TW200835984A - Liquid crystal aligning agent and liquid crystal display element - Google Patents

Abstract

Disclosed is a liquid crystal aligning agent comprising a polymerized product produced by hydrolyzing a silicon compound represented by the formula (1) alone or a combination of the silicon compound represented by the formula (1) and a silicon compound represented by the formula (2), and condensing the hydrolysis product, wherein the silicon compound represented by the formula (2) is contained in the combination in an amount of 0.5 mole or less per mole of the total amount of the silicon compound represented by the formula (1) and the silicon compound represented by the formula (2). Si(OR1)4 (1) [wherein R1 represents an alkyl group.] Rsi(OR2)3 (2) [wherein R represents a methyl or ethyl group; and R2 represents an alkyl group.] The liquid crystal aligning agent has excellent storage stability and a vertical alignment property and is reduced in the decrease of a voltage holding ratio caused by light or heat.

Description

200835984 IX. Description of the Invention [Technical Field of the Invention] The present invention relates to a liquid crystal alignment agent and a liquid crystal display element. More specifically, it is characterized in that the liquid crystal alignment property is good, and the electrical characteristics such as the voltage holding ratio are not impaired under a severe environment such as light irradiation or high temperature or after long-time driving, and a good liquid crystal alignment state is maintained. A liquid crystal alignment agent and a liquid crystal display element of a liquid crystal alignment film which is less likely to cause an afterimage. [Prior Art] Conventionally, a liquid crystal display element is formed by forming a liquid crystal alignment film made of polyamic acid, polyimine or the like on a surface of a substrate provided with a transparent conductive film as a substrate for a liquid crystal display element, and The wafers are disposed face to face and form a nematic liquid crystal layer having dielectric anisotropy as a sandwich structure cell in the gap, and the long axis of the liquid crystal molecules is continuously twisted by 90 degrees from one substrate to the other substrate. That is, a TN type liquid crystal display element having a TN type (Twisted Nematic) liquid crystal cell. In addition, an STN type (Super Twisted Nematic) liquid crystal display element which is higher in contrast than a TN type liquid crystal display element, or an IPS having a small viewing angle dependency (plane switching, In -Plane Switching type liquid crystal display element, VA (Vertical Allignment) type liquid crystal display element. The principle of operation of the above various liquid crystal display elements is roughly classified into a transmissive type and a reflective type. When the transmissive liquid crystal display element is driven by the element, the light intensity change of the light source for the backlight from the back side of the component -5-200835984 is applied. The reflective liquid crystal display element does not use the backlight ', and when the element is moved, the reflected light intensity change from the outside light such as sunlight is used. Compared with the transmissive type, since the power consumption is small, it is advantageous to recognize it. Used outside the house. The liquid crystal alignment film of the transmissive liquid crystal display element exposes light from the backlight source for a long time. In particular, it is used for a liquid crystal projector which is used for commercial use in recent years, and which requires an increase in the intensity of a liquid crystal projector such as a metal lamp. The reflective liquid crystal display element is highly likely to be used outside, and in this case, it contains a strong ultraviolet light and becomes a light source. In the principle of reflection, the light passes through the distance in the element. In the manufacturing steps of the liquid crystal display device, in terms of shortening the process and the rate of extraction, the liquid crystal dropping method, that is, the ODF I Drop Fill method is first used. The ODF method is different from the conventional method in which a liquid crystal is injected into an assembled liquid crystal cell by using a thermosetting dense resin in advance, and a liquid crystal sealing agent is applied to a necessary portion of a substrate coated with a liquid crystal alignment film to form a liquid crystal. After dropping the necessary portion and the other substrate, the entire surface of the substrate is irradiated with ultraviolet light to cure the sealing agent to form a liquid crystal cell. The ultraviolet light to be irradiated is generally one or more square centimeters of Joule or more. In the manufacturing step of the liquid crystal display element, the liquid crystal alignment film and the liquid are exposed to the intense ultraviolet light. The transmissive liquid crystal display element should be considered to have a temperature rise of the liquid crystal display element itself when driven by strong light. In addition, the liquid-driven display is specially designed as a halogen in the house, and the sunlight is better than the one-sealing agent. Yi Jingyi, Yu Jingxian-6 - 200835984 shows that the components are versatile, and both the transmissive and reflective types must be considered for use outside the house or in a self-use car that is parked, usually at a temperature higher than room temperature. Use and set up the environment. In such a liquid crystal display device, it is required to be highly functional and versatile, and it is required to be electrically exposed to liquid crystal alignment, voltage retention, etc. after being exposed to a harsh environment such as light or heat or after a long time of driving. Features, or afterimage characteristics are superior to the past. A material of a liquid crystal alignment film constituting a liquid crystal display element has been conventionally known as a resin such as polyimine, polyamine or polyester. In particular, polyimine is an organic resin which exhibits excellent physical properties such as heat resistance, affinity with liquid crystals, mechanical strength, and the like, and is used in many liquid crystal display elements. However, in recent years, liquid crystal display elements tend to be highly functional and versatile, such as the above-mentioned harsh environments such as high temperature environments or light irradiation, and increased opportunities for use, and further require shortening of processes and improvement of yield in manufacturing steps. On the other hand, liquid crystal display elements are also required to have a longer life. With the above-mentioned requirements, it is not allowed to display defects or afterimages due to insufficient resistance to high-temperature environments or light radiation within the past allowable range. However, an organic resin such as polyacrylamide or polyimine which has been widely used as a liquid crystal alignment film in the past is still insufficient in light or heat resistance. Therefore, there is a need for a novel material which is capable of uniformly aligning the liquid crystal in the plane of the liquid crystal display element and which is resistant to light or heat. Japanese Laid-Open Patent Publication No. Hei 9-28-150 discloses three alkoxy groups by using a ruthenium compound (A) having four alkoxy groups such as tetraethoxydecane and octadecyltriethoxydecane. The compound (B) is heated in an alcohol solvent in the presence of an oxalic acid catalyst at 50 to 180 ° C to form a copolycondensate polyoxane solution of (A) and (B). This solution was applied as a coating liquid to the surface of the electrode substrate, and the obtained coating film was thermally hardened at 80 to 400 ° C to obtain a vertical alignment film. This publication further demonstrates that the vertical alignment film is excellent in vertical alignment property, reproducibility, heat resistance and uniformity, and is excellent in stability as a coating liquid. However, the vertical alignment film or the method of forming the same is still insufficient. The vertical alignment agent described in the above-mentioned Japanese Laid-Open Patent Publication No. Hei No. 9-2881 is insufficient in printability. Used in manufacturing has its problems. Moreover, the vertical alignment regulation force is insufficient, which is a cause of display failure. Further, Japanese Laid-Open Patent Publication No. 2005-250244 discloses a compound of the following formula (1) and two compounds of the following formula (2), and a total of three components can form a vertical alignment film. However, as a result of repeated review, the inventors of the present invention can present a vertical alignment only by the compound of the formula (1) or the compound of the formula (1) and one compound of the formula (2) in a total of two components. The performance is as good as the previous products, and it shows superior voltage retention and printability. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid crystal alignment agent which is excellent in printability and which can form a liquid crystal alignment film which is superior in vertical alignment property, excellent in voltage retention characteristics, and excellent afterimage characteristics. . Another object of the present invention is to provide a liquid crystal alignment film having the above-described properties and a liquid -8-200835984 crystal display element comprising the liquid crystal alignment film using the liquid crystal alignment agent of the present invention. Still another object and advantages of the present invention will be apparent from the following description. The above objects and advantages of the present invention are attained by the present invention, which is achieved by a liquid crystal alignment agent characterized in that it contains only A polymer obtained by hydrolysis and condensation of a hydrazine compound represented by the following formula (1):

Si(OR1)4 (1) Here, 'R1 is a hospital base' or only the sand compound described in the above formula (1) and the sand compound described in the following formula (2), and The sand compound of the formula (1) is hydrolyzed in combination with the total amount of the sand compound described in the above formula (2), 1 mol, of the sand compound described in the above formula (2), in a combination of 0.5 mol or less. Condensed polymer: RSi(OR2)3 (2) Here, R is a methyl group or an ethyl group, and R2 is an alkyl group. According to the present invention, the above objects and advantages of the present invention are attained by a liquid crystal display element characterized by comprising a liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention. Moreover, it is preferable that the liquid crystal alignment agent contains at least one of organic solvents represented by the following formulas (ί), (II) and (III) as a solvent (I) 200835984 ch3 r2 -/"C-ch2o In (I), Ri is a hydrogen atom 'methyl, ethyl or ethyl fluorenyl group, r 2 is an alkyl group having 1 to 4 carbon atoms, and η is an integer of 1 to 3;

Ch2—ch2o tR4 (II) In the formula (II), R 3 is a hydrogen atom, a methyl group, an ethyl group or an ethyl fluorenyl group, r 4 is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 1 to 3;

II H3C—C—0—R5 (I jn In the formula (III), R 5 is an alkyl group having 2 to 5 carbon atoms. [Embodiment] The best mode for carrying out the invention [Liquid crystal alignment agent] The liquid crystal alignment agent of the invention A hydrolyzed condensate of a silica alkoxide containing one of the above formula (1) or a total of two components of the above formula (1) and the above formula (2). The hydrolysis condensate is one or two of the above. A copolymer obtained by reacting an alkoxide in the presence of water. -10- 200835984 In the formula (1), the alkyl group of R1 may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group or the like. The bases of the numbers 1 to 3 are preferred. The bases may be chain-shaped or branched, and the hydrogen atoms may be substituted by fluorine atoms or the like. The oxime compound of the above formula (1) (1) Specific examples thereof include tetramethoxynonane, tetraethoxydecane, tetra-n-propoxydecane, tetra-isopropoxydecane, tetra-n-butoxydecane, and tetra-butoxybutane. Further, it may be used alone or in combination of two or more kinds. In the formula (2), R is a methyl group or an ethyl group. The alkyl group of R2 may be exemplified by R1. phase The compound wherein R is a methyl group or an ethyl group may specifically be exemplified by methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane, and methyltris-isopropoxy group. Decane, methyltri-n-butoxydecane, methyltri-t-butoxydecane, methyltri-t-butoxydecane, etc. ethyltrimethoxydecane, ethyltriethoxydecane, Ethyl tri-n-propoxy decane, ethyl tri-isopropoxy decane, ethyl tri-n-butoxy decane, ethyl tri-second butoxy decane, ethyl tri-t-butoxy A decane or the like, wherein methyl methoxy decane, methyl triethoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, etc. are preferred. The hydrazine compound represented by the above formula (1) The oxime compound (hereinafter also referred to as "compound 2") represented by the above formula (2) is also preferably used in the following formula, and the molar ratio shown in the following formula is preferred. If the ratio is too high, it will be a cause of poor alignment. (Compound 2) / [(Compound 1) + (Compound 2)] = 0 to 0.5 (Mohrby) -11 - 200835984 The ear ratio is preferably from 0 to 0.3, and the molar ratio of 0 indicates that Compound 2 is not used, and only Compound 1. The hydrolysis condensate is such that Compound (1) or Compound (1) is compounded with (2), The water is reacted and obtained by hydrolysis and partial condensation. In order to hydrolyze and partially condense the compound (1) or the compound (1) with the compound (2), each 1 mole of alkane is bonded (formula ( 1) The OR1, or the total of the OR2 of the formula (2), is preferably 1.0 to 1.5 ounces of water. If the amount of water is 1.0 or more, the sand and oxygen institute _ The knot is unreacted and the possibility of residue is reduced, and the uniformity of the coating film is not reduced, and the possibility of lowering the storage stability of the liquid crystal alignment agent is small. The water is intermittently or continuously added to the organic solvent in which the compound (1) or the compound (1) and the compound (2) are dissolved. In this case, the reaction catalyst can be used. When a catalyst is used, the catalyst may be added to the organic solvent in advance, or may be dissolved or dispersed in water when water is added. The reaction temperature at this time is preferably from 〇 to 100 ° C, more preferably from 15 to 80 ° C. The compound (1) or the organic solvent in which the compound (1) and the compound (2) are separately hydrolyzed and partially condensed are preferably selected from the group consisting of an alcohol solvent, a ketone solvent, a guanamine solvent, an ester solvent, and an aprotic solvent. At least one of the groups formed. The alcohol solvent may, for example, be methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, third butanol, n-pentanol, isoamyl alcohol or 2-methylbutanol. , second pentanol, third pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, second hexanol, 2-ethylbutanol, second heptanol-12-200835984, Heptanol-3, n-octanol, 2-ethylhexanol, second octanol, n-nonanol, 2,6-dimethylheptanol-4, n-nonanol, second undecyl alcohol, three Methyl sterol, second-tetradecanol, second heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzene a monohydric alcohol solvent such as methanol or diacetone; ethylene glycol, -propylene glycol, 1,3-butanediol, pentanediol-2,4,2-methylpentanediol-2,4, hexanediol-2 , 5, heptanediol-2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and other polyol solvents; ethylene glycol monomethyl ether, B Glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, B Glycol monophenyl ether, ethylene glycol single 2-ethyl butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether , diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl A polyol partial ether solvent such as a group ether. These alcohol solvents may be used alone or in combination of two or more. The ketone solvent may, for example, be acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone or ethyl hydride. Butyl ketone, methyl n-hexyl ketone, di-isobutyl ketone, trimethyl decyl ketone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetone-acetone , acetophenone, fenketone (Fenchone), etc., and acetonitrile, 2,4-hexanedione, 2,4-heptanedion, 3,5-heptanedione, 2,4-octanedione, 3 ,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5 - 13-200835984 methyl 2,4-hexanedione, 2,2,6,6 Base one 3,5-heptanedione, 1,1,1,5,5,5-hexafluoro-2,4-heptanedione, etc. /3 -dione. These oxime solvents may be used singly or in combination of two or more kinds. The guanamine solvent may, for example, be methamine, N-methylformamide, N,N-dimethylformamide, N-ethylformamide, N,N-diethylformamide, B. Indoleamine, N-methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide, N-methylpropionamide, N —Methyl-port ratio succinyl ketone, N-methyl hydrazino 11 lin, N-methyl hydrazino piperidine, N-methylpyridyl pyrrolidine, N-acetyl morpholine, N-acetyl hydrazino Pyridine, N-ethinyl pyrrolidine and the like. These guanamine solvents may be used alone or in combination of two or more. The ester solvent may, for example, be diethyl carbonate, ethyl carbonate, propyl carbonate, diethyl carbonate, methyl acetate, ethyl acetate, monobutyrolactone, r-valerolactone or acetic acid. Ester, isopropyl acetate, n-butyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, second amyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, acetic acid 2-ethyl butyl ester, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-decyl acetate, methyl ethyl acetate, ethyl acetate, ethyl acetate Glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl Ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether Acid ester, dipropylene glycol monoethyl ether acetate, ethylene glycol diacetate, methoxy triethylene glycol acetate, ethyl propionate, propionic acid, n--14-200835984, butyl ester, Isoamyl acid ester, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, benzene Diethyl formate and the like. These ester solvents may be used alone or in combination of two or more. The aprotic solvent may, for example, be acetonitrile, dimethyl hydrazine, n, n, n', n'tetraethyl sulfonamide, trimethylamine hexamethylphosphate, N-methyl morpholinone, N - Methylpyrrolidine, N-ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N,N-dimethylpiped, N-methylimidazole , N-methyl-4-piperidone, N-methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1, 3 — Dimethyltetrahydro-2(1H)-pyrimidinone and the like. Among these, a polyol solvent, a polyol partial ether solvent, and an ester solvent are particularly preferable. In the hydrolysis and partial condensation reaction of the compound (1) or the compound (1) with the compound (2), a catalyst is preferably used. The catalyst may, for example, be a metal chelate compound, an organic acid, an inorganic acid, an organic base or an inorganic alkali ruthenium metal chelate compound as exemplified by titanium triacetate mono(acetylthiopyruvate) or the like. - n-propoxy-mono(ethylmercapto-pyruvate) titanium, tri-isopropoxy-mono(acetyl-pyruvyl) titanium, tri-n-butoxy-mono(acetyl-pyruvyl) titanium, Tri-t-butoxy-mono(ethylmercapto-pyruvate) titanium, di-di-di-butoxy-mono (ethanopropionate), monoethoxy bis(ethylmercaptopyruvate) Titanium, di-n-propoxy-bis(acetylthiopyruvate) titanium, di-isopropoxy bis(acetylthiopyruvate) titanium, di-n-butoxy bis(acetylthiopyruvate) Titanium, di-second butoxy•bis(ethyl-5-200835984 mercaptopyruvate) titanium, di-t-butoxy-bis(ethylmercaptopyruvate) titanium, monoethoxy•parameter Acetylpyruvate) Titanium, mono-n-propoxy-sodium (ethionylpyruvate) titanium, mono-isopropoxy-parax (acetylthiopyruvate) titanium, mono-n-butoxy (acetyl acetylpyruvate) titanium, single - Dibutoxy ginseng (acetylthiopyruvate) titanium, mono-tert-butoxy ginseng (acetyl acetylacetonate) titanium, ruthenium (acetyl acetonate) titanium, triethoxy oxi Ethylacetamidineacetic acid) titanium, tri-n-propoxy group, mono(ethylacetamidineacetic acid) titanium, tris-isopropoxy oxy-mono(ethyl acetonitrile) titanium, tri-n-butoxy (Ethylacetamidineacetic acid) Titanium, Tri-tert-butoxy-mono(ethylacetamidineacetic acid) Titanium, Tri-Tertioxy-Single (Ethylacetate) Titanium, Diethoxy Bis(ethylacetamidineacetic acid) titanium, di-n-propoxy-bis(ethylacetamidineacetic acid) titanium, di-isopropoxy bis(ethylacetamidineacetic acid) titanium, di-n-butoxy • Bis(ethylacetamidineacetic acid) titanium, di-t-butoxy•bis(acetylthiopyruvate) titanium, di-t-butoxy-bis(ethylethanoacetic acid) titanium, monoethoxy Base ginseng (ethyl acetoacetate) titanium, mono-n-propoxy ginseng (ethyl acetoacetate) titanium, mono-isopropoxy ginseng (ethyl acetoacetate) titanium, mono-n-butyl Oxygen ginseng (ethyl acetoacetate) titanium, mono-second butoxide Base ginseng (ethyl acetoacetate) titanium, mono-tert-butoxy ginseng (ethyl acetoacetate) titanium, strontium (ethyl acetoacetate) titanium, mono (ethyl phthalic acid) ginseng ( a titanium chelate compound such as ethyl acetoacetate) titanium, bis(ethylmercaptopyruvate) bis(ethyl acetonitrile) titanium, ginseng (acetyl acetonate) mono(ethyl acetonitrile) titanium; 16- 200835984 Triethoxy-mono(ethylmercaptopyruvate) pin, tri-n-propoxy group, mono(ethylmercaptopyruvate), tris-isopropoxy-mono(ethylmercaptopyruvate) Bismuth, tri-n-butoxy-mono(ethylmercaptopyruvate) ruthenium, tri-t-butoxy-mono(ethylmercapto-pyruvate) zirconium, tri-t-butoxy-mono(ethylidene) Pyruvic acid) zirconium, diethoxy bis(acetylthiopyruvate) chromium, di-n-propoxy bis(acetylthiopyruvate) zirconium, di-isopropoxy bis(ethyl fluorenylacetone) Acid) zirconium, di-n-butoxy•bis(ethylmercaptopyruvate) pin, di-t-butoxy•bis(acetylthiopyruvate) zirconium, di-t-butoxy-double (B) Mercaptopyruvate, pin, monoethoxyl Mercaptopyruvate, pin, mono-n-propoxy-glycolate, octa-isopropoxy-p-(acetyl)pyruvate, mono-n-butoxy Acetylpyruvate, pin-single-butoxy-sodium (ethionylpyruvate), mono-t-butoxy-sodium (acetyl-pyruvate), hydrazine Acid, zirconium, triethoxy, mono(ethylacetamidineacetic acid), tri-n-propoxy, mono(ethylacetamidineacetic acid) chromium, tris-isopropoxy, mono(ethylacetamidineacetic acid鍩, tri-n-butoxy•mono(ethylacetamidineacetic acid) zirconium, tri-t-butoxy•mono(ethylacetamidineacetic acid) zirconium, tri-tert-butoxy•mono(ethyl) Ethylacetate) chromium, diethoxy bis(ethylacetamidineacetic acid) chromium, di-n-propoxy bis(ethylacetamidineacetic acid) pin, di-isopropoxy bis (ethyl ethyl) Indoleacetic acid) zirconium, di-n-butoxy bis(ethylacetamidineacetic acid) chromium, di-t-butoxy bis(acetylthiopyruvate) chromium, di-t-butoxy-bis ( Ethylacetamidineacetic acid)zirconium, -17- 200835984 monoethoxyl Ethyl acetoacetate) zirconium, mono-n-propoxy ginsyl (ethyl acetoacetate) chromium, mono-isopropoxy oxy-(ethyl acetoacetate) chromium, mono-n-butoxy (ethyl acetoacetate) chromium, mono-second butoxy ginseng (ethyl acetoacetate) zirconium, mono-tert-butoxy ginseng (ethyl acetoacetate) zirconium, lanthanum (ethyl ethyl Indole acetic acid) zirconium, mono(ethylmercaptopyruvate) ginseng (ethylacetamidineacetic acid) zirconium, bis(ethylmercaptopyruvate) bis(ethylacetamidineacetic acid) pin, ginseng (acetylthiopyruvate) (Ethylacetamidineacetic acid) a zirconium chelate compound such as chromium; an aluminum chelate compound such as aluminum acetylate or ethanoacetic acid; The organic acid may, for example, be acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid or sebacic acid. , gallic acid, butyric acid, mellitic acid, arachidonic acid, schikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, Benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, rich Horse acid, citric acid, tartaric acid, etc. The inorganic acid may, for example, be hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid or the like. The organic base may, for example, be pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine or monomethyldiethanolamine. , triethanolamine, diazabicyclooctane, diazabicyclononane, tetramethylammonium hydroxide, and the like. The inorganic base may, for example, be ammonia, sodium hydroxide, potassium hydroxide, cesium hydroxide -18-200835984, or cesium hydroxide. Among these catalysts, a metal chelate compound, an organic acid or an inorganic acid is preferred, and a metal chelate compound or an organic acid is more preferred. These may be used alone or in combination of two or more. The compound (1) or a combination of the compound (1) and the compound (2) in an amount of 100 parts by weight (in terms of a fully hydrolyzed condensate) is preferably used in an amount of from 0.001 to 10 parts by weight, more preferably 〇. • A range of 001 to 1 part by weight. The liquid crystal alignment agent of the present invention is preferably obtained by hydrolyzing the above-mentioned hydrolyzed or dispersed in an organic solvent. As the organic solvent, organic solvents each represented by the following formulas (I), (11) and (in) can be used.

(II) 0

II H3C—C—Ο—R5 (III) In the formula (I), Ri is a hydrogen atom, a methyl group, an ethyl group or an acetate group. 'R 2 is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 3. In the formula (11), R3 is a hydrogen atom, a methyl group, an ethyl group or an ethyl fluorenyl group, and R4 is a C1-C4-19-200835984 alkyl group, and m is an integer of 1 to 3. In the formula (ΠΙ), R5 is a hospital base having a carbon number of 2 to 5. Specific examples of the organic solvent represented by the formula (I) are preferably 1-ethoxy-i-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and propylene glycol monoacetate. , dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol dimethyl ether and the like. Among these, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether are preferred. Specific examples of the organic solvent represented by the formula (II) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether (butyl cellosolve). Agent), ethylene glycol monopentyl ether, ethylene glycol monohexyl ether, diethylene glycol, monopropyl ether, ethylene glycol monopropyl ether, methyl cellosolve acetate, ethyl cellosolve B Acid ester, propyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, and the like. Among these, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), and ethylene glycol monopentyl ether are preferred. Specific examples of the organic solvent represented by the formula (111) include, for example, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, and acetic acid. Amyl ester, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate Ester, amyl acetate, isoamyl acetate, and the like. Among these, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, and second amyl acetate are preferred. -20- 200835984 In the liquid crystal alignment agent obtained by the present invention, a component such as an surfactant may be added. The surfactant may, for example, be a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant or the like. Further, examples thereof include a polyoxynoxy surfactant, a polyoxyalkylene surfactant, a fluorine-containing surfactant, and the like. The liquid crystal alignment agent of the present invention may further contain a compound containing a functional decane or a compound containing an epoxy group in order to improve the adhesion to the surface of the substrate. The functional decane-containing compound may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane or 2-aminopropylpropane. Triethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethyl Oxaloxane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxyl Carbonyl 3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethyl Oxonium-alkyl-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6- Diazepine acetate, 9-triethoxydecyl-1,6-dimercaptoacetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzoic acid 3-A-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxyfluorene , N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyethyl)-3-aminopropyltrimethoxydecane, N-bis(oxyethyl)-3 - Aminopropylmethyltriethoxydecane, and the like. The compound containing an epoxy-21 - 200835984 group is preferably exemplified by ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol condensate Glyceryl ether, 1,3,5,6-tetraglycidyl- 2,4-hexanediol, N,N,N',N'-tetraglycidyl-mono-tolyldiamine, 1,3 —Bis (N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like. When the ratio of the polymer to the solvent of the reaction product in the liquid crystal alignment agent of the present invention is selected in consideration of viscosity, volatility, etc., the ratio of the polymer in the liquid crystal alignment agent (solid content concentration) is to be polymerized. The ratio of the ruthenium atom contained in the substance to the SiO 2 concentration in terms of SiO 2 is preferably from 0.01 to 70% by weight, more preferably from 5% to 60% by weight, most preferably from 1 to 30% by weight. The liquid crystal alignment agent of the present invention is preferably applied to the surface of a substrate by, for example, a roll coating method, a spin coating method, a printing method, or the like, and then dried by heating to form a coating film as a liquid crystal alignment film. When the solid content concentration is less than 0.01% by weight, the film thickness of the coating film is too small, and a good liquid crystal alignment film cannot be obtained. When the solid content concentration exceeds 70% by weight, the film thickness of the coating film is too thick, and 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 property is deteriorated. Using the liquid crystal alignment agent of the present invention, a liquid crystal display element can be produced, for example, according to the method described below. (1) coating one surface of a substrate provided with a patterned transparent conductive film, -22-200835984, for example, coating a liquid crystal alignment agent of the present invention by a roll coating method, a spin coating method, a printing method, an inkjet method, or the like Then, the coated surface is heated to form a coating film. The atmosphere in the coating and heating steps can be carried out in an inert gas such as nitrogen, ammonia or argon, and if necessary, in an atmosphere in which a reducing gas such as hydrogen is mixed. Here, the substrate may use, for example, glass such as float glass or soda glass; from polyethylene terephthalate, polybutylene terephthalate, polyether mill, polymethyl methacrylate, A transparent substrate made of plastic such as polycarbonate. The transparent conductive film provided on one surface of the substrate may be a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO 2 ), an ITO film made of indium oxide-tin oxide (In203-SnO 2 ), or the like. The patterning of the transparent conductive film can be performed by a photolithography method and a method of using a photomask in advance. When the liquid crystal alignment agent is applied, in order to improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, a compound containing a functional decane or a functional epoxy group may be applied to the surface of the substrate in advance. Compounds and the like. The heating temperature after the application of the liquid crystal alignment agent is such that the substrate material does not undergo deformation temperature, preferably 20 to 300 ° C, more preferably 120 to 300 ° C. The heat source for the heat treatment may, for example, be a hot air drying furnace, an infrared heating furnace, a hot plate or the like. The formed coating film preferably has a film thickness of 0.001 to 1//Π1 and more preferably 0.005 to 0·5 // m. (2) Further, on the surface of the formed coating film, the alignment angle of the liquid crystal can be controlled by rubbing the surface. (3) Two sheets of the substrate on which the liquid crystal alignment film was formed as described above were produced, and a thermosetting sealant was applied to the peripheral portion of one of the substrates in an appropriate pattern. The two substrates are arranged in a relative gap (cell gap) in such a manner that the liquid crystal alignment directions of the respective liquid crystal alignment films are vertical or anti-parallel -23-200835984, respectively, and two sheets are disposed. After the substrate is bonded, heating causes the sealant to harden. The liquid crystal is injected into the cell gap partitioned by the surface of the substrate and the sealant, and the injection hole is encapsulated to constitute a liquid crystal cell. The liquid crystal injection step after bonding the two substrates may also be carried out by a liquid crystal dropping method, that is, an ODF (One Drop Fill) method. The liquid crystal alignment film is applied to the single-sided substrate which imparts the liquid crystal alignment energy as described above, and the ultraviolet curable sealant is applied in an appropriate pattern, and the liquid crystal is dropped into the necessary portion, and then bonded to the other surface substrate, and irradiated with ultraviolet light. The sealant hardens. Ultraviolet light exposure is not limited to full exposure, and mask exposure, scanning exposure, and the like can be used. Then, the polarizing plate is bonded to the outer surface of the liquid crystal cell, that is, the other surface of each of the substrates constituting the unit cell, and the bonding mode is such that the polarizing direction and the liquid crystal alignment direction of the liquid crystal image film formed on one surface of the substrate are aligned. Consistent or vertical, the liquid crystal display element is obtained. The liquid crystal may, for example, be a nematic liquid crystal or a smectic liquid crystal, and it is preferable to use a Schiff-base liquid crystal or an azoxy. Liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terephenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxin liquid crystal, double ring sheep Department of liquid crystal, cube house (cubane), liquid crystal, etc. Clarified liquid crystals such as chlorinated cholesterol, cholesterol citrate, and cholesterol carbonate may be added to the liquid crystals or sold under the trade name "C-1 5" and "CB-15" (manufactured by Merck). Chiral agent is used. Further, it is also possible to use p-Desiloxybenzylidene-p-amino-2-methylbutyl cynnamate or the like, such as p-Desiloxybenzylidene-p-amino-2-methylbutyl cynnamate. Dielectric liquid crystal. The polarizing plate which is bonded to the outer surface of the liquid crystal cell may be, for example, a polarizing plate formed by a polarizing film called a ruthenium film which is coated with a cellulose acetate protective film while absorbing the polyvinyl alcohol. Or a polarizing plate made of a film. EXAMPLES Hereinafter, the present invention will be more specifically illustrated by the examples, but the present invention is not limited to the examples. Synthesis Example 1 (TMOS only) In a three-necked flask having a cooling tube and having a capacity of 1 and 〇〇〇ml, 52.22 g of tetramethoxydecane and 44 8.5 8 g of 1-ethoxy-2-propanol were added. Stir at 60 ° C with heating. The aqueous maleic anhydride solution of maleic anhydride 2·5 4 7 g and water 1 0 8 · 12 g prepared in a flask having a capacity of 100 ml was added thereto, and the mixture was further heated and stirred at 60 ° C for 4 hours. A part of the solvent was distilled off from the obtained polymerization solution to obtain a raw material polymer solution weight of 356 g. Further, 1,146 g of butyl acetate was added to obtain an alignment agent coating liquid S-1 of 4% by weight of a solid content. Synthesis Example 2 (TMOS/MTMS (Morby ratio) = 90/10) In a three-necked flask equipped with a cooling tube and having a capacity of 1, 〇〇〇ml, tetramethoxy decane 1 52.22 g, methyltrimethoxy was added. The decane i5.136g and 1-25-200835984-ethoxy-2-propanol 5 08.04g were heated and stirred at 60 °C. An aqueous maleic anhydride solution prepared by adding maleic anhydride 2 prepared in a flask having a capacity of 200 mm to water and 1 1 7.1 2 g of water was further heated at 60 ° C for 4 hours. The weight of the original solution obtained by distilling off part of the solvent from the obtained polymerization solution was 3 9 8 g. Further, 1,291 g of butyl acetate was added to obtain an agent coating liquid S-2 of 4% by weight. Comparative Synthesis Example 1 (TMOS/MTMS (Morby ratio) = 10/90) In a three-necked flask equipped with a cooling tube and having a capacity of 1, 〇〇〇ml, tetramethoxydecane 1 5.222 g, methyltrimethoxy Base decane 1 22.598 g - ethoxy-2-propanol 526.3 40 g, heated and stirred at 60 ° C. An aqueous maleic anhydride solution prepared by adding maleic anhydride 1· and water 8 3.7 9 3 g in a flask having a capacity of 200 ml was further heated at 60 ° C for 4 hours. A part of the solvent was distilled off from the obtained polymerization solution to obtain a weight of the original solution of 375 g. Further, 1,2 8 5 g of butyl acetate was added to obtain an agent coating liquid R-1 having a concentration of 4% by weight. Comparative Synthesis Example 2 After dissolving 6.3 g of methyltriethoxydecane, 6.82 g of octadecyltriethoxy, and 12.67 g of tetramethoxydecane in 261.1 g of ethylene glycol monobutyl, the motor was trin. (three-one motor) stirring, and the liquid temperature was stabilized at 60 °C. Then, 46.8 g of ion-exchanged water in which 6 g of horses were dissolved was added over 1 hour. Then, the reaction product (1) obtained by reacting at 60 ° C for 4 hours is 10% by weight of SiO 2 and added to the 759 g of the stirring material, and 1 is added to the 974 g of the stirring material to form a dissolved acid. When, solution 26- 200835984 43 5 g. After the solution was cooled to room temperature, a mixed solution of methanol and ethanol was removed from the solution at 50 ° C, and 65.3 g of ethylene glycol monobutyl ether was added thereto, and the membrane was filtered through a membrane filter having a pore diameter of 2 2 / m. A liquid crystal alignment agent R-2 was obtained. Comparative Synthesis Example 3 52.8 g of ethanol was placed in a four-necked reaction flask equipped with a reflux tube, and a small amount of oxalic acid 200.0 g was added to the ethanol under stirring to prepare an ethanol solution of oxalic acid. Subsequently, the solution was heated to its reflux temperature, and a mixture of 21.8 g of tetraethoxydecane and 4.9 g of octadecyltriethoxydecane was added dropwise to the solution under reflux. After the completion of the dropwise addition, heating was continued for 5 hours under reflux, followed by cooling, and 75 g of butyl cellosolve was added to obtain a liquid crystal alignment agent R-3 having a concentration of SiO 2 of 4% by weight. Examples 1 to 2 and Comparative Examples 1 to 3 [Evaluation of EP Brushiness] A glass substrate of 127 mm (D) x 27 mm (W ) x 1 · 1 mm ( Η ) of an ITO film was integrally formed on one side, and the above experiment was obtained. The liquid crystal alignment agent was filtered on a micro-filter having a pore size of 0.2 // m, and then coated on a glass substrate using a liquid crystal alignment film coating printer (manufactured by Nippon Photographic Co., Ltd., Angstr 〇m S _ 40 L). Transparent electrode surface. The film was dried by a hot plate-type preliminary preheater set at 80 ° C, and calcined at 200 ° C for 60 minutes to form a liquid crystal alignment film on a glass substrate with an ITO film. The results are shown in Table 1. In Table 1, the spots of the obtained alignment film were visually evaluated, and those having no shrinkage spots and marks were good, and those having shrinkage spots and marks were found to be defective. -27- 200835984 The results shown in Table 1 show that the copolymers of Synthesis Example 1 and Synthesis Example 2 have superior printability to any of the liquid crystals. [Voltage Retention Rate] The liquid crystal display element was applied at a voltage of 5 V and an application time of 60 μsec at an interval of 167 msec, and the voltage holding ratio after the release of 167 msec was measured. The measuring apparatus was VHR-1 manufactured by Nippon Seongyo Technology Co., Ltd. The results are shown in Table 1. The results shown in Table 1 show that any of the coating films produced by the copolymer polyoxane solutions of Synthesis Example 1 and Synthesis Example 2 have a good voltage holding ratio. [Orientation of liquid crystal] When the voltage of the liquid crystal display element is OFF, the presence or absence of light leakage in the liquid crystal cell is observed by a microscope. For those who have no light leakage, the light leakage is observed as X, and the results are shown in Table 1. The results shown in Table 1 show that the coating film produced by the copolymer polysiloxane solution of Synthesis Example 1 and Synthesis Example 2 has excellent vertical alignment properties. Table 1 Excipient Name Printability Evaluation Liquid Crystal Alignment Voltage Retention Rate Example 1 S-1 Good 〇99 2 S-2 Good 〇99 Comparative Example 1 R-1 Poor X 97 2 R-2 Good 〇98 3 R-3 In the above, the liquid crystal alignment agent of the present invention provides a liquid crystal alignment film which is excellent in storage stability, superior in vertical alignment, and which has a small decrease in voltage holding ratio due to light or heat. -29-

Claims (1)

200835984 X. Patent Application No. 1 A liquid crystal alignment agent characterized by containing: a polymer obtained by hydrolyzing and condensing only a ruthenium compound represented by the following formula (1): Si(ORi)4 (1) Here, R1 is an alkyl group; or only the oxime compound described in the above formula (1) and the oxime compound described in the following formula (2) are composed, and the above formula (1) is The ruthenium compound and the total amount of the ruthenium compound described in the above formula (2) are 1 mol, and the ratio of the ruthenium compound described in the above formula (2) is a combination of 〇·5 mol or less, and the polymerization is carried out by hydrolysis and condensation. RSi(OR2)3 (2) Here, R is a methyl group or an ethyl group, and R2 is an alkyl group. 2. The liquid crystal alignment agent of claim 1, which further comprises at least one selected from the group consisting of organic solvents represented by the following formulas (I), (II) and (111) as a solvent: In the formula (I), Ri is a hydrogen atom, a methyl group, an ethyl group or an ethyl fluorenyl group, R 2 is an alkyl group having 1 to 4 carbon atoms, and η is an integer of 1 to 3; In the formula (II), R3 is a hydrogen atom, a methyl group, an ethyl group or an ethyl fluorenyl group, R4 is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 1 to 3; -30- 200835984 〇II H3C-c- O-R5 (ill) In the formula (III), R5 is an alkyl group having 2 to 5 carbon atoms. A liquid crystal display element characterized by comprising a liquid crystal alignment film obtained by the liquid crystal alignment agent of the first or second aspect of the patent application. -31 - 200835984 七无·· 明说单简itub # 符表为代图表表代定图指表:案代图本本表' '代定一二指c C 无八, if the case has a chemical formula , please reveal the chemical formula that best shows the characteristics of the invention: none