CN100367097C - Liquid crystal orientation agent - Google Patents

Liquid crystal orientation agent Download PDF

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CN100367097C
CN100367097C CNB2004100387595A CN200410038759A CN100367097C CN 100367097 C CN100367097 C CN 100367097C CN B2004100387595 A CNB2004100387595 A CN B2004100387595A CN 200410038759 A CN200410038759 A CN 200410038759A CN 100367097 C CN100367097 C CN 100367097C
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liquid crystal
crystal orientating
dicarboxylic anhydride
integer
formula
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CN1540403A (en
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清水成夫
大田芳久
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JSR Corp
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Abstract

Provided is a liquid crystal aligning agent for a liquid crystal display device which can yield an liquid crystal display device having excellent image retention characteristics, reliability, light resistance and heat resistance. The liquid crystal aligning agent contains imido polymer of polyamic acid having two specific structures, for example, a biphenyl skeleton and a cyclohexylmethylene skeleton.

Description

Liquid crystal orientating agent
Technical field
The present invention relates to form the employed liquid crystal orientating agent of liquid crystal orientating membrane of liquid crystal display cells.More specifically, the present invention relates to be used to prepare the liquid crystal orientating agent of the liquid crystal orientating membrane of giving excellent image retention characteristic of liquid crystal display cells and excellent long-time stability.
Background technology
Now, as liquid crystal display cells, known a kind of TN type liquid crystal display cells with so-called TN type (Twisted Nematic) liquid crystal cell, its forming process is: form liquid crystal orientating membrane by polyamic acid, polyimide etc. and as the used for liquid crystal display element ground being provided with on the surface of bottom material of nesa coating, 2 blocks of such grounds staggered relatively, in its space, form nematic crystal layer with positivity dielectric anisotropy, thereby form the box of sandwich structure, the major axis of liquid crystal molecule is twisted 90 degree from the ground of one side continuously to the ground of another side.
Also at exploitation STN (Super Twisted Nematic) type liquid crystal display cells and vertical orientation type liquid crystal display cells, compare with TN type liquid crystal display cells in addition, their contrast is higher, the visual angle dependence is littler.This STN type liquid crystal display cells mixes the material as the chirality agent of optically active substance in nematic crystal, and it is used as liquid crystal, between ground, twist turnback or the above state of twisting the continuously generation birefringence effect that forms by the major axis of liquid crystal molecule.
Yet, for existing known, use contain have polyamic acid and with its dehydration closed-loop and the liquid crystal orientating agent of polyimide based polymer make situations such as TN type liquid crystal display cells, even the ionic electric charge that produces and be adsorbed on when image shows or during impressed voltage on the liquid crystal orientating membrane can not desorb from liquid crystal orientating membrane after picture drop-out or impressed voltage are removed yet, removing behind the voltage on liquid crystal orientating membrane the residual and savings of voltage gets up, cause impressed voltage to remove the back produces image retention in display frame problem by this residual voltage, under the situation that produces this image retention, the light and shade difference diminishes when outer added-time of voltage and releasing, causes obtaining the problem of good contrast.Therefore, just waiting in expectation and developing the liquid crystal orientating agent that can reduce the liquid crystal display cells image retention.
Nearest in addition, turn to purpose with the light weight of liquid crystal display cells, attempting previously used glass substrate as resin substrate.Because the resin substrate heat resisting temperature is low, when forming liquid crystal orientating membrane, must under than usually lower low temperature, burn till processing.Firing temperature at low temperatures, the problem that exists reliability etc. significantly to reduce, existing just waiting in expectation developed the liquid crystal orientating agent that can give the excellent reliability of liquid crystal display cells.
In addition, liquid crystal indicator develops towards miniaturization, and it is on the other hand because the light intensity grow that penetrates from light source, the light intensity grow that liquid crystal display cells is accepted, and the temperature of liquid crystal display cells uprises.Therefore, for the liquid crystal display cells that in oriented film, uses the polyimide that used in the past, exist oriented film deterioration, life of product to lack and the problem of demand solution.
Summary of the invention
The present invention implements in view of above situation, and the 1st purpose of the present invention provides the liquid crystal orientating agent that is used to prepare the liquid crystal orientating membrane that makes liquid crystal display cells image retention excellent.
The 2nd purpose of the present invention provides the liquid crystal orientating agent of the liquid crystal display cells that can prepare the reliability excellence.
The 3rd purpose of the present invention provides the liquid crystal orientating agent of the liquid crystal display cells that can prepare photostability, excellent heat resistance.
The present invention also has other purposes and advantage, sets forth by following explanation.
According to the present invention, above-mentioned purpose of the present invention and advantage realize by liquid crystal orientating agent, it is characterized in that this liquid crystal orientating agent contains to be selected to satisfy at least a 1. and in the polyimide fluidized polymer of polyamic acid 2. of following condition.
1. has at least a structure that is selected from the represented separately structure in following formula (1)-(10) (below, be also referred to as " ad hoc structure 1. ").
2. has at least a structure that is selected from the represented separately structure of following formula (a)-(c) (below, be also referred to as " ad hoc structure 2. ").
Figure C20041003875900161
In the formula, R a-R xThe organic group of representing halogen atom or 1 valency independently of one another, a, b, g, h, l, n, q, r, v and x represent the integer of 0-3 independently of one another, e, f, i, j, k, m, o, p, s, t, u and w represent the integer of 0-2 independently of one another, and c and d represent the integer of 0-4 independently of one another.
In the formula, R 1'-R 3' representing the organic group of halogen atom or 1 valency independently of one another, a ', b ', c ' represent the integer of 0-3 independently of one another, the integer of d ' expression 1-5, the integer of e ' expression 0-51.
Embodiment
Below, the present invention is described in detail.Employed in the present invention polyimide fluidized polymer can react synthetic polyamic acid by make tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound in organic solvent, again it is carried out dehydration closed-loop and makes.These polymkeric substance can also 2 kinds or above mixing use.
In liquid crystal orientating agent of the present invention, preferably use the imidizate rate be 40% or more than, i.e. the imide amination polymer of 40-100%.Here so-called " imidizate rate " is meant in polymkeric substance in whole repetitives, to have the numerical value that the imide ring repetitive is represented with percent.
Any one contains ad hoc structure compound 1. at least in tetrabasic carboxylic acid dicarboxylic anhydride and the diamine compound by using, and imports ad hoc structure 1. to imide polymer.Preferred especially the use has ad hoc structure diamine compound 1..
1. ad hoc structure when improving liquid crystal display cells image retention characteristic aspect and having remarkable result, also has the reliability of raising, photostability, thermotolerance, improves the electrical stability of liquid crystal display cells, the effect of life of product.Ad hoc structure 1. in, preferred especially above-mentioned formula (1) or (2) represented structure, the represented structure of more preferably above-mentioned formula (2).
Preferably have an ad hoc structure compound 2. in the tetrabasic carboxylic acid dicarboxylic anhydride, in imide amination polymer, import ad hoc structure 2. by using.2. ad hoc structure makes the imidizate condensate that is made by the unsettled polyamic acid dehydration closed-loop that changes easily in the solution state preservation have solvent soluble, thereby has the effect that can preserve under steady state (SS).Ad hoc structure is proportional containing 1. in the imidization polymkeric substance that the present invention uses, whole repetitives with respect to whole polymkeric substance have the ratio of ad hoc structure repetitive 1., preferred 5-95 mole %, more preferably 10-80 mole %, preferred especially 10-60 mole %.
Ad hoc structure is proportional containing 2. in the imide amination polymer that the present invention uses, whole repetitives with respect to whole polymkeric substance have the ratio of ad hoc structure repetitive 2., preferred 0.1-50 mole %, more preferably 10-50 mole %, preferred especially 30-50 mole %.
The tetrabasic carboxylic acid dicarboxylic anhydride
In polyamic acid synthetic, in the tetrabasic carboxylic acid dicarboxylic anhydride of use,, for example, can enumerate 3 as having ad hoc structure tetrabasic carboxylic acid dicarboxylic anhydride 1., 3 ', 4,4 '-biphenyltetracarboxyacid acid dicarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic acid dicarboxylic anhydride, 2,3,6,7-naphthalene tetracarboxylic acid dicarboxylic anhydride, 2,3,6, the luxuriant and rich with fragrance tetrabasic carboxylic acid dicarboxylic anhydride of 7-, 3,4,5,6-fluorenes tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,6,7-anthracene tetrabasic carboxylic acid dicarboxylic anhydride etc.
Also have, as having ad hoc structure tetrabasic carboxylic acid dicarboxylic anhydride 2., for example, can enumerate 2,3,5-tricarboxylic basic ring amyl group acetate dicarboxylic anhydride, 3-Evil two ring [3.2.1] octanes-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ' 5 '-diketone), 3,5,6-three carboxyls norbornane-2-acetate dicarboxylic anhydride, (4arH, 8arH)-decahydro-1t, 4t:5c, 8c-dimethylene naphthalene-2t, 3t, 6c, 7c-tetrabasic carboxylic acid dicarboxylic anhydride etc.
In addition, in the present invention, can also use above-mentioned have ad hoc structure 1. or ad hoc structure compound 2. beyond other tetrabasic carboxylic acid dicarboxylic anhydrides.As these other tetrabasic carboxylic acid dicarboxylic anhydride, for example, can enumerate 3,5,6-three carboxyls norbornane-2-acetate dicarboxylic anhydride, 2,3,4,5-tetrahydrofuran tetrabasic carboxylic acid dicarboxylic anhydride, the BTCA dicarboxylic anhydride, 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-two chloro-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-cyclopentane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,4,5-cyclohexane tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-dicyclohexyl tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,4,5-tetrahydrofuran tetrabasic carboxylic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5 (tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5 (tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-ethyl-5 (tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-methyl-5 (tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-ethyl-5 (tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5 (tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-ethyl-5 (tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5 (tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c]-furans-1, the 3-diketone, 5-(2,5-dioxo tetrahydrochysene furfurylidene base)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid dicarboxylic anhydride, dicyclo [2,2,2]-Xin-7-alkene-2,3,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 3-Evil two ring [3.2.1] octanes-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), (4arH, 8arH)-and decahydro-1t, 4t:5c, 8c-dimethylene naphthalene-2t, 3t, 6c, 7c-tetrabasic carboxylic acid dicarboxylic anhydride, with following formula (I) and (II) aliphatics and the ester ring type tetrabasic carboxylic acid dicarboxylic anhydride of the compound etc. of expression;
Figure C20041003875900191
In the formula, R 1And R 3Expression has the divalent organic group of aromatic rings, R 2And R 4Expression hydrogen atom or alkyl, the R of a plurality of existence 2And R 4Can be identical separately also can be different.
Compound with following formula (11)-(18) expression;
Figure C20041003875900201
Compound with following formula (19)-(21) expression;
The pyromellitic acid dicarboxylic anhydride, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl ether tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-tetraphenyl silane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-furans tetrabasic carboxylic acid dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenylsulfide dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dicarboxylic anhydride, 3,3 ', 4,4 '-perfluor isopropylidene, two phthalic acid dicarboxylic anhydrides, two (phthalic acid) phenyl phosphine oxide dicarboxylic anhydride, p-phenylene-two (triphenyl phthalic acid) dicarboxylic anhydride, m-phenylene-two (triphenyl phthalic acid) dicarboxylic anhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl ether dicarboxylic anhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl methane dicarboxylic anhydride, ethylene glycol-two (dehydration trimellitate), propylene glycol-two (dehydration trimellitate), 1,4-butylene glycol-two (dehydration trimellitate), 1,6-hexanediol-two (dehydration trimellitate), 1,8-ethohexadiol-two (dehydration trimellitate), 2, aromatic tetracarboxylic acid's dicarboxylic anhydride of 2-two (4-hydroxyphenyl) propane-two (dehydration trimellitate) etc.These compounds can a kind of independent or 2 kinds or above being used in combination.
Diamine compound
In polyamic acid synthetic in the diamine compound of use, as having ad hoc structure diamine compound 1., for example, can enumerate 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-two trifluoromethyls-4,4 '-benzidine, 3,3 '-two trifluoromethyls-4,4 '-benzidine, 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamido-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 4,4 '-diamido-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-octafluoro biphenyl, 4,4 '-two (4-amino-benzene oxygen) biphenyl etc. has the diamine compound of the structure of expression in the above-mentioned formula (2); 1,5-diaminonaphthalene, 1,8-diaminonaphthalene etc. have the diamine compound of the structure of expression in above-mentioned (4); The diamine compound that has the structure of above-mentioned formula (6) expression with the compound of following formula (6-1)-(6-3) expression etc.; 2,7-diamino-fluorene, 2,7-diamido Fluorenone, 9,9-two (4-aminophenyl) fluorenes etc. have the diamine compound of the structure of expression in the above-mentioned formula (8); Has the diamine compound of the structure of representing in above-mentioned formula (10) etc. with the compound of following formula (10-1)-(10-2) expression etc.In these compounds, particularly preferredly can enumerate 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 3,3 '-two trifluoromethyls-4,4 '-benzidine, 4,4 '-diamido-2,2 '-two (trifluoromethyl) biphenyl, 1,5-diaminonaphthalene, 2,7-diamino-fluorene, 2,7-diamido Fluorenone, 9, the compound of 9-two (4-aminophenyl) fluorenes, usefulness (6-1), (10-1) expression etc.
Figure C20041003875900231
Also have, can also use above-mentioned ad hoc structure compound 1. other diamine compounds in addition that have in the present invention.As these other diamine compound, for example, can enumerate p-phenylenediamine (PPD), m-phenylene diamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ethane, 4,4 '-diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone, 4,4 '-diaminobenzene formailide, 4,4 '-diamino-diphenyl ether, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 3,4 '-diamino-diphenyl ether, 3,3 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 2,2-two [4-(4-amino-benzene oxygen) phenyl] sulfone, 1,4-two (4-amino-benzene oxygen) benzene, 1,3-two (4-amino-benzene oxygen) benzene, 1,3-two (3-amino-benzene oxygen) benzene, 4,4 '-methylene-two (2-chloroaniline), 1,4,4 '-(to the phenylene isopropylidene) diphenylamine, 4,4 '-(metaphenylene isopropylidene) diphenylamine, aromatic diamines such as 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa; 1,1-m-xylene diamine, 1,3-propanediamine, butanediamine, pentanediamine, hexane diamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, 4,4-diamido heptamethylene diamine, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene two cyclopentadienylidene diamines, six hydrogen-4, the inferior indanyl dimethylene of 7-methylene diamines, three ring [6.2.1.02,7]-undecylene dimethyl diamines, 4,4 '-methylene two aliphatics and ester ring type diamines such as (cyclo-hexylamine);
2, the 3-diamino-pyridine, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 5,6-diamido-2,3-dicyano pyrazine, 5,6-diamido-2, the 4-dihydroxy-pyrimidine, 2,4-diamido-6-dimethylamino-1,3, the 5-triazine, 1,4-two (3-aminopropyl) piperazine, 2,4-diamido-6-isopropoxy-1,3, the 5-triazine, 2,4-diamido-6-methoxyl-1,3, the 5-triazine, 2,4-diamido-6-phenyl-1,3,5-triazines, 2,4-diamido-6-methyl-s-triazine, 2, the 4-diamino-1,3,5-triazines, 4,6-diamido-2-vinyl-s-triazine, 2,4-diamido-5-phenyl thiazole, 2, the 6-diaminopurine, 5, the 6-diaminostilbene, the 3-dimethyl uracil, 3, the 5-diaminostilbene, 2, the 4-triazole, 6,9-diamido-2-ethoxy acridine lactate, 3,8-diamido-6-phenylphenanthridineand, 1,4-diamido piperazine, 3, the 6-proflavin, two (4-aminophenyl) aniline and the diamines that in molecule, has the nitrogen-atoms beyond 2 primary amino radicals and this primary amino radical with the compound of following formula (III)-(IV) expression etc.;
Figure C20041003875900241
In the formula, R 5The organic group of expression divalent, R 6Expression has 1 valency organic group of the nitrogen atom ring structure that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine.
Figure C20041003875900242
In the formula, R 8Expression has the divalent organic group of the nitrogen atom ring structure that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine, R 7The organic group of expression divalent, the R of a plurality of existence 8Can be the same or different.
Mono-substituted phenylenediamine with following formula (V) expression; Diamido organosiloxane with following formula (VI) expression;
Figure C20041003875900251
In the formula, R 9Expression is selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-the divalent organic group of CO-, R 10The expression carbon number is the alkyl of 6-30.
Figure C20041003875900252
(in the formula, R 11The expression carbon number is the alkyl of 1-12, the R of a plurality of existence 11Identical separately also can be different, p is the integer of 1-3, q is the integer of 1-20.)
With the compound of following formula (22)-(100) expressions etc.These diamine compounds can be separately or 2 kinds or above being used in combination.
Figure C20041003875900261
Figure C20041003875900281
Figure C20041003875900291
Figure C20041003875900301
Figure C20041003875900311
Figure C20041003875900321
In the formula, y is the integer of 2-12, and z is the integer of 1-5.
In these compounds, preferred p-phenylenediamine (PPD), 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl thioether, 4,4 '-diamino-diphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 4,4 '-(to the phenylene isopropylidene) diphenylamine, 4,4 '-(metaphenylene isopropylidene) diphenylamine, 1,4-thiacyclohexane diamines, 4,4 '-methylene two (cyclo-hexylamine), 1,4-two (4-amino-benzene oxygen) benzene, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, the compound of following formula (101) expression in the compound of above-mentioned formula (III) expression, dodecyloxy-2 in the compound of following formula (102) expression in the compound of above-mentioned formula (IV) expression and the compound of above-mentioned formula (V) expression, the 4-diaminobenzene, hexadecane oxygen base-2, the 4-diaminobenzene, octadecane oxygen base-2, the 4-diaminobenzene, the compound of above-mentioned formula (22)-(100) expression, as particularly preferred compound, can enumerate p-phenylenediamine (PPD), 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ether, 1, the 4-cyclohexane diamine, dodecyloxy-2, the 4-diaminobenzene, hexadecane oxygen base-2, the 4-diaminobenzene, octadecane oxygen base-2, the 4-diaminobenzene, compound with above-mentioned formula (22)-(41) expression.
Figure C20041003875900331
Synthesizing of polyamic acid
The tetrabasic carboxylic acid dicarboxylic anhydride that provides in the synthetic reaction of polyamic acid and the usage ratio of diamines, with respect to amino 1 equivalent of diamines, the anhydride group of preferred tetrabasic carboxylic acid dicarboxylic anhydride is the 0.2-2 equivalent, more preferably the 0.3-1.2 equivalent.
The synthetic reaction of polyamic acid in organic solution in being preferably-20 ℃-150 ℃, more preferably carrying out under 0-100 ℃ the temperature conditions.
Here, as organic solvent, as long as can dissolve the synthetic polyamic acid that obtains, it is not limited especially, for example, can the illustration 1-Methyl-2-Pyrrolidone, N,N-dimethylacetamide, N, non-proton class polar solvents such as dinethylformamide, dimethyl sulfoxide, gamma-butyrolacton, 4-methyl urea, HMPA; Phenol series solvents such as metacresol, xylenols, phenol, halogenated phenol.In addition, the use amount of organic solvent (α) is preferably the total amount (alpha+beta) of total amount (β) the relative response solution that makes tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound and for the amount of 0.1-30 weight % is.
In addition, in above-mentioned organic solvent,, can and be used as the alcohols, ketone, ester class, ethers, halogenated hydrocarbons, hydro carbons of polyamic acid poor solvent etc. in the scope that the polyamic acid that generates is not separated out.Object lesson as such poor solvent, for example can enumerate methyl alcohol, ethanol, isopropyl alcohol, cyclohexanol, 4-hydroxy-4-methyl-2 pentanone, ethylene glycol, propylene glycol, 1, the 4-butylene glycol, triethylene glycol, glycol monoethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy base propionic ester, ethyl ethoxy-c acid esters, diethy-aceto oxalate, the propionic acid diethylester, ether, Ethylene Glycol Methyl ether, glycol ethyl ether, the ethylene glycol n-propyl ether, the ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic acid esters, the diethylene glycol monoethyl ether acetic acid esters, tetrahydrofuran, methylene chloride, 1, the 2-ethylene dichloride, 1, the 4-dichloroetane, trichloroethanes, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, dimethylbenzene etc.
After as above implementing, obtain being dissolved with the reaction solution of polyamic acid.And, this reaction solution is injected a large amount of poor solvents obtain precipitate, by this precipitate of drying under reduced pressure, can access polyamic acid.In addition, this polyamic acid is dissolved in the organic solvent once more, then by in poor solvent, separating out, by this operation being carried out 1 time or repeatedly, can making with extra care polyamic acid.
Acyl Synthesizing of imidization polymkeric substance
The imide amination polymer that constitutes liquid crystal orientating agent of the present invention can obtain by the above-mentioned polyamic acid of dehydration closed-loop is synthetic.The dehydration closed-loop of polyamic acid can carry out by the following method: (i) method of heating polyamic acid; Perhaps (ii) polyamic acid is dissolved in the organic solvent method of in this solution, adding dewatering agent and dehydration closed-loop catalyzer and heating as required.
In the method for the heating polyamic acid of above-mentioned (i), temperature of reaction is preferably 50-200 ℃, more preferably 60-170 ℃.Temperature of reaction during less than 50 ℃ the dehydration closed-loop reaction carry out not exclusively, if temperature of reaction surpasses 200 ℃, the molecular weight of gained imide amination polymer can descend.
On the other hand, in the above-mentioned method of in polyamic acid solution, adding dewatering agent and dehydration closed-loop catalyzer (ii),, for example can use acid anhydrides such as acetic anhydride, propionic andydride, trifluoroacetic anhydride as dewatering agent.The use amount of dewatering agent is decided according to the imidizate rate of expectation, and the repetitive of polyamic acid is 1 mole relatively, is preferably the 0.01-20 mole.In addition, as the dehydration closed-loop catalyzer, for example, can use tertiary amines such as pyridine, trimethylpyridine, lutidines, triethylamine.But, be not limited to these compounds.The use amount of dehydration closed-loop catalyzer is preferably the 0.01-10 mole with respect to 1 mole of the dewatering agent that uses.The use amount of above-mentioned dewatering agent, dehydration closed-loop agent is many more, and the imidizate rate is then high more.From the viewpoint of liquid crystal display cells image retention disappearance speed, the imidizate rate be preferably 40% or more than.In addition, as the organic solvent that in the dehydration closed-loop reaction, uses, can enumerate the illustrated organic solvent of organic solvent that uses as in polyamic acid is synthetic.And the temperature of reaction of dehydration closed-loop reaction is preferably 0-180 ℃, more preferably 10-150 ℃.In addition, for the as above reaction solution of gained,, can make with extra care imide amination polymer by carrying out and same operation in the process for purification of polyamic acid.
End modified type polymkeric substance
Polyamic acid of Shi Yonging and imide amination polymer can also be the compounds of regulating the end modified type that molecular weight obtains in the present invention.By using the polymkeric substance of this end modified type, can improve the coating characteristics etc. of liquid crystal orientating agent and can not make effect of the present invention impaired.This end modified type polymkeric substance can be in synthesizing polyamides when acid, by add sour single acid anhydride (Suan Yi No water thing in reaction system), monoamine compound, monobasic isocyanate compound etc. synthesize.As the single acid anhydride of acid, for example, can enumerate maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-myristyl succinic anhydride, n-cetyl succinic anhydride etc. here.In addition, as the monoamine compound, for example, can enumerate aniline, cyclo-hexylamine, n-butylamine, n-amylamine, n-hexylamine, n-heptyl amice, n-octylame, n-nonyl amine, n-decyl amine, n-undecylamine, n-lauryl amine, n-tridecyl amine, n-tetradecy lamine, n-pentadecyl amine, n-cetylamine, n-heptadecyl-amine, n-octadecylamine, n-20 amine etc.In addition, as the monobasic isocyanates, for example, can enumerate isocyanic acid phenylester, isocyanic acid naphthyl ester etc.
The logarithm viscosity of polymkeric substance
Polyamic acid that as above obtains and imide amination polymer, its logarithm viscosity (η 1n) the preferred 0.05-10dl/g of value, more preferably 0.05-5dl/g.
Logarithm viscosity (η in the present invention 1n) value be with the N-N-methyl-2-2-pyrrolidone N-as solvent, in concentration is the solution of 0.5g/100 milliliter, under 30 ℃, carry out viscosimetric analysis, then the numerical value of trying to achieve according to following formula (i).
Figure C20041003875900351
Liquid crystal orientating agent
Liquid crystal orientating agent of the present invention normally is dissolved with above-mentioned polyamic acid and/or imide amination polymer and constitutes in organic solvent.
Temperature when preparing liquid crystal orientating agent of the present invention is preferably 0 ℃-200 ℃, more preferably 20 ℃-60 ℃.
As the organic solvent that constitutes liquid crystal orientating agent of the present invention, for example, can enumerate 1-Methyl-2-Pyrrolidone, gamma-butyrolacton, butyrolactam, N, dinethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2 pentanone, glycol monoethyl ether, butyl lactate, butyl acetate, methyl methoxy base propionic ester, ethyl ethoxy-c acid esters, Ethylene Glycol Methyl ether, glycol ethyl ether, the ethylene glycol n-propyl ether, the ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, the diglycol monotertiary methyl ether, carbiphene, the diglycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate etc.Solid component concentration in liquid crystal orientating agent of the present invention is selected on the bases such as viscosity, volatility considering, preferably in the scope of 1-10 weight %.In other words, liquid crystal orientating agent of the present invention is coated on the surface of bottom material, formation is filmed as liquid crystal orientating membrane, under the situation of solid component concentration less than 1 weight %, can not obtain good liquid crystal orientating membrane thereby this thickness of filming is too small, when solid component concentration surpasses under the situation of 10 weight %, can not obtain good liquid crystal orientating membrane thereby the thickness of filming is excessive, in addition, liquid crystal orientating agent viscosity increases, and makes the coating characteristics variation.
In the scope of not damaging destination properties,, can also contain the compound and the epoxy compound of functional silanes in the liquid crystal orientating agent of the present invention from improving viewpoint to the adhesion of surface of bottom material.As such functional silanes compound that contains, for example, can enumerate the 3-aminopropyl trimethoxysilane, the 3-aminopropyl triethoxysilane, the 2-aminopropyl trimethoxysilane, the 2-aminopropyl triethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxy carbonyl-3-aminopropyl trimethoxysilane, N-ethoxy carbonyl-3-aminopropyl triethoxysilane, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-1,4,7-three azepine decane, 10-triethoxysilyl-1,4,7-three azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic acid esters, 9-triethoxysilyl-3,6-diaza nonyl acetic acid esters, N-benzyl-3-aminopropyl trimethoxysilane, N-benzyl-3-aminopropyl triethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyl triethoxysilane, N-two (oxidation ethylidene)-3-aminopropyl trimethoxysilane, N-two (oxidation ethylidene)-3-aminopropyl triethoxysilane etc.As epoxy compound, for example, can enumerate ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, the glycerine diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-four glycidyl group-2, the 4-hexanediol, N, N, N ', N ',-four glycidyl group-m-xylene diamine, 1,3-two (N, N-glycidyl aminomethyl) cyclohexane, N, N, N ', N ' ,-four glycidyl group-4,4 '-diaminodiphenyl-methane, 3-(N-allyl-N-glycidyl) aminopropyl trimethoxysilane, 3-(N, N-diglycidyl) aminopropyl trimethoxysilane etc.
Liquid crystal display cells
Liquid crystal display cells can be by the method manufacturing for example.
(1) by for example methods such as roll coater method, rotary process, print process, coating liquid crystal orientating agent of the present invention on the one side of the ground that is provided with band pattern nesa coating is followed, and forms by the heating coated face and films.As ground, can use glass such as float glass, soda-lime glass here; The transparent ground that forms by plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate.Nesa coating as being arranged on the ground one side for example, can use by tin oxide (SnO 2) the NESA film (U.S. PPG society registered trademark), the indium oxide-tin oxide (In that form 2O 3-SnO 2) the ITO film that forms etc., the pattern of these nesa coatings can adopt photo-engraving process and use the method for prefabricated mask.In the coating of liquid crystalline directing agent, better in order to make surface of bottom material and nesa coating and to be coated with intermembranous adhesion, can be on this surface of ground coating in advance contain functional silanes compound, contain the compound of functionality titanium etc.Heating-up temperature behind the coating of liquid crystalline directing agent is preferably 80-300 ℃, more preferably 120-250 ℃.In addition, the liquid crystal orientating agent of the present invention that contains polyamic acid is by removing organic solvent after coating, and formation is filmed as oriented film, carries out dehydration closed-loop by heating again, can form further filming of imidizate.The thickness of filming that forms is preferably 0.001-1 μ m, more preferably 0.005-0.5 μ m.
(2) with the coated surface that forms with being tied with, along the fixed-direction rubbing and the processing that rubs by for example roller of fibrous cloth such as nylon, rayon, cotton.So just making films has the liquid crystal molecule directional energy, thereby forms liquid crystal orientating membrane.
In addition; liquid crystal orientating membrane by liquid crystal orientating agent formation of the present invention; for example open as shown in flat 6-222366 communique and the flat 6-281937 communique of Te Kai as the spy; change the processing at pre-oblique angle by the local irradiation ultraviolet ray; perhaps open as shown in the flat 5-107544 communique as the spy; on the liquid crystal orientating membrane surface of handling, form diaphragm partly through friction; with with previous friction handle different directions rub handle after; remove diaphragm; by changing the such processing of liquid crystal aligning energy of liquid crystal orientating membrane, the visual field characteristic of improving liquid crystal display cells is possible.
(3) make the chassis that a slice is formed with the ground of liquid crystal orientating membrane according to the method described above and does not have the electrically conducting transparent film figure respectively, become orthogonal or antiparallel by the friction direction that makes liquid crystal orientating membrane separately, 2 grounds are inserted box space (セ Le ギ ヤ Star プ) and staggered relatively, peripheral position with bonding 2 grounds of sealant, inject liquid crystal to the space of cutting apart by surface of bottom material and bonding agent and filled, thereby the sealing filling orifice constitutes liquid crystal cell.And, by on the outside surface of liquid crystal cell, promptly, on other sides of each ground that constitutes liquid crystal cell, bonding polarized light piece makes the consistent or orthogonal of friction direction of direction of polarized light and the liquid crystal orientating membrane that forms on this ground one side, make liquid crystal display cells.
Here, as sealant, for example, can use hardening agent and as epoxy resin that contains alumina balls of pad etc.
As liquid crystal, can enumerate nematic crystal and dish shape type liquid crystal, wherein preferred nematic crystal, for example, can use Xi Fushi bases liquid crystal, azoxy class liquid crystal, biphenyls liquid crystal, cyclohexylbenzene class liquid crystal, ester liquid crystal, terphenyl class liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, bicyclooctane class liquid crystal, cube alkanes liquid crystal etc.In addition, also can in these liquid crystal, add cholesterol liquid crystal such as for example cholesterol chloride, Cholesteryl pelargonate, cholesterol carbonic ester and the chirality agent of selling with commodity " C-15 " " CB-15 " (メ Le Network society system) by name etc. and using.Also have, also can use p-to take off strong dielectricity liquid crystal such as siloxy (デ シ ロ キ シ) benzal-p-amino-2-methyl butyl cinnamic acid ester.
Also have,, can enumerate, make the polyvinyl alcohol (PVA) elongation directed, absorb iodine simultaneously and be called the polarized light piece that the polarizing coating of H film is held under the arm the polarized light piece in the acetate fiber diaphragm or formed by H film itself as the polarized light piece that is bonded on the liquid crystal cell outside surface.
Embodiment
Below, by embodiment the present invention is carried out more specific description, but the present invention is not limited to these embodiment.The evaluation method of each liquid crystal display cells of making by following embodiment and comparative example is as follows.
The average imidizate rate of the imidizate rate liquid crystal orientating agent of imide amination polymer:
With polymkeric substance or liquid crystal orientating agent drying under reduced pressure at room temperature, be dissolved in then in the deuterated dimethyl sulfoxide,, at room temperature measure as standard substance with tetramethylsilane 1H-NMR tries to achieve according to the formula that following formula is (ii) represented.And the imidizate rate that will not carry out the polyamic acid of dehydration closed-loop reaction is made as 0%.
Imidizate rate (%)=(1-A 1/ A 2* α) * 100 (ii)
A 1: the peak area (10ppm) that produces by the proton of NH base
A 2: the peak area that produces by the proton of other groups
α: in the precursor (polyamic acid) of polymkeric substance, with respect to the number ratio of other protons of 1 proton of NH base
The dissolubility of imide amination polymer liquid crystal orientating agent:
With polymkeric substance or liquid crystal orientating agent drying under reduced pressure at room temperature, the room temperature vibration was dissolved in 1 hour in gamma-butyrolacton then, be mixed with the solution that solid constituent concentration is 10 weight %, by Visual Confirmation whether dissolution residual substance is arranged, consoluet note is made OK, has the note of dissolution residual substance to make NG.
The residual DC voltage of liquid crystal display cells:
Apply 30Hz, the 3.0V square wave that is superimposed with the 1.0V DC voltage to liquid crystal display cells, apply 1 hour under 70 ℃ environment temperature, after cutting off DC voltage, the residual voltage in the liquid crystal cell is tried to achieve residual DC voltage by flickering-null method.
The image retention die-out time of liquid crystal display cells:
Apply 30Hz, the 3.0V square wave that is superimposed with 3.0V DC voltage, 6.0V alternating voltage to liquid crystal display cells, after applying 20 hours under 70 ℃ the environment temperature, voltage is switched to OFF, by the time of visual mensuration up to the image retention disappearance.
The failtests of liquid crystal display cells:
Under hot and humid degree environment (70 ℃ of temperature, relative humidity 80%),, after 1500 hours, have or not the display defect of leukasmus point-like by polarization microscope observation with the rectangular wave drive liquid crystal display cells of 5V, 60Hz.
The photostability thermotolerance of liquid crystal orientating membrane:
On the one side of the ground that is provided with band pattern nesa coating, be coated with liquid crystal orientating agent of the present invention, implement 5000 hour irradiation experiment as power supply with the weatherability tester with carbon arc, use comprises that this ground of 2 grounds makes liquid crystal display cells, measure voltage retention, by removing the voltage retention measured value do not implement to shine the liquid crystal display cells that experiment makes with the same order of external application, utilize following formula to calculate the stable on heating effect coefficient of photostability.
The stable on heating effect coefficient=100-{ of photostability (not shining the voltage retention of the liquid crystal display cells after the voltage retention of the liquid crystal display cells of experiment-irradiation experiment)/the do not shine voltage retention of the liquid crystal display cells of experiment } * 100
Synthesis example 1-36 and comparison synthesis example 1-3
Shown in table 1-3, form, in the N-N-methyl-2-2-pyrrolidone N-, press diamines, tetrabasic carboxylic acid dicarboxylic anhydride (in the table, be expressed as " acid anhydrides ') order feed intake; forming solid constituent concentration is the solution of 15 weight %; at 60 ℃ of reactions 6 hours down, the polyamic acid that obtains having logarithm viscosity shown in the table 1-3.In the gained polyamic acid, add the pyridine of 5 times of moles of relative polyamic acid total amount, the acetic anhydride of 3 times of moles, be heated to 110 ℃ of dehydration closed-loop reactions of carrying out 4 hours then.Utilize Anaesthetie Ether that gained solution is precipitated again, reclaim then, drying obtains having logarithm viscosity, imide amination polymer B1-B36, the b1 of imidizate rate, b2 shown in the table 1-3.
Table 1
Synthesis example Diamine compound (mmol) Acid anhydrides (mmol) Polyamic acid (dl/g) Imide amination polymer Polymkeric substance Dissolubility
Imidizate rate (%) Logarithm viscosity (dl/g)
1 D-1(50) T-1(50) 2.6 95 2.7 B1 OK
2 D-2(50) T-1(50) 0.5 97 0.5 B2 OK
3 D-4(50) T-1(50) 0.9 98 0.8 B3 OK
Table 2
Complex Diamine compound (mmol) Acid anhydrides (mmol) Polyamic acid (dl/g) Imide amination polymer Polymkeric substance Dissolubility
Imidizate rate (%) Logarithm viscosity (dl/g)
4 D-1(45)，D-5(5) T-1(50) 0.9 97 0.9 B4 OK
5 D-1(45)，D-6(5) T-1(50) 1 98 0.9 B5 OK
6 D-1(22)，D-3(22)，D-8(6) T-1(50) 0.7 94 0.7 B6 OK
7 D-1(45)，D-10(5) T-1(50) 0.9 99 0.8 B7 OK
8 D-1(22)，D-3(22)，D-6(6) T-1(50) 0.8 98 0.8 B8 OK
9 D-1(48)，D-7(2) T-1(50) 0.8 97 0.7 B9 OK
10 D-4(48)，D-6(2) T-1(50) 0.9 94 0.8 B10 OK
11 D-1(49)，D-6(1) T-1(50) 0.8 95 0.7 B11 OK
12 D-1(48)，D-6(2) T-1(50) 0.9 97 0.9 B12 OK
13 D-1(44)，D-8(6) T-1(50) 0.9 99 0.8 B13 OK
14 D-1(48.5)，D-6(1.5) T-1(50) 0.8 97 0.7 B14 OK
15 D-1(45.5)，D-8(4.5) T-1(50) 0.8 96 0.6 B15 OK
16 D-1(47.5)，D-6(2.5) T-1(50) 0.7 94 0.7 B16 OK
17 D-1(47)，D-8(3) T-1(50) 0.8 95 0.6 B17 OK
18 D-1(48.5)，D-8(1.5) T-1(50) 0.8 97 0.7 B18 OK
19 D-1(45)，D-5(5) T-1(25)， T-2(25) 0.9 99 0.8 B19 OK
20 D-1(45)，D-6(5) T-1(25)， T-2(25) 0.7 100 0.6 B20 OK
21 D-2(45)，D-5(5) T-1(25)， T-2(25) 1.1 98 0.9 B21 OK
Table 3
Complex Diamine compound (mmol) Acid anhydrides (mmol) Polyamic acid (dl/g) Imide amination polymer Polymkeric substance Dissolubility
Imidizate rate (%) Logarithm viscosity (dl/g)
22 D-1(45)，D-10(5) T-1(25)，T-2(25) 0.9 95 0.7 B22 OK
23 D-4(45)，D-5(5) T-1(25)，T-2(25) 0.7 97 0.6 B23 OK
24 D-1(48)，D-7(2) T-1(25)，T-2(25) 0.6 98 0.5 B24 OK
25 D-4(48)，D-6(2) T-1(25)，T-2(25) 0.6 98 0.6 B25 OK
26 D-1(45)，D-5(5) T-1(25)，T-4(25) 0.9 94 0.8 B26 OK
27 D-1(45)，D-6(5) T-1(25)，T-4(25) 0.6 94 0.6 B27 OK
28 D-2(45)，D-5(5) T-1(25)，T-4(25) 0.8 94 0.7 B28 OK
29 D-1(45)，D-10(5) T-1(25)，T-4(25) 0.7 96 0.7 B29 OK
30 D-4(45)，D-5(5) T-1(25)，T-4(25) 0.6 97 0.5 B30 OK
31 D-1(48)，D-7(2) T-1(25)，T-4(25) 0.7 97 0.7 B31 OK
32 D-4(48)，D-6(2) T-1(25)，T-4(25) 0.7 97 0.5 B32 OK
33 D-1(25)，D-2(25) T-1(25)，T-4(25) 0.6 95 0.7 B33 OK
34 D-1(40)，D-6(5)， D-8(5) T-1(25)，T-4(25) 0.5 94 0.6 B34 OK
35 D-1(25)，D-3(25) T-1(50) 0.8 96 0.7 B35 OK
36 D-1(45)，D-9(5) T-2(50) 0.8 94 0.7 B36 OK
Compare synthesis example
1 D-3(50) T-1(50) 0.9 96 0.8 b1 OK
2 D-3(25)，D-11(25) T-1(25)T-4(25) 1.1 97 1 b2 OK
3 D-3(40)，D-6(19) T-3(50) 0.7 The imidizate thing does not dissolve NG
Diamine compound and tetrabasic carboxylic acid dicarboxylic anhydride kind in table 1-3 are as follows.
＜diamine compound 〉
D-1:2,2 '-dimethyl-4,4 '-benzidine
D-2:2,2 '-two trifluoromethyls-4,4 '-benzidine
D-3: p-phenylenediamine (PPD)
D-4:2,7-diamido Fluorenone
D-5: the diamines of above-mentioned formula (22) expression
D-6: the diamines of above-mentioned formula (32) expression
D-7: the diamines of above-mentioned formula (33) expression
D-8: the diamines of above-mentioned formula (34) expression
D-9: the diamines of above-mentioned formula (35) expression
D-10: the diamines of above-mentioned formula (40) expression
D-11:4,4 '-diaminodiphenyl-methane
＜tetrabasic carboxylic acid dicarboxylic anhydride 〉
T-1:2,3,5-tricarboxylic basic ring amyl group acetate dicarboxylic anhydride
T-2:3-Evil two ring [3.2.1] octanes-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ' 5 '-diketone)
T-3: pyromellitic acid dicarboxylic anhydride
T-4:(4arH, 8arH)-decahydro-1t, 4t:5c, 8c-dimethylene naphthalene-2t, 3t, 6c, 7c-tetrabasic carboxylic acid dicarboxylic anhydride
Embodiment 1
The imide amination polymer (B1) that 2g is obtained by synthesis example 1 is dissolved in the gamma-butyrolacton, and forming solid component concentration is the solution of 4 weight %, is that the filtrator of 1 μ m filters this solution with the aperture, prepares liquid crystal orientating agent of the present invention.
The printing machine that uses the coating of liquid crystalline oriented film to use, the above-mentioned liquid crystal orientating agent of coating on the transparency electrode face of the glass substrate that has the transparency electrode that constitutes by the ITO film, drying is 20 minutes on 180 ℃ heating plate, and forming dry film thickness is filming of 0.05 μ m.
By the friction machine of the roller that twines rayon cloth is housed, be that 500rpm, step step velocity are that 1cm/ second, fine hair are pressed under the condition that length is 0.4mm in the rotational speed of roller, to this processing that rubs of filming.
Then, each that handle that the back liquid crystal carries ground secretly through friction a pair of has on the outer rim of liquid crystal orientating membrane to be coated with by silk screen print method and is mixed with the epoxy adhesive that the aperture is 17 μ m alumina balls, it is relative with the liquid crystal aligning face to make a pair of liquid crystal carry ground secretly then, and the friction direction be antiparallel mode place press sticking, cure adhesive then.
Then, to between a pair of ground, fill nematic crystal (メ Le Network society system by liquid crystal injecting port, MLC-5081) after, seal liquid crystal injecting port with epoxy adhesive, ground is surveyed polarized light piece staggered relatively on the two sides outward, make the direction of polarized light of polarized light piece consistent, thereby make liquid crystal display cells of the present invention with the friction direction of the liquid crystal orientating membrane of ground separately.
Residual DC magnitude of voltage, image retention die-out time, reliability, photostability thermotolerance to the gained liquid crystal display cells are estimated.Evaluation result is shown in table 4 and table 5.
Embodiment 2-37 and comparative example 1-2
Except polymkeric substance shown in use table 4 and the table 5, carry out same operation with embodiment 1, the preparation liquid crystal orientating agent uses these directing agents to make liquid crystal display cells, and estimates.Evaluation result is shown in table 4 and table 5.
Table 4
Embodiment Polymkeric substance Residual Image retention die-out time (branch) Reliability Photostability thermotolerance effect coefficient
Kind Weight ratio DC(V)
1 B1 - 0.03 1 Well 96
2 B2 - 0.02 1 Well 96
3 B3 - 0.04 1 Well 92
4 B4 - 0.02 1 Well 93
5 B5 - 0.06 1 Well 94
6 B6 - 0.03 1 Well 90
7 B7 - 0.04 1 Well 91
8 B8 - 0.03 1 Well 90
9 B9 - 0.01 1 Well 94
10 B10 - 0.02 1 Well 95
11 B11 - 0.05 1 Well 96
12 B12 - 0.02 1 Well 95
13 B13 - 0.04 1 Well 98
14 B14 - 0.04 2 Well 95
15 B15 - 0.03 1 Well 96
16 B16 - 0.02 1 Well 96
17 B17 - 0.04 1 Well 95
18 B18 - 0.01 1 Well 96
19 B19 - 0.02 1 Well 94
20 B20 - 0.04 1 Well 95
21 B21 - 0.04 1 Well 93
22 B22 - 0.01 1 Well 94
Table 5
Embodiment Polymkeric substance Residual DC (V) Image retention die-out time (branch) Reliability Photostability thermotolerance effect coefficient
Kind Weight ratio
23 B23 - 0.02 1 Well 95
24 B24 - 0.05 1 Well 95
25 B25 - 0.04 1 Well 94
26 B26 - 0.03 1 Well 93
27 B27 - 0.03 1 Well 96
28 B28 - 0.04 1 Well 93
29 B29 - 0.03 1 Well 94
30 B30 - 0.05 1 Well 91
31 B31 - 0.04 1 Well 95
32 B32 - 0.03 1 Well 94
33 B33 - 0.05 1 Well 92
34 B1/B2 50/50 0.03 1 Well 95
35 B34 - 0.03 2 Well 90
36 B35 - 0.04 2 Well 80
37 B36 - 0.03 2 Well 78
Comparative example
1 b1 - 0.15 10 Hickie 95
2 b2 - 0.05 11 Hickie 23
As implied above, by liquid crystal orientating agent of the present invention, when forming liquid crystal orientating membrane, do not rely on process conditions such as thickness, friction condition, can obtain the reliability height, be applicable to the liquid crystal orientating membrane of liquid crystal display cells.
Also have, liquid crystal display cells with the oriented film that uses liquid crystal orientating agent formation of the present invention, reliability, photostability, excellent heat resistance, can be used for various devices effectively, for example, can be applied to display device such as desk-top computer, wrist-watch, portable phone, table clock, coefficient display board, Word message processor, PC, liquid crystal data projector, liquid crystal TV set.

Claims (7)

1. liquid crystal orientating agent is characterized in that: this liquid crystal orientating agent contains and is selected from least a in the polyimide fluidized polymer that satisfies following condition polyamic acid 1., 2. and 3. jointly,
1. have the following formula (1) that is selected from, (3), (5), (7) and (9) represented separately from the structure of tetrabasic carboxylic acid dicarboxylic anhydride and following formula (2), (4), (6), (8) and (10) represented separately from least a structure in the structure of diamine compound
2. have be selected from following formula (a)-(c) represented separately from least a structure in the structure of tetrabasic carboxylic acid dicarboxylic anhydride,
Figure C2004100387590002C1
In the formula, R a-R xThe organic group of representing halogen atom or 1 valency independently of one another, X represents 1 valency organic group or oxygen atom, a, b, g, h, l, n, q, r, v and x represent the integer of 0-3 independently of one another, e, f, i, j, k, m, o, p, s, t, u and w represent the integer of 0-2 independently of one another, c and d represent the integer of 0-4 independently of one another
Figure C2004100387590003C1
In the formula, R 1'-R 3' representing the organic group of halogen atom or 1 valency independently of one another, a ', b ', c ' represent the integer of 0-3 independently of one another, the integer of d ' expression 1-5, the integer of e ' expression 0-51,
3. have to be selected from and removed at least a structure the structure of 2 amino from following formula (22)-(100) represented separately diamine compound,
Figure C2004100387590004C1
Figure C2004100387590005C1
Figure C2004100387590006C1
Figure C2004100387590007C1
Figure C2004100387590009C1
Figure C2004100387590010C1
In the formula, y is the integer of 2-12, and z is the integer of 1-5.
2. the liquid crystal orientating agent described in claim 1, wherein imide amination polymer has the imidizate rate of 40-100%.
3. the liquid crystal orientating agent described in claim 1, wherein condition structure 1. is from diamine compound.
4. the liquid crystal orientating agent described in claim 1, wherein condition structure 1. is at least a structure that is selected from by in the represented separately structure in above-mentioned formula (1) and (2).
5. the liquid crystal orientating agent described in claim 1, wherein condition structure 1. content for whole repetitives of imide amination polymer is 5-95 mole %.
6. the liquid crystal orientating agent described in claim 1, wherein condition structure 2. content for whole repetitives of imide amination polymer is 0.1-50 mole %.
7. the liquid crystal orientating agent described in claim 1, wherein the diamine compound of condition in 3. is the represented separately diamine compounds in formula (22)-(41),
Figure C2004100387590011C1
Figure C2004100387590012C1
Figure C2004100387590013C1
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TWI386435B (en) * 2006-04-25 2013-02-21 Jsr Corp Vertical alignment mode liquid crystal alignment agent and vertical alignment mode liquid crystal display device
KR101426102B1 (en) * 2006-07-28 2014-08-05 닛산 가가쿠 고교 가부시키 가이샤 Liquid crystal aligning agent and liquid crystal displays made by using the same
CN101135813B (en) * 2006-08-29 2011-03-16 Jsr株式会社 Liquid crystal tropism agent, liquid crystal tropism film and liquid crystal display element
JP5041157B2 (en) * 2007-01-10 2012-10-03 Ｊｓｒ株式会社 Vertical alignment type liquid crystal aligning agent and vertical alignment type liquid crystal display element
JP4458299B2 (en) * 2007-09-03 2010-04-28 Ｊｓｒ株式会社 Liquid crystal aligning agent and liquid crystal display element
JP2010156934A (en) * 2008-12-02 2010-07-15 Jsr Corp Liquid crystal aligning agent and liquid crystal display element
JP5716674B2 (en) 2009-12-02 2015-05-13 日産化学工業株式会社 Liquid crystal alignment treatment agent and liquid crystal display element using the same
CN102093230B (en) * 2011-01-28 2013-06-12 成都金桨高新材料有限公司 Type I forked biphenyl diamine and preparation method and application thereof
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JP6939779B2 (en) * 2016-05-31 2021-09-22 宇部興産株式会社 Polyimide precursors, polyimides, polyimide films, and substrates, and tetracarboxylic dianhydrides used in the production of polyimides.

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