TWI359858B - Vertical liquid crystal alignment agent and vertic - Google Patents

Description

1359858 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a vertical liquid crystal alignment agent and a vertical liquid crystal display element. More specifically, it relates to a vertical liquid crystal alignment agent capable of stably forming a vertical liquid crystal alignment film having defects such as coating unevenness and small holes for a liquid crystal display element fabricated using a large substrate, and a vertical liquid crystal having the liquid crystal alignment agent. A liquid crystal display element of an alignment film. [Prior Art] At present, as a liquid crystal display element, there is known a TN type liquid crystal display element having a so-called TN type (twisted nematic) liquid crystal cell, which forms polylysine on the surface of a substrate on which a transparent conductive film is provided, A liquid crystal alignment film made of a polyimine or the like is used as a substrate of a liquid crystal display element, and two of the substrates are opposed to each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form a cell having a sandwich structure. The long axis of the liquid crystal molecules is continuously twisted by 90 degrees from one substrate to the other. Further, an S TN (Super Twisted Nematic) type liquid crystal display element having a higher contrast ratio and a smaller viewing angle dependency than a TN type liquid crystal display element has been developed. The S TN type liquid crystal display element is used as a liquid crystal by mixing an optically active substance chiral reagent in a nematic liquid crystal, and is produced by causing a long axis of liquid crystal molecules to be continuously twisted by a distance of 180 degrees or more between substrates. Birefringence effect. Further, it is known that a horizontal electric field type liquid crystal display element's two electrodes for driving a liquid crystal are provided in a comb shape on one side chassis, and an electric field parallel to the substrate surface is generated to control liquid crystal molecules. The alignment of the liquid crystal in these liquid crystal display elements 1359858 is often manifested by a liquid crystal alignment film subjected to a rubbing treatment. As the liquid crystal display element other than the above, a liquid crystal display element having a vertical alignment type liquid crystal cell in which liquid crystal molecules having negative dielectric anisotropy are vertically aligned on a substrate is known. In such a liquid crystal display element, the alignment control of the liquid crystal is usually carried out by a liquid crystal alignment film formed of a liquid crystal alignment agent containing a polymer such as polyglycolic acid or polyimine. The liquid crystal alignment film is formed by applying a liquid crystal alignment agent to a substrate with an electrode φ on which a color filter or a semiconductor is formed by a roll coater method, a spin coater method, a printing method, or the like, and baking the solvent to evaporate the solvent. However, when the coating performance of the liquid crystal alignment agent used is not sufficiently good, defects such as coating unevenness or pinholes due to uneven film thickness of the liquid crystal alignment film may occur. Since such a defect has a large influence on the liquid crystal alignment, a liquid crystal display element containing a liquid crystal alignment film having defects may not be able to obtain a beautiful image. Then, in order to obtain a liquid crystal alignment agent having excellent coating properties, techniques such as those disclosed in Patent Document 1, Patent Document 2, and Patent Document 3 have been applied to improve coating unevenness, and in the conventional liquid crystal display device manufacturing process. It performed very well, but it was the result of the contribution of the small size of the liquid crystal display element at that time. In the liquid crystal display device, a plurality of methods for producing a plurality of blocks in which a pair of mother substrates forming an alignment film are bonded to each other to form a cell, and liquid crystals are injected and then cut out are used. In the past, since the size of the manufactured liquid crystal display element is very small relative to the substrate, several to several tens of liquid crystal display elements can be obtained from a pair of mother substrates, even if the alignment film portion on the mother substrate has coating unevenness defects due to A large number of liquid crystal display elements which do not contain this portion are obtained, and thus a manufacturing efficiency of 1,359,858. However, in recent years, liquid crystal display elements have a tendency to increase in size, and liquid crystal display elements of up to 40 inches have recently been manufactured. On the other hand, in the case where the liquid crystal display element is increased in size, the size of the mother substrate is limited to a small extent due to limitations in manufacturing and transportation, and the number of liquid crystal display elements that can be obtained for a pair of mother substrates is also higher than in the past. A reduced condition has occurred. Therefore, when there is a defect in the liquid crystal alignment film formed on the mother substrate, the influence of φ on the production efficiency is remarkably increased as compared with the prior art. Therefore, there is an urgent need for a coating property which is remarkably improved and can be stably produced as compared with the prior art. A liquid crystal alignment agent for a defect-free liquid crystal alignment film is obtained. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2002-95499. SUMMARY OF THE INVENTION The object of the present invention is to provide a coating property. Excellent, stable and stable vertical liquid crystal alignment agent for vertical liquid crystal alignment films without coating unequal defects. Another object of the present invention is to provide a vertical liquid crystal display element having a vertical liquid crystal alignment film produced by the liquid crystal alignment agent of the present invention. Other objects and advantages of the present invention will be apparent from the following description. According to the present invention, the above objects and advantages of the present invention are achieved by a vertical liquid crystal alignment agent characterized by comprising a third organic solvent having a nitrogen atom in a molecule having a surface tension of 39 dynes/cm or more. Table 1359858 A mixed solvent composed of a second organic solvent containing no nitrogen atom in the molecule having a surface tension of 39 dynes/cm or more and a third organic solvent having a surface tension of 32 dynes/cm or less and dissolved in the mixed solvent Part of the ruthenium iodide polymer and/or polyimine. According to the present invention, the above objects and advantages of the present invention, and secondly, are achieved by a vertical liquid crystal display element characterized by having a liquid crystal alignment film formed of the vertical liquid crystal alignment agent of the present invention. The liquid crystal alignment agent of the present invention can stably produce a vertical liquid crystal alignment film free from coating unevenness defects even when a large substrate is used, and can be suitably used for producing an ultra-large liquid crystal display element. The liquid crystal display element of the present invention can be effectively used for various devices, for example, for display devices such as desktop computers, watches, desk clocks, mobile phones, counting display screens, word processors, personal computers, and liquid crystal televisions. [Embodiment] The liquid crystal alignment agent of the present invention is prepared by dissolving a partially ruthenium imidized polymer of polylysine and/or polyimine as described above! A solution composition obtained by mixing an organic solvent, a second βΙ organic solvent, and a third organic solvent. The above polyimine is usually obtained by dehydration ring closure of polyamic acid obtained by ring-opening polyaddition of a tetracarboxylic dianhydride with a diamine compound. The partially ruthenium iodide polymer can be generally obtained by a method of dehydrating a poly (protonic acid) moiety, or a method of bonding a phthalic acid prepolymer to a quinone imine prepolymer to form a block copolymer. <Polyamic acid> [tetracarboxylic dianhydride] 1359858 The tetracarboxylic dianhydride' may, for example, be butane tetracarboxylic dianhydride or 1,2,3,4-cyclobutane tetracarboxylic dianhydride 1,2-Dimethyl-1,2,3,4-cyclobutanetetrahydro acid dianhydride, 1,3-dimethyl], 2,3,4-cyclobutane tetracarboxylic dianhydride , 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylate Acid dianhydride, 1,2,3,4·cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-bicyclic ring Hexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5·tetrahydrofuran Carboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo--3-furanyl)-naphthalene [l,2-c] - Furan-1,3-dione, l,3,3a,4,5,9b-hexahydro•5-methyl_5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-l,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxo -3·furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,915-hexahydro-7-methyl-5-(tetrahydro- 2,5-diox 3--3-furyl)-naphthalene[l,2-c]-furan-1,3-dione' 1,3,3&,4,5,913-hexahydro-7-ethyl-5-(tetrahydrogen) -2,5-dioxo-3-furanyl)·naphthalene [l,2-c]-furan-1,3-dione, 1,3,33,4,5,91?-hexahydro-8 -methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-(:]-furan-1,3-dione, • l, 3, 3a, 4,5,9b-hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-di Ketone ' 1,3,33,4,5,91)-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l, 2-c]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuranmethylene)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride Bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione- Aliphatic and alicyclic tetracarboxylic dianhydrides such as 6-spiro-3'-(tetrahydrofuran-2',5'-dione), compounds represented by the following formulas (I) and (II), 1359858

(wherein R1 and R3 represent a divalent organic group having an aromatic ring, R2 and φ R4 represent a hydrogen atom or an alkyl group, and a plurality of R2 and R4 present may be the same or different); pyromellitic dianhydride , 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 1,4,5,8-naphthalene Carboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'- Dimethyldiphenylnonanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4, 4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl milling II> 4,4,-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-homofluoroisopropylidenediphthalic acid dianhydride, 3,3' , 4,4'-biphenyltetracarboxylic dianhydride, di(decanoic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphosphonic acid) dianhydride, m-phenylene-di (triphenylphosphonic acid) dianhydride, bis(triphenylphosphonic acid)-4,4'-diphenyl ether dianhydride Bis(triphenylphosphonic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-di(hydroper trimellitate), propylene glycol-di(hydroper trimellitate), 1,4 - Butanediol-di(hydrogen trimellitate), 1,6-hexanediol-di(hydroper trimellitate), 1,8-octanediol-di(anhydrotrimellitic acid ester) , an aromatic tetracarboxylic dianhydride such as a compound represented by the following formulas (1) to (4), 2,2-di(4--10-1359858 hydroxyphenyl)propane-di(hydrogen trimellitate) . They may be used alone or in combination of two or more. Ch3 I /CHj

(2)

(3) -11- 1359858

^ch3 vch3 (4) where 'from the viewpoint of exhibiting good liquid crystal alignment, excellent butane tetracarboxylic dianhydride, I, 2,3,4-cyclobutane tetracarboxylic dianhydride, two Methyl-1,2,3,4-cyclobutanine tetradecanoic acid dianhydride, i,2,3,4-cyclopentanyltetrahydro acid dianhydride, 1,2,4,5-cyclohexanin four residues Acid dianhydride, 2,3,5-trisole cyclopentyl acetic acid diterpene, 5-(2,5-dioxotetrahydrofuran methylene)_3_methyl-3-cyclohexyl-oxime,] -Secondary acid - wild, 1,3,33,4,5,91)-hexahydro-5-(tetrahydro-2,5-dioxo-3-pyranyl)-naphthalene [1,2- (:]-咲-1,3-dione, 1,3,33,4,5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3 -furyl)-naphthalene [1,2-(;]-furan-1,3-dione, 1,3,33,4,5,91?-/, gas-5,8--methyl_5 -(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, bicyclo[2,2,2]-oct.7 -ene-2,3,5,6_tetracarboxylic acid-hepatic, 3-oxabicyclo[3.2.1] xinyuan-2,4-dione-6-spiro-3,-(tetrahydrofuran-2',5 '-Dione), pyromellitic dianhydride, 3,3,,4,4'-benzophenonetetracarboxylic acid monoanhydride, 3,3',4,4'-phenylphenyltetracarboxylic acid Anhydride, 1,4,5 a compound represented by the following formula (8) in the compound represented by the following formula (5) to (7) and a compound represented by the above formula (II) in the compound represented by the above formula (I): 8-naphthalenetetracarboxylic dianhydride Particularly preferred are 1,2,3,4-cyclobutanetetracarboxylic dianhydride, hydrazine, 3-dimethyl-1,2,3,4·cyclobutanetetracarboxylic dianhydride, Cyclohexane tetracarboxylic dianhydride, 1359858 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5- Dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,33,4,5,91?-hexahydro-8-methyl-5 -(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-<〇-furan-1,3-dione, 3-oxabicyclo[3.2.1]octane -2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), pyromellitic dianhydride, and a compound represented by the following formula (5).

(5)

(7) (8) In particular, when the repeating unit (the valeric acid unit) represented by (1-1) and the repeating unit (the quinone imine unit) represented by the above formula (1-2) are simultaneously present, (1) 1) The tetravalent organic group represented by P1 -1 3 - 1359858 and the tetravalent organic group represented by P2 in the repeating unit (醯imino unit) represented by (1-2) may each be the same or different, as... Preferred examples of the group include a group represented by the following formula (i) and formula (Γ) and formula (ii). Preferable examples of P2 include a group having an alicyclic skeleton, and particularly preferably a group represented by the following formulas (ii) and (ii').

(ϋ)

-14- 1359858 (wherein, P1 and P2 are each independently a tetravalent organic group, Q1 and Q2 are each independently a divalent organic group, r is a halogen atom, a methyl group or an ethyl group, and a is 0 or 1 An integer, b is an integer from 0 to 5, and c and d are integers from 0 to 4. Specific examples of the tetracarboxylic dianhydride which is preferable in each of the repeating units include, for example, anthracene, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3, which constitutes a phthalic acid unit. -Dimethyl, 2,3,4-cyclobutanetetracarboxylic dianhydride, hydrazine, 2,4,5•cyclohexyltetrahydro dianhydride, 2,3,5-tricarboxycyclopentylacetate Anhydride, pyromellitic acid

—anhydride, a compound represented by the formula (5), and the like. Further, the tetracarboxylic acid monohydride constituting the quinone imine unit is preferably an aliphatic cyclic tetracarboxylic dianhydride, and particularly, 2,3,5-trimethylcyclopentyl acetic acid diano, 13, 33, 4, 5 may be mentioned. 91? hexahydro 5 (tetrahydro-2,5-dioxo-3-indolyl)_cain n,2_c]•furan-丨,3-diketone, anthracene, 3,3a,4,5,9b - hexahydro-8-methyl-5-(tetrahydro-n-dioxo...-furanylnaphthalene^"^furan-^-monoketone 3_oxabicyclo[3·2.1]octane_2 4_diketo-6-spiro-3,-(tetrahydrofuran-2',5'-dione), etc. [Diamine compound] As the diamine compound used for the synthesis of the above polyamic acid, for example, for example, p-Benzyl-amine, zhongzhong~ping-makeup-present diamine, 4,4,-diaminodiphenylmethane, 4,4,-amino-benzidine, 4,4,-diamine Diphenyl sulfide, 4,4, diaminodiphenylanthracene, 3,3'_-Tianqi 4 4,--monoamine-based, 4,4'--aminobenzoic acid aniline, base - benzoic acid, 1>5-diaminocaxene, 2,2,-dimethyl.anthracene, diamine, and 5-aminoaminophenyl)-1,3,3-trimethyl Plump, 6-amino 1 (4-fe basic) 1,3,3-trimethylindan, 3,4,-diamino Phenyl ether, benzophenone, 4,4'-diaminodiphenyl 3,3'-diaminobenzophenone, 3 -15- 1359858 ketone' 2,2-di[4-(4-amino group Phenoxy)phenyl]propane, 2s2-bis[4-(4-aminophenylphenoxy)phenyl]hexafluoropropane, 2,2-bis[4-aminophenyl]hexafluoropropyl , 2,2-bis[4-(4-aminophenoxy)phenyl]anthracene, 1,4-bis(4-aminophenoxy)benzene, iota, 3-mono(4-aminobenzene) Oxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-1〇·hydrogen, 2,7-diaminopurine, 9,9-bis(4.aminophenyl)anthracene, 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)bis(phenylamine), 4,4'-(m-phenylene isopropylidene)bis(aniline) , 2,2,-bis[4-(4-Amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino 2,2,·di ( Trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluoro , an aromatic diamine such as 4-(4-n-heptylcyclohexyl)-phenoxy-2,4-diaminobenzene; 1,1-m-xylylenediamine, 1,3-propanediamine , butanediamine, pentamethylenediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 4,4-diaminoheptyldiamine, iota, 4-aminocyclohexylamine, isophor Ketodiamine, tetrahydrodicyclopentanediamine, hexahydro #-4,7-methyleneindanylenedimethylenediamine, tricyclo[6.2.1.02,7]-undecene Aliphatic and aliphatic cyclic diamines such as dimethyldiamine, 4,4'-methylenebis(cyclohexylamine); 2,3-diaminopyridine' 2,6-diaminopyridine, 3,4 -diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyridinium, 5,6-diamino-2,4-dihydroxypyrimidine, 2 ,4-diamino-6-dimethylamino-1,3,5-trin, 1,4-bis(3-aminopropyl)anthracene, 2,4-diamino-6-iso Propoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-trin, 2,4-diamino-6-phenyl-1 ,3,5-三-16- 1359858 Trap, 2,4-diamino-6-methyl-s-tripper, 2,4-diamino-1,3,5-three tillage, 4,6 -diamino-2-vinyl-s-tripper, 2,4-diamino-5-phenylthiazole , 2,6·diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-mtriazole, 6,9-diamino-2- Ethyl acridine lactate, 3,8-diamino-6-phenylphenanthridine, 1,4-diamine oxime, 3,6-diaminoacridine, bis(4-amino Phenyl) phenylamine and a diamine having two primary amino groups in the molecule and a nitrogen atom other than the primary amino group, such as a compound represented by the following formula (ΠΙ)~(IV),

(III) (wherein R5 represents a monovalent organic group having a cyclic structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triplet, acridine and fluorene, and X represents a divalent organic group),

(IV) (wherein X represents a divalent organic group having a cyclic structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triple well, acridine, and anthracene, and R6 represents a divalent organic group; The same may be the same or different); a monosubstituted phenylenediamine represented by the following formula (V); a diamine organooxime represented by the following formula (VI);

-17- (V) 1359858 (wherein R7 represents a divalent organic group selected from the group consisting of -0-, -COO-, -OCO-, -NHCO-, -CONH-, and -CO-, and R8 represents a steroid selected from the group consisting of steroids a monovalent organic group of a skeleton, a trifluoromethyl group and a fluorine group or an alkyl group having 6 to 30 carbon atoms, R9 R9 h2n-(-ch

2-V Si-ί-Ο—Si Vf CH2VnH (VI) (wherein R 9 represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R 9 groups may be the same or different, and p is an integer of 1 to 3 q is an integer of 1 to 2 )); a compound represented by the following formulas (9) to (1 3) and the like can be given. These diamine compounds may be used singly or in combination of two or more kinds.

HiN~0~'c〇°

CH, (9)

-18- (10) 1359858

(13) (wherein y is an integer of 2 to 12, and z is an integer of 1 to 5). Among them, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,7-diamino group are preferred.莽, 4,4'-bile diphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene , 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-aminophenyl]hexafluoropropane, 4,4'-(p- Phenylene diisopropylidene) bis(aniline) ' 4,4'-(m-phenylene diisopropylidene) bis(aniline), 1,4-cyclohexanediamine, 4,4' -methylene bis(cyclohexylamine), 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, the above formula (9) a compound represented by ~(1 3), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, the above formula (111 a compound represented by the following formula (1 4 ) in the compound represented by the formula (1 4), a compound represented by the following formula (15) in the compound represented by the above formula d 1 v), and the above formula

Things. The following formula (1 6) to (2) in the compound represented by (V) represents the child A

( 1 5 )

/CH3 vch3 (16)

/CH3 XCHj (17)

(18)

-20- (19) 1359858 . Polyacetamide poor solvent alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc. may be used in combination in the solvent. Specific examples of such a poor solvent include methanol 'ethanol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, and 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 formazan, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, φ B Glycol dimethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate , diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, I,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, Heptane, octane, benzene, toluene, xylene, and the like. As described above, a reaction solution in which polylysine was dissolved was obtained. Then, the reaction solution was poured into a large amount of poor solvent to obtain a precipitate. Polyphosphate is obtained by drying the precipitate by pressure reduction. Further, the polylysine is dissolved in an organic solvent again, and then precipitated with a poor solvent, and the poly-proline can be purified by performing one or several steps. <Polyimine> The polyimine constituting the liquid crystal alignment agent of the present invention can be prepared by dehydrating and ring-closing the above polyamic acid. Dehydration ring closure of polylysine by, for example, (i) heating poly-proline, or (ii) dissolving poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, as needed The heating method proceeds smoothly. -22 - 1359858 • The reaction temperature in the above method (1) for heating poly-proline is preferably 50 to 200 ° C. More preferably 60 to 17 (TC. When the reaction temperature is less than 50 ° C, the dehydration ring closure reaction is difficult to carry out completely ' If the reaction temperature exceeds 200 ° C, the molecular weight of the obtained quinone imidized polymer may decrease. On the other hand, the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the poly (proline) solution described above (ii) In the above, 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 preferably 0.01 to 20 mol per 1 mol of the polyglycine repeating unit. Φ is a dehydration ring-closing catalyst, and a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. However, it is not limited thereto. The amount of the dehydration ring-closing catalyst is relative to that of the dehydrating agent used for 1 mol. It is preferably 0.01 to 10 mol. Further, as the organic solvent used in the dehydration ring-closure reaction, the same organic solvent as the organic solvent exemplified as the solvent used in the synthesis of polylysine may be mentioned. Further, the reaction temperature of the dehydration ring-closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. Further, the reaction solution thus obtained can be purified by the same operation as the polyamic acid purification method. Polydecyl melamine. <Partial oxime imidized polymer> The partially ruthenium iodide polymer used in the present invention has a structure obtained by imidating the above polyphosphonic acid moiety ruthenium. The ruthenium imidization ratio in the partially ruthenium iodide polymer is preferably from 10 to 90%, more preferably from 30 to 70%. Here, the "oxime imidization ratio" means formation with respect to the total number of repeating units in the polymer. The ratio of the number of repeating units of the quinone ring is represented by %. In this case, a part of the quinone ring may also be an isoindole. -23 - 1359858 . As a method of synthesizing a part of the quinone imine polymer, Using, for example, (i) a method of partially dehydrating and ring-closing by heating the above polyamic acid, (π) dissolving the above polylysine in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution according to Need heating, carry out the department a method of synthesizing by dehydration and ring closure, or (in) a method of mixing by mixing a tetracarboxylic dianhydride, a diamine compound, and a diisocyanate compound, if necessary, by heating and condensing. In the method (i) above, the reaction temperature Preferably, it is 300 ° C or less, and more preferably Φ is 100 to 250 ° C. If the reaction temperature exceeds 300. (:, the molecular weight of the obtained partially ruthenium-imided polymer may be lowered β on the other hand, as in the above ( The dehydrating agent used in the method of ii) may, for example, be an anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride. The amount of the dehydrating agent is preferably 0.2 to 20 mol per 1 mol of the polyglycine repeating unit. 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. Further, the amount of the hydrazine imidization catalyst is preferably 0.1 to 10 moles relative to the dehydration agent used for 1 mole. In addition, examples of the organic solvent used in the dehydration ring-closure reaction include the same organic solvents as those exemplified as the solvent used in the synthesis of polylysine. Further, the reaction temperature of the dehydration ring closure is preferably 〇 180 ° C, more preferably 60 to 150 ° C. Further, by subjecting the reaction solution thus obtained to the same operation as the polyamic acid purification method, a part of the ruthenium iodide polymer can be purified. Specific examples of the diisocyanate compound used in the reaction of the above (iii) include an aliphatic diisocyanate-24-1359858 ester such as hexamethylene diisocyanate; cyclohexane-1,2-diisocyanate, 1 -Methylcyclohexane-2 diester, 1,2-bis'methylcyclohexane-ω,ω'-diisocyanate, 1,4-di-5 methane-ω,ω'-diisocyanate, ·Exotic Buddha Alicyclic ketone diisocyanate, 1,3,5-tripropylcyclohexane-1ω, 2ω-diisocyanate, dicyclohexylmethane-4,4'-acid ester, etc.; , 4'-diisocyanide 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate An aromatic diisocyanate such as a diisocyanate represented by (2 2) to (26). Isocyanatocyclohexylmethyl-2-• diisocyanate, base-2,4-

(22) (23)

(24) (25) 1359858

Among them, preferred are dicyclohexylmethane-4,4'-diisocyanate, diphenylmethane-4,4,-diisocyanate, 1-methyl-2,4-phenylene diisocyanate, and 1- Methyl-2,6.phenylene diisocyanate. These may be used alone or in combination of two or more. Further, the above (in) reaction does not particularly require a catalyst, and the reaction temperature is preferably from 50 to 2,001, more preferably from 1 to 160. . . [End Modification] <Terminal Modified Polymer> The polylysine and the partially ruthenium iodide polymer may be a terminal modified polymer having a molecular weight adjusted. By using the terminal-modified polymer, the coating properties and the like of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. Such a terminal-modified polymer can be synthesized by adding, for example, a monoanhydride, a monoamine compound, a monoisocyanate compound or the like to the reaction system during the synthesis of poly-proline. Here, examples of the monoanhydride include maleic anhydride, decanoic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, and the like. . Further, examples of the monoamine compound include aniline, cyclohexylamine 'n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, and Dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, n-di- -26 - 1359858. Decalamine Wait. Further, examples of the monoisocyanate compound include phenyl isocyanate, naphthyl isocyanate, and the like. [Logarithmic Viscosity] <Logarithmic Viscosity of Polymer> The logarithmic viscosity (η In) 如上 of the polyglycine and the partially ruthenium-imided polymer obtained as above is preferably 〇. 5 to 10 dl/g, more preferably 0.05~5 dl/g. The logarithmic viscosity (ηΐπ) of the present invention is determined by using N-methyl-2-pyrrolidone as a solvent at a concentration of 0.5 g/100 ml at 30 ° C, and is determined by the following formula (A). Dear. Μ solution flow time / solvent flow time), weight concentration of η Ϊ polymer) C } [liquid crystal alignment agent] The liquid crystal alignment agent of the present invention dissolves the polyimine and/or a part of the ruthenium iodide polymer by organic In the organic solvent constituting the liquid crystal alignment agent of the present invention, a first organic solvent having a surface tension of 39 dynes/cm or more and having a nitrogen atom in the molecule is used, and the surface tension is 39 dynes/cm or more. A mixed solvent of a second organic solvent containing no nitrogen atom in the molecule and a third organic solvent having a surface tension of 32 dynes/cm or less. The mixing ratio of the first organic solvent, the second organic solvent, and the third organic solvent preferably satisfies the following formula (AxBxC) x 10'3 ^ 12 ', more preferably 14 or more, where A, B, and C are respectively the first organic The viscosity of the -27 - 1359858. based on the total weight of the solvent, the second organic solvent, and the third organic solvent is increased, and the coating property is likely to be deteriorated. Further, the temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably 〇 ° C to 200 ° C, more preferably 20 ° C to 60 ° C. The liquid crystal alignment agent of the present invention may contain a compound having an epoxy group in the molecule in order to improve the firming edge of the alignment film as needed. Preferable examples of such an epoxy group-containing 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 dihydrate, glycidyl ether 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3, 5,6-tetraglycidyl-2,4-hexanediol, ^1^', >1'-tetraglycidyl-111-xylylenediamine, 1,3-di(N,N-di Glycidylaminomethyl)cyclohexane 'N,N,N,,N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like. Further, the liquid crystal alignment agent of the present invention may optionally contain a compound having a functional oxime in order to improve the adhesion between the alignment film and the substrate. As such a compound having a functional oxime, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxy read I-based decane, 2 -Aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyl Methyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N- Ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylenetriamine, N-trimethoxysilylpropyldiethylenetriamine, 10 -trimethoxysilane-1,4,7-triazadecane, 10-triethoxydecyl 1,4,7-triazadecane, 9-trimethoxydecyl-3 6-diazaindolyl acetate, 9-triethoxy-29- 1359858 sand-based base, 3,6-diazepine acetate, N-benzyl-3-aminopropyltrimethyl Oxyl sulphate, N-benzyl_3_aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyl Ethoxygen Silane, N_ bis (hydroxyethyl) -3-aminopropyl trimethoxy Silane, N_ bis (hydroxyethyl) aminopropyl triethoxysilane _3_ Silane 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) The liquid crystal alignment agent of the present invention is applied onto one surface of a substrate provided with a patterned transparent conductive film by a method such as a roll coater method, a spin coater method, a printing method, or an inkjet method, and then passed through The coated surface is heated to form a coating film. Here, as the substrate, for example, a glass such as float glass or soda lime glass; a transparent substrate made of plastic such as polyethylene terephthalate or polybutylene terephthalate, polyether oxime or polycarbonate can be used. As the transparent conductive film provided on one side of the substrate, a NESA film (registered trademark of PPG, USA) made of tin oxide (Sn 2), an ITO film made of indium oxide-tin oxide (In203-SnO 2 ), or the like can be used. The formation of these transparent conductive film patterns is performed by photolithography and a method of using a mask in advance. A metal such as A1 or Ag, an alloy containing these metals, or the like can be used for the reflective electrode. There is no particular limitation on it as long as it has sufficient reflectance. In the application of the liquid crystal alignment agent, in order to further improve the adhesion between the surface of the substrate and the transparent conductive film or the reflective electrode and the coating film, a functional decane-containing compound or a functional titanium-containing compound may be applied to the surface of the substrate in advance. . The heating temperature after coating the liquid crystal alignment agent is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. The liquid crystal alignment agent of the present invention containing polyglycine is coated with -30-1359858. The organic solvent is removed after the cloth. Further, a coating film as an alignment film is formed, or a dehydration ring closure is performed by further heating, whereby a coating film which is further imidized can be formed. The thickness of the formed coating film is preferably 0.001 to Ιμηι, more preferably 0.005 to 0.5 μηι. (2) The surface of the coating film to be formed is a structure in which a photosensitive resin is used to form a structure on a substrate, and a vertical liquid crystal alignment film is formed thereon as shown in Japanese Patent Publication No. 2002-327058. (3) Two substrates in which the vertical liquid crystal alignment film is formed as described above are formed, and two substrates are placed opposite each other through a gap (box gap), and the peripheral portions of the two substrates are bonded together by a sealing agent to be separated from the surface of the substrate and the sealant. The liquid crystal is injected into the gap of the box to close the injection hole to form a liquid crystal cell. Then, a polarizing plate is provided on the outer surface of the liquid crystal cell, that is, on the side of the transparent substrate constituting the liquid crystal cell, to obtain a liquid crystal display element. Here, as the sealant, for example, an alumina ball-containing epoxy resin or the like as a curing agent and a separator can be used. Examples of the liquid crystal include a nematic liquid crystal and a disk-shaped liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, or a phenyl cyclohexane may be used. Liquid crystal, ester liquid crystal 'triphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubic liquid crystal, and the like. Further, in these liquid crystals, a cholesteric liquid crystal such as chlorinated cholesterol, cholesterol phthalate or cholesterol carbonate, and a pair sold under the trades "C-15" and "CB-15" (manufactured by Meruco Co., Ltd.) may be added. Use it for palm and the like. Further, a ferroelectric liquid crystal such as p-methoxybenzylidene-fluorene-amino-2-methylbutylcinnamic acid can also be used. Further, as a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing film called a ruthenium film in which a polyvinyl alcohol is extended and aligned and a ruthenium film which absorbs iodine is sandwiched between the cellulose acetate protective film can be cited. A polarizer or a polarizer made by the ruthenium itself. The invention will now be more specifically illustrated by the examples, but the invention is not limited thereto. Printing performance in the examples and comparative examples 'Vertical alignment property was evaluated by the following method. [Printing performance test of liquid crystal alignment agent] The liquid crystal alignment film of the liquid crystal alignment agent of the present invention (manufactured by Nippon Photographic Co., Ltd.) was applied to a glass substrate (300 mm x 400 mm x 0.7 mm) having a transparent electrode made of a ruthenium film. After forming a liquid crystal alignment film by baking, the peripheral portion and the central portion of the liquid crystal alignment film were observed with a microscope having a magnification of 20 times, and it was judged as "good" without coating unevenness, and uneven coating was observed. The case was judged as "bad". [Vertical Alignment] When the voltage is OFF and the 12V AC voltage (peak-peak) is applied, the liquid crystal display element is observed by crossed Nicols, and under the polarizing microscope, the presence or absence of an abnormal region is observed, and there is no abnormal region. The case was judged as "good", and the determination of the abnormal region was "poor". Synthesis Example 1 224.17 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride, and 68.13 g (0.63 mol) of p-phenylenediamine as a diamine compound. 193.44 g (0.37 mol) of the diamine compound represented by the above formula (16) was dissolved in 4500 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 6 hours. Next, the reaction solution was poured into a large excess of methanol to precipitate a reaction product, -32 - 1359858 - and then washed with methanol - by drying at 4 ° C for 15 hours under reduced pressure to obtain a logarithmic viscosity of 520 g. 57 dl / g of polyaminic acid ^ 3 〇 g of the obtained polyamine acid was dissolved in 57 〇g N -methyl-2-pyrrolidone, adding 5.7 g of pyridine and 7.4 g of acetic anhydride 'dehydration at 110 ° C After 4 hours of ring closure, the same precipitation, washing, and reduced pressure as above were carried out to obtain 19.0 g of a polyimine having a logarithmic viscosity of 〇5 〇dl/g (this is called "polyimine (PI-1)"). Synthesis Example 2 In the synthesis example 1, except that 77-86 g (0-72 mol) of p-phenylenediamine, ® 146.38 g (0.28 mol) of the diamine compound represented by the above formula (16) was used as the diamine compound, and Synthesis Example 1 was used. The same procedure was carried out to obtain a polyglycine having a logarithmic viscosity of 0.45 dl/g of 390 g. In the same manner as in Synthesis Example 1, except that 30 g of the obtained polylysine was used, ruthenium imidization was carried out to obtain a ruthenium ylide having a logarithmic viscosity of 0.56 dl/g (which is called "polyimine" (ΡΙ_2). ), Synthesis Example 3 In Synthesis Example 2, except that 95.16 g (0.88 mol) of p-phenylenediamine, 62.74 g (0.22 mol) of the diamine compound represented by the above formula (16) was used as the diamine In the same manner as in Synthesis Example 2, a poly-proline acid having a logarithmic viscosity of 0.38 dl/g was obtained in the same manner as in Synthesis Example 2. Then, except that 4.8 g of shame and 6.1 g of acetic anhydride were used, Synthesis Example 2 was used. The same operation gave 20.3 g of a polyimine having a logarithmic viscosity of 0.40 dl/g (this is called "polyimine (PI_3),). Synthesis Example 4 In Synthesis Example 3, except that 97.3 3 g (0.88 mol) of p-phenylenediamine, 37.66 g (0.1 mol) of 2,4-diamino-yt-octadecyloxybenzene was used as the diamine compound. The procedure was carried out in the same manner as in Synthesis Example 1 to obtain 24.3 g of a polythenimine having a logarithmic viscosity of 42.42 -33 to 1359858. dl/g (this is called "polyimine (PI_4),). Example 5 In Synthesis Example 1, except that 64.88 g (0.88 mol) of p-phenyl-amine, 3 6.65 g (0.1 mol) of 4·(4·n-heptylcyclohexyl)phenoxy-2,4_ was used. In the same manner as in Synthesis Example 1, diaminobenzene was used in the same manner as in Synthesis Example 1, to obtain 24 3 g of a polyimine having a logarithmic viscosity of 0.49 dl/g (this is called "polyimine (PI-5), ,). Synthesis Example 6 In Synthesis Example 1, except that 86.51 g (〇_80 mol) of p-phenylenediamine and 104.56 g (0.20 mol) of the diamine compound represented by the above formula (16) were used as the diamine compound, In the same manner as in Synthesis Example 1, 1 8.0 g of a polyimine having a logarithmic viscosity of 0.42 dl/g (this is called "polyimine (PI_6),)) was obtained. Synthesis Example 7 In Synthesis Example 1, In addition to using 75.70 g (0.70 mol) of p-phenylenediamine, 3 9.6 5 g (0.20 mol) of diaminodiphenylmethane, 5 2.2 8 g (0.10 mol) of the above formula (16) The amine compound was operated as a diamine compound in the same manner as in Synthesis Example Φ 1 to obtain a polyamidimide having a logarithmic viscosity of 0.55 dl/g (which is called "polyimine (P1). -7)"). Example 1 (Printing property test) A part of the quinone imidized polymer (PI-1) obtained in Synthesis Example 1 was dissolved in N-methyl-2-pyrrolidone/γ·butyrolactone. / Ethylene glycol monobutyl ether mixed solvent (weight ratio 70M 0 / 2 0), a solution having a solid concentration of 5% by weight, after thorough stirring, 'filter this solution with a filter having a pore size of 1 μηι In the liquid crystal alignment film printing machine (manufactured by Nippon Photographic Co., Ltd.), the above liquid crystal alignment agent is applied onto a transparent conductive film made of IT film on one side of a glass substrate. , preliminary drying for 1 minute on a hot plate at 80 ° C' followed by drying in a clean oven at 200 ° C for 1 hour to form a liquid crystal alignment film. No coating unevenness was observed in the liquid crystal alignment film, therefore, Examples The printing performance of the liquid crystal alignment agent prepared in 1 was judged as "good". (Vertical alignment test) The partially ruthenium iodide polymer (PI-1) obtained in Synthesis Example 1 was dissolved in φ N -methyl-2-pyrrolidone / γ-butyrolactone / ethylene glycol monobutyl ether In a mixed solvent (weight ratio of 7 0/1 0/2 0), a solution having a solid concentration of 3.5% by weight was prepared, and after sufficiently stirring, the solution was filtered through a filter having a pore size of Ιμπι, and applied by a spin coater. On a transparent conductive film made of a ruthenium film on one side of a glass substrate, preliminary drying was performed on a hot plate at 80 ° C for 1 minute, followed by drying at 200 ° C for 1 hour in a clean oven to prepare a liquid crystal alignment film. Transparent electrode substrate. Then, a pair of transparent electrode/transparent electrode substrates are coated on each of the outer edges of the liquid crystal alignment film coated with the liquid crystal alignment film, and an epoxy resin adhesive having an alumina ball having a diameter of 0.5 μm is applied, and then The liquid crystal alignment film faces are relatively superposed and pressed to cure the adhesive. Next, a negative liquid crystal (MLC-6608, manufactured by Meruco Co., Ltd.) was charged between the substrates through a liquid crystal injection port, and then the liquid crystal injection port was closed with an acrylic photocurable adhesive, and polarized light was applied to both sides of the substrate. The sheet' is made into a liquid crystal display element. When the vertical alignment of the obtained liquid crystal display element was evaluated, no abnormal region was generated and it was judged as "good". The results are shown in Table 2. Example 2 to 1 8 - 35 - 1359858 In addition to the formulation shown in Table 1 below, the partially ruthenium-imided polymer (ΡΙ·2) to (PI-5) obtained in Synthesis Examples 2 to 5 was dissolved. The liquid crystal alignment agent of the present invention was prepared in the same manner as in Example 1 except that the solvent was mixed. The liquid crystal alignment agent thus prepared was used in the same manner as in Example 1 to evaluate the printing performance and the vertical alignment property. The results are shown in Table 1. Comparative Examples 1 to 3 Liquid crystal alignment agents were prepared in the same manner as in the examples shown in the following Table 1. And evaluation of printing performance and vertical alignment. Results are listed in

Polymer solvent composition (AxBxC)-lOO, first organic solvent, second organic solvent, third organic solvent, example 1 ΡΙ-1 Α-Κ70) Bl(10) Cl(20) 】4 Example 2 ΡΜ Α-Κ20) Β · (20) Cl(60) 24 Example 3 ΡΙ-1 Α-Κ30) Bl(50) Cl(20) 30 Example 4 ΡΙ-1 Al(30) B_l(40) Cl(30) 36 Example 5 ΡΙ-1 Α-Κ40) Bl(45) Cl(15) 27 Example 6 ΡΙ-1 Α·1(20) Β·1(60) Cl(20) 24 . Example 7 ΡΙ-1 A-1 (20) Bl(65) Cl(15) 20 Example 8 ΡΙ-1 A-2(20) Bl(60) Cl(20) 24 Example 9 ΡΙ-1 Al(50) B-2(10) Cl (40) 20 Example 10 Ρ1-1 Al(40) Bl(45) C-2(15) 27 Example 11 ΡΙ-1 Al(40) Bl(45) C-3(15) 27 Example 12 ΡΙ -1 Al(40) Bl(45) C-4(15) 27 -36 - 1359858 Example 13 ΡΙ-2 Al(70) Β-1(10) Cl(20) 14 Example] 4 ΡΙ-3 Α ·1(70) Β·1(10) 01(20) 14 Example 55 ΡΙ-4 Al(70) Β-1(10) Cl(20) 14 Example 16 ΡΙ-5 Al(70) Β- 1(10) Cl(20) 14 Example 17 ΡΙ-6 Α·1(50) Β·2(10) Cl(40) 20 Example 18 ΡΙ-7 Α-1(50) Β-2(10) Cl(40) 20 Comparative Example 1 ΡΙ-1 Α-Ι (ΙΟΟ ) — 0 Comparative Example 2 ΡΙ-1 —— Β-Ι(ΙΟΟ) — 0 Comparative Example 3 ΡΙ-1 Α-1(95) — C-l(5) 0

Note to Table 1: In each solvent type, the number in parentheses indicates the content ratio. The symbols have the following meanings: Solvent A_1 : N-methyl-2-pyrrolidone Α-2: Ν, Ν'-dimethyl-1-imidazolidinone Β-1 : γ-butyrolactone Β-2 : propylene carbonate

C-2: diethylene glycol monomethyl ether C-3: dipropylene glycol monomethyl ether C-4 : 4-hydroxy-4-methyl-2-pentanone 1359858

Table 2 Printing performance Vertical alignment central portion Peripheral portion Example 1 Good good Good Example 2 Good good Good Example 3 Good good Good Example 4 Good good Good Example 5 Good good Good Example 6 Good good Good Example 7 Good Good Good Example 8 Good Good Good Example 9 Good Good Good Example 10 Good Good Good Example 良好 Good Good Good Example 12 Good Good Good Example 13 Good Good Good Example 14 Good Good Good Example 15 Good Good Good Example 16 Good Good Good Example 17 Good Good Good Example 18 Good Good Good Good Comparative Example 1 Good Defects Good Comparative Example 2 Poor. Poor. Good Comparative Example 3 Good Defects Good -38 -

Claims (1)

I3^9858_, Reimbursement of this amendment, No. 94122012 "Vertical liquid crystal alignment agent and vertical liquid crystal display element" patent case (Revised on November 4, 2011) X. Application patent scope: 1. A vertical liquid crystal alignment agent comprising a first organic solvent having a surface tension of 39 dynes/cm or more and having a nitrogen atom in a molecule, a second organic solvent of propylene carbonate and a surface tension of 32 dynes/ a mixed solvent composed of a third organic solvent of not more than a centimeter; and a partially ruthenium iodide polymer and/or polyimine of polyamic acid dissolved in the mixed solvent. 2. The vertical liquid crystal alignment agent of claim 1, wherein a mixing ratio of the first organic solvent, the second organic solvent, and the third organic solvent satisfies the following formula (Α χΒ XC) X 1 0 — 3 2 12, In the above, each of A, Β, and C is a weight % of the first organic solvent, a weight % of the second organic solvent, and a third organic solvent based on the total weight of the first organic solvent, the second organic solvent, and the third organic solvent. the weight of%. 3. The vertical liquid crystal alignment agent of claim 1, wherein the first organic solvent is selected from the group consisting of N-methyl-2-pyrrolidone and N,N-dimethyl-2-mi A vertical liquid crystal alignment agent according to claim 1, wherein the third organic solvent is selected from the group consisting of ethylene glycol methyl ether, ethylene glycol diethyl ether, and ethylene glycol n-propyl ether. Ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether , diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, modified this 1359858% dipropylene glycol monoethyl ether At least one of dipropylene glycol dimethyl ether and 4-hydroxy-4-methyl-2-pentanthene. A vertical liquid crystal display element characterized by having a liquid crystal alignment formed by a vertical liquid crystal alignment agent according to any one of claims 1 to 4.