TW200922975A - Polyorganosiloxane, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

Disclosed is a polyorganosiloxane which has a repeating unit represented by the general formula (1) and has a weight average molecular weight of 1,000 to 100,000: (1) wherein Z represents a photosensitive group capable of causing a crosslinking reaction or an isomerization reaction when irradiated with light having a wavelength of 200 to 400 nm; and X represents a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an alkoxyl group having 1 to 20 carbon atoms, or may be crosslinked with X in other repeating unit through -O-. The polyorganosiloxane has excellent coatability and can be used for the liquid crystal alignment film formation which can impart a liquid crystal alignment capability through the irradiation with a polarized or non-polarized radioactive ray without the need of conducting any rubbing processing.

Description

200922975 IX. Description of the Invention [Technical Field] The present invention relates to a novel polyorganosiloxane, a liquid crystal alignment film, and a liquid crystal display element. More specifically, it relates to a polyorganosiloxane which is useful for imparting liquid crystal alignment energy by polarized or non-polarized radiation and which is useful in formation of a liquid crystal alignment film, without being subjected to rubbing treatment; A liquid crystal alignment film and a liquid crystal display element having the liquid crystal alignment film. [Prior Art] In the past, a positive dielectric anisotropic nematic liquid crystal system has a substrate sandwich structure in which a transparent electrode having a liquid crystal alignment film is added, and the long axis of the liquid crystal molecules is required to be 0 to 3 60 between the substrates as necessary. A liquid crystal display element having a liquid crystal cell such as a TN (torsional nematic) type, an STN (super twisted nematic) type, or an IP (in-plane switching) type is known to be formed by continuous twisting (see Japanese Patent Laid-Open No. 56- Bulletin No. 9 1 277 and Japanese Patent Laid-Open No. 1-12〇528. In these liquid crystal cells, in order to align the liquid crystal in a certain direction with respect to the substrate surface, it is necessary to provide a liquid crystal alignment film on the surface of the substrate. The liquid crystal alignment film is usually formed by a method (rubbing method) of reciprocating rubbing of the surface of the organic film formed on the surface of the substrate in a certain direction with a cloth such as a crucible. However, when the liquid crystal alignment film is formed by the rubbing treatment, it is easy to generate dust in the production, and static electricity is generated. Therefore, dust adheres to the surface of the alignment film, which causes a display failure. In particular, in the case of a substrate having a TFT (Thin Film Transistor) device, the circuit of the TFT element is damaged due to static electricity generated, which is also a cause of a decrease in yield. Further, in order to gradually increase the density of the pixels, the liquid crystal display element having a high precision of -4-200922975 has unevenness on the surface of the substrate, so that uniform rubbing treatment is a problem. As another method of aligning a liquid crystal in a liquid crystal cell, it is known that a photosensitive film composed of polyethylene laurate, polyimide, azobenzene derivative or the like formed on a surface of a substrate is irradiated with polarized light. Or a non-polarizing radiation, thereby imparting a light alignment method to the alignment energy of the liquid crystal. According to this method, static electricity or dust does not occur, and a uniform liquid crystal alignment can be realized (refer to Japanese Laid-Open Patent Publication No. Hei 6-2 8 74 5 3, Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. H11-152475, JP-A-2000-144136, JP-A-2000-319510, JP-A-2000-283, 724, JP-A-9-2973, No. 3, No. 2003-3 Japanese Unexamined Patent Publication No. Hei. However, in a liquid crystal cell such as a TN (torsional nematic) type or an STN (super twisted nematic) type, it is necessary for the liquid crystal alignment film to have a pretilt characteristic in which liquid crystal molecules are obliquely aligned at a predetermined angle with respect to the substrate surface. When the liquid crystal alignment film is formed by the photo-alignment method, the pretilt angle is usually imparted by inclining the incident radiation from the substrate normal to the incident direction of the substrate surface. Further, as an operation mode of the liquid crystal display element different from the above, a vertical (J (homeotropic)) alignment mode in which liquid crystal molecules having negative dielectric anisotropy are vertically aligned with the substrate is known. In this mode of operation, when a voltage is applied between the substrates so that the liquid crystal molecules are aligned in a direction parallel to the substrate, it is necessary to tilt the liquid crystal molecules from the normal direction of the substrate toward one of the substrate faces. As for the method for this, there are proposed, for example, a method of providing a protrusion on a substrate surface -5 - 200922975, a method of providing a stripe on a transparent electrode, and a liquid crystal alignment film from a substrate normal direction toward a substrate surface by using a rubbing alignment film. One way to tilt (pre-tilt), etc. It is also known that the above-described photoalignment method is also useful as a method of controlling the tilt direction of liquid crystal molecules in a liquid crystal cell of a vertical alignment mode. In other words, it is known that the tilting direction of liquid crystal molecules when a voltage is applied can be uniformly controlled by using a vertical alignment film which imparts an alignment control force and a pretilt angle by a photo-alignment method (refer to Japanese Patent Laid-Open Publication No. 2003-3 0773 No. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Thus, the liquid crystal alignment film produced by the above-described photoalignment method is effective for various liquid crystal display elements. However, in the past, the light alignment film had to be irradiated with a large amount of radiation if it had to obtain a large pretilt angle, for example, it has been reported in a light alignment film containing an azobenzene derivative, in order to obtain a sufficient pretilt angle. Irradiation of a radiation of 1 j/cm 2 or more whose optical axis is inclined from the normal line of the substrate (refer to Japanese Laid-Open Patent Publication No. 2002-250924, JP-A-2004-83810, and J. of the SID 11/3, 2003, p. 579) . SUMMARY OF THE INVENTION The object of the present invention is to provide a coating which is excellent in coating properties and electrical properties, does not require rubbing treatment, and can be used to form a liquid crystal alignment film by irradiation of polarized or non-polarized radiation. Organic decane and its method of manufacture. Another object of the present invention is to provide a liquid crystal alignment film of -6-200922975 composed of the above polyorganosiloxane. Still another object of the present invention is to provide a liquid crystal display element. Still other objects and advantages of the present invention will become apparent from the following description. First, according to the present invention, the above objects and advantages of the present invention can be attained by a polysiloxane (hereinafter referred to as a polyorganosiloxane of the present invention) characterized by having a repeating unit represented by the following formula (1) And the weight average molecular weight is 1, 〇〇〇~1 00,000 range: ? -Si-O-X (1) where 'Z is a photosensitive group that produces a parent reaction or an isomerization reaction with light having a wavelength of 200 to 400 nm' X is a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 2 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or may be in another repeating unit represented by the formula (1) X - initiates cross-linking with -〇. Secondly, according to the present invention, the above objects and advantages of the present invention are more preferably achieved by the repeating unit represented by the above formula (1) being a repeating unit represented by the following formula (2) or a repeating unit represented by the following formula (3) Organic oxane to achieve:

(2) 200922975

Ο—C-0" A2 - S 卜 O - wherein A, Α 2 may be the same or different, and are an alkyl group having a carbon number of 1 to 40 substituted with a fluorine atom or an alicyclic organic group. Β!,:b2·^ is the same or different and is a fluorine atom or a cyano group, p is an integer of 〇~4, ς..., S: is the same or different and is an alkyl group having a carbon number of 1 to 20; ; ^ 1 buy a sulfhydryl group, Χ!, Χ 2 can be the same or different and is a hydroxyl group, carbon number 丨 ~ 2. The aryl group having a carbon number of 6 to 2 Å, an alkoxy group having a carbon number of 1 to 2 Å, or the same as I or I in the other repeating units represented by the same, (2) or (3) -0 - forms a crosslink. A second 'in accordance with the present invention', the above objects and advantages of the present invention provide a process for producing a polyorganosiloxane of the present invention, characterized in that it is composed of a decane compound selected from the group consisting of <RTIgt;> Group

Wherein, the definitions of A:, A Βι, B2, Si, S2 and P may be the same as or different from the above formula -8 - 200922975 and may be the same or different carbon numbers 1 to 20 Υ, Y2 and are carbon (2), ( 3) The same, the base of Rl, R2 or the aryl group having a carbon number of 6 to 20, the number of the oxy group or the chlorine atom 'n of the number 1 to 2 为 is 2 or 3. Fourthly, according to the present invention, the above objects and advantages of the present invention are preferably attained by a method for producing a polyorganosiloxane which is an organic acid in which the catalyst for hydrolysis and condensation is used. Fifth, according to the present invention, the above objects and advantages of the present invention are achieved by a method for producing the above hydrolysis and condensation in the presence of a decane compound represented by the following formula (7):

Si(R3)t(〇R4)(4·" (7) where 'R·3 is an alicyclic group-containing alkyl group having a carbon number of 1 to 40 or an aryl group having a carbon number of 6 to 2 0 'R4 It is an alkyl group having a carbon number of 1 to 20, and t is 0, 1, 2 or 3. According to the present invention, the above objects and advantages of the present invention are achieved by a liquid crystal alignment film which is The film formed of the organic siloxane is irradiated with a polarized or non-polarized radiation. According to the present invention, the above objects and advantages of the present invention are achieved by a liquid crystal display element having the above liquid crystal alignment film. In the present invention, the liquid crystal display device preferably uses a negative liquid crystal. [Embodiment] Hereinafter, the present invention will be described in detail. The polyorganosiloxane of the present invention has a weight of -9 to 200922975 represented by the above formula (1). The weight average molecular weight is 1,000 to 100,000. In the formula (1), Z is a photosensitive group which generates a crosslinking reaction or an isomerization reaction at a wavelength of 200 to 40 nm. X is a hydroxyl group and has a carbon number of 1 to 20. a base group, an aryl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or a compound represented by the formula (1) The X in the repeating unit forms a crosslink with -〇_. Preferably, X is a hydroxyl group, a methoxy group, an ethoxy group, and a group which forms a crosslink with -0- together with X of other repeating units. The repeating unit represented by the formula (1) is preferably a repeating unit of the above formula (2) or a repeating unit represented by the above formula (3). In the above formula (2) and the above formula (3), 'Αι, Α2 may be the same or different and is a monovalent organic group having a carbon number of 1 to 40 which may be substituted by a fluorine atom or an alicyclic group, and B2 may be the same or different and is a fluorine atom or a cyano group. ρ is an integer of 4~4 'S!, S2 is the same or different and is a divalent organic group having a carbon number of 2〇, and Χι and X2 may be the same or different, and are a base group and a carbon number. An alkyl group of 1 to 20, an aryl group having a carbon number of 20, a oxy group having a carbon number of ι 2 or 2, or X! or x2 in another repeating unit represented by the formula (2) or (3) - The crosslinking is formed by -0 -. Specific examples of the base of the upper position of the atom in the above formulas (2) and (3) can be exemplified by, for example, the formula (6 -1 ) to (6 -1 4 ) The construction of the representation: =-JL〇-(CH2)—Crr, H(2m+1,|)F|-〇-^^—c?^_ll 〇-(CH2)— (6-2) (6-1)

CmH(2m+1.|)F|-COO-^^~~= 〇-(CH2)- (6-3) 200922975

O JL

CmH(2m+1-l)l:rr0~~^~~^~C〇〇~^~~^一=—U-〇-(CH2)—(6-5) (6-6)

Cm H(2m+1 -|)F| - COO —^~COO —~=3~O- (CH2).

0-(CH2)- (6-7)

/=\ /=r\ 〇 OH

CmH(2m+1.,)F|-0--^V-C00-^_^= 11 O-CHg-L-CHg-O-^Ha)- (6-8) hQ^coo^Q^- =J-^ ho-ch2 丄ch2—o-(ch2)- (6-9)

O

CmHprrvM^Fi-O—COO—^~^ 广 · 1 ^ 〇-(CH2)^~〇"^~N—(CH2)- (6-10)

Cm H(2m+1 ·Ι) F|.〇· Ϊ.

Or O—(CH2)- (6-11)

〇m H(2m+1 -I) Fi’O

Or OOC-(CH2)— (6-12) -11 200922975

In the equation, m is preferably an integer from 1 to 20, 1 is an integer below 2 m+1, k is an integer from 1 to 10, q is an integer from 2 to 10, and more preferably m is from 3 to 18. 3 to 9, k is 2 to 6, q is 2 to 6, preferably m is 4 to 1 0, 1 is 3 to 7 'k is 2 to 4, and q is 2 to 4. The polyorganosiloxane of the present invention preferably has a weight average molecular weight of 1,000 to 50,000 °. The polyorganosiloxane of the present invention can be obtained by subjecting a decane compound of the above formula (4) or (5) to hydrolysis condensation. In the formulas (4) and (5), the definitions of 八, 八2, :61,:82, 31, 82 and 13 are the same as defined in the above formulas (2) and (3). Y!, Y2 can be For example, a chlorine atom and a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, an alkoxy group of a third butoxy group, etc. are mentioned. Among these, a chlorine atom, a methoxy group, and an ethoxy group are preferable. Rp R2 can be exemplified by, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decene基,正癸-12 - 200922975 基,正十二院基基,正六院基基,正20院基^ Jia is methyl, ethyl, n-dodecyl, n-tetradecyl, N-pentadecane 'n-heptadecyl group, n-octadecyl group, n-nonadecane k group' and an aryl group such as a phenyl group. Among these, it is more phenyl. Further, η in the formulas (4) and (5) is preferably 3. The compound of the formula (4) can be obtained by a known method shown in the following Reaction Formulas 1 to 3, but is not limited to these methods. However, r in the reaction formulae 1 to 3 is k-2. The compound of the formula (5) can also be obtained in the same manner.

(Βι)ρ A Ο [o-(ch2)p= H-Si-(OC2H5)3

〇-(CH2)^Si(OC2H5)3 Reaction Formula 1: The precursor of the compound of formula (4) having an ene group is heated and stirred in the presence of a very small amount of platinum catalyst with a diethoxy chopping agent. The compound of the formula (4) can be obtained by purification. -13- 200922975 (9ι)Ρ

CH2—〇~C3H6*Si-(OCH3)3 base w

O [〇-CH2

OH -^~·CH2 - 0**C3H6-Si-(0CH3)3 Reaction Scheme 2: Precursor of compound of formula (4) with carboxylic acid and 3-glycidoxypropyltrimethoxy The compound of the formula (4) can be obtained by heating and stirring decane in the presence of an alkaline catalyst such as triethylamine.

BiPil> Ο -0-(CH2)-0H + OCN-C3H6-Si-(OC2H5)3

B1P 0-(CH2)-0C0NH—C3H6—Si—(〇C2H5)3 Reaction Formula 3: Compound of formula (4) having a hydroxyl group and triethoxydecylpropyl-isocyanate in, for example, dibutyltin dilauric The compound of the formula (4) can be obtained by heating and stirring in the presence of a tin catalyst such as an acid ester. Hydrolysis and condensation method of polyorganosiloxane. The polyorganosiloxane of the present invention can be obtained by hydrolyzing and condensing a decane compound represented by the above formula (4) or (5). In this case, it is preferred to co-hydrolyze and condense in the presence of a decane compound represented by the above formula -14-200922975 (7). In the formula (7), R3 is an alkyl group having an alicyclic group or an aryl group having a carbon number of from 6 to 20, and R4 is a group having a carbon number of from 1 to 20, wherein 1 is 0, and 2 or 3. The decane compound represented by & @ ( 7 ) is exemplified by, for example, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy sulphate, "complete 'tetraisopropoxy sand garden ' tetra-n-butoxy decane 'four a second butoxy base, a tetra-butoxy decane; methyl trimethoxy decane, methyl triethoxy decane, methyl tri-n-propoxy decane, methyl triisopropoxy sand, Methyl tri-n-butoxylate, methyl tri-n-butoxy decane, methyl tri-tert-butoxy decane, methyl triphenyloxy chopping, ethyl trimethoxy decane, ethyl triethyl Oxydecane, ethyl tri-n-propoxy decane, ethyl triisopropoxy sand, ethyl tri-n-butoxy decane, ethyl tri-n-butoxy decane, ethyl tri-tert-butoxy Decane, phenyltriethoxydecane; dimethyldimethoxydecane, dimethyldiethoxydecane; trimethylmethoxydecane, trimethylethoxydecane, and the like. Preferred among these are tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy sand, phenyl trimethoxy chopping, phenyl triethoxy decane, Dimethyldimethoxydecane, dimethyldiethoxydecane, trimethylmethoxydecane, trimethylethoxydecane. With respect to 1 mole of the decane compound of the formula (4) or the formula (5), the decane compound of the formula (7) can be used in an amount of 0 to 100 mol. It is better to use 1~1〇〇 Moule, and better use 2~20 Moer. The hydrolysis and condensate can be obtained by reacting a decane compound with water, hydrolyzing, and partial condensation. In order to hydrolyze the decane compound, the partial condensation of -15-200922975 and the sum of the enthalpy of each of the 1 moles of oxime (the _Yl of the formula (4), the Υ2 of the formula (5) and the 〇R4 of the formula (7) ), it is better to use 1.0 to 1.5 moles of water. If the amount of water is more than or equal to the molar amount, the possibility that the deuterium bond is unreacted and the residue is reduced is not reduced by the uniformity of the coating film, and the storage stability of the liquid crystal alignment agent is reduced, so that it is preferable. . The water system is intermittently or continuously added in an organic solvent in which the decane compound of the present invention is dissolved. The reaction catalyst can be used at this time. In this case, 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 0 to 1 0 0 ° C, more preferably from 1 5 to 8 0. (The above-mentioned organic solvent is preferably an alcohol solvent, a ketone solvent, a guanamine solvent, an ester solvent or an aprotic solvent. These solvents may be used singly or in combination of two or more. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, third butanol, n-pentanol, isoamyl alcohol, 2-methylbutanol, second pentanol , third pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, second hexanol, 2-ethylbutanol, second heptanol, heptanol-3, n-octanol, 2-ethylhexanol 'second octanol, n-nonanol, 2,6-dimethylheptanol-4, n-nonanol, second-alkanol, trimethylnonanol, second-fourteen a monoalcohol solvent such as an alkanol, a second-pentadecanol, a phenol, a cyclohexanol, a methylcyclohexanol, a 3,3,5-trimethylcyclohexanol, a benzyl alcohol or a diacetone alcohol; 1,2-propanol, iota, 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, etc. Price-16- 200922975 Alcohol solvent; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene Alcohol monophenyl ether, ethylene glycol mono-2-ethylbutyl 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 And a part of the ether solvent such as dipropylene glycol monopropyl ether, etc. The alcohol solvents may be used alone or in combination of two or more. Examples of the ketone solvent are, for example, acetone, methyl ethyl ketone, and Base-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone , diisobutyl ketone, trimethyl ketone, cyclohexanone, 2· ketone, methylcyclohexanone, 2,4-pentanyl dihydrazide, propyl hydrazide, acetophenone, fennelone (fenchone), etc., and Mercaptoacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptane, 2,4-octanedione, 3,5-octanedione, 2,4-anthracene Ketone, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6·tetramethyl-3,5-heptanedione, L 1,1,5, a /3 -diketone agent such as 5,5-hexafluoro-2,4-heptanedione, etc. The ketone solvents may be used alone or in combination of two or more. The guanamine solvent is exemplified by, for example, formamide. N-methylformamide, N,N-dimethylformamide, N-ethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N--17 - 200922975 Mercaptomorpholine, N-methylpyridylpiperidine, N-methylpyridylpyrrolidone, N-ethinylmorpholine, N-ethinylpiperidine, N-Ethylpyrrolidone, etc. . These guanamine solvents may be used alone or in combination of two or more. The ester solvent is exemplified by, for example, diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, r-butyrolactone, r-valerolactone, n-propyl acetate, acetic acid. Isopropyl ester, n-butyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, second amyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethyl acetate Butyl ester, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-decyl acetate, methyl acetoxyacetate, ethyl acetate, ethyl acetate Alcohol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl acetate Ethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, glycol diacetate, methoxy acetate Triethylene glycol ester, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate Ester, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, and the like. These ester solvents may be used alone or in combination of two or more. Examples of aprotic solvents are, for example, acetonitrile, dimethyl hydrazine, N, N, N', Ν'-tetraethyl sulfonamide, trimethylamine hexamethylphosphate, N-methylmorpholine, N-methyl Pyrolidine, Ν-ethylpyrrole, Ν-methyl-Δ 3 -pyrionine, Ν-methyl acridine, Ν-ethylpiperidine, ν, Ν-dimethylpiperazine, Ν-methylimidazole ,Ν-甲-18- 200922975 -4-piperidone, N-methyl-2-piperidone, N-methyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinium Ketone, 1,3 -dimethyltetrahydro-2(1H)-pyrimidinone, and the like. The best of these is a polyvalent alcohol solvent 'polyvalent alcohol partial ether solvent, ester solvent. Further, in the hydrolysis and partial condensation reaction of the ruthenium compound of the present invention, a catalyst is preferably used. These catalysts can be exemplified by the following metal chelating compounds, organic acids, inorganic acids, organic bases, and inorganic bases. The metal chelate compound can be exemplified by, for example, triethoxyl-mono(ethylpyruvylacetate)titanium, tri-n-propoxyl-mono(acetylpyruvate)titanium, tri-isopropoxy-oxyl. Acid) titanium, tri-n-butoxy-mono(acetylpyruvate) titanium, tri-t-butoxy-mono(acetylpyruvate) titanium, tri-t-butoxy. mono(acetonitrile) Acid) titanium, diethoxy bis (acetyl acetonate) titanium, di-n-propoxy bis (acetyl acetonate) titanium, di-isopropoxy bis (acetyl acetonate) titanium, Di-n-butoxy bis(acetyl acetonate) titanium, di-t-butoxy bis(acetyl acetonate) titanium, di-t-butoxy bis(acetyl acetonate) titanium, Monoethoxy-parameter (acetylpyruvate) titanium, mono-n-propoxy. ginseng (acetyl acetonate) titanium, mono-isopropoxy ginseng (acetyl acetonate) titanium, mono-n-butyl Oxygen. ginseng (acetyl acetonate) titanium, mono-second butoxy ginseng (acetyl acetonate) titanium, mono-third butoxy ginseng (acetyl acetonate) titanium, bismuth (acetonitrile) Pyruvate) Titanium, Triethoxyl Mono (Ethyl Ethyl B Titanium, tri-n-propoxy-mono(ethylacetoxyacetic acid) titanium, tri-isopropoxy-mono(ethylacetoxyacetic acid) titanium, tri-n-butoxy-mono (ethyl) Ethyl mercaptoacetic acid) Titanium, tri-t-butoxy-mono(ethylacetoxyacetic acid) titanium, tri-third-19- 200922975 butoxy-mono(ethylacetoxyacetic acid) titanium, two Ethoxy bis(ethylacetoxyacetic acid) titanium, di-n-propoxy bis(ethylacetoxyacetic acid) titanium, di-isopropoxy bis(ethylacetoxyacetic acid) titanium , di-n-butoxy bis(ethylacetylacetic acid) titanium, di-second butoxy bis(ethylacetylacetic acid) titanium, di-t-butoxy bis (ethyl) Ethyl mercaptoacetic acid) titanium, monoethoxyl; cis (ethyl acetoxyacetic acid) titanium, mono-n-propoxy ginseng (ethyl ethyl acetoxyacetic acid) titanium, mono-isopropoxy phenol ( Ethyl acetyl hydrazide acetic acid) titanium, mono-n-butoxy ginseng (ethyl ethyl acetoxyacetic acid) titanium, mono-second butoxy ginseng (ethyl ethinylacetate) titanium, single-third Butoxy-paraxyl (ethylethanoacetic acid) titanium, strontium (ethyl ethyl Acetic acid) titanium, mono(acetylpyruvate) ginseng (ethylethanoacetic acid) titanium, bis(acetyl acetonate) bis(ethyl ethinylacetate) titanium, ginseng (acetyl acetonate) mono ( Titanium chelating compound such as ethyl ethionyl acetic acid) titanium; zirconium trisethoxy mono(acetyl acetonate), tri-n-propoxy singly (succinylpyruvate) zirconium, tri-isopropoxy • Single (acetylpyruvate) pin, tri-n-butoxy • mono (acetylpyruvate) zirconium, tri-t-butoxy • mono(acetylpyruvate) zirconium, tri-t-butoxy • Single (acetyl acetonate) zirconium, diethoxy bis (acetyl acetonate) ruthenium, di-n-propoxy bis (acetyl acetonate) zirconium, di-isopropoxy bis (B醯pyruvate) pin, zirconium di-n-butoxy bis(acetyl acetonate), zirconium di-t-butoxy bis(acetyl acetonate), di-t-butoxy bis (B Zirconium pyruvate, zirconium, monoethoxy, ginseng (acetonitrile pyruvate), mono-n-propoxy, ginseng (acetyl acetonate) zirconium, mono-isopropoxy ginseng (acetyl acetonate) Zirconium, mono-n-butoxy-parameter Keto acid) zirconium, mono-second-20- 200922975 butoxy-parameter (acetylpyruvate) zirconium, mono-tert-butoxy-paraben (acetylacetonate) zirconium, cerium (acetylacetonate) Chromium, triethoxyl-mono(ethylacetoxyacetic acid) zirconium, tri-n-propoxy-mono(ethylacetoxyacetic acid) hydrazine, tri-isopropoxy oxy-mono(ethylethenyl) Acetic acid) pin, tri-n-butoxy-mono(ethylacetamidoacetic acid) zirconium tris-t-butoxy-mono(ethylacetamidoacetic acid) zirconium, tri-t-butoxy-single (Ethyl ethinylacetate) zirconium, diethoxy bis(ethylacetylacetic acid) ruthenium, di-n-propoxy bis (ethyl ethinyl acetic acid) zirconium, di-isopropoxy • bis(ethylacetylacetic acid) ruthenium, di-n-butoxy bis(ethylacetoxyacetic acid) ruthenium, di-t-butoxy bis (ethyl ethinylacetate) zirconium, two - tert-butoxy bis(ethylacetoxyacetic acid) pin, monoethoxyl group (ethyl ethyl acetoxyacetic acid) zirconium, mono-n-propoxy group ginseng (ethyl ethyl thioglycolic acid) Zirconium, mono-isopropoxy-oxygen (ethylethanoacetic acid) , mono-n-butoxy ginseng (ethyl ethyl acetoxyacetic acid) zirconium, mono-second butoxy ginseng (ethyl ethinyl acetic acid) pin, single _ third butoxy gin (ethyl) Ethyl mercaptoacetic acid) zirconium, zirconium (ethyl ethinylacetate) zirconium, mono(ethylideneacetic acid) ginseng (ethylethanoacetic acid) zirconium, bis(acetylpyruvyl) bis(ethylethenyl) Acetic acid) zirconium, ginseng (acetonitrile pyruvate) mono(ethylacetylacetic acid) zirconium and the like chelating compound; aluminum chelating compound such as acetylacetate, aluminum and ginseng . The organic acid may, for example, be, for example, acetic acid, propionic acid, butyric acid, valeric acid, heptanoic acid heptanoic acid, caprylic acid, capric acid, capric acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, azelaic acid, Gallic acid, butyric acid, trimellitic acid, arachidene-21 - 200922975 acid, yak, acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, water Salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluene acid expansion, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, propionic acid, sulfonic acid, benzene Formic acid, fumaric acid, citric acid, tartaric acid, and the like. The inorganic acid may, for example, be hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid or the like. The organic base can be exemplified by, for example, pyridine, pyrrole, tanning, masculine steepness, acridine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldi Ethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, and the like. The inorganic test can be exemplified by, for example, ammonia, sodium hydroxide, oxidizing (_, hydrogen, cerium oxide, calcium hydroxide, etc. Among the catalysts, metal chelate compounds, organic acids, inorganic acids, preferably, For example, a titanium chelate compound or an organic acid may be used alone or in combination of two or more. The amount of the above catalyst used is relative to the combination of the compound (4), the compound (5) and the compound (7) ( The conversion to a complete hydrolysis condensation product is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 1 part by weight, based on 100 parts by weight. The liquid crystal alignment agent of the present invention preferably dissolves or disperses the above hydrolysis and condensation product. In an organic solvent, as the organic solvent, an organic solvent represented by the following formulas (8), (9) and -22-200922975 1 〇) may be used:

R (8)

F^Of-CH-CH2〇-jR (9) ΟII H3C — c—ο — R7 (10) In the formula (8), R3 is hydrogen, methyl, ethyl or ethyl fluorenyl, and R4 is carbon number 1~ 4 alkyl, s is an integer from 1 to 3. In the formula (9), R5 is hydrogen, a methyl group, an ethyl group or an ethyl fluorenyl group, R6 is an alkyl group having 1 to 4 carbon atoms, and η is an integer of 1 to 3. Further, in the formula (10), R7 is an alkyl group having 2 to 5 carbon atoms. Specific examples of the organic solvent represented by the formula (8) can be exemplified by 1-ethoxy-2-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. Preferred among these are propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like. Specific examples of the organic solvent represented by the formula (9) are as follows: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellulolytic) ), ethylene glycol monopentyl ether, -23- 200922975 ethylene glycol monohexyl ether, diethylene glycol, methyl fibrin acetate, ethyl fibrin acetate, propyl fibrin B Acid ester, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, and the like. Preferred among these are ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), and ethylene glycol monopentyl ether. Specific examples of the organic solvent represented by the formula (10) can be exemplified by: n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, acetic acid Dipentyl 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. Preferred among these are, for example, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, dibutyl acetate, n-amyl acetate, and second amyl acetate. A surfactant or the like may be added to the liquid crystal alignment agent obtained by the present invention. As the surfactant, for example, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant or the like can be exemplified. Further, examples thereof include a cerium oxygen surfactant, a polyalkylene oxide surfactant, a fluorine-containing surfactant, and the like. Further, the liquid crystal alignment agent of the present invention may contain a compound containing a functional decane or an epoxy group-containing compound from the viewpoint of improving the adhesion to the surface of the substrate. The functional decane-containing compound can be exemplified by, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-amino group. Propyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl-24- 200922975)-3-aminopropyl Methyl dimethoxy decane, 3-ureidopropyl trimethoxy decane, 3-ureidopropyl triethoxy decane, N-ethoxycarbonyl-3-aminopropyl trimethoxy decane, N-triethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecylpropyltriethyl Triamine, 10-trimethoxydecyl-I,4,7-triazadecane, 10-triethoxydecyl 7-triazadecane, 9-trimethoxydecyl-3,6 - diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxysulane, N -benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxy Decane, N_bis(oxiranyl)-3-aminopropyltrimethoxydecane, N-bis(epoxyethyl)-3-aminopropyltriethoxy sand, 3-shrinkage Glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxy ring Hexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, and the like. Further, examples of the epoxy group-containing compound are, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl glycol. Ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether '1,3, 5,6-tetraglycidyl-2,4-hexanediol, 1^,>^,',1^'-tetraglycidyl-m-xylylenediamine, 1,3 -bis (N, N-diglycidylaminomethyl)cyclohexane, N,N,N',N,-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like. -25- 200922975 The reaction product in the liquid crystal alignment agent of the present invention has a ratio of polyorganic oxide to solvent, although the viscosity and the volatility are selected. 'But the ratio of polyorganosiloxane in the liquid crystal alignment agent (solid content concentration) 'It is preferably 0.01 to 70% by weight, more preferably 0. 05 to 60% by weight, based on the concentration of the cerium atom contained in the polyorganoleane to be si 〇 2, and more preferably 1 ~30% by weight. The liquid crystal alignment agent of the present invention is preferably coated on the surface of the substrate by, for example, a roll coating method, a spin coating method, a printing method, or the like, followed by drying by heating to form a coating film of a liquid crystal alignment film, but when solid When the concentration of the component is less than 0.01% by weight, the film thickness of the coating film is too small, and the liquid crystal alignment film is not obtained. When the solid content concentration exceeds 7 〇% by weight, it is difficult to obtain a good film thickness due to excessive coating film thickness. In the liquid crystal alignment film, the viscosity of the liquid crystal alignment agent is also increased to deteriorate the coating properties. Liquid crystal alignment film A method of forming a liquid crystal alignment film using the liquid crystal alignment agent of the present invention is exemplified by the following method. First, the liquid crystal alignment agent of the present invention is applied to the transparent conductive film side of the substrate on which the transparent conductive film is provided, for example, by a roll coating method, a spin coating method, a printing method, an inkjet method, or the like, for example, 40 to 300°. The coating film is formed by heating at a temperature of c. At this time, the polyorganosiloxanes cause a crosslinking reaction with each other. In order to sufficiently cause cross-linking, it is preferably carried out at 15 0 to 2 50 ° C for 10 minutes to 3 hours. Heating can be carried out in air or in nitrogen. The film thickness of the coating film is preferably 0.001 to 1/m, more preferably 0.005 to 0. 5 // m, in terms of solid content. For the above substrate, for example, glass such as float glass or soda lime glass, -26-200922975 polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, etc. A transparent substrate formed. For the transparent conductive film, for example, a NESA film composed of Sn02, an ITO film composed of In203-Sn02, or the like can be used. The patterning of the transparent conductive films may be by a heat etching method or a pre-masking method. In the application of the liquid crystal alignment agent, in order to improve the adhesion between the substrate and the transparent conductive film and the coating film, a compound containing a functional decane, a titanate or the like may be applied to the substrate and the transparent conductive film in advance. Next, the coating film is irradiated with a linearly polarized light to a partially polarized radiation or a non-polarized radiation, depending on the case, and further heat-treated at a temperature of 150 to 250 ° C to impart liquid crystal alignment energy. As for the radiation, ultraviolet rays and visible light having a wavelength of 200 to 400 nm can be used. When the radiation to be used is linearly polarized to a part of the polarized light, the irradiation is performed in a direction perpendicular to the substrate surface, and the pretilt angle may be applied from the oblique direction, or may be combined. When illuminating unpolarized radiation, the direction of illumination must be oblique. As the light source, for example, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an oxygen resonance lamp, a gas lamp, an excimer laser or the like can be used. Further, the ultraviolet light of the above preferred wavelength range can be obtained by means of a filter, a grating or the like and the above-mentioned light source. Further, the "pretilt angle" in the present invention means an angle at which liquid crystal molecules are inclined from a direction parallel to the surface of the substrate. Liquid crystal display element -27- 200922975 A liquid crystal display element formed using the liquid crystal alignment agent of the present invention is produced as follows. The substrate on which the liquid crystal alignment film is formed is prepared to be disposed opposite to each other such that the polarization direction of the polarized radiation that illuminates the liquid crystal alignment film is set to a predetermined angle, and the peripheral portion between the substrates is sealed with a sealant to fill the liquid crystal. Sealing the filling holes constitutes a liquid crystal cell. Next, the liquid crystal cell is preferably heated to a temperature at which the liquid crystal used is in an isotropic phase, and then cooled to room temperature to remove the flow alignment at the time of injection. Therefore, the polarizing plate is bonded to the polarizing plate in such a manner that the polarizing direction of the polarizing plate and the alignment of the liquid crystal alignment film of each substrate are easily formed at a predetermined angle, thereby becoming a liquid crystal display element. When the liquid crystal alignment film is horizontally aligned, the two substrates on which the liquid crystal alignment film is formed can be arbitrarily obtained by adjusting the angle formed by the polarization direction of the irradiated linear polarized radiation and the angle between each substrate and the polarizing plate. A liquid crystal display element having a TN type or STN type liquid crystal cell. On the other hand, when the liquid crystal alignment film is vertically aligned, the two substrates on which the liquid crystal alignment film is formed are configured to be parallel to the alignment axis, and at this time, the alignment is easily 45 degrees with the alignment direction and the alignment. The polarizing plate is attached to the angle to form a liquid crystal display element having a vertical alignment type liquid crystal cell. As the above-mentioned sealant, for example, a hardener and an epoxy resin containing an alumina sphere as a separator can be used. As the liquid crystal, for example, a nematic liquid crystal or a smectic liquid crystal can be used. Further, in the case of a vertical alignment type liquid crystal cell, it is preferred to form a negative dielectric anisotropy of a nematic liquid crystal, for example, a dicyanobenzene liquid crystal, a tromazine liquid crystal, or a Schiff base liquid crystal, Azoxy system -28- 200922975 Liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, and the like. The polarizing plate used for the outside of the liquid crystal cell can be exemplified by a polarizing plate which is a polarizing film called a ruthenium film which absorbs iodine by sandwiching a polyvinyl alcohol while being stretched with a cellulose acetate protective film, or a polarizing plate composed of a ruthenium film. Wait. EXAMPLES Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited by the examples. Synthesis Example 1 11.8 g of the compound represented by the following formula (6-5-1-1), 8.29 g of potassium carbonate, and 1.00 g were placed in a 300 ml three-necked reaction flask equipped with a stirrer, a nitrogen introduction tube, and a thermometer under nitrogen. Potassium iodide, 4.46 g of 4-butyl-1-butane and 120 ml of 1-methyl-2-pyrrolidone were stirred at 90 ° C for 3 hours. After completion of the reaction, the mixture was extracted with toluene and water, dried over magnesium sulfate, concentrated, and then recrystallized from methanol to give 9 g of the compound of the formula (6 - 5 -1 - 2 ). Synthesis Example 2 8.0 g of the compound represented by the following formula (6-5-1-2), 5.88 g of triethoxydecane, and 40 μl of hydrazine were placed in a 100 ml three-necked reaction flask equipped with a reflux tube and a nitrogen introduction tube. .2M chloroplatinic acid hexahydrate isopropanol solution, after degassing, 'returned under nitrogen for 1 hr. Next, the reaction solution was passed through a short column of silica gel, concentrated, and sufficiently dried to obtain a white -29-200922975 color, viscous liquid. Further, the viscous liquid was purified by a gel column to obtain a compound represented by the following formula (6 - 5 -1 ) of 3.5 g.

Br-C2H4

^~co°-〇- -=-COOH (6-5-1-1) I K2C〇3 -QkcoohQ--- c (6-5-1-2) H2PtCI6 · 6H20 H-Si-(〇C2H5) ; f3c-c3h6_ coo

COO-C4H8-Si-(OC2H5)3 (6-5-1) Reaction Formula 4 In the same manner as in Reaction Scheme 4 in which the compound represented by the above (6·5_1) was produced, the following formula (6) was obtained. -2-1) A compound represented by the following formula (6 1 3 -1 ): C5Hl1~Q~~C~^ ' 1 CQO~c4H8-Si-(6-2-1)

200922975 [Weight average molecular weight] Calculated by GPC conversion to polystyrene. [Pretilt angle] The method described in T.J. Scheffer et. al. J. Appl. Phys. νο. 19, p. 20 1 3 (1 98 0) was measured by a crystal rotation method using He-Ne laser light. [Liquid alignment] When the voltage of the liquid crystal display element was turned on/off (applied or removed) by a polarizing microscope, it was judged as "good" when there was no abnormality. [Voltage Maintaining Rate] After applying a voltage of 5 V to the liquid crystal display element for 60 μsec and applying it at intervals of 1 67 msec, the voltage holding ratio after the release of the application for 67 msec was measured. The measuring device was a VHR-1 manufactured by Dongyang Technology Co., Ltd. When the voltage maintenance ratio was 90% or more, it was judged as "good", and otherwise it was judged as "poor". [Printability Evaluation] A glass substrate of 127 mm (D) x 1 27 mm (W ) χ 1 . 1 mm ( Η ) of an ITO film was prepared on one surface of a single surface, and a liquid alignment film of liquid -31 - 200922975 was used on the glass substrate. The coating printing machine (manufactured by Nippon Photo Printing Co., Ltd.) ngus 10 r 0 mer S - 40 L), and the liquid crystal alignment agent obtained in the above experiment was filtered through a microfilter having a pore size of 0.2 // m, and then coated. On the transparent electrode surface. The film was dried by a hot plate-type preliminary preheater set at 80 ° C, and fired at 200 ° C for 60 minutes to form a liquid crystal alignment film on the glass substrate to which the ITO film was attached. The spot of the obtained alignment film was visually evaluated, and those who did not have a spot were "good", and those who saw the spot were "poor". Example 1 To a 200 ml three-necked reaction flask equipped with a cooling tube, 3.1 g (5 mmol) of the compound represented by the above formula (6-5-1) and 12.7 g of tetraethoxydecane (referred to as TEOS) were added. , 60 mmoles, 37. 4 g of 1-ethoxy-2-propanol, and stirred under heating at 60 °C. At this time, an aqueous solution of 165 g of maleic anhydride and 6.95 g of anhydrous anhydrous maleic anhydride in a reaction flask of a capacity of 20 ml was added, and the mixture was further heated at 60 ° C for 4 hours and stirred. The solvent was distilled off from the obtained polymerization solution to obtain a raw material polymer solution having a weight of 0.02 g. Further, butyl acetate was added to obtain an alignment agent coating liquid S-1 having a solid concentration of 4% by weight. The weight average molecular weight measured by GPC was 2,200. Examples 2 to 4 Hydrolysis condensation was carried out in the same manner as in Example 1 in the composition shown in Table 1, and an alignment agent coating liquid was synthesized. -32- 200922975 Table 1 decane compound TEOS molecular weight alignment agent coating solution Example 1 (6-5-1) 5 millimoles 60 millimoles 2200 S-1 Example 2 (6-2-1) 5 millimoles Ear 60 millimoles 2100 S-2 Example 3 (6-13-1) 5 millimoles 60 millimoles 1900 S-3 Example 4 (6-5-1) 5 millimoles 45 millimoles 2100 S-4 Example 5 The above-mentioned alignment agent coating liquid was coated with S-1 by a spin coater to coat a transparent electrode surface of a glass substrate having a transparent electrode composed of an ITO film with a film thickness of O.lym. And drying in a nitrogen-exchanged oven at 20 (TC for 1 hour to form a film. Next, using Hg-Xe lamp and Glan-Taylor Prisms, 313 nm was contained at 0.1 J/cm2. The polarized ultraviolet light of the illuminating line illuminates the surface of the film from the direction in which the substrate normal is inclined at 40 degrees. Then, the substrate is irradiated with ultraviolet rays, and the surface of the liquid crystal alignment film is printed and coated with a diameter of 5.5 // m. After the epoxy resin of the aluminum ball is adhered, the substrate is bonded and pressed so that the direction of the projection of the ultraviolet light toward the substrate surface is anti-parallel, and the adhesive is applied at 50t. After heat curing for 1 hour, a negative liquid crystal (MLC-6608 manufactured by Merck Co., Ltd.) was charged from a liquid crystal injection port between a pair of substrates, and then the liquid crystal injection port was sealed with an epoxy-based adhesive. Further, in order to remove the liquid crystal The flow alignment during injection is allowed to slowly cool to room temperature after heating at 1500. Then, on both sides of the substrate, the polarization directions are perpendicular to each other, and the liquid crystal alignment film and the ultraviolet light axis are directed toward the substrate surface. The projection direction is applied to the polarizing plate at a 45-degree angle to form a liquid crystal display element, and any of them is displayed in a good vertical-33-200922975 alignment. A voltage of 5 V is applied and the applied voltage is turned on and off. The brightness of the display element was changed. The pretilt angle of the above-mentioned unit was evaluated to be 89·3°. The liquid crystal alignment property and the voltage maintenance ratio were both "good". Further, the printability of the above-mentioned alignment agent coating liquid S-1 was evaluated as "good". Example 6 - 8 The alignment agent coating liquids S - 2 to S - 4 were evaluated in the same manner as in Example 5. The results are shown in Table 2. Table 2 Pre-tilt angle of the alignment agent coating liquid (.) Liquid crystal alignment Voltage Holdability Printability Example 5 S-1 89.3 Good Good Good Example 6 S-2 89.2 Good Good Good Example 7 S-3 89.5 Good Good Good Example 8 S-4 89.3 Good Good Good Displayed by these data The polyorganosiloxane of the invention is excellent in coatability, sensitivity, liquid crystal alignment, and electrical properties, and can be used extremely useful in liquid crystal display elements. EFFECTS OF THE INVENTION According to the polyorganooxygenane of the present invention, a liquid crystal alignment film can be obtained with a smaller amount of radiation irradiation than in the case of the conventional photoalignment method. Therefore, when the liquid crystal alignment film is used in a liquid crystal display device, liquid crystal display can be manufactured more inexpensively than ever. Thus, the liquid crystal display elements can be effectively applied to various devices such as a desktop computer, a watch, a clock, a counting display panel, a word processor, a personal computer, or a liquid crystal television. -34-

Claims (1)

200922975 X. Patent Application Range 1. A polyorganosiloxane which is characterized by having a repeating unit represented by the following formula (1) and having a weight average molecular weight of 1,000 to 1 Å. Wherein z is a photosensitive group which generates a crosslinking reaction or an isomerization reaction with light having a wavelength of 200 to 400 nm, and X is a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number of 1 to 2 The alkoxy group of 0 may be crosslinked with -0 in the other repeating units represented by the formula (1). 2. The polyorganosiloxane according to the first aspect of the invention, wherein the repeating unit represented by the above formula (1) is a repeating unit represented by the following formula (2) or a repeating unit represented by the following formula (3): Ο ‘ ‘=—c_o_a2 35- 200922975 wherein, Αι and A2 may be the same or different, and are a monovalent organic group having a carbon number 丄~ ❻ which may be substituted by a fluorine atom, or a valence group, and Bi and B2 may be the same or different. And a fluorine atom or a cyano group, p is an integer of 〇~4, and Si and S2 may be the same or different and are a divalent organic group having an alkylene group having 1 to 2 carbon atoms, and X! and X2 may be the same or Different from each other, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or the like represented by the same formula (2) or (3) Χι* χ2 in the repeating unit - the cross-linking is formed by -〇-. 3. A method for producing a polyorganosiloxane according to the first or second aspect of the invention, characterized in that at least one selected from the group consisting of decane compounds represented by the following formulas (4) and (5) is given. Hydrolysis, condensation: Among them, Αι, Α2, Β! 'B2, S!, S2 and p are the same as above An alkoxy group or a chlorine atom of 1 to 20, and η is 2 or 3. 4_ The manufacturing method of claim 3, wherein the catalyst for hydrolysis condensation is an organic acid-36-200922975 5 · The manufacturing method of the third or fourth aspect of the patent application is based on the following formula (7) The above-mentioned hydrolysis and condensation are carried out in the presence of a decane compound: Si(R3), (〇R4)(4-t) (7) wherein R3 is an alkyl group or carbon having an alicyclic group having 1 to 40 carbon atoms An aryl group of 6 to 20, R 4 is an alkyl group having 1 to 20 carbon atoms, and t is 0, 1, 2 or 3. A liquid crystal alignment film obtained by irradiating a polarized or non-polarized radiation to a film formed of the polyorganosiloxane of the first or second aspect of the patent application. A liquid crystal display element characterized by having a liquid crystal alignment film according to claim 6 of the patent application. 8. A liquid crystal display element according to item 7 of the patent application, which uses a negative type liquid crystal. -37- 200922975 VII. Designated representative 囷: (1) The representative representative of the case is: No (2), the representative symbol of the representative 简单 is a simple description: No. 8. If there is a chemical formula in this case, please reveal the best display invention. Chemical formula of the formula: (1) - Si-O - X (1)