TW200521207A - Liquid crystal alignment agent and liquid crystal display element - Google Patents

Abstract

To provide a liquid crystal alignment agent suitable for vertical alignment type liquid crystal display elements and may form a liquid alignment film excellent in vertical alignment property of liquid crystal. A liquid crystal alignment agent comprises a polymer having on the side chains at least one structure selected from the group consisting of a structure represented by the following formula (I) and a structure represented by the following formula (II), wherein A1 and B1 independently of each other represents hydrogen atom, a halogen atom or a cyano group, but at least one of A1 and B1 is a halogen atom or a cyano group.

Description

200521207 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a liquid crystal alignment agent and a liquid crystal display element. More specifically, '' relates to a liquid crystal alignment agent having a vertical alignment property suitable for a vertical alignment type liquid crystal display device application, and a liquid crystal display device including a liquid crystal alignment film obtained from the liquid crystal alignment agent. [Prior art] At present, a liquid crystal display element is a liquid crystal alignment film formed of polyimide, polyimide, or the like on a substrate surface provided with a transparent conductive film. As a substrate for a liquid crystal display element, two sheets are opposed to each other. It is arranged in the gap to form a nematic liquid crystal layer with positive dielectric anisotropy to form a sandwich cell. The long axis of the liquid crystal molecules is twisted 90 degrees continuously from one substrate to the other substrate. TN type liquid crystal display elements of nematic) liquid crystal cells are known. In this regard, the vertical alignment type liquid crystal display element is a liquid crystal vertical alignment with negative dielectric anisotropy, and it is operated by applying a voltage to cause the liquid crystal molecules to dump, which is excellent in terms of viewing angle and contrast. Come prevalent research development. Here, in order to align the liquid crystal vertically, the liquid crystal alignment film must be made hydrophobic. Therefore, the alignment agent must contain a large amount of a hydrophobic component (hereinafter referred to as a vertical alignment component). The vertical alignment component is usually an aliphatic, alicyclic, or fluorine-containing functional group. However, when using this vertical alignment component, there is a problem that the stability of the vertical alignment is insufficient. Therefore, development of a liquid crystal alignment agent excellent in vertical alignment stability is required. [Summary of the Invention] 200521207 · The object of the present invention is to provide a vertical alignment type liquid crystal alignment agent with excellent vertical alignment stability. Another object of the present invention is to provide a liquid crystal display element including a liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention. Other objects and advantages of the present invention will be apparent from the following description. The above-mentioned object and advantages of the present invention are based on a liquid crystal alignment agent of the first system, which is characterized in that it contains at least one selected from a structure represented by the following formula (I) and a structure represented by the following formula (II) in a side chain. Polymer. [Chemical 1]

(Wherein 'A1 and B1 are independently a hydrogen atom, a halogen atom, or a cyano group, but at least one of V and B1 is a halogen atom or a cyano group] [Chemical 2]

N-N The second object and advantages of the present invention are achieved by a liquid crystal alignment film comprising a liquid crystal alignment agent of the present invention. [Effects of the Invention] According to the present invention, a liquid crystal alignment agent 200521207 for a vertical alignment type liquid crystal display element 200521207 which is suitable for forming a liquid crystal alignment film with good vertical alignment when used as a liquid crystal alignment film can be provided. [Best Mode for Carrying Out the Invention] The present invention will be described in detail below. The liquid crystal alignment agent of the present invention contains a polymer having a structure represented by the formula (I) or a structure represented by the formula (II) in a side chain (hereinafter referred to as a "specific side chain"). In the above formula (I), A1 and B1 are each independently a hydrogen atom, a halogen atom or a cyano group. Among them, at least one of A1 and B1 is a halogen atom or a cyano group. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a fluorine atom is preferred. Specific examples of the specific side chain include a base having a structure represented by the following formula (III). [Chemical formula 3], PQ-R1-R2 (i) wherein P is a single bond, -〇-, -c〇 ··, or -CONH-, and Q is a structure represented by the above formula (I) or the above formula ( II) Construction shown. In addition, in the formula (III), R1 is a divalent alicyclic group. Specific examples of the alicyclic ring of the divalent alicyclic group include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a dicyclohexyl ring, a polycyclohexyl ring, and these rings One or two or more hydrogen atoms contained in the ring may be a ring substituted with a monovalent organic group such as an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, or a halogen atom. In addition, in the formula (III), R2 represents a linear alkyl group having 1 to 22 carbon atoms, preferably a linear alkyl group having 2 to 18 carbon atoms, and more preferably 3 to 10 carbon atoms. Linear alkyl. The structure of the polymer having a specific side chain is not particularly limited, and polyimide and a polyimide obtained by dehydrating and closing the polyamidic acid are preferable in terms of excellent heat resistance and electrical characteristics. . The polyamidic acid can be obtained by polycondensing a diamine (a) represented by the following formula (IV) and an acid anhydride (b) represented by the following formula 200521207 (V). Further, the fluorene imidized polymer can be obtained by dehydrating and closing the polyfluorinated acid. The synthesis of the polyfluorinated acid having a specific side chain and the fluorinated imidized polymer used in the liquid crystal alignment agent of the present invention is a compound having a specific side chain in at least one of U) diamine and (b) anhydride.

(Wherein Z2 represents a tetravalent organic group) The above-mentioned usage ratio of the specific side chain diamine or acid field is 1 to 100 moles for all the diamines (a) and all acid anhydrides (b) used in total. The ear% is better, more preferably 5 to 50 mole%. < Diamine> A specific example of the above-mentioned amine having one of the side bonds is, for example, 1- (2,3-digas-4- (4-n-propylcyclohexyl) benzyloxy) -2,4-monoamine Phenylbenzene, 1- (2,3-digas /-4- (4-π-butylcyclohexyl) phenoxy) -2,4-diaminobenzene, fluorene- (2,3-difluoro- 4- (4 · η -pentylhexyl) benzyloxy) -2,4 -monoaminobenzene, 1- (2,3-dichloro-4 (4-n-hexylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2,3-di_-4- (4-n-heptylcyclohexyl) phenoxy) -2,4-diaminobenzene; 200521207 1- ( 2,3-dicyano-4- (4-η-propylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2,3-dicyano-4- (4- n-butylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2,3-— • chloro- 4- (4-n-pentylcyclohexyl) phenoxy)- 2,4--aminobenzene, 1- (2,3-dicyano · 4- (4-η-hexylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2, 3-dicyano-4- (4-η-heptylcyclohexyl) phenoxy) -2,4-diaminobenzene; (2,3-difluoro-4- (4-11-propyl ring Hexyl) phenyl) -3,5-diaminobenzoate, (2,3-difluoro-4- (4-η-butylcyclohexyl) phenyl) -3,5-diaminobenzene Formic acid , (2,3-difluoro-4 (4-η-pentylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2,3-difluoro-4 · (4- η-hexylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2,3-difluoro-4- (4-η-heptylcyclohexyl) phenyl) -3,5- Diaminobenzoate; (2,3-dicyano-4- (4-η-propylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2,3 · Dicyano-4- (4-η-butylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2,3-dicyano-4- (4-η-pentyl) Cyclohexyl) phenyl) -3,5-diaminobenzoate, (2,3-dicyano-4- (4-n-hexylcyclohexyl) phenyl) -3,5-diamino Benzoate, (2,3-dicyano-4- (4-n-heptylcyclohexyl) phenyl) -3,5-diaminophenylbenzoate; l- (6- (4- n-propylcyclohexyl) -3-pyridyloxy) -2,4-diaminobenzene, l- (6- (4-n-butylcyclohexyl) · 3-pyridyloxy) -2 1,4-diaminobenzene, 1- (6- (4-η-pentylcyclohexyl) · 3-pyridyloxy) -2,4-diaminobenzene, 1- (6- (4-hexyl Cyclohexyl) -3-pyridyloxy) -2,4-diaminobenzene, l- (6- (4-n-heptylcyclohexyl) -3-pyridyloxy) -2,4-di Aminobenzene; (6_ (4-n- Cyclohexyl) -3-pyridyl) -3,5-diaminobenzoate, (^ ㈠-cardiobutylcyclohexyl) ^^ yl-diaminobenzoate, -10- 200521207 (6- (4-n-pentylcyclohexyl) -3-pyridyl) -3,5-diaminophenylbenzoate, (6- (4-η-hexylcyclohexyl)- 3-pyridyl) -3,5-diaminobenzoate, (6- (4-n-heptylcyclohexyl) -3-pyridyl) -3,5-diaminobenzoic acid Esters; 1- (2-fluoro-4- (4-n-propylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2-fluoro-4- (4-n-butane Cyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2-fluoro-4- (4-n-pentylcyclohexyl) phenoxy) -2,4-diaminobenzene , 1- (2 · fluoro-4 (4-n-hexylcyclohexyl) phenoxy) · 2,4-diaminobenzene, 1- (2-fluoro-4 · (4-η-heptyl ring Hexyl) phenoxy) -2,4-diaminobenzene; 1- (3-fluoro-4- (4-η-propylcyclohexyl) phenoxy) -2,4 · diaminobenzene, 1 -(3-fluoro_4- (4-n-butylcyclohexyl) phenoxy) -2,4-diaminobenzene 1- (3-fluoro-4- (4-η-pentylcyclohexyl) Phenoxy) -2,4-diaminobenzene 1- (3-fluoro- 4- (4-η · hexylcyclohexyl) phenoxy) -2,4-diaminobenzene 1- (3-fluoro -4- (4-η-heptylcyclohexyl Phenoxy) -2,4-diaminobenzene; 1- (2-cyano-4- (4-11-propylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2-cyano-4- (4 · η-butylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (2-cyano-4 · (4-η-pentyl ring Hexyl) phenoxy) -2,4-diaminobenzene, 1- (2-cyano-4- (4-n-hexylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1 -(2-cyano-4- (4-n-heptylcyclohexyl) phenoxy) -2,4-diaminobenzene; 1- (3-cyano-4- (4-η · propyl) Cyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (3-cyano-4- (4-η-butylcyclohexyl) phenoxy) -2,4-diaminobenzene 1- (3-cyano-4 · (4-η-pentylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (3-cyano-4- (4-n- Hexylcyclohexyl) phenoxy) -2,4-diaminobenzene, 1- (3-cyano-4_ (4-n-heptylcyclohexyl) phenoxy) -2,4-diaminobenzene ; (2 · fluoro-4- (4-n-propylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2-fluoro-4- (4-n-butylcyclohexyl) ) Phenyl) -3,5-diaminobenzoate, (2-fluoro-11-200521207 -4- (4-n-pentylcyclohexyl) phenyl) -3,5 · diaminobenzene Formate, (2-fluoro-4- (4-η-hexyl) Cyclohexyl) phenyl) -3,5-diaminobenzoate, (2-fluoro-4- (4-η-heptylcyclohexyl) phenyl) -3,5-diaminobenzoic acid Ester; (3-fluoro-4- (4-η · propylcyclohexyl) phenyl) -3,5 · diaminobenzoate, (3-fluoro-4- (4-η-butyl ring Hexyl) phenyl) -3,5-diaminobenzoate, (3-fluoro-4- (4-η-pentylcyclohexyl) phenyl) -3,5-diaminobenzoate (3-fluoro-4 · (4-η-hexylcyclohexyl) phenyl) -3,5-diaminobenzoate, (3-fluoro_4- (4-η-heptylcyclohexyl) Phenyl) · 3,5-diaminophenylbenzoate; (2-cyano-4 · (4-η-propylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2-cyano-4- (4-n-butylcyclohexyl) phenyl) -3,5-diaminobenzoate, (2-cyano-4- (4-n-pentyl ring) Hexyl) phenyl) -3,5-diaminobenzoate, (2-cyano-4- (4-n-hexylcyclohexyl) phenyl) -3,5-diaminobenzoate (2-cyano-4- (4-n-heptylcyclohexyl) phenyl) · 3,5-diaminobenzoate; (3-cyano-4- (4-η-propyl) Cyclohexyl) phenyl) -3,5-diaminobenzoate, (3-cyano-4 · (4-η-butylcyclohexyl) benzene ) -3,5-diaminobenzoate, (3-cyano-4 · (4-η-pentylcyclohexyl) phenyl) -3,5-diaminobenzoate, (3 -Cyano-4- (4-n-hexylcyclohexyl) phenyl) -3,5-diaminobenzoate, (3-cyano-4- (4-n-heptylcyclohexyl) benzene Radical) -3,5-diaminobenzoate. Among these, 1- (2,3-difluoro-4- (4-η · propylcyclohexyl) phenoxy) -2,4-diaminobenzene, fluorene- (2,3- Difluoro-4- (4-η-butylcyclohexyl) phenoxy) -2,4-diaminobenzene, fluorene- (2,3-difluoro-4- (4-η-pentylcyclohexyl) ) Phenoxy) -2,4 · diaminobenzene, fluorene- (2,3-difluoro-4- (4-η-hexylcyclohexyl) phenoxy) -2,4-diaminobenzene, ΐ- (2,3-difluoro-4- (4-η-heptylcyclohexyl) phenoxy) -2,4-diaminobenzene; -12- 200521207 1- (2,3-dicyano -4- (4-n-propylcyclohexyl) phenoxy) -2,4-diaminebenzene, 1- (2,3-dicyano-4- (4-n-butylcyclohexyl) benzene (Oxy) -2,4-diphenyl, 1- (2,3-dicyano-4- (4-n-pentylcyclohexyl) phenoxy) -2,4-diphenyl, 1- (2 , 3-dicyano-4- (4-n-hexylcyclohexyl) phenoxy) -2,4-diphenyl, 1- (2,3-dicyano-4- (4-n-heptyl) Cyclohexyl) phenoxy) -2,4-diphenyl; (2,3-difluoro-4- (4-n-propylcyclohexyl) phenyl) -3,5-diaminobenzyl, (2,3-difluoro-4- (4-n-butylcyclohexyl) phenyl) -3,5-diaminophenyl ester, (2,3-difluoro-4- (4-n-pentyl) Cyclohexyl) phenyl) -3,5-diaminophenyl ester, (2,3-difluoro-4- (4-n- Cyclohexyl) phenyl) -3,5-diaminophenyl ester, (2,3-difluoro-4- (4-n-heptylcyclohexyl) phenyl) -3,5-diaminobenzene Ester; (2,3-dicyano-4- (4-n-propylcyclohexyl) phenyl) -3,5-diaminophenyl ester, (2,3-dicyano-4- (4 -11-butylcyclohexyl) phenyl) -3,5-diamino ester, (2,3-dicyano-4- (4-11-pentylcyclohexyl) phenyl) -3,5 -Dicarbamate, (2,3-dicyano-4- (4-n-hexylcyclohexyl) phenyl) -3,5-dibenzoate, (2,3-dicyano- 4- (4-n-heptylcyclohexyl) phenyl) -3,5-ylbenzoate; propylcyclohexyl) -3-pyridyloxy) -2,4-diaminobenzene, l -(6- (4-n-butylcyclohexyl) -3 -ohexyloxy) -2,4-monoaminobenzene, 1- (6 · (4-η-pentylcyclohexyl) -3- Pyridoxy) -2,4-diaminobenzene, l- (6- (4-n-hexylcyclohexyl) -3-pyridyloxy) -2,4-diaminobenzene, l- ( 6- (4-n-heptylcyclohexyl) -3-pyridyloxy) -2,4-diaminobenzene; (6- (4-n-propylcyclohexyl) -3-pyridyl)- 3,5-diaminobenzoate (6- (4-n-butylcyclohexyl) -3-pyridyl) -3,5-diaminobenzoate, aminoaminoamine Amino Acid formic acid formic acid formic acid formic acid benzylaniline diamine-13- 200521207 (6- (4-n-pentylcyclohexyl) -pyridyl) -3,5-diaminobenzoate, (6 -(4-η · hexylcyclohexylpyridyl) -3,5-diaminobenzoate, (6- (heart η-heptylcyclohexyl) -3_pyridyl) -3,5- Diaminobenzoates are preferred. Other diamines used in the synthesis of the polymer contained in the liquid crystal alignment agent of the present invention, such as phenylenediamine, phenylenediamine, 4,4, diaminodiphenylmethane, diaminodiphenylethyl Alkane, 4,4, _diaminodiphenyl sulfide, 4,4, diaminodiphenylphthalide, 3,3, _dimethyl_4,4, _diaminobiphenyl, 4, 4, _diamino N-benzidine aniline, 4,4, diamino diphenyl ether, 丨 diamino naphthalene, 2, 2, dimethyl-4, 4, diamino biphenyl, Amino-Bu (4, aminophenyl) -1,3,3-trimethylbenzyl, 6-amino · fluorene- (4, -aminophenyl) -1,3,3-trimethyl Indan, 3,4, -diaminodiphenyl ether, 3,3, diaminobenzophenone, 3,4, diaminobenzophenone, 4,4'-diaminodiphenyl Methyl ketone, 2,2_bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2 , 2-Bis (4-monthly female basic group) hexafluoromethane, 2,2-bis [4- (4-aminophenoxy) phenyl], ι, 4-bis (4-aminobenzene (Oxy) benzene, cardioaminophenoxy) benzene, ^ bis-amino-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7- Diamine Swallow, 9,9-bis (4-aminophenyl) fluorene, 4,4, -methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4, 4'-diaminobiphenyl, 2,2'-dichloro-4,4, -diamino-5,5'-monomethoxybiphenyl, 3,3'-dimethoxy-4, 4. Diamine biphenyl, -phenylene isopropylidene) bisaniline, 4,4, "m_phenylene isopropylidene) bisaniline, 2,2, -bis [4- (4- Amino-2-trifluoromethylphenoxy) phenyl] Hexapropane, 4,4, -diamino-2,2, -bis (trifluoromethyl) biphenyl, 4,4, -Bis [(4-amino-2-trifluoromethyl) phenoxy] -aromatic diamines such as biphenyl octafluoride; m-xylylenediamine, 丨, 3-propanediamine, Tetramethyldiamine, Pentamethyldiamine, -14-200521207 Hexamethyldiamine, Heptamethyldiamine, Octadiamine, Ninemethyldiamine, 4,4-Diamino Heptamethyldiamine, 1,4-Diamine Aminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienediamine, hexahydro-4,7-methanolindanedimethyldiamine, tricyclo [6.2.1.02 · 7] -eleven Aliphatic and alicyclic diamines such as dimethylene diamine, 4,4'-methylenebis (cyclohexylamine), etc .; , 2,6-diaminopyridine, 3,4-monoaminopyridine, 2,4-diaminopyridine, 5,6-diamino-2,3-dicyano卩 Bigen, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-trigon, 1,4-bis (3-Aminopropyl) piperidine, diamino-6-isopropoxy-I, 3,5-triazine, 2,4-diamino-6-methoxy-I, 3,5 · Triple well, 2, cardiodiamino group · 6-phenyl-1,3,5_ triple well, 2,4-diamino-6-methyl-s-triple, 2,4-diamine group -1,3,5-Tritrap, 4,6-diamino-2-vinyl-s-trioxine, 2,4-diamino-5 -phenylfluorene '2,6-diaminopurine tj, 5,6-diamino-dimethyluridine, diaminotriazole, 6,9-diamino-2-ethoxypyridine lactate, 3,8-diamine -6-phenylphenanthridine, 1,4-diaminopiperidin '3,6-diaminopyridine, bis (4-aminophenyl) aniline and the following formulae (VI) to (VII) Compounds such as diamines having two mono-amino groups and nitrogen atoms other than the primary amino group in the molecule;

(Wherein R3 is a monovalent organic group having a ring structure selected from pyridine, pyrimidine, triple well, piperidine, and piperidine, and X1 is a divalent organic group) [Chem. 7] -15- 200521207 h2n

17 / ί m (wherein R4 is a divalent organic group having a ring structure selected from pyridine, pyrimidine, triple well, piperidine, and piperidine, X2 is a divalent organic group, and several X2 are present It may be the same or different.) The following formula (VIII) is a mono-substituted phenylenediamine; the following formula (IX) is a diamine-based organic sand oxygen institute;

(Wherein 'R5 is a divalent organic group selected from -〇-, · ◦〇〇-, -〇c〇-, -NHCO-, -CONH-, and -C◦-' R6 has a structure selected from the group consisting of cholesterol , Trifluoromethyl and fluoro-based monovalent organic groups or alkyl groups having 6 to 30 carbon atoms) 9] H2N- (CH2) p—Si R7 1 5 R7-(CH2) p—NH2 J q Hydrocarbon group (IX) R7 • O—Si— R7 (where R7 is a hydrocarbon group having 1 to 12 carbon atoms, several existing r7 may be the same or different, P is an integer of 1 to 3, and q is 丨 to 2〇 (Integer): For example, compounds represented by the following formulae (1) to (5). These diamine compounds can be used alone or in combination of two or more. [Chemical 〇] -16- 200521207

(Where y is an integer of 2 to 12 and z is an integer of 1 to 5) Among these, P-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenyl sulfide, 1,5 · diaminonaphthalene, 2,7-diaminofluorene, 4,4'-diaminodiphenyl ether, 2,2-bis [4- (4- Aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) buckwheat, 2,2-bis [4- (4-aminophenoxy) phenyl] propane hexafluoride , 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(m-phenylene diisopropylidene) bisaniline, 1,4 · cyclohexanediamine, 4 , 4'-methylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, the above formula (1) to (5) compounds, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6 -Diaminopyridine, the compound represented by the following formula (6) among the compounds represented by the above formula (VI), -17- 200521207, the compound represented by the following formula (7) among the compounds represented by the formula (VII), and Among the compounds represented by the formula (VIII), compounds represented by the following formulae (8) to (17), and the above (IX) are not compounds Shu, 3-bis (3-aminopropyl) siloxane silica hexamethyldisilazane preferred. 【Chemical 1 1】

-18- 200521207 < Tetracarboxylic dianhydride > A tetracarboxylic anhydride having a specific side chain, for example, 1,3,3a, 4,5,9b-hexahydro-4- (2,3-difluoro-4 -(4-n-propylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c] -furan-1,3 -Dione, 1,3,3a, 4,5,9b-A hydrogen-4- (2,3-difluoro-4- (4-n-butylcyclohexyl) phenoxy) -5- (tetra Hydrogen-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro- 4- ( 2,3-difluoro-4- (4-n-pentylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2_c ] -Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (2,3-difluoro-4- (4-n-hexylcyclohexyl) phenoxy ) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3,3a, 4,5, 9b-hexahydro-4- (2,3-difluoro-4- (4-n-hexylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl)- Naphtho [1,2-(:]-furan-1,3-dione, 1,3,3 &, 4,5,91) -hexahydro-4- (2,3-difluoro-4- ( 4-11-heptylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [1,2- c] -furan-1,3-dione; 1,3,3a, 4,5,9b-hexahydro-4- (2,3-dicyano-4- (4-n-propylcyclohexyl) Phenoxy) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3 &, 4,5,91) -hexahydro-4- (2,3-dicyano-4- (4-11-butylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl -3_furanyl) -naphtho [l, 2-c; l · furan · l, 3-dione, l, 3,3a, 4,5,9b-hexahydro-4- (2,3-di Cyano-4- (4-n_pentylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [1,2-(:]-furan -1,3-dione, 1,3,3 &, 4,5,91) -hexahydro-4- (2,3-dicyano_4- (4-n-hexylcyclohexyl) phenoxy ) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5, 9b-hexahydro-4- (2,3-dicyano-4- (4 · η-heptylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl-3- 200521207 furan ) -Naphtho [l, 2-c] -furan-1,3-dione; 1,3,3a, 4,5,9b-hexahydro-4- (6- (4-n-propyl ring) Hexyl) -3-pyridoxyl) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1 , 3,3 ^ 4 , 5,91 hexahydro-4- (6- (4-11-butylcyclohexyl) -3-pyridyloxy) -5- (tetrahydro · 2,5-dicarbonyl-3-furyl)- Naphtho [l, 2 · c] -furan-1,3-diketone, 1,3,3a, 4,5,9b-hexahydro-4- (6- (4-n-pentylcyclohexyl)- : 3-pyridyloxy) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3 , 33,4,5,91) -hexahydro-4- (6- (4-11-hexylcyclohexyl) -3-pyridoxyl) -5- (tetrahydro-2,5-dicarbonyl-3 -Furanyl) -naphtho [1,2 <]-furan-1,3- φdione, 1,3,38,4,5,913-hexahydro-4- (6- (4-11-heptyl ring Hexyl) -3-pyridyloxy) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione; l , 3,3a, 4,5,9b-hexahydro-4- (2-fluoro-4- (4-n-propylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl -3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3,3 &, 4,5,913-hexahydro-4- (2-fluoro-4- ( 4-11-butylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c] -furan-1,3-di Ketone, 1,3,3a, 4,5,9b-hexahydro-4- (2-fluoro-4- (4-n-pentylcyclohexyl) phenoxy · yl) -5- (tetrahydro-2, 5-dicarbonyl-3 · Ranyl) -naphtho [l, 2-c] -furan-l, 3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (2-fluoro-4- (4- n-hexylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1 , 3,3 &, 4,5,91 ^ hexahydro-4- (2-fluoro-4- (4-11-heptylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-di Carbonyl-3-furanyl) -naphtho [l, 2-c; l · furan-l, 3-dione; l, 3,3a, 4,5,9b-hexahydro-4- (3-fluoro- 4- (4-η · propylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [1,2-〇] -furan-1, 3- -20- 200521207 dione, 1,3,32,4,5,913-hexahydro-4- (3-fluoro-4- (4-11-butylcyclohexyl) phenoxy) -5- (tetra Hydrogen-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4 -(3-fluoro-4- (4-n-pentylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c ] -Furan-1,3-dione, 1,3,32,4,5,91) -hexahydro-4- (3-fluoro-4- (4-11-hexylcyclohexyl) phenoxy)- 5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2 · c; l · furan-1,3-dione, 1,3,3a, 4,5,9b -Hexahydro-4- ( 3-fluoro-4- (4-n-heptylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c]- Furan-1,3-dione; 1,3,3a, 4,5,9b-hexahydro-4- (2-cyano-4- (4-η-propylcyclohexyl) phenoxy) -5 -(Tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c ^ furan-l, 3-dione, 1,3,3a, 4,5,9b-hexahydro -4- (2-cyano-4- (4-n · butylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl-3 · furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3,38,4,5,913-hexahydro-4- (2-cyano-4- (4-11-pentylcyclohexyl) phenoxy ) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3,3a, 4,5, 9b-hexahydro- 4- (2-cyano- 4- (4-n-hexylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [1,2-〇] -furan-1,3-dione, 1,3,3 &, 4,5,91) -hexahydro-4- (2-cyano-4- (4-11-heptane Cyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c] -furan-1,3 · dione; 1,3 , 3a, 4,5,9b-hexahydro-4- (3-cyano-4- (4-n-propylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl- 3- Ranyl) -naphtho [l, 2-c] -furan-l, 3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (3-cyano-4- (4 -n · butylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) · naphtho [1,2-c] -furan-1,3-dione , L, 3,3a, 4,5,9b-hexahydro- 4- (3-cyano-4- (4-n-pentylcyclohexyl) 200521207 phenoxy) -5- (tetrahydro-2, 5-dicarbonyl-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,32,4,5,913-hexahydro-4- (3-cyano -4- (4-11-hexylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl-3_furanyl) -naphtho [1,2 <]-furan-1,3 -Dione, 1,3,3 &, 4,5,913-hexahydro-4- (3-cyano-4- (4-11-heptylcyclohexyl) phenoxy) -5- (tetrahydro-2 , 5-dicarbonyl-3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione. Among these, 1,3,3a, 4,5,9b-hexahydro-4- (2,3-difluoro-4- (4-η-propylcyclohexyl) phenoxy) -5- (Tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro -4- (2,3-difluoro · _4- (4-n-butylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [ 1,2-c] -furan-1,3-dione, 1,3,3 &, 4,5,9) 3-hexahydro-4- (2,3-difluoro-4- (4-n -Pentylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione, l , 3,3a, 4,5,9b-hexahydro-4- (2,3-difluoro-4- (4 · η-hexylcyclohexyl) phenoxy) -5- (tetrahydro-2,5- Dicarbonyl-3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-A hydrogen-4- (2,3- Difluoro-4- (4-11-hexylcyclohexyl) phenoxy) -5 "tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c] -furan-1 , 3-dione, 1,3,3a, 4,5,9b- φ hexahydro- 4- (2,3-difluoro- 4- (4-η-heptylcyclohexyl) phenoxy) -5 -(Tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione; 1,3,3a, 4,5,9b-hexa Hydrogen-4- (2 3-dicyano-4- (4-η-propylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c ] -Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-4- (2,3-dicyano-4- (4-n-butylcyclohexyl) benzene Oxy) -5 · (tetrahydro-2,5-dicarbonyl-3 · furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3,3a, 4, 5,9b-hexahydro-4- (2,3-dicyano-4- (4-n-pentylcyclohexyl) phenoxy) -5- (tetrahydro-2,5-dicarbonyl-3- Furyl) -naphtho-22- 200521207 [1,2 <]-furan-1,3'dione, 1,3,38,4,5,91) -hexahydro-4- (2,3-di Cyano-4- (4-n-hexylcyclohexyl) phenoxy) -5- (tetrahydro · 2,5-dicarbonyl-3-furanyl) -naphtho [1,2-c] -furan- 1,3-diketone, 1,3,3a, 4,5,9b-hexahydro-4- (2,3-dicyano-4- (4-η · heptylcyclohexyl) phenoxy)- 5 · (tetrahydro-2,5-dicarbonyl-3 · furanyl) -naphtho [l, 2-c ^ furan-1,3-dione; 1,3,3a, 4,5,9b · hexa Hydrogen · 4- (6- (4-η-propylcyclohexyl) -3-pyridyloxy) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3,3 &, 4,5,913-hexahydro-4- (6- (4-11-butylcyclohexyl) -3-pyridine ) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [1,2-〇] -furan-1,3 · φ dione, 1,3,3 &, 4 , 5,91) -hexahydro-4- (6- (4-11-pentylcyclohexyl) -3-pyridyloxy) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl ) -Naphtho [l, 2-c] · furan-1,3-dione, 1,3,3 &, 4,5,91) -hexahydro-4- (6- (4-11-hexyl ring) Hexyl) -3-pyridyloxy) -5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1 , 3,3 &, 4,5,913-hexahydro-4- (6- (4-11-heptylcyclohexyl) -3-pyridyloxy) -5- (tetrahydro-2,5-dicarbonyl- 3-furyl) · naphtho [l, 2-c] -furan-1,3-dione is preferred. Other tetracarboxylic dianhydrides used in the synthesis of the polymer contained in the liquid crystal alignment agent of the present invention, such as butanetetracarboxylic dianhydride, 1,2,3, cardiocyclobutanetetracarboxylic dianhydride 1,1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride , 1,3-dichloro-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid Acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-bicyclo Hexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6-tricarboxyoranidine-2-acetic dianhydride, 2,3,4,5-tetrahydrofuran tetra Carboxylic dianhydride, 1,3,3 &, 4,5,913-hexahydro-5- (tetrahydro-2,5-dicarbonyl-3-furan-23- 200521207

) -Naphtho [l, 2-c] -furan-1,3-dione, 1,3,3 &, 4,5,913-hexahydro-5-methyl-5- (tetrahydro-2,5 -Dicarbonyl-3-furanyl) -naphtho [1,2 乂] -furan-1,3-dione, 1,3,3 &, 4,5,91) -hexahydro-5-ethyl- 5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3,32,4,5,91) -Hexahydro-7-methyl-5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3 , 3 &, 4,5,91) -hexahydro-7-ethyl-5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [1,2-c] -furan- 1,3-dione, 1,3,3 &, 4,5,91) -hexahydro-8-methyl-5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro · 8-ethyl-5- (tetrahydro-2,5-dicarbonyl- 3-furyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5 (Tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 5- (2,5-dicarbonyltetrahydrofuranyl) -3 -Methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxidized bicyclo [3,2, 1] Aliphatic and alicyclic octane-2,4-dione-6-helix-3 '· (tetrahydrofuran-2', 5'-dione), compounds represented by the following formulae (X) and (XI), etc. Tetracarboxylic dianhydride

(X)

-24- (XI) 200521207 (where 'R8 and R] ° are divalent organic groups with aromatic rings, R9 and R are hydrogen atoms or alkyl groups, and several R9 and R 1 1 may be the same or different. For example pyromellitic dianhydride, 3,3,, 4,4, -benzophenone tetracarboxylic dianhydride, 3,3,4,4'-biphenyltetracarboxylic dianhydride, 1,4,5 , 8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3,, 4,4, -diphenyl ether tetracarboxylic dianhydride, 3,3,, 4 4,4 Dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4, bis (3,4-dicarboxyphenoxy) diphenylphthalic dianhydride, 4 , 4'-bis (3,4-dicarboxyphenoxy) diphenylphthalic anhydride, 4,4, -bis (3,4-dicarboxyphenoxy) diphenylpropanedianhydride, 3,3 ,, 4,4, -Perfluorinated isopropylidene diphthalic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, P -phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis Triphenylphthalic acid) -4,4 '· diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4diphenylmethane dianhydride, ethylene glycol-bis (trimellitic acid triester), Propylene glycol-bis (trimellitic acid ester), 1,4-butanediol-bis (trimellitic acid ester), 1,6-hexanediol-bis (trimellitic acid ester), 1,8 _Octanediol bis (trimellitic acid ester), 2,2-bis (4-hydroxyphenyl) propane-bis (trimellitic acid ester), compounds represented by the following formulae (18) to (21) And other aromatic tetracarboxylic dianhydrides. These can be used alone or in combination of two or more. [Chem. 1 3] -25- 200521207

Among these, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, and 1,3-dimethyl-1 are considered in terms of having good liquid crystal alignment. , 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,5 -tricarboxycyclopentylacetic dianhydride, 5-(2,5--26-200521207 one-carbon tetrachlorosulfanyl) -3 -methyl -3 -Hexyl-1,2- Dihepatic acid diliver, 1,3,3 &, 4,5,91) -hexahydro-5- (tetrahydro-2,5-dicarbonyl-3-furanyl) naphtho [l, 2-c] Furan-1,3-dione, 1,3,3a, 4,5,9b -hexahydro-8-methyl-5- (tetrahydro-2,5-dicarbonyl-3-furanyl) naphtho [ 1,2-(:) furan-1,3-dione, 1,3,3a, 4,5,9b -hexahydro-5,8-dimethyl-5-(tetrahydro-2,5 · di Carbonyl-3-furanyl) naphtho [l, 2-c] furan-1,3-dione, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetra Carboxylic dianhydride, 3-oxobicyclo [3,2,1] octane-2,4-dione-6-spiral-3 '-(tetrahydrofuran-2,5, -dione), pyromellitic Formic acid dianhydride, 3,3,4,4, benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'biphenylphthalate dianhydride, naphthalene tetra Among the compounds represented by the formula (X), acid dianhydrides, compounds represented by the following formulae (22) to (24), and compounds represented by the formula (XI) are preferred. More preferred are 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, I, 2, 4,5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3 ^ 4,5,91) -hexahydro-5- (tetrahydro- 2,5-dicarbonyl-3-furanyl) -naphtho [1,2-(:) furan-1,3-: =: @ 11, 1,3, 4,5,9 hexahydro-8- Methyl-5- (tetrahydro-2,5 ~ peptidyl-3-amidinyl) -cyclo [3,2,1] octane-2,4-dione pyromellitic dianhydride and the following naphthalene [1,2-c] furan-1,3-dione, 3-oxo-6-6-helix-3 '-(tetrahydrofuran-2,5, dione), and a compound represented by formula (22).

27- 200521207

I .23)

ο -ί (25) ο < Synthesis of polyamines > The ratio of tetracarboxylic dianhydride to diamine used in the synthesis of polyamino acids is four for one equivalent of the amine group of diamine. The acid anhydride group of the carboxylic dianhydride is preferably 0.2 to 2 equivalents, and more preferably 0.3 to 1.2 equivalents. The synthesis reaction of polyamic acid is performed in an organic solvent, preferably at a temperature of -20 to 150 t, and more preferably at a temperature of 0 to 100 ° C. Here, the organic solvent is not particularly limited as long as it can dissolve and synthesize polyamidonic acid. For example, -28- 200521207 1-methyl-2-pyrrolidone, N, Nc methylacetamide, ν, N- Aprotic polar solvents such as dimethylformamide, dimethylphthalide, butyrolactone, tetramethylurea, hexamethylphosphorylamide, etc .; m_cresol, xylenol, phenol, halogenated A phenol-based solvent such as phenol. The amount (α) of the organic solvent is preferably 0.1 to 30% by weight based on the total amount (β) of the tetracarboxylic dianhydride and the diamine compound, and the total amount of the reaction solution (α + β). In addition, the above-mentioned organic solvents may be used in the range of the polyamines which do not precipitate out, such as alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc. . Specific examples of the lean solvent include methanol, ethanol, isopropyl alcohol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, 1,4-butanediol, and triethylene glycol. Alcohol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxide Propionate, ethyl ethoxy propionate, diethyl oxalate, diethyl propionate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol-η-propyl ether, ethylene glycol Small alcohol propyl ether, ethylene glycol-η-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether Ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4- Dichlorobutane, trichloroethane, chlorobenzene, 0-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like. As described above, a reaction solution prepared by dissolving polyamic acid was prepared. Then, the reaction solution was poured into a large amount of a lean solvent to obtain a precipitate, and the precipitate was dried under reduced pressure to obtain a polyamic acid. In addition, by dissolving the polyamic acid in an organic solvent again, and performing the process of -29-200521207 for precipitation of one or more lean solvents, the polyamino acid can be purified. < Synthesis of fluorene imidized polymer > The fluorene imidized polymer constituting the liquid crystal alignment agent of the present invention can be synthesized by dehydrating and closing the polyamic acid. The dehydration ring closure of the polyamic acid can be achieved by heating the polyamic acid, or (II) dissolving the polyamic acid in an organic solvent, and adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, depending on its location. Need to be heated. In addition, the fluorene imidized polymer used in the present invention may also include a partially dehydrated ring-closed fluorinated imidization ratio (expressed as a percentage of the repeat units formed by the fluorene imide ring in all the repeat units in the polymer ) Small φ is less than 100% of fluorinated imidized polymer. The reaction temperature of the method for heating the polyamic acid of the above (I) is 50 ~ 200 ° (: better, more preferably 60 ~ 170 ° (:. The reaction temperature is less than 50 ° (: Fully proceeded, and the molecular weight of the fluorene imidized polymer (B) obtained when the reaction temperature was higher than 200 ° C. In addition, in the method of adding a dehydrating agent and a dehydration ring-closing catalyst to the polyamic acid solution of (II), For example, acetic anhydride, propionic anhydride, trifluoric acetic anhydride, and the like can be used as the dehydrating agent. The amount of the dehydrating agent depends on the desired fluorination rate φ, and is 1 unit of polyamine repeating unit. 0.01 to 20 moles is preferred. In addition, for dehydration ring-closing catalysts, for example, tertiary amines such as pyridine, trimethylpyridine, dimethylpyridine, and triethylamine can be used. However, they are not limited to these. The amount of catalyst used is preferably from 0.0 1 to 10 moles for the dehydrating agent used for 1 mole. The imidization rate is higher as the above-mentioned dehydrating agent and dehydration ring-closing agent are used more. Organic solvents used in dehydration ring-closing reactions, such as those exemplified by users of polyamine synthesis Organic solvent. Then, the reaction temperature of the dehydration ring-closing reaction is 0 to 18 (TC is preferred, and more preferably 10 to -30-200521207 · 150 ° C. In addition, the reaction solution thus obtained is carried out by The same operation as the method for purifying polyamic acid can purify fluorinated polymers. ≪ Terminal modified polymers > Polyfluorinated acids and fluorinated polymers can also be terminals with adjusted molecular weight. Modified type. By using the terminal modified type polymer, the coating characteristics of the liquid crystal alignment agent can be improved without impairing the effect of the present invention. The terminal modified type can be used in the synthesis of polyamic acid by The reaction system is synthesized by adding an acid anhydride, a monoamine compound, a monoisocyanate compound, etc. Here, the acid anhydride is, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, η-decylsuccinic anhydride, η-dodecylsuccinic anhydride. Η-tetradecyl succinic anhydride, η-hexadecyl succinic anhydride, etc. Also, monoamine compounds such as aniline, cyclohexylamine, η-butylamine, η-pentylamine, η-hexylamine, η -Heptylamine, η-octylamine, η-nonylamine, η-decylamine, η-deca Amine, η-dodecylamine, η-tridecylamine, η-tetradecylamine, η-pentadecylamine, η-hexadecylamine, η-heptadecylamine, η-octadecylamine, η-icosamine, etc. In addition, monoisocyanate compounds such as phenyl isocyanate, naphthyl isocyanate, etc. < Liquid crystal alignment agent > The liquid crystal alignment agent of the present invention is a polymer which dissolves a polymer having a specific side chain in an organic solvent, and is usually a poly The fluorinated acid and / or the fluorinated imidized polymer are composed. The temperature when preparing the liquid crystal alignment agent of the present invention is preferably 0 to 200 ° C, and more preferably 20 to 60 ° C. The composition of the liquid crystal alignment agent of the present invention The organic solvent is, for example, a solvent exemplified by a user of a synthetic reaction of polyamic acid. Further, a poor solvent exemplified by a user used in the synthetic reaction of a polyamic acid may be appropriately selected. Among these, 1-methyl-2-pyrrolidone and a solvent having a surface tension of 32 dyn / cm or less are better than -31-200521207. Solvents with a surface tension of 32 dyn / cm or less, such as 4-hydroxy-4-methyl-2-heptanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl acetate Ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol-η-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-η-butyl ether, ethylene glycol di Methyl ether, ethylene glycol ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate Esters, diethylene glycol monoethyl ether acetate, and the like. The ratio of 1-methyl-2-pyrrolidine to a solvent having a surface tension of 32 dyn / cm or less, with 1-methyl-2-pyrrolidone being 20 to 60% by weight and a solvent having a surface tension of 32 dyn or less is 80 to 40 weight % Is better. When the ratio is outside the range, sufficient printability cannot be obtained because polymer precipitation occurs and the horizontality is insufficient. The solid content concentration of the liquid crystal alignment agent of the present invention can be selected in consideration of viscosity, volatility, etc., and is preferably 1 to 10% by weight. In other words, the liquid crystal alignment agent of the present invention is coated on the substrate surface to form a liquid crystal alignment film coating film, but when the solid content concentration is less than 1% by weight, the film thickness of the coating film is too small to make a good liquid crystal alignment film, and the solid content concentration is greater than At 10% by weight, the film thickness of the coating film is too large to make a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases, resulting in poor coating characteristics. The liquid crystal alignment agent of the present invention includes a functional silane-containing compound and an epoxy compound within the range of physical properties that do not damage the objective, and can improve the adhesion to the substrate surface. The functional silane-containing compound such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxy Silyl, N_ (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl200521207 methyldimethoxysilane, 3 -ureidopropyltrimethoxysilane, 3 -ureidopropyltriethoxysilane, N -ethoxycarbonyl-3 -aminopropyltrimethoxysilane, N -ethoxymine -3-Aminopropyltriethoxy Mortar, N-triethoxysilylpropyltriethylenetriamine, N · trimethoxysilylpropyltriethylenetriamine, 10-trimethoxy Silyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-di Azanonyl acetate, 9-triethoxysilyl-3,6-diazenonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl 3-aminoaminotriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-φaminopropyltriethoxysilane, N- double Ethylene oxide) -3 - aminopropyl trimethoxy hospital sand, N - bis (ethylene Institute) -3 - aminopropyl triethoxy sand homes. Examples of the epoxy-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Neopentyl alcohol diglycidyl ether; 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl alcohol diglycidyl ether, 1, 3,5,6 -tetraglycidyl-2,4-hexanediol, N, N, N ', N' · tetraglycidyl-m-diphenyldimethylamine, 1,3-bis ( N, N-Diglycidylaminomethyl) cyclohexane, φ N, N, N ', N'-Tetraglycidyl-4,4'-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane, 3- (N, N-glycidyl) aminopropyltrimethoxysilane, and the like. < Liquid crystal display element > The liquid crystal display element obtained by using the liquid crystal alignment agent of the present invention can be produced, for example, by the following method. (1) On one side of a substrate provided with a patterned transparent conductive film, the liquid crystal compound of the present invention is applied by, for example, a roll coating method, a spinner, or a printing method, and the coating agent is then applied. The cover is heated to form a coating film. Here, the substrate may be, for example, a glass such as flat glass or alkali glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether phthalate, polycarbonate, or the like. The transparent conductive film provided on one side of the substrate can be a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO2), and an ITO film made of indium oxide-tin oxide (In2〇3-Sn〇2) For patterning of these transparent conductive films, a photolithography method or a method of preparing a photomask can be used. When the liquid crystal alignment agent is applied, in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film, the surface of the substrate is coated with a compound containing a functional silane and a compound containing a functional titanium in advance. . The heating temperature after the liquid crystal alignment agent is applied is preferably 80 to 300 ° C, and more preferably 120 to 250 ° C. In addition, the liquid crystal alignment agent of the present invention containing polyamic acid forms a coating film as an alignment film by removing an organic solvent after coating, and further dehydrates and closes the ring by heating to form a more imidized coating film. The film thickness of the formed coating film is preferably 0.001 to 1 μm, and more preferably 0.005 to 0.5 μm. (2) The formed coating film surface is rubbed in a certain direction with a roll wrapped with a cloth made of fibers such as nylon, thunder, cotton, etc., as required, for rubbing treatment. φ can make the liquid crystal molecules on the coating film have a pretilt angle, and can control the direction in which the liquid crystal molecules fall when a voltage is applied. In addition, if necessary, the coating film can be irradiated with polarized or unpolarized ultraviolet rays, or ion beams to impart a pretilt angle without rubbing. In addition, in the vertical alignment type liquid crystal display element of the present invention, when the tilting direction of the liquid crystal molecules when a voltage is applied is controlled by the transverse electrical boundary, the protrusion on the substrate, etc., the above-mentioned friction and other treatments are not necessarily required, and the above-mentioned coating film can be directly used. As a liquid crystal alignment film. -34- 200521207 (3) Make two substrates with the liquid crystal alignment film formed as described above, and make the rubbing direction of each liquid crystal alignment film (or the direction in which the liquid crystal molecules are tilted when a voltage is applied) is anti-parallel. They are arranged opposite to each other through a gap (cell gap), and the two substrates are bonded together with a sealant on the substrate surface. The liquid crystal is injected into the cell surface and the cell gap separated by the sealant, and the injection hole is sealed. Forms a liquid crystal cell. Then, on the outer surface of the liquid crystal cell, that is, on the other surface of each substrate constituting the liquid crystal cell, the direction of polarization of the polarizing plate and the rubbing direction of the liquid crystal alignment film formed on one surface of the substrate (or the liquid crystal molecules are dumped when a voltage is applied (Direction) is bonded at 45 ° to obtain a liquid crystal display element. Here, as the sealant, for example, a hardener and an epoxy resin containing aluminum oxide balls as a pitch control plate can be used. The liquid crystal includes, for example, a nematic liquid crystal and a smectic liquid crystal. Among them, nematic liquid crystals are preferred. For example, Schiff base liquid crystals, azo oxide liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, bitriphenyl liquid crystals, and biphenyl can be used. Cyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, dicyclooctane-based liquid crystals, and Cooper (transliterated) liquid crystals. In addition, to these liquid crystals, φ can be added to cholesterol-type liquid crystals such as chlorinated cholesterol, cholesterol naphthalate, and cholesterol carbonate, or the market names of "C-15" and "CB-15" (manufactured by Meru Valley). Sale of palm agent. In addition, a strong dielectric liquid crystal such as P-decoxybenzylidene monthyl-2-methylbutylcinnamate can be used. In addition, a polarizing plate attached to the outer surface of the liquid crystal cell, for example, a polarizing plate in which the polarizing film is stretched and aligned with the iodine-absorbing ytterbium film is sandwiched by a cellulose acetate protective film or a polarizing plate A polarizing plate made of diaphragm. [Embodiment] -35- 200521207 In the following, the present invention will be described more specifically by way of examples, but the present invention is not limited by these examples. The evaluation methods of the liquid crystal display elements of the following examples and comparative examples are as follows. (Pre-tilt angle of the liquid crystal display element) Based on the method described in T. J. Scheffer, et, al., J. Appl. Phys., Vol. 19, 2013 (1 980), He-Ne laser light was used It is measured by the crystal rotation method (here, the pretilt angle is defined as the angle at which the alignment direction of the liquid crystal molecules is inclined from the substrate surface). Synthesis Example 1 Polymerization of polyamic acid caused 0.1 mol (22.4 g) of 2,3,5 · tricarboxycyclopentylacetic dianhydride and 0.1 mol (40.3 g) of 1- (2,3-difluoro -4- (4-11-hexylcyclohexyl) phenoxy) -2,4-diaminobenzene was dissolved in 300 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours. Then, the reaction mixture was poured into an excess of methanol to precipitate a reaction product. Next, it was washed with methanol and dried under reduced pressure at 40 ° C for 15 hours' to obtain 62 g of polyamidic acid (hereinafter referred to as "polymer la").醯 Imidization reaction added power to 31.2 grams of polymer ia □ 3 80 g of N-methyl-2-pyrrolidone, 7.9 grams of elderidine and 10 · 2 grams of acetic anhydride, 醯 imidization at 120 ° C 4 hour. Then, the reaction mixture is poured into excess methanol to precipitate the reaction product. Next, it was washed with methanol and dried under reduced pressure for 15 hours to obtain a perylene imidized polymer (hereinafter referred to as "polymer i b"). Synthesis Example 2 Polymerization of Polyamino Acid Except 0.1 mol (4 3.1 g) (2,3-dicyano-4- (4-η-pentylcyclohexyl) 200521207 base) -3,5- Monoamine basic formate substituted with 0.01 mole (40.1 g) 丨 (2,3-difluoro-4- (4-η · hexylcyclohexyl) phenoxy) · 2,4-diamine Except for benzene, in the same manner as in Synthesis Example 1, 64 g of polyamic acid (hereinafter referred to as "Polymer 2 &") was obtained. The fluorene imidization reaction was carried out in the same manner as in Synthesis Example 1 except that 32.8 g of the polymer 2a was used instead of 31.2 g of the polymer. . Synthesis Example 3 Polymerization of polyamidoacid except that 0.1 旲 (36.8 g) (6 (4-η-hexylcyclohexyl) -3 -pyridyloxy) -2,4-monoaminobenzene was substituted.丨 Moore (deduction ^ g) 〖^^-difluoro_4_ (4_n-B-cyclohexyl) phenoxy) _2,4-diamino benzene was prepared in the same manner as in Synthesis Example 丨 5 7 G of polyamic acid (hereinafter referred to as "Polymer 3 a"). Perylene imidization reaction In the same manner as in Synthesis Example 1 except that 29.6 g of polymer 3a was used in place of 31.2 g of polymer la, 26 g of perylene imidized polymer (hereinafter referred to as "polymer 3b") was prepared. Synthetic Example 4 Polyacrylamide's conjugate makes 0.1 mol (54.6 g) 1,3,3 &, 4,5,91: -hexahydro-4- (6- (4-11-pentyl ring) Hexyl) -3 -pyridyloxy) _5- (tetrahydro-2,5-dicarbonyl-3-furanyl) -naphtho [l, 2-c] -furan-i, 3-dione with 〇 · Mol (10.8 g) of phenylenediamine was dissolved in 300 g of N-methyl-2-pyrrolidone and reacted at 60π for 6 hours. Then, the reaction mixture was poured into excess methanol to precipitate a reaction product. Next, it was washed with methanol and dried under reduced pressure at 4 ° C for 15 hours to obtain 64-37-200521207 g of polyamidic acid (hereinafter referred to as "polymer 4a"). 32.7 g of polymer 4a was substituted for 31.2 g of polymer la, and 26 g of fluorenimidized polymer (hereinafter referred to as "polymer 4b") were obtained in the same manner as in Synthesis Example 1. Comparative Synthesis Example 1 Polyamic acid Polymerization dissolves 0.1 mol (22.4 g) of 2,3,5-tricarboxycyclopentyl acetate dino and 0.1 mol (10.8 g) of p-phenylenediamine in 300 g of N-methyl In 2-pyrrolidinone, react at 60 ° C for 6 hours. Then, pour the reaction mixture into excess methanol to precipitate the reaction product. Next, wash with methanol and dry under reduced pressure at 40 ° C for 15 Hours, 27 grams of polyamidoic acid (hereinafter referred to as "Polymer A a") was prepared. 醯 imidization reaction To 16.6 grams of polymer Aa was added 3 80 grams of N-methyl-2-pyrrolidone and 7.9 grams of pyridine And 10.2 g of acetic anhydride, and then reacted with imidization at 120 ° C for 4 hours. Then, the reaction mixture was poured into excess methanol to precipitate the reaction product φ. Second It was washed with methanol and dried under reduced pressure for 15 hours to obtain 13 g of fluorinated imidized polymer (hereinafter referred to as "polymer Ab"). Example 1 (1) Preparation of liquid crystal alignment agent: Synthesis Example The polymer (1) obtained in 1 was dissolved in 7.butyrolactone to form a 2.5% by weight solid content solution, and the solution was filtered through a filter having a pore size of 1 μm to prepare the liquid crystal alignment agent of the present invention. (2) Liquid crystal Production of display elements: -38- 200521207 1) A transparent conductive film made of ιτ〇 film is provided on one side of a glass substrate with a thickness of 1 mm, and the liquid crystal alignment agent of the present invention prepared as described above is coated with a spinner. Dry for 1 hour at ° C to form a coating film with a dry film thickness of 800 angstroms. 2) The formed coating film surface is subjected to a rubbing treatment using a rubbing machine having a roll wound with a dragon resistant cloth to produce a liquid crystal alignment film. Among them, the friction treatment conditions are 500 rpm of the rotation speed of the roller and icm / second of the moving speed of the table. 3) Two substrates having the above-mentioned liquid crystal alignment film formed, each of which was coated with an epoxy-based adhesive containing alumina balls with a diameter of 17 μm by screen printing on the outer edge of the substrate, and each The rubbing directions of the liquid crystal alignment film are anti-parallel to each other, so that the two substrates are arranged to oppose each other through the gap, and the outer edges are connected and pressure-melted to harden the adhesive. 4) Inject the pseudo-nematic liquid crystal "MLC-6608" (made by Meru Valley, Inc.) into the cell gap between the substrate surface and the outer edge separated by the adhesive, and then 'ring the injection hole An oxygen-based adhesive is sealed to form a liquid crystal cell. Next, on the outer surface of the liquid crystal cell, the polarizing direction and the rubbing direction of the liquid crystal alignment film are at an angle of 45 degrees, and the polarizing plates are bonded to each other at right angles to produce a liquid crystal display element. g 5) The pretilt angle of the liquid crystal in the liquid crystal display element produced as described above is 89 degrees. In addition, when a voltage is applied to and released from the liquid crystal cell, there is no abnormal range, and the alignment of the liquid crystal is good. Examples 2 to 4 A liquid crystal display device was produced in the same manner as in Example 1 except that the polymers (2b) to (4b) obtained in Synthesis Examples 2 to 4 were used instead of the polymer (lb). The alignment and pretilt angle of the liquid crystal in the produced liquid crystal cell were evaluated. The results are shown in Table 1. Example 5 -39- 200521207 A liquid crystal display device was produced in the same manner as in Example 1 except that the polymer (4 a) obtained in Synthesis Example 4 was used instead of the polymer (lb). The alignment and pretilt angle of the liquid crystal in the produced liquid crystal cell were evaluated. The results are shown in Table 1.

-40- 200521207 Table 1 Example polymer pretilt angle (°) 1 lb 89 2 2b 88 3 3b 87 4 4b 89 5 4 a 87 Comparative Example Except the polymer (Ab) substituted polymer obtained in Comparative Synthesis Example 1 ( lb) φ, a liquid crystal display element was produced in the same manner as in Example 1. The pretilt angle of the liquid crystal in the produced liquid crystal display element was 1 degree or less, and there was no vertical alignment.

-41-

Claims (1)

200521207 10. Scope of patent application: 1. A liquid crystal alignment agent, which is characterized by having on the side chain at least one polymer selected from the group consisting of the structure represented by the following formula (I) and the structure represented by the following formula (Π) ' (Wherein A1 and B1 are independently a hydrogen atom, a halogen atom or a cyano group, but at least one of A1 and B1 is a halogen atom or a cyano group), Ν—Ν •.. * · · · · · · · · · · · · · 2. OM 2. As the liquid crystal alignment agent in the scope of patent application No. 1, wherein the polymer has the following formula (III) The group shown is a polymer with a side chain, —PQ-R1—R2 (πι) φ (wherein P is a single bond, -0-, -COO-, or -CONH-, and Q is the above formula (I) The structure shown or the structure shown by the above formula (11), R 1 is a divalent alicyclic group, and R 2 is a linear alkyl group having 1 to 22 carbon atoms). 3. The liquid crystal alignment agent according to item 1 or 2 of the patent application scope, wherein the polymer has a polyamidic acid structure and / or a polyamidoimine structure in the main chain. 4. A liquid crystal display element, comprising a liquid crystal alignment film formed of a liquid crystal alignment agent according to any one of claims 1 to 3. -42- 200521207 VII. Designated representative map (1) The designated representative map in this case is: None. (2) Brief description of the component symbols of this representative figure: Μ 〇 j \ \\ 8. If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: (I) (II)