TW200846451A - Liquid crystal alignment agent and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent and a liquid crystal display element. The liquid crystal alignment agent consists of polyamic acid polymers and/or polyimides thereof, which is made by the reaction of (a) a tetracarboxylic acid dianhydride, (b1) at least a diamine, and (b2) at least a diamine other than (b1). The liquid crystal alignment agent has excellent printability and renders a liquid crystal alignment film having slight accumulated charges while maintaining high voltage holding, and excellent electrostatic leaking. The liquid crystal alignment agent is particularly useful in vertical-orientation liquid crystal display element.

Description

200846451 IX. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment agent and a liquid crystal display element having a liquid crystal alignment film. More specifically, it is excellent in printability, and the obtained liquid crystal alignment film has a small charge accumulation amount, has a cell voltage holding ratio, and is excellent in electrostatic leakage property, and is particularly suitable for a liquid crystal alignment agent of a vertical liquid crystal display element, and has a high-quality display. Performance of liquid crystal display elements. [Prior Art] At present, as a liquid crystal display element, a ΤΝ-type liquid crystal display element having a so-called 扭曲 (twisted nematic) type liquid crystal cell is known, and a substrate having a transparent conductive film such as yttrium (indium tin oxide) is provided. A liquid crystal alignment film formed of polyacrylic acid, polyimine or the like is formed on the surface, and as a substrate for a liquid crystal display element, two of the substrates are opposed to each other, and a positive dielectric anisotropy is formed in the gap. The layer of the columnar liquid crystal constitutes a cell of the sandwich structure, and the long axis of the liquid crystal molecule is continuously twisted by 90 degrees from one substrate to the other substrate. Further, an STN (Super Twisted Nematic) type liquid crystal display element having a higher contrast ratio and a smaller viewing angle dependency than a ΤΝ-type liquid crystal display element has been developed. Such an STN type liquid crystal display device uses a liquid crystal of a nematic liquid crystal as a liquid active material as a liquid crystal, which is used by making the long axis of the liquid crystal molecules continuously twist 180 degrees or more between the substrates. The birefringence effect produced by the state of the amplitude. Further, in recent years, a horizontal electric field type liquid crystal display element has been proposed in which two electrodes for driving a liquid crystal are provided in a comb shape on one side substrate, and an electric field parallel to the substrate surface is generated to control liquid crystal molecules. This component is commonly referred to as the 200846451 in-plane switching type (IP s type) and is known to have excellent wide viewing angle performance. In particular, when an IPS type element is used in combination with an optical compensation film, the viewing angle performance can be further improved, and the remarkable feature of obtaining a wide viewing angle comparable to that of a cathode ray tube having no color tone inversion and color tone change can be obtained. In addition, a vertical alignment type liquid crystal display element called MVA (Multi-domain Vertical Alignment) type or PVA (Modeled Vertical Alignment) type in which liquid crystal molecules having negative dielectric anisotropy are vertically aligned on a substrate has been proposed. (Refer to Patent Document 1 and Non-Patent Document 1). These vertical alignment type liquid crystal display elements are excellent not only in viewing angle and contrast, but also in the process of forming a liquid crystal alignment film, and it is not necessary to perform a sanding treatment or the like, and is excellent in terms of manufacturing steps. However, in recent years, LCD TVs have become popular, and a large-scale production line called the “seventh generation” has been put into operation. Moreover, the construction of a larger “eighth generation” production line is also under planning. The advantages of using a large-scale production line to increase the size of the substrate include the following: Since a plurality of panels can be produced from one substrate, the step time can be shortened and the cost can be reduced, and the liquid crystal display element itself can be enlarged. On the other hand, as a disadvantage of increasing the size of the substrate, it is difficult to ensure uniformity of printing of the liquid crystal alignment agent over a large area, and the liquid crystal alignment film may be unqualified due to poor printing of the liquid crystal alignment agent. Case. In a large-sized substrate manufactured by a large-scale production line, in order to manufacture a liquid crystal display element with high yield, the demand for a liquid crystal alignment agent excellent in printability has been increasing. Further, in recent years, the demand for improvement in display quality has become more demanding, and in particular, for liquid crystal alignment and electrical properties, a liquid crystal alignment film having the above properties of 200846451 has been sought. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2 5 8 60 5 [Non-Patent Document 1] "Liquid Crystal", Vol. 3 (No. 2), pi 17 (1999). SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] The present invention has been made in view of the above circumstances, and an object thereof is to provide excellent printability, improve product yield in a large-scale production line manufacturing step, and obtain a charged accumulation amount of a liquid crystal alignment film. A liquid crystal alignment element which exhibits a high voltage retention ratio and which can form a liquid crystal alignment film excellent in electrostatic leakage property, and a liquid crystal display element which exhibits high quality display performance. Other objects and advantages of the invention will be apparent from the description which follows. [Means for Solving the Problems] According to the present invention, the above object of the present invention, first, is achieved by a liquid crystal alignment agent containing tetracarboxylic dianhydride represented by the following formula (1) and @1) 0 Polylysine prepared by at least one of the diamines represented by the following formulas (2) to (5) and (b2) at least one selected from the group consisting of diamines represented by the following formula (6) or (7) (hereinafter referred to as "specific polylysine") and/or its quinone imidized polymer, 〇0:0 0 0 (in the formula (1), R1 is a tetravalent organic group) 200846451

(In the formulae (2) to (5), R2 to R5 are an alkyl group having a branched or cyclic group of carbon atoms or an alkenyl group having a carbon number of 4 to 40 or a cyclic group, and R2 to R5 have a hydrogen atom in which a fluorine atom is substituted, and A1 and A2 are each independently a linear, linear, branched 1 to 15 of a hydrogen atom, or a methyl group. (7) (6) 200846451 X1— R6 H2N NH2

(In the formulae (6) and (7), X1 and X2 are each independently a divalent group represented by -〇_, -OCO-, and R6 is a group having a steroid skeleton. R7 is a steroid skeleton. Valence organic group). The above object of the present invention, and secondly, it is shown by a liquid crystal which has a liquid crystal alignment film produced from the above liquid crystal alignment agent. Since the liquid crystal alignment agent of the present invention is excellent in printability, the yield of the product can be improved in the production line production step, and the electrostatic leakage property from the crystal alignment film is excellent, so that the occurrence of adverse effects due to the influence of the production step can be suppressed to a minimum level. . Further, the liquid crystal alignment film produced by the liquid crystal alignment agent is particularly suitable for a vertical alignment type liquid crystal display element due to electrical properties. The liquid crystal display device of the present invention can be applied to display devices such as various devices, watches, desk clocks, mobile phones, counting panels, text personal computers, and liquid crystal televisions. [Embodiment] The liquid crystal alignment agent of the present invention contains the above specific polyamidoximine imidized polymer. Hereinafter, the tetracarboxylic dianhydride and the diamine used for the synthesis of the liquid crystal alignment agent C of the present invention will be described. <(a) Tetracarboxylic dianhydride> The specific polyamic acid and/or its quinone imidized polymer 10,000-COO- or a valence organic group is achieved, and in the case of a large-sized liquid, the electrostatic charge is The invention is excellent, for example, the calculation processor, the acid, and/or the 200846451 (a) tetracarboxylic dianhydride used in the polymerization 5 of the above is a compound represented by the above formula (1), and examples thereof include aliphatic tetracarboxylic acid. A dianhydride, an alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride, or the like. The aliphatic tetracarboxylic dianhydride may, for example, be butane tetracarboxylic acid dianhydride or the like. Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-anthracene, and 2,3,4·cyclobutane. Alkanetetracarboxylic dianhydride, 1,2-diethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, i,3-dimethyl-1,2,3,4-cyclobutane Alkanetetracarboxylic dianhydride, hydrazine, 3-diethyl-ns, #·cyclobutane tetracarboxylic dianhydride, hydrazine, 3·dichloro-12,3,4-cyclobutane tetracarboxylic dianhydride 1,2,3,4-Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,4 _cyclopentane tetracarboxylic dianhydride, 1,2 , 4,5-cyclohexanetetracarboxylic dianhydride, 3,3,4,4, dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3, 5 , 6 _ tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, H 4 -tricarboxycyclopentyl acetic acid dianhydride, 1,3,3 a,4, 5,9 b -hexahydro-5 (tetrahydro-2,5-diketo-3-furanyl)-naphthalene [l,2-c]·furan-indole, 3-dione, 1,3,3&amp ;,4,5,91)_hexahydro-5-methyl-5(tetrahydro-2,5-diketo-3-ylfuranyl)-naphthalene[1,2-indole]-furan_1,3 -dione, l,3,3a,4,5,9b-hexahydro-5-B Base_5 (tetrahydro-2,5-diketo-3-furanyl)·naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5 ,91)_hexahydro-7-methyl-5(tetrahydro-2,5-dione-3-furanyl)-naphthalene [1,2-(^]-furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro-7-ethyl-5(tetrahydro-2,5-diketo-3-furanyl)-naphthalene [1,2 - c ]- Furan-1,3-dione, 1,3,3 a,4,5,9 b-hexahydro-8-methyl-5 (tetrahydro-2,5-dione-3-furanylnaphthalene [ Lhc]-weiner-I% diketone, 1,3,3&,4,5,9-hexahydro-8-ethyl-5(tetrahydro-2,5-diketo-3-furanyl) -naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91)_hexahydro-5,8-dimethyl^10» 200846451 -5( Tetrahydro-2,5-diketo-3-furanyl)-naphthalene [l,2-c]·furan-1,3-dione, 5-(2,5-dionetetrahydrofuranyl)-3 -methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, bicyclo [2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2. 2]-oct-4-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.1]-heptane-2,3,5,6-tetracarboxylic dianhydride, tetracyclo[ 4.4.0.12 '5.17'1()] dodecane-3,4,8,9-tetracarboxylic dianhydride, the following formula (8) or (9),

(In the formulae (8) and (9), R8 and R1() represent a divalent organic group having an aromatic ring, R9 and R11 represent a hydrogen atom or an alkyl group, and a plurality of R9 and R11 present may be the same or may be the same. different). Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 3,3',4,4'- Diphenylphosphonium tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,2',3,3'- Biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic dianhydride ,3,3',4,4'-four-11- 200846451 phenyl sand garden tetradecanoic acid dianhydride, 1,2,3,4 · pentanoic acid dianhydride, 4,4,-two (3 , 4 - a basic oxy) monophenyl sulfide dianhydride, 4,4, bis(3,4-diphenoxyphenoxy)diphenyl phthalic anhydride, 4,4,-di (3 , 4·dicarboxyphenoxy)diphenylpropane dianhydride, 3,3′,4,4′-perfluoroisopropylidene diphthalic dianhydride, 3,3′,4,4′- Biphenyltetracarboxylic dianhydride, di(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenyl) Phthalic acid) dianhydride, bis(triphenylphthalic acid) _4,4,-diphenyl ether dianhydride, two Triphenylphthalic acid)-4,4,-diphenylmethane dianhydride, ethylene glycol di(dehydrated trimellitate), propylene glycol-di(hydrogen trimellitate), butanediol - bis (dehydrated trimellitate), 1,6-hexanediol-di (anhydrotrimellitic acid ester), 1,8-octanediol-di (dehydrated trimellitate), 2, 2 _Bis(4-hydroxyphenyl)propane-di(hydrogen trimellitate) and the like. These (a) tetracarboxylic dianhydrides may be used alone or in combination of two or more. The (a) tetracarboxylic dianhydride used in the synthesis of the specific polyamic acid is preferably an alicyclic tetracarboxylic dianhydride, more preferably 50 mol% or more based on the entire tetracarboxylic dianhydride. Selected from 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4·cyclobutane tetracarboxylic dianhydride, l,2-diethyl Base-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-diethyl Base-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2, 3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,3 ,3&,4,5,91)-hexahydro-8-methyl-5(tetrahydro-2,5-dione-3-furanyl)-naphthalene[l,2-c]-furan-1 ,3-dione, 1,3,3&,4,5,9-hexahydro-8-ethyl-12- .200846451 • 5 (tetrahydro-2,5-monoketo-3-furanyl At least one tetracarboxylic dianhydride of naphthalene [1,2 · c ]-furan·1,3-dione is more preferably 70 mol% or more from the viewpoint of improving the performance of the obtained liquid crystal alignment film. Tejia contains 80 moles the above. <Diamine> The diamine used in the synthesis of the specific polyamic acid and/or its quinone imidized polymer is (b 1 ) selected from the diamines represented by the above formulas (2) to (5). At least one (hereinafter referred to as "diamine (bl),") and (b2) is at least one selected from the group consisting of diamines represented by the above formula (6) or (7) (hereinafter referred to as "diamine (b2), ,). In the diamine (b1) represented by the above formulas (2) to (5), the linear alkyl group having 1 to 40 carbon atoms represented by R2 to R5 may, for example, be an n-hexyl group or an n-octyl group. N-decyl, n-dodecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, n-icosyl, etc.; as a branched alkyl group, for example, 1-methyl group Hexyl, 1-ethylhexyl, 2-methylhexyl, 2-ethylhexyl, 1-ethyloctyl, 2-ethyloctyl, ethyloctyl, 1,2·dimethylhexyl, 1, 2-Diethylhexyl, 1,2-dimethyl-octyl, 1,2-diethyloctyl, methylmethyl, 1-ethylindenyl, 2-methylindenyl, 2-ethyl A mercapto group or the like; examples of the cyclic alkyl group include cyclobutane, cyclopentane, cyclohexane, cyclodecane, norbornane, bicyclooctane, dicycloundecane, adamantane, and cholesterol. a group obtained by removing one hydrogen atom from a cycloalkane such as a cholalkanol. The linear, branched or cyclic alkenyl group having 4 to 40 carbon atoms represented by R2 to R5 is exemplified by one or more of the carbon-carbon bonds of the alkyl group exemplified above. Group. -13- 200846451 As the diamine (b1), preferably represented by the above formula (2), more preferably R2 in the above formula (2) is a linear, branched or cyclic group having a uo number of carbon atoms. An alkyl group or a linear, branched or cyclic alkenyl group diamine having 4 to 20 carbon atoms and having one or more unsaturated bonds. Preferable specific examples of the diamine (b 1 ) include, for example, 1 - (3,5 · diaminophenyl)-3 · 18-yard benzyl imino, 1-(3,5 - Diaminophenyl)-3 - 12-yard group. In a preferred embodiment of the diamine (b 2 ), the compound represented by the above formula (6) may, for example, be a compound represented by the following formulas (10) to (19), 200846451

(1 2 ) -15- 200846451

(15) -16- 200846451

-17 - (18) 200846451

The compound represented by i @ (7) may, for example, be a compound shown below.

[19) Formula (20) or (21) Table (20)

With respect to the total amount of the diamine (bl) and the diamine (b2), 1 to 60 mol% is used, and more preferably 10 to 50 mol%. (21) The diamine (b 1 ) is preferably -18-200846451 <other diamines> In addition to the diamine (bl) and the diamine (b 2), in the synthesis of the specific polyamine Use other diamines in combination. The other diamine may, for example, be an aromatic diamine, an aliphatic or alicyclic diamine, a diamine having two first-order amine groups in the molecule, and a nitrogen atom other than the first-order amine group. Examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenylethane. 4'-Diaminodiphenyl sulfide, 4,4'-diaminodiphenyl maple, 3,3, dimethyl-based-4,4,-diaminobiphenyl, 4,4,- Diaminobenzimidamide, 4,4,-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5 -amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 6-aminoaminophenyl)-1,3,3-trimethylindan, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2 ,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-di (4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]anthracene, 1,4-bis(4-aminophenoxy)benzene, 1,3-1 bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydrogen Bismuth, 2,7-diaminopurine, 9,9-di(4-aminophenyl) ) 荞, 4,4,-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-di Chloro 4,4'-diamino-5,5'.dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4' -(p-phenylene isopropylidene)diphenylamine, 4,4'-(m-phenylene isopropylidene)diphenylamine, 2,2'-bis[4-(4-amino-2-yl) Fluoromethylphenoxy)phenyl]hexafluoropropane, 4,4,-diamino-2,2,-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino) -2-trifluoromethyl)phenoxy]-octa-19- 200846451 Fluorine biphenyl, 4-(4-n-heptylcyclohexyl)phenoxy-2,4-diaminobenzene, the following formula (22 )~(25) indicates a compound, etc.

(twenty two)

(twenty four)

Examples of the aliphatic or alicyclic diamine include 1,1-m-xylylenediamine, 1,3-propanediamine, butanediamine, pentamethylenediamine, hexamethylenediamine, heptanediamine, and octane. Diamine, decanediamine, 4,4-diaminoheptyldiamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene diamine, hexahydro-4 , 7-methyl-extension dimethylene diamine, tricyclo[6.2.1. 02,7]-undececyldimethyldiamine, -20-.200846451 4,4'-methylene II ( Cyclohexylamine or the like; as the diamine having two primary amine groups in the molecule and a nitrogen atom other than the primary amine group, for example, 2,3-diaminopyridine, 2 5 6 ·diamine Pyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyridinium, 5,6-diamino-2,4 -dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-u, % tritonic, u-bis(3-aminopropyl) pipe trap, 2,4·diamino-6- Isopropoxy-U,5·three tillage, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1, 3,5-tripper, 2,4-diamino-6, Φmethyl-s-tripper, 2,4-diamino-1,3,5·three tillage, 4, 6-Diamino-2-vinyl-s-triazine, 2,4·diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6, diamine 1,3 - Dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridol lactate, 3,8-diamino- 6-phenylphenanthridine, it diaminopiperazine, 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine, and the like. These other diamine compounds may be used singly or in combination of two or more. In the synthesis of a specific polyamine, when the diamine (bl) and the diamine (b2) are used in combination with the diamine, the ratio of use of the other diamine is preferably 90 mol% relative to the total diamine. the following. <Synthesis of Specific Polylysine> Hereinafter, a method for synthesizing a specific polyamine which can be contained in the liquid crystal alignment agent of the present invention will be described. The specific polyamine can be preferably obtained by mixing the above tetracarboxylic dianhydride with the diamine (bl) and the diamine (b2) and, if necessary, other organic amines in an organic solvent, preferably at -2 0 °c~1. At a temperature of 50 ° C, more preferably 0 to 100 ° C, it is preferred to carry out the reaction from 21 to 200846451 for 1 to 30 hours. The ratio of use of the tetracarboxylic dianhydride to the diamine to be supplied to the specific polyamic acid synthesis reaction is preferably 'relative to the amine group of one equivalent of the diamine, so that the acid anhydride group of the dicarboxylic acid dioxane is 0.5 to 2 equivalents. Better to make it a ratio of ο.?~12 equivalents. Here, 'the organic solvent is not particularly limited as long as it can dissolve the specific poly-amino acid synthesized, and examples thereof include 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, and n. Aprotic polar solvents such as N-dimethylformamide, dimethyl arsenic I, r-butyrolactone, tetramethylurea, hexamethylphosphonium triamine; m-methylphenol, xylenol, phenol , halogenated phenol and other terpenoid solvents. Further, the amount (α) of the organic solvent is preferably such that the ratio of the total amount (β) of the tetracarboxylic dianhydride and the diamine compound to the total amount (α + β) of the reaction solution (Wu concentration) is 〇· An amount of 1 to 30% by weight. In the above organic solvent, a solvent alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, or a hydrocarbon may be used in combination with a specific polyamine in a range in which the specific polyamine is not precipitated. Wait. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, 4, methyl-4-methyl-2-pentanone, ethylene glycol, propylene glycol, hydrazine, and 4; Butylene glycol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, Butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether , ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ether acetate, diglyme, diethylene glycol diethyl ether, digan-22- 200846451 alcohol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4· dichloride Butane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octyl, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutyrate, isoamyl ether, and the like. As described above, a reaction solution in which a specific polyamine is dissolved is obtained. Then, the reaction solution is poured into a large amount of a poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure or the reaction solution is evaporated under reduced pressure with an evaporator to obtain a polyamic acid. Further, the specific polylysine is redissolved in an organic solvent, and then precipitated with a poor solvent or the reaction solution is distilled under reduced pressure with an evaporator, and the specific polyamine acid can be purified by performing one or several steps. <Synthesis method of quinone imidized polymer of specific polyamic acid> Next, a method for synthesizing a quinone imidized polymer of a specific polyamine which can be contained in the liquid crystal alignment agent of the present invention will be described. The quinone imidized polymer of a specific polyamic acid can be synthesized by dehydration ring closure of a part or all of the proline structure of the above specific polyamic acid. The ruthenium iodide polymer which can be used in the present invention may have a ratio of repeating units having a quinone ring in all repeating units (hereinafter, also referred to as "deuterated imidization ratio") may be less than 100%. Partially dehydrated closed loop product. The ruthenium imidization ratio of the quinone imidized polymer of the specific polyaminic acid is preferably from 50 to 100%, more preferably from 70 to 100%. The dehydration ring closure reaction of the specific polyamine can be carried out by (i) heating a specific poly-23-200846451 proline, or (π) dissolving a specific polyamine in an organic solvent, and adding a dehydrating agent to the solution. And dehydration of the closed-loop catalyst and heating according to the method required. In the above method (i) of heating a specific polyaminic acid, the reaction temperature is preferably from 50 to 200 ° C, more preferably from 60 to 170 ° C. When the reaction temperature is less than 50 °C, the dehydration ring-closure reaction cannot be sufficiently performed. If the reaction temperature exceeds 20 (TC, the molecular weight of the obtained quinone imidized polymer may decrease. On the other hand, in the above (Π In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to a specific polyaminic acid solution, as the dehydrating agent, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. Depending on the desired imidization ratio, it is preferably 0.01 to 20 moles per 1 mole of the repeating unit of the specific poly-proline. As the dehydration ring-closing catalyst, for example, pyridine, trimethylpyridine or lutidine can be used. And a third-grade amine such as triethylamine. However, it is not limited thereto. The amount of the dehydration ring-closing catalyst is preferably 0.01 to 1.0 mole relative to the dehydrating agent used for 1 mole. The above dehydrating agent and the dehydration ring-closing catalyst The higher the amount of the ruthenium, the higher the yield of the ruthenium amide. The organic solvent used in the dehydration ring-closure reaction is exemplified as the organic solvent exemplified as the solvent used in the synthesis of the specific polylysine. The reaction temperature of the dehydration ring closure reaction is preferably from 〇 to 180 ° C, more preferably from 10 to 150 ° C. The obtained reaction solution can be purified by the same operation as in the specific polyamic acid purification method. The imidized polymer. <Terminal-modified polymer> The specific polyaminic acid or its quinone imidized polymer used in the present invention may also be a terminal-modified polymer having a molecular weight adjusted. 24-200846451 The terminal-modified polymer can improve the coating characteristics of the liquid crystal alignment agent without impairing the effects of the present invention, etc. The terminal-modified polymer can be reacted by reaction in the synthesis of a specific poly-proline. A monobasic acid anhydride, a monoamine compound, a monoisocyanate compound, etc. are added to the system and synthesized, and examples of the monobasic acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, and Alkyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, etc. Examples of the monoamine compound include aniline, cyclohexylamine, and n-butylene. Amine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, positive Pentadecylamine, n-hexadecaneamine, n-heptadecaneamine, n-octadecylamine, n-icosylamine, etc. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate. Ester, etc. <Solution viscosity of polymer> The specific polylysine and its quinone imidized polymer obtained as above are preferably 20 to 800 mPa, s when formulated into a solution of 1% by weight. The viscosity 'better has a viscosity of 30 to 500 mPa's. In addition, the solution viscosity (mPa's) of the polymer is a prescribed solvent, and the solution having a solid content concentration of 1% by weight is diluted with an E-type rotational viscometer at 2 Measured at 5 °C. <Other Polymers> In the liquid crystal alignment agent of the present invention, a part of the above specific polyaminic acid or its quinone imidized polymer may be selected from other polyamines without impairing the effects of the present invention. At least one of the acid and its oxime imidized polymer is replaced by -25-46446451 (hereinafter referred to as "other polymer"). The above-mentioned other polymer is not particularly limited as long as it is a polyamic acid other than a specific polyamic acid or a quinone imidized polymer thereof, and is preferably a tetracarboxylic acid represented by the above formula (1). A polymer obtained by reacting an anhydride with the above other diamine or a quinone imidized polymer thereof. The tetracarboxylic dianhydride used herein is preferably an alicyclic tetracarboxylic dianhydride or an aromatic tetracarboxylic dianhydride, particularly preferably 1,2,3,4-cyclobutanetetracarboxylic dianhydride or both. Pyromellitic dianhydride. As the other diamine used herein, an aromatic diamine is preferable, and 4,4 '-diaminodiphenylene methane or 4,4'-diaminodiphenyl ether is particularly preferable. The synthesis of this other polymer, in addition to the use of other diamines in place of the diamine (bl) and the diamine (b2), can be combined with the specific polyamine and its hydrazine imidization. »rr . . . f * VIII _ tv I rr ^ tuu Z—* 籾tr, j H 様 様 当 当 当 ° When the liquid crystal alignment agent of the present invention contains other polymers, the proportion of other polymers used, relative to the specific polyamine and its hydrazine The total amount of the imidized polymer and other polymers is preferably 90% by weight or less, more preferably 80% by weight or less. ® <Other Components> The liquid crystal alignment agent of the present invention contains the above specific polyamic acid and/or its ruthenium iodide polymer as an essential component, but may optionally contain other components. As such other additives, for example, a functional decane compound, an epoxy compound, or the like can be given. These functional decane compounds and epoxy compounds may be added to increase the adhesion of the resulting liquid crystal alignment film to the surface of the substrate. Examples of the functional decane compound include 3-aminopropyl-26-200846451-based trimethoxydecane, 3-aminopropyltriethoxydecane, and 2-aminopropyltrimethoxysulfonate. 2-aminopropyltriethoxydecane, n-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyl Methyl dimethoxy decane, 3- ureidopropyl trimethoxy decane, 3- ureidopropyl triethoxy decane, N-ethoxycarbonyl-3-aminopropyl trimethoxy decane, N - ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10_ Trimethoxydecane-1,4,7-triazadecane, 1〇-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl- 3,6 -diazepine acetate, 9-triethoxydecyl-3,6-diazadecyl acetate, N-mercapto-3-fe:propylpropyl dimethoxy cleavage , N-nodal-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxyoxycracking, μ-phenyl-3-amine Propyltriethoxydecane, anthracene-bis(oxyvinyl)-3.aminopropyltrimethoxydecane, anthracene-bis(oxyvinyl)-3-aminopropyltriethoxydecane, and the like. Examples of the epoxy group compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentane. Glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetrahydration Glyceryl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl) Cyclohexane, >1,>^chuan '5^-tetraglycidyl-4,4'-diaminodiphenylmethane, 3-(!^allyl-N-glycidyl) Aminopropyltrimethoxydecane, 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, N,N-diglycidyl--27- 200846451 benzylamine, N,N - diglycidyl-aminomethylcyclohexane or the like. The amount of these functional decane compounds or epoxy compounds is relatively more than 100 parts by weight of the total polymer (refers to the specific polyamine and its ruthenium iodide polymer and all other polymers, the same below) It is preferably 50 parts by weight or less, more preferably 0.1 to 30 parts by weight. <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention is preferably prepared by dissolving a specific polyamic acid and/or its quinone imidized polymer and optionally other components in an organic solvent. The organic solvent used in the liquid crystal alignment agent of the present invention may, for example, be a solvent exemplified as a solvent used in the specific polyamine acid synthesis reaction. Further, it is also possible to appropriately select a poor solvent which is exemplified as a poor solvent which can be used in combination in the specific polyamine acid synthesis reaction. The particularly preferable organic solvent used in the liquid crystal alignment agent of the present invention may, for example, be N-methyl-2-pyrrolidone, γ-butyrolactone, r-butylide or N,N-dimethylformamidine. Amine, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, Ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether , ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Acetate, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-hexyloxy-N,N-dimethyl Propionamide, diethyl carbitol, ethyl carbitol acetate, butyl carbene-28- 200846451 alcohol, triethylene glycol dimethyl ether, isoamyl isobutyrate, isoamyl ether, and the like. They may be used singly or in combination of two or more. In the liquid crystal alignment agent of the present invention, the solid content concentration (the total weight of the components other than the solvent in the liquid crystal alignment agent divided by the total weight of the liquid crystal alignment agent) is preferably in the range of 1 to 10% by weight in view of viscosity, volatility, and the like. . Applying the liquid crystal alignment agent of the present invention to the surface of the substrate to form a coating film as a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the thickness of the coating film is too small, so that a good liquid crystal alignment film cannot be obtained; On the one hand, when the solid content concentration exceeds 10% by weight, the thickness of the coating film is too thick, so that a good liquid crystal alignment film cannot be obtained, and the viscosity of the liquid crystal alignment agent increases to cause deterioration of coating properties. The situation is therefore not good. Further, a particularly preferable solid-containing concentration range differs depending on the method used when the liquid crystal alignment agent is applied to the substrate. For example, when the spin coating method is employed, it is particularly preferably in the range of 1.5 to 4.5% by weight. When the printing method is employed, the solid content concentration is preferably in the range of 3 to 9 % by weight, so that the viscosity of the solution 0 can be made to fall within the range of 12 to 50 mPa.s. When the ink jet method is employed, it is particularly preferable that the solid content concentration is in the range of 1 to 5 % by weight, so that the solution viscosity can be made to fall within the range of 3 to 15 mPa·s. <Liquid Crystal Display Element> The liquid crystal display element of the present invention is characterized by having a liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention obtained as described above. The liquid crystal display element of the present invention can be produced, for example, by the following steps (1) and (2). (1) applying a liquid crystal alignment agent of the present invention to a substrate provided with a patterned transparent conductive film via a suitable -29-200846451 coating method such as an offset printing method, a spin coating method, or an inkjet printing method. Next, a coating film is formed by heating the coated surface. As a coating method suitable for the liquid crystal alignment agent of the present invention, an ink jet printing method is preferred. Here, as the substrate, for example, glass such as floating glass or soda lime glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether maple or polycarbonate can be used. As the transparent conductive film provided on one side of the substrate, a NESA film made of tin oxide (Sn〇2) (registered trademark of PPG, USA), an ITO film made of indium tin oxide (PnO203®-Sn02), or the like can be used. The formation pattern of the transparent conductive film is a photolithography method or a method of using a mask when the transparent conductive film is formed. In the application of the liquid crystal alignment agent, in order to further improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, a functional decane-containing compound or a functional titanium-containing compound may be applied to the surface of the substrate in advance. . The heating temperature after the application of the liquid crystal alignment agent is preferably from 80 to 300 ° C, more preferably from 12 0 to 2 50 ° C. Further, the liquid crystal alignment agent of the present invention removes an organic solvent to form a coating film as an alignment film, and when the liquid crystal alignment agent of the present invention contains a polymer having a guanine unit, it may further be formed after the coating film is formed. The proline unit is subjected to dehydration ring closure by heating to form a further yttrium-imided coating film. The thickness of the formed coating film is preferably 0.01 1 to 1 μm, more preferably 0.005 to 0.5 μπι (2) two substrates are formed as above to form a liquid crystal alignment film, and the two substrates are passed through a gap (cell gap). In the opposite position, the peripheral portions of the two substrates are bonded together with a sealant, and a liquid crystal cell is formed by filling a cell gap of -30-200846451 liquid crystal into the cell gap which is separated from the surface of the substrate and the sealant. Then, a polarizing plate is disposed on the outer surface of the liquid crystal cell, i.e., the transparent substrate side constituting the liquid crystal cell, to obtain a liquid crystal display element. Here, as the sealant, for example, an alumina ball-containing epoxy resin or the like as a curing agent and a separator can be used. Examples of the liquid crystal include nematic liquid crystals and dish-shaped liquid crystals. Among them, nematic liquid crystals are preferable, and for example, Schiff's base liquid crystal, oxidized azo-based liquid crystal, or biphenyl liquid crystal can be used. , phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, ® pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubic liquid crystal, etc. . Further, a cholesteric liquid crystal such as cholesteryl cholesteryl, cholesteryl phthalate or cholesteryl carbonate may be added to these liquid crystals, and a trade name thereof may be mentioned. C-i 5 ", "C B - i 5 " (manufactured by M e r c k) is used for palmizers and the like. Further, a ferroelectric liquid crystal such as p-methoxybenzylidene-p-aminomethylbutylcinnamate may also be used. The polarizing plate to be bonded to the outer surface of the liquid crystal may be a polarizing plate or a ruthenium film obtained by sandwiching a polarizing film called a ruthenium film obtained by stretching a polyvinyl alcohol and absorbing iodine, which is sandwiched between a protective film of acetate. A polarizing plate made by itself. [Examples] Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to these examples. In the following examples, the evaluation of the prepared liquid crystal alignment agent was carried out in the following manner. [Evaluation of Voltage Retention Rate] -31- 200846451 The liquid crystal alignment agent prepared in each of the examples was applied by spin coating on the ΐτ electrode of the glass substrate on which the ITO electrode was formed, and heated at 200 ° C for 60 minutes. A pair of (two pieces) glass substrates having a coating film having a film thickness of about 〇·〇8 μm were produced. Next, on each of the outer edges of the liquid crystal alignment film of the liquid crystal alignment film coating substrate of the pair of transparent electrodes/transparent substrates, an alumina ball having a diameter of 5.5 μm is applied in addition to the liquid crystal injection port. The epoxy resin adhesive then polymerizes and presses the liquid crystal alignment film surface to solidify the adhesive. Next, the liquid crystal injection port is used to charge the alignment liquid crystal between the substrates (negative type, manufactured by Merck Co., Ltd., MLC-203 8), and then the liquid crystal injection port is sealed with an acrylic photocurable adhesive, and the two sides of the substrate are attached. Combined polarization tr 丨.... I~V c=trrr 斤 'destroyed 攸龅 兀忏 兀忏 ° At 60 ° C in the time span of 16.7 milliseconds, apply 5 V voltage to the liquid crystal display element, voltage application The time was 60 microseconds, and then the voltage holding ratio from the voltage release to 16.7 milliseconds was measured. [Evaluation of Residual Voltage] ® For the liquid crystal display element produced above, a DC voltage of 17.0 V was applied for 20 hours in a temperature environment of 100 ° C. After the DC voltage was cut off, it was left to cool at room temperature for 15 minutes. The flicker elimination method determines the voltage remaining in the liquid crystal cell as a residual DC voltage. The evaluation was good when the enthalpy was 1 500 mV or less. [Evaluation of Electrostatic Leakage] After the DC voltage of 1 10 0 was applied to the liquid crystal display element produced above by a glass substrate for 15 minutes, the brightness was reduced by -32 to 200846451 to 50% brightness with respect to the voltage immediately after the voltage was released. The time required, as the static leakage time, to check which level of the following five levels. Level 5: The static leakage time is within 30 minutes. Level 4: The case where the electrostatic leakage time exceeds 30 minutes and is within 1 hour. Level 3: The case where the electrostatic leakage time exceeds 1 hour and is within 2 hours. Level 2: The situation where the electrostatic leakage time exceeds 2 hours and is within 3 hours. Level 1: The case where the electrostatic leakage time exceeds 3 hours. Among them, when it is level 5 or level 4, the electrostatic leakage property is called good.八—12^ ΛΓΜ σ′ PX m <Synthesis Example of Diamine (bl)> Monomer Synthesis Example 1 (1-(3,5-Diaminophenyl)-3-octadecyl Amber Synthesis of Amine) Into a 3 〇Oml three-necked flask ventilated with nitrogen gas, 12.81 g (0.07 mol) of 3,5-dinitroaniline and 70 ml of acetic acid were stirred while stirring with nitrogen to dissolve the solid matter. . 24.64 g (0.07 mol) of octadecyl succinic anhydride was added thereto, and the mixture was refluxed under nitrogen for 20 hours to cause a reaction. After the reaction solution was cooled to room temperature, 70 ml of methanol was added and the mixture was allowed to stand overnight. The precipitated solid was filtered, washed with methanol and dried to give 30 g (yield: 83%) of 1-(3,5-dinitrophenyl)-3- octadecyl succinimide. Then, to a 500 ml flask ventilated with nitrogen, 30 g (0.0 5 8 m·l) of 1-(3,5-dinitrophenyl)-3-octadecyl-33-200846451 synthesized above was added. Amber succinimide, 100 ml of ethanol, 1 〇〇 ml of tetrahydrofuran (THF) and 25 g of procatalyst palladium on carbon (Pd/C) at 7 Torr. (The mixture was stirred for 1 hour. 42.5 ml (43.7 5 g) of hydrazine monohydrate was added thereto, and the mixture was heated under reflux for 6 hours to cause a reaction. Pd/C was filtered off, and the filtrate was concentrated in a rotary evaporator. The product was heated and dissolved in N-methyl-2-pyrrolidone, and recrystallized by cooling to obtain 14.6 g (0.03 2 mol of yield 55%) of the desired product (1,5-diaminophenyl)-3- Octaalkyl amber imine. Monomer Synthesis Example 2 (Synthesis of 1-(3,5-diaminophenyl)-dodecyl amber ylide) In addition to the use of 18.76 g (〇.〇7 mol) The dodecyl succinic anhydride was replaced with 24.64 g (0.07 mol) of octadecyl succinic anhydride, and operated in the same manner as in Monomer Synthesis Example 1 to obtain 118 (0.03 〇 111 〇 1, yield 51%) 1 -(355-diaminophenyl)-3-dodecyl succinimide. Monomer Synthesis Example 3 (1-(3,5-Diaminophenyl)-3 -17-yard-4 - Synthesis of methylmaleimide) To a 2000 ml three-necked flask ventilated with nitrogen, 31.5 g (0.25 mol) of dimethyl maleic anhydride and 89.0 g (0.5 mol) of N-bromine , l. g (4.15 mmol) of dibenzoguanidine peroxide and 15 000 ml of carbon tetrachloride, heated back The reaction mixture was cooled to room temperature, and after standing overnight at room temperature, it was filtered. After washing the filtrate with water, the organic layer was concentrated in a rotary evaporator. The crude oily product was distilled under high vacuum. (120~125 ° C /2 mmHg), 20.0 g (0.1 mol, yield 39%) of intermediate 3 -bromomethyl-4-methylmaleic anhydride was obtained. Then, to 20 ventilated by argon gas 〇Oml three-necked flask was charged with -34-.200846451 16.4g (8〇mmol) of 3-bromomethyl-4-methylmaleic anhydride prepared above, 1.52g (8.0mmol) copper iodide, 400ml of diethyl ether and After 160 ml of HMPA (hexamethylphosphonium triamine), it was cooled to -5 to (TC) under argon atmosphere. While stirring the mixture, a separately prepared 400 dissolved in 400 ml of diethyl ether was added dropwise over about 20 minutes. A solution of methyl cetylmagnesium bromide. The mixed liquid was allowed to warm to room temperature and stirred for another 8 hours. Then, the mixed liquid was diluted with 600 ml of diethyl ether, and then 600 ml of 4 N sulfuric acid was added to make the solution acidic. The layer was further washed with 200 ml of diethyl ether and the organic layer was combined. The organic layer was washed with water and water was removed with sodium sulfate. The solution was concentrated in a rotary evaporator to give a crude product as an oil. The crude product was purified on a silica gel column eluted with petroleum ether/ethyl acetate (1 9:1) as an eluting solvent to give 1 4 · 0 g (0 . 〇4 m 〇i, yield 50%) 3 -heptadecyl-4-methylmaleic anhydride. Then, 6.4 g (0.03 5 mol) of 3,5-dinitroaniline and 35 ml of acetic acid were placed in a 200 ml three-necked flask which was purged with nitrogen. The mixture was stirred while passing nitrogen gas to dissolve the solid matter. 12.3 g (0.035 mol) ^ or more of 3-heptadecyl-4-methyl maleic anhydride was added thereto, and the mixture was refluxed under nitrogen for 20 hours to cause a reaction. After cooling the reaction mixture to room temperature, 3 ml of methanol was added and the mixture was allowed to stand overnight. The solid component was filtered off, washed with methanol and dried to give 14.4 g (0.02 g, yield 81%) of 1-(3,5-dinitrophenyl)-3-heptadecyl-4-methyl. Yttrium. Then, to a 300 ml flask ventilated with nitrogen, 13.4 g (0.026 mol) of 1-(3,5·dinitrophenyl)-3-heptadecyl-4-methylmaleimide was added. 50 ml of ethanol, 50 ml of THF and 12.5 g of a reduction catalyst Pd/C were stirred at 70 ° C for 1 hour. Then, 19 ml (19.6 g) of hydrazine monohydrate-35-200846451 was added, and the mixture was heated under reflux for 6 hours to cause a reaction. The Pd/C was filtered off and the filtrate was concentrated in a rotary evaporator. The obtained crude product was dissolved in N-methyl-2-pyrrolidone by heating, and recrystallized by cooling to obtain 6.6 g (0.015 mol, yield 56%) of desired product 1-(3,5-diaminophenyl)-3. -heptadecyl-4-methylmaleimide. Monomer Synthesis Example 4 (Synthesis of 1-(3,5-diaminophenyl)-3-hexadecyloxymethyl-4-methylmaleimide) to 300 ml ventilated by nitrogen After adding _ 12.81 g (0.07 mol) of 3,5-dinitroaniline and 70 ml of acetic acid to a three-necked flask, the mixture was stirred while passing nitrogen gas to dissolve the solid matter. 14.35 g (0.07 mol) of 3-(bromomethyl)-4 - Φ-based maleic anhydride synthesized in the same manner as the intermediate of the monomer synthesis example 3 was added thereto, and the mixture was refluxed under nitrogen for 20 hours to cause a reaction. After the reaction solution was cooled to room temperature, 70 ml of methanol was added and the mixture was allowed to stand overnight. The solid component was filtered off and washed with methanol and dried to give 1 8.9 g (0. 〇5 1 m ο 1, yield 73%) 1-(3,.5-dinitrophenyl)-3-bromomethyl 4-methylmaleimide. ^ Next, 18.1 g (0.049 mol) of 1-(3,5-dinitrophenyl)-3-bromomethyl-4-methylmaline was added to a 500 ml three-necked flask ventilated with nitrogen. After the imine, 12.9 g (〇.〇49m〇l) of 1-hexadecanol sodium salt and 100 ml of dimethylarylene, the mixture was stirred at 100 ° C for 10 hours to cause a reaction. After cooling the reaction mixture to room temperature, 70 ml of methanol was added and allowed to stand overnight. The solid component was filtered off, washed with methanol and dried to give 20.8 g (0.0 3 9 m ο 1. yield § 〇%) 1 · (3,5 _ nitro-amino)-3 -hexayloxy Methyl-4-methyl maleimine. Then 'to a 300 ml flask ventilated with nitrogen, add -36-200846451 13.8 g (0.026 mol) l-(3,5-dinitrophenyl)-3-hexadecyloxymethyl-4- Methyl maleimide, 50 ml of ethanol, 50 ml of THF, and 12.5 g of a reduction catalyst Pd/C were stirred at 70 ° C for 1 hour. Then, 19 ml (19.6 g) of hydrazine monohydrate was added, and the mixture was heated under reflux for 6 hours to cause a reaction. The Pd/C was filtered off and the filtrate was concentrated in a rotary evaporator. The obtained crude product was dissolved in N-methyl-2-pyrrolidone by heating, and recrystallized by cooling to obtain 8.2 g (〇s 〇 18 mol, yield 67%) of the desired product 1-(3,5-diaminophenyl)- 3-hexadecyloxymethyl-4.methylmaleimide. φ <Synthesis of polyaminic acid and its quinone imidized polymer> Synthesis Examples 1 to 9 To the N-methylpyrrolidone, a diamine and a tetracarboxylic dianhydride having the compositions shown in Table 1 were sequentially added, A solution having a monomer concentration of 20% by weight was allowed to react at 60 ° C for 4 hours to obtain a solution containing polyglycine. To each of the obtained polyaminic acid solutions, the molar amount (equivalent) of pyridine and acetic anhydride shown in Table 1 were added to the total amount (molar) of the proline units in the solution, respectively, at U 〇 ° C. The mixture was heated for 4 hours to carry out a dehydration ring closure reaction. The ruthenium iodide polymer (P - 1) ~ (P - 9) was obtained by reprecipitating the φ solution in diethyl ether, recovering, and drying under reduced pressure. The oxime imidization ratio of these quinone imidized polymers is shown in Table 1. Synthesis Examples 10 to 14 To a N-methylpyrrolidone, a diamine and a tetracarboxylic dianhydride having the compositions shown in Table 1 were successively added, and a solution having a monomer concentration of 2% by weight was prepared at 60 ° C. The reaction was carried out for 4 hours. The obtained solution was reprecipitated in diethyl ether, recovered, and dried under reduced pressure to give polylysine (P-1) to (P-i 4). Further, in Synthesis Examples 10 to 14, the oxime imidization reaction of polyglycolic acid was not carried out. -37- .200846451 Table 1

Will be a commission - diamine (morby) tetracarboxylic dianhydride pyridine acetic anhydride S imidization rate polymer diamine (bl) diamine (b2) other diamine (morbi) (mole multiple) Mo Ear multiple) (%) Name 1 Dl(20) D-5(10) D-7(70) Γ-1(50), Τ-2(50) 1.5 1.5 65 Ρ-1 2 Dl(20) D- 6(10) D-7(70) Τ-2(100) 1.5 1.5 63 Ρ-2 3 D-2(20) D-5(10) D-7(70) Γ-1(50)5Τ-2 (50) 1.5 1.5 66 Ρ-3 4 D-2(20) D-6(10) D_7(70) Τ-2(100) 1.5 1.5 68 Ρ-4 5 D-3(20) D-5(10 ) D-7(70) Γ-1(50), Τ-2(50) 2.0 2.0 72 Ρ-5 6 D-4(20) D-5(10) D-7(70) Τ-2(100 ) 2.0 2.0 75 Ρ-6 7 D-2(20) D-5(10) D-8(70) Τ-2(100) 3.0 3.0 85 Ρ-7 8 D-3(20) D-5(10 D-9(70) Γ-1(50), Τ_2(50) 3.0 3.0 83 Ρ-8 9 D-2(20) D-5(10) D-7(70) Γ-1(50), Τ-4(50) 2.5 2.5 80 Ρ-9 10 Dl(20) D-5(10) D-7(70) Τ-2(100) — — — Ρ-10 11 D-2(20) D- 5(10) D-7(70) Γ-1(50)?Τ-2(50) I,———— Ρ-11 12 D-3(20) D-5(10) D-7(70) Γ -2(50),Τ-5(50) — — — Ρ-12 13 — — D-8(100) Γ-3(10), Τ·5(90) — — Ρ-13 14 — — D- 9(100) Γ-3(20), Τ-5(80) — — — Ρ-14 In Table 1, for diamines and tetracarboxylic dianhydrides, the numbers in parentheses indicate the ratio of use of monomers (mol ratio), and the symbols in the table have the following meanings. <Diamine compound> Diamine (bl); D-1: 1-(3,5-Diaminophenyl)-3-octadecylsuccinimide D-2: 1-(3, 5-Diaminophenyl)-3-dodecyl succinimide-38- 200846451 D - 3: 1-(3,5-Diaminophenyl)-3-heptadecyl-4- Methyl maleimide D — 4: 1-(3,5·diaminophenyl)-3-hexadecyloxymethyl-4-methylmaleimide diamine (b2); D - 5 · Compound D - 6 represented by the above formula (11) - Compound represented by the above formula (15), other diamine; _ D - 7 : p-phenylenediamine D-8: 4,4'-diamine Diphenylmethane D-1: 4,4'-diaminodiphenyl ether <tetracarboxylic dianhydride> T-1: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride T 2: 5-(2,5-diketotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride T-3: pyromellitic dianhydride® T-4: 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dione-3-furanyl)-naphthalene [1,2- (:]-furan-1,3-dione T-5: 1,2,3,4-cyclobutanetetracarboxylic dianhydride Example 1 The ruthenium iodide polymer obtained in Synthesis Example 1 ( P - 1) is soluble in γ-butyrolactone / Ν-methyl - In a 2-pyrrolidone/butyl cellosolve mixed solvent (weight ratio of 40 / 30 / 30), 20 parts by weight of an epoxy compound Ν, Ν, Ν ', Ν ' is added to 100 parts by weight of the polymer. - tetraglycidyl-4,45-diaminodiphenylmethyl-39-200846451 alkane and dissolved to give a solution having a solid content concentration of 4% by weight. The solution was filtered through a filter having a pore size of 1 μηι A liquid crystal alignment agent was prepared. Evaluation of voltage holding ratio, residual voltage, and electrostatic leakage property was carried out by the above method using the alignment agent. The results are shown in Table 2. Examples 2 to 22 except for the polymer mixed in the liquid crystal alignment agent The liquid crystal alignment agents were prepared in the same manner as in Example 1 except for the types shown in Table 2. The evaluation results were evaluated by the above methods, and the evaluation results are shown in Table 2. # Further, in Table 2, the polymer name was followed by a parenthesis. The number inside indicates the amount (parts by weight) of the polymer used. 200846451 Table 2

Polymer (parts by weight) Voltage holding ratio (%) Residual voltage Electrostatic leakage Example 1 P1 (100) > 99% Good 4 Example 2 P-2 (100) > 99% Good 4 Example 3 P- 2 (100) > 99% Good 4 Example 4 P-2 (100) > 99% Good 4 Example 5 P-3 (100) > 99% Good 4 Example 6 P-3 (100) &gt 99% Good 4 Example 7 P-3 (100) > 99% Good 5 Example 8 P-4 (100) > 99% Good 4 Example 9 P-5 (100) > 99% Good 4 Example 10 P-6 (100) > 99% Good 4 Example 11 P-7 (100) > 99% Good 4 Halon side 19 P-8 (100) > 99 〇 / 〇 a 碎 4 Implementation Example 13 P-9 (100) > 99% Good 5 Example 14 P-10 (100) > 99% Good 5 Example 15 P-11 (100) > 99% Good 4 Example 16 P-12 (100) > 99% Good 4 Example 17 P-3/P-13 (50/50) > 99% Good 5 Example 18 P-3/P-13 (50/50) > 99% Good 5 Example 19 P-3/P-13(50/50) >99% Good 5 Example 20 P-4/P_14(5〇/5〇) >99% Good 5 Example 21 P-3/ P-13(50/50) >99% Good 5 Example 22 P-3/P-13(50/50) >99% Good 5 [Simple diagram] Μ 〇 j\\\ [Main component symbol description] Μ 〇 y\\\ -41-

Claims (1)

200846451 X. Patent application scope: 1. A liquid crystal alignment agent characterized by containing (a) a tetracarboxylic dianhydride represented by the following formula (1) and (bl) selected from the following formulas (2) to (5) At least one of the diamines and (b2) a polyamic acid prepared by at least one reaction selected from the group consisting of diamines represented by the following formula (6) or (7) and/or a ruthenium iodide polymer thereof , In the formula (1), R1 is a tetravalent organic group. In the formulae (2) to (5), R2 to R5 are a linear or branched alkyl group having a carbon number of 1 to 40, or a linear or cyclic alkyl group having 4 to 40 carbon atoms. a chain, a branched or a cyclic alkenyl group, wherein 1 to 15 of the hydrogen atoms of R 2 to R 5 may be substituted by a fluorine atom, and each of A 1 and A 2 is independently a hydrogen atom or a methyl group. (6) (7) In the formulae (6) and (7), X1 and X2 are each independently a divalent group represented by -0-, -COO- or -OCO-, and R6 is a monovalent organic group having a steroid skeleton R7 is a divalent organic group having a steroid skeleton. 2. The liquid crystal alignment agent of claim 1, wherein the (bl) diamine is represented by the above formula (2), and R2 is a linear or branched chain having 1 to 20 carbon atoms; An alkyl group or a diamine having one or more unsaturated bonds and having 4 to 2 Å @ linear, branched or cyclic alkenyl groups. A liquid crystal display element characterized by having a liquid crystal alignment film produced by a liquid crystal alignment agent as disclosed in claim 1 or 2. -43· 200846451 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: No 0 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: