TW200948861A - Liquid crystal aligning agent and liquid crystal display element - Google Patents

Abstract

The present invention relates to a liquid crystal aligning agent and liquid crystal display element. The said liquid crystal aligning agent has excellent printing property even face to the substrate having difference in level, and forms liquid crystal alignment film which could stability express high pre-tilting angle. The said liquid crystal aligning agent comprises at least one polymer selected from the group consisting of follows; the said group is made of polyamic acid and the imiding polymer form by cyclodehydration of the said polyamic acid; the said polyamic acid is made of diamine and tetracarboxylic dianhydrate. The said diamine comprises 3, 5-diaminobenzoic cholestanyl ester as the representative specific compound and the compound represented by the following formula (B-1) as the representative specific compound.

Description

200948861 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment agent and a liquid crystal display element. [Prior Art] At present, a liquid crystal display element having a TN (Twisted Nematic) type or an STN (Super Twisted Nematic) type liquid crystal cell is known which forms a polyglycine or ruthenium on a surface thereof through a transparent conductive film. A layer of nematic liquid crystal having positive dielectric anisotropy is formed between the two substrates of the liquid crystal alignment film of the imine polymer, and is configured as a sandwich structure, and the long axis of the liquid crystal molecules is continuously twisted between the substrates. 9 (Γ). A so-called TFT liquid crystal display panel in which the TN type liquid crystal display element operates by TFT driving has been widely used in place of the conventional cathode ray tube. The alignment of liquid crystals in these liquid crystal display elements is usually imparted by sanding treatment or the like. A liquid crystal alignment film having a liquid crystal molecule alignment energy is realized. Further, as a liquid crystal display element different from the above, it is known to provide a vertical alignment type liquid crystal in which liquid crystal molecules having negative dielectric anisotropy are vertically aligned on a substrate. a liquid crystal display element of a cell. In such a liquid crystal display element, the alignment control of liquid crystal molecules is usually also carried out by a poly-proline-containing acid A liquid crystal alignment film formed of a liquid crystal alignment agent of a polymer such as a polymer and having such a polymer as a main component is produced. In recent years, in order to obtain a more vivid and beautiful image, the liquid crystal display element has a high aperture ratio. For this reason, in the TN type liquid crystal display device, a liquid crystal alignment film capable of stably generating a pretilt angle larger than before is required. In addition, a vertical alignment type liquid crystal display element having excellent viewing angle is mostly used for a monitor. For use, TV use, and it is necessary to have a liquid crystal alignment film capable of stably generating a pretilt angle of about 90. The liquid crystal alignment film is usually formed by applying a liquid crystal alignment agent to a substrate by a printing machine and baking it, and if it is baked, When the thickness of the liquid crystal alignment film formed is not uniform, unevenness may occur in an image displayed by a liquid crystal display element having such a liquid crystal alignment film. Therefore, a liquid crystal alignment agent excellent in coatability (particularly, printability) is required. In the liquid crystal alignment film having a polymer as a main component, it is known that the pretilt angle depends on the substituent which the polymer has. For example, in Patent Document 1, it is disclosed that a monomer having a bulky substituent having 1-octadecyloxy-2,4-diaminobenzene in a side chain (hereinafter referred to as a monomer having a pretilt angle) is used. The liquid crystal alignment film which has the obtained poly φ compound as a main component will produce a pretilt angle, but since it is stably produced with 1-octadecyloxy-2,4-diaminobenzene, a sufficiently large pretilt angle is obtained. Since the compound must be used in a large amount, the liquid crystal alignment agent containing the obtained polymer is not sufficiently printed. Therefore, the liquid crystal display element having the liquid crystal alignment film formed therewith cannot display a beautiful image. 2, which discloses 4-(4-(4-n-pentylcyclohexyl)cyclohexyl-2,6-difluorophenyl)oxydifluoromethyl-1,3-phenylenediamine Six kinds of diamines, and it is described that when 90% by mole of these diamines are used relative to the total amount of the diamine used in the synthesis of the polymer, a high pretilt angle can be produced. However, a liquid crystal alignment agent containing a polymer obtained by using 90 mol% of the diamine has a problem that printing property is not good enough, and a liquid crystal display element having a liquid crystal alignment film formed therefrom has a problem that a beautiful image cannot be displayed. As described above, the printability of the liquid crystal alignment agent and the performance of the pre-tilt angle of the formed liquid crystal alignment film are in a paradoxical relationship, and therefore both are sought to coexist. Patent Documents 3 and 4 disclose liquid crystal alignment agents containing polyaminic acid or a quinone imidized polymer having a specific diamine synthesis having a steroid skeleton 200948861. The technique can be seen that the ability to produce a polymer having a high pretilt angle with a small amount of the above specific diamine is achieved by using a liquid crystal alignment agent containing the polymer to achieve printability and formed liquid crystal alignment film. The high pretilt angle produces an excellent technique for coexistence of performance. Therefore, the liquid crystal display element having the liquid crystal alignment film formed using the liquid crystal alignment agent can display a beautiful image, and solves the above problems of the prior art. However, with the development of animation fixing technology, liquid crystal display elements require a finer and more beautiful display, and even highly moving images must be able to respond quickly and correctly when moving fast. For this reason, there is a tendency that the level difference formed on the substrate inevitably increases due to the problem of electrical technology, and the improvement of the printability of such a large-order difference portion is becoming a new important topic of the liquid crystal alignment agent. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 17] Japanese Laid-Open Patent Publication No. Hei 5-170044 [Non-Patent Document 1] TJ Scheffer, et. al., J. Appl. Phys., Vol. 0 1 3 (1 9 80) [Description of the Invention] The present invention has been made based on the above circumstances. A first object of the present invention is to provide a liquid crystal alignment agent capable of stably exhibiting a high pretilt angle of a liquid crystal alignment film even if it has excellent printability for a substrate having a large step difference. A second object of the present invention is to provide a liquid crystal display element which is capable of finely performing beautiful display and which can correctly correspond even when a highly moving image is rapidly moved. The inventors of the present invention have intensively studied in order to achieve the above object, and have achieved the present invention. That is, the above objects and advantages of the present invention, first, achieved by a liquid crystal alignment agent comprising at least one polymer selected from the group consisting of polylysine and the polyamic acid a ruthenium-imided polymer obtained by dehydration ring closure, which is obtained by reacting a diamine with a tetracarboxylic dianhydride containing a compound represented by the following formula (Α) and the following formula (Β) Compound expressed, 200948861

(A) (In the formula (A), A1 represents a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, a fluoromethylene group or a fluoroalkylene group having 2 to 6 carbon atoms. A2 represents -〇-, -COO-, -OCO-, -NHCO-, -CONH- or -CO-, and ΟA3 represents a monovalent organic group having a steroid skeleton).

(B) (CH2)b1-B1—((CH2)b2-〇)b3-B2 (in the formula (B), B1 is -0-, -COO-, -OOC·, -CONH- or -NHCO-, B2 is a biphenyl group, a cyanobiphenyl group, a fluorobiphenyl group, an (alkylcyclohexyl)phenyl group having an alkyl group having 1 to 32 carbon atoms, and an alkane having a carbon atom number of 1 to 32. An alkoxybenzyl group of a oxy group, a dialkoxyphenyl group or an alkoxybiphenyl group, a fluoroalkoxybiphenyl group having a fluoroalkoxy group having 1 to 32 carbon atoms or a carbon number It is an alkyl group of 1 to 32, and each of bl and b3 is 〇 or 1, and b2 is an integer of 2 to 22). 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. The liquid crystal alignment agent of the present invention has excellent printability even for a substrate having a large step difference, and can form a 200948861 liquid crystal alignment film capable of stably exhibiting a high pretilt angle. The liquid crystal display element of the present invention having such a liquid crystal alignment film is capable of finely performing beautiful display and can correctly correspond even when a highly moving image is rapidly moved. The liquid crystal display element of the present invention can be effectively used for various devices, for example, display devices applicable to calculators, watches, clocks, mobile phones, counting display panels, word processors, personal computers, liquid crystal televisions, and the like. [Embodiment] Hereinafter, the present invention will be specifically described. The liquid crystal alignment agent of the present invention comprises at least one polymer selected from the group consisting of polylysine and a ruthenium-imided polymer obtained by dehydration of the polyglycine. The polyamic acid is obtained by reacting a diamine with a tetracarboxylic dianhydride containing the compound represented by the above formula (A) and a compound represented by the above formula (B). <Diamine> The diamine used in the synthesis of the above polyamic acid contains the compound represented by the above formula (A) and the compound represented by the above formula (B). 〇 is an alkylene group having 2 to 12 carbon atoms in A1 of the above formula (A), preferably an alkylene group having 2 to 4 carbon atoms. More preferably 1,2-ethylidene, 1 , 3 - propyl, 1,4 - butyl. The fluoromethylene group is preferably -CF2-. The fluororetinyl group having a carbon number of 2 to 6 is preferably a perfluoroalkylene group having a carbon number of 2 to 4, more preferably a 1,2-perfluoroextended ethyl group or a 1,3-allyl group. Fluoride propyl, 1,4-perfluorobutylene. As A2, it is preferably -0. The steroid skeleton ' in A3' means a structure composed of a cyclopentane-perhydrophenanthrene nucleus or a structure in which one or two or more of the carbon-carbon bonds are changed to a double bond. 200948861 is a monovalent organic group having such a skeleton, and is preferably a group having 17 to 40 carbon atoms. Specific examples of the compound represented by the formula (a) include, for example, 1-cholestyloxymethyl-2,4-diaminobenzene and 2-cholestyloxyethyl-2. 4-diaminobenzene, 3_cholestyloxypropyl-2,4-diaminobenzene, 4_cholestyloxybutyl-2,4-diaminobenzene, 1-cholestene Oxymethyl-3,5-diaminobenzene, 2-cholesteneoxyethyl-3,5-diaminobenzene, 3-cholestyloxypropyl-3,5-diamino Benzene, 4-cholesteneoxybutyl-3,5-diaminobenzene, 1-(1-cholestene-deceneoxy-1,1-difluoromethyl)-2,4-diamino Benzene, 1-(2-cholestenyloxy-1,1,2,2-tetrahydroethyl)-2,4-diaminobenzene, 1-(3-cholestyloxyoxyl-1,1, 2,2,3,3-hexafluoropropyl) 2,4-diaminobenzene, 1-(4-cholesteneoxy-1,1,2,2,3,3,4,4 -8 Fluorobutyl)-2,4-diaminobenzene, 1-(1-cholestenyloxy-1,1-difluoromethyl)-3,5-diaminobenzene, 1-(2-biliary Terpeneoxy-1,1,2,2-tetrafluoroethyl)-3,5-diaminobenzene, 1-(3-cholesteneoxy-1,1,2,2,3,3 -hexafluoropropyl)-3,5-diaminobenzene, 1-(4-cholestrenyloxy-1,1,2,2,3,3,4,4-octafluorobutyl)-3 , 5-diaminobenzene, 1-biliary Oxymethyl-2,4-diamino φ benzene, 2-cholestyloxyethyl-2,4-diaminobenzene, 3-cholestyloxypropyl-2,4-diamine Benzobenzene, 4-cholestyloxybutyl 2,4-diaminobenzene, 1-cholestyloxymethyl-3,5-diaminobenzene, 2-cholestyloxyethyl · 3,5-Diaminobenzene, 3-Bile oxypropyl-3,5· _•Aminobenzene, 4-Bile oxybutyl-3,5-diaminobenzene, 1 -(1-cholestyloxy-1,1-difluoromethyl)-2,4-diaminobenzene, 1-(2-cholestyloxy-1,1,2,2-tetrafluoro Ethyl)-2,4-diaminobenzene, 1-(3-cholestyroxy-1,1,2,2,3,3-hexafluoropropyl)-2,4-diaminobenzene , 1-(4-cholestyloxy-1,1,2,2,3,3,4,4-octafluorobutyl)-2,4-diaminobenzene, 1-(1-cholesteryl) Alkoxy-1,1-difluoromethyl)-3,5-diaminobenzene, 1-(2- -10- 200948861 cholestyloxy-1,1,2,2-tetrafluoroethyl -3,5-diaminobenzene, 1-(3-cholestyloxy-1,1,2,2,3,3-hexafluoropropyl)-3,5-diaminobenzene, 1 -(4-cholestyloxy-1,1,2,2,3,3,4,4-octafluorobutyl)-3,5-diaminobenzene, 3-(2,4-diamine Phenyl methoxy)-4,4-dimethylcholestane, 3-(2-(2,4-diamine) Phenyl)ethoxy)-4,4-dimethylcholestane, 3-(3-(2,4-diaminophenyl)propoxy)-4,4-dimethylcholyl Alkane, 3-(4-(2,4-diaminophenyl)butoxy)-4,4-dimethylcholestane, 3-(3,5-diaminophenylmethoxy) -4,4-dimethylcholestane, 3-(2-(3,5-diaminophenyl)ethoxy)-4,4-dimethylcholestane, ❹ 3-(3- (3,5-Diaminophenyl)propoxy)-4,4-dimethylcholestane, 3-(4-(3,5-diaminophenyl)butoxy)-4, 4-dimethylcholestane, 3-(1-(2,4-diaminophenyl)-1,1-difluoromethoxy)-4,4-dimethylcholestane, 3- (2-(2,4-Diaminophenyl)-1,1,2,2-tetrafluoroethoxy)-4,4-dimethylcholestane, 3-(3-(2,4) -diaminophenyl)-1,1,2,2,3,3-hexafluoropropoxy)-4,4-dimethylcholestane, 3-(4-(2,4-diamine) Phenyl)-1,1,2,2,3,3,4,4-octafluorobutoxy)-4,4-dimethylcholestane, 3-(1-(3,5-di) Aminophenyl)-1,1-difluoromethoxy)-4,4-dimethylcholestyl Q-, 3-(2-(3,5-diaminophenyl)-1,1, 2,2-tetrafluoroethoxy)-4,4-dimethylcholestane, 3-(3-(3,5-diaminophenyl) -1,1,2,2,3,3-hexafluoropropoxy)-4,4-dimethylcholestane, 3-(4-(3,5-diaminophenyl)-1, 1,2,2,3,3,4,4-octafluorobutoxy)-4,4-dimethylcholestane, 3-(2,4-diaminophenyl)methoxycholane -24 - cetyl acid ester, cetyl 3-(2-(2,4-diaminophenyl)ethoxy)cholane-24-ate, 3-(3-(2, 4-Diaminophenyl)propoxy)cholane-24-acid cetyl ester, 3-(4-(2,4-diaminophenyl)butoxy)cholane-24-acid Cetyl ester, cetyl 3-(3,5-diaminophenyl)methoxycholane-24-ate, -11- 200948861 3-(2-(3,5-diamine) Phenyl phenyl) ethoxy) cetyl-24-acid cetyl ester, 3-(3-(3,5-diaminophenyl)propoxy)cholane-24-acid cetyl Ester, cetyl 3-(4-(3,5-diaminophenyl)butoxy)cholane-24-ate, 3-(1-(3,5-diaminophenyl) -1,1-difluoromethoxy)cholane-hexadecyl hexadecyl ester, 3-(2-(3,5-diaminophenyl)-1,1,2,2-tetrafluoro Ethoxy)cholane-24·hexadecyl acid, 3-(3-(3,5-diaminophenyl)-1,1,2,2,3,3-hexafluoropropoxy Cholenet-24- Cetyl acid ester, 3-(4-(3,5-diaminophenyl)-1,1,2,2,3,3,4,4-octafluorobutoxy)cholane - 24 - cetyl acid ester, octadecyl 3-(3,5-diaminophenylmethoxy)cholane-24-ate, 3-(2-(3,5-diamino) Phenyl)ethoxy)cholene-24-octadecyl ester, 3-(3-(3,5-diaminophenyl)propoxy)cholane-24-octadecyl ester , 3-(4-(3,5-diaminophenyl)butoxy)cholane-24-octadecyl ester, 3-((3,5-diaminophenyl)-1, 1-Difluoromethoxy)cholane-24-acid octadecyl ester, 3-(2-(3,5-diaminophenyl)-1,1,2,2-tetrafluoroethoxy Cholecylate-24-octadecyl ester, 3-(3-(3,5-diaminophenyl)-1,1,2,2,3,3-hexafluoropropoxy)cholane -24-octadecyl acid ester or 3-(4-(3,5·diaminophenylphenyl)-1,1,2,2,3,3,4,4-octafluorobutoxy) Cholecylate-24-octadecyl ester, 1-cholesteneoxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholesteryl ester, 1-cholestyloxy Base-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoate, and the like. Among them, from the viewpoint of being able to produce a high pretilt angle, it is preferred to use 1-cholestenoxymethyl-2,4-diaminobenzene, 1-cholestenoxymethyl-3,5. -diaminobenzene, 1-(1-cholestenyloxy-1,1-difluoromethyl)-2,4-diaminobenzene, 1-(1-cholesteneoxy-1,1 -difluoromethyl)-3,5-diaminobenzene, 1-(1-cholestyloxy-1,1-difluoromethyl)-2,4-diaminobenzene, 1-(1 -cholestaneoxy-12- 200948861 base · 1,1-difluoromethyl)-3,5-diaminobenzene, 3-(2,4-diaminophenylmethoxy)-4,4 - dimethylcholestane, 3-(1-(2,4-diaminophenyl)-1,1-difluoromethoxy)·4,4-dimethylcholestane, 3-( 3,5-Diaminophenylmethoxy)-4,4-dimethylcholestane, 3-(1-(3,5-diaminophenyl)-1,1-difluoromethoxy -4,4-dimethylcholestane, 3-((2,4-diaminophenyl)methoxy)cholane-24-acid cetyl ester, 3-(1-( 2,4-Diaminophenyl)·1,1-difluoromethoxy) Cetyl-24-acid cetyl ester, 3-((3,5-diaminophenyl)methoxy Cetyl-24-acid cetyl ester, 3-(1-(3,5-diaminophenyl)-1,1·difluoromethoxy) 0 Alkane-24-acid cetyl ester, 3-(2,4-diaminophenylmethoxy)cholane-24-octadecyl ester, 3-(1-(2,4-di) Aminophenyl)-1,1-difluoromethoxy) octadec-24-octadecanoate, 3-(3,5-diaminophenylmethoxy)cholane-24-acid Octadecyl ester, 3-(1-(3,5-diaminophenyl)-1,1-difluoromethoxy) cholane-24-octadecyl ester, 1-cholestene Oxy-2,4·diaminobenzene, cholesteryl 3,5-diaminobenzoate, 1-cholestyloxy-2,4-diaminobenzene and 3,5-diamine One or more selected from the group consisting of cholesteryl benzoate. Moreover, from the viewpoint of producing a particularly high pretilt angle 以 with a small use ratio, the use of 1-cholesteneoxy-2,4-diaminobenzene, 3,5-di is particularly preferred. One or more selected from the group consisting of cholesteryl aminobenzoic acid ester, 1-cholestyloxy-2,4-diaminobenzene, and cholesteryl 3,5-diaminobenzoic acid . The compound represented by the above formula (Α) can be obtained, for example, by the method described in Patent Document 5 (Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. . Since the liquid crystal alignment agent of the present invention contains a polymer having a repeating structural unit derived from the compound represented by the above formula (Α), it can be formed to exhibit high pretilt expression without impairing the printability of -13 to 200948861. Liquid crystal alignment film. As B1 in the above formula (B), it is preferably -0- or -COO-* (wherein the bonding arm with " " and -((CH2)b2-)b3-B2 bond), Preferably, the biphenyl group, the cyanobiphenyl group, the fluorobiphenyl group and the fluoroalkyl biphenyl group of 〇B2 are preferably bonded to the 4-position of the biphenyl group. The cyano group, the fluoro group and the fluoroalkyl group are preferably each located at the 0 4' position of the biphenyl group. The alkylcyclohexyl group of the (alkylcyclohexyl)phenyl group is preferably bonded to the para position of the phenyl group, and the alkyl group is preferably bonded to the 4' position of the cyclohexyl group. The alkoxybenzyl group is preferably a monoalkoxybenzyl group or a dialkoxybenzyl group. In this case, the alkoxy group of the monoalkoxybenzyl group is preferably bonded to the para position, and the alkoxy group of the dialkoxybenzyl group is preferably bonded to the 3,5 position. The fluoroalkoxy group of the fluoroalkoxybiphenyl group preferably has 1 to 6 carbon atoms. The alkyl group of the (alkylcyclohexyl)phenyl group and the alkoxy group of the alkoxybenzyl group each preferably have 5 to 12 carbon atoms. φ The two cyano groups in the above formula (B) are preferably at the 2, 4 or 3, 5 position relative to -(CHObi-Bi-UCHOu- 0)b3-B2. Specific examples of the compound represented by the above formula (B) include compounds represented by the following formulas (B-1) to (B-22). -14- 200948861

(Β·6) 200948861

(B-12)

(B-13)

(B-14) -16 200948861

❹ h2n_^^〇^^0~c7H15 NH2 (B-18)

The compound represented by the above formula (B) can be, for example, patent documents 7 to 13 (International Publication No. 04/052962 pamphlet, International Publication No. 02/05 1 909 -17-200948861 pamphlet, International Publication No. 02/0 51908 pamphlet The method described in the method described in Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. The liquid crystal alignment agent of the present invention has excellent printability because it contains a structural unit polymer having a compound derived from the above formula (B). As the diamine used in the synthesis of the above polyamic acid, the compound represented by the above formula (A) and the compound represented by the above formula (B) or the compound represented by the above formula (A) and the above may be used. In addition to the compound represented by the formula (B), it may be used together with other diamines. As other diamines which can be used herein, for example, p-phenylenediamine, m-phenylenediamine, 4,4,-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4 ,4,-Diaminodiphenyl sulfide, 4,4,-diaminodiphenylphosphonium, 3,3,-dimethyl-4,4,-diaminobiphenyl, 4,4, -diaminobenzimidamide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 5-amino-1-(4'-aminophenyl)-1,3 ,3-trimethylindan, 6-amino-1-(4-aminophenyl)-1,3,3-trimethylindan, 3,4,-diaminodiphenyl ether, 3 , 3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4,-diaminobenzophenone, 2,2-bis[4-(4-aminophenoxyl) Phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, two [4-(4-Aminophenoxy)phenyl] milled, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1 , 3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-1〇-hydroquinone, 2,7-diaminopurine, 9,9-di ( 4-aminophenyl), 2, 2, 5, 5 ,-tetrachloro-4,4'-diaminobiphenyl, 2,2,-dichloro-4,4,-diamino-5,5'dimethoxybiphenyl, 3,3'- Dimethoxy-4,4,-diaminobiphenyl, 4,4'-(p-phenylene diisopropanoid • 18 - 200948861 yl)diphenylamine, 4,4'-(m-phenylene di Isopropyl)diphenylamine, 2,2,-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4,-diamino-2 , 2'-bis(trifluoromethyl)biphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl or 4,4'-bis[(4-amino-2-yl) An aromatic diamine compound such as fluoromethyl)phenoxy]-octafluorobiphenyl; m-xylylenediamine, 1,3-propylenediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, Octanediamine, decanediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene diamine, hexahydro-4,7-methylene fluorene dimethylene An aliphatic or alicyclic diamine compound such as φ diamine, tricyclo[6.2.1.02,7]undecene dimethyldiamine, 4,4,-methylenebis(cyclohexylamine); 3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2.4-diaminopyrimidine, 5,6-diamino-2,3-dicyanide Pyridin, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5·triple, 1,4-bis(3) -aminopropyl)oxime, 2,4-diamino-6-isopropoxy-1,3,5-tris, 2.4-diamino-6-methoxy-1,3,5 -Tri-trap, 2,4-diamino-6-phenyl-1,3,5-three tillage, 2,4·diamino-6-methyl-s-three tillage, 2,4-diamine Base-1,3,5- Φ three tillage, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diamine Base, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxy Acridine lactate, 3,8-diamino-6-phenylphenanthridine, 1,4-diamine hydrazine, 3,6-diaminoacridine, bis(4-aminophenyl) a phenylamine, a compound represented by the following formula (D-I),

(In the formula (D-I), R1 represents a monovalent organic group having a structure selected from the group consisting of pyridine, pyrimidine, tri-farming, acridine, and -19-200948861 sorghum' χ1 represents a 2-valent organic a group, a compound represented by the following formula (D-II), or a diamine compound having two primary amino groups in the molecule and a nitrogen atom other than the primary amine group, η2 (D-Π) (Formula D-II) In the formula, R2 represents a divalent organic group having a structure selected from the group consisting of pyridine, pyrimidine, triterpene, fluorene®, and argon, and X2 represents a divalent organic group, respectively; a compound such as D-III), such as a diamine organooxane, R3 R3 • nh2

Si — _(〇—s丨)(CH^-f R3 R3 (D-III) (In the formula (D-III), each of R3 in which R3 represents a hydrocarbon group having a carbon number of ～i2, respectively] may be The same or different, each p is an integer of 1 to 3, and q is an integer of 1 to 20); a compound represented by the following formulas (D-1) to (D-7), -20-200948861

H2n

O-(-c2h4-o

(D-4) h2n-

NHz (D-5)

(wherein y in the formula (D-4) is an integer of 2 to 12, and an integer of the formula (D-5). Among these other diamines, z in the -5) from the synthesis of the poly-proline is 1 polymerization. Sex angle 21 - 200948861, preferably containing p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diamine Naphthyl, 2,7-diaminopurine, 4,4, _-yl-based acid, 2,2 -*[4-(4-aminophenoxy)phenyl]propyl, 9, 9. Di(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl) Hexafluoropropane, 4,4,-(p-phenylene diiso-propyl)diphenylamine, 4,4'-(m-phenylene diisopropyl)diphenylamine, 1,4-cyclohexane Amine, 4,4'-methylenebis(cyclohexylamine), 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl , 4,4'-diamino-2,2'-bis(trifluoromethyl) fluorene biphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl, 2,6- Diamine-based, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, in the compound represented by the above formula (D-I) The compound represented by the following formula (D-8), the compound represented by the following formula (D-9) in the compound represented by the above formula (D-II), and the compound represented by the above formula (D-III) At least one selected from the group consisting of the compound represented by the formula (D - 6) and the compound represented by the above formula (D-6) and the compound represented by the above formula (d-7) (hereinafter referred to as "other specific two

Η2Ν_^3~ΚΖ)-〇3Η6~~{Ζ/ν~^^~ι

Ch3 ch3 -22-.200948861 The diamine used in the synthesis of the above polyamic acid preferably contains 0.1 to 50 mol% of the compound represented by the above formula (A), and more preferably contains all of the diamine. 0.5 to 30 mol%, and the special system contains 1 to 20 mol%. When the use ratio of the compound represented by the above formula (A) falls within the above range, the obtained liquid crystal alignment film can exhibit excellent coatability, particularly excellent printability, and a liquid crystal alignment film formed therefrom It is possible to exhibit a high pretilt angle more stably', and thus it is preferable from this point of view. When the use ratio of the compound represented by the above formula (A) is in the range of from 〜5 to 0% by mole based on the entire diamine, the liquid crystal alignment agent of the present invention can be particularly suitably used for the TN type and STN type liquid crystal display elements. When the use ratio of the compound represented by the above formula (A) falls within the range of 10 to 25 mol% with respect to the entire diamine, the liquid crystal alignment agent of the present invention can be particularly suitably used for a VA liquid crystal display element. The diamine used in the synthesis of the polyamic acid preferably contains 5 to 80 mol% of the compound represented by the above formula (Β) with respect to all the diamines, more preferably 10 to 60 mol. %, especially good contains 2 0~5 0 mol%. The diamine used in the synthesis of the above polyamic acid preferably contains 10 to 95 mol% of the other specific diamine as described above, more preferably 20 to 90 mol%, based on the total diamine. , especially good contains 40~80 mol%. <tetracarboxylic dianhydride> Examples of the tetracarboxylic dianhydride used in the synthesis of the polyamic acid include butane tetracarboxylic dianhydride and 1,2,3,4-cyclobutane IV. Carboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane IV Carboxylic dianhydride, l,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-ring Butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, -23- 200948861 3,3' , 4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5:6-dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3&,4,5,91)-hexahydro-5-(tetrahydro-2,5 -dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro-5-methyl -5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,915- Hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1 3,3&,4,5,91)-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-φ naphthalene [l,2-c]- Furan-1,3-diketone, 1,3,3&,4,5,913-hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene l,2-c]-furan-1,3-dione, 1,3,3&,4,5,915-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3 -furyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,913-hexahydro-8-ethyl-5-(tetrahydro-2, 5-dioxo-3-furanyl)-naphthalene [1,2-indolyl]-furan-1,3-dione, 1,3,3&,4,5,91>-hexahydro-5,8 -Dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-c]-furan-1,3-dione, 5-(2,5- Dioxotetrahydrofuranyl)_3_methyl_3_cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]-oct-7-eneΟ-2,3,5,6-tetracarboxylic acid An aliphatic or alicyclic tetracarboxylic dianhydride such as a dianhydride or a compound represented by the following formula (T-Ι) and (T-II),

Q R7 R7 P

-24- .200948861 (In the formulas (Τ-I) and (Τ_ΙΙ), R4 and R6 each represent a divalent organic group having an aromatic ring, and R5 and R7 each represent a hydrogen atom or an alkyl group, and a plurality of R5 and R7 can be the same or different); pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenyl maple Tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether Tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonanetetracarboxylic dianhydride, 3 , 3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 0 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy Diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl maple dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy Diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropenyldiphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, Di(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenyl) Phthalic anhydride) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, two (three) Phenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-di(decyl trimellitate), propylene glycol-di(hydrogen trimellitate), 1,4 - Butanediol-di(hydrogen trimellitate), 1,6-hexanediol-di(hydroper trimellitate), 1,8-octanediol-di(anhydrotrimellitic acid ester) , 2,2-bis(4-hydroxyphenyl)propane-di(hydroper trimellitate), 2,3,4,5-pyridinetetracarboxylic dianhydride, 2,6-di(3,4- An aromatic tetracarboxylic dianhydride such as a compound represented by the following formula (T-1) to (T-4) of dicarboxyphenyl)pyridine. They may be used alone or in combination of two or more. -25- 200948861

In the above, the tetracarboxylic dianhydride used in the synthesis of the polyamic acid is preferably a butane tetracarboxylic acid from the viewpoint of exhibiting a liquid crystal alignment property in which the formed liquid crystal alignment film is excellent. Anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5: 6-dianhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, l,3,3a,4,5,9b- Hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5 , 9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-indolyl]-furan-1,3-dione, 1 ,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furan-26- 200948861 naphthalene n,2-c ]_furan.υ·dione, bicyclo[2.2 2]•xin_7|2 3′5 6_ tetraresidic acid di, pyromellitic acid dihepatic, 3,3,,4,4,<benzophenone Tetraphthalic acid dianhydride, ^,, ^,-diphenyl maple four with two Naphthyltetradecanoic acid is the compound represented by the above formula (T - I), and the compound represented by the following formula (τ_5) to (τ_7) and the compound of the above formula (τ-Π) A tetracarboxylic dianhydride of at least one selected from the group consisting of compounds represented by the formula (τ-8) (hereinafter referred to as "specific tetracarboxylic dianhydride").

Ο

Particularly preferred specific tetracarboxylic dianhydride is 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid Diacetate, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornazole, 2:3,5:6-dianhydride, 1,3 ,38,4,5,915-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1, 3,3a,4,5,9b-hexahydro_8_methyl_5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan-I, 3-diketone, pyromelli-4-27-200948861 Acid dianhydride and at least one selected from the group consisting of compounds represented by the above formulas (Τ-5)~(Τ-8). The tetracarboxylic dianhydride used in the synthesis of the polyamic acid is preferably contained in an amount of 80 mol% or more of the specific tetracarboxylic dianhydride as described above with respect to all tetracarboxylic dianhydrides. 90% or more of Mo, more than 95% Mo. &lt;Synthesis of Polyproline&gt; The polyglycolic acid ' used in the present invention can be synthesized by reacting the tetracarboxylic dianhydride as described above with a diamine. The ratio of the tetracarboxylic dianhydride to be used for the reaction of the poly-proline is preferably from 1 to 2 equivalents based on 1 equivalent of the amine group contained in the diamine. The ratio is preferably such that it is a ratio of 〇.7 to 1.2 equivalents. When the acid anhydride group of the tetracarboxylic dianhydride is in a ratio of 0.5 to 2 equivalents, the degree of polymerization is likely to be improved, which is preferable from this point. If the ratio is from 0.7 to 1.2 equivalents, the degree of polymerization is particularly easy to increase, and thus it is more preferable from this point. 〇 The above polylysine may also be a terminally modified polylysine having a molecular weight adjustment. By using the terminal-modified polyacrylic acid, the coating performance and the like of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention. Such a terminal-modified polyglycolic acid can be synthesized by adding a suitable molecular weight modifier such as a monoanhydride, a monoamine compound or a monoisocyanate compound to the reaction system during the synthesis of polyamic acid. As the above monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride or n-hexadecyl amber may be mentioned. Anhydride, etc. As the monoamine-28-.200948861 compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecane may be mentioned. Amine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecaneamine, n-heptadecaneamine, n-octadecylamine or n-icosylamine . The monoisocyanate compound may, for example, be phenyl isocyanate or naphthyl isocyanate. The ratio of use of the molecular weight modifier is preferably 20 parts by weight or less, more preferably 10 parts by weight based on the total amount of the tetracarboxylic dianhydride and the diamine used in the synthesis of the polyglycolic acid. The following. The synthesis reaction of polylysine is carried out in an organic solvent, preferably at -20 to 150 ° C, more preferably at a temperature of 0 to 100 ° C, and the reaction time is preferably 0.5 to 120 hours. The better system is 2 to 1 hour. Here, the organic solvent is not particularly limited as long as it is a solvent capable of dissolving the synthesized polyaminic acid, and examples thereof include N-methyl-2-foslacone and N,N-dimethyl B. Aprotic polar solvents such as decylamine, N,N-dimethylformamide, dimethyl sulfoxide, r-butyrolactone, tetramethylurea, hexamethylphosphonium triamine; G-m-methylphenol a phenolic solvent such as xylenol, phenol or a halogenated phenol. In addition, the amount (a) of the organic solvent is preferably such that the total amount of the tetracarboxylic dianhydride and the diamine (b) is relative to the total amount of the reaction solution. The amount (a + b) is an amount of 0.1 to 30% by weight. Further, when the organic solvent is used in combination with the following poor solvent, the amount of the above organic solvent means the total amount of the organic solvent and the poor solvent. In the above organic solvent, a poor solvent alcohol of polyacrylic acid, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon, or the like may be used in combination in a range in which the produced polyamine acid is not precipitated. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, C--29-200948861 diol, 1,4-butanediol, triethylene glycol, and ethylene. Alcohol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methoxy propionate Ester, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene Alcohol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Methyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, φ dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-di Chlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, and the like. When the organic solvent and the poor solvent are used, the ratio of the use of the poor solvent is preferably 50% by weight or less, more preferably 20% by weight or less, and particularly preferably 20% by weight or less based on the total amount of the organic solvent and the poor solvent. 10% by weight or less. As described above, a reaction solution in which polylysine was dissolved was obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal alignment agent, or the polyphthalic acid contained in the reaction solution may be separated and supplied to the liquid crystal alignment agent, or the separated polyamic acid may be refined. The preparation of the liquid crystal alignment agent is supplied. The separation of the polyamic acid can be carried out by introducing the reaction solution into a large amount of a poor solvent to obtain a precipitate, and then drying the precipitate under reduced pressure or by subjecting the reaction solution to distillation under reduced pressure using an evaporator. . Further, the poly-proline can be purified by a method of re-dissolving the polyamine in an organic solvent once or several times and then precipitating it with a poor solvent or by distilling off under reduced pressure with an evaporator. &lt;醯i-Iminylated Polymer&gt; -30- 200948861 The ruthenium iodide polymer used in the present invention can be synthesized by dehydrating and ring-closing the polylysine as described above. a dehydration ring closure of polylysine, which may be (I) by heating poly-proline, or (II) by dissolving poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution according to It needs to be carried out by heating. The reaction temperature in the method for heating poly-proline in the above (I) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 °C, the dehydration ring-closure reaction cannot be sufficiently carried out. If the reaction temperature exceeds 200 °C, the molecular weight of the obtained quinone imidized polymer may decrease. The reaction time is preferably from 1 to 120 hours, more preferably from 2 to 30 hours. In the method of adding a dehydrating agent and a dehydrated closed-loop catalyst to the polyamic acid solution of the above (II), an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent is preferably 0.01 to 20 moles per 1 mole of the repeating unit of the polyglycolic acid. Further, as the dehydration ring-closure catalyst, for example, a tertiary amine such as pyridine, trimethylpyridine, dimethylpyridine or triethylamine can be used, but it is not limited thereto. The amount of the dehydration ring-closing oxidizing agent is preferably 0.01 to 10 moles per mole of the dehydrating agent used. The organic solvent used in the dehydration ring-closure reaction may, for example, be an organic solvent exemplified as a solvent used in the synthesis of polyglycolic acid. Further, the reaction temperature of the dehydration ring closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C. The reaction time is preferably from 0.5 to 30 hours, more preferably from 2 to 10 hours. The quinone imidized polymer obtained in the above method (I) may be directly supplied to a liquid crystal alignment agent, or may be obtained by refining the obtained quinone imidized polymer and then supplying it to a liquid crystal alignment agent. Further, in the above method -31-200948861 (II), a reaction solution containing a ruthenium iodide polymer is obtained. The reverse can be directly supplied to the preparation of the liquid crystal alignment agent, or the liquid crystal can be prepared by removing the dehydrating agent and the dehydration ring-closing catalyst, and the preparation of the supply liquid can be separated after the separation of the ruthenium iodide polymer, or can be separated. The quinone imidized polymer concentrates the formulation of the liquid crystal alignment agent. The dehydrating agent ring catalyst is removed from the reaction solution, and a method such as solvent replacement can be employed. Separation and purification of the quinones can be carried out in the same manner as described above for the polyacetin 0 purification method. The ruthenium iodide polymer used in the present invention may be a complete dehydration ring-closed structure of the valine acid structure of the amine acid, or may be a partial valerate structure dehydration ring closure, a structure and a quinone ring. Coexisting quinone imide. The oxime imidization ratio of the ruthenium iodide polymer is preferably from 1 to 10%, more preferably from 40 to 90%. The "yttrium imidation rate" refers to the enthalpy expressed as a percentage of the quinone imine ring structure relative to the total amount of valeric acid and quinone ring in the polymer. At this time, a part of the quinone ring may also be an imine ring. The ruthenium amination rate can be arbitrarily controlled by adjusting the above-described dehydration ring closure conditions. &lt;Solid viscosity of polyaminic acid and ruthenium iodide&gt; When the polyglycine and the ruthenium iodide polymer used in the present invention are formulated into a solution having a concentration of 10% by weight, preferably 20 The solution viscosity of ~ s is better than the solution viscosity (mPa_s) of the above-mentioned polymer having a solubility of 30 to 500 mPa.s, which is obtained by using the solution and the reaction solution to the compounding agent of the agent. Separation of dehydrated amylation polymerization, pro-polymerization of polyamidated proline sulphate ~100%, the so-called structure quantity ratio is used as the inverse of the isoindole reaction, when respectively -8 0 0 m P a * e viscosity. Polymer -32- 200948861 Good solvent (such as N-methyl-2-pyrrolidone, butyrolactone, etc.) formulated as a 〇 〇 weight % polymer solution, measured with an E-type rotary viscometer at 25 ° C Hey. &lt;Other Ingredients&gt; The liquid crystal alignment agent of the present invention comprises at least one polymer selected from the group consisting of a specific polyamic acid and a quinone imidized polymer as described above without impairing the effects of the present invention. Other ingredients may optionally be included on the premise of the advantages. Examples of such other components include a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy compound"), a functional decane compound, and the like. For example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 , 6-hexanediol diglycidyl ether, glycerol diglycidyl charm, 2,2-dibromo neopentyl glycol diglycidyl ether, \:^"', :^'-tetraglycidyl-m-phenylene Methylamine, 1,3-bis(1^,;^-dihydrogen glycerylaminomethyl)cyclohexane, N,N,N',N'·tetraglycidyl·4,4′- Aminodiphenylmethane, anthracene, hydrazine-diglycidyl-benzylamine, hydrazine, hydrazine-diglycidyl-aminomethylcyclohexane, etc. The mixing ratio of these epoxy compounds is relative to 100 The part by weight of the polymer is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight. The decane compound may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane or 2-aminopropyltriethoxylate. Decane, Ν-(2·aminoethyl)-3-aminopropyltrimethoxydecane, Ν-(2-aminoethyl)-3-aminopropyl-33- 200948861 methyldimethoxy Baseline, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3 -Aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxydecane -1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazaindole Acetate, 9-triethoxydecyl-3,6-diazadecyl acetate, methyl 9-trimethoxydecyl-3,6-diazadecanoate, 9-three Ethoxy decyl hydrazine - methyl 3,6-diazepine, N-benzyl-3.aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxy矽Alkane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, glycidoxymethyltrimethoxydecane, propylene-propylene Oxymethyltriethoxydecane, 2-glycidoxyethyltrimethoxydecane, 2-glycidoxyethyltriethoxydecane, 3-glycidoxypropyltrimethoxy A decyl alkane, a 3-glycidoxypropyltriethoxy decane, etc. The mixing ratio of these functional decane compounds is preferably 2 parts by weight or less based on 100 parts by weight of the polymer, more preferably The liquid crystal alignment agent of the present invention is preferably obtained by dissolving the above-mentioned polymer and optionally other components in an organic solvent. The organic solvent which can be used in the liquid crystal alignment agent of the present invention may, for example, be a solvent exemplified as a solvent used in the synthesis reaction of polyglycine. It is also possible to appropriately select a solvent which is exemplified as a poor solvent which can be used in the synthesis reaction of polyproline. -34- 200948861 A particularly preferred organic solvent which can be used in the liquid crystal alignment agent of the present invention is, for example, N-methyl-2-pyrrolidone, r-butyrolactone, r-butyrolactone, hydrazine, hydrazine-II. Methylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methoxypropyl Methyl ester, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol Dimethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, Diethylene glycol monoethyl ether acetate, isoamyl propionate, isoamyl isobutyrate, isoamyl ether, ethylene carbonate, propylene carbonate, and the like. They may be used singly or in combination of two or more. A particularly preferable solvent composition is a composition obtained by combining the above solvents, and is a composition in which the polymer does not precipitate from the alignment agent and the surface tension of the alignment agent falls within the range of 25 to 40 mN/m. The solid content concentration of the liquid crystal alignment agent of the present invention (the ratio of the total weight of the components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) Q is selected in consideration of viscosity, volatility, and the like. It is preferably from 1 to 10% by weight. That is, the liquid crystal alignment agent of the present invention forms a coating film as a liquid crystal alignment film by applying it to the surface of the substrate and then removing the solvent, and when the solid content concentration is less than 1% by weight, the coating film is caused. If the thickness exceeds 4, it is difficult to obtain a good liquid crystal alignment film, and when the solid content concentration exceeds 10% by weight, the thickness of the coating film is too thick and it is also difficult to obtain a good liquid crystal alignment film, and the liquid crystal alignment agent may be sticky. The increase in the properties leads to a deterioration in coating performance, and thus is not preferable. The particularly preferable solid content concentration range differs depending on the method used to apply the liquid crystal alignment agent to the -35-200948861 substrate. For example, when the spin coating method is employed, it is preferably 1.5 to 4.5 weight%. The scope. When the printing method is employed, it is preferable that the solid content concentration is in the range of 3 to 9 % by weight, so that the viscosity of the solution falls within the range of 12 to 50 rnPa's. When the ink jet method is employed, it is preferable that the solid content concentration is in the range of 1 to 5% by weight, so that the solution viscosity falls within the range of 3 to 15 mPa's. The temperature at which the liquid crystal alignment agent of the present invention is formulated is preferably 〇 ° C to 200 ° C, more preferably 20 ° C to 60 ° 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. The liquid crystal display element of the present invention can be produced, for example, by the following methods (1) to (3). (1) The liquid crystal alignment agent of the present invention is applied to a transparent conductive film provided with a substrate on which a patterned transparent conductive film is formed by an appropriate coating method such as a roll coating method, a spin coating method, a printing method, or an inkjet method. On one side, a coating film is formed by heating the coating surface. As the substrate, for example, glass such as float glass or soda lime glass, polyethylene terephthalate, polybutylene terephthalate, polyether maple, polycarbonate, or polycyclic ring can be used. A transparent substrate made of plastic such as olefin). As the transparent conductive film, a NESA film made of Sn02, an ITO film made of ln203-Sn02, or the like can be used. For forming the patterned transparent conductive film, a method of forming a pattern by photolithography after forming a transparent conductive film without patterning, and forming a pattern directly by using a mask having a desired pattern when the transparent conductive film is formed may be employed. A method of forming a transparent conductive film or the like. -36- 200948861 In the application of the liquid crystal alignment agent, in order to further improve the adhesion between the substrate and the transparent conductive film and the coating film, a functional decane compound, titanate, or the like may be previously coated on the substrate and the transparent conductive film. . The heating temperature after the application of the liquid crystal alignment agent is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. The heating time is preferably from 5 to 200 minutes, more preferably from 10 to 100 minutes. The liquid crystal alignment agent of the present invention forms a coating film as a liquid crystal alignment film by coating the organic solvent as described above, and when the polymer contained in the liquid crystal alignment agent of the present invention is a poly-proline or a φ is present When the imine-imided polymer of the imine ring structure and the proline structure is formed, it is also possible to carry out a dehydration ring-closure reaction by further heating after forming a coating film to form a coating film which is further imidized. The thickness of the formed coating film is preferably 0.001 to 1 mm, more preferably 0.005 to 0.5/zm, as the thickness after solvent removal. In addition, when the liquid crystal display element to which the liquid crystal alignment agent of the present invention is applied is a VA type liquid crystal display element, a projecting structure can be formed on the substrate as described in, for example, JP-A-2002-327058. The liquid crystal alignment agent is applied afterwards to achieve the purpose of improving the viewing angle performance. (2) The coating film formed as described above may be used as the liquid crystal alignment film of the VA liquid crystal display element as it is, or may be subjected to the following polishing treatment as needed. When the coating film is used as a liquid crystal alignment film of a TN type or STN type liquid crystal display element, the surface of the coating film formed as described above is fixed by a roll wrapped with a cloth made of a fiber such as nylon, rayon, or cotton. Grinding treatment of direction friction. Thus, the coating film is imparted with the alignment energy of the liquid crystal molecules to form a liquid crystal alignment film. By the liquid crystal alignment film formed as described above, the ultraviolet light is partially irradiated as shown in the patent document No. 37-200948861, for example, the patent document 15 (Japanese Patent Laid-Open Publication No. H22366) or the patent document 16 (JP-A-6-2 81937). In the process of changing the pretilt angle, or after partially forming a resist film on the surface of the liquid crystal alignment film which has been subjected to the rubbing treatment as shown in the patent document 17 (Japanese Laid-Open Patent Publication No. H5-107544), After the polishing process is performed in different directions, the resist film is removed, so that the liquid crystal alignment of the liquid crystal alignment film can be changed, and the field of view of the liquid crystal display element can be improved. b - 〇 (3) Two pieces of liquid crystal are formed as described above. The substrate of the alignment film is placed opposite to each other through a gap (cell gap). The peripheral portions of the two substrates are bonded together with a sealant, and liquid crystal is injected into the cell gap surrounded by the surface of the substrate and the sealant, and the injection holes are closed to constitute a liquid crystal cell. Then, a polarizing plate was provided on each of the outer surfaces of the liquid crystal cells, i.e., on the transparent substrate side of both, to obtain a liquid crystal display element. Here, as the sealant, for example, an epoxy resin or the like containing alumina balls as a curing agent and a separator can be used. Examples of the liquid crystal include nematic liquid crystals and dish-shaped liquid crystals, of which Ο is preferably a nematic liquid crystal, and for example, a Schiff's-type liquid crystal, an oxidized azo-based liquid crystal, a biphenyl-based liquid crystal, or a phenyl ring can be used. A hexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenyl cyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, or a cuba liquid crystal. Further, in these liquid crystals, cholesteric liquid crystals such as cholesteryl cholesteryl, cholesteryl phthalate, and cholesteryl carbonate may be added under the trade names "C-1 5" and "CB-15" (manufactured by Merck & Co., Inc.). The sale is performed on the palm and the like. The polarizing plate to be bonded to the outer surface of the liquid crystal may be a polarizing film called "ruthenium film" which is obtained by stretching and dispersing polyvinyl alcohol and simultaneously absorbing iodine - 38- « 200948861 A polarizing plate, or a polarizing plate made of a ruthenium film itself. EXAMPLES Hereinafter, the present invention will be more specifically illustrated by the examples, but the present invention is not limited to the examples. The solution viscosity of the polymer and the ruthenium iodide ratio of the ruthenium iodide polymer in the following synthesis examples were evaluated by the following methods. [Solid viscosity of the polymer] 溶液 The solution viscosity (mPa·s) of the polymer was measured at 25 ° C for each polymer solution using a Ε-type rotational viscometer. [The ruthenium imine ratio of the ruthenium iodide polymer] The ruthenium iodide polymer is dried under reduced pressure at room temperature, and then dissolved in deuterated dimethyl hydrazine, using tetramethyl decane as a reference. The W-NMR measured at room temperature was determined by the following formula (i). Ruthenium amination rate (%) = (1 - A^A^cOxlOO (i) A1: peak area from the NH matrix near 10 ppm Ο A2: peak area from other protons α: relative to 醯The ratio of the number of other nh protons in the imidized polymer precursor (polyproline), the number of other protons. Synthesis Example 1 (synthesis of hydrazide polymer Α1) will be used as tetracarboxylic dianhydride 3,5,6-tricarboxy-2-carboxymethylnorbornyl-2:3,5:6-dianhydride 1258 (0.50 mol), 147 g of the compound represented by the above formula (^-1) as a diamine (0.24 mol), p-phenylenediamine 26 g (0.24 mol) and 3,5-aminobenzoic acid gallstones vinegar 10.4 g (〇.〇2 mol) dissolved in 1230 g N-methyl-2 In pyrrolidone, the reaction is carried out at 60 ° C for 6 hours. The poly-proline acid solution obtained by adding -39-200948861 is added to N-methyl-2-pyrrolidone to form a polyglycine concentration of 1 〇. The solution viscosity of the % solution was determined to be 50 mP a·s. Then, 190 g of r-butyrolactone was added to the obtained polyamid acid solution, and then 80 g of pyridine and 1 g of acetic anhydride were added. Dehydration ring closure reaction at °C for 4 hours. Thereafter, by replacing the solvent in the system with a new r-butyrolactone solvent (in this operation, the pyridine and acetic anhydride used in the dehydration ring-closure reaction were removed to the outside of the system), about 1 900 g of 15% by weight of hydrazine was obtained. A solution of the imidized polymer A1 having an imidization ratio of about 80%. ❹ A small amount of the solution is diluted with 7&quot;-butyrolactone to form a solution having a concentration of 10% by weight of the ruthenium iodide polymer. The measured solution viscosity was 40 mP as. Synthesis Examples 2 to 8, Comparative Synthesis Examples 1 to 6 (synthesis of ruthenium iodide polymers A2 to A8 and comparative ruthenium iodide polymers R1 to R6) In the same manner as in the above Synthesis Example 1, except that the diamine and the tetracarboxylic dianhydride were listed in the same manner as in the above, the ruthenium-containing polymer A2 to A8 and the comparative ruthenium-based polymer R1 were respectively obtained. The solution of the arsenazolylized polymer was listed in Table 1. In addition, in Table 1, "Compound A" and "Compound B" refer to the above formula (A). a compound and a compound represented by the above formula (B), and the abbreviations of the respective compounds mean the following meanings, respectively The unit of the "amount" of the compound is Mohr. In Comparative Synthesis Examples 1 to 6, two other diamines are used in each case. &lt;Diamine&gt; [Compound represented by the above formula (A)] bl: Cholesteryl 3,5-diaminobenzoate b2: 1-cholestyloxy-2,4-diaminobenzene-40- 200948861 [Compound represented by the above formula (B)] b3 : Compound b4 represented by the formula (B-2): the compound b5 represented by the above formula (B-2): the compound b6 represented by the above formula (B-3): the compound b7 represented by the above formula (B-7): the above formula (B) - the compound b8 represented by the above formula (B-11): the compound represented by the above formula (B-17) ❹ blO : the compound represented by the above formula (B-21) [other diamine] bll: 1-octadecyloxy-2,4-diaminobenzene bl2: p-phenylenediamine &lt;tetracarboxylic dianhydride&gt; al : 3,5,6-tricarboxy-2-carboxymethylnorbornane - 2:3,5:6-dianhydride a2: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride

-41 - 200948861 Table 1 Diamine tetracarboxylic acid dianhydride hydrazide polymer compound (Α) Compound (B) Other diamine name acid imidization ratio (%) Observation amount Surface (quantity) Type (quantity) Surface (quantity) Synthesis Example 1 bl (0.02) b3 (0.24) bl2 (0.24) al (0.5) A1 80 Synthesis Example 2 bl (0.02) b4 (0.24) bl2 (0.24) al (0.5) A2 75 Synthesis Example 3 b 1(0.02) b5(0.24) bl2(0.24) al(0_5) A3 78 Synthesis Example 4 bl(0.02) b6(0.24) bl 2(0.24) al(0.5) A4 77 Synthesis Example 5 bl(0.02) b7(0.24 ) bl 2(0.24) al(0.5) A5 85 Synthesis Example ό b2(0.03) b8(0.23) bl2(0_24) a2(0.5) A6 84 Synthesis Example 7 b2(0.01) b9(0.09) bl2(0.4) al( 0.5) A7 80 Synthesis Example 8 b2(0.01) bl0(0.09) bl2(0.4) a2(0.5) A8 85 Comparative Synthesis Example 1 - b3(0.2) bll(Ol) bl2(0.2) al(0.5) R1 85 Comparative Synthesis Example 2 - b4(0.2) bll(Ol) bl2(0.2) al(0.5) R2 81 Comparative Synthesis Example 3 - b5(0.2) bll(Ol) bl2(0.2) al(0.5) R3 83 Comparative Synthesis Example 4 - b6 (0.2) bll(Ol) bl2(0.2) al(0.5) R4 78 Comparative Synthesis Example 5 - b7(0.2) bll(Ol) bl2(0.2) al(0.5) R5 79 Comparative Synthesis Example 6 - b8(0.2) bll (Ol) bl2(0.2) al(0.5) R6 77 实施 Example 1 ❹ &lt;Preparation of Liquid Crystal Aligning Agent&gt; To a solution containing ruthenium iodide polymer A1 prepared in the above Synthesis Example 1, relative to 100 parts by weight of the ruthenium iodide polymerization contained in the above polymer solution A1, adding 5 parts by weight of 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane as an epoxy compound, and then adding r-butyrolactone, N-methyl-2- Pyrrolidone and butyl cellosolve were formulated to have a solvent composition of r-butyrolactone: N-methyl-2-pyrrolidone: butyl cellosolve = 71: 17: 12 (by weight), and a solid content concentration of 4% by weight. This solution was filtered through a filter having a pore diameter of -42 to 200948861 l#m to prepare a liquid crystal alignment agent. Various evaluations were carried out as follows using this liquid crystal alignment agent. &lt;Printability Evaluation&gt; The liquid crystal alignment agent prepared above was applied with a thickness of 200 nm and a width of 20# m at intervals of 100 using a liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.). The transparent electrode surface of the glass substrate of the transparent electrode of the strip-shaped ITO film was formed by heating at 8 ° C for 1 minute to form a coating film. When the coating film was observed with an optical microscope at a magnification of 20 times, the stepped portions of the base plate were uniformly covered, and no defects were observed on the coating film, and the printing property was good. &lt;Production of Liquid Crystal Cell&gt; The liquid crystal alignment agent prepared above was applied onto the transparent electrode surface of a glass substrate made of a transparent electrode made of an ITO film by spin coating, and then heated on a hot plate for 1 minute, and then The film was heated on a hot plate at 200 ° C for 10 minutes to form a coating film having an average thickness of 600 A. The coating film is polished by a grinding machine equipped with a roller wound with a rayon cloth at a roller speed of 500 rpm, a table moving speed of ❹ 3 cm/sec, and a fluffing length of 0.4 mm. The coating film is given a liquid crystal alignment energy. Then, the substrate having the coating film was ultrasonically washed in ultrapure water for 1 minute, and then dried in a 100 ° C clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film on the transparent electrode. This operation was repeated to fabricate a pair of (two pieces) substrates having a liquid crystal alignment film on the surface of the transparent electrode. Then, on each of the outer edges of the pair of substrates having the liquid crystal alignment film, an epoxy resin adhesive having an alumina ball having a diameter of 5.5/zm is applied, and then the liquid crystal alignment film faces are relatively pressed and pressed together. And then make the adhesive -43- 200948861 cure. Then, a nematic liquid crystal (MLC-6221, manufactured by Merck & Co., Inc.) was charged between a pair of substrates through a liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a liquid crystal cell. &lt;Measurement of Pretilt Angle&gt; According to the method described in Non-Patent Document 1 (TJ Scheffer et al., J. Appl. Phys., Vol. 19 '2013 (1980)), a crystal rotation method using He-Ne laser The pretilt angle was measured for the liquid crystal cell manufactured above, and the pretilt angle was 5°, which showed a high 値 〇 〇 Examples 2 to 8 and Comparative Examples 1 to 6 except for the type of the polymer contained in the polymer solution used. As shown in Table 2, a liquid crystal alignment agent was prepared and evaluated in the same manner as in the above Example 1. The evaluation results are shown in Table 2. Further, in the evaluation of the printability of Comparative Examples 1 to 6 in Table 2, since the liquid depression occurred in the step portions of all the substrates, the portion where the coating film was not formed was present, and the printability of each of the substrates was judged as " bad". 〇 -44- .200948861 Table 2 Liquid alignment agent Liquid crystal cell Polymer type Printability Pretilt angle Example 1 A 1 Good 5° Example 2 A2 Good 5. Example 3 A3 Good 6° Example 4 A4 Good 5° Example 5 A5 Good 6° Example 6 A6 Good 7° Example 7 A7 Good 6. Example 8 A8 is good 6° Comparative Example 1 R1 failed 5 . Comparative Example 2 R2 failed 4° Comparative Example 3 R3 failed 5 Comparative Example 4 R4 failed 5° Comparative Example 5 R5 failed 6° Comparative Example 6 R6 Unsatisfied 5° It is understood from the above examples that the compound represented by the above formula (A) and the compound represented by the above formula (B) are contained. The liquid crystal alignment agent of the present invention which is a diamine-synthesized polymer exhibits excellent printability' and the formed liquid crystal alignment film exhibits a high pretilt angle (Examples 1 to 8). On the other hand, in Comparative Examples 1 to 6 in which 1-octadecyloxy-2,4-diaminobenzene was used in place of the compound represented by the above formula (A), the printability of the liquid crystal alignment agent was poorly obtained. result. [Simple description of the diagram] None. [Main component symbol description] None. -45-

Claims (1)

200948861 VII. Patent application scope: 1. A liquid crystal alignment agent characterized by comprising at least one polymer selected from the group consisting of polylysine and dehydration of the polyglycolic acid. A ruthenium-imided polymer obtained by reacting a diamine with a tetracarboxylic dianhydride containing a compound represented by the following formula (A) and expressing the following formula (B) compound of, In the formula (A), A1 represents a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, a fluoromethylene group or a fluoroalkylene group having 2 to 6 carbon atoms, and A2 represents - 0-, -COO-, -OCO-, -NHCO-, -CONH- or -CO-, A3 represents a monovalent organic group having a steroid skeleton, In the formula (B), B1 is -0-, -COO., -OOC-, -CONH- or -NHCO-, B2 is a biphenyl group; a cyanobiphenyl group; a fluorobiphenyl group; having a carbon number An (alkylcyclohexyl)phenyl group having 1 to 32 alkyl groups; an alkoxybenzyl group having a carbon number of 1 to 32, a dialkoxyphenyl group or an alkoxybiphenyl group; a fluoroalkoxybiphenyl having a fluoroalkoxy group having 1 to 32 carbon atoms; or an alkyl group having 1 to 32 carbon atoms, bl and b3 each -46-.200948861 , b2 is an integer of 2 to 22. 2. The liquid crystal alignment agent according to the above aspect of the invention, wherein the ratio of the compound represented by the above formula (A) in the amine is 0.1%. 3. The liquid crystal alignment agent according to claim 1 or 2, wherein the compound represented by the formula (A) is cholesteneoxy-2, benzene, cholesteryl 3,5-diaminobenzoic acid The ester, the cholestanediamine benzene, and the cholesteryl 3,5-diaminobenzoate constitute at least one selected. A liquid crystal display element comprising a film formed of the liquid crystal alignment agent according to any one of claims 1 to 3. ❹ The above two - 50 moles, of which the upper 4-diaminooxy-2,4- group of patents range liquid crystal alignment -47- 200948861 IV. Designated representative map: (1) The representative representative of the case is: no. (2) A brief description of the symbol of the representative figure: te 〇 jw\ 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: