trimellitate), 2,2-two (4-hydroxyphenyl) propane-two (dehydration trimellitate), and following formula (1)-(4) representatives belong to aromatic tetracarboxylic acid's dianhydride.These materials can use separately, also two or more compounds can be used in combination.
＜diamine 〉
The diamine that uses among the present invention preferably contains 15 moles more than the % in whole diamines, be preferably and contain 20-100 mole %, is more preferably and contains 2 of 20-80 mole %, 2-two [4-(4-amino-benzene oxygen) phenyl] propane.By containing 15 moles of 2 more than %, 2-two [4-(4-amino-benzene oxygen) phenyl] propane is even tilt angle is the liquid crystal orientation film that also can obtain good liquid crystal aligning below 4 degree.
In the present invention, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane also can be used in combination with other diamine, diamino-diphenyl ether for example, diaminodiphenyl-methane and by at least a diamine in the diamine of following formula (III) expression.These diamine compounds can use separately, also two or more compounds can be used in combination.By using these diamines, can more be increased the liquid crystal orientation film of confidence level.
(in the formula, R
5Expression from-O-,-COO-,-OCO-,-CONH-,-NHCO-and-the divalent organic group selected the CO-, R
61 valency organic group of expression steroid skeleton or trifluoromethyl)
Can enumerate the object lesson of the diamine shown in following formula (5)-(10) as the diamine of following formula (III) expression.
＜synthesizing polyamides acid 〉
The tetracarboxylic dianhydride that confession synthesizing polyamides acid-respons is used and the ratio of diamine compound are: for 1 contained in diamine compound equivalent amino, ratio is to contain the 0.2-2 equivalent preferably, is more preferably to contain acid anhydride base contained among the normal tetracarboxylic dianhydride of 0.3-1.4.Under the ratio less than 0.2 normal situation of the acid anhydride base that contains among the tetracarboxylic dianhydride and exceed under the 2 normal situations, the polymericular weight of gained is all too small, and the spreading property of liquid crystal aligning agent has the situation that becomes bad.
The polyamic acid that constitutes liquid crystal aligning agent of the present invention is by tetracarboxylic dianhydride and diamine compound reaction synthetic.The condition of polyamic acid building-up reactions is in organic solvent, better be at 0-150 ℃, is more preferably to carry out under 0-100 ℃ temperature.When temperature of reaction was lower than 0 ℃, compound poorly soluble in solvent when surpassing 150 ℃, had the low situation of molecular weight of polymkeric substance sometimes.
The organic solvent of synthesizing polyamides acid is the solvent that does not have particular restriction that can dissolve the polyamic acid of tetracarboxylic dianhydride, diamine compound and reaction gained, adducible example has gamma-butyrolactone, N-methyl 2-Pyrrolidone, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), 4-methyl urea, hexamethyl phosphine triamide, 1, the polar solvent of 3-dimethyl-non-proton classes such as 2-imidazole diketone; Phenol solvents such as meta-cresol, xylenol, phenol, halogenated phenol.
The usage quantity of organic solvent is (A), accounts for the 0.1-30 weight % that reaction soln is all measured (A+B) as the tetracarboxylic dianhydride of reaction raw materials and the total amount of diamine compound for (B) is preferably.
In addition, in above-mentioned organic solvent, need only the scope of separating out at the polyamic acid that can not make generation, also can be used in combination alcohols, ketone, ester class, ethers, halogenated hydrocarbon, hydrocarbon polymer etc. as the poor solvent of polyamic acid.The object lesson of this poor solvent has: as methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, 1, the 4-butyleneglycol, triethylene glycol, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, ritalin, vinyl acetic monomer, N-BUTYL ACETATE, oxalic acid diethyl ester, diethyl malonate, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic ester, the diethylene glycol monoethyl ether acetic ester, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene-glycol ethyl ether, Propylene Glycol Dimethyl Ether, the propylene glycol diethyl ether, dipropylene glycol methyl ether, the dipropylene glycol ether, the dipropylene glycol dme, the dipropylene glycol diethyl ether, ethyl cellosolve acetate, 4-hydroxy-4-methyl-2 pentanone, the 2 hydroxy propanoic acid ethyl ester, ethyl lactate, methyl lactate, n-Butyl lactate, the oxyethyl group vinyl acetic monomer, the hydroxacetic acid ethyl ester, 2-hydroxy-3-methyl methyl-butyrate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-methyl-3-methoxyl group butanone, 3-ethyl 3-methoxyl group butanone, 2-methyl-2-methoxyl group butanone, 2-ethyl-2-methoxyl group butanone, 3-methyl-3-oxyethyl group butanone, 3-ethyl-3-oxyethyl group butanone, 2-methyl-2-oxyethyl group butanone, 2-ethyl-2-oxyethyl group butanone, tetrahydrofuran (THF), methylene dichloride, 1, the 2-ethylene dichloride, 1, the 4-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene, hexane, heptane, octane, benzene, toluene and dimethylbenzene etc.These solvents can use separately, also can be used in combination of two or more.
By above building-up reactions, can obtain having dissolved the polymers soln of polyamic acid.So this polymers soln is injected in a large amount of poor solvents can obtains precipitate, with this precipitate decompression down drying can obtain polyamic acid.Then,, separate out by one or many with poor solvent subsequently and carry out this operation, then can make with extra care polyamic acid again with this polyamic acid of organic solvent dissolution.
＜imide amination polymer 〉
Can be by above-mentioned polyamic acid dehydration closed-loop being obtained constituting the imide amination polymer of liquid crystal aligning agent of the present invention.Polyamic acid dehydration closed-loop (i) can be undertaken by the method for heating polyamic acid, or (ii) can add dewatering agent and dehydration closed-loop catalyzer in this solution by dissolve polyamic acid in organic solvent, and the method that also should heat is carried out in case of necessity.
In the method for the heating polyamic acid of above-mentioned (i), temperature of reaction is preferably 50-200 ℃, is more preferably at 60-170 ℃.When temperature of reaction was lower than 50 ℃, the dehydration closed-loop reaction can not react completely, when temperature of reaction surpasses 200 ℃, and the imide amination polymer molecular weight and molecular weight of gained.
On the other hand, (ii) in polyamic acid solution, in the method for adding dewatering agent and dehydration closed-loop catalyzer, can use for example acetic anhydride above-mentioned, propionic anhydride, the acid anhydrides of trifluoro-acetic anhydride etc. is as dewatering agent.It is 0.01-20 mole dewatering agent that the consumption of dewatering agent is preferably corresponding to 1 mole of repeating unit of polyamic acid.And can be with 3 grades of amine of for example pyridine, trimethylpyridine, lutidine, triethylamine etc. as the dehydration closed-loop catalyzer.But, be not limited to these materials.The dehydration closed-loop catalyst consumption is preferably: corresponding to 1 mole of dewatering agent 0.01-10 mole dehydration closed-loop catalyzer.And can be identical with the used exemplary organic solvent of synthesizing polyamides acid as the used organic solvent of dehydration closed-loop reaction.Thereby the temperature of reaction of dehydration closed-loop reaction better is 0-180 ℃, is more preferably 10-150 ℃.In addition, for the reaction soln that obtains like this, can use and the refining imide amination polymer of the method identical operations of refining polyamic acid.
＜terminal follow-on polymkeric substance 〉
Constitute the polyamic acid and/or the imide amination polymer of liquid crystal aligning agent of the present invention, preferably use terminal follow-on polymkeric substance.Can not damage effect of the present invention by regulating terminal follow-on polymericular weight, and improve the characteristic of smearing of liquid crystal aligning agent.Can add acid anhydrides in reaction system when synthesizing polyamides acid, monoamine compound or monoisocyanates compound react the synthetic terminal modified version polymkeric substance that obtains
For obtaining the terminal polymkeric substance that improves type, added acid anhydrides can be used for example maleic anhydride, Tetra hydro Phthalic anhydride, itaconic anhydride, n-decane base succinyl oxide, dodecyl succinyl oxide, n-tetradecane base succinyl oxide and n-hexadecyl succinyl oxide etc. in the reaction system when synthesizing polyamides acid.In addition, added monoamine compound can be with the aniline that for example belongs to alkyl amine, hexahydroaniline, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, positive undecylamine, positive amino dodecane, positive tridecyl amine, positive tetradecy lamine, positive pentadecyl amine, positive cetylamine, positive heptadecyl-amine, positive stearylamine, positive 20 amine etc. in the synthesizing polyamides reaction system in when acid; 3-aminopropyl methyldiethoxysilane, 3-[N-allyl group-N-(2-amino-ethyl)] TSL 8330, N-(2-amino-ethyl)-3-aminocarbonyl propyl methyl dimethoxysilane, N-[(3-trimethoxysilyl) propyl group] Diethylenetriaminee (DETA) etc.In addition, the example as the monoisocyanates compound has for example phenyl isocyanate, naphthyl isocyanic ester etc.
＜liquid crystal aligning agent 〉
Liquid crystal aligning agent of the present invention is to form like this, and dissolving contains above-mentioned polyamic acid and/or imide amination polymer, the liquid crystal aligning agent of formation in organic solvent usually.
Liquid crystal aligning agent of the present invention also can contain the polymkeric substance more than 2 kinds.Under this situation, all benzene tertacarbonic acid's dianhydride is that 15 moles of used tetracarboxylic dianhydride's total amount are more than the %, 2, the ratio of 2-two [4-(4-amido phenoxy group) phenyl] propane is 15 moles of used diamine total amount more than the %, also particular polymers and other polyamic acids and/or imide amination polymer can be mixed and use.Particularly the polyamic acid and other the imide amination polymer of particular polymers can be mixed use.
The organic solvent that constitutes liquid crystal aligning agent of the present invention can be enumerated the exemplary solvent identical solvent used with the synthesizing polyamides acid-respons.And choose suitable solvent the poor solvent of use capable of being combined can be from the polyamic acid building-up reactions time and be used in combination.
Consider viscosity, volatility etc., the concentration of the solid ingredient of liquid crystal aligning agent of the present invention better are chosen in 1-10 weight % scope.In other words, be to form filming of liquid crystal orientation film, liquid crystal aligning agent of the present invention is applied to substrate surface, and is lower than in the concentration of solids component under 1% the situation, and this film thickness of filming is too small, is difficult to obtain good liquid crystal orientation film.When the concentration of solids component surpasses under 10% the situation, this film thickness of filming is excessive, also is difficult to obtain good liquid crystal orientation film, and the viscosity of liquid crystal aligning agent increases the spreading property variation.In addition, the temperature when preparing liquid crystal aligning agent of the present invention is preferably at 0-200 ℃, is more preferably at 20-60 ℃.
In liquid crystal aligning agent of the present invention,, contain the compound of functional silanes or contain the compound of epoxy group(ing) better from improving and the close-burning idea of substrate surface.Can have as this example that contains the compound of functional silanes: 3-TSL 8330 for example, the 3-aminopropyltriethoxywerene werene, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxycarbonyl-3-aminopropyltriethoxywerene werene, N-triethoxysilylpropyltetrasulfide three ethylene triamines, N-trimethoxy-silylpropyl three ethylene triamines, 10-trimethoxy first silica-based alkyl-1,4,7-three azepine decane, 10-three ethoxymethyl silylation-1,4,7-three azepine decane, 9-trimethoxysilyl 3,6-diaza nonyl acetic ester, 9-triethoxysilyl-3,6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, N-two (oxygen ethylidene)-3-TSL 8330 and N-two (oxygen ethylidene)-3-aminopropyltriethoxywerene werene etc.
In addition, example preferably as the compound that contains epoxy group(ing) can have: ethylene glycol bisthioglycolate glycidyl ethers for example, polyoxyethylene glycol diepoxy propyl ether, propylene glycol diepoxy propyl ether, tripropylene glycol diepoxy propyl ether, polypropylene glycol diepoxy propyl ether, neopentyl glycol diepoxy propyl ether, 1,6-hexylene glycol diepoxy propyl ether, glycerol diepoxy propyl ether, 2,2-dibromoneopentyl glycol diepoxy propyl ether, 1,3,5,6-Fourth Ring oxygen propyl group-2, the 4-hexylene glycol, N, N, N ', N '-Fourth Ring oxygen propyl group-m-xylenedimaine, 1,3-two (N, N-epoxypropyl amino methyl) hexanaphthene, N, N, N ', N '-Fourth Ring oxygen propyl group-4,4 '-diaminodiphenyl-methane etc.Particularly as N, N, N ', N '--Fourth Ring oxygen propyl group-m-xylenedimaine, 1,3-two (N, N-epoxypropyl amino methyl) hexanaphthene, N, N, N ', N '-Fourth Ring oxygen propyl group-4, the compound that contains epoxy group(ing) of nitrogen atoms such as 4 '-diaminodiphenyl-methane is better.With respect to the polymkeric substance of 100 weight parts, this contains the functional silanes compound and is preferably below 40 weight parts with the configuration proportion that contains epoxy compounds, is more preferably the weight part at 0.1-30.
＜liquid crystal display device 〉
Liquid crystal display device of the present invention can be according to the following method manufacturing that exemplifies.
(1) for example use rolling method being provided with on the surface of the substrate of the nesa coating of wiring patternization, modes such as spin-coating method and print process are smeared the liquid crystal aligning agent that forms liquid crystal orientation film of the present invention, then, smear the surface by heating and form and film.Wherein, described substrate can be used for example float glass process (FLOAT) glass, the glass of alkaline ripple glass etc.; The transparency carrier that the plastics of polyethylene terephthalate, polybutylene terephthalate, polyethersulfone or polycarbonate etc. are made.As the nesa coating that is provided with on a surface of substrate can be by stannic oxide (SnO
2) the NESA film (registered trademark of U.S. PPG company), the Indium sesquioxide-stannic oxide (In that make
2O
3-SnO
2) the ITO film that makes etc.Available light obtains the wiring pattern of this nesa coating according to the method for etching method and pre-cut mask.When smearing liquid crystal aligning agent, for make substrate surface and nesa coating and film between cohesiveness better, on this surface of substrate, can smear the compound that contains functional silanes, the compound that contains the functionality titanium in advance.Smear liquid crystal aligning agent Heating temperature afterwards and be preferably 80-300 ℃, be more preferably at 120-250 ℃.After smearing the liquid crystal aligning agent that the present invention contains polyamic acid,, also can carry out dehydration closed-loop, form bigger the filming of degree of imidisation by further heating though can form filming that alignment films constitutes by removing organic solvent.The coating thickness that forms is preferably the 0.001-1 micron, is more preferably the 0.005--0.5 micron.
(2) use nylon, artificial silk, the roller that the cloth that fibers such as cotton are made twines carries out friction treatment in a certain direction to formed film coated surface friction.Give the liquid crystal molecular orientation energy to film coated surface like this, form liquid crystal orientation film.
And, in the liquid crystal orientation film that forms by liquid crystal aligning agent of the present invention, open flat 6-222366 communique and disclosed such processing of the flat 6-281937 communique of Te Kai with for example spy, change tilt angle by shining with ultraviolet part, or use the spy to open disclosed such processing of flat 5-107544 communique, through friction treatment the upper surface of liquid crystal orientation film divide to form etchant resist, carry out removing etchant resist after the friction treatment in the direction different with previous friction treatment direction, change the liquid crystal aligning energy of liquid crystal orientation film thus, thereby may improve the viewing angle characteristic of liquid crystal display device.
(3) make 2 pieces of substrates that are formed with liquid crystal orientation film in order to upper type, between 2 pieces of substrates, get involved gap (gap, pond) configuration relatively, the periphery of 2 pieces of substrates is fitted with sealing agent, in the gap, pond of substrate surface and sealing agent qualification, inject and filling liquid crystal, seal filling orifice then and constitute the liquid crystal pond.Then, the outside surface in the liquid crystal pond that is to say the outside of each substrate that constitutes the liquid crystal pond by the applying Polarizer, to obtain STN type liquid crystal display device.
Wherein can use stiffening agent for example and contain Resins, epoxy as spherical alumina at interval as seal gum.
Liquid crystal can be with the nematic liquid crystal of example shown in following: for example Schiff's base is that liquid crystal, azoxy are that liquid crystal, biphenyl are that liquid crystal, Santosol 360 are that liquid crystal, ester are that liquid crystal, terphenyl are that liquid crystal, cyclohexyl biphenyl hexane are that liquid crystal, pyrimidine are that liquid crystal, dioxan are that liquid crystal, bicyclooctane liquid crystal, cubane (キ ユ バ Application) are liquid crystal etc.And in these liquid crystal, can add the cholesteryl liquid crystal of courage steroid chlorine, courage steroid ester in the ninth of the ten Heavenly Stems, courage steroid carbonic ether etc., and the commodity commercially available chirality agent of " C-15 " " CB-15 " (メ Le Network society system) by name.
In addition, the example of the Polarizer of fitting as the outside surface in liquid crystal pond can be: when polyvinyl alcohol is extended orientation calling the light polarizing film that absorbs the H film that iodine makes, the Polarizer of clamping with the cellulose acetate protective membrane, or the Polarizer of itself making by the H film.
Embodiment
Followingly specify the present invention, but the invention is not restricted to these embodiment according to embodiment.
The tilt angle of the liquid crystal display device that makes with the liquid crystal orientation film of the embodiment of this specification sheets and comparative example, angle, response speed and orientation are according to following method evaluation.
(tilt angle)
After the method preparation according to record in " T.J.Scheffer, et.al., J.Appl.Phys., vol.19,2013 (1980) ", measure by the crystallization rotary method with He-Ne Lasers.
(angle)
Under the common white mode activated, liquid crystal pond positive dirction is shifted to tilted direction, observes viewpoint with eyes and moves, and the angle that begins not see drive part is exactly an angle.
(response speed)
At first, in the common white pattern, measure the impressed voltage and the light transmission rate in liquid crystal pond, obtain transmitance and be 0 o'clock impressed voltage V
0Then the liquid crystal pond is applied impressed voltage V
0, measure up to transmitance and become time in response time of 0, to the evaluation of this value be: the more little response speed of this value is fast more.
(liquid crystal aligning)
After making the liquid crystal pond,, estimate the zone that has or not orientation bad thus with this liquid crystal pond of observation by light microscope.
Synthesis example 1
Will be as tetracarboxylic dianhydride's pyromellitic acid anhydride 174.5 grams (0.8 mole), 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 44.83g (0.2 mole), as 2 of diamine compound, 2-two [4-(4-amino-benzene oxygen) phenyl] propane 410.52 grams (1.0 moles) dissolve with N-N-methyl-2-2-pyrrolidone N-4500 grams, and reaction is 6 hours under 60 ℃.Then, reaction soln is injected in the big excessive methyl alcohol evolution reaction resultant.Afterwards, use the methanol cleaning product, the following 40 ℃ of dryings that reduce pressure obtained the 410 gram polyamic acids (this material is known as polyamic acid (A-1)) of logarithm viscosity 0.90dl/g in 15 hours.
Synthesis example 2
Diamine in the synthesis example 1 is become 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane 82.10 grams (0.2 mole), and 4, outside 4 '-diaminodiphenyl-methane, 158.62 grams (0.8 mole), obtain the 380 gram polyamic acids (this material is known as polyamic acid (A-2)) of logarithm viscosity 1.51dl/g with the same procedure of synthesis example 1.
Synthesis example 3
Diamine in the synthesis example 1 is become 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane 82.10 grams (0.2 mole), and outside diamino-diphenyl ether 160.19 grams (0.8 mole), obtain the 412 gram polyamic acids (this material is known as polyamic acid (A-3)) of logarithm viscosity 0.98dl/g with the same procedure of synthesis example 1.
Synthesis example 4
Diamine in the synthesis example 1 is become 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane 82.10 grams (0.2 mole), 4, outside diamine 5.23 grams (0.01 mole) of 4 '-diaminodiphenyl-methane, 156.64 grams (0.79 mole) and above-mentioned chemical formula (5) expression, obtain the 398 gram polyamic acids (this material is known as polyamic acid (A-4)) of logarithm viscosity 1.87dl/g with the same procedure of synthesis example 1.
Synthesis example 5
Diamine in the synthesis example 1 is become 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane 82.10 grams (0.2 mole), 4, outside diamine 5.23 grams (0.01 mole) of 4 '-diamino-diphenyl ether, 158.19 grams (0.79 mole) and above-mentioned chemical formula (5) expression, obtain the 367 gram polyamic acids (this material is known as polyamic acid (A-5)) of logarithm viscosity 0.99dl/g with the same procedure of synthesis example 1.
Synthesis example 6
Diamine in the synthesis example 1 is become 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane 205.25 grams (0.5 mole), 4, outside diamine 5.23 grams (0.01 mole) of 4 '-diaminodiphenyl-methane, 97.16 grams (0.49 mole) and above-mentioned chemical formula (5) expression, obtain the 356 gram polyamic acids (this material is known as polyamic acid (A-6)) of logarithm viscosity 1.90dl/g with the same procedure of synthesis example 1.
Synthesis example 7
Tetracarboxylic dianhydride in the synthesis example 1 is become pyromellitic acid anhydride 174.5 gram (0.8 mole) and tetramethylene tetracarboxylic dianhydride 39.22 grams (0.2 mole) in addition, obtain 420 of logarithm viscosity 1.21dl/g with the same procedure of synthesis example 1 and restrain polyamic acids (this material is known as polyamic acid (A-7)).
Synthesis example 8
Tetracarboxylic dianhydride in the synthesis example 2 is become pyromellitic acid anhydride 174.5 gram (0.8 mole) and tetramethylene tetracarboxylic dianhydride 39.22 grams (0.2 mole) in addition, obtain 485 of logarithm viscosity 1.18dl/g with the same procedure of synthesis example 2 and restrain polyamic acids (this material is known as polyamic acid (A-8)).
Synthesis example 9
Tetracarboxylic dianhydride in the synthesis example 3 is become pyromellitic acid anhydride 174.5 gram (0.8 mole) and tetramethylene tetracarboxylic dianhydride 39.22 grams (0.2 mole) in addition, obtain 420 of logarithm viscosity 0.98dl/g with the same procedure of synthesis example 3 and restrain polyamic acids (this material is known as polyamic acid (A-9)).
Synthesis example 10
Tetracarboxylic dianhydride in the synthesis example 4 is become pyromellitic acid anhydride 174.5 gram (0.8 mole) and tetramethylene tetracarboxylic dianhydride 39.22 grams (0.2 mole) in addition, obtain 420 of logarithm viscosity 0.95dl/g with the same procedure of synthesis example 4 and restrain polyamic acids (this material is known as polyamic acid (A-10)).
Synthesis example 11
Tetracarboxylic dianhydride in the synthesis example 5 is become pyromellitic acid anhydride 174.5 gram (0.8 mole) and tetramethylene tetracarboxylic dianhydride 39.22 grams (0.2 mole) in addition, obtain 408 of logarithm viscosity 0.99dl/g with the same procedure of synthesis example 5 and restrain polyamic acids (this material is known as polyamic acid (A-11)).
Synthesis example 12
Tetracarboxylic dianhydride in the synthesis example 6 is become pyromellitic acid anhydride 174.5 gram (0.8 mole) and tetramethylene tetracarboxylic dianhydride 39.22 grams (0.2 mole) in addition, obtain 398 of logarithm viscosity 0.97dl/g with the same procedure of synthesis example 6 and restrain polyamic acids (this material is known as polyamic acid (A-12)).
Synthesis example 13
Tetracarboxylic dianhydride in the synthesis example 1 is become pyromellitic acid anhydride 109.06 gram (0.5 mole) and tetramethylene tetracarboxylic dianhydride 98.06 grams (0.5 mole) in addition, obtain 485 of logarithm viscosity 0.99dl/g with the same procedure of synthesis example 1 and restrain polyamic acids (this material is known as polyamic acid (A-13)).
Synthesis example 14
Tetracarboxylic dianhydride in the synthesis example 2 is become pyromellitic acid anhydride 109.06 gram (0.5 mole) and tetramethylene tetracarboxylic dianhydride 98.06 grams (0.5 mole) in addition, obtain 485 of logarithm viscosity 1.29dl/g with the same procedure of synthesis example 2 and restrain polyamic acids (this material is known as polyamic acid (A-14)).
Synthesis example 15
Tetracarboxylic dianhydride in the synthesis example 3 is become pyromellitic acid anhydride 109.06 gram (0.5 mole) and tetramethylene tetracarboxylic dianhydride 98.06 grams (0.5 mole) in addition, with the same procedure of synthesis example 3 obtain logarithm viscosity 1.11dl/g, amidation ratio be 0% 420 restrain polyamic acids (this material is known as polyamic acid (A-15)).
Synthesis example 16
Tetracarboxylic dianhydride in the synthesis example 4 is become pyromellitic acid anhydride 109.06 gram (0.5 mole) and tetramethylene tetracarboxylic dianhydride 98.06 grams (0.5 mole) in addition, obtain 420 of logarithm viscosity 0.98dl/g with the same procedure of synthesis example 4 and restrain polyamic acids (this material is known as polyamic acid (A-16)).
Synthesis example 17
Tetracarboxylic dianhydride in the synthesis example 5 is become pyromellitic acid anhydride 109.06 gram (0.5 mole) and tetramethylene tetracarboxylic dianhydride 98.06 grams (0.5 mole) in addition, obtain 400 of logarithm viscosity 1.02dl/g with the same procedure of synthesis example 5 and restrain polyamic acids (this material is known as polyamic acid (A-17)).
Synthesis example 18
Tetracarboxylic dianhydride in the synthesis example 6 is become pyromellitic acid anhydride 109.06 gram (0.5 mole) and tetramethylene tetracarboxylic dianhydride 98.06 grams (0.5 mole) in addition, obtain 398 of logarithm viscosity 0.99dl/g with the same procedure of synthesis example 6 and restrain polyamic acids (this material is known as polyamic acid (A-18)).
Synthesis example 19
Tetracarboxylic dianhydride in the synthesis example 1 is become pyromellitic acid anhydride 109.06 gram (0.5 mole) and hexanaphthene tetracarboxylic dianhydride 110.06 grams (0.5 mole) in addition, obtain 408 of logarithm viscosity 1.05dl/g with the same procedure of synthesis example 1 and restrain polyamic acids (this material is known as polyamic acid (A-19)).
Synthesis example 20
Tetracarboxylic dianhydride in the synthesis example 2 is become pyromellitic acid anhydride 109.06 gram (0.5 mole) and hexanaphthene tetracarboxylic dianhydride 110.06 grams (0.5 mole) in addition, obtain 411 of logarithm viscosity 1.05dl/g with the same procedure of synthesis example 2 and restrain polyamic acids (this material is known as polyamic acid (A-20)).
Synthesis example 21
Tetracarboxylic dianhydride in the synthesis example 3 is become pyromellitic acid anhydride 109.06 gram (0.5 mole) and hexanaphthene tetracarboxylic dianhydride 110.06 grams (0.5 mole) in addition, obtain 391 of logarithm viscosity 1.02dl/g with the same procedure of synthesis example 3 and restrain polyamic acids (this material is known as polyamic acid (A-21)).
Synthesis example 22
Tetracarboxylic dianhydride in the synthesis example 4 is become pyromellitic acid anhydride 109.06 gram (0.5 mole) and hexanaphthene tetracarboxylic dianhydride 110.06 grams (0.5 mole) in addition, obtain 388 of logarithm viscosity 0.92dl/g with the same procedure of synthesis example 4 and restrain polyamic acids (this material is known as polyamic acid (A-22)).
Synthesis example 23
Tetracarboxylic dianhydride in the synthesis example 5 is become pyromellitic acid anhydride 109.06 gram (0.5 mole) and hexanaphthene tetracarboxylic dianhydride 110.06 grams (0.5 mole) in addition, obtain 392 of logarithm viscosity 1.08dl/g with the same procedure of synthesis example 5 and restrain polyamic acids (this material is known as polyamic acid (A-23)).
Synthesis example 24
Tetracarboxylic dianhydride in the synthesis example 6 is become pyromellitic acid anhydride 109.06 gram (0.5 mole) and hexanaphthene tetracarboxylic dianhydride 110.06 grams (0.5 mole) in addition, obtain 402 of logarithm viscosity 1.02dl/g with the same procedure of synthesis example 6 and restrain polyamic acids (this material is known as polyamic acid (A-24)).
Synthesis example 25
Tetracarboxylic dianhydride in the synthesis example 1 is become pyromellitic acid anhydride 109.06 grams (0.5 mole) and 1,2-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride 112.10 grams (0.5 mole) obtain the 392 gram polyamic acids (this material is known as polyamic acid (A-25)) of logarithm viscosity 0.88dl/g in addition with the same procedure of synthesis example 7.
Synthesis example 26
Tetracarboxylic dianhydride in the synthesis example 2 is become pyromellitic acid anhydride 109.06 grams (0.5 mole) and 1,2-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride 112.10 grams (0.5 mole) obtain the 390 gram polyamic acids (this material is known as polyamic acid (A-26)) of logarithm viscosity 1.09dl/g in addition with the same procedure of synthesis example 2.
Synthesis example 27
Tetracarboxylic dianhydride in the synthesis example 3 is become pyromellitic acid anhydride 109.06 grams (0.5 mole) and 1,2-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride 112.10 grams (0.5 mole) obtain the 389 gram polyamic acids (this material is known as polyamic acid (A-27)) of logarithm viscosity 1.11dl/g in addition with the same procedure of synthesis example 3.
Synthesis example 28
Tetracarboxylic dianhydride in the synthesis example 4 is become pyromellitic acid anhydride 109.06 grams (0.5 mole) and 1,2-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride 112.10 grams (0.5 mole) obtain the 392 gram polyamic acids (this material is known as polyamic acid (A-28)) of logarithm viscosity 1.09dl/g in addition with the same procedure of synthesis example 4.
Synthesis example 29
Tetracarboxylic dianhydride in the synthesis example 5 is become pyromellitic acid anhydride 109.06 grams (0.5 mole) and 1,2-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride 112.10 grams (0.5 mole) obtain the 355 gram polyamic acids (this material is known as polyamic acid (A-29)) of logarithm viscosity 1.07dl/g in addition with the same procedure of synthesis example 5.
Synthesis example 30
Tetracarboxylic dianhydride in the synthesis example 6 is become pyromellitic acid anhydride 109.06 grams (0.5 mole) and 1,2-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride 112.10 grams (0.5 mole) obtain the 367 gram polyamic acids (this material is known as polyamic acid (A-30)) of logarithm viscosity 1.02dl/g in addition with the same procedure of synthesis example 6.
Synthesis example 31
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 224.17 grams (1 mole), the diamine of representing as P-pHENYLENE dI AMINE 107.06 grams (0.99 mole) and the above-mentioned chemical formula (5) of diamine compound 5.23 restrain (0.01 mole), with the 4500 gram dissolvings of N-N-methyl-2-2-pyrrolidone N-, reacted 6 hours down at 60 ℃.Then, reaction soln is injected in the big excessive methyl alcohol evolution reaction resultant.Afterwards, use the methanol cleaning product, the following 40 ℃ of dryings that reduce pressure obtained logarithm viscosity 0.90dl/g in 15 hours, and the imidization rate is 0% 410 gram polyamic acids.Polyamic acid 30 grams that obtain thus are dissolved in the N-N-methyl-2-2-pyrrolidone N-of 570 grams, add pyridine 23.4 grams and Glacial acetic acid 18.1 grams, under 110 ℃, carry out 4 hours dehydration closed-loop reaction, precipitate with above-mentioned same method, washing and decompression, obtaining logarithm viscosity is 0.85dl/g, and the imidization rate is 100% 17.5 gram polyimide (this material is known as polyimide (B-1)).
Synthesis example 32
Diamine in the synthesis example 31 is become 4, diamine 5.23 grams (0.01 mole) of 4-diaminodiphenylmethane 196.29 grams (0.99 mole) and above-mentioned chemical formula (5) expression in addition, same procedure with synthesis example 31 obtains logarithm viscosity 1.16dl/g, and the amidation rate is 100% polyimide 22.2 grams (this product is called as " polyimide (B-2) ").
Compare synthesis example 1
Diamine 26.15 grams (0.05 mole) that diamine in the synthesis example 1 is become P-pHENYLENE dI AMINE 102.73 gram (0.95 mole) and above-mentioned chemical formula (5) expression in addition, obtaining logarithm viscosity with the same procedure of synthesis example 1 is that 276 of 1.01dl/g restrains polyamic acids (this material is known as polyamic acid (A-31)).
Compare synthesis example 2
Diamine in the synthesis example 14 is become 4, diamine 26.15 grams (0.05 mole) of 4 '-diaminodiphenyl oxide 190.23 gram (0.95 mole) and above-mentioned chemical formula (5) expression in addition, obtaining logarithm viscosity with the same procedure of synthesis example 14 is that 300 of 1.02dl/g restrains polyamic acids (this material is known as polyamic acid (A-32)).
Compare synthesis example 3
Diamine in the synthesis example 21 is become 4, diamine 26.15 grams (0.05 mole) of 4 '-diaminodiphenyl oxide 190.23 gram (0.95 mole) and above-mentioned chemical formula (5) expression in addition, obtaining logarithm viscosity with the same procedure of synthesis example 21 is that 234 of 1.14dl/g restrains polyamic acids (this material is known as polyamic acid (A-33)).
Compare synthesis example 4
Tetracarboxylic dianhydride in the synthesis example 1 is become tetramethylene tetracarboxylic acid dianhydride 196.12 gram (1 mole) in addition, and obtaining logarithm viscosity with the same procedure of synthesis example 1 is that 415 of 1.08dl/g restrains polyamic acids (this material is known as polyamic acid (A-34)).
Embodiment 1
The polyamic acid (A-1) of synthesis example 1 gained is dissolved with N-N-methyl-2-2-pyrrolidone N-// gamma-butyrolactone/ethylene glycol butyl ether mixed solvent (weight ratio 45: 5: 50), add 20 weight part N to 100 parts by weight polymer, N, N ', N '-Fourth Ring Ethylene Oxide-4,4 '-diaminodiphenylmethane obtains the solution that solid component concentration is 4 weight %, with the aperture is that 1 micron strainer filters this solution, makes liquid crystal aligning agent of the present invention.Smear the printing press that liquid crystal orientation film uses and above-mentioned liquid crystal aligning agent is spread upon on the transparency electrode face of the glass substrate that is attached with the transparency electrode of making by the ITO film, on 230 ℃ electric furnace dry 10 minutes, form the overlay film of exsiccant average film thickness 500 dusts.With rubbing machine this overlay film carried out friction treatment with the roller that has twined the cloth that artificial silk makes.The above-mentioned substrate of having smeared alignment films flooded 1 minute in water after, on 100 ℃ electric furnace with both sides drying substrates 5 minutes.Then, the outside separately that has liquid crystal orientation film at a pair of holding liquid crystal of crossing through friction treatment with substrate, smear and be mixed with the epoxy adhesive that diameter is 5.5 microns a ball-aluminium oxide, in the relative mode in liquid crystal orientation film surface a pair of holding liquid crystal is overlapped crimping with substrate afterwards, make the binding agent sclerosis.Subsequently, between a pair of substrate, fill nematic liquid crystal (manufacturing of Mei Luoke company, ZLI-2293) from liquid crystal injecting port, seal liquid crystal injecting port with acrylic acid series photo-hardening binding agent afterwards, two surperficial applying Polarizers in the substrate outside are made liquid crystal display device.The tilt angle that it demonstrates 3.5 degree has the angle of 150 degree, and response speed is 100 milliseconds.
Embodiment 2-32 and comparative example 1-4
Except the polyamic acid among the embodiment 1 (A-1) is replaced with the polymkeric substance of table shown in the 1-2, use the method identical to obtain liquid crystal aligning agent and make liquid crystal display device with embodiment 1, it is estimated.The results are shown among the table 1-2.Wherein, in embodiment 31 and 32, the blending ratio of polyamic acid and polyimide is: weight ratio is 8: 2.
Table 1
| Embodiment | Polymkeric substance | Tilt angle (degree) | Angle (degree) | Time of response (millisecond) | Orientation (having or not the farmland) | |
| Embodiment | 2 | A-2 | 2.0 | 140 | 110 | No farmland |
| 3 | A-3 | 2.1 | 145 | 100 | No farmland | |
| 4 | A-4 | 2.2 | 150 | 110 | No farmland | |
| 5 | A-5 | 1.9 | 135 | 110 | No farmland | |
| 6 | A-6 | 2.9 | 140 | 120 | No farmland | |
| 7 | A-7 | 2.5 | 135 | 120 | No farmland | |
| 8 | A-8 | 3.0 | 145 | 130 | No farmland | |
| 9 | A-9 | 2.4 | 145 | 120 | No farmland | |
| 10 | A-10 | 2.8 | 145 | 110 | No farmland | |
| 11 | A-11 | 2.7 | 145 | 130 | No farmland | |
| 12 | A-12 | 3.5 | 135 | 120 | No farmland | |
| 13 | A-13 | 3.3 | 135 | 110 | No farmland | |
| 14 | A-14 | 3.2 | 130 | 120 | No farmland | |
| 15 | A-15 | 2.8 | 140 | 130 | No farmland | |
| 16 | A-16 | 3.6 | 135 | 120 | No farmland | |
| 17 | A-17 | 3.9 | 145 | 110 | No farmland | |
| 18 | A-18 | 3.2 | 135 | 120 | No farmland | |
| 19 | A-19 | 3.5 | 140 | 110 | No farmland | |
| 20 | A-20 | 3.0 | 140 | 110 | No farmland | |
Table 2
| The embodiment comparative example | Polymkeric substance | Tilt angle (degree) | Angle (degree) | Time of response (millisecond) | Orientation (having or not the farmland) | |
| Embodiment | 21 | A-21 | 3.0 | 145 | 100 | No farmland |
| 22 | A-22 | 3.2 | 145 | 120 | No farmland | |
| 23 | A-23 | 3.3 | 150 | 110 | No farmland | |
| 24 | A-24 | 3.8 | 145 | 110 | No farmland | |
| 25 | A-25 | 3.6 | 145 | 120 | No farmland | |
| 26 | A-26 | 3.7 | 135 | 120 | No farmland | |
| 27 | A-27 | 3.5 | 145 | 130 | No farmland | |
| 28 | A-28 | 3.0 | 150 | 120 | No farmland | |
| 29 | A-29 | 3.4 | 145 | 130 | No farmland | |
| 30 | A-30 | 3.3 | 130 | 120 | No farmland | |
| 31 | A-1+B-1 | 3.7 | 150 | 120 | No farmland | |
| 32 | A-1+B-2 | 3.8 | 150 | 120 | No farmland | |
| Comparative example | 1 | A-31 | 3.5 | 140 | 120 | The farmland is arranged |
| 2 | A-32 | 6.0 | 108 | 240 | No farmland | |
| 3 | A-33 | 6.2 | 110 | 220 | No farmland | |
| 4 | A-34 | 4.5 | 110 | 180 | The farmland is arranged | |
The invention effect
Under the situation as liquid crystal display cells, liquid crystal orientation film of the present invention can make excellent high angle, high-speed response, without the bad STN type liquid crystal display cells of orientation.
And the liquid crystal display cells that can will have liquid crystal orientation film of the present invention is used in the various devices effectively, for example, can be used on desk-top calculator, wrist-watch, and timer, the coefficient display board, word processor, personal computer is in the display unit such as LCD TV.
Claims (6)
1. liquid crystal aligning agent, this liquid crystal aligning agent is to contain the polyamic acid of tetracarboxylic dianhydride and diamine reaction gained and/or the liquid crystal aligning agent of the imide amination polymer formation that this polyamic acid dehydration closed-loop obtains, it is characterized in that wherein 15-80 mole % is a pyromellitic acid anhydride among the tetracarboxylic dianhydride, 15-100 mole % is 2 in the diamine, 2-two [4-(4-amino-benzene oxygen) phenyl] propane, and by the tilt angle that the liquid crystal orientation film that is obtained by this liquid crystal aligning agent presents be 4 the degree below.
2. liquid crystal aligning agent as claimed in claim 1, wherein the tetracarboxylic dianhydride except pyromellitic acid anhydride uses the ester ring type tetracarboxylic dianhydride.
3. liquid crystal aligning agent as claimed in claim 1, wherein as 2, diamine outside 2-two [4-(4-amino-benzene oxygen) phenyl] propane is at least a diamine of selecting from the group that the diamine shown in diaminodiphenyl oxide, diaminodiphenyl-methane and the following formula (III) is formed
In the formula, R
5Expression from-O-,-COO-,-OCO-,-CONH-,-NHCO-and-the divalent organic group selected the CO-, R
6Expression has 1 valency organic group of steroid skeleton or trifluoromethyl.
4. liquid crystal aligning agent as claimed in claim 1 wherein also contains the compound of epoxy group(ing).
5. liquid crystal aligning agent according to claim 1, it is that STN type liquid crystal display device uses.
6. a STN type liquid crystal display device is characterized in that, it has the liquid crystal orientation film that is made by the described liquid crystal aligning agent of claim 1.
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| JP250363/2000 | 2000-08-21 | ||
| JP250363/00 | 2000-08-21 | ||
| JP2000250363A JP2002062537A (en) | 2000-08-21 | 2000-08-21 | Liquid crystal aligning agent for stn (supertwisted nematic) liquid crystal display element and stn liquid crystal display element |
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| JP4600637B2 (en) * | 2002-04-30 | 2010-12-15 | Ｊｓｒ株式会社 | Liquid crystal alignment agent |
| US7289179B2 (en) | 2002-11-08 | 2007-10-30 | Samsung Electronics Co., Ltd. | Liquid crystal display |
| JP4671015B2 (en) * | 2003-12-17 | 2011-04-13 | Ｊｓｒ株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| TWI359189B (en) * | 2004-01-27 | 2012-03-01 | Jsr Corp | Liquid crystal alignment agent, liquid crystal ali |
| TWI360680B (en) * | 2004-02-24 | 2012-03-21 | Jsr Corp | Liquid crystal alignment agent and manufacturing m |
| JP4968422B2 (en) * | 2004-12-15 | 2012-07-04 | Ｊｓｒ株式会社 | Method for producing liquid crystal alignment film |
| KR101363224B1 (en) * | 2005-05-25 | 2014-02-12 | 닛산 가가쿠 고교 가부시키 가이샤 | Liquid crystal aligning agent and liquid crystal dispaly device using same |
| KR20070116562A (en) * | 2006-06-05 | 2007-12-10 | 제이에스알 가부시끼가이샤 | Liquid crystal aligning agent and horizontal electric-field type liquid crystal display |
| CN101466774B (en) * | 2006-07-18 | 2012-07-04 | 三菱瓦斯化学株式会社 | Polyimide resin |
| TWI406838B (en) * | 2006-08-04 | 2013-09-01 | Jnc Corp | Diamide,liquid crystal alignment agent,liquid crystal alignment film and liquid crystal display |
| JP5077558B2 (en) * | 2007-02-15 | 2012-11-21 | Ｊｓｒ株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| JP5041163B2 (en) * | 2008-06-18 | 2012-10-03 | Ｊｓｒ株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| CN102209928B (en) * | 2008-10-22 | 2014-02-26 | 日产化学工业株式会社 | Liquid crystal aligning agent and liquid crystal element using same |
| JP5849391B2 (en) * | 2010-01-19 | 2016-01-27 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| WO2012133826A1 (en) * | 2011-03-31 | 2012-10-04 | 日産化学工業株式会社 | Liquid crystal aligning agent and liquid crystal alignment film using same |
| CN104704421B (en) * | 2012-08-10 | 2018-01-16 | 日产化学工业株式会社 | Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells |
| TWI617595B (en) * | 2013-03-08 | 2018-03-11 | Nissan Chemical Ind Ltd | Liquid crystal alignment agent, liquid crystal display element obtained, and method of manufacturing the same |
| WO2015012316A1 (en) * | 2013-07-24 | 2015-01-29 | 日産化学工業株式会社 | Liquid crystal aligning agent and liquid crystal aligning film using same |
| CN103739205B (en) * | 2013-11-08 | 2017-06-13 | 北京京东方光电科技有限公司 | Functional material and preparation method thereof, display structure form material, color membrane substrates, display device |
| US9690035B2 (en) | 2014-07-29 | 2017-06-27 | Boe Technology Group Co., Ltd. | Functional material, its preparation method, light guide ink, and light guide plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07281192A (en) * | 1994-04-07 | 1995-10-27 | Hitachi Ltd | Liquid crystal oriented film |
| JPH08146431A (en) * | 1994-11-24 | 1996-06-07 | Hitachi Ltd | Composition for liquid crystal oriented film, and liquid crystal oriented film |
| JP3612832B2 (en) * | 1995-12-28 | 2005-01-19 | Ｊｓｒ株式会社 | Method for producing imide group-containing polyamic acid and liquid crystal aligning agent |
| JP3918247B2 (en) * | 1997-09-05 | 2007-05-23 | チッソ株式会社 | Resin composition for liquid crystal alignment film, liquid crystal alignment film, liquid crystal sandwich substrate, and liquid crystal display element |
-
2000
- 2000-08-21 JP JP2000250363A patent/JP2002062537A/en active Pending
-
2001
- 2001-08-10 TW TW90119683A patent/TW538290B/en not_active IP Right Cessation
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| Publication number | Publication date |
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| CN1339554A (en) | 2002-03-13 |
| JP2002062537A (en) | 2002-02-28 |
| TW538290B (en) | 2003-06-21 |
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