CN101042504A - Liquid crystal aligning agent and film and liquid crystal display device - Google Patents
Liquid crystal aligning agent and film and liquid crystal display device Download PDFInfo
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- CN101042504A CN101042504A CNA2007100869144A CN200710086914A CN101042504A CN 101042504 A CN101042504 A CN 101042504A CN A2007100869144 A CNA2007100869144 A CN A2007100869144A CN 200710086914 A CN200710086914 A CN 200710086914A CN 101042504 A CN101042504 A CN 101042504A
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Abstract
The invention relates to a liquid crystal alignment agent, a liquid crystal alignment film and a liquid crystal display member. The invention provides a liquid crystal alignment agent capable of forming a liquid crystal alignment film with a good liquid crystal alignment performance, the formed liquid crystal alignment film, and a liquid crystal display member having the liquid crystal alignment film. The invention is a liquid crystal alignment agent composed of polyamide acid obtained by reacting tetracarboxylic acid dianhydride with diamine compounds, an imide polymer having a structure obtained by dehydrating and loop-closing the polyamide acid, or a mixture of the polyamide acid and the imide polymer, the liquid crystal alignment agent is prepared by the liquid crystal alignment film and the liquid crystal display member, the liquid crystal alignment agent is a solution containing at least a solvent selected from a group of amide solvents composed of 3-alkoxy-N, N-dimethyl propionamide, the liquid crystal display member comprises the liquid crystal alignment film formed from the liquid crystal alignment agent.
Description
Technical field
The present invention relates to aligning agent for liquid crystal, more particularly, relate to the aligning agent for liquid crystal that can form the good liquid crystal orientation film of liquid crystal aligning.
Background technology
So far, known TN type liquid crystal display cells with TN (Twisted Nematic) type liquid crystal cell, described liquid crystal cell by nesa coating between 2 substrates that formed liquid crystal orientation film on the surface, formation has the nematic crystal layer of positive dielectric anisotropy, constitute the box of sandwich construction, the major axis of above-mentioned liquid crystal molecule is turned round continuously to another piece substrate from a substrate and is turn 90 degrees.The orientation of liquid crystal in the liquid crystal display cells such as this TN type liquid crystal display cells realizes with the liquid crystal orientation film of orientation energy by give liquid crystal molecule by grinding process usually.Here, as the material of the liquid crystal orientation film that constitutes liquid crystal display cells, according to resins such as the known polyimide of prior art, polyamide and polyester.Polyimide particularly is because thermotolerance, good with the compatibility of liquid crystal, physical strength etc. is used in most liquid crystal display cells.
In addition, also propose on ITO to form projection and come the vertical alignment-type liquid crystal display device that is referred to as the MVA type that the direction of orientation of liquid crystal is controlled.The liquid crystal display cells of MVA type is good at aspects such as visual angle, contrasts, and can not need to carry out grinding process etc. in the process that forms liquid crystal orientation film, thereby also is good aspect manufacturing process.As the liquid crystal orientation film that is applicable to the MVA type, require to have performances such as vertical orientated property is good, the image retention cancellation time of liquid crystal display cells is short.
And in recent years, the exploitation of novel liquid crystal display element is also very active, as one of them, a kind of transverse electric field pattern liquid crystal display cells has been proposed, 2 electrodes that its driving liquid crystal is used with the setting of broach shape, produce the electric field parallel with real estate on a side group plate, the control liquid crystal molecule.This element is commonly called switch type (IPS type) in the face, because of its wide viewing angle excellent performance known.And recently, the wide viewing angle performance is further improved, it is possessed obtain to reverse and the illustrious feature of the wide viewing angle that cathode-ray tube (CRT) of tonal variation can both compare favourably with no tone by using optical compensation films.
But, when the liquid crystal display cells of the liquid crystal orientation film that make to adopt the known in the past imide amination polymer aligning agent for liquid crystal gained that contains polyamic acid and its dehydration closed-loop of coating, the variation of environment temperature etc. in the time of can occurring along with printing and produce the thickness inequality, the display performance of liquid crystal display cells is produced dysgenic problem.And, when when relatively poor, produce depression in the time of can occurring printing and the bad problem of local liquid crystal aligning takes place for the dissolubility of the polyimide of solvent.
Summary of the invention
The purpose of this invention is to provide a kind of aligning agent for liquid crystal, even environment temperature changes when printing, it also can produce the good film uniformity that is coated with.Another object of the present invention provides a kind of aligning agent for liquid crystal, and it can reduce the depression when printing and produce the good film uniformity that is coated with.
Other purposes of the present invention and advantage can be learned by the following description.
According to the present invention; Above object and advantages of the present invention; Reached by a kind of aligning agent for liquid crystal; It is characterized in that: according to the present invention; (1) is the aligning agent for liquid crystal of mixture that contains polyamic acid, the imide amination polymer with polyamic acid dehydration closed-loop resulting structures or polyamic acid and the imide amination polymer of tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound reaction gained; (2) be contain that the amide solvent that is selected from by following general formula (A) expression forms group the solution of at least a solvent
(in the formula (A), R
1The expression carbon number is 1～4 alkyl, R
2Be that carbon number is 1～8 alkyl, benzyl or phenethyl.)
According to aligning agent for liquid crystal of the present invention,, also can form high the filming of film thickness uniformity, thereby can form liquid crystal orientation film with good liquid crystal aligning even environment temperature changes when printing.Therefore, can make the bad liquid crystal display cells of nothing orientation.
Liquid crystal display cells with the liquid crystal orientation film that forms with aligning agent for liquid crystal of the present invention, except being applicable to TN type, MVA type, IPS type liquid crystal display cells, can also be by selecting used liquid crystal, and be applicable to the liquid crystal display cells etc. of STN (Super Twisted Nematic) type, SH (Super Homeotropic) type, ferroelectricity and anti-ferroelectricity.
And, liquid crystal display cells with the liquid crystal orientation film that forms with aligning agent for liquid crystal of the present invention can be used for various devices effectively, for example can be used for display device such as desk-top calculator, wrist-watch, table clock, counting display screen, word processor, personal computer, liquid crystal TV set.
Embodiment
Below, the present invention is described more specifically.
＜polyamic acid 〉
The polyamic acid that constitutes aligning agent for liquid crystal of the present invention can make by making the reaction of tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound.
＜tetrabasic carboxylic acid dicarboxylic anhydride 〉
As tetrabasic carboxylic acid dicarboxylic anhydride used in the polyamic acid synthetic reaction, use the BTCA dicarboxylic anhydride, 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, 1,2,3,4-cyclopentane tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 5-(2,5-dioxo tetrahydrofuran methylene)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, dicyclo [2.2.2]-Xin-7-alkene-2,3,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, the pyromellitic acid dicarboxylic anhydride, cis-3,7-dibutyl cyclooctane-1,5-diene-1,2,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic acid dicarboxylic anhydride and 3,5,6-three carbonyls-2-carboxyl norbornane-2:3,5:6-dicarboxylic anhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone).They can be used in combination separately or more than 2 kinds.If use these tetrabasic carboxylic acid dicarboxylic anhydrides, then can obtain to show the aligning agent for liquid crystal of good especially liquid crystal aligning.
In the present invention, as required, can also be with other tetrabasic carboxylic acid dicarboxylic anhydrides with the coupling of above-mentioned tetrabasic carboxylic acid dicarboxylic anhydride.As this other tetrabasic carboxylic acid dicarboxylic anhydride, for example, can enumerate 1,2-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, 1,2,4,5-cyclohexane tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-dicyclohexyl tetrabasic carboxylic acid dicarboxylic anhydride, 3,5,6-three carboxyls norbornane-2-acetic acid dicarboxylic anhydride, 2,3,4,5-tetrahydrofuran tetrabasic carboxylic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, following formula (I) and aliphatics and the alicyclic tetrabasic carboxylic acid dicarboxylic anhydrides such as compound (II) represented;
(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
4Separately can be identical, also can be different);
2,3,6,7-naphthalene tetracid 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, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl ether tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,4,5-furans tetrabasic carboxylic acid dicarboxylic anhydride, 3-trifluoromethyl pyromellitic 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, two (phthalic acid) phosphniline oxide dicarboxylic anhydride, right-phenylene-two (triphenyl phthalic acid) dicarboxylic anhydride, between-phenylene-two (triphenyl phthalic acid) dicarboxylic anhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl ether dicarboxylic anhydride, two (the adjacent stupid dioctyl phthalate of triphenyl)-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), 2,2-two (4-hydroxyphenyl) propane-two (dehydration trimellitate), aromatic tetracarboxylic acid's dicarboxylic anhydrides such as compound of following formula (1)～(4) expression.
In these other the tetrabasic carboxylic acid dicarboxylic anhydride, from showing the angle of good liquid crystal aligning, preferred 1,2-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, 1,2,4,5-cyclohexane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, the alicyclic tetrabasic carboxylic acid dicarboxylic anhydrides such as compound of following formula (8) expression in the compound of alicyclic tetrabasic carboxylic acid dicarboxylic anhydride such as the compound of following formula (5)～(7) expression in the compound of above-mentioned formula (I) expression and above-mentioned formula (II) expression.These other tetrabasic carboxylic acid dicarboxylic anhydride can a kind separately or be used in combination more than 2 kinds.
These other tetrabasic carboxylic acid dicarboxylic anhydride preferably uses 0～1 mole of % with respect to 1 mole of tetrabasic carboxylic acid dicarboxylic anhydride that the invention described above is essential.
＜diamine compound 〉
As polyamic acid synthetic in used diamine compound, use p-phenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl sulfide, 1, the 5-diaminonaphthalene, 2, the 7-diamino-fluorene, 4,4 '-diamino-diphenyl ether, 2,2 '-dimethyl-4,4 '-benzidine, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 4,4 '-(-the phenylene isopropylidene) diphenylamine, 4,4 '-(right-the phenylene diisopropylidene) diphenylamine, 1, the 4-cyclohexane diamine, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, 4,4 '-methylene two (hexamethylene alkanamine) and 1,4-two (4-amino-benzene oxygen) benzene.It can be used in combination separately or more than 2 kinds.
In the present invention, as required, can also be with other diamine compound with above-mentioned diamine compound coupling.
As this other diamine compound, between for example can enumerating-phenylenediamine, 4,4 '-diamido diphenylethane, 4,4 '-diamino diphenyl sulfone, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 4,4 '-diaminobenzene formailide, 3,3 '-dimethyl-4,4 '-benzidine, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 3,4 '-diamino-diphenyl ether, 3,3 '-diamido benzophenone, 3,4 '-diamido benzophenone, 4,4 '-diamido benzophenone, 2,2-two [4-(4-amino-benzene oxygen) phenyl] sulfone, 1,3-two (4-amino-benzene oxygen) benzene, 1,3-two (3-amino-benzene oxygen) benzene, 9,9-two (4-aminophenyl)-10-hydrogen anthracene, 4,4 '-methylene-two (2-chloroaniline), 2,2 '-two (trifluoromethyl)-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, 1,4,4 '-(right-the phenylene isopropylidene) diphenylamine, 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamido-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-octafluoro biphenyl, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3, aromatic diamines such as 5-diaminobenzoic acid ester;
1,3-two (aminomethyl) cyclohexane, 1,3-propane diamine, butanediamine, pentanediamine, hexane diamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, 4,4-diamido heptamethylene diamine, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene bicyclopentadiene diamines, six hydrogen-4,7-methanoindene dimethylene diamines, three rings [6,2,1,0
2.7Aliphatics and ester ring type diamines such as]-undecylene two methanediamines;
2, the 3-diamino-pyridine, 2, the 6-diamino-pyridine, 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, the 5-triazine, 2,4-diamido-6-methyl-s-triazine, 2, the 4-diaminostilbene, 3, the 5-triazine, 4,6-diamido-2-vinyl-s-triazine, 2,4-diamido-5-phenyl thiazole, 3, the 5-diaminostilbene, 2, the 4-triazole, 2, the 6-diaminopurine, 5, the 6-diaminostilbene, the 3-dimethyl uracil, 6,9-diamido-2-ethoxy acridine lactate, 3,8-diamido-6-phenylphenanthridineand, 1,4-diamido piperazine, the diamines that has 2 primary amino radicals and this primary amino radical nitrogen-atoms in addition in two (4-aminophenyl) phenyl amine equimolecular;
The compound of following formula (9)～(13) expression,
(in the formula, y is 2～12 integer, and z is 1～5 integer.)
Single-substituted two amines of following formula (III) expression; The diamido organosiloxane of following formula (IV) expression;
(in the formula, X represents to be selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-the divalent organic group of CO-, R
5Be that to have steroid backbone, carbon number be 10～20 alkyl or 1 fluorine-based valency organic group, R
6The expression carbon number is 1～12 alkyl, the R of a plurality of existence
6Can be the same or different separately, p is 1～3 integer, and q is 1～20 integer.)
Object lesson as the diamines of above-mentioned formula (III) expression, can enumerate for example dodecyloxy-2,4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, hexadecane oxygen base-2,4-diaminobenzene, octadecane oxygen base-2, the compound of 4-diaminobenzene, following formula (14)～(18) expression.
In above-mentioned formula, the divalent organic group that X and Y represent for-O-,-COO-,-OCO-,-NHCO-,-CONH-, CO-, methylene, carbon number are 2～6 alkylidene or phenylene.
These diamine compounds can be used in combination separately or more than 2 kinds.
In these other the diamine compound, from showing the angle of good liquid crystal aligning, between preferred-phenylenediamine, 4,4 '-diamido diphenylethane, 4,4 '-diamino diphenyl sulfone, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene formailide, 3,3-dimethyl-4,4 '-benzidine, 3,3 '-diamido benzophenone, 3,4 '-diamido benzophenone, 4,4 '-diamido benzophenone, 4,4 '-(right-the phenylene isopropylidene) diphenylamine, 1, the 4-diamino-cyclohexane, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 1,3-two (aminomethyl) cyclohexane, 1, the 3-propane diamine, butanediamine, pentanediamine, hexane diamine, the compound of above-mentioned formula (9)～(11) expression, dodecyloxy-2, the 4-diaminobenzene, pentadecane oxygen base-2, the 4-diaminobenzene, hexadecane oxygen base-2, the 4-diaminobenzene, octadecane oxygen base-2, the 4-diaminobenzene, the compound of above-mentioned formula (14)～(18) expression.
These other diamine compound preferably uses 0～5 mole of % with respect to 1 mole of diamine compound that the invention described above is essential.
Supply with the tetrabasic carboxylic acid dicarboxylic anhydride of polyamic acid synthetic reaction and the usage rate of diamine compound, preferably with respect to contained amino in the 1 equivalent diamine compound, making anhydride group contained in the tetrabasic carboxylic acid dicarboxylic anhydride is the ratio of 0.2～2 equivalent, more preferably is the ratio of 0.3～1.4 equivalent.When ratio less than 0.2 equivalent of anhydride group contained in the tetrabasic carboxylic acid dicarboxylic anhydride and when any one situation that surpasses 2 equivalents, all can make the molecular weight of resulting polymers too small, thereby the situation of aligning agent for liquid crystal screening characteristics difference occur.
The polyamic acid that constitutes aligning agent for liquid crystal of the present invention is synthetic by tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound reaction.The synthetic reaction of polyamic acid is preferable over 0～150 ℃, more preferably carries out under 0～100 ℃ temperature conditions in organic solvent.If temperature of reaction is below 0 ℃, the situation of compound for the solvent borne variation of solvent then can appear, if surpass 150 ℃, the situation of the molecular weight and molecular weight of resulting polymers then can appear.
As used organic solvent in polyamic acid synthetic, as long as can dissolve the polyamic acid that tetrabasic carboxylic acid dicarboxylic anhydride, diamine compound and reaction generate, then it is had no particular limits, for example can enumerate gamma-butyrolacton, N-N-methyl-2-2-pyrrolidone N-, N, dinethylformamide, N, N-dimethyl acetamide, dimethyl sulfoxide (DMSO), tetramethylurea, HMPA, 1,3-dimethyl-aprotic polar solvents such as 2-imidazolidinone; Between-phenol solvent such as cresols, xylenols, phenol, halogenated phenol; 3-methoxyl-N, N-dimethyl propylene acid amides, 3-butoxy-N, N-dimethyl propylene acid amides, the own oxygen base-N of 3-, amide solvents such as N-dimethyl propylene acid amides.
It is the amount of 0.1～30 weight % with respect to the total amount (A+B) of reaction solution that the consumption of organic solvent (A) is preferably the total amount (B) that makes reaction raw materials tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound.
In addition, in the scope that the polyamic acid that does not make generation is separated out, can also unite the poor solvent alcohols that uses polyamic acid, ketone, ester class, ethers, halogenated hydrocarbon, hydro carbons etc. in the above-mentioned organic solvent.Object lesson as this poor solvent, can enumerate for example methyl alcohol, ethanol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1, the 4-butylene glycol, triethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethy-aceto oxalate, diethyl malonate, ether, glycol monoethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, diethylene glycol dimethyl ether, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic acid esters, the diethylene glycol monoethyl ether acetic acid esters, 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 dimethyl ether, 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, butyl lactate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 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-methoxybutanol, 3-ethyl-3-methoxybutanol, 2-methyl-2-methoxybutanol, 2-ethyl-2-methoxybutanol, 3-methyl-3-ethoxy butanols, 3-ethyl-3-ethoxy butanols, 2-methyl-2-ethoxy butanols, 2-ethyl-2-ethoxy butanols, tetrahydrofuran, methylene chloride, 1, the 2-ethylene dichloride, 1, the 4-dichloroetane, trichloroethanes, chlorobenzene, neighbour-dichloro-benzenes, hexane, heptane, octane, benzene, toluene, dimethylbenzene etc.They can a kind separately or be used in combination more than 2 kinds.
By above synthetic reaction, obtained dissolving the polymer solution of polyamic acid.Then, this polymer solution is put in a large amount of poor solvents, obtained precipitate, can get polyamic acid by this precipitate of drying under reduced pressure.And, once more this polyamic acid is dissolved in the organic solvent, separate out with poor solvent then, by carrying out once or this operation several times, can make with extra care polyamic acid.
＜imide amination polymer 〉
The imide amination polymer that constitutes aligning agent for liquid crystal of the present invention can be modulated by following method (1)～(2).In addition, a part of dehydration closed-loop of polyamic acid repetitive is that the polymkeric substance of so-called imidizate rate less than 100% is also applicable to aligning agent for liquid crystal of the present invention.
Method (1): the method for heating polyamic acid dehydration closed-loop
Temperature of reaction is preferably 50～200 ℃ in this method, more preferably 60～200 ℃.When 50 ℃ of temperature of reaction less thaies, then imidization reaction is carried out fully inadequately, if temperature of reaction surpasses 200 ℃, the too little situation of molecular weight of gained polyimide then can occur.
Method (2): polyamic acid is dissolved in the organic solvent, in this solution, adds dewatering agent and imidization catalyst and the method that heats as required.
In the method, as dewatering agent, can use for example acid anhydrides such as acetic anhydride, propionic andydride, trifluoroacetic anhydride.The consumption of dewatering agent with respect to the repetitive of 1 mole of polyamic acid, is preferably 0.01～20 mole.In addition,, can use for example tertiary amines such as pyridine, collidine, lutidines, triethylamine, still, be not limited to these as imidization catalyst.The consumption of imidization catalyst with respect to 1 mole of used dewatering agent, is preferably 0.01～10 mole.In addition, as the organic solvent that uses in the imidization reaction, can enumerate the identical solvent of illustrative organic solvent with synthesize middle solvent for use as polyamic acid.And the temperature of reaction of imidization reaction is preferably 0～180 ℃, more preferably 10～150 ℃.
The limiting viscosity of＜polyamic acid and imide amination polymer 〉
As above the limiting viscosity of the polyamic acid of gained and imide amination polymer (30 ℃ are measured in the N-N-methyl-2-2-pyrrolidone N-, down together) is preferably 0.05～10dl/g, more preferably 0.05～5dl/g.
＜end modified type polymkeric substance 〉
Used polyamic acid and imide amination polymer can also be end modified type polymkeric substance in the aligning agent for liquid crystal of formation liquid crystal orientation film of the present invention.This end modified type polymkeric substance has carried out molecular-weight adjusting, can improve the coating characteristic of aligning agent for liquid crystal etc. under the prerequisite of not damaging effect of the present invention.End modified type polymkeric substance can be by in synthesizing polyamides when acid, adds acid anhydrides, monoamine compound or monoisocyanates compound and synthesize in reaction system.
As for obtain the acid anhydrides that end modified type polymkeric substance adds in reaction system when synthesizing polyamides is sour, can enumerate for example maleic anhydride, phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinic anhydride, n-tetradecane base succinic anhydride, n-hexadecyl succinic anhydride etc.In addition, as the monoamine that in reaction system, adds, can enumerate for example alkyl amines such as aniline, cyclohexylamine, n-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine, n-tridecane amine, n-tetradecane amine, n-pentadecane amine, n-hexadecane amine, n-heptadecane amine, n-octadecane amine, n-eicosane amine; 3-aminopropyl methyldiethoxysilane, 3-[N-allyl-N-(2-amino-ethyl)] TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-[(3-trimethoxy silane base) propyl group] diethylene triamine, 4-aminophenyl octadecyl ether etc.In addition, as the monoisocyanates compound, can enumerate for example phenyl isocyanate, isocyanic acid naphthyl ester etc.
＜aligning agent for liquid crystal 〉
Aligning agent for liquid crystal of the present invention typically by with above-mentioned polyamic acid and/or imide amination polymer usually the dissolving aligning agent for liquid crystal that is contained in the organic solvent to be constituted form.
As the organic solvent that constitutes aligning agent for liquid crystal of the present invention, can enumerate the amide solvent of above-mentioned formula (A) expression.As the object lesson of this solvent, can enumerate 3-butoxy-N, N-dimethyl propylene acid amides, 3-methoxyl-N, N-dimethyl propylene acid amides, the own oxygen base-N of 3-, N-dimethyl propylene acid amides etc.
These organic solvents can be separately or are used together more than 2 kinds, consider other orientation characteristic or viscosity, the volatility etc. beyond the printing, preferably contain other solvents.As the example of this solvent can enumerate with as solvent for use in the polyamic acid synthetic reaction and the identical solvent of illustrative solvent.In addition, can also suitably select as solvent that can coupling when the polyamic acid synthetic reaction and illustrative poor solvent carries out coupling, preferred especially gamma-butyrolacton, butyl cellosolve and 3-butoxy-N, the mixed solvent of N-dimethyl propylene acid amides.With respect to whole mixed solvents, be that 0～90 weight %, butyl cellosolve are 5～60 weight %, 3-butoxy-N with gamma-butyrolacton more preferably, N-dimethyl propylene acid amides is that the ratio of 1～50 weight % is mixed use.
Supply with in the aligning agent for liquid crystal of liquid crystal orientation film of the present invention solids content concn and consider viscosity, volatility etc. and select, be preferably the scope of 1～10 weight %.That is to say that aligning agent for liquid crystal of the present invention is coated on substrate surface, form that when solids content concn less than 1 weight %, the thickness that will cause this to film is too small and be difficult to obtain good liquid crystal orientation film as the filming of liquid crystal orientation film.When solids content concn surpasses 10 weight %, will cause coating thickness blocked up and be difficult to obtain good liquid crystal orientation film, and the viscosity of aligning agent for liquid crystal increase, and makes coating characteristic variation easily.Temperature when in addition, modulating aligning agent for liquid crystal of the present invention is preferably 0 ℃～200 ℃, more preferably 20 ℃～60 ℃.
The aligning agent for liquid crystal that forms liquid crystal orientation film of the present invention can contain the compound that has an epoxy radicals in the molecule at least as required.As the epoxy compounds that has an epoxy radicals in the molecule at least, preferably can enumerate for example ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-four glycidyl group-2, the 4-hexanediol, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1,3-two (N, N-diglycidyl amino methyl) cyclohexane, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane etc.
From improving the fusible angle of substrate surface is considered, can also further be contained compound in the aligning agent for liquid crystal of formation liquid crystal orientation film of the present invention with functional silanes.As this compound with functional silanes, can enumerate for example 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-carbethoxyl group-3-TSL 8330, N-carbethoxyl group-3-aminopropyltriethoxywerene werene, N-tri-ethoxy silylpropyl diethylenetriamine, N-trimethoxy silane base propyl group diethylenetriamine, 10-trimethoxy silane-1,4,7-three azepine decane, 10-triethoxysilicane alkyl-1,4,7-three azepine decane, 9-trimethoxy silane base-3,6-diaza nonyl acetic acid esters, 9-triethoxysilicane alkyl-3,6-diaza nonyl acetic acid esters, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, N-two (oxyethylene group)-3-TSL 8330, N-two (oxyethylene group)-3-aminopropyltriethoxywerene werene etc.
＜liquid crystal display cells 〉
The liquid crystal display cells that uses aligning agent for liquid crystal of the present invention to obtain can be by for example following method manufacturing.
(1) by for example methods such as roll coater method, spin coater method, print process, the aligning agent for liquid crystal that forms liquid crystal orientation film of the present invention is coated on the substrate one side that is provided with the nesa coating that forms pattern, then,, applicator surface films by being added thermosetting.Here, as substrate, can use for example glass such as float glass, soda-lime glass; Plastics system transparency carriers such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate.Simultaneously go up set nesa coating as substrate, can use tin oxide (SnO
2) system NESA film (U.S. PPG register of company trade mark), indium oxide-tin oxide (In
2O
3-SnO
2) the ITO film etc. of system.The formation of these electrically conducting transparent film figures can be adopted photoetch method and use the method for mask in advance.When the coating of aligning agent for liquid crystal, for the cohesive of further improving substrate surface and nesa coating and filming, can also be on this surface of substrate coating in advance contain functional silanes compound, contain the compound of functionality titanium etc.Heating-up temperature behind the coated with liquid crystal alignment agent is preferably 80～300 ℃, more preferably 120～250 ℃.In addition, contain the aligning agent for liquid crystal of the present invention of polyamic acid, by removing organic solvent after the coating, formation is filmed as alignment films, and it can also carry out dehydration closed-loop by further heating, forms filming of further imidizate.Formed thickness of filming is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
(2) for example being tied with to the film coated surface usefulness that is formed by aligning agent for liquid crystal, the roller of fibrous cloth such as nylon, regenerated fiber, cotton carries out grinding process with certain direction friction.Like this, make give film with liquid crystal molecular orientation can liquid crystal orientation film.In addition, except that the method for grinding process, can also be by surface resin film irradiation polarized UV rays, ion beam, electron beam etc. being produced the method for orientation energy, or uniaxial tension method, method that Langmuir-acquisitions such as Bu Luoer Ztel (Langmure-Blodgett) method are filmed etc., form liquid crystal orientation film.In addition, the micro mist (foreign matter) that produces when removing grinding process etc. makes the surface reach the state of cleaning, preferably the liquid crystal orientation film that forms is washed with isopropyl alcohol etc.In addition; by the part irradiation ultraviolet radiation is carried out on formed liquid crystal orientation film surface; ion beam; electron beam etc. and make processing that tilt angle changes (referring to for example Japanese kokai publication hei 6-222366 communique; Japanese kokai publication hei 6-281937 communique; Japanese kokai publication hei 7-168187 communique; Japanese kokai publication hei 8-234207 communique); perhaps divide ground to form diaphragm in formed liquid crystal orientation film upper surface; after carrying out grinding process with the direction different with previous grinding process; remove said protection film; the processing (referring to for example Japanese kokai publication hei 5-107544 communique) that the orientation of liquid crystal orientation film can be changed can improve the viewing angle characteristic of the liquid crystal display cells of manufacturing.
(3) make 2 substrates that as above form liquid crystal orientation film, 2 substrates are staggered relatively by gap (box gap), make the orientation process direction of the liquid crystal orientation film separately vertical mutually or antiparallel of direction of promptly polishing, fitted with sealant in 2 substrate periphery positions, in the box gap that is partitioned into by substrate surface and sealant, annotate the topping up crystalline substance, the sealing filling orifice constitutes liquid crystal cell.Then, at the outside surface of liquid crystal cell, promptly constitute the polaroid of fitting on the face of each substrate opposite side of liquid crystal cell, it is consistent or vertical to make its polarization direction and this substrate simultaneously go up the polishing direction of the liquid crystal orientation film that forms, and makes liquid crystal display cells.
Here, as sealant, for example can use epoxy resin as the salic ball of hardening agent and separator etc.
As liquid crystal, can enumerate nematic crystal, for example schiff base class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, cyclohexylbenzene class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cube alkanes liquid crystal etc.In addition, also can add cholesteryl liquid crystal such as for example cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate in these liquid crystal and the chirality agent of selling with trade name " C-15 ", " CB-15 " (メ Le Network corporate system) etc. and using.And, can also use right-last of the ten Heavenly stems oxygen base benzylidene-right-ferroelectric liquid crystals such as amino-2-methyl butyl cinnamate.
In addition, as the polaroid of fitting on the liquid crystal cell outside surface, can enumerate polyvinyl alcohol (PVA) is extended that the polarizing coating that is referred to as the H film that orientation absorbs iodine simultaneously is clipped in the acetate fiber diaphragm and the polaroid that polaroid of making or H film self are made.
Embodiment
Below, by embodiment the present invention is carried out more specific description, but the present invention is not limited to these embodiment.In addition, the assessment item and the evaluation method of the aligning agent for liquid crystal of being modulated in following examples and the comparative example are as follows.
[liquid crystal aligning]
The liquid crystal display cells that adopts gained to film as liquid crystal orientation film by polarized light microscope observing when open cutting off (applying releasings) voltage has or not abnormal area, judgement " well " during no abnormal zone.
[with the homogeneity of filming of aligning agent for liquid crystal printing]
The average thickness that employing probe-type thickness instrumentation is filmed surely and poor (deviation) of maximum ga(u)ge and minimum thickness.
[with the surface state of filming of aligning agent for liquid crystal printing]
Preparation has formed the glass substrate of 127mm (D) * 127mm (the W) * 1.1mm (H) of ITO film on whole an of side, under the environment of 25 ℃ or 35 ℃, be coated with application printing machine (オ Application グ ス ト ロ one マ one S-40L that Nissha Printing Co., Ltd makes) on this glass substrate with liquid crystal orientation film, is after 0.2 μ m micro-filter filters, it to be coated on the transparency electrode face the aligning agent for liquid crystal of gained in the above-mentioned experiment with the aperture.Carry out drying by the heating plate driving fit formula pre-dryers that is set at 80 ℃, 200 ℃ of following roastings 60 minutes, on the glass substrate that has the ITO film, form liquid crystal orientation film again.Gained film central part 10cm by inquiry
2The number of printing depression is estimated the depression number in the scope.
Synthesis example 1
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 112.09g (0.5 mole), 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone 157.14g (0.5 mole), p-phenylenediamine 94.62g (0.875 mole) as diamine compound, diamido propyl group tetramethyl disiloxane 24.85g (0.1 mole), 3,6-two (4-aminobenzoic acyl-oxygen base) cholestane 6.43g (0.01 mole), 4-aminophenyl octadecyl ether 4.04g (0.03 mole) is dissolved in the 4500g N-N-methyl-2-2-pyrrolidone N-, reacts 6 hours down at 60 ℃.Then, reaction solution is put in the big excessive methyl alcohol, made the reaction product precipitation.Then, use methanol wash, in 40 ℃ of dryings 15 hours, obtaining 370g logarithm viscosity was the polyamic acid of 0.82dl/g by under reduced pressure.30g gained polyamic acid is dissolved in the 570g N-N-methyl-2-2-pyrrolidone N-, add 23.4g pyridine and 18.1g acetic anhydride, 110 ℃ of following dehydration closed-loops 4 hours, carry out above-mentioned same precipitation, washing, decompression, obtain the polyimide that 18.5g logarithm viscosity is 0.77dl/g (it is as " polyimide (A-1) ").
Synthesis example 2
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 112.09g (0.5 mole) and 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone 157.15g (0.5 mole) is as the p-phenylenediamine 90.03g (0.8325 mole) of diamine compound, diamido propyl group tetramethyl disiloxane 24.85g (0.1 mole) and 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester 26.3g (0.06 mole), aniline 1.396g (0.015 mole) as monoamine is dissolved in the 4500g N-N-methyl-2-2-pyrrolidone N-, reacts 6 hours down at 60 ℃.Then, reaction solution is put in the big excessive methyl alcohol, made the reaction product precipitation.Then, use methanol wash, in 40 ℃ of dryings 15 hours, obtaining 400g logarithm viscosity was the polyamic acid of 0.81dl/g by under reduced pressure.30g gained polyamic acid is dissolved in the 570g N-N-methyl-2-2-pyrrolidone N-, add 23.4g pyridine and 18.1g acetic anhydride, 110 ℃ of following dehydration closed-loops 4 hours, carry out above-mentioned same precipitation, washing, decompression, obtain the polyimide that 18.01g logarithm viscosity is 0.75dl/g (it is as " polyimide (A-2) ").
Synthesis example 3
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 224.18g (1.0 moles), be dissolved in the 4500g N-N-methyl-2-2-pyrrolidone N-as the p-phenylenediamine 86.52g (0.8 mole) of diamine compound, the diamines 104.56g (0.2 mole) of formula (14) expression, reacted 6 hours down at 60 ℃.Then, reaction solution is put in the big excessive methyl alcohol, made the reaction product precipitation.Then, use methanol wash, in 40 ℃ of dryings 15 hours, obtaining 400g logarithm viscosity was that 0.73dl/g, imidizate rate are 0% polyamic acid by under reduced pressure.30g gained polyamic acid is dissolved in the 570g N-N-methyl-2-2-pyrrolidone N-, add 5.7g pyridine and 7.4g acetic anhydride, 110 ℃ of following dehydration closed-loops 4 hours, carry out above-mentioned same precipitation, washing, decompression, obtain the polyimide that 19.2g logarithm viscosity is 0.61dl/g (it is as " polyimide (A-3) ").
Synthesis example 4
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 224.18g (1.0 moles) is as 4 of diamine compound, 4 '-diaminodiphenyl-methane 198.27g (1.0 moles) is dissolved in the 800g N-N-methyl-2-2-pyrrolidone N-, reacts 4 hours down at 60 ℃.Then, reaction solution is put in the big excessive methyl alcohol, made the reaction product precipitation.Then, use methanol wash, in 40 ℃ of dryings 15 hours, obtaining 390g logarithm viscosity was the polyamic acid of 0.32dl/g by under reduced pressure.25g gained polyamic acid is dissolved in the 475g N-N-methyl-2-2-pyrrolidone N-, add 39.5g pyridine and 30.6g acetic anhydride, 110 ℃ of following dehydration closed-loops 4 hours, carry out above-mentioned same precipitation, washing, decompression, obtain the polyimide that 19.5g logarithm viscosity is 0.64dl/g (it is as " polyimide (A-4) ").
Synthesis example 5
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 224.18g (1.0 moles) is dissolved in the 800g N-N-methyl-2-2-pyrrolidone N-as the p-phenylenediamine 108.14g (1.0 moles) of diamine compound, 60 ℃ of reactions 4 hours down.Then, reaction solution is put in the big excessive methyl alcohol, made the reaction product precipitation.Then, use methanol wash, in 40 ℃ of dryings 15 hours, obtaining 390g logarithm viscosity was the polyamic acid of 0.41dl/g by under reduced pressure.25g gained polyamic acid is dissolved in the 475g N-N-methyl-2-2-pyrrolidone N-, add 39.5g pyridine and 30.6g acetic anhydride, 110 ℃ of following dehydration closed-loops 4 hours, carry out above-mentioned same precipitation, washing, decompression, obtain the polyimide that 17.9g logarithm viscosity is 0.77dl/g (it is as " polyimide (A-5) ").
Synthesis example 6
Will be as tetracarboxylic dianhydride's 1,2,3,4-cyclo-butane tetracarboxylic dianhydride 196.12g (1.0 moles), as 4 of diamine compound, 4 '-diamino-diphenyl ether 200.24g (1.0 moles) is dissolved in the 4500g N-N-methyl-2-2-pyrrolidone N-, reacts 3 hours down at 40 ℃.Then, reaction solution is put in the big excessive methyl alcohol, made the reaction product precipitation.Then, use methanol wash, in 40 ℃ of dryings 15 hours, obtain the polyamic acid that 369.12g logarithm viscosity is 0.89dl/g (it is as " polyamic acid (B-1) ") by under reduced pressure.
Synthesis example 7
Will be as tetracarboxylic dianhydride's pyromellitic acid dicarboxylic anhydride 109.06g (0.5 mole) and 1,2,3,4-cyclo-butane tetracarboxylic dianhydride 98.06g (0.5 mole), as 4 of diamine compound, 4 '-diaminodiphenyl-methane 198.27g (1.0 moles) is dissolved in the 4500g N-N-methyl-2-2-pyrrolidone N-, reacts 3 hours down at 40 ℃.Then, reaction solution is put in the big excessive methyl alcohol, made the reaction product precipitation.Then, use methanol wash, in 40 ℃ of dryings 15 hours, obtain the polyamic acid that 411.21g logarithm viscosity is 0.93dl/g (it is as " polyamic acid (B-2) ") by under reduced pressure.
Embodiment 1
(1) polyamic acid (B-1) that makes in the polyimide (A-1) that makes in the synthesis example 1, the synthesis example 6 and the compound that contains epoxy radicals are dissolved in gamma-butyrolacton/3-methoxyl-N, in the N-dimethyl propylene acid amides/butyl cellosolve mixed solvent (weight ratio 70/17/13), make the solution that solids content concn is 4 weight %, is the filter filtration of 1 μ m with this solution with the aperture, the modulation aligning agent for liquid crystal.In addition, polyimide and polyamic acid are with polyimide: the ratio of polyamic acid=1: 4 (weight ratio) is used, and the compound that contains epoxy radicals is modulated into respect to 100 parts by weight polymer and contains 2 weight portions.
(2) above-mentioned aligning agent for liquid crystal is adopted liquid crystal orientation film be coated with on the transparency electrode face that the application printing machine is coated on the glass substrate that has the transparency electrode of being made by the ITO film, through on 200 ℃ heating plate dry 10 minutes, formation was filmed.This thickness state of filming is: average film thickness is 510 dusts under 25 ℃ of environment, and maximum deflection difference value is 11 dusts, and average film thickness is 498 dusts under 35 ℃ of environment, and maximum deflection difference value is 13 dusts.The depression number is per 10 square centimeters 2.
(3) adopt the sander that the roller that twines Artificial Fibers cloth is housed, with roller rotating speed 400rpm, operator's console translational speed 3cm/ second, fine hair is clamp-oned the condition that length is 0.4mm, and filming of forming of aligning agent for liquid crystal carried out grinding process.With the coating above-mentioned liquid crystal orientation film substrate in water, flood 1 minute after, on 100 ℃ heating plate the drying 10 minutes.Then, on each outer rim of the above-mentioned coated with liquid crystal alignment films substrate of a pair of transparency electrode/transparent electrode substrate with liquid crystal orientation film, it is the epoxy adhesive of the alumina balls of 5.5 μ m that coating has added diameter, then, the liquid crystal aligning face is overlapped and pressing relatively, bonding agent is solidified.Then, (メ Le Network society system MLC-6221), is sealed liquid crystal injecting port with the acrylic compounds Photocurable adhesive then, and the polaroid of fitting on the two sides in the substrate outside is produced liquid crystal display cells to fill nematic crystal by liquid crystal injecting port between substrate.Do not find the inhomogeneous and display defect of contrast.
Embodiment 2～9 and comparative example 1～2
According to the prescription shown in the table 1, the polyamic acid that makes in polyimide that makes in the employing synthesis example 1～5 and the synthesis example 6～7 is modulated aligning agent for liquid crystal similarly to Example 1.Then, adopt the aligning agent for liquid crystal that so obtains respectively, make liquid crystal display cells similarly to Example 1.Each gained aligning agent for liquid crystal being carried out the orientation and the storage stability of formed thickness state of filming, liquid crystal display cells estimates.The results are shown in table 1.
Table 1
| Polyimide | Polyamic acid | Solvent | Thickness | Liquid crystal aligning | The depression number is (individual/10cm 2) | ||
| 25 ℃ 35 ℃ average () | 25 ℃ 35 ℃ maximum deviations () | ||||||
| Embodiment 1 | A-1 | B-1 | a/d/f＝70/17/13 | 510 498 | 11 13 | Well | 2 |
| Embodiment 2 | A-1 | B-2 | a/d/f＝70/17/13 | 508 490 | 10 14 | Well | 3 |
| Embodiment 3 | A-2 | B-1 | a/d/f＝70/17/13 | 497 482 | 9 11 | Well | 4 |
| Embodiment 4 | A-2 | B-2 | a/d/f＝70/17/13 | 501 484 | 11 13 | Well | 1 |
| Embodiment 5 | A-3 | d/f＝50/50 | 505 491 | 10 11 | Well | 4 | |
| Embodiment 6 | A-4 | a/d/f＝70/20/10 | 513 499 | 9 12 | Well | 2 | |
| Embodiment 7 | A-5 | a/d/f＝70/20/10 | 507 492 | 10 13 | Well | 3 | |
| Embodiment 8 | A-1 | B-1 | a/c/f＝72/15/13 | 508 496 | 10 14 | Well | 2 |
| Embodiment 9 | A-4 | a/e/f＝75/15/10 | 512 500 | 10 14 | Well | 3 | |
| Comparative example 1 | A-1 | B-1 | a/b＝80/20 | 520 495 | 75 98 | Take place to show bad | 34 |
| Comparative example 2 | A-3 | a/b＝50/50 | 530 499 | 64 89 | Take place to show bad | 57 | |
Solvent types is as follows in the table 1.
(a) gamma-butyrolacton (b) N-N-methyl-2-2-pyrrolidone N-(c) 3-butoxy-N, N-dimethyl propylene acid amides (d) 3-methoxyl-N, the own oxygen base-N of N-dimethyl propylene acid amides (e) 3-, N-dimethyl propylene acid amides (f) butyl cellosolve
According to aligning agent for liquid crystal of the present invention,, also can form high the filming of film thickness uniformity, thereby can form liquid crystal orientation film with good liquid crystal aligning even environment temperature changes when printing.Therefore, can make the bad liquid crystal display cells of nothing orientation.
Liquid crystal display cells with the liquid crystal orientation film that forms with aligning agent for liquid crystal of the present invention, except being applicable to TN type, MVA type, IPS type liquid crystal display cells, can also pass through to select used liquid crystal, and be applicable to STN (Super Twisted Nematic) type, SH (Super Homeotropic) type, ferroelectricity and anti-ferroelectricity liquid crystal display cells etc.
And, liquid crystal display cells with the liquid crystal orientation film that forms with aligning agent for liquid crystal of the present invention can be used for various devices effectively, for example can be used for display device such as desk-top calculator, wrist-watch, table clock, counting display screen, word processor, personal computer, liquid crystal TV set.
Claims (3)
1. aligning agent for liquid crystal, it is characterized in that: (1) is the aligning agent for liquid crystal of potpourri that contains polyamic acid, the imide amination polymer with polyamic acid dehydration closed-loop resulting structures or the polyamic acid and the imide amination polymer of tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound reaction gained, (2) be the solution that contains at least a solvent that is selected from the group who forms by the amide solvent of following general formula (A) expression
In the formula (A), R1 represents that carbon number is 1～4 alkyl, and R2 is that carbon number is 1～8 alkyl, benzyl or phenethyl.
2. the described aligning agent for liquid crystal of claim 1, wherein the tetrabasic carboxylic acid dicarboxylic anhydride is for being selected from the BTCA dicarboxylic anhydride, 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, 1,2,3,4-cyclopentane tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 5-(2,5-dioxo tetrahydrofuran methylene)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, dicyclo [2.2.2]-Xin-7-alkene-2,3,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, the pyromellitic acid dicarboxylic anhydride, cis-3,7-dibutyl cyclooctane-1,5-diene-1,2,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic acid dicarboxylic anhydride and 3,5,6-three carbonyls-2-carboxyl norbornane-2:3, the 5:6-dicarboxylic anhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone) at least a, and diamine compound is for being selected from p-phenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl sulfide, 1, the 5-diaminonaphthalene, 2, the 7-diamino-fluorene, 4,4 '-diamino-diphenyl ether, 2,2 '-dimethyl-4,4 '-benzidine, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 4,4 '-(-the phenylene isopropylidene) diphenylamine, 4,4 '-(right-the phenylene isopropylidene) diphenylamine, 1, the 4-cyclohexane diamine, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, 4,4 '-methylene two (hexamethylene alkanamine) and 1,4-two (4-amino-benzene oxygen) benzene at least a.
3. a liquid crystal display cells is characterized in that having the liquid crystal orientation film that makes with claim 1 or the described aligning agent for liquid crystal of claim 2.
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| JP2006-079086 | 2006-03-22 | ||
| JP2006079088A JP4844721B2 (en) | 2006-03-22 | 2006-03-22 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| JP2006079086 | 2006-03-22 | ||
| JP2006-079088 | 2006-03-22 | ||
| JP2006079088 | 2006-03-22 | ||
| JP2006079086A JP4775559B2 (en) | 2006-03-22 | 2006-03-22 | Liquid crystal aligning agent and horizontal electric field type liquid crystal display element |
| JP2006083628 | 2006-03-24 | ||
| JP2006-083628 | 2006-03-24 | ||
| JP2006083628A JP4788899B2 (en) | 2006-03-24 | 2006-03-24 | Liquid crystal aligning agent and liquid crystal display element |
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| JP2007256485A (en) | 2007-10-04 |
| JP4844721B2 (en) | 2011-12-28 |
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