TW200401926A - Liquid crystal alignment agent and forming method of liquid crystal alignment film - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent and forming method of liquid crystal alignment film, which has good alignment property of liquid crystal, and has electrical characteristics such as voltage holding rate that are not affected even under harsh environment like optical irradiation or high temperature or after being driven for a long time, so as to keep good alignment state of liquid crystal and not prone to generate residual images. By the coating step, thin film can be made on the substrate, and the liquid crystal alignment agent with inorganic film can be made. For example, coat the liquid crystal alignment agent containing the partly hydrolyzed/condensed product of tungsten compound, molybdenum compound or niobium compound having alkyl group on the substrate, so as to make the thin film, the surface of the film made is irradiated/impacted by ions, and thus form the liquid crystal alignment film.

Description

200401926 ⑴ Rose, description of the invention [Technical field to which the invention belongs] The present invention relates to a liquid crystal alignment agent and a method for forming a liquid crystal alignment film. More details are related to the good alignment of the liquid crystal, and the electrical characteristics such as voltage retention are not affected by the harsh environment of light irradiation or high temperature or long-term driving. The alignment state of the liquid crystal is maintained well and it is difficult to form afterimages. A liquid crystal alignment agent of a phenomenonal liquid crystal alignment layer and a method for forming a liquid crystal alignment film using the liquid crystal alignment agent. [Prior art] At present, it is known that a liquid crystal display element is formed on the surface of a substrate provided with a transparent conductive film, for example, a liquid crystal alignment film made of polyamic acid, polyimide, or the like as a substrate for a liquid crystal display element. The substrate is arranged in two opposite directions, and a layer of nematic liquid crystal with positive dielectric anisotropy is formed in the gap. As a crystal chamber with a sandwich structure, the long axis of the liquid crystal molecules is directed from one of the substrates to the other. A substrate is continuously twisted by 90 degrees, which is a so-called TN type liquid crystal display element having a TN type (Twisted Nematic) liquid crystal cell. In addition, STN (Super Twisted Nematic) type liquid crystal display elements that can achieve higher contrast than TN type liquid crystal display elements or IPS (In-Plane Switiching) type liquid crystal display elements that have lower viewing angle dependency than TN type liquid crystal display elements or VA (Vertical Allignment) type liquid crystal display element. The operation principle of such a liquid crystal display element can be largely classified into a transmissive type and a reflective type. -5- (2) (2) 200401926 When a transmissive liquid crystal display device is driven by an element, the transmitted light intensity of the backlight light source on the back of the element changes to display. Reflective liquid crystal display elements do not use a light source for backlighting. When driving with elements, the reflected light intensity of external light, such as sunlight, changes and the display is performed. The power consumption is lower than that of the transmissive type, so it is suitable for outdoor use. Its liquid crystal alignment film is often under a light source for backlight. In particular, in addition to business applications, liquid crystal projectors that have increased demand for home theaters in recent years have used light sources, such as halogen lamps, with very high intensity. Reflective liquid crystal display elements can be used outdoors. In this case, sunlight containing strong ultraviolet light is used as the light source. The reflective type theoretically has a longer distance for light to pass through the element than the transmissive type. In the manufacturing steps of the liquid crystal display element, from the viewpoint of shortening the steps and improving the yield, this is a liquid crystal dropping method, that is, an ODF (One Drop Fill) method. The ODF method is different from the conventional method of injecting liquid crystal into an empty liquid crystal cell assembled with a thermosetting sealant in advance. After applying a UV-curable sealant to a place where a single-sided substrate of a liquid crystal alignment film is coated, The liquid crystal is dropped into the necessary place, and after bonding another substrate, the entire surface is irradiated with ultraviolet light to harden the sealant to make a liquid crystal cell. The ultraviolet light radiated at this time is usually an intensity of several joules per square centimeter or more. In other words, in the manufacturing steps of the liquid crystal display element, the liquid crystal alignment film and the liquid crystal are both under the strong ultraviolet light. The transmissive liquid crystal display element considers that as the intensity of light is irradiated, the temperature of the system of the liquid crystal display element increases during driving. With the multi-purpose use of liquid crystal display elements, in addition to the transmissive type, the reflective type is also considered for outdoor use, etc., or for installation in a car while parked. It is higher than room temperature use and design. -6-

a J (3) (3) 200401926 environment. In this way, the liquid crystal display element is highly functional and versatile. At the same time, it is required to have excellent electrical characteristics or afterimage characteristics such as liquid crystal alignment or voltage retention even after being exposed to a severe environment of light or heat, or after being driven for a long time. Materials for constituting the liquid crystal alignment film of a liquid crystal display element include resins such as polyimide, polyimide, and polyester. In particular, polyimide exhibits excellent physical properties such as heat resistance, affinity with liquid crystals, and mechanical strength among organic resins, and is therefore often used for liquid crystal display elements. However, in recent years, due to the high functionality and versatility of liquid crystal display elements, the opportunities for use in harsh environments such as the above-mentioned high-temperature environment or light irradiation have increased. At the same time, further shortening of manufacturing steps and improvement of yield are required. It is required to have a longer life span, which does not allow the range allowed in the past, that is, display defects or afterimages caused by insufficient resistance to high-temperature environments or light irradiation. Therefore, the organic resins of polyamic acid or polyimide, which have been widely used as liquid crystal alignment films in the past, have insufficient light or heat resistance. Therefore, there is a need for a new material that does not reduce the ability to uniformly align liquid crystals in the plane of a liquid crystal display element and has good resistance to light or heat. [Summary of the Invention] [Problems to be Solved by the Invention] The purpose of the present invention is to provide the ability of the liquid crystal alignment to be not reduced ', and the reduction of the voltage retention rate to light or heat is small. After driving for a long time, an afterimage can also be formed Liquid crystal alignment agent for liquid crystal alignment layer with good characteristics. -7- (4) (4) 200401926 Another object of the present invention is to provide a method for forming a liquid crystal alignment film having the above-mentioned excellent characteristics using the liquid crystal alignment agent of the present invention. The other objects and advantages of the present invention are as follows. [Method for solving the problem] According to the present invention, according to the above-mentioned object and advantages of the present invention, the first can be achieved by the following. A thin film can be produced on a substrate by a coating step, and an organic / inorganic composite material can be produced. The liquid crystal alignment agent of the formed thin film is preferably, for example, (i) containing a material selected from the group consisting of the following formulae (1) -OR · · · (1) (R is an alkyl group, an aryl group, an aralkyl group, or an aryloxyalkyl group) A liquid crystal alignment agent for a partially hydrolyzed / condensed compound of at least one of the groups of organic-based tungsten compounds, molybdenum compounds, niobium compounds, and macro compounds shown in). (ii) containing RJaSi (OR2) 4.a (5) (wherein R is a hydrogen atom, a fluorine atom, or a monovalent organic group, R2 is a monovalent organic group, and a is An integer from 0 to 2) and the following formula (6) R3b (R40) 3.bSi- (r7) d.Si (OR5) 3-cR6c (6) (R3, R4, R5, and R6 may be the same or different, A monovalent organic group 'b and c, respectively, may be the same or different integers of 0 to 2, Ri is an oxygen atom or-(CH2) n-, and d is 0 or ρ is an integer of 1 to 6) Liquid crystal alignment agent for partial hydrolysis / condensation of at least one compound in the group of compounds. -8-(5) (5) 200401926 (iii) contains the following formula (7)

SiHxR8y (7) (where R8 is a monovalent organic group, X is a number of 0.01 to 33, y is a number of 0.01 to 3 但是, but x + does not matter, and the weight average molecular weight of polyethylene is at least A liquid crystal alignment agent of a silicon polymer of 2,000. (Iv) a liquid crystal alignment agent containing polytitanoxane and one of the polytitanoxane modified by other organic compounds, and (v) a liquid crystal alignment agent containing Partial hydrolysis of a compound represented by the formula (9) A1 (OR9) xQ3.x (9) (where R9 is a monovalent organic group, Q is / 3-dicarbonyl compound, and X is an integer of 1 to 3) / Liquid crystal alignment agent of condensate. According to the present invention, the above-mentioned object and advantages of the present invention can be achieved in the second way by coating the above-mentioned liquid crystal alignment agent of the present invention on a substrate, and forming the surface of the film obtained through film formation. A method for forming a liquid crystal alignment film characterized by impact. The organic and inorganic composite material of the present invention refers to a material that is chemically bonded between an inorganic part and an organic part and has two parts at the same time. "Application of Sols and Gels (1 997, Agune Chengfeng)", Chem. Master. 5 8, 1667 ( 1996)). The transparency of organic and inorganic composite materials is higher than that of organic materials such as polyamic acid or polyimide used as liquid crystal alignment agents in the past. Therefore, it is not easy to produce chemical reactions due to absorption of light and has high light resistance. The skeleton of this material is higher than that of organic materials. The structure of carbon and carbon bonds has a high bond energy. -9- (6) (6) 200401926, so the heat resistance is higher than organic materials. These materials are based on It is dissolved or dispersed in an organic solvent for bonding, and a coating film can be formed by a roll coating method, a spin coating method, a printing method, or the like. In order not to reduce the ability of the liquid crystal to align in the plane of the liquid crystal display element, A method for encapsulating a liquid crystal alignment film made of an organic or inorganic composite material with a liquid-to-day alignment objective b is, for example, the above-mentioned method of the present invention in which a coating film is irradiated with, for example, an ion beam to impact the coating film. [Embodiments of the invention] [Liquid crystal alignment agent] The concentration of the solid content of the liquid crystal alignment agent used in the present invention can be selected in consideration of viscosity, volatility, etc. The concentration is 〇 · 〇 丨 ~ 70% by weight, preferably 〇5 ~ 60% by weight, more preferably 1 ~ 30% by weight. The liquid crystal alignment agent of the present invention can be coated on the substrate surface by using a roll coating method, a spin coating method, a printing method, and the like, and then heated and dried to form a liquid crystal alignment film. When the solid content concentration is less than 0. 0 1% by weight, the film thickness of the coating film is too thin, and sometimes a good liquid crystal alignment film cannot be obtained. When the solid content concentration exceeds 70% by weight, the film of the coating film The thickness is too thick, and sometimes it is difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent is increased, and the coating characteristics are poor. The liquid crystal alignment agent of the present invention dissolves the organic and inorganic composite materials (i) to (v) described above. Or dispersed in organic solvents. The organic solvent used in the present invention is not particularly limited as long as it can dissolve or disperse the materials used. : Some of these cereals can be used alone or in combination of two or more. It is difficult to dissolve the poor solvent of -10- (7) (7) 200401926, and the solvent can be added in a range where the solid content does not precipitate. Specific examples of such solvents include n-pentane, isopentane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, Methylcyclohexane, decane, dicyclopentadiene, benzene, toluene, xylene, hardyne, indene, tetralin, decalin, tridecane, ethylbenzene, trimethylbenzene, methyl Hydrocarbon solvents of ethylethylbenzene, n-propylbenzene, cumene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, n-pentylnaphthalene, and trimethylbenzene; methanol , Ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, third butanol, n-pentanol, isoamyl alcohol, dimethyl butanol, second pentanol, third Amyl alcohol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, second hexanol, 2-ethylbutanol, second heptanol, heptanol-3, n-octanol, 2-ethyl alcohol Hexyl alcohol, second octanol, n-nonanol, 2,6-dimethylheptanol-4, n-decanol, 211stanol, trimethylnonanol, 214stanol, 217 alcohol, phenol, cyclohexanol, methylcyclohexanol, 3, 3, 5— Methylcyclohexanol, benzyl alcohol, phenylmethyl methanol, diacetone alcohol, cresol monool solvents; ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, pentanediol-2, 2-Ethylhexylene glycol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol polyol solvent; acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl alcohol N-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, methyl amyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, dipropyl ketone, di Isobutyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, methylcyclohexanone, cycloheptanone, 2,4-pentanedione, acetoacetone, acetophenone, acetone, ketone solvents ; Diethyl ether, di-n-propyl ether, di-isopropyl ether, di-n-butyl ether, di-isobutyl ether, di-n-hexyl ether, diethyl-11-(8) (8) 200401926 hexyl ether, cycloethylfluorene, 1, 2—Cyclopropaneol, Dioxane, 4-methyldioxane, dioxane, dimethyldioxane, phenyl ether, diphenyl ·, ethylene glycol monomethyl ether, ethyl Glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl , Glycol monopropyl ether, Glycol dipropyl ether, Glycol monobutyl ether, Glycol dibutyl ether, Glycol monohexyl ether, Glycol monophenyl ether, Glycol phenyl methyl ether , Ethylene glycol single 2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, Diethylene glycol dibutyl ether, diethylene glycol methyl ether, diethylene glycol monohexyl ether, ethoxy triethanol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol Monoethyl ether, propylene glycol diethyl ether, propylene glycol monopropyl ether, propylene glycol dipropyl ether, propylene glycol monobutyl ether, propylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyl Tetrahydrofuran solvent; diethyl carbonate, propylene carbonate, r-butyrolactone, r-valerolactone, methyl acetate, ethyl acetate, n-propionic acid acetate, isopropyl acetate, n-butyl acetate, acetic acid Isobutyl ester, second butyl acetate, n-valeric acid acetate, second pentyl acetate, 3-methoxybutyl acetate, Methyl amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate, acetic acid Methyl cyclohexyl acetate, n-nonyl acetate, methyl ethyl acetate, ethyl ethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether ester, acetic acid Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate , Propylene glycol monopropyl ether acetate, vinegar-12- (9) (9) 200401926 propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethylene glycol diacetate, methyl acetate Oxytriethylene glycol, ethyl phenyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl propionate, ethyl propionate, n-propyl propionate, propane Isopropyl ester, n-butyl propionate, isobutyl propionate, isoamyl propionate, benzyl propionate, ethoxyethyl propionate, oxalic acid Ethyl ester, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, n-pentyl lactate, methyl formate, ethyl formate, n-propyl formate, Isopropyl formate, n-butyl formate, isobutyl formate, n-amyl formate, isoamyl formate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl Ester solvents for butyl ester, isobutyl butyrate, diethyl malonate, dimethyl phthalate, diethyl phthalate, and ethyl pyruvate; N —methylformamide, N, N— Dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropylamine, N -Amidamine solvent of methylpyrrolidone; Sulfur-containing solvent of dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfide, cyclobutane, 1,3-propane sultone and the like. The liquid crystal alignment agent of the present invention may contain a functional silane-containing compound or an epoxy group-containing compound from the viewpoint of improving the adhesion to the substrate surface. Examples of functional silane-containing compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, and 2-aminopropyltriethyl N- (2-aminoethyl) -3-aminopropyltrimethoxysilicon, N- (2-aminoethyl) -3-aminopropylmethyldimethoxy Silane, 3-ureidopropyl-13- (10) (10) 200401926 trimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyl Trimethoxysilane, N-ethoxycarbonyl-1 3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylene triamine, N-trimethoxysilylpropyl Tris-triethyl triamine, 10-trimethoxysilyl-1,4,7-triaza-n-decadecane, 10-triethoxysilyl group, 1,4,7-triazine Shiyuan, 9-trimethoxysandyl—3,6-diazanonyl acetate, 9-triethoxysilyl-3,6—diazanonyl acetate, N— Benzyl- 3 -aminopropyltrimethoxysilane, N-benzyl-3 -aminopropyltrimethoxy Oxysilane, N-phenyl- 3 -aminopropyltrimethoxysilane, N-phenyl-3 -aminopropyltriethoxysilane, N-bis (oxyethylene) -3 -aminopropyl Trimethoxysilane, N-bis (oxyvinyl) -3-aminopropyltriethoxysilane, etc. The epoxy compounds include, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. Ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether Ether, 1,3,5,6 -tetraepoxypropyl -2,4-hexanediol, N, N, N ,, N, tetraepoxypropyl -m-xylylenediamine, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N, 'Ν'-tetraglycidyl-4,4, -diaminodiphenylmethane and the like. The compounding ratio of these functional silane-containing compounds or epoxy-containing compounds is kt when the organic / inorganic composite material is 1 part by weight, and contains 40 parts by weight or less, preferably 0.1 to 30 parts by weight. In the present invention, the liquid crystal alignment agent represented by the above-mentioned (i) (hereinafter sometimes referred to as (composition 1) (11) (11) 200401926) is selected from the group consisting of a crane compound having an organic group represented by the following formula (1), Partially hydrolyzed / condensed group of at least one compound (hereinafter also referred to as "specific compound") grouped by a group compound, a niobium compound, and a macro compound, the partial hydrolysate can be modified with other organic compounds, or with this modified product The mixture is an OR… (1) (R is a courtyard, a square radical, an aromatic radical or an aryloxy radical). The "partially hydrolysate" in the present invention refers to a part of the hydrolyzable group (for example, -0 R group in the specific compound of Composition 1), such as only one hydrolyzed person, two or more hydrolyzed persons, or Hydrolysis of these mixtures. The "condensate" in the present invention refers to those in which the aforementioned partial hydrolysate is condensed to form a -0-bond, and the partial hydrolysate does not need to be condensed in its entirety. 'Including only a part of the hydrolysate to be condensed, and mixtures having different degrees of condensation. Specific examples of the aforementioned specific compounds are represented by formula (2):

Qn- M (OR) m… (2) (but Q is hydrogen atom, halogen atom, alkyl group or hydroxyl group, M is tungsten, molybdenum, niobium, or giant, R is as described above, η is an integer from 0 to 5, and ❿ is An integer from 1 to 6, and m + n is equal to the valence of M) or formula (3): (0) q = M (OR) p… (3) (but M and R are as described above; q is 1 or 2) Integer, p is an integer from 1 to 4, and 2q + p is equal to the valence of M). Among these, a compound of η = 0 of the formula (2) is preferred. The price of tungsten is 5 or 6, the price of molybdenum is 5 or 6, the price of niobium is 5, and the price of -15- (12) (12) 200401926 is 6. In the organic group R of the formula (1), the alkyl group includes, for example, methyl, ethyl, propyl, isopropyl, butyl, third butyl, pentyl, and hexyl. Number of courtyards from 1 to 4. Examples of the aryl group include phenyl and naphthyl. Examples of the aralkyl group include benzyl and phenylethyl. The aryloxyalkyl group is, for example, a phenoxyethyl group. Specific examples of the specific compound include tungsten methanol, tungsten ethanol, tungsten isopropoxide, tungsten n-butoxide, tungsten phenol, tungsten phenylethanol, tungsten phenoxyethanol, and the formula: 0 = W-(0 C Η 3) The compound represented by 4 has the following structural formula:

II o = w-〇ch3

I 〇ch3 Compounds not shown, molybdenum methanol, molybdenum ethanol, molybdenum isopropanol, molybdenum n-butanol, molybdenum phenol, phenyl molybdenum molybdenum, phenoxyethanol molybdenum, niobium methanol, ethanol niobium, niobium isopropanol, Butanol niobium, phenol niobium, phenylethanol niobium, phenoxyethanol niobium, methanol giant, ethanol giant, isopropanol giant, n-butanol giant, phenol giant, phenylethanol giant, phenoxyethanol giant, and these Metal alkoxides, metal phenates, aryl metal alkoxides, aryloxy metal alkoxides, etc., obtained by the transesterification reaction of compounds with alcohols or phenols. These can be used alone or in combination of two or more. The composition 1 of the present invention can be produced by subjecting a specific compound to partial hydrolysis to produce a metal hydroxide in the presence of an organic solvent, and by a general method of condensation. -16- (13) (13) 200401926 Partially hydrolyzed products generally generate M-0-M (M is the aforementioned metal) bond, resulting in a condensate having repeating unit one (M-0)-. In the production of the partial hydrolysis / condensation product, when the specific compound is partially hydrolyzed and condensed, the amount of water added is -OR group of the specific compound at 1 mol, and it is preferable to add 0.2 to 0.5 mol. The weight-average molecular weight of the partially hydrolyzed / condensed product thus obtained, measured by gel permeation chromatography (GPC), in terms of polystyrene, is preferably from 100 to 100, 000. In the composition 1, the partial hydrolysis / condensation product described above can be used in a non-modified state or a modified state according to the required characteristics of the liquid crystal alignment agent. The modified product includes, for example, other known organic compounds, and is preferably one modified with a thermosetting organic compound. The modified product of the partially hydrolyzed / condensed product, for example, the partially hydrolyzed / condensed product of the modified part of the thermosetting organic compound is usually produced by adding a suitable amount of a thermosetting compound when partially hydrolyzing or condensing a specific compound. The thermosetting compound has, for example, the following formula (4): -N—CH2 OX ··· (4)

A compound of an organic group represented by I (X represents an alkyl group or a hydrogen atom) (hereinafter referred to as a thermosetting compound (4)) is preferred. The alkyl group of X in the above formula is preferably an alkyl group having 1 to 6 carbon atoms. The thermosetting compound (4) may be an oligomer. Specific examples of the thermosetting compound (4) include N, N, N, N, N, N, N to (hexamethoxymethyl) melamine, N-substituted alkoxymethyl or hydroxymethyl melamines, or N, N— (dibutoxymethyl) -17- (14) (14) 200401926 Benzoguanamine with N-substituted alkoxymethyl or hydroxymethyl, N, N, N, N— (tetramethoxymethyl) glycoluril with N-substituted alkoxymethyl or hydroxymethyl glycoluril, N, N, N, N— (tetramethoxymethyl ) Urea with N-substituted alkoxymethyl or methylol. Melamines having N-substituted alkoxymethyl or hydroxymethyl, such as commercially available Simel 300, 301, 303, 350, 760, 738, 370, 771, 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272 > 254, 235, 202, 1156, 1158 (The above is made by Mitsui Sianzmid (stock)). Benzoguanamine with N-substituted alkoxymethyl or hydroxymethyl, for example, commercially available Simel 1123, 1123-10, 1125-80, 1128 (the above are manufactured by Mitsui Sinzmid (stock)) and the like. Glyurides having N-substituted hydroxymethyl groups or methyl groups are commercially available, for example, Simel 1170, 1171, 1174, and 1172 (the above are manufactured by Mitsui Sianzmid). Urines having N-substituted alkoxymethyl or hydroxymethyl include, for example, commercially available UFR6 5, 300 (the above are manufactured by Mitsui Sianzmid (stock)). Other thermosetting compounds include, for example, the thermosetting properties of melamine-formaldehyde resin, benzoguanamine-formaldehyde resin, glycoluril-formaldehyde resin, urine-formaldehyde resin, thiourea-formaldehyde resin, guanamine-formaldehyde resin N-substituted alkoxymethyl or hydroxymethyl compounds are introduced into the resin. The above thermosetting compounds can be used alone or in combination of two or more. -18- (15) (15) 200401926 The addition amount of the thermosetting compound when the partial hydrolysis / condensation of the aforementioned specific compound is modified is based on the specific compound 〖〇 () parts by weight, add 50 ~ 3 0 0 Parts by weight are preferred. In the composition 1 of the present invention, various additives such as a preservation tincture, a surfactant, a radiation absorbent, an antifoaming agent, and an adjuvant can be added within a range that does not affect the effect of the present invention. Preservative stabilizers include, for example, acetoacetone or acetoacetone ethyl acetate and / or / 3-ketoester. Surfactants have the effect of improving coatability, streaking, and wettability. Such surfactants are, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and polyethylene glycol dilaurate. , Non-ionic surfactants such as polyethylene glycol distearate. Commercial products include, for example, organic silicone polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic (co) polymer Poly flow No. 57, 95 (Kyoei Chemical Co., Ltd.) System), F TOP EF101, EF 204, EF 303, 352 (manufactured by TOCHEMPRODUCT Co., Ltd.), Megafac F171, 172, 173 (manufactured by Dainippon Ink Co., Ltd.), Florad FC43 0, FC 431, FC135, FC93 (Sumitomo Corporation) 3M Co., Ltd.), Asahi Guard AG71 0, Surflone S-3 82, SC-101, 102, 103, 104, 1 05, 1 06 (manufactured by Asahi Glass Co., Ltd.), etc. When the compounding amount of such a surfactant is 100 parts by weight based on the solid content of the composition 1, it is preferably 15 parts by weight or less, and more preferably 10 parts by weight or less. In the present invention, the liquid crystal alignment agent shown in the above (ii) (hereinafter sometimes referred to as (composition 2) in (16) 200401926) is selected from a compound represented by the following formula (5) (hereinafter referred to as compound (5)) and the following The partial hydrolysis / condensation of at least one compound grouped by the compound represented by the formula (6) (hereinafter referred to as the compound (6)). The compound (5) and the compound (6) can be used respectively in two or more kinds. R'aSi (OR2) 4.a (5) (where R1 is a hydrogen atom, a fluorine atom, or a monovalent organic group, R2 is a monovalent organic group, and a is an integer from 0 to 2), R3b (R40) 3.bSi- (R7) d.Si (OR5) 3.cR6c (6) (R3, R4, R5, and R6 may be the same or different, respectively, they represent monovalent organic groups; b and C may be the same or different An integer of 0 to 2, R7 is an oxygen atom or — (CH2) n—, and d is 0 or 1511 is an integer of i to 6) In the above formula (5), an organic group of one of the valencies of Ri and R2 is, for example, an aryl group , Allyl, ethenyl, glycidyl, etc. When multiple ... and R2 are contained, each R1 and each R2 may be the same or different.

The k group includes, for example, methyl groups, ethyl groups, propyl groups, butyl groups, and the like, and k groups having a carbon number of 5 to 5 are more k. These alkyl groups may be chained or branched, and hydrogen atoms may be replaced by fluorine atoms or the like. Examples of the aryl group include phenyl, naphthyl, methylphenyl, ethylphenyl, chlorophenyl, bromophenyl, and fluorophenyl. Specific examples of the compound (5) include M, trimethoxysilane, triylsilane, tri-n-propoxysilane, silane, tri-butoxysilane, Shi Xiyuan, M dimethoxy sand plant, fluorine Silane, fluorotriisopropoxysilane, diisopropoxysilane, tri-n-butoxydi-third-butoxysilane, triphenoxydiethoxy5, fluorotri-n-propoxyfluorotri N-butoxysilane, fluorine three second

-20- (17) (17) 200401926 butoxysilane, fluorotri-tert-butoxysilane, fluorotriphenoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, Tetraisopropoxysilane, tetra-n-butoxysilane, tetra-second butoxysilane, tetra-third butoxysilane, tetraphenoxysilane, etc .; methyltrimethoxysilane, methyltriethoxy Silane, methyltri-n-propoxysilane, methyltri-isopropoxysilane, methyltri-n-butoxysilane, methyltri-n-butoxysilane, methyltri-n-butoxysilane, methyl Triphenyloxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, ethyl Ethyltris-butoxysilane, ethyltris-butoxysilane, ethyltrisphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane , Vinyltriisopropoxysilane, vinyltri-n-butoxysilane, vinyltri-n-butoxysilane, vinyltri-n-butoxysilane , Vinyltriphenoxy sand institute, n-propyltrimethoxysilane institute, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltriisopropoxysilane, n-propyl Tritri-n-butoxysilane, n-propyl-tributoxysilane, n-propyl-tertiary-butoxysilane, n-propyltriphenoxysilane, isopropyltrimethoxysilane, isopropyl Triethoxysilane, Isopropyltri-n-propoxysilane, Isopropyltriisopropoxy sand, Isopropyldi-n-butoxy sand, Isopropyltri-n-butoxysilane, Iso Propyltri-tert-butoxysilane, isopropyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyl Triisopropoxysilane, n-butyltri-n-butoxysilane, n-butyltri-second-butoxysilane, n-butyltri-third-butoxysilane, n-butyltriphenoxysilane, second Butyltri-21-(18) (18) 200401926 methoxysilane, second butyltriethoxysilane, second butyltri-n-propoxysilane, second butyltriisopropoxysilane, First Butyl tri-n-butoxysilane, second butyl tri second butoxy silane, second butyl tri third butoxy silane, second butyl triphenoxy silane, third butyl trimethoxy Silane, third butyl triethoxy silane, third butyl tri-n-propoxy silane, third butyl tri-isopropoxy silane, third butyl tri-n-butoxy silane, third butyl tri- Second butoxysilane, third butyl tri-three butoxy silane, third butyl triphenoxy silane, phenyl trimethoxy silane, phenyl triethoxy silane, phenyl tri-n-propane Oxysilane, phenyltriisopropoxysilane, phenyltri-n-butoxysilane, phenyltrisecond-butoxysilane, phenyltrithird-butoxysilane, phenyltriphenoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, r-aminopropyltrimethoxysilane, r-aminopropyltriethoxysilane, 7-glycidoxypropyltrimethoxysilane, r-glycidoxypropyltriethoxysilane, τ-trifluoropropyltrimethoxysilane, r-trifluoropropyltriethoxysilane, etc .; dimethyldimethoxysilane Dimethyl diethoxy silane, dimethyl di-n-propoxy silane, dimethyl diisopropoxy silane, dimethyl di-n-butoxy silane, dimethyl di-n-butoxy silane, Dimethyldi-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldi-n-propoxysilane, diethyl Diisopropoxysilane, diethyldi-n-butoxysilane, diethyldi-second-butoxysilane, diethyldi-third-butoxysilane, diethyldiphenoxysilane, two N-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyldi-n-propoxysilane, di-n-propyldiisopropoxysilane, di-n-propyl-22- (19) 200401926-based di-n-butoxysilane, di-n-propyl-di-butoxysilane, di-n-propyl-tertiary-butoxysilane, di-n-propyldiphenoxysilane, diisopropyldimethoxy Silane, diisopropyldiethoxysilane, diisopropyldi-n-propoxysilane, diisopropyldiisopropoxysilane, diisopropyldi-n-butoxysilane, diisopropyl two Second butoxysilane, diisopropyl second tertiary butoxysilane, diisopropyldiphenoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di N-butyldi-n-propoxysilane, di-n-butyldiisopropoxysilane, di-n-butyldi-n-butoxysilane, di-n-butyldi-second-butoxysilane, di-n-butyldi- Tributoxysilane, di-n-butyldiphenoxysilane, di-second butyldimethoxysilane, di-second butyldiethoxysilane, di-second butyldi-n-propoxysilane, Di-second butyl diisopropoxysilane, di-second butyl di-n-butoxysilane, di-second butyl-di-butoxysilane, di-second butyl-di-butoxysilane , Second second butyl diphenoxy silane, second third butyl dimethoxy silane, second third butyl diethoxy silane, second third butyl di-n-propoxy silane, second third butyl Diisopropoxysilane, di-third-butyl-di-n-butoxysilane, di-third-butyl-di-butoxysilane, di-third-butyl-di-butoxysilane, di-third-butane Diphenyl Oxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, di

Second butoxysilane, diphenyl second tertiary butoxysilane, diphenyldiphenoxysilane, divinyltrimethoxysilane, 7-aminopropyltrimethoxysilane, r-aminopropyl Triethoxysilane, 7-glycidoxypropyltrimethoxysilane, r-glycidoxypropyltriethoxysilane, 7-tri-23- (20) (20) 200401926 fluoropropane Trimethoxysilane, r-trifluoropropyltriethoxysilane, and the like. Among the compounds (5), tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetraphenoxysilane, etc. are preferred; methyltrimethoxysilane, Methyltriethoxysilane, Methyltri-n-propoxysilane, Methyltriisopropoxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Vinyltrimethoxysilane, Vinyl Triethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyl Didiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, triethylmonomethoxy Silane, triethylmonoethoxysilane, triphenylmonomethoxysilane, triphenylmonoethoxysilane, etc. These may be used singly or in combination. Examples of the monovalent organic group in the formula (6) include the same organic group as the formula (5). In the above formula (6), compounds in which R7 is an oxygen atom include, for example, hexamethoxydisilaxane, hexaethoxydisilaxane, hexaphenoxydisilaxane, 1,1,1,3,3 —Pentamethoxy-3-methyldisilaxane, 1,1,1,3,3 —pentaethoxy-3-methyldisilaxane, 1,1,1,3,3--5 Methoxy-3 —phenyldisilazane, 1,1,1,3,3 —pentaethoxy-3-phenylphenyloxide, 1,1,3,3-tetramethoxy-1 , 3-dimethyldisilaxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisilaxane, 1,1,3,3-tetramethoxy-1 , 3-diphenyldisilaxane, 1,1,3,3-tetraethoxy-1,3-diphenyldisilaxane, 1,1,3-trimethoxy-1,3, 3-trimethyldisilaxane, 1 -24- (21) (21) 200401926, 1,3-triethoxy-1,3,3-trimethyldisilaxane, 1,1,3 —Trimethoxy-1,3,3-triphenyldisilaxane, 1,1,3-triethoxy-1,3,3-triphenyldisilaxane, 1,3-dimethyl Oxy-1,1,3,3-tetramethyldisilaxane 1,3-diethoxy-1,1,3,3-tetramethyldisilaxane, 1,3-dimethoxy-1,1,3,3-tetraphenyldisilaxane, 1,3-diethoxy-1,1,3,3-tetraphenyldisilazane and the like. Among them, preferred are hexamethoxydisilaxane, hexaethoxydisilaxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisilaxane, 1,1 , 3,3-tetraethoxy-1,3-dimethyldisilaxane, 1,1,3,3-tetramethoxy-1,3-phenylphenyl disoxazine, 1,3 — __ • methoxy-1,1,3,3-tetramethyldisilaxane, 1,3-diethoxy-1,1,3,3-tetramethyldisilaxane, 1, 3-dimethoxy-1,1,3,3-tetraphenyldisilazane, 1,3-diethoxy-1,1,3,3-tetraphenyldisilazane. In the above formula (6), the compound where d is 0 includes, for example, hexamethoxydisilazane, hexaethoxydisilazane, hexaphenoxydisilazane, 1,1,1,2,2-pentamethoxy-2 —Methyldisilanes, 1,1,1,2,2-pentaethoxy-2 —methyldisilanes, 1,1,1,2,2 —pentamethoxy-2 —phenyldisilanes, 1,1,1,2,2-pentaethoxy-2-phenyldisilazane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilazane, 1,1,2 '2 —Tetraethoxy-1,2 —one ^ methyl_ * Shi Xiyuan, 1,1,2,2 —Tetramethoxy-1,2-diphenyldisilazane, 1,1,2 , 2-tetraethoxy-1,2-diphenyldisilanes, 1,1,2-trimethoxy-1,2,2-tris-25- (22) (22) 200401926 methyldisilanes, 1,1,2-triethoxy-1,2,2-trimethyldisilazane, 1,1,2-trimethoxy-1,2,2-triphenyldisilazane, 1,1,2 —Triethoxy—1,2,2-triphenyldisila, 1,2—dimethoxy—1,1,2,2-tetramethyldisila, 1,2—diethoxy— 1,1,2,2-tetramethyl Silane, 1,2 - dimethoxy a 1,1,2,2 - tetraphenyl Silane, 1,2-diethoxy-1,1,2,2-tetraphenyl a Silane like. In the above formula (6), compounds in which R7 is mono (CH2) η- include, for example, bis (hexamethoxysilyl) methane, bis (hexaethoxysilyl) methane, and bis (hexaphenoxysilyl) methane , Bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, bis (dimethoxyphenylsilyl) methane, bis (diethoxyphenylsilyl) ) Methane, bis (methoxydimethylsilyl) methane, bis (ethoxydimethylsilyl) methane, bis (methoxydiphenylsilyl) methane, bis (ethoxydiphenyl) Silyl) methane, bis (hexamethoxysilyl) ethane, bis (hexaethoxysilyl) ethane, bis (hexaphenoxysilyl) ethane, bis (dimethoxymethylsilyl) ) Ethane, bis (diethoxymethylsilyl) ethane, bis (dimethoxyphenylsilyl) ethane, bis (diethoxyphenylsilyl) ethane, bis (methoxy Dimethylsilyl) ethane, bis (ethoxydimethylsilyl) ethane, bis (methoxydiphenylsilyl) ethane, bis (ethoxydiphenyl) Silyl) ethane, 1,3-bis (hexamethoxysilyl) propane, 1,3-bis (hexaethoxysilyl) propane, 1,3-bis (hexaphenoxysilyl) propane , 1,3-bis (dimethoxymethylsilyl) propane, 1,3-bis (diethoxymethylsilyl) propane-26- (23) (23) 200401926 alkane, 1,3 — Bis (dimethoxyphenylsilyl) propane, 1,3-bis (diethoxyphenylsilyl) propane, 1,3-bis (methoxydimethylsilyl) propane, 1,3 -Bis (ethoxydimethylsilyl) propane, 1,3-bis (methoxydiphenylsilyl) propane, 1 '3-bis (ethoxy- ^ phenylsulphonyl) propane Wait. Among them, hexamethoxydisilanes, hexaethoxydisilanes, hexaphenoxydisilanes, 1,1,2,2-tetramethoxy-1,2-dimethyldisilanes, 1, 1,2,2-tetraethoxy-1,2-dimethyldisilanes, 1,1,2,2-tetramethoxy-1,2-diphenyldisilanes, 1,1,2, 2-tetraethoxy-1,2-diphenyldisila, 1,2-dimethoxy-1,1,2,2-tetramethyldisila, 1,2-diethoxy-1 , 1,2,2-tetramethyldisilanes, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilanes, 1,2-diethoxy-1,1,2 , 2-tetraphenyldisila, bis (hexamethoxysilyl) methane, bis (hexaethoxysilyl) methane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethyl) Silyl) methane, bis (dimethoxyphenylsilyl) methane, bis (diethoxyphenylsilyl) methane, bis (methoxydimethylsilyl) methane, bis (ethoxy) Dimethyl dimethyl silicon base, base A), bis (methoxydiphenylsilyl) methane, bis (ethyl Diphenyl cut hospital-yl) methane. When the compound (5) and / or the compound (6) is partially hydrolyzed / condensed, when the group represented by R30-, R4-0- or R50- is 1 mole, water of 0.25 to 3 moles is preferably used. Use 0 · 3 to 2 · 5 ears of water. When the amount of water added is 0.2 to 3 to 3 mol, the uniformity of the coating film may not be reduced, and the storage stability of the composition 2 is less likely to decrease. -27- (24) 200401926 Specifically, water is continuously or intermittently added to an organic solvent in which the compound (5) and / or the compound (6) is dissolved. In this case, the catalyst can be added to an organic solvent in advance or dissolved or dispersed in water when water is added. The reaction temperature at this time is 0 to 100 ° C, and ideally 15 to 80 ° C. When the composition 2 uses two or more kinds of compounds, (a) two or more kinds of compounds (5) and / or compound (6) are mixed and then hydrolyzed, condensed, or (b) two or more kinds of compounds are separately used (5) and / or compound (6) are individually hydrolyzed and condensed, and then mixed and used. It is particularly preferred that a catalyst is used when (b) ° hydrolyzes and partially condenses compound (5) and / or compound (6). Examples of the catalyst used at this time include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases. Specific examples of the metal chelate compound of the catalyst include triethoxy · mono (ethylfluorenylacetone) titanium, tri-n-propoxy · mono (ethylfluorenylacetone) titanium, and triisopropoxy · mono (Ethyl acetone) titanium, tri-n-butoxy • mono (ethyl acetone) titanium, three second butoxy • mono (ethyl acetone) titanium, three third butoxy • mono (ethyl acetone) Acetone) titanium, diethoxy · bis (ethynylacetone) titanium, di-n-propoxy • bis (ethynylacetone) titanium, diisopropoxy • bis (ethynylacetone) titanium, two N-butoxy · bis (ethenylacetone) titanium, second and second butoxy • bis (ethenylacetone) titanium, second and third butoxy • bis (ethenylacetone) titanium, monoethoxy • Ginseng (acetylacetone) titanium, mono-n-propoxy • Ginseng (ethynylacetone) titanium, monoisopropoxy • Ginseng (ethynylacetone) titanium, mono-n-butoxy • Ginseng (acetamidine) Acetone) titanium, mono-n-butoxy • ginseng (ethynylacetone) titanium, mono-second butyl • 28- (25) (25) 200401926 oxy-ginseng (ethynylacetone) titanium, mono-tert-butyl Oxygen Acetone) Titanium, Ethyl (Ethyl Acetyl Acetate) Titanium, Triethoxy • Mono (Ethyl Acetate) Titanium, Tri-n-propoxy • Mono (Ethyl Acetate) Titanium, Tri-Second Butoxy • Titanium mono (ethyl acetate), tri-tert-butoxy • Titanium mono (ethyl acetate), diethoxy • Titanium bis (ethyl acetate), di-n-propoxy • bis (Ethyl Acetate) Titanium, Diisopropoxy • Bis (Ethyl Acetate) Titanium, Di-n-butoxy • bis (Ethyl Acetate) Titanium, Two Second Butoxy • Bis ( Ethyl Acetate) Titanium, Second and Third Butoxy • Bis (Ethyl Acetate) Titanium, Monoethoxy • Ginseng (Ethyl Acetate) Titanium, Mono-n-propoxy · Ginseng (Ethyl Acetate) Ethyl acetate) Titanium, monoisopropoxy • ginseng (ethyl acetate) Titanium, mono-n-butoxy • ginseng (ethyl acetate) Titanium, single second butoxy • ginseng (ethylacetate) Ethyl) Titanium, Mono-Thirty-Butoxy • Ginseng (Ethyl Acetate) Titanium, Ethyl (Ethyl Acetate) Titanium, Mono (Ethyl Acetate) Titanium (Ethyl Ethyl Acetate) Titanium, Double (Ethyl acetone)醯 Ethyl acetate) Titanium, Titanium chelate (Ethylacetone) Titanium, etc .; Triethoxy • mono (Ethylacetone) Chromium, Tri-n-propoxy • mono ( Acetylacetone) Zirconium, triisopropoxy · mono (ethylacetone) 鍩, tri-n-butoxy · mono (ethylacetone) 鍩, three second butoxy • mono (ethylacetone) Tables, three Tertiary butoxy • mono (acetamidineacetone) zirconium, diethoxy • mono (acetamidineacetone) zirconium, di-n-propoxy · bis (acetamidineacetone) zirconium, diisopropoxy · bis (ethyl)醯 acetone) pin, di-n-butoxy • bis (acetamidine acetone) pin, second and second butoxy • bis (acetamidine acetone) zirconium, second and third butoxy · bis (acetamidine acetone) pin, single Ethoxy • ginseng (acetamidineacetone) chromium, mono-n--29-(26) (26) 200401926 propoxy · ginseng (acetamidineacetone) chromium, monoisopropoxy • ginseng (acetamidineacetone) zirconium, Mono-n-butoxy • ginseng (ethyl acetone) osmium, mono-second butoxy ginseng (acetyl acetone) zirconium, mono-third butyl oxy-ginseng (acetyl acetone) chromium, acetic acid (ethyl acetoacetate) Ketoester) zirconium, triethoxy Mono (ethyl acetate) zirconium, tri-n-propoxy · mono (ethyl acetate) chrome, triisopropoxy · mono (ethyl acetate) zirconium, tri-n-butoxy • mono ( Ethyl Acetate) Pin, Tri-Second Butoxy • Mono (Ethyl Acetate) Chromium, Tri-Third Butoxy • Mono (Ethyl Acetate) Zirconium, Diethoxy • Bis (ethyl醯 ethyl acetate) chromium, di-n-propoxy • bis (ethylacetate) chromium, diisopropoxy • bis (ethylacetate) zirconium, di-n-butoxy • bis (ethylacetate) Ethyl) samarium, second and second butoxy • bis (ethyl ethyl acetate) zirconium, second and third butoxy • bis (ethyl ethyl acetate) zirconium, monoethoxy • gin (ethyl acetate Ethyl acetate) Zirconium, mono-n-propoxy • ginseng (ethyl acetate) zirconium, monoisopropoxy • ginseng (ethyl acetate) pin, mono-n-butoxy • ginseng (ethyl acetate) (Ester) osmium, mono-second butoxy • ginseng (ethyl acetate), tertiary butoxy-ginseng (ethyl acetate), zirconium (ethyl acetate) zirconium, mono ( Ethylacetone) ginseng Esters) Zirconium chelate compounds such as chromium, bis (ethylacetone) bis (ethylacetate), ginseng (ethylacetone) mono (ethylacetate), etc .; ginseng (acetone) aluminum Specific examples of organic acids, such as aluminum chelate compounds such as acetic acid, ethyl acetate, aluminum, etc., include acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, caprylic acid, nonanoic acid, and capric acid. , Oxalic acid, maleic acid, methyl malic acid, adipic acid, sebacic acid, gallic acid, butyric acid, pyromethylene-30- (27) (27) 200401926 acid, arachidic acid, 2- Hexylhexanoic acid, oleic acid, stearic acid, linolenic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloride Acetic acid, trifluoroacetic acid, formic acid, malic acid, sulfonic acid, phthalic acid, maleic acid, citric acid, tartaric acid, etc. Specific examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid. Specific examples of organic tests include pyridoxine, pyrrole, piperazine, hexahydropyridine, pyrrolidine, methylpyridine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, and dimethylmonoethanolamine. , Monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazacycloundecene, tetramethylammonium hydroxide, and the like. Examples of inorganic tests include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide. Among these catalysts, a metal chelate compound, an organic acid, and an inorganic acid are more preferable, and a titanium chelate compound and an organic acid are more preferable. These compounds can be used alone or in combination of two or more. When the amount of the catalyst used is 100 parts by weight of compound (5) and / or compound (6) (completely hydrolyzed / condensed), 0.001 to 10 parts by weight is usually used, and preferably 0.01 to 10 parts by weight is used. . The composition 2 is a compound (5) and / or a partial hydrolysis / condensation of the compound (6) is dissolved or dispersed in an organic solvent. The organic solvents used in the present invention can be selected from those listed above. The composition 2 contains the above-mentioned organic solvent, and when the compound (5) and / or the compound (5) and (28) (28) 200401926 compound (6) are partially hydrolyzed and condensed, the same solvent can be used. The alcohol content in the composition 2 is 20% by weight or less, and preferably 5% by weight or less. When the compound (5) and / or the compound (6) are partially hydrolyzed and condensed, alcohol may be generated, and the alcohol may be removed by distillation or the like so that the rhenium content is 20% by weight or less, and preferably 5% by weight or less. The following / 3-dione may be added to the composition 2. Ethyl ethyl acetone, 2,4-hexanedione, 2,4-heptanedione, 3,5 ~ heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonadione Ketones, 3,5-nonane, 5-methyl-2,4-hexamethylene, 2,2,6,6-tetramethyl-1,3,5-heptanedione, 1,1,1,5 One, two or more of 5,5-hexafluoro-2,4-heptanedione, etc. In the present invention, the / 3-dione content in the composition 2 is from i to 50% by weight of the total solvent, and preferably from 3 to 30% by weight. When / 3 is added in this range—dione, a certain storage stability can be obtained, and at the same time, the characteristics of the coating film uniformity of the composition are less reduced. The composition 2 may contain components such as colloidal silica, colloidal alumina, organic polymer, and surfactant. Colloidal silica refers to, for example, a dispersion liquid in which high-purity silicic anhydride is dispersed in the aforementioned hydrophilic organic solvent, and preferably contains a solid content concentration of 10 to 40% by weight and an average particle size of 5 to 3 0 // m , More preferably particles having an average particle diameter of 10 to 20 // m. Examples of such colloidal silica include Nissan Chemical Co., Ltd., methanol oxidized silica sol and isopropanol oxidized silica sol; catalyst chemical industry (OS), and OSUKAR. The colloidal alumina is, for example, alumina sol-32- (29) (29) 200401926 520, 100, 200 made by Nissan Chemical Co., Ltd .; oxidized Clear sol made by Kawasaki Finechemical Co., Ltd., alumina sol 10, 132 etc. Examples of the organic polymer include a compound having a polyalkylene oxide structure, a compound having a sugar chain structure, a vinylamine polymer, a (meth) propionate compound, an aromatic vinyl compound, and a network polymer. , Polyimide, polyamidic acid, polyarylene, polyimide, polyquinoxaline, polyoxodifluoride, fluoropolymer, etc. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Other classifications include poly-sand-oxygen-based surfactants, poly-oxygen-based surfactants, and fluorine-containing surfactants. In the present invention, the liquid crystal alignment agent (hereinafter sometimes referred to as “composition 3”) shown in the above (iii) is a part of silicon atoms bonded to a monovalent organic group, a part is bonded to a hydrogen atom, and a part is contained to hydrogen Atom-bonded silicon polymer. The silicon polymer is substantially represented by the following formula (7) and has a polystyrene-equivalent weight average molecular weight of at least 2,000 and siHxR8y (7) (wherein R8 is a monovalent organic group, and X is 〇 · 〇. The number 1 to 3 is 3, and y is the number 11 to 3, but x + y $ 4). When the composition 3 is represented by the above formula (7), it may contain two or more polymers in different combinations of fluorene and y. X is the number of hydrogen atoms bonded to the silicon atom.

The range is from 0.01 to 3, preferably from 0.05 to 2, and more preferably from 0.07 to 1.5. When X is less than 0.01, the prepared silicon polymer has poor solubility in organic solvents -33- (30) (30) 200401926, and when x exceeds 3, stability is poor. y is the number of monovalent organic groups bonded to the silicon atom, and the range of y for one silicon atom is 0.0 1 to 3, ideally 0 · 0 5 to 2, and more preferably 0 · 1 to 1 · 5 . When y is less than 0, the prepared silicon polymer has poor solubility in organic solvents, and when y exceeds 3, coating properties are poor. But x + y € 4. The silicon polymer used in the present invention is described in detail in Japanese Patent Application Laid-Open No. 200 1 — 1 1 1 84 and Japanese Patent Application Laid-Open No. 200 1 — 8 95 72. The following formula (8) R8SiX3 (8 ) (Wherein R8 is a monovalent organic group, which is the same as R8 of formula (8), and X is a halogen atom), the reaction product obtained by reacting the silicon halide with metal lithium and / or metal magnesium is reduced by Li A1H4 Steps to manufacture. The coating film obtained using the composition 3 is converted into a polysiloxane film by heat treatment and / or light irradiation as described in the above publication. The present invention can also use these processes as a liquid crystal alignment film. In the above formulae (7) and (8), R8 is a monovalent organic group, and specific examples include a linear or branched aliphatic group having 1 to 10 carbon atoms such as an alkyl group, an alkenyl group, and an alkynyl group; Alkyl, cycloalkenyl, bicycloalkyl and the like have alicyclic groups having 3 to 20 carbons; aryl having 6 to 20 carbons; and aralkyl having 6 to 20 carbons. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, third butyl, n-pentyl, isopentyl, neopentyl, decyl and the like. Examples of alkenyl include propenyl, 3-butenyl, and 3-hexenyl. Examples of the alkynyl group include propynyl, 3-methylpropynyl, and 3-ethylpropynyl. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and norbornyl. Examples of the aryl group include -34- (31) (31) 200401926 phenyl, tolyl, xylyl, α-naphthyl, mononaphthyl, thienyl, / 5-thienyl, and the like. Examples of the aromatic group include benzyl, benzylethyl, phenylpropyl, phenylbutyl and the like. From the viewpoint of the stability of the sand polymer produced, these substituents are preferably tertiary butyl, hexyl, phenylethyl, norbornyl. The liquid crystal alignment agent obtained by dissolving or dispersing the above-mentioned silicon polymer in an organic solvent is not suitable. To the extent that the purpose or function of the present invention is affected, a small amount of specific surface tension modifiers such as fluorine-based, polysiloxane-based, and non-ionic systems may be added as necessary. The liquid crystal alignment agent shown in (iv) above (sometimes below) The composition 4) is a polycondensate containing a hydrolyzable titanium alkoxide compound through hydrolysis and condensation to produce Ti—10—Ti bonds, with one (Ti0) — as a repeating unit. In the present invention, the polytitanium siloxane as a constituent of the composition 4 may be modified by other organic compounds, or a non-modified or a mixture of modified materials. Modified products include, for example, modified polysilicone modified with at least one of the group consisting of organopolysiloxane, acid anhydride and carboxylic acid (for example, modified organic polysiloxane with modified titanium sand oxygen plant, modified with acid anhydride) Polytitanylsiloxane, carboxylic acid modified polytitanylsiloxane). This polytitanyl oxaxane is produced by hydrolyzing a hydrolyzable alkoxyl compound, for example, tetraalkoxytitanium, in the presence of an organic solvent to produce a titanium alcohol, and is produced by a general method of condensation. The above hydrolyzable titanium alkoxy compound may contain alkoxy groups of methoxy, ethoxy, propoxy, and butoxy; phenoxy, methylbenzyloxy, phenylethoxy, and phenoxyethoxy Groups such as naphthyloxy, hydroxyl, etc., for example, tetramethoxytitanium, tetraethoxytitanium, tetraisopropyl-35- (32) (32) 200401926 titanium titanate, tetrabutoxytitanium , Tetrakis (methoxypropoxy) titanium, Tetranonyloxytitanium, Tetraphenoxytitanium, Tetramethyloxytitanium, Tetraphenylethoxytitanium, Tetraphenoxyethoxytitanium, Tetranaphthyloxy Titanium oxide and titanium oxide obtained by exchange reaction of these tetraalkoxy titanium with alcohols. The amount of water added during the partial hydrolysis and condensation of Siyuan Oxytitanium is 1 to 2 moles of Oxygen in Siyuan Oxygen, and it is preferable to add 0.2 to 0.4 moles. Among the aforementioned polytitanylsiloxanes, the organopolysilicone modified polytitanylsiloxane is preferably used in the preparation of the composition, when mixing the silane compound and titanium tetraalkoxide, adding an appropriate amount of water to make the silane compound and Tetraalkoxy titanium is produced by hydrolysis and (staggered) condensation. The organic polysilicone modified polytitanylsiloxane thus obtained contains: one of the Ti—O—Ti bonds (TiO) produced by the hydrolysis and condensation of tetraoxytitanium titanium—polytitanium silicon that is a repeating unit Oxane; one of the si-0 -Si bonds (SiO) produced by the hydrolysis and condensation of a hydrolyzable organosilane compound; an organopolysiloxane with repeating units; titanium tetraalkoxide and hydrolyzable organosilane Condensation polymer of Si-0-Ti bond produced by common hydrolysis and staggered condensation of compounds. The hydrolyzable organic silane compound used herein is preferably the compound (5) or the compound (6) shown in the above (ii). The present invention is to manufacture polytitanylsiloxane and organopolysiloxane separately. This mixture can be used as a polytitanylsiloxane containing organopolysiloxane. It can be used instead of organopolysiloxane to modify polytitanium silicon. Oxane. Various additives can be added to the composition 4 as long as the effect of the present invention is not affected. Examples of the additives include a surfactant, a radiation absorber, and the like. The aforementioned surfactants have the effects of improving coating properties, streaking phenomenon, wetting, and the like -36- (33) (33) 200401926. Such surfactants are, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and polyethylene glycol dilaurate. , Non-ionic surfactants such as polyethylene glycol distearate. Commercially available products include, for example, organic silicone polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic (co) polymer Poly flow No. 57, 95 (Kyoei Chemical Co., Ltd.) Manufacturing), F TOP EF101, EF 204, EF 303, 352 (manufactured by TOCHEMPRODUCT Co., Ltd.), M eg af ac F 1 7 1, 1, 7 2, 1 7 3 (manufactured by Dainippon Ink Co., Ltd.), Florad FC43 0, FC 431, FC135, FC93 (made by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflone S— 3 82, SC— 101, 1 02, 1 03, 1 04, 1 05, 1 06 (Asahi Glass Co., Ltd.)制) and so on. When the compounding amount of such a surfactant is 100 parts by weight based on the solid content of the composition 4, it is preferably 15 parts by weight or less, and more preferably 10 parts by weight or less. In the present invention, the liquid crystal alignment agent represented by (V) (hereinafter sometimes referred to as i 爯 m composition 5) is a partially hydrolyzed / condensed compound containing a compound represented by the following formula (9), A1 (OR9) xQ3- x (9) (wherein R9 is a monovalent organic group, Q is a 0-dicarbonyl compound, and X is an integer of 1 to 3). In the above formula (9), R9 includes, for example, an alkyl group, an aryl'allyl group, and the like. Examples of the group include a methyl group, an ethyl group, a propyl group, a butyl group, and the like. The alkyl groups having 1 to 5 'carbon atoms may be chain or branched, and a hydrogen atom may be substituted by a fluorine atom or the like. -37- (34) 200401926 Ethylphenyl, chlorophenyl Aryl includes, for example, phenyl, naphthyl, methylphenyl, bromophenyl, and fluorophenyl. Specific alkoxides represented by the above formula (9) include, for example, aluminum butoxide, butanol bis (ethyl acetate) aluminum, tris (ethyl acetate) aluminum, dibutanol diethylacetate aluminum, Aluminum diisopropoxide, ethyl ethyl acetate, aluminum triethanolate, aluminum ethoxylate, aluminum hexafluoropentanediol, aluminum hydroxy-2, 2-methyl-4, aluminum pyran, aluminum triisopropoxide, 9-10 Octaenylacetamidate diisopropyl 2,2, ό, 0-tetramethylaluminum monoalcohol, 2,4-aluminum monopentoxide, aluminum benzyl alcohol 3,5-pentadiol glycol and the like. When the water used in the alcohol hydrolysis of the specific hospital is 1 mol of the hydrolyzable group of the specific alkanol, 0.1 to 2 mol is used, and preferably 0.3 to 1 mol. The hydrolysis and condensation of specific alcohols are usually carried out in organic solvents. Examples of organic solvents that can be used include organic solvents used in the liquid crystal alignment agent of the present invention. The conditions for partial hydrolysis and condensate are ideally 0 to 150, and the reaction time is 30 minutes to 10 hours. The liquid crystal display element obtained using the liquid crystal alignment agent of the present invention can be produced, for example, by the following method. (1) For example, the liquid crystal alignment agent of the present invention is applied to one surface of a substrate provided with a patterned transparent conductive film by a roll coating method, a spin coating method, a printing method, an inkjet method, or the like, and then applied by heating The surface forms a coating film. The coating and heating atmosphere is an atmosphere of an inert gas such as nitrogen, ammonia, and argon, and a reducing gas such as hydrogen may be mixed if necessary. For the substrate, for example, apatite glass, soda lime glass, or the like can be used; polyethylene terephthalate, polybutylene terephthalate, polyether mill, polymethyl methacrylate, polycarbonate -38- (35) (35) 200401926 and other transparent substrates made of plastic. The transparent conductive film provided on one side of the substrate can be a NESA film (registered trademark of the United States PPG Corporation) composed of tin oxide (Sn02), and ITO composed of indium oxide-tin oxide (In2 03-Sn〇2). Film, etc. The pattern of these transparent conductive films can be formed by a photo-etching method, a method using a photomask in advance, and the like. When the liquid crystal alignment agent is applied, in order to further improve the adhesion between the substrate and the transparent conductive film and the coating film, the surface of the substrate may be previously coated with a functional silane-containing compound, a functional titanium-containing compound, or the like. The heating temperature after the application of the liquid crystal alignment agent is preferably a temperature at which the substrate material is not deformed, preferably 20 to 300 ° C, and more preferably 120 to 300 ° C. Examples of heat sources for the heat treatment include a hot-air drying furnace, an infrared heating furnace, and a heating plate. The film thickness of the coating film to be formed is usually 0.001 to lum, preferably 0.005 to 0.5um. (2) For the surface of the formed coating film, a liquid crystal alignment energy is provided by a step of impacting the surface. Specific impact methods used include, for example, ion beams, molecular beams, atomic beams, electron beams, halo discharges, polarized ultraviolet rays, and other irradiation or honing treatments. Among them, radiation is better, and ion beam is better. The acceleration voltage of the ion beam is 50 ~ 500V, the irradiation angle is 0 ~ 90 °, and the irradiation time is preferably 1 second to 2 minutes. It can be adjusted as appropriate by the type of liquid crystal alignment film or the pretilt angle to be imparted. As the ideal ion species, an ion beam of an inert gas such as nitrogen, ammonia, argon, or neon can be used. It is desirable to supply electrons for ion neutralization during or after ion beam irradiation. A method for aligning a liquid crystal with an irradiated surface using an ion beam is disclosed in Japanese Patent Application Laid-Open No. 1 1-2 7 1 773 and the like. However, in the same publication, the method of forming a liquid crystal alignment layer does not use a polymer, but a method of forming a liquid crystal alignment layer using a hydrogenated diamond-39- (36) 200401926-like fe (DLC) covalent bond material gas environment adhesion method. The widely used car coating process. Since the present invention is a liquid, a device for spin-coating a liquid crystal alignment film can be directly used. Liquid crystals which can be used in the ion beam method No. 8-313912, No. 8-3139] and No. 1 1-2 3 7 6 3 8 disclose or soluble polyfluorene imine. As mentioned above, the liquid crystal system after driving down or after driving for a long time can use polyimide which has no good properties. The method of flat liquid crystal alignment agent No. 6-2223 66 of the present invention or the method of irradiating ultraviolet rays in the flat-opening section, or as a special method, the liquid crystal alignment film can be improved in multiple steps to improve the view of the liquid crystal display element (3). The two substrates of the above-mentioned alignment film are prepared, and one of the base sealants is coated on an appropriate pattern. The cell gap is arranged oppositely, so that the directions are orthogonal or antiparallel, and the patch is hardened. Liquid crystal is injected into the non-aqueous layer by chemical vapor deposition or the like, and conventional liquid crystal alignment coating methods, spin coating methods, and printing methods are not used. Crystal alignment agents are provided in the form of solutions, printing methods, and other conventional applications. Specific examples of the coating agent include Japanese Patent Application Laid-Open No. 3, and 8-3 1 3 9 1 6 male liquid crystal alignment agent. Polyamic acid can be used in the harsh environment of light or heat. Orientation or afterimage characteristics. According to the invention, the conventional field characteristics of polyamic acid or a soluble liquid crystal alignment film are shown in, for example, Japanese Unexamined Patent Publication No. 6-2 8 1 93 7 and Japanese Unexamined Japanese Patent Publication No. 10-96928. . The peripheral part of the liquid crystal panel to which the liquid crystal alignment ability is given is formed, and the two substrates of thermosetting property are passed through the gap (the liquid crystal alignment film of the liquid crystal alignment film is combined with the two substrates, and then the surface of the sealing substrate and the sealant are distinguished by heating. Between -40- (37) (37) 200401926, the liquid crystal element is formed by sealing and filling holes. From the bonding of two substrates to the liquid crystal injection step, the liquid crystal drop method, that is, ODF (One Drop Fill) method can be used. Coating As described above, the liquid crystal alignment film is coated on one side of the substrate to which the liquid crystal alignment ability is given, with a UV curable sealant applied in an appropriate pattern, the liquid crystal is dripped where necessary, and then bonded to other substrates, and the sealant is irradiated with ultraviolet rays. Hardening. Irradiation of ultraviolet rays is not limited to full exposure, and appropriate methods such as mask exposure and scanning exposure can be used. The polarizing plate is attached to the outer surface of the liquid crystal element, that is, the other * surface side of each substrate constituting the liquid crystal element. The polarization direction is the same as or orthogonal to the liquid crystal alignment direction of the liquid crystal alignment film formed on one surface of the substrate, and a liquid crystal display element can be obtained. Liquid crystals and layered liquid crystals, of which nematic liquid crystals are preferred, such as Schiff test liquid crystals, azo oxide liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, and terphenyl liquid crystals. , Biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, disilaxane-based liquid crystals, bicyclooctane-based liquid crystals, CUB ANE-based liquid crystals, etc. These liquid crystals can be added with, for example, cholesteryl chloride, cholesteryl nonanoic acid Cholesteric liquid crystals such as esters, cholesteric carbonates, etc., or palmars sold under the trade names "C-15" and "CB-15" (Merck), etc. Furthermore, a pair of sunflowers can also be used. Strongly dielectric liquid crystals such as oxybenzylidene-p-amino-methyl cinnamate, etc., and a polarizing plate attached to the outer surface of the liquid crystal element, for example, a state where the polyvinyl alcohol is stretched and aligned In the following, a cellulose acetate protective film is used to hold -41-(38) (38) 200401926, which is a polarizing film called a holmium film, or a polarizing plate made of a holmium film, etc. in the following examples. Examples specifically illustrate the present invention, but the present invention is not limited thereto. Synthesis Example 1 After dissolving 106.4 g of silane in 298 g of propylene glycol monopropyl ether, the solution was stirred with a carbonless brush motor to stabilize the solution temperature at 60 ° C. Then, 50 g of ion-exchanged water dissolved in 2.1 g of maleic acid was added to the solution in 1 hour. Inside the solution. Then, after reacting at 60 ° C for 4 hours, the reaction solution was cooled to room temperature. 90g of the solution containing methanol in the reaction solution was removed by evaporation at 5 ° C, then 643 g of propylene glycol monopropyl ether was added, and the pore size was 0.2. Filter by #m of membrane filter to obtain liquid crystal alignment agent (A). Synthesis Example 2 A 4-necked flask equipped with a thermometer, a cooling pipe, a dropping funnel, and a stirring device with a content of 3 L was replaced with argon gas. 1 L of dry tetrahydrofuran and 60 g of magnesium metal were charged, and then bubbles were generated with argon gas. 1,000 mL (1.0 mol) of a third butyl magnesium chloride solution in tetrahydrofuran was added, and 170 g of tetrachlorosilane was gradually added from a dropping funnel while stirring at 20 ° C. When 20 g was initially added, the reaction system started to reflux, and the system was colored brown. Then slowly drip the remaining tetrachlorosilane mixture 'so that the system -42- (39) (39) 200401926 can be continuously refluxed without heating. The dark brown reaction mixture obtained in this step (1) was added to a solution of 100 g of LiAlH4 suspended in 300 mL of tetrahydrofuran and reacted at room temperature for 5 hours. Then, the reaction mixture in this step (2) was poured into 15 L of ice water to precipitate a polymer. The resulting polymer was thoroughly washed with water and dried under vacuum to obtain 70 g of a brown solid polymer. The GPC polystyrene equivalent weight average molecular weight of this polymer was 23,000, and the degree of dispersion (weight average molecular weight / number average molecular weight) representing the molecular weight distribution was 3.5. This polymer was dissolved in toluene and filtered through a membrane filter with a pore size of 0.2 // m to obtain a liquid crystal alignment agent (B) at a concentration of 6 wt%. Synthesis Example 3

In a separable flask equipped with a thermometer and a cooling tube, 8484 parts by weight of titanium tetraisopropoxide was added under a stream of nitrogen, and then a mixed solution of 29 parts by weight of water and 1,0 8 by weight of ethyl lactate was added dropwise to 8 Stir at 5 ° C. After 1 hour, 200 parts by weight of ethyl acetone was added, and after stirring at room temperature for 30 minutes, it was filtered through a membrane filter with a pore size of 0.2 // m to obtain a liquid crystal alignment agent (C Synthesis Example 4 mixed with diisopropanol ethyl acetate ethyl acetate). 75% by weight of isopropyl alcohol solution of aluminum ester 3 6 5 parts by weight and 11.8 parts by weight of propylene glycol monopropyl ether. With stirring, this solution was dripped with water 2 7 parts by weight and propylene glycol monopropylene at room temperature for 1 hour. Ether 5 1 0 parts by weight of the mixed solution. After heating and stirring at 6 ° C, it was filtered through a membrane filter with a pore size of 0 · 2 // m to obtain a liquid crystal alignment agent (〇-43- (40) (40) 200401926 Synthesis Example 5 After adding 0.88 parts by weight of tungsten ethoxide and 6,000 parts by weight of ethyl lactate into a flask, a mixed solution of 108 parts by weight of water and 2,400 parts by weight of ethyl lactate was added dropwise at 60 ° C. Heat and stir. After 6 hours, filter through a membrane filter with a pore size of 0.2 // m to obtain a liquid crystal alignment agent (E). Synthesis Example 6 After adding 3 1 8 parts by weight of ethanol niobium and 4,600 parts by weight of ethyl lactate to the flask 4 5 parts by weight of water was dropped, and heated and stirred at 60 ° C. After 2 hours, a membrane filter with a pore diameter of 0.2 // m Filtration was performed to obtain a liquid crystal alignment agent (f Synthesis Example 7) After adding 406 parts by weight of ethanol and 4,000 parts by weight of ethyl lactate to a flask, 45 parts by weight of water was added dropwise, and the mixture was heated and stirred at 60 ° C. After 2 hours, the pore diameter Filter through a membrane filter of 0 · 2 // m to obtain a liquid crystal alignment agent (g Comparative Synthesis Example 1 Pyromellitic dianhydride 218.lg (1.0 mole) and 4,4'-diaminodiphenylmethane 198.27 g (1.0 mol) was dissolved in 1,600 g of N-methyl-2-pyrrolidone, and the solution was reacted at 20 ° C for 6 hours. Then -44- (41) 200401926 The solution was injected into a large amount of excess acetone to 'precipitate the reactants, and separate, wash, and dry the reaction products' to obtain 4 0.3 g of amine acid. This polymer was dissolved in 7-butyrolactone, with a pore size of // m Membrane filter to obtain a solid content? Liquid crystal agent (Η) with a degree of 4%. Comparative Synthesis Example 2 1, 3, 3 a, 4, 5, 9b —Hexahydro 8 —Methyl 5 (Four 2 , 5-dioxo-3-furanyl) -naphthalene [1,2-c] monofuran-3-dione 314.30 g (1.0 mole), p-phenylenediamine 91.88 g (mol), I— (3,5 -Diaminophenyl fluorenyloxy) -4- (4-methylphenylfluorenyloxy) -cyclohexane 63.36 g (0.1515 mol) dissolved-methyl-2-pyrrolidone 1,900 g The solution was reacted at 20 ° C for 1 hour, and then the prepared reaction solution was poured into a large amount of excess acetone to precipitate the reaction product. 30.0 g of the prepared reaction product was dissolved in 270 g of r lactone, 20 g of pyridine and 45 g of acetic anhydride were added, and the mixture was closed in water at 80 ° C for 4 hours. Then, the reaction product was separated, washed, and 28.3 g of a soluble polyfluorene imine polymer was obtained. This polymer was dissolved in butyrolactone and filtered through a membrane filter having a pore size of 0.2 // m to obtain a liquid crystal alignment agent (I) having a concentration of 4%. [Liquid crystal alignment] Observe the liquid crystal display element with a microscope by examining the presence or absence of abnormal regions in the crystal cell at voltages of 0N and 0 FF. When there are no abnormal regions, it is judged as "good formation of polyfluorene 0.2, aligned hydrogen -1, 0.85 trifluoride at N" i 26, and dried the yoke to the solid liquid -45- (42) (42) 200401926 After making the liquid crystal display element, the following light was irradiated, and then observed after heat treatment. [The afterimage of the liquid crystal display element Elimination time] 30 Hz rectangular wave of 3.0 Hz with DC 3.0 V and AC 6.0 V (peak-to-peak) overlapped, and applied to the liquid crystal display element at an ambient temperature of 70 ° C for 20 hours to drive the liquid crystal display element Then, the voltage was turned off, and the time until afterimage elimination was measured visually. [Voltage retention rate of the liquid crystal display element] A voltage of 5V was added to the liquid crystal display element 60 microseconds in addition to time 'with a span of 1 67 milliseconds ( After the span is applied, the voltage retention rate after the applied voltage is released to 1 67 milliseconds is measured. The measurement device is performed at 60 ° C using VHR-1 manufactured by Toyo Technology Co., Ltd. After producing a liquid crystal display element, the following is described below. After light irradiation, observe after heat treatment. [Light irradiation] After making the liquid crystal display element, use a metal halide lamp as the light source to irradiate the element surface. Use a filter to irradiate a wavelength of 300 to 450 nm Range, irradiation energy is 2J / cm2. [Heat treatment] After placing the manufactured liquid crystal display element in an oven at 1000 ° C for 3 weeks, take it out and slowly cool it to room temperature. _ 46-(43) (43) 200401926 Example 1 A liquid crystal alignment agent was applied on a transparent electrode surface of a glass substrate containing a transparent electrode composed of an IT0 film by a spin coating method, and dried on a hot plate at 300 ° C for 30 minutes to form a dry average film. A coating film having a thickness of 7 0 A. The coating film was irradiated with an acceleration voltage of 200V from an argon ion beam at a direction of 40 ° from the substrate for 10 seconds. An epoxy resin containing alumina balls having a diameter of 5.5 // m The resin adhesive is screen-printed and coated on the outer edges of a pair of liquid crystal holding substrates having a liquid crystal alignment film after the ion beam treatment, and the liquid crystal alignment film surfaces of the pair of liquid crystal holding substrates are opposite to each other, and the ion beam irradiation direction In an orthogonal state, heavy Then, the adhesive is hardened. Then, a pair of substrates are filled with a nematic liquid crystal (Merck Corporation, MLC-6221) through a liquid crystal injection port, and then the liquid crystal injection port is closed with an acrylic light-curing adhesive, so that In a state where the polarizing direction of the polarizing plate is consistent with the ion beam irradiation direction of the liquid crystal alignment film of each substrate, the polarizing plates are attached to the two outer surfaces of the substrate to produce a liquid crystal display element. Observe the liquid crystal alignment of the liquid crystal display element prepared as described above, The voltage holding ratio was measured. Using the liquid crystal alignment agent (A), three liquid crystal display elements prepared as described above were prepared, one of which was observed for liquid crystal alignment and measured voltage retention after light irradiation, and the other was subjected to heat treatment to observe liquid crystal alignment and measured. The voltage holding rate, the remaining one was measured by the method described above. The results are shown in Table 1. -47- (44) (44) 200401926 Examples 2 to 7 According to the place shown in Table 1, the liquid crystal alignment agent obtained in Synthesis Examples 2 to 7 was used to perform the same alignment treatment as in Example 1, and was the same as in Example 1. Production of a liquid crystal display device. Each of the prepared liquid crystal display elements was evaluated as shown in Example 1 ', and the alignment of the liquid crystal, the voltage holding ratio, and the time for removing afterimages were evaluated. The results are shown in Table 1. Comparative Example 1 The liquid crystal alignment agent (Η) obtained in Comparative Synthesis Example 1 was coated on a transparent electrode surface of a glass substrate containing a transparent electrode composed of an ITO film by a spin coating method, and a heating plate at 200 ° C Heating and drying for 20 minutes to form a coating film with a dry average film thickness of 600A. This coating film was subjected to a rubbing machine with a rubbing machine using a roller wound with a cloth made of rayon, with a drum rotating speed of 500 rpm, a platform moving speed of 1 cm / sec, and a close hair length of 0.4 mm. Next, an epoxy resin adhesive containing alumina balls with a diameter of 5.5 [m] / m is screen-printed and coated on each outer edge of the liquid crystal holding substrate of a pair of friction-treated liquid crystal holding substrates, and a pair of The surface of the liquid crystal alignment film of the liquid crystal holding substrate is opposite to each other, and the rubbing direction is orthogonal, and the adhesive is hardened after being overlapped and pressed. Subsequently, the liquid crystal injection port is used to fill a pair of substrates with a nematic liquid crystal (Merck 6221, manufactured by Merck), and then the liquid crystal injection port is closed with an epoxy-based adhesive so that the polarization direction of the polarizing plate and the substrates are aligned. Liquid crystal -48- (45) (45) 200401926 The state of the rubbing direction of the alignment film is the same. 'Polarizing plates are bonded to both outer surfaces of the substrate to produce the liquid crystal display element of the present invention. The liquid crystal alignment property of the obtained liquid crystal display device was evaluated for its voltage retention rate and the time for eliminating afterimages. The results are shown in Table 1. Comparative Example 2 The liquid crystal alignment agent (I) obtained in Comparative Synthesis Example 2 was applied to a transparent electrode surface of a glass substrate containing a transparent electrode made of an ITO film by a spin coating method, and a heating plate at 180 ° C Heating and drying for 20 minutes to form a coating film with a dry average film thickness of 700 A. Next, alignment processing was performed in the same manner as in Comparative Example 1 to produce a liquid crystal display element. The liquid crystal alignment property of the obtained liquid crystal display device was evaluated in the same manner as in Example 1 and the voltage retention rate and the time for removing afterimages were evaluated. The results are shown in Table 1. -49- (46) (46) 200401926 Table 1 Example Comparative Example Liquid crystal alignment voltage retention ratio (%) Afterimage removal time (min) Immediately after light irradiation and heat treatment after fabrication Immediately after light irradiation and heat treatment after fabrication 1 Good good good 97 97 96 3 2 good good good 98 98 97 3 solid 3 good good good 97 97 95 5 application 4 good good good 97 97 95 4 case 5 good good good 97 97 95 6 6 good good good 97 97 95 5 7 Good Good Good 97 97 95 6 Comparative Real 1 Good Good No Alignment 83 80 76 30 or more Example 2 Good Slightly Good 97 95 91 10 [Inventive Effect] According to the present invention, the liquid crystal alignment using organic and inorganic composite materials is used Agent, and the ion beam irradiation impact method is used to form the liquid crystal alignment layer, which can produce liquid crystal alignment, voltage retention, and afterimage characteristics even after being exposed to the harsh environment of light irradiation or heat treatment, or after long-term driving. Liquid crystal display elements with significantly improved materials in the past. The liquid crystal alignment agent can form a liquid crystal alignment layer with good afterimage characteristics with less reduction. The liquid crystal display element produced by using the liquid crystal alignment agent obtained in accordance with the method of the present invention is applicable to TN-type and S TN-type liquid crystal display elements. In addition, -50- (47) (47) 200401926 can be selected, and the liquid crystal used can also be applied. For SH (Super Homeotropic) type, IPS (In — Plane Switching) type, ferroelectric and anti-ferroelectric liquid crystal display elements, etc. A liquid crystal display element having an alignment film formed using the liquid crystal alignment agent of the present invention has excellent alignment and reliability of liquid crystal, and can be used in various devices, such as a desktop computer, a watch, a clock, a number display board, a word processor, a personal Display devices for computers, LCD projectors, LCD TVs, electronic paper, etc.

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Claims (1)

(1) (1) 200401926 Scope of patent application 1. A liquid crystal alignment agent, which is characterized in that a thin film can be manufactured on a substrate through a coating step, and a thin film made of an organic-inorganic composite material is produced. 2. The liquid crystal alignment agent according to item 1 of the patent application scope, which contains a liquid crystal alignment agent selected from the group consisting of the following formulae (1) -OR. (1) (R is alkyl, aryl, aralkyl, or aryloxyalkyl ) Shows a partial hydrolysis / condensation of at least one compound in the group of tungsten compounds, molybdenum compounds, niobium compounds, and macro compounds having a φ machine base. 3. The liquid crystal alignment agent 'as claimed in item 1 of the scope of patent application, which contains a liquid crystal alignment agent selected from the following formula (5) RiaSi (OR2) [a (5) (where R1 is a hydrogen atom, a fluorine atom, or a monovalent organic Group, R2 is a monovalent organic group, a is an integer of 0 to 2) and the following formula (6) R3b (R40) 3-bSi- (R7) d-Si (OR5) 3-〇R6c (6) · (R3, R4, R5, and R6 are monovalent organic groups that may be the same or different; b and c are integers of 0 to 2 that may be the same or different; r7 is an oxygen atom or — (CH2) n—, d Is 0 or 1, and η is an integer of 1 to 6) Partially hydrolyzed 7 condensate of at least one compound grouped by the compound shown. 4 · If the liquid crystal alignment agent of item 1 of the scope of the patent application, it contains the following formula (7) SiHxR8y (7) -52- (2) (2) 200401926 (where R8 is a monovalent organic group, X is 0.01 to 3, and y is 0.01 to 3, but x + yg is a silicon polymer having a weight average molecular weight of at least 2,000 as shown in 4). 5. The liquid crystal alignment agent 'according to item 1 of the patent application scope, which contains polytitanoxane and polytitanoxane modified with other organic compounds or one of them. 6. The liquid crystal alignment agent according to item 1 of the patent application scope, which contains the following formula (9) A1 (OR9) xQ3-x (9) · (where R9 is a monovalent organic group, Q is / 3- Dicarbonyl compound, X is an integer of 1 to 3) Partial hydrolysis / condensation of the compound. 7. A method for forming a liquid crystal alignment film 'is characterized in that the liquid crystal alignment agent in the first patent application range is coated on a substrate to form a film' and impacts the surface of the obtained film. 8 · The method according to item 7 of the patent application scope, which irradiates the film with an ion beam and impacts the surface of the film. -53- 200401926 Lu, (1), the designated representative of this case is: None (II), the component representative symbols of this representative map are simply explained: Μ 柒 If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: sister -4-