TW201132703A - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent which has an excellent storage stability and can form a liquid crystal alignment film that continues displaying with high quality even if a liquid crystal display device is used for a long time. The liquid crystal alignment agent comprises at least one polymer selected from a group consisting of a polyamic acid formed by reacting tetracarboxylic acid dianhydride with diamine, and a polyimide formed by a dehydration-closed ring reaction of the polyamic acid, wherein the tetracarboxylic acid dianhydride comprises 5 to 80 mol% of at least one component selected from the group consisting of 1S, 2S, 4R, 5R- cyclohexane tetracarboxylic acid dianhydride and 1R, 2S, 4S, 5R- cyclohexane tetracarboxylic acid dianhydride with respect to the weight of the total tetracarboxylic acid dianhydride.

Description

201132703 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a liquid crystal alignment agent and a liquid crystal display element. More specifically, the present invention relates to a liquid crystal alignment agent and a liquid crystal alignment film which are excellent in storage stability and particularly excellent in heat resistance, and a liquid crystal display element which can exhibit high quality and suppress display deterioration due to thermal stress and can be operated for a long period of time. [Prior Art] Resin materials such as polyimine, polyamide, polyamic acid, and polyester are known as materials for the liquid crystal alignment film used in the liquid crystal display device. In particular, a liquid crystal alignment film formed of polyglycine or polyimine is excellent in heat resistance, mechanical strength, and affinity for liquid crystal, and is used in most liquid crystal display elements (Patent Document 1). ~6). Among them, since polylysine has high solubility in a usual organic solvent, it has an advantage that a liquid crystal alignment agent can be easily obtained by a printing step in a production step of a liquid crystal display element, and the resin is inexpensive. However, the liquid crystal display element of the liquid crystal alignment film formed of polylysine is weak in thermal stress T, and when the liquid crystal display element is operated for a long period of time, there is a problem that the liquid crystal alignment film is deteriorated and the voltage holding ratio is lowered. In recent years, the design of the life of liquid crystal display elements has been based on LCD TVs for a period of more than one year. Therefore, in order to maintain a high-quality display when the liquid crystal display element is operated for a long period of time, it is important to exhibit a stable voltage holding ratio for a long period of time, and it is urgent to improve the heat resistance reliability of the alignment film. With respect to a currently known method for improving the heat resistance reliability (thermal stress tolerance) of an alignment film, a method of increasing the chemical stability of a liquid crystal alignment film by mixing an epoxy compound in a liquid crystal alignment agent by 201132703 has been proposed ( Patent Document 7); a method of forming intermolecular cross-linking at the time of firing of a liquid crystal alignment film by using a polyamic acid into which a monomer having a carboxylic acid is introduced, thereby increasing the stability of the film (Patent Document 8) )Wait. However, in order to exhibit desired performance by these techniques, it is necessary to use a large amount of an epoxy compound or a carboxylic acid, which may impair the reworkability of the liquid crystal alignment film (the ease of peeling off the coating film when the liquid crystal alignment agent is poorly printed), and resistance. Grindability, etc., need further improvement. On the other hand, the liquid crystal alignment film containing the polyimine has a relatively high heat resistance, although the solubility of the liquid crystal alignment film obtained is relatively high, but the polyetherimine which is currently known has insufficient solubility in a common organic solvent. Therefore, there is a problem in the storage stability of the liquid crystal alignment agent. Based on such a problem, there is a need for a polyglycolic acid/polyimine liquid crystal alignment agent which can form a liquid crystal alignment film which has sufficient solubility to a common organic solvent and is excellent in thermal stress resistance. A method for stereoselectively producing cyclohexanetetracarboxylic dianhydride has been developed, and 1S, 2S, 4R, 5R-cyclohexane tetracarboxylic dianhydride and 1R, 2S, 4S, 5R- can be selectively produced separately, respectively. Cyclohexane tetracarboxylic dianhydride (Patent Document 9, Patent Document 10, and Non-Patent Document 1). Patent Documents 9 and 10 describe the use of 1 〇 % of the above diastereomers as polyphthalic acid synthesized by tetracarboxylic dianhydride, and it is explained that these are polymers having a sufficiently high molecular weight. Further, it is described that the above polylysine can be used in the liquid crystal alignment film of a liquid crystal display device, but none of these documents has any properties for the alignment film of the liquid crystal 201132703, and there is no tetracarboxylic acid as a raw material. The structure of the acid dianhydride is related to the storage stability of the obtained liquid crystal alignment agent and the thermal stress tolerance of the formed liquid crystal alignment film. [Prior Art] [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 4 - 1 5 3 6 2 2 [Patent Document 2] Japanese Patent Laid-Open No. 60-110 Japanese Patent Laid-Open No. Hei 56-91277 [Patent Document 5] Japanese Patent No. 5,928,73 No. 3 [Patent Document 6] Japan [Patent Document 7] Japanese Laid-Open Patent Publication No. 2009-157351 (Patent Document 9) JP-A-2009-191253 (Patent Literature) Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 14] Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] The present invention has been made in view of the above problems, and an object thereof is to provide a liquid crystal alignment agent, Excellent storage stability to the liquid crystal alignment agent, i.e., may be formed so that the liquid crystal display element for a long time, the liquid crystal may be continuously displayed with high quality alignment film. Another object of the present invention is to provide a liquid crystal display element which can be continuously displayed with high quality even when used for a long period of time. Other objects and advantages of the invention will be apparent from the following description. [Means for Solving the Problems] According to the present invention, the above objects and advantages of the present invention are first achieved by a liquid crystal alignment agent containing polyphosphoric acid and dehydrating the polyamic acid. At least one polymer selected from the group consisting of a closed-loop formed polyimine, which is obtained by reacting a tetracarboxylic dianhydride with a diamine, wherein the above tetracarboxylic dianhydride is relative to all Tetracarboxylic dianhydride containing 5 to 80 mol% of a group consisting of 13,23,411,511-cyclohexanetetracarboxylic dianhydride and 1R, 2S, 4S, 5R-cyclohexane tetracarboxylic dianhydride At least one selected from the group. The above objects and advantages of the present invention, and secondly, are achieved by a liquid crystal display element having a liquid crystal alignment film formed of the above liquid crystal alignment agent. [Effect of the Invention] The liquid crystal alignment agent of the present invention is excellent in storage stability, and can provide a liquid crystal alignment film which can be continuously displayed with high quality even when it is used for a long time when it is used in a liquid crystal display element. Therefore, the liquid crystal display element of the present invention having the liquid crystal alignment film formed of the liquid crystal alignment agent can maintain high-quality display even when used for a long period of time. The liquid crystal display element of the present invention can be effectively applied to various devices, such as a clock, a portable game machine, a word processor, a notebook computer, a navigation system, a video camera, a mobile information terminal, a digital camera, a mobile phone, and various monitors. It is used in display devices such as LCD TVs. [Embodiment] [Form of Embodiment of the Invention] The liquid crystal alignment agent of the present invention is at least one selected from the group consisting of polylysine and polyamidomine formed by dehydration of the polyglycolic acid. a liquid crystal alignment agent for a polymer obtained by reacting a tetracarboxylic dianhydride with a diamine, wherein the above tetracarboxylic dianhydride contains 5 to 80 mol% based on the total tetracarboxylic dianhydride. At least one selected from the group consisting of 1 S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride and 1R, 2S, 4S, 5R-cyclohexane tetracarboxylic dianhydride. At least one polymer selected from the group consisting of a polyamic acid obtained by reacting a specific tetracarboxylic dianhydride and a diamine with a polyamidene formed by dehydration of the polyglycolic acid, In the specification, hereinafter referred to as "specific polymer". <tetracarboxylic dianhydride> 201132703 As a tetracarboxylic dianhydride for synthesizing the polylysine in the present invention, it will be composed of 13,23,411,511-cyclohexanetetracarboxylic dianhydride and 111,28,43,511 At least one selected from the group consisting of cyclohexanetetracarboxylic dianhydride is used together with other tetracarboxylic dianhydrides. Here, it is selected from the group consisting of 13,28,411,511-cyclohexanetetracarboxylic dianhydride and 111,23,48,5-dicyclohexane-tetracarboxylic dianhydride relative to all tetracarboxylic dianhydride. At least one of the use ratios is 5 to 80 mol%, preferably 10 to 60 mol%, more preferably 15 to 50 mol%. When the ratio is less than 5 mol%, the heat resistance reliability of the formed liquid crystal alignment film may be poor; on the other hand, when the content exceeds 80 mol%, the storage stability of the obtained liquid crystal alignment film may be poor, so it is not suitable. . More preferably, the tetracarboxylic dianhydride contains 13,28,411,511-cyclohexanetetracarboxylic dianhydride in the above range. Examples of the other tetracarboxylic dianhydride include aliphatic tetracyanic acid dianhydride, alicyclic tetrahydro acid dianhydride, aromatic tetradecanoic dianhydride, and the like, as specific examples thereof. Examples of the aliphatic tetra-residual acid dianhydride include butane tetracarboxylic dianhydride; and examples of the alicyclic tetracarboxylic dianhydride include hydrazine, 2,3,4-cyclobutane tetracarboxylic acid. Acid dianhydride, 2,3,5·tricarboxycyclopentyl acetic acid dianhydride, l,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-side oxygen_3_ Furyl)_naphthalene [1,2-(;]furan-1,3-dione, 1,3,3&,4,5,913-hexahydro-8-methyl-5-(tetrahydro-2,5) -2-sided oxy-3-furanyl)-naphthalene [1,2-(;]furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2,4-dione-6 - spiro_3'_(tetrahydrofuran-2,5·-dioxime), 201132703 5-(2,5-dioxatetrahydro-3-furanyl)-3-methyl-3-cyclohexene- 1,2-di-residual anhydride, 3,5,6-tricarboxy-2-carboxymethylnordecane-2:3,5:6-dianhydride, 2,4ϊ6,8-tetracarboxybicyclo[3.3. 0] octane-2··4,6··8-dianhydride, 4,9-dioxatricyclo[5.3.1.02·6]Η——carbon-3,5,8,10-tetraketone, etc. ; In the case of the aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, and the like, and the tetracarboxylic dianhydride described in Patent Document 14 (Japanese Patent Laid-Open Publication No. 2010-97188) are used. The tetracarboxylic dianhydride preferably comprises 1,2 5 3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a ,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene [l,2-c]furan-1,3-dione' 1,3 ,3&,4,5,9-seven-hexahydro-8-methyl-5-(tetrahydro-2,5-one oxy-3-indolyl)-naphthalene [1,2-(:]咲--1,3-diketone, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3,-(tetrahydrofuran-2,5'-dione), 5 -(2,5-dihydrotetrahydro-3-3-furanyl)-3-methyl-3-cyclohexene-12•dicarboxylic anhydride, 3,5,6-tricarboxy-2-methylcarboxyl Decane-2 ·_3,5 :6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride and 4,9-di At least one selected from the group consisting of oxatricyclo[5.3.1.02·6]undec-3-3,8,1〇-tetraketone (hereinafter, referred to as "specific tetracarboxylic dianhydride") The above specific tetracarboxylic dianhydride The ratio of the whole is preferably 5 〇 mol% or more, more preferably 8 〇 mol% or more, particularly preferably 100 mM mol% relative to the other tetracarboxylic dianhydride described above. <Diamine> 10-201132703 The diamine used for the synthesis of the poly-proline in the present invention may, for example, be an aliphatic diamine, an alicyclic diamine or an aromatic diamine 'diamine-based organodecane. As a specific example thereof, 'as an aliphatic diamine, respectively, for example, m-xylylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, and hexa Methyldiamine or the like; as the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(amine) Methyl)cyclohexane or the like; as the aromatic diamine, for example, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide , 4,4'-diaminodiphenylamine, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamine Benzyl-2,2'-bis(trifluoromethyl)biphenyl, 2,7-diaminofuran, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4- Aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylenediphenyl)bis(aniline), 4,4'-(m-phenylene isopropylidene) Diphenylamine 'I,4-bis(4-aminophenoxy)benzene, 4,4'-bis (4 -aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6 -diaminocarbazole, N-methyl-3,6-diaminocarbazole 'N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminoguanidine Oxazole, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-indole, Ν'-dimethylbenzidine, 1,4- Di-(4-aminophenyl)-piperidin' 3,5-diaminobenzoic acid, cholestyloxy-3,5-diaminobenzene, cholesteneoxy-3,5-di Aminobenzene, cholestyloxy-2,4-diaminobenzene, cholesteneoxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestane-11- 201132703 Base ester, cholesteryl 3,5-diaminobenzoic acid, lanosteryl 3,5-diaminobenzoic acid, 3,6-bis(4-aminobenzylideneoxy) cholestene Decane, 3,6-bis(4-aminophenoxy)cholestane, 4-(4,-trifluoromethoxybenzylideneoxy)cyclohexyl-3,5-diaminobenzoic acid Ester, 4-(4,-trifluoromethylbenzylideneoxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)) Phenyl) 4_ Butylcyclohexane, 1,1·bis(4-((aminophenyl)methyl)phenyl)_4_heptylcyclohexyl, 1,1-bis(4-((aminophenoxy) )methyl)phenyl)_4_heptylcyclohexane, anthracene, bis(4-((aminophenyl)methyl)phenyl)_4_(4-heptylcyclohexyl)cyclohexane and the following a compound represented by the formula (A-1);

In the formula (A-1), X1 is an alkylene group having a carbon number of 丨~3, *_〇-, , COO- or *-〇C〇_ (wherein, a bond with "*,, and two Aminophenyl linkage), a is 〇 or i, b is an integer of 0 to 2, and c is an integer of 1 to 2 0; and as the diamine organic oxirane, for example, 1,3-double (for example) 3-aminopropyl)-tetramethyldioxane, and the like, and the diamine described in Patent Document 14 (Japanese Patent Laid-Open Publication No. 2010-97188), and X1 in the above formula (A-1) Preferred are an alkyl group having 1 to 3 carbon atoms, *-0- or *-COO- (wherein a bond of "*," and a diaminophenyl bond). Specific examples of the CeH2e+1- group include, for example, a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl 'n-heptyl group, an n-octyl'-n-decyl group, N-decyl, n-dodecyl, n-tridecyl 'n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-dec-12- 201132703 octadecyl, N-nonadecyl, n-icosyl and the like. The two amine groups of the diaminophenyl group are preferably the 2,4-position or the 3,5-position relative to the other groups. Specific examples of the compound represented by the above formula (A-1) include, for example, dodecyloxy-2,4-diaminobenzene and tetradecyloxy-2,4-diamine. Phenyl, pentadecyloxy-2,4-diaminobenzene, cetyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, twelve Alkoxy-2,5-diaminobenzene, tetradecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, hexadecyloxy-2 , 5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, and a compound represented by the following formula (human-1-1) to (human-1-3), respectively.

(A-1-2) In the above formula (A-1), a and b are preferably not 0 at the same time. The above diamine preferably comprises p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2 , 2·-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-diamine At least one selected from the group consisting of bisphenylamine and 4,4'-(m-phenyleneisopropylidene)diphenylamine (hereinafter, referred to as "specific diamine-13-201132703 additionally" of the present invention When the liquid crystal alignment agent is used to form a liquid crystal alignment film in a vertical alignment type (VA type) liquid crystal display element, it is preferably further contained by a cholesteryl group of _3,5-diamino group in addition to the above specific diamine. Benzene cholestyryloxy-3,5-diaminophenyl 'cholesteryloxy-2,4-diaminobenzene, cholesteneoxy-2,4-diaminobenzene, 3,5 - cholesteryl diaminobenzoic acid, cholesteryl 3,5-diaminobenzoic acid, lanosteryl 3,5-diaminobenzoic acid, 3,6-bis(4-amine Selected from the group consisting of benzylideneoxy)cholesterol, 3,6-bis(4-aminophenoxy)cholestane and the compound represented by the above formula (A-1) At least one of the following (hereinafter referred to as "specific diamine 2"). The liquid crystal alignment agent of the present invention, when used to form a liquid crystal alignment film of a VA type vertical alignment type liquid crystal display element, the above specific diamine 1 and specific The preferred ratio of use of diamine 2 to all diamines is as follows: Specific diamine 1 : preferably 20 to 97 mol %, more preferably 50 to 95 mol %, particularly preferably 60 to 90 mol Specific diamine 2: preferably 3 to 80 mol%, more preferably 5 to 50 mol%, particularly preferably 10 to 40 mol%. In this case, the above specific diamine 1 The total use ratio of the specific diamine 2 is preferably 1.0% by mole relative to the total of the diamine. In another aspect, the liquid crystal alignment agent of the present invention is used for forming a liquid crystal display element other than the VA type (for example, TN ( Twisted Nematic, Twisted Nematic, STN (Super Twisted Nematic), Transverse Electric Field (eg IPS (In-Plane Switching), FFS (Fringe -14- 201132703)

In the case of the liquid crystal alignment film in the field switching or the like, the specific use ratio of the specific diamine 1 and the specific diamine 2 to all the diamines is as follows. The specific diamine 1 is preferably 50 mol% or more, more preferably 80 mol% or more, and particularly preferably 100 mol%. The specific diamine 2 is preferably 30 mol% or less, more preferably 1 mol% or less, and particularly preferably 0 mol%. In this case, as far as the diamine is concerned, it is preferred to make the above specific diamine 1 and specific diamine 2 a total of 1 〇 〇 mol %, more preferably only a specific diamine 1 °. <Molecular weight modifier> In the synthesis of the above polyamic acid, a terminal modified polymer can be synthesized using a suitable molecular weight modifier 'and a tetracarboxylic dianhydride as shown above together with a diamine. By making the poly-proline acid the terminal-modified polymer, the liquid crystal alignment agent containing at least one polymer selected from the group consisting of the poly-proline and the polyimine formed by dehydration and ring closure is not impaired According to the effect of the present invention, the coatability (printability) can be further improved. The molecular weight modifier may, for example, be an acid monoanhydride, a monoamine compound, a monoisocyanate compound or the like. Specific examples thereof include, as the acid monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl salicylic anhydride, n-dodecyl salicylic anhydride, and positive Tetradecyl salicylic anhydride, n-hexadecyl salicylic anhydride, etc.; as the monoamine compound, for example, aniline, cyclohexylamine, -15-201132703 n-butylamine, n-pentylamine, n-hexylamine 'n-glycol An amine, n-octylamine, etc.; as a monoisocyanate compound, a phenyl isocyanate, a naphthyl isocyanate, etc. are mentioned, for example. The ratio of use of the molecular weight modifier is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total of the tetracarboxylic dianhydride and the diamine used. <Synthesis of Polylysine> The ratio of the use of the tetracarboxylic dianhydride and the diamine used in the synthesis reaction of polyglycine is based on the amine group of one equivalent of the diamine, and the tetracarboxylic dianhydride. The acid anhydride group is preferably in a ratio of 0.2 to 2 equivalents, more preferably in a ratio of 0.3 to 1.2 equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at -20 ° C to 150 ° C, more preferably at 0 ° c to 100 t:, preferably at 0.1 to 24 hours, more preferably Good for 〇. 5~12 hours. Here, examples of the organic solvent include an aprotic polar solvent, phenol and a derivative thereof, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon, and the like. Specific examples of the organic solvent are the above-mentioned aprotic polar solvent, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-. Dimethyl carbamide, dimethyl hydrazine, γ-butyrolactone, tetramethyl urea, hexamethylphosphonium triamide, etc.; as the above phenol derivative, for example, m-cresol, xylenol And halogenated phenol, etc.: -16- 201132703 As the above-mentioned alcohol, for example, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, and ethylene may be mentioned. The alcohol is monomethyl ether or the like; examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and examples of the ester include ethyl lactate and butyl lactate. Methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, etc.; as the ether, for example, two Ethyl ether 'ethylene glycol methyl ether, ethylene glycol decyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl Ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol single Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, etc.; as the halogenated hydrocarbon, for example, two Methyl chloride, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, etc.; examples of the hydrocarbon include hexane, heptane, and octane. Alkane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, and the like. Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and phenol and a derivative thereof (organic solvent of the first group) or selected from the above first group are preferably used. One or more selected from the group consisting of an organic solvent and a group consisting of an alcohol 'ketone, an ester, an ether, a halogenated hydrocarbon, and a hydrocarbon (the organic solvent of Group 2-17-201132703). In the latter case, the use ratio of the organic solvent in the second group is preferably 50% by weight or less based on the total amount of the organic solvent of the first group and the organic solvent of the second group, and more preferably The weight % or less is further more preferably 30% by weight or less. The amount of the organic solvent used is preferably the total amount of the tetracarboxylic dianhydride and the diamine (b). The total amount (a + b) relative to the reaction solution is an amount of from 0.1 to 50% by weight. As described above, a reaction solution in which polylysine is dissolved can be obtained. The reaction solution can be directly used for preparing a liquid crystal alignment agent, and can also be used for preparing a liquid crystal alignment agent after separating the polyamic acid contained in the reaction solution, or after refining the separated polyamic acid. Agent. When the poly (proline) is dehydrated and closed to form a polyimine, the above reaction solution can be directly used for the dehydration ring closure reaction; or the polylysine contained in the reaction solution can be separated and used for the dehydration ring closure reaction; or the separation can be carried out. After the polyamic acid is refined, it is used for the dehydration ring closure reaction. The separation and purification of polylysine can be carried out by a known method. <Synthesis of Polyimine> The above polyimine can be obtained by hydrazine hydrazide by dehydration of the polylysine synthesized as above. The polyimine in the present invention may be a complete hydrazine imide of a glycine structure having a glycine structure as a precursor of polyproline, or may be a part of the structure of a proline which is dehydrated and closed, and the guanamine The partial oxime imide of the acid structure and the quinone ring structure is more preferably 30% or more of the polyimine in the present invention, more preferably 5% or more, and particularly preferably - 18- 201132703 5 5 % or more. The ruthenium imidization ratio is a ratio indicating the amount of ruthenium in a percentage, and the ratio of the number of valeric acid structures of the polyimine and the total amount of yttrium. Here, a part of the quinone ring is a quinone ring. The dehydration ring closure of the polyamic acid is preferably carried out by heating the polyfluorene method or dissolving the polyaminic acid in an organic solvent, and in the method of heating the dehydrating agent and the dehydration ring-closing catalyst as needed, preferably One way to proceed. In the method of adding a dehydrating agent to the polyamic acid solution and dehydrating, the dehydrating agent may, for example, be an acid anhydride such as acetic anhydride or trifluoroacetic anhydride. The amount of the dehydrating agent is preferably 0.01 to 20 moles relative to the structure of the valine acid of the valine. The catalyst may, for example, be a tertiary amine such as pyridine, trimethylpyridinepyridine or triethylamine. The dehydrating agent used for the dehydration ring-closure catalyst is preferably an organic solvent used in the ring closure reaction of 〇.〇1~1〇莫耳, and the organic solvent exemplified for the polyglycolic acid is exemplified. Solvent. The reaction temperature for dehydration is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C. It is preferably 1.0 to 120 hours, more preferably 2 to 0 to 30 hours. Thus, a reaction solution containing polyimine can be obtained. The method can be directly used for preparing a liquid crystal alignment agent, and can also be used for preparing a liquid crystal alignment agent after preparing a liquid crystal with a dehydrating agent and a dehydration ring-closing catalyst, and can be used for preparing a liquid crystal alignment agent; The ring structure may be added in the form of a solution of isostamic acid. Its cyclic catalyst anhydride, propionic acid 1 mole condensation dehydration ring closure, dimethyl amount, phase. In the case of dehydration as a synthesis, a ring closure reaction, a reaction time, a reaction solution, a solution-removing agent, and a method of preparing a liquid crystal alignment agent after the purification of the polysiloxane of 201132703 is carried out. These purification operations can be carried out according to a known method. <Solid viscosity of polymer> The specific polymer obtained as above preferably has a solution viscosity of 20 to 800 mPa's, more preferably 30 to 500 mPa, when it is formed into a solution having a concentration of 丨0% by weight. .s solution viscosity. The solution viscosity (mPa.s) of the above polymer is a good solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) using the polymer to prepare a polymer solution having a concentration of 1% by weight. The enthalpy measured at 25 ° C using a 旋转-type rotary viscometer. <Other Additives> The liquid crystal alignment film of the present invention contains the above specific polymer as an essential component. Depending on the necessity, other components may be contained. The other component may, for example, be another polymer, a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy compound"), a functional decane compound or the like. [Other Polymers] The above other polymers can be used to improve solution properties and electrical properties. The other polymer is a polymer other than the specific polymer, and examples thereof include a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine, and 13, 23, 411 with respect to all tetracarboxylic dianhydrides. The content of at least one selected from the group consisting of 511-cyclohexanetetracarboxylic dianhydride and 1R, 2S, 4S, 5R-cyclohexyltetradecanoic acid dianhydride is less than 5 mol%, or more than 8 〇. Mole% -20-201132703 Poly-proline (hereinafter referred to as "other poly-proline"), polyimine formed by dehydration of the polyamine (hereinafter referred to as "other poly"醯imino"), polyphthalate, polyester, polyamine, polyoxyalkylene, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-phenyl malayan Amine derivatives, poly(meth)acrylates, and the like. Among them, other polyamines and other polyimines, more preferably other polyamines, are preferred. The tetracarboxylic dianhydride used for the synthesis of the above other polyaminic acid or other polyimine may be the same as the other tetracarboxylic dianhydride which is preferably used for synthesizing a specific polymer. The tetracarboxylic dianhydride is preferably used from 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. And l,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene[1,2-c]furan-1,3 - At least one selected from the group consisting of diketones. As the diamine for synthesizing the above other polyaminic acid or other polyimine, it is preferred to use at least one selected from the diamines exemplified above as the diamine used in the synthesis of the specific polymer. One. For the diamine used for the synthesis of other poly-proline or other polyimine, it is preferred to use 4,4'-diaminodiphenylmethane, 2,2.-dimethyl-4, 4'-diaminobiphenyl, cholesteryl-2,4-diaminobenzene, 3,5-diaminobenzoic acid and 1,4-bis-(4-aminophenyl) piperidine At least one selected from the group consisting of. With respect to the ratio of use of other polymers, it is preferably 50% by weight or less, more preferably 40% by weight based on the total amount of the polymer (refer to the total amount of the above specific polymer and other polymers, the same applies hereinafter). Below, further better - 21 - 201132703 is 30% by weight or less. When other polymers are used, they are used in proportion to the total amount of the polymer, and as long as it is 0.1% by weight or more, the effect of the addition can be intentionally found. [Epoxy compound] The epoxy compound may be contained in the liquid crystal agent of the present invention for the purpose of further improving the adhesion and heat resistance of the obtained liquid crystal alignment film pair. The epoxy compound is preferably a compound having 2 or more epoxy groups in the molecule, and examples thereof include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol diglycidyl ether. Glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol di-distillate, trimethylolpropane triglycidyl ether, 2, 2-Dibromo neopentyl diglycidyl ether, N,N,N',N'-tetraglycidyl-m-xylylenediamine, bis(indole, hydrazine-diglycidylaminomethyl)cyclohexane Alkane, N, N, N', N'-tetraglyceryl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-amine, N,N-diglycidyl-amine Methylcyclohexane, N,N-dihydrocarbyl-cyclohexylamine, and the like. If the epoxy compound is used in a too small proportion, the above-mentioned desired effect cannot be sufficiently obtained. On the other hand, if the use ratio is too large, the reworkability and abrasion resistance of the liquid crystal alignment film are impaired. Based on this viewpoint, the total proportion of the polymer is 100 parts by weight, and the mixing ratio of the epoxy compound is more than 3 parts by weight, more preferably 0.1 to 15 parts by weight, and even more preferably, the substrate is aligned with the glycerin. The propanol diglycerol di1,3-1,3-hydric benzyl glycerol is preferably from 5.5 to 8 -22 to 201132703 parts by weight, particularly preferably from 1 to 3 parts by weight. [Functional decane compound] The above functional decane compound may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane or 2-aminopropyltrimethoxy Baseline, 2-aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3 Aminopropylmethyldimethoxydecane, 3-guanidinopropyltrimethoxydecane, 3-guanidinopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxy Baseline, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxymethylidenepropyltriethylenetriamine, N-trimethoxymethylidenepropyltrifate Ethyltriamine, 10-trimethoxycarbamimidyl-1,4,7-triazadecane, 10-triethoxycarbamido-1,4,7-triazadecane, 9- Trimethoxycarbamido-3,6-diazadecyl acetate, 9-triethoxycarbamido-3,6-diazadecyl acetate, 9-trimethoxyformane Methyl-3,6-diazadecanoate, methyl 9-triethoxycarbamido-3,6-diazepine, Ν·benzyl-3_amino Propyltrimethoxydecane, N.benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyl Triethoxy decane, glycidoxymethyl trimethoxy decane, glycidoxymethyl triethoxy decane, 2-glycidoxyethyl trimethoxy sulane, 2-glycidoxy Ethyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and the like. The mixing ratio of these functional decane compounds -23 to 201132703 is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight, based on 100 parts by weight of the total of the polymer. <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention is obtained by dissolving and dissolving the above specific polymer and other additives optionally mixed as needed in a preferred organic solvent. Examples of the organic solvent used in the liquid crystal alignment agent of the present invention include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, hydrazine, hydrazine-dimethyl methacrylate. Indoleamine, hydrazine, hydrazine-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methoxypropionate Ester, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl 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, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, Diisoamyl ether, ethylene carbonate, propylene carbonate, and the like. They may be used singly or in combination of two or more. The solid content concentration in the liquid crystal alignment agent of the present invention (the ratio of the total weight of the components other than the solvent of the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc., preferably 1 to 1范围 The range of weight %. That is, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate as described later, preferably by heating to form a coating film of a liquid crystal alignment film or a coating film formed by a liquid crystal alignment film of -24-201132703, but in a solid content. When the concentration is less than 1% by weight, the film thickness of the coating film is too small, and it may be difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film is too large, and it is difficult to obtain a good liquid crystal. The alignment film, and the viscosity of the liquid crystal alignment agent is increased, and the coating property is insufficient. The range of the particularly preferable solid content concentration varies depending on the method employed in coating the liquid crystal alignment agent on the substrate. For example, when the spin coating method is used, the solid content concentration is particularly preferably in the range of from 1.7 to 4.5% by weight. When the printing method is used, the solid content concentration is in the range of 3 to 9 % by weight, whereby the solution viscosity is particularly preferably in the range of 12 to 5 OmP a·s. When the inkjet method is used, the solid content concentration is in the range of 1 to 5 wt%, whereby the solution viscosity is particularly preferably in the range of 3 to 15 mPa-s. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably from 10 to 50 ° C, more preferably from 20 to 30 ° C. <Liquid Crystal Display Element> The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention as described above. More specifically, the liquid crystal display element of the present invention is formed by arranging a polarizing plate on both outer surfaces of the liquid crystal cell, wherein the liquid crystal cell has a substrate in which two liquid crystal alignment films are opposed to each other to make each liquid crystal The alignment film surface faces the structure of the liquid crystal layer sandwiching the gap' and the liquid crystal alignment film is formed of the liquid crystal alignment agent of the present invention. The liquid crystal display element of the present invention can be produced, for example, by the following steps (1) to (3). Step (1) is different depending on the desired operating mode, using the substrate -25- 201132703. Steps (2) and (3) are the same in various operating modes. (1) First, the liquid crystal alignment agent of the present invention is applied onto a substrate, and then a coating film is formed on the substrate by heating the coated surface. (1-1) When manufacturing a TN type, STN type, or VA type liquid crystal display element, a pair of two substrates on which a patterned transparent conductive film is provided on one surface is formed in a pair, and each of the transparent conductive film forming surfaces is formed. Preferably, the liquid crystal alignment agent of the present invention is applied by a lithography method, a spin coating method or an inkjet printing method, and then each coating surface is heated to form a coating film. At this time, as the substrate, for example, glass such as float glass or soda glass; polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, poly A transparent substrate formed of plastic such as (alicyclic olefin). As the transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark of PPG, USA) formed of tin oxide (SnO 2 ), an ITO film formed of indium oxide-tin oxide (In 2 03 -SnO 2 ), or the like can be used. In order to obtain a patterned transparent conductive film 'a method of forming a pattern by photo-etching after forming a pattern-free transparent conductive film, for example, when a transparent conductive film is formed, a method using a photomask having a desired pattern or the like is obtained. . When the liquid crystal alignment agent is applied, in order to improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, a functional decane compound or a functional titanium compound may be applied to the surface of the substrate on which the coating film should be formed. Pre-processing. After the liquid crystal alignment agent is applied, it is preferably preheated (pre-baked) for the purpose of preventing the flow of the coated alignment agent droplets. The prebaking temperature is preferably from 30 to 200 ° C, more preferably from 40 to 150 ° C, and particularly preferably from 40 to 1 °. Hey. Pre-supply -26- 201132703 The baking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Thereafter, based on the complete removal of the solvent, the target of the poly-proline is thermally imidized as needed to carry out the firing (post-baking) step. The firing (post-baking) temperature is preferably from 80 to 300 ° C, more preferably from 120 to 2 50 ° C. The post-baking time is preferably from 5 to 200 minutes', more preferably from 10 to 100 minutes. Thus, the film thickness of the formed film is preferably 〇·〇〇1~1μηι ’ more preferably 0.005 〇.5μηι. (1-2) On the other hand, when manufacturing a liquid crystal display element of a horizontal electric field type, a conductive film forming surface of a substrate on which a transparent conductive film of a comb-shaped pattern is formed and a counter substrate on which a conductive film is not provided are provided On one side, the liquid crystal alignment agent of the present invention is applied, and then each coating surface is heated to form a coating film. The material of the substrate and the transparent conductive film used at this time, the patterning method of the transparent conductive film, the pretreatment of the substrate, the method of applying the liquid crystal alignment agent, the heating method after applying the liquid crystal alignment agent, and the film thickness of the formed coating film and the above (1 -1) is the same. (2) When the liquid crystal display element produced by the method of the present invention is a VA type liquid crystal display element, the coating film formed as described above can be directly used as a liquid crystal alignment film, and if necessary, the following rubbing treatment can be used. On the other hand, when a liquid crystal display element other than the VA type is produced, the coating film formed as described above is subjected to a rubbing treatment to form a liquid crystal alignment film. The rubbing treatment is carried out by rubbing a coating film formed as described above on a roll formed of a fabric such as nylon, rayon, cotton or the like in a certain direction by rubbing -27-201132703. Thus, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. Then, the liquid crystal alignment film formed as described above is treated, for example, by irradiating a part of the liquid crystal alignment film with ultraviolet rays and changing the pretilt angle of a partial region of the liquid crystal alignment film (refer to Japanese Patent Laid-Open No. Hei 6-222366) In the case of forming a photoresist film on a part of the surface of the liquid crystal alignment film, after performing rubbing treatment in a direction different from the previous rubbing treatment, the photoresist is removed. In the treatment of the film, the viewing angle property of the obtained liquid crystal display element can be improved by having different liquid crystal alignment ability in each region of the liquid crystal alignment film (refer to Japanese Laid-Open Patent Publication No. Hei No. 5-105044). Two substrates in which the liquid crystal alignment film is formed as described above are prepared, and liquid crystal cells are produced by disposing liquid crystal between the two substrates arranged in the opposite direction. Here, when the coating film is subjected to rubbing treatment, the two substrates are opposed to each other so that each The rubbing directions of the coating film are at a predetermined angle to each other, for example, orthogonal or antiparallel. When manufacturing the liquid crystal cell, for example, the following two types may be mentioned. The first method is a currently known method. First, the liquid crystal alignment films are opposed to each other, and the two substrates are arranged to face each other by a gap (cell gap), and the peripheral portions of the two substrates are used using a sealant. After bonding, the liquid crystal cell can be manufactured by injecting the liquid crystal into the cell gap divided by the surface of the substrate and the sealant, and sealing the injection hole. The second method is called 〇DF (〇ne Drop Fill). A method of coating, for example, a UV curable sealing material on a substrate of one of two substrates forming a liquid crystal alignment film, and then dropping it at a prescribed number of positions on the liquid crystal alignment film surface After the liquid crystal, the other substrate is bonded and the liquid crystal alignment film is opposed to 'the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealing agent, thereby producing a liquid crystal cell. In the case of the method, it is desirable to reheat the liquid crystal cell produced as above to the temperature of the liquid crystal isotropic phase to be used, and then slowly cool to room temperature to remove the flow alignment during liquid crystal injection. In the following, a liquid crystal display element of the present invention can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell. In this case, as the sealing agent, for example, an epoxy resin containing a curing agent and an alumina ball as a separator can be used. For the liquid crystal, a nematic liquid crystal, a dish liquid crystal, or the like can be used. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxidized azo liquid crystal, or a 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. In these liquid crystals, a cholesteric liquid crystal such as dihydrocholesterol chloride, cholesterol decanoate or cholesterol carbonate may be further added; a chiral reagent sold under the trade names C-15 and CB-15 (manufactured by Merck); A ferroelectric liquid crystal such as p-oxybenzylidene-p-amino-2-methylbutyl cinnamate or the like. For the polarizing plate attached to the outer surface of the liquid crystal cell, a cellulose acetate protective film clip for a polarizing film in which the absorbing iodine is called a "ruthenium film" is used as a -29-201132703 延-stretching polyvinyl alcohol. A polarizing plate that lives or a polarizing plate that is formed by the diaphragm itself. [Examples] Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited by the examples. The solution viscosity of each of the polymer solutions in the polymerization example and the oxime imidization ratio of the polyimine were measured by the following methods. [Solution viscosity of polymer solution] The solution viscosity (mPa_s) of the polymer was measured at 25 ° C using an E-type rotational viscometer under the solvents and concentrations described in the respective synthesis examples. [Iridium imidization ratio of polyimine] A small amount of a solution of polyimine is taken, and it is poured into pure water, and the obtained precipitate is sufficiently dried under reduced pressure at room temperature, and then dissolved in dimethyl hydrazine. In the above, 1H-NMR was measured at room temperature using tetramethylnonane as a reference material. From the obtained 1H-NMR spectrum, the oxime imidization ratio was determined from the formula represented by the following formula (1).醯imination rate (%) = (l-AWA^cOxlOO (1) In the mathematical formula (1), A1 is the peak area of the proton from the NH group which appears near the chemical shift l〇ppm, and A2 is from other The peak area of the proton, α is the ratio of the number of other protons to the protons of the sulfhydryl group in the precursor of one polymer (polyproline). -30- 201132703 <Synthesis and Stability Evaluation of Polymer for TN Type Liquid Crystal Aligning Agent> [Synthesis Example of Polylysine as Specific Polymer] Synthesis Example Α-ΤΝ1 112 g as tetracarboxylic dianhydride (〇.50) Mohr) 13,23,411,511_cyclohexanetetracarboxylic dianhydride and l〇9g (〇.50 mol) pyromellitic dianhydride and 198 g (1.0 mol) 4,4'-diamine as diamine Diphenylmethane was dissolved in a mixed solvent of 246 g of N-methyl-2-pyrrolidone and 2,213 g of γ-butyrolactone, and reacted at 40 ° C for 3 hours to obtain 1 5 A solution of wt% polyaminic acid (A-TN1). The solution had a solution viscosity of 179 mPa.s. The polymer solution was allowed to stand at 20 ° C for 3 days without gelation, and the storage stability was good. Synthesis Example A - TN 2 67 g (0.30 mol) of 111,28,43,511-cyclohexanetetracarboxylic dianhydride and 153 g (〇.7〇mol) pyromellitic dianhydride as tetracarboxylic dianhydride And 198 g (1.0 mol) of 4,4·-diaminodiphenylmethane as a diamine dissolved in 246 g of N-methyl-2-pyrrolidone and 2,213 g of γ-butyrolactone The reaction was carried out at 40 ° C for 3 hours in a mixed solvent to obtain a solution containing 15% by weight of polyaminic acid (A-TN 2 ). The solution had a solution viscosity of 153 mPa.s. The polymer solution was allowed to stand at 20 ° C for 3 days without gelation, and the storage stability was good. [Synthesis Example of Other Polylysine] Synthesis Example a - TN 3 i〇9g (〇_50 mol) pyromellitic dianhydride as tetracarboxylic dianhydride and -31-201132703 98g (0.50 mole) ) 1,2,3,4-cyclobutane tetracarboxylic dianhydride and 198 g (1.0 mol) of 4,4'-diaminodiphenylmethane as a diamine, dissolved in N by 23 〇g -Methyl-2-pyrrolidone and 2,068 g of γ-butyrolactone in a mixed solvent 'reacted at 4 ° C for 3 hours to obtain 15% by weight of polyglycine (a-TN3) Solution. The solution has a solution viscosity of l93 mPa.s. The polymer solution was allowed to stand at 201 for 3 days without gelation, and the storage stability was good. [Synthesis Example of Polyimine as a Specific Polymer] Synthesis Example B-TN1 112 g (0.50 mol) of 13,28,411,511-cyclohexanetetracarboxylic dianhydride and 112 g of tetracarboxylic dianhydride ( 0.50 mol) 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and l〇6g (0.985 mol) p-phenylenediamine as a diamine and 7.8 g (0.015 mol) 3-(3,5- The diaminobenzimidyloxy)cholestane was dissolved in 3,042 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 6 hours to obtain a solution containing polylysine. The solution of the polyaminic acid solution obtained here has a viscosity of 160 mPa-se. In the obtained polyaminic acid solution, 3,380 g of N-methyl-2-indolepyridone is added with 3 9.5 g of pyridine and 3 0 6 g acetic anhydride, at! A 4 hour dehydration ring closure reaction was carried out at 丨〇 °c. After the dehydration ring closure reaction, the solvent in the system is replaced with a new γ-butyrolactone solvent (by the operation, the pyridine and acetic anhydride used in the oxime imidization reaction are removed to the outside of the system, the same applies hereinafter), Concentrated to give a solution containing 10% by weight of polyamidimide (Β - Τ Ν 1) having a ruthenium iodide ratio of about 94%. -32- 201132703 A small amount of this solution was taken', and γ-butyrolactone was added to form a solution having a concentration of 6% by weight, and the measured solution viscosity was 28 mPa's. The polymer solution was allowed to stand at 20 °C for 3 days without gelation, and the storage stability was good. [Synthesis Example of Other Polyimine] Synthesis Example b-TN2 ll〇g (〇.5〇莫耳) 2,3,5-trimethylcyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride 155g (0.50 mole) 1,3,3&,4,5,915-hexanitro-8-methyl-5·(tetrahydro-2,5-di-oxo-3-furanyl)naphthalene [l,2- c] furan dioxime, 92 g (0.87 mol) p-phenylenediamine as a diamine, 25 g (〇. 1 mol) bis(aminopropyl)tetramethyldioxane and 13 g ( 0.02 mol) 3,6_bis(4-aminobenzylideneoxy) biliary hospital and 2.7 g (〇.〇3〇mol) aniline as a monoamine, dissolved to 960 g of N-methyl- In 2-pyrrolidone, a solution containing polylysine is obtained by reacting at 6 (rc for 6 hours). A small amount of the obtained polyamic acid solution is added to the solution of N-methyl-2-indole. A solution having a concentration of polyacrylic acid of 1% by weight was measured to have a solution viscosity of 59 mPa·s. Next, 2,700 g of N-methyl-2-pyrrolidone was added to the obtained polyaminic acid solution to add 396 g. Pyridine and 409 g of acetic anhydride were subjected to dehydration ring closure at 110 ° C for 4 hours. After dehydration ring closure reaction, the solvent in the system was treated with new γ - butyrolactone. The agent was replaced, and further concentrated to obtain about 2,520 g of a solution containing 15% by weight of a polyamidimide (b-TN2) having a ruthenium iodide ratio of about 95%. A small amount of the polyimine solution was added to add γ - Butyrolactone, a solution having a polyamidene concentration of 6.0% by weight, and a solution viscosity of i8 rnPa.s. -33- 201132703 The polymer solution was allowed to stand at 20 ° C for 3 days without gelation and stable storage. Good performance. Synthesis Example b-TN3 224 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride and 106 g (0.985 mole) as a diamine Phenylenediamine and 7.8 g (0.015 mol) of 3-(3,5-diaminobenzylideneoxy)cholestane, dissolved in 3, g42 g of N-methyl-2-pyrrolidone, The reaction was carried out at 60 ° C for 6 hours to obtain a solution containing polylysine. The solution viscosity of the polyamic acid solution obtained here was 181 mPa*s. 3,380 g was added to the obtained polyaminic acid solution. N-.methyl-2-pyrrolidone, adding 395 g of pyridine and 306 g of acetic anhydride, and performing a dehydration ring-closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system is treated with a new γ-butyrolactone solvent. Set And further concentrated to obtain a solution containing 1% by weight of hydrazine imidization of about 95% of polyimine (b-TN3). The solution was added in small portions, and γ-butyrolactone was added to form a concentration of 6% by weight. Solution, the measured solution viscosity was 35xnPai» The polymer solution was allowed to stand at 20 ° C for 3 days, without gelation, and the storage stability was good. <Synthesis and Stability Evaluation of Polymer for VA Type Liquid Crystal Alignment Agent> [Synthesis Example of Polyimine as Specific Polymer] Synthesis Example B-VA1 112 g (0.50 mol) as tetracarboxylic dianhydride 13,23,411,511-cyclohexanetetracarboxylic dianhydride and 112 g (0.50 mol) 2,3,5-tricarboxycyclopentylethyl-34-201132703 acid dianhydride and 52 g as a diamine (0.1 Mo Ear) cholesteryl 3,5-diaminobenzoate, 49 § (0.1 mol) cholestyloxy-2,4-diaminobenzene and 87 g (0.80 mol) p-phenylenediamine, The solution was dissolved in 1,652 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 6 hours to obtain a solution of polylysine. A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 79 mPa·s. Next, the obtained polyamine was obtained. 3,835 g of N-methyl-2-pyrrolidone was added to the acid solution, and 79 g of pyridine and 1 g of acetic anhydride were added, and dehydration ring closure was carried out for 4 hours at ll °C. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent to obtain a polyimine (B _ containing about 15% by weight of ruthenium iodide ratio of about 51%, respectively). A solution of VA 1 ). A small amount of the obtained polyimine solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a concentration of 10% by weight of polyimine. The measured solution viscosity was 102 mPa·s. The polymer solution was After standing at 20 ° C for 3 days, there is no gelation, and the storage stability is good. Synthetic Example B-VA2 will be used as H2g of tetracarboxylic dianhydride (0.50 Moer's four-residual acid dianhydride and 112g (0.50 mol) 2,3,5-three-residual cyclopentyl acetic acid dianhydride and 52 g (〇.l mole) 3,5-diaminobenzoic acid as a diamine, biliary, 49 § (0.1 Mo Ear) bile-retained oxy-2,4-diaminobenzene and 87g (0.80 mol) p-phenylamine, dissolved in 1,652 g of N-methyl-2-indole-35-201132703 Medium 'reaction at 60 ° C for 6 hours to obtain a solution of poly-proline. The obtained poly-proline solution was added in small portions, and N-methyl-2-pyrrolidone was added to form a polymer concentration of 10% by weight. The solution was measured to have a solution viscosity of 71 mPa. S ° Next, 3,835 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 79 g of pyridine and 102 g of acetic anhydride were added thereto at 11 Torr. (: 4 hours of dehydration After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent to obtain a polyimine (B·) containing about 15% by weight of a ruthenium iodide ratio of about 48%. a solution of VA 2 ). The obtained polyimine solution was added in small portions, and N-methyl-2-pyrrolidone was added to form a solution having a concentration of 10% by weight of polyimine, and the viscosity of the solution was determined to be 9 9 m. P a. s. The polymer solution was allowed to stand at 20 ° C for 3 days without gelation, and the storage stability was good. Synthesis Example B - VA 3 45 g (0.20 mol) as a tetracarboxylic dianhydride 1S , 2S, 4R, 5R-cyclohexane tetracarboxylic dianhydride and 180g (0.80 mole) 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and lQ5g (0.20 mole) as a diamine 3,5 - cholesteryl diaminobenzoate and 87 g (0.80 mol) of p-phenylenediamine, dissolved in 1,663 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 6 hours. A solution of polylysine was obtained. The obtained poly-proline solution was added in small portions, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 1% by weight, and the measured solution viscosity was 59 mPa-s. Then, in the resulting poly 3,8 6 lg of N-methyl-36-201132703 -2 -pyrrolidone was added to the amine acid solution, and 79 g of pyridoxine and 102 g of acetic anhydride were added, and dehydration ring closure was carried out for 4 hours at ii ° ° C. After the reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent to obtain a solution containing about 15% by weight of a polyamidimide (B-VA3) having a ruthenium iodide ratio of about 47%. . A small amount of the obtained polyimine solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a polyamidene concentration of 10% by weight, and the measured solution viscosity was 80 mPa·s. The polymer solution was allowed to stand at 20 ° C for 3 days without gelation, and the storage stability was good. Synthesis Example B - VA 4 45 g (0.20 mol) of 1 bar, 28,43,511-cyclohexanetetracarboxylic dianhydride and 180 g (0.80 mol) of 2,3,5-tricarboxyl as tetracarboxylic dianhydride Cyclopentyl acetic acid dianhydride and as a diamine, 5 g (0.2 mol) of 3,5-diaminobenzoic acid cholesteryl ester and 87 g (0.80 mol) of p-phenylenediamine, dissolved to 1,66 3 g of N-methyl-2-pyrrolidone was reacted at 60 ° C for 6 hours to obtain a solution of polylysine. A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 1% by weight, and the measured solution viscosity was 6 6 m P a · s 〇 Next, To the obtained polyaminic acid solution, 3,861 g of N-methyl-2-pyrrolidone was added, and 79 g of pyridine and 1 g of acetic anhydride were added, and dehydration ring closure was carried out for 4 hours at li ° C. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent to obtain a polyimine (B-VA4) containing about 15% by weight of hydrazine imidization rate of about 50%. )The solution. A small amount of the obtained polyimine solution was added, and N-methyl-2-pyrrolidone was added to form a solution of poly-37-201132703 yttrium imine concentration of 〇% by weight, and the measured solution viscosity was 89 mPa·s. The polymer solution was allowed to stand at 2 ° C for 3 days without gelation, and the storage stability was good. Synthesis Example B-VA5 135 g (0.60 mol) of 13,23,411,511-cyclohexanetetracarboxylic dianhydride and 90 g (0.40 mol) of 2,3,5-tricarboxycyclopentane as tetracarboxylic dianhydride Acetic acid dianhydride and as a diamine, 5 g (0.2 Torr) 3,5-diaminobenzoic acid cholesteryl ester, 65 g (0.60 mol) p-phenylenediamine and 30 g (0.20 mol) 3,5-Diaminobenzoic acid was dissolved in 1,697 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 6 hours to obtain a polyaminic acid solution. A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 50 mPa·s. Next, 3,939 g of N-methyl-2-pyrrolidone was added to the obtained polyaminic acid solution, and 1 19 g of pyridine and 153 g of acetic anhydride were added thereto, and the mixture was subjected to 1 hour at 10 ° C for 4 hours. Dehydration closed loop. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent to obtain a polyamidene containing about 15% by weight of ruthenium iodide (B- Solution of VA5). A small amount of the obtained polyimine solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a concentration of 10% by weight of polyimine, and the viscosity of the solution was determined to be 79 mPa·S 0 . The polymer solution was 20 After standing at °c for 3 days, there was no gelation and the storage stability was good. Synthesis Example B - VA 6 -38- 201132703 45 g (0-20 mol) of 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride and 179 g (0.80 mol) 2 as tetracarboxylic dianhydride. 3,5-tricarboxycyclopentyl acetic acid dianhydride and 131 g (0.25 mol) of cholesteryl 3,5-diaminobenzoic acid as a diamine, 53 g (0.50 mol) of p-phenylenediamine and 38 g (0.25 mol) 3,5-diaminobenzoic acid was dissolved in 1,697 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 6 hours to obtain a polyaminic acid solution. A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 5 8 m P a · s. Next, 3,939 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 19 g of pyridine and 153 g of acetic anhydride were added, and dehydration ring closure was carried out for 4 hours at 1 l °C. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent to obtain a polyimine (B-VA6) containing about 15% by weight of an oxime imidization rate of about 69%. The solution. A small amount of the obtained polyimine solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a polypyridamine concentration of 10% by weight, and the measured solution viscosity was 81 mP a.s. The polymer solution was allowed to stand at 20 ° C for 3 days without gelation, and the storage stability was good. [Synthesis Example of Other Polyimine] Synthesis Example b - VA 7 224 g (l. oxime) 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride and as a diamine 52 g (〇.10 mol) 3,5-diaminobenzoic acid cholesteryl ester, 49 g (0.10 mol) cholestyloxy-2,4-diaminobenzene and 87 g (0.80 Mo The o-phenylenediamine was dissolved in 1,652 g of N-methyl-2-pyrrole-39-201132703 steep ketone and reacted at 60 ° C for 6 hours to obtain a polyaminic acid solution. A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 70 mPa.s. Next, 3,83 5 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 79 g of pyridine and 102 g of acetic anhydride were added thereto at 11 Torr. (: 4 hours dehydration ring closure. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent to obtain a sulfonium iodide ratio of about 15% by about 15%. a solution of polyimine (b-VA7). The obtained polyimine solution was added in small portions, and N-methyl-2-pyrrolidone was added to form a solution having a concentration of 10% by weight of polyimine, and the solution was determined. The viscosity is 80 mPa·s. The polymer solution is allowed to stand at 2 (TC for 3 days, no gelation, and the storage stability is good " Synthesis Example b - VA 8 will be 224 g (1.0 mol) of tetracarboxylic dianhydride. 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and l〇5g (0.20 mol) 3,5-diaminobenzoic acid cholesteryl ester as a diamine, 65 g (0.60 mol) Phenylenediamine and 30 g (0.20 mol) of 3,5-diaminobenzoic acid were dissolved in 1,697 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours to obtain a poly Proline acid solution. The obtained poly-proline solution was added in small portions, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 10% by weight. The measured solution viscosity was 50 mPa's. Income 3,939 g of N-methyl-2-pyrrolidone was added to the polyaminic acid solution, and 1 19 g of pyridine and 153 g of acetic anhydride were added to carry out dehydration ring closure at 1 l ° C for 4 hours. The solvent in the solvent was replaced with a new N-methyl-2-pyrrolidone solvent of -40-201132703 to obtain a polyimine (b - VA 8) containing about 15% by weight of ruthenium iodide of about 67%. A solution of the obtained polyimine solution was added in small portions, and N-methyl-2-pyrrolidone was added to form a solution having a concentration of 10% by weight of polyimine, and the viscosity of the solution was determined to be 73 mPa_s. After standing at 20 ° C for 3 days, there was no gelation and the storage stability was good. <Synthesis and Stability Evaluation of Polymer for IPS Type Liquid Crystal Alignment Agent> [Synthesis Example of Polylysine as Specific Polymer] Synthesis Example A-IPS 1 45 g (0.20 M) as tetracarboxylic dianhydride Ear) 13,28,411,511-cyclohexanetetracarboxylic dianhydride and 174 g (0.80 mol) pyromellitic dianhydride and as a diamine, 8 g (l. mol) p-phenylenediamine, dissolved The reaction was carried out at 1,900 g of N-methyl-2-pyrrolidone at 40 ° C for 3 hours to obtain a solution containing 15% by weight of polyaminic acid (A-IPS 1). A small amount of this solution was taken, and N-methyl-2-pyrrolidone was added to form a solution having a polyamine concentration of 10% by weight, and the measured solution viscosity was 75 mPa's. The polymer solution was allowed to stand at 20 ° C for 3 days without gelation, and the storage stability was good. [Synthesis Example of Other Polylysine] Synthesis Example a -1P S 2 In addition to 190 g (0.85 mol) of 1 ft, 23,43,511-cyclohexanetetracarboxylic dianhydride and 33 g (0.15 mol) of benzene were used. The acid dianhydride was obtained as a tetracarboxylic dianhydride in the same manner as in the synthesis example A-1S S 1 . /〇polyglycolic acid -41 - 201132703 (a-IPS2) solution. A small amount of the solution was taken, N-methyl-2-pyrrolidone was added to form a solution having a polyglycine concentration of 10% by weight, and the measured solution viscosity was 63 mPa's. » The polymer solution was allowed to stand at 20 ° C. When it was placed for 3 days, gelation was observed and the storage stability was poor. The polyamic acid (a-IPS2) was not subjected to other evaluation. [Synthesis Example of Polylysine as Specific Polymer] Synthesis Example A -1P S 3 180 g (0.80 mol) of 13,28,411,511-cyclohexanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 44 g (0.20 mol) of pyromellitic dianhydride and 160 g (0.80 mol) of 4,4'-diaminodiphenyl ether as diamine and 110 g of p-phenylenediamine. The solution was dissolved in 2,300 g of N-methyl-2-pyrrolidone, and reacted at 40 ° C for 3 hours to obtain a solution containing 15% by weight of poly-proline (A-IPS3). A small amount of this solution was taken, and N-methyl-2-azalidone was added to form a solution having a polyamine concentration of 10% by weight, and the measured solution viscosity was 74 mPa·s. When the polymer solution was allowed to stand at 20 ° C for 3 days, it was not gelated and the storage stability was good. Synthesis Example A -1P S 4 In addition to using 180 g (0.80 mol) of 111,23,43,511-cyclohexanetetracarboxylic dianhydride and 44 g (0.20 mol) of pyromellitic dianhydride as the tetracarboxylic dianhydride, In the same manner as in Synthesis Example A-IPS3, a solution containing 15% by weight of poly-proline (A-IPS4) was obtained. -42- 201132703 A small amount of this solution was taken, and N-methyl-2-pyrrolidone was added to form a solution having a polyglycine concentration of 10% by weight, and the measured solution viscosity was 60 mPai. When the polymer solution was allowed to stand at 20 ° C for 3 days, it was not gelated, and the storage stability was good. Synthesis Example A-IPS5 180 g (0.80 mol) of 1S, 2S, 4R, 5R·^ hexane tetracarboxylic dianhydride and 44 g (0.20 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride and as 200 g (1.0 mol) of 4,4'-diaminodiphenylamine of diamine was dissolved in 2,400 g of N-methyl-2-pyrrolidone and reacted at 40 ° C for 3 hours to obtain A solution containing 15% by weight of polyaminic acid (A-IPS5). A small amount of this solution was taken and 'N-methyl-2-pyrrolidone was added to form a solution having a polypyridic acid concentration of 1% by weight. The solution viscosity was determined to be 6 5 mP a.s. When the polymer solution was allowed to stand at 20 ° C for 3 days, it was not gelated, and the storage stability was good. Synthesis Example A-IPS6 In addition to using 180 g (0.80 mol) of 1 Han, 23, 43, 511-cyclohexane tetracarboxylic dianhydride and 44 g (0.2 Torr) of pyromellitic dianhydride as tetracarboxylic dianhydride, respectively Using 10 〇g (〇·50 mol) of 4,4,-diaminodiphenyl ether and 100 g (0.5 Torr) of 4,4'-diaminodiphenylamine as tetracarboxylic dianhydride A solution containing 5% by weight of polyglycine (A-IPS6) was obtained in the same manner as in Synthesis Example A-IPS5. A small amount of this solution was taken and 'N-methyl-2-pyrrolidone was added to form a solution having a polyaminic acid concentration of 1% by weight, and the measured solution viscosity was 70 mPa·s. -43- 201132703 When the polymer solution was allowed to stand at 20 ° C for 3 days, it was not gelled and the storage stability was good. [Synthesis Example of Other Polylysine] Synthesis Example a-IPS 7 224 g (l. oxime) 13, 28, 411, 511-cyclohexane tetracarboxylic dianhydride as a tetracarboxylic dianhydride and as a diamine L〇8g (l. 〇mol) p-phenylenediamine, dissolved in 1,900 g of N-methyl-2-pyrrolidone, reacted at 40 ° C for 3 hours to obtain 15 A solution of wt% polyaminic acid (a-IPS7). A small amount of this solution was taken, and N-methyl-2-pyrrolidone was added to form a solution having a polyglycine concentration of 10% by weight, and the measured solution viscosity was .99 mPa·s. When the polymer solution was allowed to stand at 20 ° C for 3 days, gelation was observed and the storage stability was poor. No other evaluation was made on this polyaminic acid (a-IPS 7). Synthesis Example a-IPS8 In the same manner as in Synthesis Example A -1P S 5 except that 224 g (1.0 mol) of one foot and 23,43,511-cyclohexanetetracarboxylic dianhydride were used as the tetracarboxylic dianhydride. A solution of wt% polyaminic acid (a-IPS8). This solution was in the form of a solution at a reaction temperature (40 t), and gelation occurred during cooling to room temperature, so that the viscosity could not be measured. No other evaluation was made for this polyamine acid (a-IPS 8). Synthesis Example a-IPS9 220 g (1.0 mol) pyromellitic dianhydride as a tetracarboxylic dianhydride and 110 g (1.0 mol) p-phenylenediamine as a diamine were dissolved to 1,800 g of -44 - 201132703 N-methyl-2-pyrrolidone was reacted at 40 ° C for 3 hours to obtain a solution containing 15% by weight of polyaminic acid (a-IPS9). The solution viscosity of the solution was 180 mPa-S. . When the polymer solution was allowed to stand at 20 ° C for 3 days, it was not gelated, and the storage stability was good. Synthesis Example a -1P S 1 0 220 g (1.0 mol) pyromellitic dianhydride as tetracarboxylic dianhydride and 160 g (0.80 mol) 4,4'-diaminodiphenyl as diamine The ether and 22 g (0.20 mol) of p-phenylenediamine were dissolved in 2,300 g of N-methyl-2-pyrrolidone and reacted at 40 ° C for 3 hours to obtain 15 wt% polyfluorene. A solution of aminic acid (a-1P S 1 0). A small amount of the solution was taken and 'N-methyl-2-pyrrolidone was added to form a solution having a polyaminic acid concentration of 1% by weight, and the measured solution viscosity was 71 mP a·s. When the polymer solution was allowed to stand at 20 ° C for 3 days, it was not gelated and the storage stability was good. Synthesis Example a -1P S 1 1 20 〇g (〇.90 mol) pyromellitic dianhydride and 20 g (0.10 mol) 1,2,3,4-cyclobutane as tetracarboxylic dianhydride Alkane tetracarboxylic dianhydride and 160 g (0.80 mol) of 4,4'-diaminodiphenyl ether as diamine and 22 g (0.20 mol) of p-phenylenediamine dissolved in 2,300 g of N-methyl In 2-pyrrolidone, the reaction was carried out at 40 ° C for 3 hours to obtain a solution containing 15% by weight of poly-proline (a _ I ps 1 1). A small amount of this solution was taken and 'N-methyl-2-pyrrolidone was added to form a solution of polyfluorene-45-201132703 having an amine acid concentration of 1% by weight. The measured solution viscosity was 77 mPa·s'. When the polymer solution was allowed to stand at 20 ° C for 3 days, it was not gelated, and the storage stability was good. [Synthesis Example of Polyimine as Specific Polymer] Synthesis Example B-IPS1 112 g (0.50 mol) of 13,4,411,5-dicyclohexanetetracarboxylic dianhydride and 112 g of tetraresic acid dianhydride (0.50 mol) 2,3,5·tricarboxycyclopentyl acetic acid dianhydride and 86 g (0.80 mol) p-phenylenediamine as diamine, 23 g (0.10 mol) 4,4'-diaminodi Phenylmethane and 32 g (0.10 mol) of 4,4,-diamino-2,2'-bis(trifluoromethyl)biphenyl dissolved in 2,100 liters of N-methyl-2-pyrrolidone The reaction was carried out at 40 ° C for 3 hours to obtain a poly-branched acid solution. A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 40 mPa*s. Next, 2,800 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 400 g of pyridine and 3 10 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out for 1 hour at 1 1 (TC). After the dehydration ring closure reaction, the solvent in the system was replaced with a new butyrolactone solvent, and then, by concentration, 2,300 g of a polybendimimine (B-IPS1) containing 15% by weight of a ruthenium iodide ratio of about 92% was obtained. The solution was taken in small portions, and γ-butyrolactone was added to form a solution having a concentration of 10% by weight of polyimine, and the measured solution viscosity was 36 mPa's. The polymer solution was allowed to stand at 20 ° C for 3 days. , no gelation's good storage stability. Synthesis Example B-IPS2 -46 - 201132703 In addition to using 112g (0.50 mole) 111,23,43,511-cyclohexanetetracarboxylic dianhydride and 112g (0.50 mole) 2 3,5-tricarboxycyclopentyl acetic acid dianhydride was used as the tetracarboxylic dianhydride, and a polylysine solution was obtained in the same manner as in the synthesis example B-1P S 1. A small amount of the solution was taken to add N-methyl group. -2 - Pyrrolidone 'forming a solution having a polymer concentration of 10% by weight' The measured solution viscosity was 35 mPa·8. Next, the same as Synthesis Example B-IPS1 After performing the dehydration ring closure reaction, the solvent in the system was replaced with γ-butyrolactone solvent. Then, by concentrating, 2,300 g of a polymer containing 15% by weight of ruthenium iodide was about 94%. A solution of bismuth imine (B-IPS2). The solution was added in small portions, and γ-butyrolactone was added to form a solution having a concentration of 1 〇 wt% of polyimine. The measured viscosity was 34 mPa_s. The polymer solution was at 20°. When it was allowed to stand for 3 days at C, there was no gelation, and the storage stability was good. Synthesis Example B_IPS3 112 g (〇.50 mol) of tetracarboxylic dianhydride, 13,23,411,511-cyclohexanetetracarboxylic acid II Anhydride and 112 g (〇.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 9 7 g (0·90 mol) p-phenylenediamine and 32 § (0.10 Mo as a diamine) 4) 4,4,-Diamino-2,2'-bis(trifluoromethyl)biphenyl' dissolved in 2,000 g of N-methyl-2-pyrrolidone and reacted at 40 ° C The poly-proline solution was obtained in an hour. The obtained poly-proline solution was added in small portions, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 1% by weight. The measured solution viscosity was 46 mPa. s. Next, in the resulting 2,70 〇g of N-methyl-2-pyrrolidone was added to the proline solution, 400 g of pyridine and 310 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out for 4 hours at -1 - 201132703 at 1 l ° C. After the ring closure reaction, the solvent in the system was replaced with a γ-butyrolactone solvent, followed by concentration to obtain 2,300 g of a polyimine containing 15% by weight of a ruthenium iodide ratio of about 93% (8- 1?33) solution. A small amount of the solution was taken, and γ-butyrolactone was added to form a solution having a concentration of 10% by weight of polyimine, and the measured solution viscosity was 42 mPa_s. When the polymer solution was allowed to stand at 2 ° C for 3 days, it was not gelled and the storage stability was good. Synthesis Example B-IPS4 except that 112 g (0.50 mol) of 1 ft, 23, 48, 5 ft-cyclohexane tetracarboxylic dianhydride and 112 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid were used. A phthalic acid solution was obtained in the same manner as in the synthesis example B-IPS3 except that the dianhydride was used as the tetracarboxylic dianhydride. A small amount of the solution was taken and 'N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 35 mPa·s. » Next, the dehydration ring closure was carried out in the same manner as in Synthesis Example B-IPS3. After the reaction, the solvent in the system was replaced with a γ-butyrolactone solvent, followed by concentration to obtain 2,300 g of a polyimine (B) containing 15% by weight of a ruthenium iodide ratio of about 91%. - IPS4) solution. The solution was added in small portions, and γ-butyrolactone was added to form a solution having a concentration of 10% by weight of polyimine, and the measured solution viscosity was 33 mPa·s. When the polymer solution was allowed to stand at 20 ° C for 3 days, it was not gelated and the storage stability was good. [Synthesis Example of Other Polyimine] Synthesis Example b-IPS5 In addition to using 220 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride-48-201132703 as tetracarboxylic dianhydride, and Synthesis Example B - IP S 1 A polylysine solution was obtained in the same manner. The solution was added in small portions, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 10% by weight, and the solution viscosity was determined to be 48 mPa·s. Then, after the dehydration ring closure reaction was carried out in the same manner as in the synthesis example B-IPS1, the solvent in the system was replaced with a γ-butyrolactone solvent, followed by concentration to obtain 2,300 g of 15% by weight of quinone imine. A solution of about 93% polyethylenimine (b-IPS5). The solution was taken in small portions, and γ-butyrolactone was added to form a polyimine concentration of 10% by weight. /. The solution was measured to have a viscosity of 45 mPa·s. When the polymer solution was allowed to stand at 20 t for 3 days, it was not gelated and the storage stability was good. Synthesis Example b -1P S 6 A polyfluorene was obtained in the same manner as in Synthesis Example B - IP S 4 except that 220 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride was used as the tetracarboxylic dianhydride. Amino acid solution. A small amount of this solution was taken, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 1% by weight, and the measured solution viscosity was 45 mPa_s. Then, after the dehydration ring-closure reaction was carried out in the same manner as in the synthesis example B-IPS4, the solvent in the system was replaced with a γ-butyrolactone solvent, and then, by concentration, 2,300 g of 15% by weight of quinone imine was obtained. A solution of about 9 3 % polybendimimine (b-ips6). A small amount of the solution was taken, and γ-butyrolactone was added to form a solution having a concentration of 10% by weight of polyimine. The measured viscosity was 41 mPa's. When the polymer solution was allowed to stand at 20 ° C for 3 days, 'no gelation. 'The storage stability is good. <Preparation and Evaluation of TN Type Liquid Crystal Aligning Agent> -49-201132703 Example ΤΝ-1 (I) Preparation of Liquid Crystal Aligning Agent The polyprene acid obtained by combining the above synthesis examples A-TN1 as a specific polymer The solution of A-TN1) is polypyridinium (b-TN2) obtained by converting the polyacetic acid (A-TN1) to 80 parts by weight and the above-mentioned synthesis example b-TN 2 as another polymer. The solution is converted to poly(imine) (b-TN2) in an amount equivalent to 20 parts by weight, to which N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (BL) and butyl are added. Fibrous agent (BC), and the final solvent composition is NMP:BL:BC=17:71:12 (weight ratio), then add 2 parts by weight of N,N,N',N'-four as epoxy compound Glycidyl-4,4'-diaminodiphenylmethane was prepared to prepare a solution having a solid concentration of 3.5% by weight. After the solution was thoroughly stirred, it was filtered using a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent. (II) Evaluation of Liquid Crystal Aligning Agent (1) Production of ΤΝ-type liquid crystal cell Using a liquid crystal alignment film printing machine (manufactured by Japan Photo Printing Co., Ltd.), a transparent electrode surface of a glass substrate having a transparent electrode formed of a ruthenium film The liquid crystal alignment agent prepared above was applied and heated on a hot plate at 80 ° C for 1 minute (prebaking), and after removing the solvent, it was heated on a hot plate at 200 ° C for 1 minute (post-baking). A coating film having an average film thickness of 600 A was formed. The coating film was subjected to a rubbing treatment at a roll rotation number of 50 rpm, a platen moving speed of 3 cm/sec, and a pile press-in length of 0.4 mm by using a friction device having a roll of rayon wound to impart a liquid crystal alignment. ability. Thereafter, ultrasonic cleaning was performed for 1 minute in -50-201132703 ultrapure water, followed by drying in a 100 °c clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair of (two pieces of substrates having a liquid crystal alignment film). Next, an alumina ball having a diameter of 5.5 μm was applied to the outer edge of one of the pair of substrates having the liquid crystal alignment film. The epoxy resin adhesive cures the adhesive after the pair of substrates are pressed against each other in such a manner that the liquid crystal alignment film faces. Next, a nematic liquid crystal (MLC-6221, manufactured by Merck) was placed between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a liquid crystal cell. (2) Evaluation of heat resistance stability The durability against thermal stress was evaluated by the voltage holding ratio index. As a measuring device for the voltage holding ratio, a device of the model "V H R -1 " manufactured by TOYO Technica Co., Ltd. was used. With respect to the liquid crystal cell produced as described above, a voltage of 5 V was applied to the liquid crystal display element at an application time of 60 μsec at an interval of 60 μsec at 60 ° C, and then the voltage retention after the application of the voltage was released to 167 ms was measured. Rate (initial voltage retention rate VHR0). Then, the liquid crystal display element f after the application of the thermal stress and the voltage holding ratio was allowed to stand in an oven at 100 ° C for 1,000 hours, and after applying thermal stress, the voltage holding ratio was again measured in the same manner as described above (heat application was applied). The voltage holding ratio after stress is VHR1). Using the enthalpy of VHR0 and VHR1 measured as described above, the difference ΔVHR between the voltage holding ratios before and after the application of the thermal stress was obtained by the following formula (1). -51 - 201132703 Δ VHR = VHR0-VHR 1 (1) When the enthalpy is within 5%, the heat resistance stability is evaluated as good. The evaluation results are shown in Table 1. Examples TN-2 and TN-3 and Comparative Examples tn-Ι and tn-2 In addition to the above-mentioned examples. TN-1, 'as the specific polymer and other polymers, respectively, the type and amount contained in Table 1 were used. A liquid crystal alignment agent was prepared and evaluated in the same manner as in Example TN-1 except that the solution of the polymer was added to each solvent so that the final solvent composition was as described in Table 1. The evaluation results are shown in Table 1. Table 1 indicates that the polymer conforming to this column is not used. In Comparative Example tn-Ι, two polymers were used in combination as the other polymer. The abbreviations of the solvents in Table 1 are respectively the following meanings. NMP: N-methyl-2-pyrrolidone BL : γ-butyrolactone BC : butyl cellosolve -52- 201132703 Heat stability 1 « | 1 1 I 1 1 g ϋ inch oi <N oo a\ 1-^ 班挂•R ¢: ^ m ^ ^ g 1® > 习 S 96.5 96.2 1- 96.9 1 1 88.9 92.1 Initial voltage holding ratio VHR0 (%) 98.9 99.4 99.0 98.7 1 99.2 Solvent Composition i BC (Army%) (S <s in 2 in mesh* 佩 pr NMP (% by weight) 卜o 〇 polymer other polymer amount (parts by weight) ogo 1 type b-TN2 b-TN2 1 a-TN3 1 b-TN2 b-TN3 specific polymerization Quantity (parts by weight) • gg 〇oo Type A-TN1 A-TN2 Γ B-TN1 1 1 Example ΤΝ-1 Example TN-2 Example TN-3 Comparative Example to-1 Comparative Example tn-2 201132703 <Preparation and Evaluation of VA Type Liquid Crystal Aligning Agent> Example VA-1 (I) Preparation of Liquid Crystal Aligning Agent Polyimine (B-VA1) obtained by the above Synthesis Example B-VA1 as a polymer N-methyl-2-pyrrolidone and butyl cellosolve were added to the solution, and then 5 parts by weight of N, N, N', N'- as an epoxy compound was added to 1 part by weight of the polyamidiamine used. Tetraglycidyl-m-xylylenediamine was thoroughly stirred to form a solution having a solvent composition of N-methyl-2-pyrrolidone: butyl cellosolve = 50:50 (weight ratio) and a solid concentration of 3.5% by weight. This solution was filtered using a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent. (II) Evaluation of liquid crystal alignment agent (1) Production of VA type liquid crystal cell was carried out by using a spin coater on one side of a glass substrate having a thickness of 1 mm. On the transparent conductive film composed of the ITO film, the liquid crystal alignment agent prepared above was applied, prebaked on a hot plate at 80 ° C for 1 minute, and then post-baked at 210 ° C on a hot plate. 3 minutes, a coating film having a film thickness of 80 nm (liquid crystal alignment film) was formed. This operation was repeated to obtain two (one pair) substrates having a liquid crystal alignment film. Next, an epoxy resin adhesive having a diameter of 3.5 μm is applied to the outer edge of one of the pair of substrates having the liquid crystal alignment film, so that the liquid crystal alignment film faces the pressure in a relative manner. After a pair of substrates are attached, the adhesive is cured. Next, a negative liquid crystal (manufactured by Merck Co., Ltd., MLC-6608) was placed between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic-54-201132703 photocurable adhesive to produce a liquid crystal cell. (2) Evaluation of heat resistance stability The liquid crystal cell produced as described above was evaluated for heat resistance stability in the same manner as in the above Example TN-1. However, in the case of the VA type liquid crystal cell, when the difference ΔVHR 电压 between the voltage holding ratios before and after the application of the heat stress is within 2%, the heat resistance stability can be evaluated as good. The evaluation results are shown in Table 2. Examples VA-2 to VA-6 and Comparative Examples va-Ι and va-2 Except for the above-mentioned Example V A-1, a solution containing the polymer described in Table 2 was used as the polymer, and Examples A liquid crystal alignment agent was prepared in the same manner as in VA-1, and evaluated. The evaluation results are shown in Table 2. Table 2 indicates that the polymer conforming to this column is not used. The abbreviation of the solvent in Table 2 is the same as that in Table 1. -55- 201132703 Heat stability I system ^ 龆tzhi ^ S < 1—Γ 晒, 习赋 VO 00 \〇cn (N (N class speak sharp circle j dad ^ > 习 S 97.4 97.6 97.6 98.0 1 98.0 96.2 97.0 initial voltage retention rate VHRO (%) 99.0 99.4 99.2 99.5 99.1 1 99.3 99.3 99.2 Solvent composition BC (% halo) NMP (% by weight) Polymer Other polymer dosage I (parts by weight) 〇〇〇〇〇〇100 〇Type _I 1 1 1 1 1 1 b-VA7 b -VA8 Specific polymer amount (parts by weight) 100 〇r-^ 100 100 〇〇〇〇Type I B-VA1 B-VA2 B-VA3 [B-VA4 B-VA5 1 1 B-VA6 1 1 Example VA- 1 Example VA-2 Example VA-3 Example VA-4 Example VA-5 Example VA-6 Comparative Example va-1 Comparative Example va-2 201132703 <Preparation and Evaluation of I p S Type Liquid Crystal Aligning Agent> Example IPS-1 (I) Preparation of Liquid Crystal Aligning Agent Polyisamic acid (A-IPS1) obtained in the above Synthesis Example A-IPS1 as a polymer To the solution, N-methyl-2-pyrrolidone and butyl cellosolve as a solvent are added, and then 5 parts by weight of hydrazine, hydrazine, as an epoxy compound is added to 1 part by weight of the polylysine used. Ν', Ν'-tetraglycidyl-m-xylylenediamine, fully stirred to form a solvent composition of Ν-methyl-2-pyrrolidone: butyl cellosolve = 80:20 (weight ratio), solid concentration 3.5% by weight solution. This solution was filtered using a filter having a pore size of Ιμπι to prepare a liquid crystal alignment agent. (II) Evaluation of Liquid Crystal Aligning Agent (1) Production of Liquid Crystal Cell A liquid crystal cell was prepared in the same manner as in the Example ΤΝ-1 except that the liquid crystal alignment agent prepared above was used, and the heat resistance stability was evaluated. The evaluation results are shown in Table 3. Further, the liquid crystal cell produced here is a ruthenium type liquid crystal cell, and the inventors have confirmed by experience that a sputum type liquid crystal cell can be used instead of the IP S type liquid crystal cell as a sample for evaluation of heat resistance stability. Examples IPS-2 to IPS-5 and Comparative Examples ips-b ips-3 except that in the above-mentioned Example IPS-1, 'as a polymer, respectively, a solution containing the polymer described in Table 3 was used, and Example ip sl A liquid crystal alignment agent was prepared in the same manner and evaluated. -57- 201132703 The evaluation results are shown in Table 3. Example 1 to 3-6 to 9 and Comparative Example 8-4 and Comparative Example? 8-5 In addition to the above-mentioned Example IPS-1, a solution containing the polymer described in Table 3 was used as a polymer, and N-methyl-2-pyrrolidone (NMP) and γ-butyl were used as a solvent, respectively. Lactone (BL) and butyl cellosolve (BC) were prepared in the same manner as in Example IPS-1 except that these various solvents were added and the final solvent composition was NMP:BL:BC = 10:70:20 (weight ratio). The liquid crystal alignment agent was evaluated. The evaluation results are shown in Table 3. Table 3 indicates that the polymer conforming to this column is not used. The abbreviation of the solvent in Table 3 is the same as that in Table 1. -58- 201132703 U撇] Heat resistance stability Difference in voltage holding ratio before and after applying heating stress AVHR(%) 〇 (N rn 'Ο vq — inch* <N 〇\ On 〇pm od o Voltage holding ratio after heating stress VHR1 (%) 95.5 j 94.4 94.8 94.0 95.0 98.0 97.8 98.0 98.3 90.0 I- 90.9 88,5 94.5 94.0 Initial voltage holding ratio VHR0 (%) 97.5 97.6 99.3 98.6 ____1 99.2 99.2 99.7 98.9 99.3 98.3 98.4 98.6 99.6 99.1 Solvent composition BC (Military%%) BL (Mm%) 〇Ο Ο ο oooooooooo NMP ί 雷量%) gggggoooogggoo Polymer other polymer dosage (parts by weight) 〇 ο ο ο ooooooooo 0 1 i Category 1 1 I 1 1 1 1 1 1 a-IPS9 a-IPSlO a-IPSll b-EPS5 b-EPS6 Specific polymer amount (parts by weight) 〇Ο Ο 100 o 100 ooo 〇ooo 〇 Category A-IPS1 A-IPS3 A-IPS4 A-IPS5 A-IPS6 B-IPS1 B-EPS2 B-IPS3 B-IPS4 1 1 1 1 1 Example PS-ι Example IPS-2 Example IPS-3 Example IPS*4 Example IPS-5 Example IPS-6 Example IPS-7 Example EPS-8 Example IPS-9 Comparative Example ips-1 Comparative Example ips-2 Comparative Example ips-3 Comparative Example ips-4 Comparative Example Ips-5 -6ς· 201132703 [Simple description of the diagram] 〇y\\\ [Description of main component symbols] 〇 - 60

Claims (1)

201132703 VII. Patent application scope: 1. A liquid crystal alignment agent. The liquid crystal alignment agent contains a polylysine obtained by reacting tetracarboxylic dianhydride and a group formed by dehydrating and blocking the polyamine to form an imine. At least one polymer selected from the group' is characterized in that the tetracarboxylic dianhydride has 5 to 80 mol% of 13,23,4 ft, 511-cyclohexane tetracarboxylic acid relative to all tetracarboxylic acid One of the groups consisting of 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride is selected. 2. The liquid crystal alignment agent of claim 1, wherein the tetracarboxylic acid step comprises 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5·tributyl acetic acid Dihydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-difuranyl)-naphthalene [l,2-c]furan-1,3-dione, l,3,3a,4,5,9b-Ayl-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene [1,2-(:]furanone, 3-oxo Heterobicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetra-2',5'-dione), 5-(2,5-di-oxo-tetragen- 3-furyl)-3 -methyl stilbene-1,2-diphthalic anhydride, 3,5,6-tricarboxy-2-indolemethyl-lowering dianhydride, 2,4,6,8-tetracarboxyl Selected from the composition of bicyclo[3.3.0]octane-2:4,6:8-dianhydride dioxatricyclo[5.3.1.0'6]undecano-3,5,8,10-tetraketone At least one of the following: 3. The liquid crystal alignment agent of claim 1 wherein the diamine is composed of p-phenylenediamine, 3,5-diaminobenzoic acid, 4,V-diaminodiphenyl ί Aminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminobiphenyl, amine-2,2'-bis(trifluoromethyl)biphenyl, 4,4'_ Polyanhydride of diaminodiphenyl and diamine, containing dianhydride and The group of the acid dianhydride carboxyl ring side oxy-3-hydro-8-methyl-1,3-dihydrofuran-3-cyclohexane 2:3, 5:6- and 4,9 · contains a bond, 4,4'-4,4,-diylamine and -61 - 201132703 4,V-(m-phenylene isoparous. 4 . As claimed in the patent range j further contains in the sub = 5. - type liquid crystal alignment film item a liquid crystal alignment agent selected from any one of the group consisting of at least one of the liquid crystal alignment film propyl) diphenylamine selected from the group consisting of liquid crystal alignment liquids, wherein A compound having at least one epoxy group therein, which is characterized by being formed of an alignment agent as in the first to fourth aspects of the patent application. 戸' is characterized by having a prescribed representative image as in the scope of the patent application No. 5-62-201132703. (1) The representative representative of the case is: No. (2) The symbol of the symbol of the representative figure is simple: 4fr- 〇j\ w 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: