TW200401025A - Liquid crystal alignment agent and method for producing liquid crystal display - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent having an excellent vertical alignment, a reduced residue image after being illuminated for a long time, and a high reliability. The invention also provides a method for producing a liquid crystal display, which comprises using a liquid crystal alignment agent for the vertical alignment of a polyamic acid having specific two types of repeating unit.

Description

200401025 (1) 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a liquid crystal alignment agent. In detail, the present invention relates to a liquid crystal display element that has good vertical alignment and does not require rubbing treatment. Even after long time lighting, there is almost no residual image, and it is a highly reliable liquid crystal alignment agent. . [Prior technology] At present, liquid crystal display elements are formed on the surface of a substrate provided with a transparent conductive film. A liquid crystal alignment film made of polyamic acid and polyimide is used as a substrate for a liquid crystal display element. A layer of nematic liquid crystal with positive dielectric anisotropy is formed in the gap to form a unit cell with a sandwich structure. The long axis of the liquid crystal molecules is from one substrate to the other substrate. A continuous TN twist of 90 degrees is known as a TN type liquid crystal display element having a TN (Twisted Nematic) type liquid crystal cell. Compared with TN type liquid crystal display elements, S TN (Super Twisted Nematic) type liquid crystal display elements or vertical alignment type liquid crystal display elements with high contrast and low viewing angle dependence have been developed. This STN type liquid crystal display element is a pair of optically active substance mixed with nematic liquid crystal as a liquid crystal, and the long axis of the liquid crystal molecules passes through a continuous twisted state of more than 180 degrees between the substrates. Refraction (birefringence) effect to make use of. In contrast, a vertical alignment type liquid crystal called MVA (Multi (2) (2) 200401025 domain Vertical Alignment) method or PVA (Patterned Vertical Alignment)-no element has been proposed . The liquid crystal display elements of the MV A method or the P VA method are excellent in viewing angle and contrast. There is an advantage that a honing process is not required in the formation of the liquid crystal alignment film, and it is also excellent in terms of manufacturing steps. Suitable for MVA or PVA liquid crystal alignment film. It is required to have excellent vertical alignment, short afterimage erasing time of liquid crystal display elements, etc., and further improve the performance of liquid crystal display elements, even after long time lighting. There is almost no residual image, and it is a highly reliable liquid crystal alignment agent. [Summary of the invention] [Invention to solve the problem] The object of the present invention is to provide a liquid crystal alignment agent, which has excellent vertical alignment. 'Even after long time lighting, no residual image of the liquid crystal display element is seen. It is a highly reliable liquid crystal alignment Agent. Other objects and advantages of the present invention will be apparent from the following description. [Means for Solving the Problem] According to the present invention, the above-mentioned objects and advantages of the present invention are polymers containing a repeating unit represented by the following formula (1_1) and a repeating unit represented by the following formula (I-2) (hereinafter referred to as Is "specific polymer"), and is achieved by a liquid crystal alignment agent. (3) 200401025

HOOC -HNOC

< COOH CONH-Y

(M)

HOOC -HNOC

(1-2) 4 (where x1 and x2 are tetravalent organic groups, Y1 is a divalent group represented by the following formula (i), and Y2 is a base represented by the following formula (ii) or the following formula (iii ) As shown.)

(In the formula, Z is a single bond, one 0 —, one CO —, one C 〇 0 —, one 0 C 0 —, one NHCO — '— CONH —, — S — or an arylene group, and R1 is An alkyl group having 10 to 30 carbon atoms, a monovalent organic group having an aliphatic ring skeleton with 4 to 40 carbon atoms, or a monovalent organic group having 6 to 20 carbon atoms in fluorine.) Φ

(iii) (In the formula, each R2 is an independent methyl group or a trifluoromethyl group.) -7- (4) (4) 200401025 Aspects of the Invention The present invention will be described in detail below. -The liquid crystal alignment agent-based specific polymer of the present invention is generally composed of an organic solvent and a solvent. The specific polymer is obtained by reacting a tetracarboxylic dianhydride and a diamine with a repeating unit represented by the above formula (1-1) and a polyamine acid having a repeating unit represented by the above formula (1-2). The specific polymer < tetracarboxylic dianhydride > The structure of the tetracarboxylic dianhydride used in the synthesis of the specific polymer is represented by the following formula.

(In the formula, X1 and X2 are a tetravalent organic group.) The tetracarboxylic diamino is a compound represented by the following formula (iv ′) and a compound represented by the following formula (v (tetramellitic dianhydride) (this And other compounds (also referred to as "specific anhydrides") are preferred.

-8- 200401025

(In the formula, each R3 represents a hydrogen atom independently, a hydrocarbon group having 6 carbon atoms or a dentified hydrocarbon group having 1 to 6 carbon atoms.) These can be used alone or in combination of two or more. Specific examples of the compound represented by the formula (iv,) include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetra Carboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4 ~ tetramethylmono, 2,3,4 ring Butane tetracarboxylic dianhydride and the like. Among them, 1,2,3,4-cyclobutane tetracarboxylic dianhydride and pyromellitic dianhydride are particularly preferred. The use ratio of the specific acid anhydride is the ratio of the total amount of the specific acid anhydride in the all-tetracarboxylic dianhydride used in the synthesis of the specific polymer. It is more than 50 mol%. By using a specific acid anhydride ratio of 10 mol% or more, the effect of reducing the afterimage of the liquid crystal display element can be obtained. Other acid dianhydrides that can be used with specific acid anhydrides include 1,2,3,4 ~ cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride '3,3 ', 4,4' — Dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutylcyclooctyl-1,5-di-bis-1,2,5,6-tetracarboxylic dianhydride '2 , 3,5 —Tri-residue cyclopentylacetic dianhydride, 3,5,6-tricarbonyl-2-carboxybiscycloheptane-2: 3,5: 6-dianhydride, 2,3,4,5— Tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a, 4; 5,9b —Hexahydro-9- (6) (6) 200401025 —5 (Tetragas—2,5 — _Oxygen —3 —Furan Radical) mononaphtho [1 '2 — c] a mouthful -1, 3 — a pyrene' 1, 3,3a, 4,5,9b —hexaki-5 —methyl-5 (tetraoxy-2, 5 1-side oxygen-1 3-pyranyl) -Cai [1,2-c] —furan-1,3-dione, 1,3,3a, 4,5,9b —hexahydro-5 —B A-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5, 9b —hexahydro—7—methyl—5 (tetranitro-2,5 — one side oxygen—3—pyranyl) —Cai [1,2— c] —D-Fran-1,3—two Ketone, 1,3,3a, 4,5,9b—hexahydro-7-ethyl-5 (tetrahydro-2,5-dioxan-3-furanyl) -naphtho [1,2-c] —Furan—1,3—monofluorene, 1,3,3a, 4,5,9b —hexachloro-8-methyl-5 (tetrachloro-2,5 — _ pendant oxygen —3 -fluoranyl) —Nano [1,2 — c] —Xanan-1,3,2,2,1,3,3a, 4,5,9b —Hexahydro-8 —Ethyl-5 (tetrahydro-2,5 — Dioxan- 3 -furanyl) —naphtho [1,2 — c] —furan-1,3 —divalent, 1,3,3a, 4,5,9b —hexagas —5,8 — _ • Methyl-5 (tetraammine-2,5 — _ pendant oxygen —3 -pyranyl) —neo [1 '2 — c] —fluoran —1,3 — __. Ketone, 5 — (2 , 5-Dioxo-tetrahydrofuran methylidene) -3 -methyl_ 3 -cyclohexene -1,2-dicarboxylic acid dianhydride, bicyclo [2,2,2] -oct-7-ene-2, 3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3,2,1] Xinyuan-1,4— _Remuneration-6—spiro — 3— (tetrachlorofuran—2 ', 5'-dione), and alicyclic tetracarboxylic acids such as those shown in the following formulae (I) and (II) Dianhydride; -10-, 1 r 200401025.

(In the formula, R4 and R7 represent a divalent organic group having an aromatic ring, R5 and R6 represent a hydrogen atom or an alkyl group, and most of R5 and R6 may be the same or different.) Butane tetracarboxylic dianhydride, etc. Aliphatic tetracarboxylic dianhydride; there are 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'monobiphenyltetracarboxylic dianhydride, 1 , 4,5,8-naphthyltetracarboxylic dianhydride, 2,3,6,7-naphthyltetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4 Monofurantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) Diphenylsulfonic anhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidene diphthalic acid Dianhydride, 3,3 ', 4,4'monobiphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride. P-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis- (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'_diphenyl -11-(8) 200401025 ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-1 Bis (anhydrous trimellitate), 1,4 butanediol-bis (anhydrous trimellitate), 1,6-hexanediol-bis (anhydrous trimellitate), 1,8 -octanediol Monobis (anhydrous trimellitate), 2,2-bis-4 monohydroxyphenyl) propane hydrazone anhydrous trimellitate These can be used alone or in groups of more than one spring > < Synthesis of specific polymers The diamine used is a diamine having a group represented by the formula (i) (diamine represented by the following formula (Γ)) and a diamine having a group represented by the above (ii) (the following formula (Π ' ) And / or a diamine (4,4-diaminodiphenyl ether) having a group represented by the formula (iii) above. Z——R1 (i,) H2N NH 2

(ii,) (wherein, Z, R1, and R2 are defined according to the above formulae (i) and (ii)). In the above formula (i), the alkyl group having 10 to 30 carbon atoms represented by R1 is, for example, n-decyl, n-dodecyl, n-pentadecyl, n-hexadecyl, n-octadecyl , Eicosyl. In addition, the organic group having an aliphatic cyclic -12-(9), (9), 200401025 skeleton having 4 to 40 carbon atoms represented by R1 in the above formula (i) includes, for example, cyclobutane'cyclopentane derived from a cycloalkane. Alkane, cyclo_hexane, cyclodecane and the like have a group having an aliphatic cyclic skeleton. Cholesterol, cholestanol, and other groups have a steroid skeleton, bicycloheptane (norbornane), adamantane, and other groups have a bridging lipid __ fatty cyclic skeleton. Particularly preferred among these is a base having a steroid skeleton. The organic group having the above-mentioned aliphatic cyclic skeleton may be a halogen atom, preferably a fluorine atom, or a group substituted with a fluoroalkyl group, preferably a trifluoromethyl group. _ Furthermore, the group represented by R1 in the formula (i) having a fluorine atom having 6 to 20 carbon atoms, for example, a straight alkyl group having 6 or more carbon atoms such as n-hexyl, n-octyl, and n-decyl; cyclohexyl 6, cyclooctyl and other aliphatic cyclic hydrocarbon groups with 6 or more carbons: phenyl and biphenyl aromatic hydrocarbons with 6 or more carbons, etc. Part or all of the hydrogen atoms in organic groups are fluorine atoms or trifluoro A group substituted with a fluoroalkyl group such as a methyl group. Also 'Z-type single bond in the above formula (i),-C0—, one C 0 0—, one 0 C 0—, one NHC0—, — C0NH—, one S—, or arylene' The arylene group includes a phenylene group, a tolylene group, a biphenylene group, and a naphthylene group. Particularly preferred among these are the bases shown by 10-, one coo-, and 0C0-. Specific examples of the diamine having the group represented by the formula (i) include dodecanoxy, 2,4-diaminobenzene, and pentadecyloxy-2,4-diaminobenzene. The preferred examples of hexaalkoxy-2,4-diaminobenzene and octadecyloxy-2,4-diaminobenzene are as shown in the following formulae (1) to (6) '-13- (10) 200401025 compound. ? Hs ch3

The ratio of the diamine having the structure of the formula (i) in the synthesis of the tertiary polymer is preferably -14-(11) (11) 200401025 among the total diamines used in the synthesis of specific polymers. 90 mol%, more preferably 10 to 80 mol%, and most preferably 15 to 70 mol%. By using 5 mol% or more of the diamine having the structure of the above formula (i), a liquid crystal alignment film having a liquid crystal alignment film excellent in vertical alignment can be obtained. The diamines having the group represented by the formula (ii) include 2,2'-dimethyl-4,4'-diaminobiphenyl and 2,2'-fluorenetrifluoromethyl-4,4'-two Amino biphenyl. The diamine having a group not represented by the formula (ii) and the diamine having a group represented by the formula (iii) may be used alone or as a mixture of two or more. The total usage ratio of the diamine having the group represented by the formula (ii) and the diamine having the group represented by the formula (iii) in the synthesis of the specific polymer is among the total diamines used in the synthesis of the specific polymer. It is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, and most preferably 30 to 85 mol%. The use of the ratio of the diamine to 10 mol% or more is extremely effective in reducing the residual phase of the liquid crystal display element. When synthesizing specific polymers, other diamines may be used in addition to the diamines described above. Other diamines that can be used are p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diamino Diphenyl sulfide, 4,4'-diaminodiphenylhydrazone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzidine aniline (benzanilide), 1,5-Diaminonaphthalene, 3,3-Dimethyl-4,4, -Diaminobiphenyl, Amino-1- (4'-aminophenyl) -1,3,3-trimethylindane (Indan), 6-amino-1- (4, monoaminophenyl) -1,3,3 trimethylindane, 3,4'-diaminodiphenyl ether, 3,3'diaminodiphenyl Benzophenone, 3,4 'diaminobenzophenone, 4,4'-15- (12) (12) 200401025 diaminobenzophenone, 2,2-bis [4 one (4 one Aminophenoxy) phenyl] propane, 2,2-bis [4-mono (4-monoaminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminoaminophenyl) hexaoxypropane ' 2,2 —bis [4-mono (4-aminophenoxy) phenyl] maple '1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene , 1, 3-double (3- ammonia (Oxy) benzene, 9,9_bis (4-aminoaminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis (4-aminophenyl)苐 '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 Phenylisopropylidene) bisaniline, 4,4 'mono (m-phenylene isopropylidene) bisaniline, 2,2' one bis [4 one (4 one amino one 2-trifluoromethylphenoxy Phenyl) phenyl] hexafluoropropane, 4,4'-diamino-2,2'bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) Phenoxy] octafluorobiphenyl and other aromatic diamines. 1, 1-m-xylenediamine, 1,3-propanediamine, butanediamine, pentanediamine, hexamethylenediamine, heptaethylenediamine, octanediamine, nonanediamine, 4, 4-diaminoheptamethylene diamine, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene diamine, hexahydro-4,7-methylene Methanoindanylene dimethylene diamine, tricyclic [6.2.1.02,7]--(-undecylene dimethyl diamine, 4,4 'monomethylene bis (cyclohexyl Amines) and other aliphatic and aliphatic cyclic diamines. 2,3-diamino D [t Didine, 2,6-diamino D [t Didine, 3,4-diamino D pyridine, 2,4 Diaminopyrimidine, 5,6-diamino-2,3-dicyanopyridine D, -16-(13) 200401025 5,6-diamino-2,4-dihydroxypyrimidine '2,4-diamino —6 —dimethylamine-1,3,5-triazine, 1,4-bis (3-aminopropyl) hexahydropyridine,

2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine '2,4-bis Amino-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 ——amino group-1,3 — — • Methyluria (uracil), 3,5- —amino —1,2,4-triazole, 6,9 —diamino-2 —ethoxyacridine lactate, 3,8 -Diamino-6-phenylphenanthridine, 1,4-diaminohexahydrophenone D, 3,6-diaminoacridine 'bis (4-aminophenyl) phenylamine, etc. have molecules Diamine within two primary amino groups and nitrogen atoms other than the primary amino group. There is a diaminoorganosiloxane represented by the following formula (III). These diamines can be used alone or in combination of two or more.

R8 R8 .11 N2H-fcH2i—Sif〇-SiV-(-CH2) —NH2 (III) R «R8 " (wherein R8 represents a hydrocarbon group having 1 to 12 carbon atoms, and most of the R8 present may be the same or the same phase Different, P is an integer of 1 to 3, and q is an integer of 1 to 20.) Among these, p-phenylene diamine, 4,4'-diaminodiphenylmethane, 4,4'-amino-benzene sulfurized Compounds, 1,5 -aminoamino, 2,7-_aminoamino, 2,2-bis [4-mono (4-aminophenoxy) phenyl] propane, 9,9-bis (4-amino- = 'rfr

1 H -17- (14) (14) 200401025 phenyl) manganese, 2,2-bis [4- (4-aminoaminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminobenzene Hexafluoropropane, 4,4 'mono (p-phenylene diisopropylidene) bisaniline, 4,4, mono (m-phenylene diisopropylidene) bisaniline, 1,4 monocyclohexane Diamine, 4,4, monomethylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benzene, 4,4,1-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine '2,4-diaminopyrimidine Ife, 3,6-diaminopyridine π, steep, as shown in the above formula (IΠ) And so on. These can be used alone or in combination of two or more. Synthesis of specific polymers The ratio of the use of tetracarboxylic dianhydride and diamine to the specific polymer synthesis reaction is 1 equivalent to the amino group of the diamine, and the anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents. The ratio is preferably 0.3 to 1.2 equivalents. The synthesis reaction of polyamic acid is carried out in an organic solvent at a temperature of usually 20 ° C to 150 ° C, preferably 0 to 100 ° C. Here, there is no restriction if the organic solvent is capable of dissolving the synthesized polymer ', such as N_methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N ~ dimethyl Non-protonic polar solvents such as formamidine, dimethylasicon, γ-butyrolactone, tetramethylurea, hexamethylphosphorylamide, etc .; for example, m-methoxycresol, xylenol, phenol '' Phenolic solvents such as halogenated phenols. The amount (α) of the organic solvent is usually the total amount (β) of the tetracarboxylic dianhydride and diamine compound, and it is best that the amount is 0.1 to 30% by weight relative to the total amount of the reaction solution (α + β). . The above organic solvents include alcohols which are inferior solvents of polyamino acids, ketones 18- (15) 200401025, range alcohols, ketones (glycol ethyl ketobutyl ester, ether, methyl ether methyl monoethyl ester, Alkane, benzene, solution amines, halogenated hydrocarbons, and the polyamine acids produced do not precipitate, and can be used in combination with hydrocarbons. Specific examples of these inferior solvents are, for example, methyl alcohol isopropanol, cyclohexane Alcohol, 4-monohydroxy-4 monomethyl-2-pentanepropanol) 'ethylene glycol' propylene glycol, 1,4-butanediol, triethyl 'ethyl = alcohol monomethyl ether, ethyl lactate, butyl lactate Esters, acetone, methyl, methyl-isobutanone 'cyclohexanone, methyl acetate, ethyl acetate,' methoxytrimethoxypropionate, ethylethoxypropionate, diethylpropionate oxalate Acid diethyl ether, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ethyl-n-propyl alcohol-i-propyl ether, ethylene glycol n-butyl, ethyl = alcohol dimethyl ether, ethylene glycol Diethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol di'ethylene glycol monomethyl ether acetate, diethylene glycol Monoethyl ether acetate Tetraammonia, dichloromethane '1,2 dichloroethane, 1,4-dichlorobutanedichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, toluene toluene, etc. As described above, a reaction solution can be obtained in which the polyamic acid is dissolved. Precipitation is obtained by injecting this reaction into a large number of solvents, and the step of re-dissolving the polyamino acid in an organic solvent and then precipitating it with a poor solvent is obtained by drying the precipitate under reduced pressure. It is carried out one or several times, and the polyamino acid can be purified. Terminal-modified polymer The specific polymer used in the present invention may be a terminal-adjusted molecular weight -19- 143? (16) (16) 200401025 modified type. The use of this terminal-modified polymer does not impair the effect of the present invention 'and can improve the coating characteristics of the liquid crystal alignment agent. When these terminally modified polymers are synthesized into polyamino acids, acid anhydrides, monoamine compounds, monoisocyanate compounds, etc. can be added to the reaction system to synthesize them. The anhydrides here include, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylbutane Dianhydride, etc. Monoamine compounds include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecane Amine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine and the like. Monoisocyanate compounds include phenyl isocyanate and naphthyl isocyanate. Logarithmic Viscosity of Specific Polymer The specific polymer used in the present invention has 値 'of the logarithmic viscosity (ηΐη) of preferably 0.05 to 10 dl / g', more preferably 005 to 5 di / g. The logarithmic viscosity (η! N) of the present invention is based on the use of N-methyl-2-pyrrolidone as a solvent, and the concentration of the solution is 0.5 g / 1 000 ml at 30 ° C. Viscosity is measured and obtained by the following formula (丨). Solution flow down time / solvent flow down time η η (weight of polymer (1) liquid crystal alignment agent The liquid crystal alignment agent of the present invention, the specific polymer is usually made by dissolving in -20- (17) (17) 200401025 organic solvent It is composed of a solution. The temperature when preparing the liquid crystal alignment agent of the present invention is preferably 0 ° C to 200 ° C, more preferably 20 to 60 ° C. The organic solvent constituting the liquid crystal alignment agent of the present invention is, for example, N-methyl 1 2-oxalidone 'γ-butyrolactone (buty 1 r ο 1 act ο ne), γ-butyrolactam, Ν, Ν-dimethylformamide, N, N-dimethyl Acetylamine, 4-hydroxy-4 monomethyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate , Ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol i-propyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether Acid ester, 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, etc. The solid content concentration in the alignment agent of the present invention 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 in The substrate surface is coated to form a liquid crystal alignment film. However, when the solid content concentration is less than 1% by weight, the thickness of the coating film is too small to obtain a good liquid crystal alignment film, and the solid content concentration exceeds 10 When the weight percentage is too large, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases, and the coating characteristics are deteriorated. The liquid crystal alignment agent of the present invention does not damage the purpose. Within the range of physical properties, a functional group-containing silane compound and an epoxy compound may be contained from the viewpoint of improving the adhesion to the substrate surface. The so-called functional group-containing silane compounds include, for example, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxy-21-(18) (18) 200401025

Silane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N— (2-aminoethyl) —3-aminopropyltrimethoxysilane, N— (2-aminoethyl) — 3-aminopropylmethyldimethoxysilane, 3-ureyldotrimethoxysilane, 3-ureylpropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethyl Oxysilane, N-ethoxycarbonyl-3 -aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylene triamine, N-trimethoxysilylpropyltriethylene Triamine, 10-trimethoxysilyl-1,4,7-triaza-n-decadecane, 10-triethoxysilyl-1,4,7-triaza-n-decadecane, 9-trimethyl Oxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate 'N-benzyl-3-aminopropyl Trimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyldimethoxysilane, N-phenyl-3 -aminopropyldisilane Ethoxysilane, N-bis (oxyethylene) -3-amino Trimethoxy Silane, N - bis (oxy extending ethyl) - 3 - aminopropyltriethoxysilane Silane like. Also related epoxy compounds are, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol Glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol di Glycidyl ether, 1,3,5,6 -tetraglycidyl-2,4-hexanediol, N, N, N ', N' tetraglycidyl ether-diamine, 1 , 3-bis (N, N-di-glycidylaminomethyl) cyclohexane, N, N, N ', N, -tetra-glycidyl-4,4'-diaminodiphenylmethane, 3 — -22- (19) (19) 200401025 (N-allyl) -N-epoxypropyl) aminopropyltrimethoxysilane, 3 _ (N, N -diepoxypropyl) aminopropyltrimethyl Oxysilane and so on. The compounding ratio of the functional group-containing silane compound or epoxy compound is usually 40 parts by weight or less with respect to 1,000 parts by weight of the entire polymer, and preferably 0.1 to 30 parts by weight. In particular, by adding an epoxy compound, the scratch resistance of the obtained liquid crystal alignment film can be further improved. Particularly preferred epoxy compounds are, N, N, N ', N'-tetraglycidyl-stubble diamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexyl Alkane, ν, Ν, Ν ', Ν'-tetra-epoxypropyl-4,4'-monoamino-benzylamine, 3- (Ν-susyl-N-epoxypropyl) aminopropyltrimethyl Nitrogen-containing epoxy compounds such as oxysilane, 3- (N, N_diepoxypropyl) aminopropyltrimethoxysilane, and the like. Liquid crystal display element The liquid crystal alignment agent of the present invention can be suitably used in a vertical alignment type liquid crystal display element in which at least one of the substrates forming a liquid crystal cell has a protrusion shape or a pattern shape. The above shape is applied as a means for regulating the alignment of the element. Such liquid crystal display elements include, for example, MVA-type liquid crystal display elements. The so-called MV V Α mode is, for example, as shown in the liquid crystal V 〇 1 · 3 N 〇 2 I 1 7 (1999 years) "or Japanese Unexamined Patent Publication No. 1 1 -2 5 8605. The vertical alignment pattern, protrusions and patterns of the alignment specification means can also be formed on the TFT substrate and the color filter. For example, there are protrusions on the color filter, patterns on the TFT, etc., and both can have alignment specifications. Means: The liquid crystal display element obtained by using the liquid crystal formulation of the present invention can be manufactured, for example, by the following method. -23- (20) (20) 200401025 (0 on a substrate provided with a patterned transparent conductive film On one side, the liquid crystal alignment agent of the present invention is coated by, for example, a roll coating method (spinner method), a spinner method, a printing method, or the like, and then a coating film is formed by heating the coated surface. Here, the substrate For example, glass such as float glass, soda glass, etc .; transparent substrates made of plastics such as ethylene terephthalate, polypropylene polytitanate, polyether maple, polycarbonate, etc. are provided on one side of the substrate Transparent conductive film, NES made of tin oxide (Sn02) A film (registered trademark of PPG in the United States), IT0 film made of indium trioxide and tin oxide (ln203 — Sn02). The patterning of these transparent conductive films is by photoetching or using a mask in advance. Method: When the liquid crystal alignment agent is applied, in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film, the surface of the substrate is coated with a functional group-containing silane compound and a functional group-containing titanium compound Etc. The heating temperature after coating of the liquid crystal alignment agent is 80 ~ 3 00 ° C, preferably 120 ~ 25 ° C. The liquid crystal alignment agent of the present invention is a coating for forming an alignment film after removing the organic solvent after coating. The film can be dehydrated and closed-loop by heating, and it can also become a coating film of imidization. The film thickness of the formed coating film is usually preferably 0.005 to 0.5 μm. (2) Two liquid crystal alignment films are made as described above. The formed substrate is arranged in such a way that two substrates are passed through the cell gap, and the peripheral portions of the two substrates are bonded together with a sealant. Liquid crystal is injected into the cell interval divided by the substrate surface and the sealant. And filling it 'will inject The liquid crystal cell is formed by sealing. Then, on the other side of the outer surface of the liquid crystal cell, that is, on the other side of each substrate of the liquid crystal cell-24-(21) (21) 200401025, a polarizing plate is bonded to obtain a liquid crystal. Display element. Here, a 'sealant can be used, for example, epoxy resin containing lead oxide balls as a hardener and a spacer. The liquid crystal includes so-called nematic liquid crystal and smectic liquid crystal. Among them, a nematic liquid crystal is preferred. For example, a Schiff base liquid crystal 'azoxy liquid crystal' biphenyl liquid crystal, a benzene cyclohexane liquid crystal, an ester liquid crystal, and a biphenyl liquid crystal can be used. Triphenyl-based liquid crystals, biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxin-based liquid crystals, bicyclooctane-based liquid crystals, and cubane-based liquid crystals. In these liquid crystals, for example, cholesteric liquid crystals such as chocholesteryl chloride, cholesteryl nonate, and steryl carbonate can be added, or added under the trade name "C-15" "CB-15" (manufactured by Merck) is used as a chiral agent. In addition, a strong dielectric liquid crystal such as p-disyloxybenzylidene-p-amino-2-methylbutyl cinnamate can also be used. The polarizing plate attached to the outer surface of the liquid crystal cell has a polarizing film that extends the alignment of polyvinyl alcohol and can absorb iodine. The polarizing film known as the H film is sandwiched by a protective film of cellulose acetate. Or the polarizing plate formed by the H film itself. [Embodiments] [Examples] -25- (22) (22) 200401025 & The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. [Manufacturing method of liquid crystal display element] On a transparent conductive film made of an ITO film provided on one side of a glass substrate having a thickness of 1 mm, a turntable is used to coat the liquid crystal alignment agent, at 80 ° C for one minute. 8 (TC is dried for one hour to form a coating film with a dry film thickness of 600 angstroms. As described above, a substrate formed by two liquid crystal alignment films is prepared, and the outer edge of each substrate is coated with alumina containing After the epoxy-based adhesive, they are arranged opposite to each other between the two substrates, so that the outer edge portions are blocked and pressed to harden the adhesive. The adhesive is formed from the substrate surface and the outer edge portion. In the divided cell interval, a negative nematic liquid crystal is injected and filled, and then the injection hole is sealed with an epoxy-based adhesive to make a vertical alignment type liquid crystal display element. Observe the liquid crystal display element under crossed nicol when the voltage is OFF and AC 1 2 V (peak-to-peak) ° [Voltage retention] Apply 5V to the liquid crystal display element (imPress) 60 micro Extra time plus seconds' in the range of 1 67 milliseconds (Span) after the voltage is applied from the measured voltage applied to a release voltage of 167 ms measured -26- retention ° (23). (23) given apparatus based .200401025 using Toyo Corporation's VHR- 1..

[Residual image erasing time of liquid crystal display element] .. DC 6.0V, AC 6.0V (peak-to-peak) overlapped 30Hz '3.0V rectangular wave (retangular wave) at 70 °: ambient temperature plus After 67 hours from the liquid crystal display element, the voltage was set to 0FF, and the time until afterimage erasure was measured visually. [Evaluation of the reliability of liquid crystal alignment agent] DC 6.0 · 0 V AC 6.0 V (peak 値 peak 値) is a rectangular wave of 3.0 Hz and 3.0 V superimposed on the liquid crystal display at an ambient temperature of 70 ° C After 16 to 7 hours, the voltage was set to 0f ρ ·. After the residual image was eliminated, it was visually confirmed whether it was spotless and uniformly aligned vertically. ≪ Synthesis of specific polymer > Synthesis Example 1 ~ 1 9 φ With the composition shown in Table 1, diamine and tetracarboxylic dianhydride were sequentially added to N-methyl ~ 2-amyrolidone 300 g, at a solid content concentration of 20% at 60 ° C. The reaction was performed for 6 hours' to obtain polyamino acids (1) to (1 9) having logarithmic viscosity shown in Table 1. -27- (24) (24) 200401025 [Table 1] Examples of synthetic polymer anhydride diamine log viscosity (dL / g) 1 (1) CB (50) MTB (25) / diamine ① (25) 1.32 2 ( 2) CB (50) MTB (31.25) / diamine① (18.75) 1.38 3 (3) CB (50) 1 ^ butyl 8 (37.5) / diamine®) ^ '') 1.40 4 (4) PMDA (10) / CB (40) MTB (25) / diamine① (25) 1.39 5 (5) PMDA (15) / CB (35) MTB (25) / diamine① (25) 1.40 6 (6) PMDA (15) / CB (35) MTB (37 · 5) / diamine① (12.5) 1.41 7 ⑺ PMDA (25) / CB (25) MTB (25) / diamine① (25) 1.40 8 (8) PMDA (25) / CB (25) ΜΤΒ (37 · 5) / = Κφ (12.5) 1.40 9 (9) PMDA (50) ΜΤΒ (25) / diamine① (25) 1.41 10 (10) CB (50) DDE (25) / Diamine① (25) 1.30 11 (11) CB (50) 00 £ (37.5) / diamine 0 (12.5) 1.33 12 (12) PMDA (10) / CB (40) DDE (37.5) / I: K ® (12.5) 1.34 13 (13) PMDA (15) / CB (35) DDE (25) / diamine① (25) 1.35 14 (14) PMDA (15) / CB (35) DDE (37.5) /: ^ $ ® (12.5) 1.36 15 (15) PMDA (25) / CB (25) DDE (25) / diamine① (25) 1.37 16 (16) PMDA (25) / CB (25) DDE (37.5) / two Amine ① (12.5) 1.37 17 (17) PMDA (50) DDE (37.5) /: ZK〇 (l2.5) 1.39 18 (18) PMDA (50) ΜΤΒ (37.5) /: Κφ (ΐ2.5) 1.41 19 (19) CB (50) PDA (25) / diamine① (25) 1.33 0 The number in Moore% CB: 1,2,3,4-cyclobutane tetracarboxylic anhydride PMDA: pyromellitic acid di Anhydride PDA: p-phenylenediamine 1 ^ 1 but 8: 2,2'-dimethyl-4,4'-diaminobiphenyl DDE: 4,4'-diaminodiphenyl ether diamine ①: top The diamine 28- (25) (25) 200401025 shown in formula (2) in Examples 1 to 19, Comparative Examples The specific polymers obtained in Synthesis Examples 1 to 19, and N, N, as necessary additives, Ν ′, Ν′—tetraepoxypropyl-4,4′—diaminodiphenylmethane (epoxy compound), mixed with the composition shown in Table 2 to prepare a solid content concentration of 6.0% to obtain the present invention. Vertical alignment type liquid crystal alignment agent. A liquid crystal display element was produced using this liquid crystal alignment agent, and various evaluations were performed. The results are shown in Table 3.

-29- (26) (26) 200401025 [Table 2] Polymer 1 Cereal Additive Example 1 ⑴ NMP (50) / BC (50) 20 Example 2… (2) NMP (50) / BC (50) 20 Example 3 (3) NMP (50) / BC (50) 20 Example 4 (4) NMP (50) / BC (50) 20 Example 5 (5) NMP (50) / BC (50) 20 Implementation Example 6 (6) NMP (50) / BC (50) 20 Example 7 (7) NMP (50) / BC (50) 20 Example 8 (8) NMP (50) / BC (50) 20 Example 9 (9) NMP (50) / BC (50) 20 Example 1 0 (10) NMP (50) / BC (50) 20 Example 1 1 on NMP (50) / BC (50) 20 Example 1 2 ( 12) NMP (50) / BC (50) 20 Example 1 3 (13) NMP (50) / BC (50) 20 Example 1 4 (14) NMP (50) / BC (50) 20 Example 1 5 (15) NMP (50) / BC (50) 20 Example 1 6 (16) NMP (50) / BC (50) 20 Example 1 7 (16) NMP (50) / BC (50) Example 1 8 (17) NMP (50) / BC (50) 20 Example 1 9 (18) NMP (50) / BC (50) 20 Comparative Example 1 (19) NMP (50) / BC (50) 20 Comparative Example 2 (19) NMP (50) / BC (50) — * The numbers in 0 are as described below. Solvent:% by weight of each solvent type with respect to the entire solvent. Additive: Part by weight of the additive with respect to 100 parts by weight of the polymer. * The abbreviations of solvent types are as follows. NM: N-methyl-2-pyrrolidone (27) 200401025 [Table 3] Vertical alignment voltage retention rate (%) Afterimage erasure time (seconds) Reliability (uniformity) Example 1 Good 99.0 10 Uniform Example 2 Good 98.8 12 Uniform Example 3 Good 98.9 15 Uniform Example 4 Good 98.8 11 Uniform Example 5 Good 98.8 13 Uniform Example 6 Good 98.7 13 Uniform Example 7 Good 98.9 11 Uniform Example 8 Good 98.8 12 Uniform Example 9 Good 98.7 10 Tubo Example 1 〇 Good 99.0 13 Uniform Example Π Good 98.9 13 Uniform Example 1 2 Good 98.9 11 Uniform Example 1 3 Good 99.0 12 Uniform Example 1 4 Good 98.8 12 Uniform Example 1 5 Good 98.9 14 Uniform Example 1 6 Good 98.7 15 Uniform Example 1 7 Good 98.8 12 Uniform Example 1 8 Good 98.9 10 Uniform Example 1 9 Good 98.7 10 Uniform Comparative Example 1 Good 98.5 200 or more Uniform Comparative Example 2 Good 95.0 200 or more unevenness (28) (28) 200401025 [Effect of the invention] The liquid crystal alignment agent according to the present invention has excellent vertical alignment Will not even see the liquid crystal display element after the afterimage time of lighting, may be displayed to the liquid crystal element and a high degree of reliability can be obtained of extremely excellent liquid crystal alignment film.

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Claims (1)

(1) 200401025 Patent application scope 1. A liquid crystal alignment agent characterized by containing a polymer having a repeating unit represented by the following formula (I-1) and a repeating unit represented by the following formula (I-2) HOOC, HNOC ^ < COOH CONH-Y (Μ) HOOC -HNOC 、 / C > &c; COOH ONH-Y 2 (1 * 2) (Wherein x1 and x2 are tetravalent organic groups, Y1 is a divalent group represented by the following formula (i), and Y2 is a base represented by the following formula (ii) or a base represented by the following formula (iii)) (i) (In the formula, 'Z is a bond, —0 —, — CO —, —C Ο Ο —, —0 C 〇 —, —NHCO—, —CONH— — —S —, or arylene, R1 is Alkyl group having 10 to 30 carbon atoms, monovalent organic group having an aliphatic ring skeleton with 4 to 40 carbon atoms, or monovalent organic group having 6 to 20 carbon atoms in fluorine) -33- (2) 200401025 (iii) (wherein each R2 is an independent methyl group or a trifluoromethyl group). 2 _ If the liquid crystal alignment agent of item i in the patent application scope, wherein X1 in formula (I-1) and X2 in formula (I-2) are independent of each other, at least one selected from the group consisting of the following formula (iv) Base and base shown in (v) below R3 R3 (In the formula, 'each R3 represents a hydrogen atom independently, a hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon group having 1 to 6 carbon atoms]. 3. The liquid crystal alignment agent according to item 1 or 2 of the scope of patent application, wherein the ratio of the repeating unit represented by the formula (I-1) in the polymer's total repeating unit is 5 to 90 mol%, and the formula (1- 2) The ratio of the repeating unit shown is 10 to 90 mole%. 4 _If you apply for a liquid crystal alignment agent for items 1, 2, or 3 of the patent scope, where the liquid crystal alignment agent is used for a vertical alignment type liquid crystal display element. 5. A method for manufacturing a vertical alignment type liquid crystal display element, characterized in that -34- (3) 200401025 is a film obtained by coating the liquid crystal alignment agent in the scope of patent application No. 1 on a substrate without honing. And as a liquid crystal alignment film user. -35- 200401025 Lu, (1), the designated representative of this case is: None (II), the component representative symbol of this representative is simply explained: None 柒 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: / HOOC, / ΟΟΗ —L-HNOC " ^ ^ conh-y (Μ) HOOC, 2 / COOH ^ CONH-Y (1-2)