TW200844141A - Vertical alignment mode liquid crystal alignment agent and liquid crystal display device - Google Patents

Abstract

To provide a liquid crystal alignment agent, which has good printability and can form a liquid crystal alignment film having outstanding vertical alignment and reliability, and a liquid crystal display device provided with a liquid crystal alignment film made of the same. The liquid crystal alignment agent comprises a polymer and a specific epoxy-based compound. The polymer is made by the reaction of tetracarboxylic acid dianhydride and diamine compound, and is constituted of a repeating unit represented by formula ( I - 1) or formula ( I - 2), in which the repeating unit possesses organic groups having two valence bonds represented by formula (II - 1) or formula (II - 2) to provide as Q1 and Q2. (P1, P2 is a group originating from acid; Q1, Q2 is a group originating from diamine; X1 is -, -O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -S-, methylene group, alkylene group of C2 to C6, phenylene group; R1 is alkyl group of C10 to C20, alicyclic skeleton-containing group of C4 to C40, fluorine atom-containing group of C6 to C20; R2 is alicyclic skeleton-containing group of C4 to C40, fluorine atom-containing group of C5 to C30.)

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vertical alignment type liquid crystal alignment agent and a liquid crystal display element. More specifically, it relates to a vertical alignment type liquid crystal alignment agent excellent in printability, vertical alignment, and reliability. And a liquid crystal display element produced from the perpendicular alignment type liquid crystal alignment agent. [Prior Art] As a liquid crystal display device, TN (Tw1Sted Nematic) type, STN (Super Twisted Nematic) type, IPS (In Plane Switching) type, etc. are known. a liquid crystal display element of a liquid crystal cell, which forms a liquid crystal alignment film on the surface of a substrate on which a transparent conductive film is provided, and as a substrate for a liquid crystal display element, two substrates are disposed opposite to each other, and a positive dielectric is formed in a gap therebetween The anisotropic nematic liquid crystal layer constitutes a unit cell of a sandwich structure, and the long axis of the liquid crystal molecules is continuously twisted from one substrate to the other substrate by 0 to 3 60 degrees (refer to Patent Document 1 and Patent Document 2). In such a liquid crystal cell, the liquid crystal alignment film is usually formed by a method of rubbing the surface of the organic film formed on the surface of the substrate in one direction with a fabric such as rayon (nibbing method). As such an organic film, a film obtained by polycondensation of a diamine compound and a dianhydride by a polycondensation reaction is widely used from the viewpoint of heat resistance and electrical properties. However, for liquid crystal cells of TN (Twisted Nematic) type, STN (Super Twisted N ematic) type, etc., the liquid crystal alignment film must have a pretilt angle which makes the liquid crystal molecules obliquely aligned at a certain angle (usually 3 to 10°) with respect to the substrate. Sex 200844141 can. Here, the "pretilt angle" as used herein means an angle at which liquid crystal molecules are inclined from a direction parallel to the substrate surface. Further, as a mode of operation of the liquid crystal display element different from the above, a vertical (isotype) alignment method in which liquid crystal molecules having negative dielectric anisotropy are perpendicular to the substrate, that is, a pretilt angle of about 90° is also known. In this mode of operation, once a voltage is applied between the substrates, the liquid crystal molecules are tilted from the normal direction of the substrate toward one direction in the substrate surface. It is known that in order to exhibit the high pretilt angle required for these various modes, the liquid crystal alignment film may be a polyimine resin having a bulky substituent such as octadecyl group. Among such substituents, a group having a large volume and having a rigid skeleton is particularly advantageous because it can exhibit a high pretilt angle. Such a polyimine resin having a large volume of a substituent can be obtained by synthesizing a diamine compound or a dianhydride having a bulky substituent. Further, in recent years, liquid crystal display elements have been used under various conditions and environments. Therefore, as one of the performances required for liquid crystal alignment agents, reliability has been increasingly recognized. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. JP-A-2004-331937 [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. A vertically aligned liquid crystal alignment agent excellent in liquid crystal alignment film. Another object of the present invention is to provide a liquid crystal display element having a liquid crystal alignment film produced by the above-described vertical alignment type liquid crystal alignment agent. The vertical alignment type liquid crystal alignment agent of the present invention is characterized by comprising: a polymer obtained by a reaction of a tetracarboxylic dianhydride and a diamine compound, selected from the following formula (1-1) and the following formula (1-2) constituting at least one repeating unit of the group consisting of the repeating units represented by each, and containing at least one of the divalent organic groups represented by the following formulas (II-1) and (II.2) A repeating unit which is Q2 in the following formula (1-1) and Q2 in the following formula d-2); and an epoxy group compound represented by the following formula (III).

(In the formula (1-1), p1 is a tetravalent organic group derived from tetradecanoic acid, and Q1 is a divalent organic group derived from a diamine compound. Further, in the formula (II-2), P2 is derived from In the tetravalent organic group of the tetracarboxylic acid, Q2 is a divalent organic group derived from a diamine compound.) 200844141 (II-1)

(In the formula (II-1), X1 is a single bond, -0-, -CO-, -C〇〇-, -〇c〇-, -NHC〇-, -C〇NH-, -S·, sub a methyl group having a carbon number of 2 to 6 or a phenyl group; R1 is an alkyl group having a carbon number of 10 to 20, a monovalent organic group having an alicyclic skeleton having a carbon number of 4 to 40, or carbon. a monovalent organic group having a fluorine atom of 6 to 20. Further, in the formula (II-2), X1 is a single bond, -〇-, -C〇-, -C〇〇-, _〇C〇 _, .NHC〇_, _C〇NH_, _S_, methylene, an alkyl group having a carbon number of 2 to 6 or a phenyl group; and R2 is a divalent organic having an alicyclic skeleton having a carbon number of 4 to 40. a group or a divalent organic group having a fluorine atom of 5 to 30 carbon atoms.)

(In the formula (III), a is an integer of 2 to 4, and R3 is an organic group having a valence'. A site bonded to N is an aliphatic carbon.) The liquid crystal alignment agent according to the present invention can be obtained. Good printability' at the same time enables the formation of a liquid crystal alignment film excellent in vertical alignment and reliability. The liquid crystal display element of the present invention can be effectively used in various devices', for example, can be applied to a desktop calculator, a watch, a desk clock, a mobile phone, a counting display screen, a word processor, a personal computer, a liquid crystal television, etc. Display device of 200844141. [Embodiment] Hereinafter, the present invention will be specifically described. The vertical alignment type liquid crystal alignment agent (hereinafter also referred to as "liquid crystal alignment agent") according to the present invention is obtained by reacting tetracarboxylic dianhydride with a diamine compound, or by the above formula (1-1) or A polymer composed of a repeating unit represented by the formula (1-2) and an epoxy compound represented by the above formula (III). The C. polymer (hereinafter also referred to as "specific polyphthalic acid polymer") containing the repeating unit represented by the above formula (1-1) in the above repeating unit can usually be obtained by making tetracarboxylic dianhydride and diamine The compound is obtained by reacting in an organic solvent. Further, a polymer containing a repeating unit represented by the above formula (1-2) (hereinafter also referred to as "specific polyimine polymer") can be obtained by dehydrating a phthalic acid moiety of a specific polyaminic acid polymer. be made of. Hereinafter, a method for producing a specific polyamic acid polymer and a specific polyimine polymer constituting the liquid crystal alignment agent of the present invention will be described. Ij [tetracarboxylic dianhydride] As the tetraruthenic dianhydride which can be used for the preparation of the specific polyaminic acid polymer and/or the specific polyimine polymer constituting the liquid crystal alignment ij of the present invention, for example, Butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutanine tetraresic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-diethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3 -dimethyl-1,2,3,4-cyclobutylene tetracarboxylic dianhydride, 1, 3-Diethyl-1,2,3,4·cyclobutanetetracarboxylic acid, 1,1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane-10-200844141 tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride 1,2,4-tricarboxycyclopentyl acetic acid dianhydride, bicyclo[2,2,1]-heptane-2,3,5,6-tetracarboxylic dianhydride, 3,5,6-tricarboxyl Norbornane-2-acetic acid dianhydride, tetracyclo[4,4,0,12'5,17'1()]dodecane-3,4,8,9-tetracarboxylic 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, 1,3,38,4,5,913-hexahydro-5-methyl-5(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan-1, 3-diketone, 1,3,3&,4,5,91)-hexahydro-5-ethyl-5(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l, 2-c]-furan-1,3-dione, 1,3,3&,4,5,913-hexahydro-7-methyl-5(tetrahydro-2,5-dioxo-3-furanyl )-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5(tetrahydro-2,5-di Oxo-3-furanyl)-naphthalene [l,2_c]-furan-1,3-dione, 1,3,3&,4,5,913-hexahydro-8-methyl-5(tetrahydro-2 ,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro-8- Ethyl-5(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3&,4,5 ,91)-hexahydro-5,8-dimethyl-5(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan-1,3-di Ketone, 5-(2,5-dioxotetrahydrofuranmethylene)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2,2,2]-oct-4- Alkene-2,3,5,6-tetracarboxylate Aliphatic anhydride, bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, compounds represented by the following formulas (1) and (2), and the like Cyclotetracarboxylic dianhydride; pyromellitic dianhydride, 3,3',4,4'-dione tetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid Dihydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, -11- 200844141 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyl Ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-di (3,4 -Dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoro Isopropylenedicarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, di(phthalic acid) phenylphosphine oxide dianhydride, ethylene glycol-di (dehydration partial Triglyceride), propylene glycol-di (dehydrated trimellitic acid ester), 1,4-butanediol-di (hydrogen trimellitate) 1,6-hexanediol-di(hydroper trimellitate), 1,8-octanediol-di(hydroper trimellitate), 2,2-bis(4-hydroxyphenyl)propane- An aromatic tetracarboxylic dianhydride such as a compound represented by the following formulas (3) to (6), (dehydrated trimellitate). They may be used alone or in combination of two or more.

(wherein R11 and R12 represent a divalent organic group having an aromatic ring, R4 and R5 represent a hydrogen atom or an alkyl group, and a plurality of R4 and R5 present may be the same or different from each other -12-200844141.)

Among them, it is preferable to contain 50% by mole or more of all of the tetracarboxylic dianhydride from 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2-dimethyl-1. 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-diethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-diethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2 , 3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, bicyclo [2.2.1]- Heptane-2,3,5,6-tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride 1,3,3&,4,5,913-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-(:]-furan-1,3- Diketone, 1,3,3&,4,5,913-hexahydro-5-methyl-5(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]- Furan-1,3-dione, 1,3,3&,4,5,91^hexahydro-5-ethyl-5(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,913-hexahydro-7-methyl-5(tetrahydro-2,5-dioxo-3 -furyl)- -13- 200844141 naphthalene [l,2-c]-furan-1, 3-diketone, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2< ]-furan-1,3-dione, l,3,3a,4,5,9b-hexahydro-8-methyl-5(tetrahydro-2,5-dioxo-3-furanyl)· Naphthalene [l,2-c]-furan-1,3·-one, 1,3,3&,4,5,91^hexahydro-8-ethyl-5(tetrahydro-2,5-dioxo -3--3-pyranyl)-naphthalene [1,2-(:]-furan-1,3-dione, l,3,3a,4,5,9b-hexahydro-5,8--methyl -5(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 2,3,5-tricarboxycyclopentyl acetic acid The at least one tetracarboxylic acid monoanhydride in the dianhydride is more preferably contained in an amount of 70 mol% or more from the viewpoint of improving performance. [Diamine compound] The repeating unit represented by the above formulas (1-1) and (1_2) Q1 and Q2 in the organic group derived from the diamine compound correspond to a residue in which the diamine compound removes two amine groups. In the present invention, a polymer containing the above formula (II) is used. -1) and at least one of the organic groups represented by the above formula (11_2) as a repeating unit of Q1 and Q2 (hereinafter referred to as "specific repeat c, single "). In the above formula (II-1), 'R1 is an alkyl group having a carbon number of 10 to 2 Å, a monovalent organic group having an alicyclic skeleton having a carbon number of 4 to 40, or a fluorine having a carbon number of 6 to 20. A monovalent organic group of an atom. Here, 'as an alkyl group having a carbon number of 1 〇 to 2 〇, for example, a n-decyl group, a n-dodecyl group, a n-pentadecyl group, a n-hexadecyl group, an n-octadecyl group, a positive teflon Further, the alkyl group having the alicyclic skeleton having a carbon number of 4 to 40 may have, for example, a group derived from cyclobutane, cyclopentane or cycloheximide. The alicyclic skeleton of the ring hospital and other hospitals; the icy ring-shaped skeleton such as the ice-receiving house and the diamond plant; the monovalent organic group of the steroid skeleton such as cholesterol and cholestyl alcohol. The above monovalent organic group having an alicyclic skeleton may also be a group substituted by a halogen atom, preferably a fluorine atom. In addition, examples of the monovalent organic group having a fluorine atom having 6 to 20 carbon atoms include a linear group having a carbon number of 6 to 20 such as n-hexyl, n-octyl or n-decyl; cyclohexyl, An alicyclic hydrocarbon group having a carbon number of 6 to 20 such as a cyclooctyl group; a part or all of a hydrogen atom in an organic group such as an aromatic hydrocarbon group having a carbon number of 6 to 20 such as a phenyl group or a biphenyl group; a fluoroalkyl or fluoroalkoxy-substituted group. Further, in the above formula (II-1), the group represented by X1 is a single bond, -〇-, _C〇-, _C〇〇_, -〇C〇_, -NHC〇·, _C〇NH_, _S_, sub The methyl group and the alkylene group having a carbon number of 2 to 6 and the phenyl group are particularly preferred, and examples thereof include a group represented by -〇-, -CO-, -CO〇-, and -〇C〇-. Q, as a specific example of the diamine compound having the group represented by the above (II-1), preferred are dodecyloxy-2,4-diaminobenzene and pentadecyloxy-2. 4 -monoaminobenzene, hexadecanthoxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, a compound represented by the following formula (7) to (22) . -15- 200844141

-16- 200844141

In the above formula (I I-2), R2 is a divalent organic group having a divalent organic group having an alicyclic skeleton or a fluorine atom having 5 to 30 carbon atoms having a carbon number of 4 to 40. Here, 'the divalent organic group having an alicyclic skeleton having a carbon number of 4 to 40 may, for example, be an alicyclic ring derived from a cycloalkane such as cyclobutane, cyclopentane, cyclohexane or cyclodecane. Type skeleton; norbornane, adamantane and the like having a bridged ring skeleton; a divalent organic group temple of a steroid skeleton such as cholesterol or cholestyl alcohol. The above-mentioned monovalent organic group having a cyclofluorene ring skeleton may also be a group substituted by a halogen atom, preferably a fluorine atom. Further, 'a specific example of the divalent organic group -17-200844141 having a fluorine atom having 5 to 30 carbon atoms' may be a linear chain having a carbon number of 5 to 30 such as n-hexyl, n-octyl or n-decyl group. a part of a hydrogen atom in an organic group such as an aromatic hydrocarbon group having a carbon number of 6 to 30 such as a phenyl group or a biphenyl group, and a alicyclic hydrocarbon group such as a cyclohexyl group or a cyclopentyl group; Or a group entirely substituted by a fluorine atom or a fluoroalkyl group. The specific example of the diamine compound which is a group represented by the above formula (II-2) is preferably a compound represented by the following formulas (23) to (27).

In the specific polyaminic acid polymer and/or the specific polyimine polymer used in the present invention, the ratio of the specific repeating unit is preferably 7 moles in all the repeating units from the viewpoint of the vertical alignment property. More than or equal to, more preferably from -18 to 200844141 1 0% by mole or more. In the mouth of the specific polystyroic acid polymer and/or the specific polyiminoimine polymer used in the present invention, the present invention is not impaired. In the range of the effect ', a group other than the divalent organic group represented by the above formula (11-) or the above formula (ΙΙ-2) may be further contained as a repeating unit of Q1 and Q2 (hereinafter referred to as "other repeating unit" "). Examples of the diamine compound used to obtain other repeating units include p-phenylenediamine, 2-methyl-1,4-phenylenediamine, and 2-ethyl-1,4-phenylenediamine.

V 2,5-dimethyl-1,4-phenylenediamine, 2,5-diethyl-1,4-phenylenediamine, 2,3,5,6-tetramethyl-1,4-benzene Diamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4 , 4'-diaminodiphenylphosphonium, 2,2'-dimethyl-4,4,-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4' - Diaminobiphenyl, 2,2,-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3' - bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diamine linkage C; benzene, 4,4'-diamino Benzoquinone aniline, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5-amino group -1-(4'-aminophenyltrimethylindan, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 3,4' -diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-di [4-(4-Aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexa Fluoropropane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2·bis[4-(4-aminophenoxyl) Phenyl] phenyl], 1,4-bis(4- -19- 200844141 aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-di(3) -aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 2,7-diaminopurine, 9,9-bis(4-aminophenyl)芴, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4,-diaminobiphenyl, 2,2'-dichloro -4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4' - (p-phenylene isopropylidene) diphenylamine, 4,4'-(meta-phenylisopropylene)diphenylamine, 2,2'-bis[4-(4-amino-2-trifluoro Methylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl) hydrazine, 4,4'-bis[(4-amino) Aromatic diamines such as 2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 4-(4-n-heptylcyclohexyl)phenoxy-2,4-diaminobenzene; 1,3 - bis(aminomethyl)benzene, 1,3-propanediamine, butanediamine, Aliphatic diamines such as diamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 4,4-diaminoheptyldiamine; 2,3-diaminopyridine, 2,6-diamine Pyridine, 3,4-diaminopyridine, 2.4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4-di Hydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1.4-*(3-aminopropyl) foxberry, 2,4 -*amine -6-isopropoxy-1,3,5-diazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6 -phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4, 6-Diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3 -Dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridinyl lactate, 3,8-diamino -6-phenylphenanthridine, 1,4-diaminopyridazine, 3,6-diaminoacridine, di-20- 200844141 (4-aminophenyl)phenylamine, etc. a diamine having a first-order amine group and a nitrogen atom other than the first-order amine group; and the following formula (28)~ 30) compound represented by the. These diamine compounds may be used singly or in combination of two or more.

(28) (29) (3〇) (wherein R6 represents a hydrocarbon group having a carbon number of 1 to 12, and a plurality of R6 groups are present (; each may be the same or different, p is an integer of 1 to 3, and Q is 1) An integer of -20, y is an integer of 2 to 12, and z is an integer of 1 to 5. Among them, preferred examples thereof include p-phenylenediamine and 2-methyl-1,4-phenylenediamine. , 2-ethyl-1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,5-monoethyl-1,4-phenylenediamine, 2,3, 5,6-tetramethyl-i,4-phenylenediamine, 4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4,-diaminobiphenyl, 2, 2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2,-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl -4,4'-diaminobiphenyl, 3,3'-diethyl-21 - 200844141 -4,4,-two-limb phenyl, 3,3,-bis(trifluoromethyl)-4 , 4,-di-j benzene, 4,4,-diaminodiphenyl ether, 4,4'-diaminobenzophenone, (4-aminophenyl) propylene, 2,2-di ( 4_Aminophenyl)hexafluoropropene, 2, pyridine, 3,4-diamino _ D determinate ° [Synthesis of specific poly-proline polymer] Supply of specific polyglycolic acid The ratio of use of the tetracarboxylic acid diamine compound in the synthesis reaction is preferably from 1 to 2 equivalents of the diamined amine group, and the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2.0 equivalents. 0 · 8~1 · 2 equivalent ratio. The synthesis reaction of the specific polyaminic acid polymer is usually carried out at a temperature of -20 ° C to 150 ° C, preferably 0 to 100 ° C in an organic solvent. The organic solvent is not particularly limited as long as it can dissolve the synthesized tertiary amino acid polymer, and specific examples thereof include p-methyl-2-pyrrolidone and N,N-dimethylacetamide. Methylformamide, dimethyl hydrazine, r-butyrolactone, tetramethylurea, aprotic system polar solvent such as j-phosphonium triamine; m-methylphenol, dimethyl phenol, halogenated phenol, etc. Further, the amount (α) of the organic solvent is usually preferably such that the total amount (/3) of the tetracarboxylic acid and the diamine compound is relative to the total amount of the reaction solution (c is 0.1 to 30% by weight. Further, in the above organic solvent, a specific polyfluorene may be used in a range in which the specific polypolymer to be formed is not precipitated. Examples of acid-polymeric poor solvents such as alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons based on 2,2--6-dihydrophilic anhydrides and dimers. For example, as a specific example of such a poor solvent, methanol may be mentioned. Ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, 1,4·butanediol, triethylene glycol, ethylene glycol monomethyl ether, lactic acid Ethyl ester, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethoxy propyl Ethyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, Ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl 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, o-dichlorobenzene, Alkane, heptane, octane, benzene, toluene, xylene, and the like. As described above, a reaction solution in which a specific polyamine polymer is dissolved is obtained. Then, the reaction solution is poured into a large amount of a poor solvent to obtain a 1/precipitate, and the precipitate is dried under reduced pressure, or the reaction solution is distilled off under reduced pressure in an evaporator to obtain a specific polyamine polymer. . Further, the specific polyamine can be purified by performing one or several times of dissolving the specific polyaminic acid polymer in an organic solvent, and then precipitating it with a poor solvent, or by distilling off the distillation process with an evaporator. Acid polymer. [Synthesis of Specific Polyimine Polymer] The specific polyimine polymer constituting the liquid crystal alignment agent of the present invention can be synthesized by dehydrating and ring-closing a specific polyaminic acid polymer. The specific polyimine polymer used in the present invention -23- 200844141 may also be a partially dehydrated ring-closed polymer having a quinone imidization ratio of less than 100%. The "yttrium imidation ratio" as used herein means the ratio of the ratio of the repeating unit having a quinone ring or an isoindole ring in all repeating units of the polyimine in percentage. The specific polyaminic acid polymer and/or the specific polyimine polymer used in the present invention preferably has a ruthenium azide ratio of 40% or more. The dehydration ring closure of a specific polyaminic acid polymer may be carried out by (i) heating a specific polyaminic acid polymer, or (Π) by dissolving a specific polyaminic acid polymer in an organic solvent, to the solution f A method in which a dehydrating agent and a dehydration ring-closure catalyst are added and condensed according to a method of heating as needed. In the above method (i) for heating a specific polyaminic acid polymer, the reaction temperature is preferably from 50 to 200 ° C, more preferably from 60 to 170 ° C. When the reaction temperature is less than 50 °C, the dehydration ring-closure reaction may not proceed sufficiently. When the reaction temperature exceeds 200 °C, the molecular weight of the obtained polyimine may decrease. On the other hand, in the method of adding the dehydrating agent and the dehydration ring-closure catalyst to the specific polyamido acid polymer solution of the above (ii), as the dehydrating agent, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. . The amount of the dehydrating agent is, depending on the desired ruthenium iodide ratio, preferably a repeating unit relative to 1 mole of the specific polyaminic acid polymer, which is 〇1 to 20 moles. Further, as the dehydration ring-closure catalyst, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. However, it is not limited to these. The amount of the dehydration ring-closing catalyst is preferably from 0. 0 1 to 1 0 mol with respect to 1 mol of the dehydrating agent. The more the amount of the above-mentioned dehydrating agent and dehydration ring-closing catalyst is -24-200844141, the higher the sulfhydrylation rate can be obtained. Further, as the organic solvent used in the reaction, the same organic solvent as exemplified as the solvent used in the synthesis of the specific polycondensate can be mentioned. Further, the reaction temperature of the ring reaction is preferably 0 to 180 ° C, more preferably 10. Further, by subjecting the reaction solution thus obtained to the same operation as in the specific polymer purification method, the specific polycondensate can be purified. [End-Modified Polymer] The specific poly-proline polymer and the specific polymer used in the present invention may also be a terminal-modified type whose molecular weight is adjusted by using the terminal-modified polymer, without damaging the fruit. The coating characteristics and the like of the liquid crystal alignment agent are improved on the premise. This type of polymer can be synthesized by adding a monobasic acid anhydride, a monoamine compound, monoisocyanate or the like to a synthesis system of a specific polyaminic acid polymer. Here, examples of the monobasic acid anhydride include methic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl anhydride, n-tetradecyl succinic anhydride, n-hexadecyl amber, and as a monoamine. The compound may, for example, be aniline, cyclobutylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, or Inch pentadecylamine, n-hexadecaneamine, n-heptadecaneamine, n-octadecylamine, and the like. Further, the monoisocyanate compound ' can be, for example, phenyl isocyanate or tertyl isocyanate. Water closed-loop reversed acid polymerization, dehydration closed ~150 〇C. Proline polyimine polymerization Polyimine polymer. In the case of the terminal modification of the present invention, an acid anhydride, a dialkyl succinic anhydride or the like is obtained for the transester compound 7. Hexylamine, n-amine, n-decylamine, alkylamine, exemplified by the example-25-200844141 [Solid viscosity] The polymer used in the alignment agent of the present invention is preferably a solution of 1% by weight. It has a viscosity of 20 to 800 mPa's, more preferably a viscosity of 30 to 500 m P a · s. Further, the solution viscosity (m Pa a · s) of the polymer was measured by using a designated solvent, and the solution having a solid content concentration of 1 〇 % was measured at 25 ° C using an E-type rotational viscometer. [The yield of ruthenium iodide of the polymer] The specific polyiminoimine polymer obtained as described above preferably has a ruthenium iodide ratio of 40% or more from the viewpoint of improving the voltage holding performance. The oxime imidization ratio of the specific polyimine polymer used in the present invention is obtained by dissolving the polyimine in a deuterated dimethyl hydrazine after drying under reduced pressure at 60 ° C. Using dimethyl decane as a reference, iH-NMR was measured at room temperature, and hydrazine was obtained by the formula shown by the following formula (ii). Formula (ii): oxime imidization ratio (%) = (1-Α1/Α2χα) χ 100 (J Here, A1 is the peak area derived from the NH matrix (10 ppm), and A2 is the peak area derived from the aromatic ring proton (7 to 8 ppm), where α is the ratio of the number of protons derived from the aromatic ring in the polymer precursor (specific poly-proline polymer) relative to one ruthenium matrix. [Vertical alignment type liquid crystal alignment agent In order to obtain the liquid crystal alignment agent of the present invention, a specific polyaminic acid polymer and/or a specific polyimine polymer is preferably dissolved in an organic solvent. Further, when the liquid crystal alignment agent of the present invention is prepared, The temperature is preferably -26-200844141 0 ° C to 200 ° C, more preferably 20 ° C to 60 ° C. The organic solvent used in the liquid crystal alignment agent of the present invention may, for example, be N-methyl-2. -pyrrolidone, 7-butyrolactone, r-butyrolactam, N,N-methylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone , Ethyl alcohol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol Ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol oxime _ dimethyl ether , diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, etc. A preferred solvent composition is a composition obtained by combining the above solvents, and is a composition which does not precipitate a polymer in the alignment agent and causes the surface tension of the alignment agent to fall within a range of 30 to 40 mN/m. The solid content concentration is selected in consideration of viscosity, volatility, etc., and is preferably in the range of 1 to 10% by weight. That is, (: the liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the thickness of the resin film is too small, so that a good liquid crystal alignment film cannot be obtained; when the solid content concentration exceeds 10% by weight, the thickness of the resin film is too thick. Therefore, a good liquid crystal alignment film cannot be obtained, and The viscosity of the liquid crystal alignment agent is increased, resulting in deterioration of coating characteristics. Further, a particularly preferable solid content concentration range differs depending on the method used when the liquid crystal alignment agent is applied to the substrate. For example, when spin coating is employed When it is used in the printing method, it is particularly preferable to make the solid content concentration to be in the range of 4 to 10% by weight, so that the viscosity of the solution can be made to fall in the range of 1.5 to 4.5% by weight. When the inkjet method is employed, it is particularly preferable to set the solid content concentration to a range of 2 to 5% by weight, so that the viscosity of the solution can fall within the range of 5 to 15 mPa's. The epoxy group-based compound (hereinafter referred to as "specific epoxy compound") represented by the above formula (III) of the liquid crystal alignment agent may, for example, be hydrazine, hydrazine, hydrazine, or N'-tetraglycidyl. -1,2-diaminocyclohexane, N,N,N',N'-tetraglycidyl-1,3-diaminocyclohexane, f 1 Ν,Ν,Ν', N' - Tetraglycidyl-1,4-diaminocyclohexane, bis(N,N-diglycidyl-4-aminocyclohexyl)methane, di( N,N-diglycidyl-2-methyl-4-aminocyclohexyl)methyl, a *(N , N - —* glycidyl-3-methyl-4-aminocyclohexyl)methane , 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,4-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,3 _Bis(N,N-diglycidylaminomethyl)benzene, 1,4-bis(indene, Ν·diglycidylaminomethyl)benzene, 1,3,5-tris(Ν,Ν - diglycidylaminomethyl)cyclohexane; alkane, 1,3,5-tris(Ν,Ν-diglycidylaminomethyl)benzene, represented by the following formulas (31) to (35) Compounds, etc. The content of the epoxy group-containing compound is preferably from 1 to 5 % by weight, more preferably from 5 to 4 % by weight, based on the reliability of the liquid crystal alignment agent. -28- 200844141

In the liquid crystal alignment agent of the present invention, an epoxy group compound other than the specific epoxy compound (hereinafter referred to as "other epoxy compound") may be used without impairing the effects of the present invention. Preferred examples of the other epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl glycol. Ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5, 6-tetraglycidyl-2,4-hexanediol, N,N,N ' ,N '-tetraglycidyl-p-phenylenediamine, N,N,N ',N '-tetraglycidyl- M-phenylenediamine, hydrazine, hydrazine, hydrazine, N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,N, ,N'-tetraglycidyl-4, 4'-Diaminodiphenyl ether, n,N,N',N'-tetraglycidyl-2,2'-dimethyl-4,4'-diaminobiphenyl, and the like. Further, in the liquid crystal alignment agent of the present invention, a compound containing a functional decane may be contained from the viewpoint of improving the adhesion to the surface of the substrate from the viewpoint of not impairing the physical properties of the object. As such a compound containing a functional 矽-29-200844141 alkane, for example, 3-aminopropyltrimethoxyaminopropyltriethoxydecane, 2-aminopropyltrimethoxydecylpropane can be mentioned. Triethoxy decane, N_(2-aminoethyl)-3-aminopropyl decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy-3-urea Propyltrimethoxydecane, 3-ureidopropyltriethoxyethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonylyltriethoxydecane, N-triethyl Oxidylalkylpropyltriazine, N-trimethoxydecylpropyltriethylethylamine, 10-trimethoxyn-1,4,7-triazanonane, 10-triethoxydecane Base-1,4,7-alkane, 9-trimethoxydecyl-3,6-diazaindolyl acetate, decylalkyl-3,6-diazaindolyl acetate, N- Benzyl-3-aminooxydecane, N-benzyl-3-aminopropyltriethoxydecane, 1 aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltri Alkane, N-bis(oxyvinyl)-3-aminopropyltrimethoxydecane, I alkenyl)-3-aminopropyltriethoxydecane, 3-(N-allyl-Ny group )amine Propyltrimethoxydecane, 3-(N,N-diglycidyl; methoxytrimethoxydecane, etc. [Production of display element using liquid crystal alignment agent] Liquid crystal display using the vertical alignment type liquid crystal alignment agent of the present invention The method is produced, for example, by the following method: (1) The liquid crystal alignment agent of the present invention is applied onto one surface of a substrate on which a pattern is formed by, for example, a roll coating method, a spin coating method, a printing method, or an inkjet sweep, and then passed through Heating the coated surface to form a coating film decane, 3-alkane, 2-aminotrimethoxydecane, decane, N--3-aminopropyltriamine, decyltriazinium 9-triethoxypropyl Trimethylphenyl-3-ethoxyindole L bis(oxyethylene glycidol _) aminopropyl acrylate element, 5, etc., a conductive film. Here, -30- 200844141 as a substrate, for example, float glass, Glass such as soda lime glass; transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, etc.

For the transparent conductive film, a NESA film made of tin oxide (Sn〇2) (registered trademark of PPG, USA), an ITO film made of indium oxide-tin oxide (In2〇3-Sn〇2), or the like can be used. . These transparent conductive film patterns are formed by photolithography or a method of using a mask in advance. In the application of the liquid crystal alignment agent, in order to further improve the adhesion between the surface of the substrate and the resin film, for example, a compound containing a functional decane, a compound containing a functional titanium, or the like may be applied in advance to f \ 1 . The heating temperature after the application of the liquid crystal alignment agent is preferably from 80 to 300 ° C, more preferably from 120 to 25 ° C. Further, the liquid crystal alignment agent of the present invention removes an organic solvent by coating to form a resin film as an alignment film, and when it has not been completely imidized, it can be further subjected to dehydration ring closure by heating to form a further yam. Aminated resin film. The thickness of the formed resin film is preferably 0.001 to 1 mm, more preferably 0.005 to 0.5 // m. (2) Two substrates on which the vertical liquid crystal alignment film is formed are formed, and the two substrates are opposed to each other through a gap (cell gap), and the peripheral portions of the two substrates are bonded together with a sealant, and are separated from the surface of the substrate and the sealant. The liquid crystal gap is injected into the cell gap to close the injection hole to form a liquid crystal cell. Then, a polarizing plate is disposed on the outer surface of the liquid crystal cell, that is, on the transparent substrate side constituting the liquid crystal cell, to obtain a liquid crystal display element. Here, as the sealant, for example, an alumina ball-containing epoxy resin as a curing agent and a spacer may be used. -31- 200844141 The liquid crystal may be a nematic liquid crystal or a smectic liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxidized azo liquid crystal, or a biphenyl liquid crystal can be used. A phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenylcyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cuba liquid crystal or the like. Further, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl phthalate, and cholesteryl carbonate may be added to these liquid crystals, and sold under the trade names "C_15" and "CB-15" (manufactured by Merck). It is used as a chiral agent or the like. Further, it is also possible to use a ferroelectric liquid crystal such as p-methoxybenzylidene-p-amino-2-methylbutylcinnamate. In addition, as a polarizing plate to be bonded to the outer surface of the liquid crystal, a polarizing plate or a crucible formed by sandwiching a polyvinyl alcohol and absorbing iodine, which is a bismuth film, is sandwiched between a protective film of cellulose acetate. A polarizing plate made of the film itself. [Embodiment] t Hereinafter, the present invention will be more specifically described by way of Examples, but the present invention is not limited to these Examples. Further, various measurements of the examples and comparative examples were carried out in the following manner. (1) The oxime imidization 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, based on tetramethyl decane. The material was measured for iH-NMR at room temperature and determined by the formula shown by the following formula (i). Amidization rate (TcO^^l-Ai/A^cOxlOO (i) -32- 200844141 A1: Peak area derived from NH proton (10 ppm) A2: Peak area derived from other protons ^ : Polymer The ratio of the number of other protons in the precursor (polyproline) relative to one NH matrix. (2) Solution viscosity of the polymer The solution viscosity (mPa_s) of the polymer is the specified solvent, for the solid The solution diluted to a concentration of 10% by weight was measured at 25 ° C using an E-type rotational viscometer. k (3 ) Vertical alignment evaluation The vertical alignment type liquid crystal display element produced by the above method was subjected to orthogonal polarization (cross) In the case where no voltage is applied and a voltage of 8 V (peak-peak) is applied, when the liquid crystal display element is visually observed from the vertical direction, the white display having no display failure such as light leakage is evaluated as "good". Printability evaluation Modulation viscosity: 15 to 25 mPa, s (solid content concentration: 6.0% by weight to y 8.0% by weight), solvent composition of r - butyrolactone: N-methyl-2-pyrrolidone: butyl cellosolve = 0 :5 0:50 or 40:3 0:30 (by weight) solution, dissolved with this modulation The coating film was formed by a printing method, and after baking, the coating film was visually observed. The evaluation of the coating film without disassembly and coating unevenness was "good". (5) Reliability evaluation was expressed in the above (1). The liquid crystal display element of a good vertical alignment was continuously driven for 48 hours in a thermostat at 60 ° C, and it was confirmed that the display failure or the occurrence of spots and the change in voltage holding ratio were judged. -33- 200844141 Synthesis Example (1 6 ~2 1) According to the composition in Table 1, the N-methyl-2-oxo [: oxalic acid ketone is added in the order of the diamine compound and the tetracarboxylic dianhydride (in the table, it is expressed as "anhydride,"). A solution having a solid concentration of 20% by weight was prepared and reacted at 60 ° for 4 hours to obtain a polyphthalic acid polymer solution (ΡΑ-1) to (P A-6). The solution viscosity of the acid polymer is shown in Table 1. (Synthesis Examples 1 to 15) According to the compositions shown in Tables 1 and 2, to n-methyl-2-pyrrolidone

C A diamine compound and a tetracarboxylic dianhydride (indicated as "anhydride" in the table are prepared as a solid component having a solid concentration of 20% by weight, and reacted at 60 ° C for 4 hours to obtain a polylysine. The polymer is added to the obtained poly-proline polymer, and after adding the oxime of the Wuer multiple shown in Table 1 to the total amount of the poly-proline polymer, the mixture is heated to 1 1 〇 ° C. After 4 hours of dehydration ring closure reaction, after the imidization reaction, the solvent in the system was replaced with a new 7-butyrolactone (by this operation, the pyridinium used in the ruthenium reaction, acetic anhydride Excluding the system), a solution of the polymer (PI-1) to (PI-15) of the solution viscosity and oxime imidation rate shown in Table 1 was obtained. -34- 200844141 Table 1

Synthesis Example Diamine Compound: %) Anhydride (Mole %) Pilot (Molar Multiple) Acetic Anhydride (Molar Multiple) Solution Viscosity (mPa.s) Polymer 醯 Imidization Rate Polymer 1 Dl (10 ), D-5(90) T-2(100) 1.0 1.0 75 54 PI-1 2 Dl(20), D-5(80) T-2(100) 1.0 1.0 66 52 PI-2 3 Dl(20 ), D-6(80) Τ-2(100) 1.0 1.0 47 49 PI-3 4 Dl(10), D-6(20), D-5(70) Τ-2(100) 2.0 2.0 75 75 PI-4 5 Dl(10), D-6(20), D-5(70) Τ-2(80), Τ-4(20) 2.0 2.0 85 81 PI-5 6 Dl(10), D- 7(20), D-5(70) Τ-2(100) 2.0 2.0 75 77 PI-6 7 Dl(15), D-6(50), D-5(35) Τ-2(100) 2.0 2.0 56 81 PI-7 8 Dl(20), D-8(60), D-5(20) Τ-2(100) 2.0 2.0 66 71 PI-8 9 D-2(30), D-6( 20), D-5(50) Τ-2(100) 1.0 1.0 47 69 PI-9 10 D-3(10), D-5(90) Τ-2(100) 1.0 1.0 75 54 PI-10 11 D-3(20), D-5(80) Τ-2(100) 1.0 1.0 85 54 PI-11 12 Dl(5), D-3(5), D-5(90) Τ-2(100 ) 1.0 1.0 75 53 PI-12 13 Dl(5), D-3(15), D-5(80) Τ-2(100) 1.0 1.0 75 49 PI-13 14 D-4(30), D- 5(70) Τ-2(100) 1.0 1.0 56 48 PI-14 15 D-4(15), D-6(50), D-5(35) Τ-2(100) 2.0 2.0 66 80 PI- 15 16 D-7(100) T-K50), Τ-5(50) - - 75 - PA-1 17 D-6(100) Τ-3(50), Τ-5(50) - - 66 - PA -2 18 D-7(100) Τ·3(50), Τ-5(50) - - 66 - PA-3 19 D-7(100) Τ-3(100) • - 56 - PA-4 20 D-8(100) Τ-3(100) - - 66 - PA-5 21 D-8(100) Τ-3(50), Τ-5 (50) - - 66 - PA-6 -35- 200844141 In the diamine compound and the acid anhydride in Table 1, the numbers in parentheses indicate the content ratio, and the symbols in Table 1 have the following meanings. <Diamine compound> D-1: diamine compound D-2 represented by the above formula (1): a compound D-3 represented by the above formula (11): diamine compound represented by the above formula (13) D-4: diamine compound D-5 represented by the above formula (21): p-phenylenediamine I D-6 : 4,4'-diaminodiphenylmethane D-7 : 4,4'-diamine Diphenyl ether D_8 : 2,2'-dimethyl-4,4'-diaminobiphenyl <tetracarboxylic dianhydride> T-1 : 1,2,4,5-cyclohexane Tetracarboxylic dianhydride T-2: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride T-3 : 1,2,3,4-cyclobutane tetracarboxylic dianhydride T-4: l, 3 ,3a,4,5,9b-hexahydro-8-methyl-5(tetrahydro-2,5-dioxo-3- ◎ : 'J furanyl)-naphthalene [l,2-c]-furan -1,3-dione T-5: pyromellitic dianhydride (Example 1) The polymer (PI-1) obtained in Synthesis Example 1 was dissolved in 7-butyrolactone/N-gastric acid- In a mixed solution of 2-pyrrolidone/butyl cellosolve (r BL/NMP/BC), 20 parts by weight of 1,3-bis(N,N-diglycidylamino group) is dissolved relative to 100 parts by weight of the polymer. Base) benzene (Additive A), the solvent composition is T 3 乙川^^/:^= 0/50/50 (weight ratio), solid concentration is 6 % by weight of -36- 200844141 solution. Then, the liquid crystal alignment agent of the present invention was obtained by filtration using a filter having a pore size of 0 · 2 / m. The liquid crystal alignment agent was evaluated for printability, and no repulsion or uneven coating was observed on the coating film, and it was confirmed that the printing property was excellent. Then, the liquid crystal alignment agent of the present invention was prepared in the same manner as described above except that a solution having a solid concentration of 4% was prepared. The obtained liquid crystal alignment agent was applied by spin coating to a transparent conductive film made of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm, and dried at 200 ° C for 60 minutes to form a dry film thickness. 〇.〇8 // m (filming. Using a grinding machine equipped with a roller of woven fabric made of rayon, the surface of the coating is at a speed of 400 μrpm, and the moving speed of the table is 3 cm/sec. The liquid crystal alignment film is formed by grinding in a condition of a length of 0.4 mm. The substrate for liquid crystal display elements is produced in such a manner that the outer diameter of the surface of each liquid crystal alignment film of the liquid crystal display element substrate is coated. After the epoxy resin adhesive of the alumina ball of 3 · 5 # m, the gap formed by the liquid crystal alignment films is overlapped and pressed, and the adhesive is cured in this state. Then, the self-preset liquid crystal The negative electrode liquid crystal (MLC-6690) manufactured by Merck & Co., Ltd. is filled in the cell gap between the substrates for liquid crystal display elements, and the injection port is sealed with an acrylic photocurable adhesive for liquid crystal display elements.A polarizing plate was bonded to both sides of the board to prepare a liquid crystal display element. The vertical alignment property of the obtained liquid crystal display element was evaluated, and the reliability measurement experiment was carried out even at a constant temperature continuous driving -37-200844141 It was confirmed that the unevenness, the spots, and the voltage holding ratio were lowered, and the reliability was good. (Examples 2 to 28, Comparative Examples 1 to 6) According to the formulation shown in Table 2 below and Table 3 below, Example 1 A solution having a solid content concentration of 6% was prepared in the same manner to obtain a liquid crystal alignment agent, and the solubility and printability of the liquid crystal alignment agent were evaluated. In the same manner, a film-forming composition having a solid concentration of 4% was prepared. Liquid crystal display element. Then, vertical alignment evaluation and reliability test were carried out. The results are shown together in Table 2 and Table 3. -38- 200844141 Table 2 Example solid content solvent composition (TBL/NMP/BC) (% by weight) Printing Sexual Vertical Alignment Reliability Polymer Additive (% by weight) 1 PI-1 Additive A(20) 0/50/50 Good Good Good 2 PI-2 Additive A(5) 0/50/50 Good Good Good 3 PI- 2 added A(10) 0/50/50 Good Good Good 4 PI-2 Additive A(20) 0/50/50 Good Good Good 5 PI-2 Additive A(10) 0/50/50 Good Good Good 6 PI-2 Additive B ( 10) 0/50/50 Good Good Good 7 PI-2 Additive C(10) 0/50/50 Good Good Good 8 PI-3 Additive A(20) 0/50/50 Good Good Good 9 PI-4 Additive A (20) 40/30/30 Good Good Good 10 PI-5 Additive A(10) 40/30/30 Good Good Good 11 PI-6 Additive A(20) 40/30/30 Good Good Good 12 PI-7 Additive A(10) 40/ 30/30 Good Good Good 13 PI-8 Additive A(10) 40/30/30 Good Good Good 14 PI-9 Additive A(10) 0/50/50 Good Good Good 15 PI-10 Additive A(20) 0/50/50 Good and Good Good 16 PI-11 Additive A(10) 0/50/50 Good Good Good 17 PI-12 Additive A(20) 0/50/50 Good Good Good 18 PI-13 Additive A(20) 0/50/50 Good Good Good 19 PM4 Additive A(20) 0/50/50 Good Good Good 20 PI-15 Additive A(20) 40/30/30 Good Good Good 21 ΡΙ·2, PA-1 Additive A(10) 0/50/50 Good Good Good 22 PI-2, PA-2 Additive A(20) 0/50/50 Good Good Good 23 Π-2, PA-3 Additive A(10) 0/50/50 Good Good Good 24 PI-2, PA-4 Additive A (20 ) 0/50/50 Good Good Good 25 PI-2, PA-5 Additive A(20) 0/50/50 Good Good Good 26 Π-2, PA-6 Additive A(10) 0/50/50 Good Good Good 27 PI -7, PA-2 Additive A(20) 40/30/30 Good Good Good 28 PI-7 'PA-3 Additive A(20) 40/30/30 Good Good Good-39- 200844141 Table 3 Comparative Solids Solvent composition (TBL/NMP/BC) (% by weight) Printability vertical alignment reliability polymer additive (% by weight) 1 ΡΙ-2 - 0/50/50 Good good bad 2 ΡΙ-2 Additive D(20) 0 /50/50 Good good bad 3 ΡΙ-2 Additive D(40) 0/50/50 Good good bad 4 ΡΙ-2 Additive E(20) 0/50/50 Good good bad 5 ΡΙ-2 Additive F(20) 0/50/50 Good good bad 6 ΡΙ-6 Additive D(20) 0/50/50 Good good bad Example 2 in Table 2 1~2 8 of the polymer, the mixing ratio of the two polymers is 50/50 (% by weight). In addition, the additives shown in Table 2 and Table 3 are as follows. <Additive> Additive A: 1,3-bis(N,N-diglycidylaminomethyl)benzene additive B: 1,4-bis(N,N-diglycidylaminomethyl) Benzene additive C: 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane additive D ·· N,N,N′ ,N′-tetraglycidyl-p-phenylenediamine additive E: N, N, N,, N'-tetraglycidyl-4,4'-diaminodi-Q-phenylmethane' additive; F ··polyethylene glycol diglycidyl ether (molecular weight of about 400 From the results, it was confirmed that the liquid crystal alignment agent of the present invention has good printability and can form a liquid crystal alignment film excellent in vertical alignment and reliability. [Simple description of the diagram] te 〇 [Description of main component symbols] 4trr. -40-

Claims (1)

200844141 X. Patent Application Range: 1. A vertical alignment type liquid crystal alignment agent comprising: a polymer selected from the group consisting of the following formula (1-1) and the following formula (1-2) At least one repeating unit of the group consisting of at least one of the divalent organic groups represented by the following formulas (ΙΙ-1) and (ΙΙ-2) as the following formula (1_1) Qi in the formula and Q2 in the following formula (1-2); and 环 an epoxy group compound represented by the following formula (III), (In the formula (1-1), Ρ1 is a tetravalent organic group derived from a tetracarboxylic acid, Q1 is a divalent organic group derived from a feel compound, and in the formula 2), p2 Ο is derived from four a tetravalent organic group of a carboxylic acid, Q2 is a divalent organic group derived from a diamine compound), (II-2) Λχ1_,2_χ1_0__ (in the formula (ΙΙ-1), X1 is a single bond, each, _C0·, _c〇〇_, -〇c〇_, -NHCO-, -CONH-, -S-, Methylene group, alkyl group having 2 to 6 carbon atoms or phenyl group R' is an alkyl group having a carbon number of 1 〇 2 〇, and a carbon number of 4 to 4 - -41- 200844141 having an alicyclic skeleton a monovalent organic group or a monovalent organic group having a fluorine atom of 6 to 20 carbon atoms. Further, in the formula (II-2), X1 is a single bond, _〇_, _C〇_, _C〇〇 _, _〇C〇_, _NHC〇_, _C〇NH_, _S_, methylene, an alkylene group having a carbon number of 2 to 6 or a phenyl group, and f is an alicyclic ring having a carbon number of 4 to 40. a divalent organic group of a skeleton or a divalent organic group having a fluorine atom of 5 to 30, (III) (In the formula (III), a is an integer of 2 to 4, R3 is an a-valent organic group, and a part bonded to N is an aliphatic carbon). 2. The vertical alignment type liquid crystal alignment agent according to claim 1, wherein the polymer contains two or more of the total repeating units of 7 mol% or more of each of the formulae (II-1) and (II-2). At least one hydrazine in the valence organic group is a repeating unit of Q2 in Q1 and (Ι·2) in the formula (1-1). 3. The vertical alignment type liquid crystal alignment agent according to claim 1 or 2, wherein the tetracarboxylic dianhydride for obtaining the repeating unit represented by the formula (1-1) or the formula (1-2) comprises 2 , 3,5-tricarboxycyclopentyl acetic acid dianhydride. The vertical alignment type liquid crystal alignment agent according to any one of claims 1 to 3, wherein the polymer comprises at least one compound represented by formula (1-2) containing more than 40% by mole of all repeating units. The vertical alignment type liquid crystal alignment agent according to any one of claims 1 to 4, wherein the epoxy compound comprises R3 in the formula (III). A compound of a ring skeleton or an alicyclic skeleton. The vertical alignment type liquid crystal alignment agent according to any one of claims 1 to 5, wherein the content of the formula (III) is 5 to 45% by weight in the solid content. A liquid crystal display element characterized by having a liquid crystal alignment agent obtained by a vertical alignment type liquid crystal alignment agent according to any one of claims 1 to 6. -43- 200844141 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 〇 y \ \\ C 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: