TW200934859A - Liquid crystal aligning agent and method for forming liquid crystal alignment film - Google Patents

Abstract

Disclosed is a liquid crystal aligning agent containing a radiation-sensitive polyorganosiloxane which is obtained by reacting a compound represented by Formula (1) with a specific polyorganosiloxane having an epoxy group. (In Formula (1), RI represents a hydrogen atom or a monovalent organic group having 1-40 carbon atoms; RII, RIV and RV independently represent a hydrogen atom, a methyl group, a cyano group or a fluorine atom; and when RI is a hydrogen atom, RIII represents a monovalent organic group having 1-40 carbon atoms, but when RI is other than a hydrogen atom, RIII represents a carboxyl group.)

Description

200934859 IX. Description of the Invention [Technical Field] The present invention relates to a method for forming a liquid crystal alignment agent and a liquid crystal alignment film. [Prior Art] Conventionally, it is known that a nematic liquid crystal having positive dielectric anisotropy is formed into a sandwich structure with a transparent electrode substrate having a liquid crystal alignment film, and the long axis of the liquid crystal molecules is on the substrate. A liquid crystal display element having a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, an IPS (In Plane Switching type) type liquid crystal cell, etc. Japanese Laid-Open Patent Publication No. Hei. No. 1 277 and JP-A No. Hei. In the liquid crystal cell, in order to align the liquid crystal molecules to the substrate surface in a specific direction, it is necessary to provide a liquid crystal alignment film on the surface of the substrate. In the liquid crystal alignment film, the surface of the organic film formed on the surface of the substrate is usually formed by a rubbing method (friction method) in a single rubbing direction. However, when the liquid crystal alignment film is formed by the rubbing treatment, dust or static electricity is easily generated in the step, and the adhesion of dust to the surface of the alignment film causes a problem of display failure. In particular, in the case of a substrate having a TFT (Thin Film Transistor) element, the TFT element circuit is broken due to static electricity generated, and there is a problem that the yield is lowered. Further, in the liquid crystal display device which is becoming more and more refined in the future, it is difficult to uniformly perform the rubbing treatment due to the unevenness of the pixel on the surface of the substrate. Other means for aligning the liquid crystal in the liquid crystal cell, the photosensitive film of polyvinyl cinnamate, polyimine, azobenzene derivative, etc. formed on the substrate surface -4-200934859 is irradiated with polarized or non-polarized light. Radiation, and the optical alignment method that gives the liquid crystal alignment energy. According to this method, uniform liquid crystal alignment can be achieved without generating static electricity or dust (Japanese Laid-Open Patent Publication No. Hei 6-287453, Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Unexamined Patent Publication No. Publication No. Publication No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. Nos. JP-A-2004-163646 and JP-A-2002-250924 are incorporated herein by reference. However, in the liquid crystal cell of the TN (Twisted Nematic) type or the STN (Super Twisted Nematic) type, the liquid crystal alignment film needs to have a pretilt characteristic which causes the liquid crystal molecules to be inclined at a specific angle with respect to the substrate surface. When the liquid crystal alignment film is formed by the photo-alignment method, the pretilt angle characteristic is usually imparted by irradiation of radiation inclined 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, it is also known that liquid crystal molecules having a negative dielectric anisotropy are vertically aligned in a homeotropic alignment mode on a substrate. In this operation mode, when a liquid crystal molecule is applied between the substrates, when the liquid crystal molecules are tilted in the parallel direction, the liquid crystal molecules are required to be inclined from the normal direction of the substrate toward the single direction in the substrate surface. As a means of this, for example, a method of providing a protrusion on a surface of a substrate, a method of providing a stripe shape on a transparent electrode, and a liquid alignment of a liquid crystal molecule from a normal direction of a substrate toward a single direction in a substrate surface by using a rubbing alignment film are proposed (for example) The method of making the pretilt). The aforementioned photoalignment method is also known as a method of controlling the tilt direction of liquid crystal molecules of the liquid crystal cell of the liquid crystal cell in the vertical alignment mode. In other words, it is known that the tilting direction of the liquid crystal molecules at the time of voltage application can be controlled to be uniform by using a vertical alignment film which imparts an alignment regulation property and a pretilt angle exhibitability by a photo-alignment method (Japanese Patent Laid-Open Publication No. 2003-307736, JP-A-2003-307736) Japanese Laid-Open Patent Publication No. 2004-163646, JP-A-2002-250924, JP-A-2004-83810, JP-A-H09---- No. In this way, the liquid crystal alignment film produced by the photo-alignment method is suitable for various liquid crystal display elements. However, in the conventional light alignment film, there is a problem that a large amount of radiation irradiation is required in order to obtain a large pretilt angle. For example, when a film containing an azobenzene derivative is given a liquid crystal alignment energy by a photo-alignment method, in order to obtain a sufficient pretilt angle, it is necessary to irradiate the radiation whose optical axis is inclined from the substrate normal line at 10,000 J/m 2 or more. (JP-A-2002-250924 and JP-A-2004-83 8 1 0 and J. of the SID 11/3, 2003, p579 for reference). In addition, the liquid crystal alignment film produced by the photo-alignment method has a photosensitive portion in the side chain of the polymer of the main component ©, and the conventional photo-alignment material cannot be excluded from the photosensitive portion of the side chain in the liquid crystal panel manufacturing. The heating of the step creates the possibility of thermal decomposition, which is an undesired situation in which the substrate or panel manufacturing line is contaminated. As described above, there is currently no liquid alignment method with a small amount of radiation exposure, and a liquid crystal alignment film having good liquid crystal alignment energy, excellent electrical characteristics, and high heat resistance can be formed, and liquid crystal alignment without thermal decomposition problems in post-baking can be produced. Agent. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a liquid crystal which is excellent in storage stability and which can be irradiated with polarized light or non-polarized light without performing rubbing treatment, even with a small exposure amount. A liquid crystal alignment element which is an alignment aligning liquid crystal alignment film, a liquid crystal alignment film which has excellent electrical properties and heat resistance, and a liquid crystal display element which exhibits excellent performance such as display characteristics and reliability. According to the present invention, the above object of the present invention is to provide the following formula (1) by including Φ

(In the formula (1), R1 is a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, and R11, RIV& Rv are each independently a hydrogen atom, a methyl group, a cyano group or a fluorine atom, and when R1 is a hydrogen atom; R1U is a monovalent organic group having 1 to 40 carbon atoms, and when R1 is a hydrogen atom, R111 is a carboxyl group.) The compound represented by the formula (si): -Si-〇--Y1 (sl) (In the formula (s1), x1 is an organic group having a valence of an epoxy group, Y1 is a hydroxyl group, an alkoxy group having a carbon number of 1 to 10, an alkyl group having a carbon number of 1 to 20, or a carbon number of 6 to 20 200934859 a liquid crystal containing a radiation-sensitive polyorganosiloxane obtained by reacting at least one selected from the group consisting of a polyorganosiloxane having a repeating unit and a condensate of a hydrolyzate and a hydrolyzate thereof It is achieved by an alignment agent. According to the above object of the present invention, the second aspect is achieved by applying the liquid crystal alignment agent onto a substrate to form a coating film, and forming a liquid crystal alignment film by irradiating the coating film with radiation. D. BEST MODE FOR CARRYING OUT THE INVENTION <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention contains the compound represented by the above formula (1) (hereinafter referred to as "cinnamic acid derivative (1)") and the above formula At least one selected from the group consisting of a polyorganic shale compound having a repeating unit and a condensate of a hydrolyzate and a hydrolyzate thereof (hereinafter referred to as "a polyorganosiloxane having an epoxy group" (hereinafter referred to as "s-ι") The radiation-containing polyorgano-oxygenane obtained by the reaction was carried out. Q The cinnamic acid derivative (1) used in the present invention is a compound represented by the above formula (1). In the above formula (1), each of R11, Han 1 and Rv is preferably a hydrogen atom. The cinnamic acid derivative (1) is represented by the following formula (2)

(In the formula (2), R11, RIV and Rv are respectively synonymous with the above formula (1), and rVI is a single bond, an ether bond, a thioether bond, an ester bond, a thioester bond or an acid amine bond, and R VII is 200934859 An alkyl group having a carbon number substituted by a fluorine atom or an alicyclic group having a carbon number of 3 to 40 which may be substituted by a fluorine atom.) A compound represented by the formula or the following formula (3)

(In the formula (3), 'R11, Rlv and Rv are the same as those in the above formula (1), and RVMI is an alkyl group having 1 to 30 carbon atoms which may be substituted by a fluorine atom or a carbon number of 3 to 40 which may be substituted by a fluorine atom. The compound represented by the alicyclic group.) is preferred. In the above formula (2), RV1 is preferably an oxygen atom or an ester bond (except that an oxygen atom is bonded to the group RVI1). Rvn is preferably an alkylcyclohexyl group having a carbon number of from 1 to 20, a Cholestanyl group, a cholesenyl group, a cyclohexyl group or a substituent having a carbon number of from 1 to 20 which may be substituted by a fluorine atom.例 Examples of the compound represented by the above formula (2) ' For example, the following formula (2-1)~(2-1〇) 200934859

-10-^-6)200934859

CaH2a+i_〇 ο

CH=CH-COOH

CbF2b+1CcH2c A Χ Χ^Ν-〇-ο CH=CH-COOH ¢-7) Ο

CH=CH-COOH

〇 (2-8) Ο

CH=CH-COOH Ο (2-9) c5h” Ο ο CH=CH-COOH ¢-10)

(a in the formulas (2-1) and (2-6) are integers of 1 to 20, respectively, and b in the formula (2-7) is an integer of 1 to 3, respectively, and c is 0 to 10, respectively. The compound represented by the above formula (3) is preferably an alkane having a carbon number of 1 to 20 (: <^2<1+1 (:26-(in this case, (1 is an integer of 1 to 3, 6 is 0 to 10.), Cholestanyl group, cholesenyl group, cyclohexyl group or alkylcyclohexyl group having a number of 1 to 10. In terms of the alkylcyclohexyl group, a cyclohexyl group or a 4-pentylcyclohexyl group is preferred. And (2-integer.) Base, base integer: base carbon 4-butyl-11 - 200934859 The cinnamic acid derivative (1) can be synthesized by a common method of organic chemistry. For example, the above formula (2 - 1) a compound represented by a combination of (2 - 5), for example, an ester compound which can react with a compound of the desired compound Rvn-OH and a trimellitic anhydride halide to synthesize an intermediate, and then the ester compound and the 4-amino group The cinnamic acid is reacted and synthesized. The synthesis of the intermediate ester compound is preferably carried out in the presence of a basic compound in a suitable solvent, and a solvent which can be used herein, for example, tetrahydrofuran, For the compound, for example, triethyl Q-amine, etc. The reaction of the ester compound with 4-aminocinnamic acid can be carried out, for example, by refluxing both of them in acetic acid, and the two are suitably contained in toluene or xylene. (For example, an acid catalyst such as sulfuric acid or an alkali catalyst such as triethylamine), a method of refluxing, etc., for example, a compound represented by the above formulas (2-6) and (2-7) can be 5-hydroxy phthalic acid is subjected to dehydration ring closure to an acid anhydride in, for example, diethylbenzene under reflux, and then reacted with 4-aminocinnamic acid in the same manner as above to synthesize a first intermediate quinone imine compound. Next, the quinone imine compound is synthesized by reacting a compound RVII-X (where X is a secluded atom) corresponding to a desired compound. The reaction is preferably carried out in a suitable solvent in the presence of a basic compound. The solvent which can be used herein is, for example, a guanamine compound such as N,N-dimethylacetamide or the like, and a basic compound such as potassium carbonate or the like. For example, the above formula (2-8) to (2- The compound represented by 10) can be made, for example, by The compound RVII-〇H corresponding to the desired compound is reacted with 4-fluoro-indole-xylene to synthesize an ether compound of the first intermediate, and then the ether compound is oxidized and then dehydrated by heating to synthesize a second intermediate. Acid-12-200934859 An acid anhydride which is synthesized by reacting the acid anhydride with 4-aminocinnamic acid. The synthesis of the ether compound of the first intermediate is preferably carried out in the presence of a basic compound in a suitable solvent. The solvent can be used, for example, tetrahydrofuran or the like, and the basic compound, for example, tert-butoxy potassium, etc. The synthesis of the anhydride of the ether compound and the reaction of the acid anhydride with the 4-aminocinnamic acid can be carried out according to the above formula (2). The method for synthesizing the compounds represented by -6) and (2-7), respectively. Further, for example, a compound represented by the above formula (3), a 4-nitrocinnamic acid halide obtained by treating 4-indole nitrocinnamic acid with, for example, a sulfonium halide, and a compound corresponding to the desired compound Rvm After the reaction of hydrazine H, the ester compound of the first intermediate is synthesized, and then the nitro group having the ether compound is reduced to an amine group to obtain a second intermediate, and the second intermediate is further reacted with trimellitic anhydride to synthesize. The synthesis of the ester compound of the first intermediate is preferably carried out in the presence of a basic compound such as triethylamine. The reduction reaction of the nitro group with the nitro group is preferably carried out via a suitable reduction system such as a combination of zinc and ammonium chloride or tin chloride. The reaction of the second intermediate with hydrazine trimellitic anhydride can be carried out by reacting the synthesized ester compound of the compound represented by the above formulas (2-1) to (2-5) with 4-amino cinnamic acid. <Polyorganooxane having an epoxy group> The polyorganosiloxane having an epoxy group which can be used in the present invention is a polyorganosiloxane having a repeating unit represented by the above formula (S-1) And at least one selected from the group consisting of a hydrolyzate and a condensate of a hydrolyzate. In the X1 aspect of the above polyorganosiloxane having an epoxy group, the following -13-200934859 formula (X^l) or (Xi-2)

(X1-2) © The base shown is preferred. The alkoxy group having a carbon number of 1 to 10 in Y1, for example, a methoxy group, etc.; an alkyl group having a carbon number of 1 to 20 'e.g., methyl group, ethyl group, η-η-butyl group, η-pentyl group, η -hexyl, η-heptyl, η-octyl, η-fluorenyl, η-~(--hospital, η-twelve, η- thirteen, η-ten, η-fifteen Alkyl 'n-hexadecyl, η-heptadecyl, η-octadecyl. η-nonadecyl, η-icosyl, etc.; an aryl group having a carbon number of 6 to 20, such as a phenyl group W polyepoxyalkylene having an epoxy group, the polystyrene-equivalent weight average molecular weight measured by colloidal permeation (GPC) is preferably 100,000 '1,000 〜1 〇, 〇〇〇 preferably, 1, 〇〇〇 〜5〇〇〇] The polyalkylene oxide having an epoxy group, preferably a mixture of a decyl compound having an epoxy group or a decane compound having an epoxy group, preferably The synthesis is carried out by hydrolysis or hydrolysis/condensation in the presence of a suitable organic solvent or a medium. Examples of the above-mentioned epoxy group-containing decane compound include 3 g-glycidyloxypropyltrimethoxydecane and 3-oxidation B. Oxypropyl. , η-癸tetraalkylalkyl, surface, for example, chromatographic method 500 ~ g. By oxidizing the material with its water and oxidative condensation water gan-14- 200934859 oleyl propyl triethoxy decane, 3-oxidation Glycidylpropylmethyldimethoxydecane, 3-oxyglycidylpropyldimethoxydecane, 3-oxyglycidylpropyldimethylmethoxydecane, 3-oxidized glycidol Propyl dimethyl ethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy sand, 2-(3,4-epoxycyclohexyl)ethyltriethoxy sand The above other decane compounds may, for example, be tetrachlorodecane, tetramethoxydecane, tetraethoxydecane, tetra-n-propoxydecane, tetra-i-propoxydecane 0, tetra-n-butyl Oxydecane, tetra-sec-butoxydecane, trichlorodecane, trimethoxydecane, triethoxydecane, tri-n-propoxydecane, tri-i-propoxydecane, tri-n- Butoxy decane, tris-butoxybutane, fluorotrichlorodecane, fluorotrimethoxydecane, fluorotriethoxydecane, fluorotri-n-propoxydecane, fluorotri-i-propoxy Decane, fluorine tri-η-butoxy Decane, fluorotri-sec-butoxydecane, methyltrichlorodecane, methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane, methyltri-i- Propoxydecane, methyl tri-n-butoxydecane, methyl tris-sec-butoxydecane Φ, 2-(trifluoromethyl)ethyltrichlorodecane, 2-(trifluoromethyl) Ethyltrimethoxydecane, 2-(trifluoromethyl)ethyltriethoxydecane, 2-(trifluoromethyl)ethyltri-n-propoxydecane, 2-(trifluoromethyl) Ethyl tri-i-propoxydecane, 2-(trifluoromethyl)ethyltri-n-butoxydecane, 2-(trifluoromethyl)ethyltris-butoxybutane, 2 -(perfluoro-η-hexyl)ethyltrichlorodecane, 2-(perfluoro-η-hexyl)ethyltrimethoxydecane, 2-(perfluoro-η-hexyl)ethyltriethoxydecane, 2-(perfluoro-η-hexyl)ethyltri-n-propoxydecane, 2-(perfluoro-η-hexyl)ethyltri-i-propoxydecane, 2-(perfluoro-η- Hexyl)ethyltri-n-butoxydecane, 2-(perfluoro-η-hexyl)ethyltri-see-butoxyfluorene-15- 200934859 alkane, 2-(perfluoro-η-octyl) Ethyl trichlorodecane, 2-(perfluoro- -octyl)ethyltrimethoxydecane, 2-(perfluoro-η-octyl)ethyltriethoxydecane, 2-(perfluoro-η-octyl)ethyltri-n-propoxy Decane, 2-(perfluoro-η-octyl)ethyltri-i-propoxydecane, 2-(perfluoro-η-octyl)ethyltri-n-butoxydecane, 2-(all Fluoro-η-octyl)ethyltris-sec-butoxydecane, hydroxymethyltrichloromethane^, hydroxymethyltrimethoxydecane, hydroxyethyltrimethoxydecane, hydroxymethyltri-n-propyl Oxydecane, hydroxymethyltri-i-propoxydecane, hydroxy 0 methyltri-n-butoxydecane, hydroxymethyl tris-sec-butoxydecane, 3-(methyl)propene oxime Propyltrichlorodecane, 3-(methyl)propenyloxypropyltrimethoxydecane, 3-(methyl)propenyloxypropyltriethoxydecane, 3-(methyl)propene oxime Oxypropyl tri-n-propoxydecane, 3-(methyl)propenyloxypropyltri-i-propoxydecane, 3-(methyl)propenyloxypropyltri-n- Butoxy decane, 3-(methyl) propylene oxypropyl tris-sec-butoxy decane, 3-mercaptopropyltrichloro decane, 3-mercaptopropyltrimethoxy Baseline, 3-mercaptopropyltriethoxydecane, 3-mercaptopropyltri-n-propoxydecane, 3-mercaptopropyltri-i-propoxydecane, 3-mercapto Propyltris-n-butoxydecane, 3-mercaptopropyltris-sec-butoxydecane, mercaptomethyltrimethoxydecane, mercaptomethyltriethoxydecane, vinyltrichloromethane , vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tri-η-propoxy decane, vinyl tri-i-propoxy decane, vinyl tri-n-butoxy decane, ethylene Tris-sec-butoxydecane, allyltrichloromethane, allyltrimethoxydecane,allyltriethoxydecane,allyltri-n-propoxydecane,allyl III -i-propoxydecane, allyl tri-n-butoxydecane, allyl tri-sec-butoxydecane, phenyltrichlorodecane, phenyltrimethoxydecane, -16- 200934859 benzene Triethoxy decane, phenyl tri-n-propoxy decane, phenyl tris-propoxy decane, phenyl tri-n-butoxy decane, phenyl tri-sec-butoxy decane, A Dichlorodecane, methyldimethoxydecane, methyldi Oxy decane, methyl di-η-propoxy decane, methyl di-i-propoxy decane, methyl di-η-butoxy decane, methyl di-sec-butoxy decane, dimethyl Dichloro. decane, dimethyldimethoxydecane, dimethyldiethoxydecane, dimethyldi-n-propoxydecane, dimethyldipropoxydecane, dimethyldi _ @η-butoxydecane, dimethyldi-sec-butoxydecane, (methyl)[2-(perfluoro-η-octyl)ethyl]dichlorodecane, (methyl)[2 -(perfluoro-n-octyl)ethyl]dimethoxydecane, (methyl)[2-(perfluoro-η-octyl)ethyl]diethoxydecane, (methyl)[2 -(perfluoro-η-octyl)ethyl]di-η-propoxydecane, (methyl)[2-(perfluoro-η-octyl)ethyl]di-i-propoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-n-butoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-sec -butoxydecane, (methyl)(3-mercaptopropyl)dichlorodecane, (methyl)(3-mercaptopropyl)dimethoxydecane, (methyl)(3-mercaptopropylidene Diethyl ethoxy decane, (methyl) (3-巯Propyl)di-η-propoxydecane, (methyl)(3-mercaptopropyl)di-i-propoxydecane, (methyl)(3-mercaptopropyl)di-η- Butoxy decane, (methyl) (3-mercaptopropyl) bis-sec-butoxydecane, (methyl) (vinyl) dichlorodecane, (methyl) (vinyl) dimethoxy Decane, (meth)(vinyl)diethoxydecane, (methyl)(vinyl)di-n-propoxy fluorene, (methyl)(ethenyl)di-i-propoxy Comparative hospital '(methyl)(vinyl) bis-n-butoxydecane, (methyl)(vinyl)bis-sec-butoxydecane, divinyldichlorodecane, divinyldimethoxy Pyridinium, divinyldiethoxylate, triethylphosphonium-n-propoxy sand, diethylenedipropoxy-17-200934859 decane, divinyldi-n-butoxy Base decane, divinyl sec-butoxy decane, biphenyl dichloro decane, biphenyl dimethoxy decane, biphenyl diethoxy decane, biphenyl di- η - propoxy Decane, biphenyl di-i-propoxydecane, biphenyl di-n-butoxydecane Biphenyl bis- sec-butoxy decane, chlorodimethyl decane, methoxy dimethyl decane, ethoxy dimethyl decane, chlorotrimethyl decane, bromotrimethyl decane, iodine trimethoxide Base decane, methoxy trimethyl decane, ethoxy trimethyl decane, η-propoxy trimethyl decyl decane, i-propoxy trimethyl decane, η-butoxy trimethyl decane, sec -butoxy trimethyl decane, t-butoxy trimethyl decane, (chloro) (vinyl) dimethyl decane, (methoxy) (vinyl) dimethyl decane, (ethoxy) (vinyl) dimethyl decane, (chloro) (methyl) diphenyl decane, (methoxy) (methyl) diphenyl decane, (ethoxy) (methyl) diphenyl decane, etc. In addition to the decane compound having one ruthenium atom, _ may be, for example, a trade name, KC-89, KC-89S, X-21-3153, X-21-5841, © X-21-5842 'X-21-5843' X-21-5844 'X-21-5845 ' X-21- 5 846, X-2 1 -5847, X-2 Bu 5 84 8, X-22- 1 60AS, X-22-1 70B, X- 22- 1 70BX, X-22- 1 70D, X-22- 1 70DX, X-22- 1 76B, X-22- 1 76D, X-22- 1 76DX, X-22-1 76 F, X-40-23 08, X-40-265 1, X-40-265 5A, X-40-267 1, X-40-2672, X-40-9220 'X-40-9225 ' X- 40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41-1053, X-41-1056, X-41-1805, X-41- 1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, -18- 200934859 KR311, KR401N, KR500, KR510, KR5206, KR5230, KR523 5, KR9218, KR9706 (above, Shin-Etsu Chemical Co., Ltd.); 01 & 38 1^3111 (Showa Denko (share) system); 311804, 3^1805, 3118086, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411 SR2416, SR2420 (above, Toray Dao Ning (share) system); Thai FZ3711, FZ3722 (above, Japanese unicar (J^)); DMS-S12, DMS-S15, DMS-S21 'DMS-S27, DMS-S31 , DMS-S32, 〇DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45 > DMS-S5 1 ' DMS-227, PSD-03 32, PDS-1615, PDS-993 1, XMS-5025 (above, Chisso); methyl phthalate MS51, methyl phthalate MS56 (above, Mitsubishi (manufactured by the company); ethyl phthalate 28, ethyl phthalate 40, ethyl phthalate 48 (above, manufactured by Colcoat); GR100, GR650, GR908, GR950 (above, Showa Electric ( Part of the polymer). Among these other decane compounds, tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, 3-(methyl) propylene methoxy propyl trimethoxy Base decane, 3-(meth) propylene methoxy propyl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, allyl trimethoxy decane, allyl triethoxy Basear, phenyltrimethoxydecane, phenyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, decylmethyltrimethoxydecane, Mercaptomethyltriethoxydecane, dimethyldimethoxydecane or dimethyldiethoxydecane is preferred. The polyorganosiloxane having an epoxy group can be used in the present invention, and the epoxy-19-200934859 equivalent is preferably 100 to l, 〇〇〇g/mole, and more preferably 150 to 1,000 g/mole. . Further, when a polyorganosiloxane having an epoxy group is synthesized, the ratio of the use of the epoxy group-containing decane compound to the other decane compound is preferably adjusted so that the obtained polyorganosiloxane has an epoxy equivalent in the above range. An organic solvent which can be used in the synthesis of a polyorganosiloxane having an epoxy group. Aspects such as hydrocarbons, ketones, esters, ethers, alcohols and the like. Examples of the hydrocarbon include, for example, toluene, xylene, and the like: Φ the above ketone, such as methyl ethyl ketone, methyl isobutyl ketone, methyl η - amyl ketone, diethyl ketone, cyclohexanone, etc.; In terms of, for example, ethyl acetate, η-butyl acetate, i-pentyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, lactated ethyl group, etc.; Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran 'dioxane, etc.; each of the above alcohols may, for example, be 1-hexanol, 4-methyl-2-pentanol or decyl alcohol monomethyl Ether, ethylene glycol monoethyl ether, ethylene glycol mono-η-propyl ether, ethylene glycol mono-η-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-η-propyl ether Wait. Among these, it is preferred that the water is not water soluble. These organic solvents may be used singly or in combination of two or more kinds. The organic solvent is used in an amount of preferably 10 to 1 Torr, 〇〇〇 by weight, more preferably 50 to 1,000 parts by weight based on 100 parts by weight of the total decane compound to produce a polyorganosiloxane having an epoxy group. The amount of water used is preferably from 0.5 to 100 times moles, more preferably from 1 to 20 to 200934859 to 30 times moles, relative to the total decane compound. As the above catalyst, for example, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound or the like can be used. The alkali metal compound may, for example, be sodium hydroxide, potassium hydroxide, sodium alkoxide, potassium methoxide, sodium ethoxide or potassium ethoxide. Each of the above organic bases may, for example, be ethylamine, diethylamine, piperazine, piperidine, pyrrolidine or pyrrole-like organic amines of 1 to 2; φ triethylamine, tri-n-propylamine, three - η-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene-like organic amine; tetramethylammonium hydroxide-like organic amine. Among these organic bases, triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine-like organic amine; tetramethylammonium hydroxide Class 4 organic amines are preferred. In the case of producing a polyorganosiloxane having an epoxy group, an alkali metal compound or an organic base is preferred. By using an alkali metal compound or an organic base as a catalyst and not causing a side reaction such as ring opening of an epoxy group, the desired polyorganosiloxane can be obtained at a high hydrolysis/condensation rate, and the production stability is excellent. good. Further, the liquid crystal alignment agent of the present invention containing a reaction product of an epoxy group-containing polyorganosiloxane and an cinnamic acid derivative (1) synthesized using an alkali metal compound or an organic base as a catalyst has excellent storage stability. Therefore, it is suitable. The reason is presumed to be that a random structure, a ladder type structure, or a cage structure is formed by using an alkali metal compound or an organic base as a catalyst for hydrolysis and polymerization as indicated by Chemical Reviews, 95, pi 409 (1995). A polyorganosiloxane having a small content of a stanol group can be obtained. Since the content ratio of the stanol group is small, the condensation of the stanol groups with each other can be suppressed. The reaction of the liquid crystal aligning agent of the present invention is further improved by the above-mentioned other polymer, since the stanol group and other polymers can be inhibited. The polymerization reaction is presumed to be excellent as a result of excellent storage stability. In terms of catalysts, organic bases are preferred. The amount of the organic base to be used may be appropriately set depending on the reaction conditions of the type of the organic base, the temperature, and the like, and is preferably 0.01 to 3 times, more preferably 0.05 to 1 times, based on the total decane compound. Moor. g Hydrolysis or hydrolysis/condensation reaction in the production of a polyorganosiloxane having an epoxy group, in which an epoxy group-containing decane compound and other decane compounds necessary for dissolving in an organic solvent are used to make the solution with an organic base and water. The mixing is preferably carried out, for example, by heating in an oil bath or the like. In the hydrolysis/condensation reaction, the heating temperature is preferably 130 ° C or less, more preferably 40 0 to 100 ° C, preferably 〇 5 5 ° 1 2 hours, more preferably 1 to 8 hours. . The mixture may be stirred or placed under reflux during heating. After the completion of the reaction, it is preferred to wash the organic solvent layer separated from the reaction liquid with water. In the case of washing, the washing operation is facilitated by washing with a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2% by weight. After the washing is carried out until the water layer is neutral, the organic solvent layer may be dried with a suitable desiccant such as anhydrous calcium sulfate or molecular sieve, and then the solvent is removed to obtain a polyorganic having an epoxy group. Oxane. In the present invention, a commercially available polyorganosiloxane having an epoxy group can be used. Such commercially available products include, for example, DMS-E01, DMS-E12, DMS-E21' EMS-32 (above, Chisso). -22- 200934859 <Sensory Radiation Polyorganooxane> The radiation sensitive polyorganosiloxane used in the present invention can be derived by using a polyorganosiloxane having an epoxy group as described above and cinnamic acid. The substance (1) is preferably synthesized by carrying out a reaction in the presence of a catalyst. Here, the amount of the cinnamic acid derivative (1) used is preferably 0.001 to 1.5 mol, more preferably 0.01 to 1 mol, and still more than 1 mol of the epoxy group of the polyorganosiloxane. Good for 0 0.05 ~ 0.9 Mo. As the above catalyst, an organic base or a conventional compound which promotes the reaction of an epoxy compound with an acid anhydride, that is, a hardening accelerator can be used. Each of the above organic bases may, for example, be ethylamine, diethylamine, piperazine, piperidine, pyrrolidine or pyrrole-like organic amines of 1 to 2; triethylamine, tri-n-propylamine, tri-n a butylamine, a pyridine, a 4-dimethylaminopyridine, a diazabicycloundecene-like organic amine: a tetramethylammonium hydroxide-like organic amine or the like. Among these organic bases, triethylamine, tri-n-propylamine, tri-n-butylamine oxime, pyridine, 4-dimethylaminopyridine-like organic amine; tetramethyl hydroxide Ammonium grade 4 organic amines are preferred. The hardening accelerator may, for example, be benzyldimethylamine, 2,4,6-gin(dimethylaminomethyl)phenol, cyclohexyldimethylamine or triethanolamine-like tertiary amine; 2-methyl Imidazole, 2-η-heptyl imidazole, 2-η-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1- Benzyl-2-phenylimidazole, iota, 2, dimethylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-methylimidazole, 1-(2 -cyanoethyl)-2-η-undecyl-23- 200934859 imipenoid, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)_2_ Ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di(ylmethyl)imidazole, 1_(2•cyano) Ethyl)_2_phenyl_4,5-bis[(2'-cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl--alkylimidazole guntrimellitic acid, 1- (2-cyanoethyl)-2-phenylimidazole key trimellitic acid, 1-(2-cyanoethyl)_2-ethyl-4-methylimidazole gun trimellitic acid, 2,4- Diamino-6-[2'-methylimidazolylethyl-s-triazine, 2,4-diamino- φ 6-(2'-11-undecylimidazolyl)ethyl- 3_Triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]ethyl-s-triazine, 2-methylimidazole Cyanuric acid adduct, isophenyl cyanide adduct of 2-phenylimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl- Isoimide compound of s-triazine isomeric cyanuric acid addition: diphenylphosphine, triphenylphosphine, triphenylphosphorus organophosphorus phosphite; benzyltriphenylphosphonium chloride, tetra-n- Butyl bromide, methyltriphenyl bromide, ethyltriphenyl bromide, η-butyltriphenylphosphonium bromide, tetraphenyl rust bromide, ethyltriphenyl scale Iodide, ethyltriphenyl rust acetate, tetra-n-butyl fluorene, 〇-diethyl dithiophosphate, tetra- n-butylphosphonium Benzotriazolate, tetra-n-butyl quaternary tetrafluoroboron Acid ester, tetra-n-butyl quaternary tetraphenyl borate, tetraphenyl rust tetraphenyl borate grade 4 sulfonium salt: 1,8-diazabicyclo[5.4·〇]undecene or Organic acid salt-like diazabicycloalkenes; zinc octylate, tin octylate, Ming acetyl acetonide complex organometallic compounds; -24- 200934 859 tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride-like 4-grade ammonium salt; boron trifluoride, triphenyl borate Boron compound; zinc chloride, chlorinated second tin-like metal halide compound; dicyandiamide or amine and epoxy resin addition product, etc., amine addition molding, high melting point dispersion potential of accelerators, etc. a hardening accelerator; a microcapsule-type latent hardening accelerator coated with a polymer such as an imidazole compound, an organophosphorus compound or a phosphinic acid salt or the like; an amine salt type latent hardener accelerator; A latent hardening accelerator such as a high-temperature dissociative thermal cationic polymerization type latent curing accelerator such as a strontium salt or a bronze sulphate. Among these, preferred are tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride-like 4-grade ammonium salt. The amount of the catalyst used is preferably 1 part by weight or less, more preferably 1 part by weight to 1 part by weight, more preferably 1 part by weight to 1 part by weight of the polyorganooxysiloxane having an epoxy group. Preferably, it is 0.1 to 20 parts by weight. The reaction temperature is preferably from 〜200 ° C, more preferably from 50 to 150. (: The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours. The synthesis reaction of the radiation-sensitive polyorganosiloxane can be carried out as needed; and the organic solvent can be used. For example, a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, a guanamine compound, an alcohol compound, etc. The solubility of the raw material and the product, and the ease of purification of the product, the ether compound, the ester compound, and the ketone compound are used. It is preferable that the solvent is a solid content concentration (the ratio of the total weight of the components other than the solvent in the reaction solution to the total weight of the solution) is preferably 0.1% by weight or more, and more preferably 5 to 5 0. The amount of the weight percent is used. The radiation-sensitive polyorganosiloxane of the present invention is introduced by the open-loop addition of epoxy by polyorganosiloxane having an epoxy group, and is introduced from cinnamic acid. This manufacturing method is simple and can be used as a method which is highly suitable for the introduction of a structure derived from a cinnamic acid derivative. 0 Further, the radiation-induced linear aggregation of the present invention In the synthesis of the oxime oxane, one part of the above cinnamic acid derivative (1) may be represented by the following formula (4) RIX-Z (4) (in the formula (4), the RDX may be substituted by fluorine and the carbon number is 4 to 20 An alkyl group or an alicyclic group-containing organic group having a carbon number of from 3 to 40, and z is selected from the group consisting of a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR, -CH=CH2, and -S02C1. a compound of 1 valence 0.) substituted with a compound represented by formula (4). The RIX aspect of the formula (4) is an alkylphenyl group having an alkyl group which may be substituted by fluorine (except that the carbon number of the alkyl group is 8 to 20). The alkoxy group which may be a fluorine-substituted alkoxy group (only the carbon number of the alkoxy group is 8 to 20) is preferred. In the Z aspect, a carboxyl group is preferred. The specific compound represented by the above formula (4) For example, for example, the following formula (4-1) to (4-4) (4-1)

CfF2f+1CgH2g-COOH -26- 200934859

ChH2h+i~〇

—COOH (4-2)

(in the formula (4-1), f is an integer of 1 to 3, g is 3 to 18, and h is an integer of 5 to 20, and i in the formula (4-3) is an integer of 0 to 18 1 to 3, In the formula (4-4), k is an integer of 1 to 18. In the compound represented by the above formula (4), the compound represented by the above-mentioned fin is preferably the following formula (4-3-1) to (4_). 3-3) !, the integer represented by the formula (4-2), j is the representation represented by the formula; (4-3)

The compounds represented by the respective are better. The compound represented by the above formula (4) can be reacted with a polyorganosiloxane having an epoxy group under the same reaction conditions as the cinnamic acid derivative (1) -27-200934859 to introduce a photosensitive polyorganosiloxane. alkyl. The compound represented by the above formula (4) is preferably 50% by mole or less, more preferably 3 3 in terms of the total of the cinnamic acid derivative (1) and the compound represented by the above formula (4). The percentage of moles below. When the ratio of the use of the compound represented by the above formula (4) exceeds the use ratio of the cinnamic acid derivative (1), when the obtained liquid crystal display element is turned ON (voltage-applied state), an abnormal region is generated. . <Other components> The liquid crystal alignment agent of the present invention contains the above-mentioned radiation-sensitive polyorganisms. The liquid crystal alignment agent of the present invention may further contain other components in addition to the above-mentioned radiation-sensitive polyorganosiloxane, without impairing the effects of the present invention. Such other components include, for example, a polymer other than a radiation-sensitive polyorganosiloxane (hereinafter referred to as "another polymer"), a hardener, a hard G-catalyst, a hardening accelerator, and at least one molecule. An epoxy group compound (hereinafter referred to as "epoxy compound"), a functional decane compound, a surfactant, and the like. <Other Polymers> The above other polymers can be used to further improve the solution characteristics of the liquid crystal alignment agent of the present invention and the electrical characteristics of the obtained liquid crystal alignment film. In terms of the other polymer, for example, at least one polymer selected from the group consisting of polylysine and polyimine, and the following formula (S-2) -28- 200934859

r X2 1 I --Si*0-- L Ϋ2 (S-2) (In the formula (S-2), X2 is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon number of 1 to 6 An alkoxy group or an aryl group having 6 to 20 carbon atoms, Y2 being a hydroxyl group or an alkoxy group having a carbon number of from 1 to 10, which is a group of a polyoxyalkylene represented by hydrazine, a hydrolyzate thereof and a condensate of a hydrolyzate thereof. At least one selected (hereinafter referred to as "other polyoxane"), polyphthalate, polyester, polyamine, cellulose derivative, polyacetal, polystyrene derivative, poly(benzene) Ethylene-phenylmaleimide derivatives, poly(meth)acrylates, and the like. [Polyuric acid] The above polylysine can be obtained by reacting a tetracarboxylic dianhydride with a diamine to obtain a fluorene phthalic acid. For the synthesis of a tetracarboxylic dianhydride, for example, butane tetracarboxylic acid Anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl Base-1,2,3,4-cyclobutane tetraresic acid dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanine tetradecanoic acid dianhydride, i, 2, 3, 4 -tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexane Tetracarboxylic dianhydride '3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxy norbornazole Alkane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, -29- 200934859 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2, 5-dioxo-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-methyl- 5(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]-furan-l,3-dione, l,3,3a,4,5,9b-six Hydrogen-5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3, 3a,4,5,9b-hexahydro-7-methyl-5-(•tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]-furan-1, 3-diketone, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene 0 and [l, 2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furan -Naphtho[1,2-indolyl]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-ethyl-5-(tetrahydro-2, 5-dioxo-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-di Methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 5-(2,5-dioxo Tetrahydrofuranyl-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octyl-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5,-dione), 5-φ (2,5-dioxo) Tetrahydro-3-furanyl-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo[5.3.1.0'6]undecane-3,5,8,10-tetraone and the following formulas (TI) and (T-II) -30 - 200934859

© (In the formulas (τ-1) and (Τ-II), R1 and R3 are each a divalent organic group having an aromatic ring. 'R2 and R4 are each a hydrogen atom or an alkyl group, and a plurality of ... and R4 may each be Aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride of the same or different compounds, etc.; pyromellitic dianhydride, 3,3',4,4'-diphenyl Methyl ketone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl maple tetra-residual dianhydride ' 1,4,5,8 -naphthalene tetraphthalic acid dianhydride, 2,3,6,7 -naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, ❹ 3,3',4,4'-dimethyldiphenyl sand tetradecanoic acid Dihydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-di Carboxyphenoxy)diphenylsulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4'-bis(3,4-dicarboxyl Phenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene di phthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic acid Dihydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) Phenylphosphine oxide dianhydride, P-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)- -31 - 200934859 4,4'-diphenylmethane dianhydride, ethylene glycol-bis(trimellitic anhydride), double ( Trimellitic anhydride), 1,4-butanediol-bis(trimellitic anhydride), alcohol-bis(trimellitic anhydride), 1,8-octanediol-bis(trimellitic anhydride (4-hydroxyphenyl)propane-bis(trimellitic anhydride), Formula (T-1) Propylene Glycol-1,6-hexane, 2,2-bis-(T-4)

-32- 200934859

Benzene ring aromatic tetracarboxylic dianhydride of a compound tetracarboxylic dianhydride represented by 33-200934859. The above aromatic ' may be substituted with one or two or more carbon atoms of 1 to 41 monoalkyl groups (preferably methyl groups). These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

'butane tetracarboxylic dianhydride' 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylate Acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3&,4,5,91?- Hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, l,3,3a,4,5, 9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[i,2-c]furan-1,3-dione, 1,3 ,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan- 1,3-diketone, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octyl-2,4 -dione-6-spiro-3,-(tetrahydrofuran-2, '5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-ring Hexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-anhydride, 4,9-dioxatricyclo[5.31〇 2'6] deca-alcohol_3581 perylenetetraketone, pyromellitic dianhydride, 3,3,,4,4,_benzophenone tetracarboxylic dianhydride, 3,3',4,4'- Biphenyl-tetracarboxylic dianhydride '2,2,3,3,biphenyl four An acid anhydride, 1,4,5,8 - naphthalene tetracarboxylic dianhydride, the following formula (Τ-5) compound represented by the above formula (T-I) in the ~ (Τ-7) -34- 200934859

The compound represented by the above and the compound represented by the above formula (τ_π) have the following formula (Τ-8)

(Τ-8) 化合物 The compound represented by ❿ is preferable from the viewpoint of exhibiting good liquid crystal alignment. Particularly preferred are, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3&, 4,5,913 - hexahydro-5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-£:]furan-1,3-dione, 1,3,3&,4 ,5,91>-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]furan-1,3-dione , 3-oxabicyclo[3.2.1]octyl-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxo) Tetrahydro-3-furanyl-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxy-35- 200934859 base norbornene-2 : 3 ' 5 : 6 -dianhydride, 4,9-dioxatricyclo[5-3.1.〇2'6]undecane-3,5,8,10-tetraone, pyromellitic dianhydride And the compound represented by #(T-5) above. The above diamine can be used in the synthesis of polylysine, such as Ρ-phenyl diene, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4,-diaminodi Benzene brothel, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl oxime, 3,3'-dimethyl-4,4'-diamino Biphenyl, 4,4'-diaminobenzimidamide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4'4 '-Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-di-l-methyl 1 4,4,-diaminobiphenyl , 3,3,-Ditrifluoromethyl-4,4,-diaminobiphenyl, 5-amino-1-(4,-aminophenyl)-1,3,3-trimethylhydrazine Full, 6-aminoaminophenyl)-1,3,3-trimethylindan, 3,4'-diaminodibenzoate, 3,3'-diaminobenzophenone, 3 , 4'-diaminobenzophenone, diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane _ 2,2-bis[4 -(4-Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-amino)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy) Phenyl]milled, 1,4-bichoxyphenoxy)benzene, 1,3-bis(4-amine Phenoxy group) benzene, 1,3-bis(3-amine succinyloxy)benzene, 9,9-bis(4-aminophenyl)-1 fluorene hydroquinone, 2,7-diamino group 9,9-dimethyl-2,7-diaminopurine, 9,9-bis(4-aminophenyl)anthracene,

, methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-diamino 2,2'-dichloro-4,4'-diamine Base-5,5'-dimethoxybiphenyl, 3,3'-dimethyl

,l,4,4'-(p-phenylisopropylene)diphenylamine, -(m-phenylisopropylene)diphenylamine, phenoxy)phenyl]hexafluoropropane, 4; 2, 2'-bis[4-(4-amino-2-trifluoro 4,4'-diamino-2,2'-bis(trifluoromethyl-36-200934859)biphenyl, 4,4'- An aromatic diamine such as bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl; 1,1-m-xylylenediamine, 1,3-propanediamine , tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, 1,4-diamine Cyclohexane, isophorone II. Amine, tetrahydrodicyclopentadienyldiamine, hexahydro-4,7-methyleneindandimethylenediamine, tricyclo[6.2.1.02'7] -undecene dimethyldiamine, 4,4'-methylene 0 bis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(amino group A) An aliphatic diamine such as cyclohexane or the like and an alicyclic diamine; 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-di Aminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4-dihydroxy Pyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis(3-aminopropyl)piperazine, 2,4-diamino -6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6- Phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-didecylamino-1,3,5-triazine, 4, 6-Diamino-2-vinyl-S-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3 -dimethyl uracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxy acridine lactate, 3,8-diamino- 6-phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, oxime, Ν'- Bis(4-aminophenyl)-benzidine, the following formula (DI) -37- 200934859 h2n d xv=7vnh2 (DI) (in the formula (DI), R5 is selected from the group consisting of shame, chew, and a monovalent organic group having a nitrogen atom in a group of a group consisting of a azine, a pulse, and a piperazine, and X3 is a divalent organic group. Compound represented by the following formula (D-II)

(In the formula (D-II), R6 is a divalent organic group having a ring structure of a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triazine, piperidine and piperazine, and each of X4 is a divalent organic group. The X4 present in the plural may be the same or different. The compound represented by the same is equivalent to a diamine having two primary amine groups in the molecule and a nitrogen atom other than the primary amine group; h2n

(D-III) (In the formula (D-ΙΠ), R7 is a divalent organic group selected from the group consisting of -0, -COO-, -OCO-, -NHCO-, -CONH-, and -CO- , R8 is a monovalent of a steroid skeleton, a trifluoromethylphenyl group, a trifluoromethoxyphenyl group or a fluorophenyl group having a -38-200934859 organic group or a carbon number of 6 to 30 alkyl groups. Monosubstituted phenylenediamine; Formula (D-IV) R9 R9 NH: H2N-(-CH2^-Si-f〇-Si^f-CH2)^ R9 R9 (D-IV) (Formula D-IV In the above, each of R9 is a hydrocarbon group having a carbon number of 1 to 12, and a plurality of R9 groups may be the same or different, P is an integer of 1 to 3, and q is an integer of 1 to 20). Amino-based organooxane; formula (D-1) to (D-5)

-39- 200934859

,ch3 Όη3 (D-2)

-40- 200934859

Ο~^~〇2Η4~

Ηη2 (D-5) Ο (wherein y in the formula (D-4) is an integer of 2 to 12, and ζ in the formula (D-5) is an integer represented by 1 to 5). The aromatic diamine, the benzene ring of the compound represented by the above formulas (D-Ι) to (D-III) and (D-1) to (D-5) may have one or two or more carbon numbers. A 1 to 4 alkyl group (preferably a methyl group) is substituted. These diamines may be used alone or in combination of two or more. Among these, ρ-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2' -Dimethyl- 4,4'-diaminoaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 2,7-diaminopurine, 4, 4'-Diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2, 2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylene II Isopropyl)diphenylamine, 4,4'-(m-phenylenediisopropylidene)diphenylamine, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis ( 4-aminophenoxy)biphenyl, 1,4-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane a compound represented by the above formula (D-1) to (D-5), 2,6-diaminopyristidine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6 - -41 - 200934859 —fee based on a steep, 3,6-diamino group, N-methyl- 3,6-diamino group, N-ethyl-3,6-diaminocarbazole , N-phenyl-3,6-diaminocarbazole, N , N, _ (4-amino basic group)-linked amine, the compound represented by the above formula (D-i), the following formula (D-6)

(D-6) The compound represented by the above formula (D-7) and the compound represented by the above formula (D-II) (D-7) (D-7) H2N~~C_3~N\ ^~~〇3Ηβ~ a compound represented by ~^, a dodecyloxy-2,4-diaminobenzene or a pentadecyloxy-2,4-diaminobenzene in the compound represented by the above formula (D-III), Hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecaoxy-2,5-diaminobenzene, pentadecyloxy -2,5-diaminobenzene, hexadecyloxy-2,5--aminobenzene, octadecyloxy-2,5-diaminobenzene, the following formula (D-8)~( D-16)

-42- 200934859

-43- 200934859

The compound represented by the above and the 1,3-bis(3-aminopropyl)-tetramethyldioxane represented by the above formula (D-IV) are preferred. The ratio of the tetracarboxylic dianhydride to the synthesis reaction of the poly-proline is preferably in the range of 0.2 to 2 equivalents based on 1 equivalent of the amine group contained in the diamine, and more preferably The ratio of equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent at a temperature of -20 to 150 ° C, more preferably at a temperature of 0 to 10 ° C for 1 to 48 hours, more preferably 2 to 2 1 hour. In this regard, in the case of dissolving the synthesized polylysine, there is no acid in the compound which uses dianhydride 0.3 to 1.2, preferably, preferably organic solvent is particularly limited -44-200934859 ' For example, N-methyl-2-pyrrolidone, hydrazine, hydrazine-dimethylacetamide, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylimidazolidinone, dimethyl hydrazine, γ_ An aprotic polar solvent such as butyrolactone, tetramethyl urea or hexamethylphosphoric acid triamide; a phenolic solvent such as m-cresol, xylenol, phenol or halogenated phenol. The amount of the organic solvent used (a) is preferably from 0.1 to 30% by weight based on the total amount (b) of the tetracarboxylic dianhydride and the diamine relative to the reaction. The total amount (a + b) of the solution is preferably from 0.1 to 30% by weight. When the organic solvent and the poor solvent described later are used, the amount (a) of the organic solvent used is the total amount of the organic solvent and the poor solvent. In the above organic solvent, a poor solvent of polyglycine, that is, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon, or the like which is generally considered, may be used in the range in which the polyamic acid formed is not precipitated. Specific examples of the poor solvent, such as methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl Ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate , Ethyl ethoxylated propionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-η-propyl Ether, ethylene glycol-i-propyl ether, ethylene glycol-η-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, two Ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, Tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, guanidine-dichlorobenzene, hexane, heptane, octane, benzene, toluene , xylene, isoamyl propionate, isoamyl isobutyrate, diisoamyl Ether, etc. -45- 200934859 When the polyacetate is used in the production of the above-mentioned poor solvent in an organic solvent, the use ratio may be suitably set in the range in which the produced polyamine does not precipitate, preferably in the total solvent. 50% by weight or less, more preferably 20% by weight or less. As described above, a reaction solution in which polylysine is dissolved can be obtained. The anti-solution solution can be directly supplied to the preparation of the liquid crystal alignment agent' or the poly-proline acid contained in the reaction solution can be isolated for the preparation of the liquid crystal alignment agent, or the mono-isomerized polyglycolic acid can be supplied to the liquid crystal alignment. Modulation of the agent. The separation of the polyamic acid can be carried out by injecting the above reaction solution into a large amount of a poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure, or by subjecting the reaction solution to a vacuum distillation under reduced pressure. The method is carried out. Further, the polyglycine is purified by redissolving it in an organic solvent, followed by precipitation in a lean solvent, or a step of distilling off under reduced pressure in an evaporator one or several times. [Polyimine] The above polyimine can be synthesized by dehydration ring closure of a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine. The tetracarboxylic dianhydride which can be used for the synthesis of the above polyimine is exemplified by the same compound as the tetracarboxylic dianhydride which can be used for the synthesis of the above polyamic acid. In the case of the tetracarboxylic dianhydride which can be used for the synthesis of the polyimine in the present invention, it is preferred to use a tetracarboxylic dianhydride containing an alicyclic tetracarboxylic dianhydride. Particularly preferred aspects of alicyclic tetracarboxylic dianhydrides such as 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2 ,5-dioxo-3-furanyl)-naphtho-46- 200934859 [l,2-c]pyran-1,3-dione, l,3,3a,4,5,9b-hexahydro- 8-Methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]furan-1,3-dione, 3-oxabicyclo[3.2. 1] Octane-2,4-dione-6-spiro-3,-(tetrahydrofuran-2,5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)- 3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5:6-two or or 4,9 - Dioxatricyclo[5_3·1 ·02'6]undecane-3,5,8,10-tetraone. In the synthesis of the above polyimine, an alicyclic tetracarboxylic dianhydride and 0 other tetracarboxylic dianhydride can be used. In this case, the ratio of the alicyclic tetracarboxylic dianhydride contained in the total tetracarboxylic dianhydride is preferably 1% by mole or more, more preferably 50% by mole or more. The diamine which can be used for the synthesis of the above polyimine can be exemplified by the same compound as the diamine which can be used for the synthesis of the above polyamic acid. In the present invention, in view of the diamine which can be used for the synthesis of polyimine, a diamine containing a diamine represented by the above formula (D-III) is preferred. Preferred examples of the compound include, for example, dodecyloxyindenyl-2,4-diaminobenzene and pentadecyloxy-2,4-di in the compound represented by the above formula (D-III). Aminobenzene, hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, ten Pentameryl-2,5-diaminobenzene, cetyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene and the above formula (D-8) ) The compound represented by the difference of (D-16). In the synthesis of the above polyimine, the diamine represented by the above formula (D-III) and other diamines may be used. Preferred of the other diamines are, for example, anthracene-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diamine Naphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-tris-47- 200934859 fluoromethyl-4,4'-diaminobiphenyl, 2 , 7-diaminopurine, 4,4,-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis (4 _Aminophenyl) hydrazine, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoride, 4,4'-(p-phenylene diisopropylidene)diphenylamine, 4,4'-(m-phenylenediisopropylidene)diphenylamine, anthracene, 4_cyclohexanediamine, • 4 , 4'-methylenebis(cyclohexylamine), 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, the above formula (n)~(D_5) respectively, the compound represented by 〇, 2,6-diamine-based shame, 3,4-diaminopurine, steepness, 2,4-diaminopyrimidine, 3,6-di Acridine, ν, Ν, - bis(4-aminophenyl)-benzidine, anthracene, Ν'-bis(4-aminophenyl)-indole, Ν'-dimethyl-benzidine a compound represented by the above formula (D-6) in the compound represented by the above formula (D-Ι), or a compound represented by the above formula (D-7) in the compound represented by the above formula (D-II) And the compound represented by the above formula (D-IV), such as bis-aminopropyl) tetramethyldioxane. When the diamine represented by the above formula (D-III) and the other diamine are used, the use of the diamine represented by the above formula (D-III) is preferably 〇·5% by weight based on the total diamine. The above is particularly preferably 1% by weight or more. The dehydration ring-closing reaction of the polyimine which can be used in the present invention can be carried out by (i) heating the poly-proline, or by dissolving the poly-proline in an organic solvent and adding dehydration to the solution. The agent and the dehydration ring-closing catalyst are subjected to heating as needed. The reaction temperature of the above method (i) for heating the polyamic acid is preferably from 50 to 200 ° C', more preferably from 60 to 170 ° C. When the reaction temperature is less than 50 ° C, the dehydration ring closure reaction is incomplete and the reaction temperature exceeds 200. (:, the molecular weight of the obtained ruthenium iodide polymer is lowered. The reaction time of the method for heating polyglycine -48-200934859 is preferably 0 · 5 to 4 8 hours, more preferably 2 2 Further, in the above method (ii) wherein a dehydrating agent and a dehydration ring-closing catalyst are added to the polyaminic acid solution, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride may be used as the dehydrating agent. The amount of the agent used is 1 mol of the polyamine structure, and it is preferably 1 to 20 mols. Further, the dehydration ring-closing catalyst can be used, for example, pyridine, trimethylpyridine or dimethyl. A tertiary amine such as a pyridine or a trimethylamine. However, it is not limited thereto. The amount of the dehydration ring-closing catalyst used is preferably from 0.01 to 10 moles per mole of the dehydrating agent used. The organic solvent used for the dehydration ring-closure reaction may, for example, be an organic solvent exemplified for the synthesis of polylysine. The reaction temperature of the dehydration ring-closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. , the reaction time, preferably from 0.5 to 24 hours, more preferably from 1 to 1 hour. The above method (i) Polyimine, which can be directly supplied to a liquid crystal alignment agent, or can be supplied to a liquid crystal alignment agent after purification. In addition, in the above method (Π), a reaction solution containing polyimine can be obtained. The reaction solution may be directly supplied to the liquid crystal alignment agent, or may be supplied to the liquid crystal alignment agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, or may be separated from the polyimine and then supplied to the liquid crystal alignment. Preparation of the agent, or purification of the separated polyimine and supply to the liquid crystal alignment agent. The dehydrating agent and the dehydration ring-closing catalyst are removed from the reaction solution, and a method such as solvent substitution can be used, for example, separation of the polyimine. Purification, as a method for separation and purification of polylysine, can be carried out in the same manner as described above. -49- 200934859 Polyimine which can be used in the present invention, which can be in the structure of water painter or proline A part of the amine ring structure and the proline structure are used. The polyimine of the present invention may be used in the above-mentioned subliminal limbs, more preferably 85% or more. Here, "| Lieutenant The ratio of acid structure to yttrium imine represents the ratio of the number of quinone imine rings. At this time, deer 0 is an isoindole ring. The rate of ruthenium iodide can be a poly(3) solvent (for example, dimethyl dihydrogenation) Sub-grinding, using ΙΖΪ substance, the result of 1H-NMR measurement at room temperature. 醯 imidization rate (%) = (1 - A 1 / A2 X a) X 1 0 0 (in the formula (1), Α1 is the peak area of the proton of Q with a chemical shift of 10 ppm, and A2 is the ratio of the number of other protons from the precursor of other profilings relative to polyimine (polyproline).) - Polymerization of terminal modification The above-mentioned poly-proline and polyimine can be a modified type. Such a terminal modified type is synthesized by adding a molecular weight modifier to the reaction system. In terms of, for example, the acid monoanhydride, the monoamine compound, and the monoisoamic acid structure are all de-closed, and the enthalpy of hydrazine is preferably present, and the ratio of the number of phases is preferably 80%. One part of the amine ring can be dissolved in an appropriate heavy hydrogen methyl decane as a reference. The area of the peak from the NH group appearing in (1) by the following formula (i), and the proton of α, which is a sulfhydryl group, is adjusted. In the case of valine, the above-mentioned molecular weight modifier cyanate compound or the like can be used. -50- 200934859 In this case, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, mercapto succinic anhydride 'n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, η - Cetyl succinic anhydride or the like. Further, in terms of monoamine compounds, for example, 'aniline, cyclohexylamine, η-butylamine, η-pentylamine, η-hexylamine, η-heptylamine, η-octylamine, η-decylamine, η_Mercaptoamine, η-undecylamine, η-dodecylamine, η-tridecylamine, η-tetradecylamine, η-pentadecylamine, η-hexa Alkylamine, η-heptadecylamine, η-octadecylamine 'η-icosylamine, and the like. Further, as the monoisocyanate compound, for example, phenyl isocyanate or naphthyl isocyanate is used. The amount of the molecular weight modifier used is preferably 20 parts by weight or less, more preferably 5 parts by weight or less based on 100 parts by weight of the total of the tetracarboxylic dianhydride and the diamine used in the synthesis of the polyamic acid. -Solid viscosity - When the polyglycine or polyimine obtained as above is made into a solution having a concentration of 1% by weight, it is preferred to have a solution viscosity of 20 to 800 mPa's to maintain 30 to 500 mPa*. The viscosity of the solution of s is better. The solution viscosity (mP^s) of the above polymer is a good solvent (for example, N-methyl-2-pyrrolidone) using the polymer, and a polymer solution having a concentration of 10% by weight 'using E-type rotational viscosity Measured at 25 ° C. [Other Polyoxane] At least one selected from the group consisting of polyoxyalkylene having a repeating unit and a condensate of a hydrolyzate and a hydrolyzate thereof represented by the above formula (S-2) (other polyoxyalkylene) Further, in the above formula (S-2), X2 is preferably an alkyl group having 1 to 20 carbon atoms or a polyorganosiloxane having an aryl group having 6 to 20 carbon atoms. The other polyorganosiloxane may be preferably at least one decane compound (hereinafter referred to as "raw material decane compound") selected from the group consisting of an alkoxy decane compound and a halogenated decane compound. In the presence of an organic solvent, in the presence of water, a solvent, and a catalyst, hydrolysis, hydrolysis, and condensation are carried out to synthesize 〇©. The raw material decane compound which can be used herein may, for example, be tetramethoxy decane, tetraethoxy sand, or four. -η-propoxy collateral, four-iso-propoxy cleavage, tetra-n-butoxylate, four-sec-butoxylate, tetra-tert-butoxy decane, tetrachloro Decane; methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane, methyltri-iso-propoxydecane, methyltri-n-butoxydecane, Methyl tris-sec-butoxydecane, methyl tri-tert-butoxydecane, methyltriphenyloxydecane, methyltrichlorodecane, ethyltrimethoxydecane, ethyltriethoxydecane , ethyl tri-n-propoxydecane, decyl tri-iso-propoxydecane, ethyl tri-n-butoxydecane, ethyl tri-sec-butoxydecane, Tris-tert-butoxydecane, ethyltrichlorodecane, phenyltrimethoxydecane, phenyltriethoxydecane, phenyltrichlorodecane; dimethyldimethoxydecane, dimethyldi Ethoxy decane, dimethyl dichloro decane; trimethyl methoxy decane, trimethyl ethoxy decane, trimethyl chloro decane, and the like. Among these, tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, dimethyl Dimethoxy decane, dimethyl diethoxy decane, trimethyl methoxy decane or trimethyl ethoxy decane is preferred. -52- 200934859 When the other polyorganosiloxane is synthesized, the organic solvent which can be optionally used may, for example, be an alcohol compound, a ketone compound, a guanamine compound or an ester compound or the other aprotic compound. These may be used alone or in combination of two or more. The above alcohol compound may, for example, be methanol, ethanol, η-propanol, i-propanol, η-butanol, i-butanol 'sec-butanol, t-butanol 'n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, η-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, Sec - heptanol, heptanol-3, η η-octanol, 2-ethylhexanol, sec-octanol, η-mercaptool, 2,6-dimethylheptanol-4, η-nonanol , sec-undecyl alcohol, trimethyldecyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5- Monool compounds such as trimethylcyclohexanol, benzyl alcohol, diacetone alcohol, etc. ethylene glycol, 1,2-propanediol, 1,3-butanediol, pentanediol-2,4,2-methyl Pentyl glycol-2,4, hexanediol-2,5, heptanediol-2,4,2-ethylhexanediol-1,3,diethylene glycol, dipropylene glycol, triethylene glycol, three a polyvalent alcohol compound such as propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol single Phenyl acid, ethylene glycol mono-2-ethylate , 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 A partial ether of a polyvalent alcohol compound such as monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether or dipropylene glycol monopropyl ether. These alcohol compounds may be used singly or in combination of two or more kinds. -53- 200934859 Each of the above ketone compounds may, for example, be acetone, methyl ethyl ketone, methyl-η-propyl hydrazine, methyl-η-butyl hydrazine, monoethyl hydrazine, methyl-i-butyl fluorene, methyl- Η-amyl ketone, ethyl-η-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethyl fluorenone, cyclohexanone, 2-hexanone, methylcyclohexanone a monoketone compound such as 2,4-pentanedione, acetonylacetone, acetophenone or fenketone t acetamidine, 2,4-hexanedione, 2,4-heptanedione, 3,5-g Diketone, 0 2,4-octanedione, 3,5-octanedione, 2,4-decanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2 a β-diketone compound such as 2,6,6-tetramethyl-3,5-heptanedione or 1,1,1,5,5,5-hexafluoro-2,4-heptanedione or the like. These ketone compounds can be used singly or in combination of two or more kinds. The above guanamine compound may, for example, bemethantamine, hydrazine-methylformamide, hydrazine, hydrazine-dimethylformamide, hydrazine-ethylformamide, hydrazine, hydrazine-diethylformamide, B. Indoleamine, hydrazine-methylacetamide, hydrazine, hydrazine-dimethylacetamide, hydrazine-ethylacetamide, hydrazine, hydrazine-diethylacetamide, hydrazine-methyl propylamine, hydrazine -methylpyrrolidone G, Ν-methylmercaptomorpholine, Ν-methylhydrazine piperidine, Ν-methylpyridylpyrrolidine, Ν-ethinylmorpholine, Ν-ethinylpiperidine, Ν-acetamidine Pyrrolidine and the like. These guanamine compounds may be used alone or in combination of two or more. Examples of the above vinegar compound include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, and η-propyl acetate. , i-propyl acetate, η-butyl acetate, i-butyl acetate, sec-butyl acetate, η-amyl acetate, sec-amyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate Ester, 2-ethyl butyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate -54- 200934859 ester, η-decyl acetate, methyl acetoxyacetate Ethylacetate, ethyl acetate, monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diacetic acid Alcohol mono η·butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether • dipropylene glycol monoethyl ether , ethylene glycol diacetate, methoxy triethylene glycol acetate, ethyl propionate, η-butyl propionate, i-pentyl propionate, diethyl phthalate , di-n-butyl oxalate, methyl lactate, ethyl lactate, η-butyl lactate, η-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, etc. . These ester compounds may be used alone or in combination of two or more. The above other aprotic compound may, for example, be acetonitrile, dimethyl hydrazine, hydrazine, hydrazine, hydrazine, Ν'-tetraethyl sulfonamide, trimethylamine hexamethylphosphate, hydrazine-methylmorpholine, hydrazine - Methylpyrrole, Ν-ethylpyrrole, Ν-methyl-Δ3 -pyrroline, Ν-methylpiperidine, Ν-ethylpiperidine, hydrazine, hydrazine-dimethylpiperazine, hydrazine-methylimidazole, Ν-Methyl-4-piperidone, Ν-methyl-2-piperidone, Ν-methyl-2-pyrrolidone Φ, 1,3-dimethyl-2-imidazolidinone, 1,3- Dimethyltetrahydro-2(1?)-pyrimidinone and the like. Among these solvents, a polyvalent alcohol compound or a partial ether or ester compound of a polyvalent alcohol compound is particularly preferable. The ratio of the water used in the synthesis of the other polyorganosiloxane is preferably from 0.5 to 100 mol, more preferably from 1 to 100 mol, based on the total amount of the alkoxy group and the halogen atom of the starting decane compound. 30 moles, further preferably 1 to 1 · 5 moles. As the catalyst which can be used in the synthesis of other polyorganosiloxanes, for example, gold-55-200934859 is a chelate compound, an organic acid, an inorganic acid, an organic base, ammonia, an alkali metal compound or the like. The above metal chelate compound may, for example, be triethoxy.mono(acetonitrile) titanium, tri-n-propoxy mono(acetonitrile) titanium, tri-i-propoxy. mono(acetonitrile) Titanium, tri-n-butoxy-mono(acetonitrile) titanium, tris-s-butoxy·. mono(acetonitrile) titanium, tri-t-butoxy. mono(acetonitrile) Titanium, diethoxy bis (acetyl acetonide) hydrazine, di- η - propoxy bis (ethyl acetonide) titanium, di-i propyl oxy. bis (acetyl acetonide) titanium, two - Η-butoxy bis(acetonitrile) titanium, bis-sec-butoxy. bis(acetonitrile) titanium, di-t-butoxy bis(acetonitrile) titanium, monoethoxy Base (acetylacetone) titanium, mono-η-propoxy. ginseng (acetonitrile) titanium, mono-i-propoxy ginseng (acetonitrile) titanium, mono-η-butoxy参(acetonitrile) hydrazine, mono-sec-butoxy ginseng (acetamidine acetonide), mono-t-butoxy ginseng (acetonitrile) titanium, tetrakis(acetonitrile) titanium, triethyl Oxygen mono(ethylacetamidineacetic acid) titanium, tris-n-propoxy mono(ethylacetoxyacetic acid) titanium, trisodium propoxy. Single ( Ethylacetic acid) titanium, tris-n-butoxy mono(ethylacetamidineacetic acid) ruthenium titanium, tris-sec-butoxy. mono(ethylacetamidineacetic acid) titanium, tri-t-butoxy Mono-(ethylacetamidineacetic acid) titanium, diethoxy bis(ethylacetamidineacetic acid) titanium, di-n-propoxy. bis(ethylacetamidineacetic acid) titanium, di-i-propyl Oxy. Bis(ethylacetamidineacetic acid) titanium, di-η-butoxy. bis(ethylacetamidineacetic acid) titanium, di-sec-butoxy. bis(ethylacetamidineacetic acid) titanium, two -t-butoxy bis(ethylacetamidineacetic acid) titanium, monoethoxy. ginseng (ethyl acetoacetate) ruthenium, mono-η-propoxy ginseng (ethyl acetoacetate) titanium, Single small propoxy thiophene (ethyl acetoacetate) titanium, mono-η-butoxy ginseng (ethyl acetoacetate) titanium, mono-sec. butoxy. gin (ethyl acetoacetic acid) Titanium, mono-t-butoxy. ginseng (ethyl acetoacetate) titanium, tetrakis(ethyl acetamidine-56-200934859 acetic acid) titanium, mono(acetonitrile) ginseng (ethyl acetoacetate) titanium, Bis(acetylacetone) bis(ethylacetamidineacetic acid) titanium, ginseng (acetonitrile) mono(ethylacetamidineacetic acid) titanium, etc. Chelating compound; triethoxy. mono(acetonitrile) ruthenium, tri-n-propoxy-mono(acetonitrile)zirconium, tri-i-propoxy-mono(acetonitrile)zirconium, three -η-butoxy.single (acetylacetone) zirconium, tris-succinyl mono(ethyl acetonide) zirconium, tris-t-butoxy mono(acetonitrile) oxime, diethoxy Zirconium (acetyl acetonide) zirconium, di-n-propoxy ρ. bis(acetonitrile)zirconium, di-i-propoxy. bis(acetonitrile)zirconium, di-n-butoxy . Bis(acetyl acetonide) zirconium, di-sec-butoxy. bis(acetonitrile)zirconium, di-t-butoxy. bis(acetonitrile)zirconium, monoethoxy. ginseng Acetone) Zirconium, mono-η-propoxy-sodium (acetylacetone) chromium, mono-i-propoxy. ginseng (acetamidine) oxime, mono-η-butoxy ginseng (acetamidine) Chromium, mono-sec-butoxy. Zirconium (acetylacetone) zirconium, mono-t-butoxy-paraben (acetonitrile) zirconium, tetrakis(acetonitrile), triethoxy-mono (ethyl) Acetyleneacetate), tri-n-propoxy. Mono(ethylacetamidineacetic acid) zirconium, tri-i-propoxy mono(ethylacetamidineacetic acid) pin 'D tri-n -butoxy.mono(ethylacetamidineacetic acid) zirconium, tris-sec-butoxy.mono(ethylacetate acetate), bis-t-butoxy.mono(ethylethanoacetic acid). Diethoxy-bis(ethylacetamidineacetic acid) zirconium, di-n-propoxy-bis(ethylacetamidineacetic acid) hydrazine, di-i-propoxy. bis(ethylacetamidineacetic acid) pin , bis_butoxy-bis(ethylacetamidineacetic acid) zirconium bis- sec-butoxy. bis(ethylacetamidineacetic acid) pin, di-t-butoxy bis(ethyl acetamidine) Acetic acid) hydrazine, monoethoxy. ginseng (ethyl acetoacetate) zirconium, mono-η-propoxy ginseng (ethyl acetoacetate) chromium, mono-i-propoxy. Indoleacetic acid) chromium, mono-η-butoxy. ginseng (ethylacetamidineacetic acid) hydrazine, mono-sec-butoxy. ginseng (ethyl acetoacetic acid) pin, mono-1 - butoxy. 57- 200934859 (Ethylacetamidineacetic acid) pin, tetrakis(ethylacetamidineacetic acid) zirconium, mono(acetamidineacetone) ginseng (ethylacetamidineacetic acid) chromium, bis(acetamidineacetone) bis (ethyl acetamidine) a chromium chelate compound such as chromium acetate, ginseng (acetonitrile) mono(ethylacetonitrile acetate) zirconium; Ketone) aluminum, ginseng (ethyl acetyl acetate), such as aluminum compounds the aluminum bonding beetle and the like. • The above organic acid may, for example, be acetic acid, propionic acid, butanoic acid, pentanoic acid, hexane acid, heptanoic acid, octanoic acid, decanoic acid, decanoic acid, oxalic acid, maleic acid, methyl propyl Diacid, adipic acid, sebacic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, shikimic acid, 2-ethyl hexane acid, oleic acid, octadecanoic acid, linoleic acid, linolenic acid , salicylic acid, benzoic acid, p-amino benzoic acid, P-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, Phthalic 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 or phosphoric acid. The above organic base may, for example, be pyridine, pyridyl, oxazine, pyrrolidine, piperidine, methyridine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldi Ethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, and the like. The alkali metal compound may, for example, be sodium hydroxide, potassium hydroxide, cesium hydroxide or calcium hydroxide. These catalysts may be used together with one type or two or more types. Among these catalysts, a metal chelate compound, an organic acid or a mineral acid is preferably -58 to 200934859, more preferably a titanium chelate compound or an organic acid catalyst is used in an amount of 100 parts by weight relative to the starting decane compound. It is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 1 part by weight. The water added in the synthesis of the other polyorganosiloxane may be added intermittently or continuously in the raw decane compound or in a solution in which the decane compound is dissolved in an organic solvent. The catalyst may be previously added to the raw material decane compound or dissolved in a solution of the decane compound in the hydrazine organic solvent, or dissolved or dispersed in the already added water. The reaction temperature at the time of synthesis of the other polyorganosiloxane is preferably from 0 to 100 ° C, more preferably from 15 to 8 (TC. The reaction time is preferably from 0.5 to 24 hours, more preferably from 1 to 8 hours. Ratio of Other Polymers] The liquid crystal alignment agent of the present invention contains other polymers in combination with the above-mentioned cinnamic acid-containing polyoxalate of the present invention, and the content of other polymers is relatively linear with respect to the radiation. 100 parts by weight of the organic oxirane is preferably 10,000 parts by weight or less. The content of other polymers is more preferable depending on the type of other polymers. The liquid crystal alignment agent of the present invention contains a radiation-sensitive polyorganosiloxane, And at least one polymer selected from the group consisting of polylysine and polyamidiamine, preferably used in a ratio of 100 parts by weight relative to the radiation-sensitive polyorganosiloxane, as poly-proline and poly The total amount of quinone imine is 100 to 5,000 parts by weight, more preferably 200 to 2,000 parts by weight. -59- 200934859 In addition, the liquid crystal alignment agent of the present invention is a radiation-sensitive polyoxyalkylene and other polyoxane. When the two are better used, the ratio is relatively clear. 100 parts by weight of other polyoxonium containing cinnamic acid polyoxyxane, 100 to 2,000 parts by weight. The liquid crystal alignment agent of the present invention contains a radiation-sensitive polyorganism. When compared with other polymers, other polymers In terms of the type, at least one polymer selected from the group consisting of _acid and polyimine, or a cerium oxide is preferred. <Reinforcing agent, curing catalyst, and hardening accelerator> The catalyst may be contained in the liquid crystal of the present invention for the purpose of making the cross-linking reaction of the radiation-sensitive polyorganism stronger, and the above-mentioned hardening accelerator is used for the liquid crystal alignment agent of the present invention for the purpose of promoting the hardening reaction of the curing agent. As the hardener, a hard curing agent generally used for a curable composition containing an epoxy compound or an epoxy group-containing compound, for example, a polyvalent amine, a polyvalent carboxylic anhydride, or a polyvalent carboxylic acid can be used. In the case of a polyvalent carboxylic anhydride, for example, cyclohexanetricarboxylic acid is free from other polyvalent carboxylic acid anhydrides. Specific examples of the cyclohexane tricarboxylic anhydride include, for example, 1,3,4-tricarboxylic acid-3,4- Anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride- 1,2,3-tricarboxylic acid-2,3-anhydride, etc., other polyvalent carboxylic anhydrides, 4-methyltetrahydrophthalic anhydride, methyl nadic anhydride, dodecene anhydride, succinic anhydride, Malay Anhydride, phthalic anhydride, trimellitic acid, organic hydrazine in the amount of the hair oxane, polyoxane polyamidamine polyoxyalkylene complexing agent, can contain water for sclerolysis and hexane-, cyclohexyl , for example, succinic anhydride, lower -60- 200934859, (5) Ο

Ο (In the formula (5), r is an integer of 1 to 20^) In the synthesis of the compound and the polyamic acid represented by the formula (5), in addition to the tetracarboxylic dianhydride which can be generally used, 尙 has α-terpinene. And a Diels-Alder reaction product of a conjugated double bond, such as a blisterene, and a Diels-Alder reaction product of maleic anhydride or such a hydride. For the above-mentioned curing catalyst, for example, a ruthenium fluoride compound, a phosphorus oxyfluoride compound, aluminum triacetonitrile or the like can be used. These catalysts can be thermally catalyzed by cationic polymerization of epoxy groups. The above hardening accelerator, for example, an imidazole compound; a 4-stage phosphorus compound; a 4-grade amine compound; 1,8-diazabicyclo[5.4.0]undecene-7 or an organic acid salt-like diazabicycloalkene thereof; Zinc octylate, tin octylate, aluminum acetyl acetonate complex organometallic compound; boron trifluoride, triphenyl boron compound of boric acid; zinc chloride, tin chloride-like metal halide compound, dicyandi A high-melting point-dispersion latent hardening accelerator for the addition of diamine, an amine, and an epoxy resin. The surface of the grade 4 scale salt is polymer-coated. Capsule-type latent hardening accelerator; amine salt-type latent hardener accelerator; Lewis acid, brown sulphate-like high-temperature dissociation type thermal cation. Polymeric latent hardening accelerator. <Epoxy compound> From the viewpoint of improving the adhesion of the substrate surface of the liquid crystal alignment agent of the present invention, the above epoxy compound can be used. Examples of the epoxy compound, such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl Ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 0 1 ,3,5,6-tetraglycidyl-2,4-hexanediol, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl-m-xylenediamine, 1,3-bis(Ν, Ν-diglycidylaminomethyl)cyclohexane, hydrazine, hydrazine, Ν', Ν'-tetraglycidyl _4,4'-diaminodiphenylmethane, hydrazine, hydrazine-diglycidyl Preferred are benzyl-benzylamine, hydrazine, hydrazine-diglycidyl-aminomethylcyclohexane and the like. The ratio of use of these epoxy compounds to the total of the polymers (refers to the total amount of the radiation-sensitive polyorganosiloxane and other polymers. The same applies hereinafter.) 1 part by weight, preferably 40 parts by weight. Hereinafter, it is more preferably 1 to 30 parts by weight. -62- 200934859 &lt;Functional decane compound&gt; In terms of the above functional decane compound, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethyl Oxydecane, 2-aminopropyltriethoxydecane, n-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3 -Aminopropylmethyldimethyl-methoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxy, decane, N-ethoxycarbonyl-3-aminopropyl Trimethoxy decane, N-ethoxycarbonylcarbonyl-3-aminopropyltriethoxy decane, N-triethoxydecylpropyltrivinyl, N-trimethoxydecylpropyltri Vinyl, 10-trimethoxydecyl-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazanonane, 9-trimethoxydecane Base-3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxy Baseline, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-amine Propyltriethoxysilane Silane, N- bis (oxyethylene) -3-aminopropyl trimethoxy Silane ®, N- bis (oxyethylene) -3-aminopropyl triethoxy silane-like. The functional decane compound is used in a proportion of 100 parts by weight or less, preferably 4 parts by weight or less based on the total of the polymer. &lt;Interactive Agent&gt; For the above surfactant, for example, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, an anthrone surfactant, a polyalkylene oxide surfactant, or the like Fluorine surfactant, etc. -63-200934859 When the liquid crystal alignment agent of the present invention contains a surfactant, the content ratio thereof is preferably 10 parts by weight or less, more preferably 10 parts by weight or less, based on the total amount of the liquid crystal alignment agent. It is preferably 1 part by weight or less. &lt;Liquid Crystal Aligning Agent&gt; The liquid crystal alignment agent of the present invention contains the sensitized radiopolyorganosiloxane as an essential component as described above, and further contains other components which are required to be required, and is preferably prepared into components. A solution composition of an organic solvent. The organic solvent which can be used for the liquid crystal alignment agent of the present invention is prepared to dissolve the radiation-sensitive polyorganosiloxane and other components which are used arbitrarily, and it is preferred that the reaction is not carried out. Suitable organic solvents which can be used in the liquid crystal alignment agent of the present invention vary depending on the type of other polymer to be added. When the liquid crystal alignment agent of the present invention is a polymer containing at least one polymer selected from the group consisting of a radiation-sensitive polyorganosiloxane and a polyamic acid and a polyimine, a preferred organic solvent is used as the organic solvent. The solvent exemplified above for the synthesis reaction of polylysine. Here, as a compound which can be used in the synthesis reaction of polylysine, the poor solvent exemplified above can be suitably selected and used. Particularly good organic solvents which can be used at this time, such as N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, ν, ν-di Methylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxylate Propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-η-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-η-butyl ether (butyl cellosolve Agent), ethylene glycol-64 - 200934859 dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl acid, diethylene glycol diethyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, isoamyl propionate, isoamyl isobutyrate, Diisopentyl awake and so on. These may be used singly or in combination of two or more. Further, the liquid crystal alignment agent of the present invention is preferably an organic solvent when the polymer contains only a radiation-sensitive polyorganosiloxane, or when it contains a radiation-sensitive polyorganofluorene or a cyclopentane. For example, 1-ethoxy-2-propanol 'propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, Dipropylene glycol propyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), Ethylene glycol monopentyl ether, ethylene glycol monohexyl ether, diethylene glycol, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve Acetate, methyl carbitol, ethyl Φ carbitol, propyl carbitol, butyl carbitol, η-propyl acetate, i-propyl acetate, η-butyl vine acetate, acetic acid i- Butyl ester, sec-butyl acetate, n-amyl acetate, sec-amyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethylbutyl acetate, acetic acid 2-ethylhexyl ester, benzyl acetate, η-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate, and the like. Among them, preferred are, for example, η-propyl acetate, i-propyl acetate, η-butyl acetate, i-butyl acetate, sec-butyl acetate, η-amyl acetate, sec-amyl acetate, and the like. The solid content concentration in the liquid crystal alignment agent of the present invention (the ratio of the total weight of the components other than the solvent to the liquid crystal alignment agent in the -65 to 200934859 liquid crystal alignment agent) is selected in consideration of viscosity, volatility, and the like. Preferably, the solid content concentration is in the range of 〜10% by weight. In other words, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a coating film which becomes a liquid crystal alignment film. However, when the solid content concentration is less than 1% by weight, the thickness of the coating film is too small, and it is difficult to obtain a good liquid crystal alignment film. When the solid content concentration exceeds ίο重量%, the thickness of the coating film becomes too large, and it is difficult to obtain a good liquid crystal alignment film. Further, the viscosity of the liquid crystal alignment agent is increased to 0, which is a poor coating property. The range of particularly preferable solid content concentration varies depending on the method used when the liquid crystal alignment agent is applied to the substrate. For example, the spin coating method is particularly preferably in the range of 1.5 to 4.5% by weight. In the printing method, the solid content concentration is in the range of 3 to 9 % by weight, and therefore, the solution viscosity is particularly preferably in the range of 12 to 5 OmPa·s. When the ink jet method is used, the solid content concentration is in the range of 1 to 5% by weight, whereby the viscosity of the solution is in the range of 3 to 15 mPa*s, particularly preferably. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably 〇 ° C to 〇 200 ° C, more preferably 20 ° C to 60 ° C. &lt;Method of Forming Liquid Crystal Alignment Film&gt; The liquid crystal alignment agent of the present invention can be suitably used for forming a liquid crystal alignment film by a photo-alignment method. In the method of forming a liquid crystal alignment film, for example, a liquid crystal alignment film of the present invention is applied onto a substrate to form a coating film, and then a method of imparting liquid crystal alignment energy to the coating film by photoalignment is employed. First, the liquid crystal alignment agent of the present invention is applied to a film side of a transparent conductive-66-200934859 film having a patterned transparent conductive film, for example, by a roll coating method, a spin coating method, a printing method, an inkjet method, or the like. The coating method is applied, for example, at a temperature of 40 to 250 ° C for 1 to 120 minutes to form a coating film. The film thickness of the coating film and the thickness after removal of the solvent are preferably 0.001 to Ιμηη, more preferably 0.005 to 0.5 μm. For the above substrate, for example, glass such as float glass, soda lime glass, polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, poly (aliphatic ring) can be used. A transparent substrate made of a plastic such as an olefin is used. For the transparent conductive film, a NESA film made of Sn 2 or an ITO film made of In 2 03-SnO 2 can be used. For the patterning of the transparent conductive film, a light etching method or a method of using a mask when forming a transparent conductive film can be used. Next, the coating film is irradiated with linearly polarized light or partially polarized radiation or non-polarized radiation, and further heated at a temperature of Φ'1 to 150 °C, preferably 1 to 120 minutes, depending on the case. It is a liquid crystal alignment film which imparts liquid crystal alignment energy. Here, as the radiation, for example, ultraviolet light and visible light having a wavelength of 150 to 800 nm can be used, but ultraviolet light having a wavelength of 300 to 4 nm is preferable, and 300 nm or more is less than 3 5 5 nm. The ultraviolet light of the wavelength of light is better. The liquid crystal alignment agent of the present invention does not cause photoreaction due to long-wavelength light having a wavelength of 365 nm or more, so that the liquid crystal panel can be manufactured without the step of discomfort, and the backlight of the liquid crystal panel has light. The advantage of long-term stability. When the radiation is linearly polarized or partially polarized, the irradiation may be performed in a straight direction from the substrate surface -67 to 200934859, and may be performed in an oblique direction in order to impart a pretilt angle, or may be performed in combination. When the non-polarized radiation is irradiated, the direction of the irradiation is necessary in the oblique direction. The irradiation amount of the radiation is preferably less than 10,000 J/m2 in U/m2 or more, more preferably 1 to 3,000 J/m2. In addition, when the liquid crystal alignment energy is imparted to the coating film formed by the conventional liquid alignment agent, the amount of radiation irradiation of 10,000 J/m 2 or more is necessary. However, when the liquid crystal alignment agent of the present invention is used, the radiation exposure amount in the photo-alignment method is 3,00 J/m 2 or less, and the liquid crystal alignment property can be imparted to the liquid crystal display element in the step of 1,000 J/m 2 or less. Manufacturing costs. &lt;Manufacturing Method of Liquid Crystal Display Element&gt; The liquid crystal display element formed using the liquid crystal alignment agent of the present invention can be produced as follows. As described above, a pair of (two sheets) of the substrate Φ on which the liquid crystal alignment film is formed is prepared, and the liquid crystal alignment films which are provided are opposed to each other such that the polarization direction of the linearly polarized radiation is at a specific angle, and the inter-substrate is The peripheral portion is sealed with a sealant, and liquid crystal is injected and filled, so that the liquid crystal injection port is closed to constitute a liquid crystal cell. Next, the liquid crystal cell is heated until the liquid crystal used has reached the isothermal phase, and after cooling to room temperature, the flow alignment at the time of injection is preferably removed. Then, on both sides, the polarizing plate is bonded to the liquid crystal alignment film at a specific angle with respect to the alignment axis of the liquid crystal alignment film of the individual substrate, and can be a liquid crystal display element. -68- 200934859 When the liquid crystal alignment film is horizontally oriented, the TN can be obtained by adjusting the angle of the polarization direction of the linear polarized radiation irradiated to the two substrates on which the liquid crystal alignment film is formed and the angle between the individual substrate and the polarizing plate. A liquid crystal display element of a type or STN type liquid crystal cell. Further, when the liquid crystal alignment film has a vertical alignment property, the direction of the easy axis of alignment of the two substrates on which the liquid crystal alignment film is formed is parallel to form a unit cell, and thus the polarized light is formed. The board is bonded to the alignment sensing easy axis by an angle of 45°, and can be a liquid crystal display element having a vertical alignment type liquid crystal cell. As the sealant, for example, an epoxy resin containing alumina balls and a hardener as a partition wall can be used. As the liquid crystal, for example, a nematic liquid crystal, a smectic phase liquid crystal, or the like can be used. When it is a TN type liquid crystal cell or a S TN type liquid crystal cell, it is preferable to use a positive dielectric anisotropy, and for example, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, or an ester liquid crystal can be used. A terphenyl group liquid crystal, a biphenylcyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cuba liquid crystal, or the like. Further, in the liquid crystal, a cholesteric liquid crystal such as cholestyl chloride 'cholesteryl phthalate or cholesteryl carbonate; a commercially available chiral reagent of the trade name Ο-ΐ 5 and CB-1 5 (manufactured by Merck); Further, a ferroelectric liquid crystal such as P-decyloxybenzylidene-P-amino-2-methylbutylcinnamate or the like can be further added. Further, in the case of a vertical alignment type liquid crystal cell, it is preferable to use a nematic liquid crystal having a negative dielectric anisotropy, such as a dicyanobenzene liquid crystal, a pyridazine liquid crystal, or a Schiff base liquid crystal. An azo-based liquid crystal, a biphenyl-69-200934859-based liquid crystal, a phenylcyclohexane-based liquid crystal, or the like. The polarizing plate used for the outer side of the liquid crystal cell may be a polarizing plate or a ruthenium film which is held by a cellulose acetate protective film, which is a polarizing film called a "ruthenium film" which is obtained by stretching a polyvinyl alcohol while absorbing iodine. Become a polarizing plate, etc. Further, the liquid crystal display element of the present invention produced is excellent in performance such as display characteristics and long-term reliability. [Embodiment] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. In the following examples, the weight average molecular weight is a polystyrene-converted oxime determined by colloidal osmosis chromatography under the following conditions.

Column: Tosoh Co., Ltd., TSKgelGRCXLII Solvent: Tetrahydrofuran Ο Temperature: 40 ° C Pressure: 68 kgf/cm 2 The epoxy equivalent is determined by the "hydrochloric acid-methyl ethyl ketone method" of JIS C2 105. In the following synthesis examples, the following synthesis routes are repeated as necessary to ensure the necessary amount of products used in the subsequent synthesis examples and examples. &lt;Synthesis of polyorganosiloxane having epoxy group&gt; Synthesis Example 1 (1) -70- 200934859 In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube, 2-(3, 4) was added. - Epoxycyclohexyl)ethyltrimethoxy chopped 100.Og, methyl isobutyl ketone 500g and triethylamine i.g., mixed at room temperature. Next, deionized water was added dropwise to the funnel for 30 minutes, and then mixed under reflux to carry out a reaction at 80 ° C for 6 hours. After completion of the reaction, the 'extracted organic layer' was washed with 0.2% by weight aqueous ammonium nitrate solution until the water was neutralized, and then the solvent and water were distilled off under reduced pressure to obtain a polyorgano group having an epoxy group having Q. A viscous transparent liquid of the oxime EPS-1. About this polyorganooxane EPS-1, 1H-NMR analysis was carried out, and a peak of an epoxy group having a theoretical strength was obtained in the vicinity of a chemical shift (δ) = 3·2 ΡΡιη, and it was confirmed that there was no epoxy group side reaction in the reaction. . The viscosity, Mw and epoxy equivalent of this polyorganooxynonane EPS-1 are shown in Table 1. Synthesis Example 1 (2) and 1 (3) 0 In the same manner as in the synthesis example 1 (1), the polyorganosiloxanes EPS-2 and 3 having an epoxy group were obtained, except that the materials to be added were as shown in the first table. Viscous transparent liquid. The Mw and epoxy equivalents of these polyorganosiloxanes are as shown in Table 1. Synthesis Example 1 (4) In a reaction vessel equipped with a stirrer and a thermometer, 5.4 g of an aqueous solution of isopropanol I 50 g and tetramethylammonium hydroxide in an amount of 5.4 wt% (containing tetramethylammonium hydroxide 5.93 mm〇l and water) After 270 mmol of water and 12 g of water, 41-5 g (180 mmol) of γ-glycidoxypropyltrimethoxylamine was added slowly, and stirring was continued at room temperature for 20 hours to carry out a reaction. After the completion of the reaction, 200 g of toluene was added to the reaction mixture, and isopropyl alcohol was removed under reduced pressure. With respect to the residue, the reaction solution was washed with distilled water using a separatory funnel. The mixture was washed with distilled water until the aqueous layer of the separatory funnel became neutral, and then the organic layer was taken out and dehydrated with anhydrous sodium sulfate, and then toluene was distilled off under reduced pressure to obtain a polyorganosiloxane having an epoxy group. EPS-4. 0 The weight average molecular weight Mw and epoxy equivalent of the polyorganooxynonane EPS-4 are as shown in Table 1. Further, the abbreviations of the raw material decane compounds in the first table are as follows. ECETS: 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane MTMS: methyltrimethoxydecane PTMS: phenyltrimethoxydecane GPTMS: 3-oxyglycidylpropyltrimethoxydecane -72- 200934859

Mlifl _ ff ter] / Ό 00 Ο 228 mm PK aldoxime) Mw o (N &lt; N 2,500 2,000 3,000 00 Η CL, 〇Ο Ο 42.5 Ο I &lt;n PTMS o ο Ο κη Η o Ο ο Μ ECETS o § ο Sir _, tread EPS-1 EPS-2 EPS-3 EPS-4 /—V g δ ^ρ &lt;π &lt;π &lt;Π &lt;Π -73 200934859 [The compound represented by the above formula (2) Synthesis] Synthesis Example 2 (1) According to the following path

0 CICO

C2F5-C3H6-OH + 〇 c2f5-c3h6-oco

ο η2ν

CH=CH—COOH

C2F5—ΟβΗρ—OCO ο CH=CH—COOH (2-1-1) The compound (2-1-1) was synthesized. (Synthesis of compound (2-ll A)) 5 〇〇 mL section 4,4,5,5,5-pentafluoropentanol 18 g, triethylamine n. 5 〇mL with ice cream and dropping funnel and ice-cold . Here, the solution of 21 g of the dropping funnel and 200 mL of tetrahydrofuran was further stirred for 2 hours to carry out a reaction. After the reaction of 5 〇〇mL of ethyl acetate and 5 〇〇mL of water, the liquid mixture was mixed, and g and tetrahydrofuran oxime trimellitic anhydride chlorine were added for 30 minutes or more. After S was added, the organic layer was added with sulfur-74-200934859. The magnesium sulfate was dried, concentrated, and recrystallized from a mixed solvent of ethyl acetate and hexane to give compound (2 -1 -1 A) 2 9 g. (Synthesis of Compound (2-1-1)) 28 g of the above-obtained compound (2-l-1A), 13 g of 4-aminocinnamic acid and 150 mL of acetic acid were placed under reflux for 2 hours to carry out a reaction. After the completion of the reaction, the reaction mixture was extracted with ethyl acetate. The extract was washed with water, dried over magnesium sulfate, and then purified on a silica gel column, and further purified by a solvent mixture of ethanol and tetrahydrofuran. Crystallization gave the crystal of the compound (2-1 -1) (purity 9 8.0 %) 1 8 g. Synthesis Example 2(2) According to the following path ❹ -75- 200934859

Synthesis of Compound (2-4A) A UOOmL eggplant-shaped flask equipped with a thermometer and a dropping funnel was placed, and 3 9 g of cholalkanol, mg of triethylamine and 200 mL of toluene were added thereto, followed by ice cooling. Here, the solution of 21 g of trimellitic anhydride chloride and 200 mL of tetrahydrofuran placed in the dropping funnel was dropped for 30 minutes or more, and the reaction was further carried out under stirring for 2 hours. After completion of the reaction, 500 mL of toluene and 500 mL of water were added, and the mixture was separated, and the organic layer was dried over magnesium sulfate, concentrated, and then recrystallized from a solvent mixture of ethyl acetate and hexane to give compound (2-4A). 48g. -76-200934859 Synthesis of Compound (2-4) 46 g of the obtained compound (2-4A), 13 g of 4-aminocinnamic acid and 300 mL of acetic acid were mixed under reflux for 2 hours to carry out a reaction. After the completion of the reaction, the reaction mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate, and then purified on a hydrazine column and further mixed with ethyl acetate and hexane. Crystallization gave the crystal of the compound (2_4) (purity 98.1%) 20 g. Synthesis Example 2(3) according to the following path

HO

COOH

COOH diethylbenzene reflux, 1 hr

CH=CH a COOH THF reflux

CH=CH—COOH (2-6-1A) K2C03 CF3C3H6-I O CF3C3H6-Ov^^^^ o CH=CH—COOH (2-6-1) -77- 200934859 'Synthetic compound (2-6 -1 ). (Synthesis of Compound (2-6-1 A)) In a 300 mL three-necked flask equipped with a Dean-Stark tube, 18 g of 5-hydroxyphthalic acid and diethylbenzene 〇〇mL' were added under reflux for 1 hour. . Next, 16 g of 4-aminocinnamic acid, triethylamine, 42 mL, and 100 mL of tetrahydrofuran were added thereto, and the reaction was carried out under reflux for 1 hour. After the reaction was completed, ethyl acetate was added to the reaction mixture for extraction, and the extract liquid was washed successively with dilute hydrochloric acid and water, then dried over magnesium sulfate, concentrated, and then recrystallized from ethyl acetate. Compound (2 - 6 - 1 A ) 1 4 g. (Synthesis of Compound (2-6-1)) The above obtained product was added to a 300 mL flask containing a dropping funnel. Compound (2-6-lA) 12 g and N,N-dimethylacetamide 70 mL, Stirring was carried out for 1 hour at room temperature. Next, 30 mL of 4,4,4-trifluoro-1-iodobutane 1 lg and ^N,N-dimethylacetamide were added dropwise for 30 minutes or more, and the reaction was carried out directly at room temperature for 8 hours. After completion of the reaction, ethyl acetate was added to the reaction mixture for extraction, and the extract was washed three times with water, followed by drying over magnesium sulfate, concentration, purification on a silica gel column, and recrystallization from ethanol. The crystal of the compound (2-6-1) was 12 g. [Synthesis of the compound represented by the above formula (3)] Synthesis Example 3 (1) According to the following route -78- 200934859 0?Ν

CH=CH—COOH SOCI2

〇2N CH=CH—COCI (3-1A) c2f5-c3h6-oh ❹ NO2NO- CH=CH—COO—C3H6-C2F5 (3-1B) SnCI2 H2N—^=\_CH=CH-CO〇-C3H6- C2F5 '~~' (3-1C)

❿ o A COO-C3H6-C2F5 (3-1) Synthetic compound (3 -1) (Synthesis of compound (3-1B)) Added to a 300 mL eggplant-shaped flask equipped with a reflux tube. 9 g of citric acid, sulfurous acid醯Chlorinium chloride and N,N-dimethylforma were reacted at 80 ° C for 1 hour. After the reaction, the organic layer was obtained by adding 'dichloromethane under reduced pressure, and the organic layer was washed with an aqueous solution of 4-nitro sulphate: 50 μί, sulphur sulphate and sodium bicarbonate-79-200934859. After drying over magnesium sulfate and concentration, tetrahydrofuran was added to obtain a tetrahydrofuran solution of the compound (3 -1 A). Next, 18 g of 4,4,5,5,5-pentafluoropentanol, 18 ml of triethylamine and 100 mL of tetrahydrofuran were placed in a 500 mL three-necked flask different from the above. This solution was ice-cooled, and the tetrahydrogen and furan solution of the above compound (3-1 A) was gradually dropped, and further stirred for 2 hours to carry out a reaction. After the completion of the reaction, the extract obtained by extraction with ethyl acetate was dried over magnesium sulfate, and then concentrated, and then recrystallized from ethanol to obtain crystals of compound (3 -1 B) of 2 9 g. (Synthesis of Compound (3 -1 C)) Into a 30 mL flask equipped with a thermometer and a nitrogen introduction tube, 28 g of the compound (3-lB), 181 g of tin chloride, and 301 g of ethanol were added. 7 (TC was stirred for 1 hour to carry out the reaction. After the reaction was completed, the reaction mixture was poured into ice water, neutralized with a 2 M aqueous sodium hydroxide solution, and ethyl acetate was added to remove the precipitate. Then, ethyl acetate was added to the filtrate. The extract was washed with water, dried over magnesium sulfate, concentrated, and dried to give 20 g of compound (3-lC). (Synthesis of compound (3-1)) 200 mL of reflux tube and nitrogen inlet tube 16 g of the obtained compound (3-lC), 9.6 g of trimellitic anhydride, and 150 mL of acetic acid were added to the eggplant-shaped flask, and the reaction was carried out under reflux for 1 hour. After the completion of the reaction, the reaction mixture was extracted with ethyl acetate. After washing with water, it is dried with sulfuric acid-80-200934859 magnesium, concentrated, dried, and recrystallized from a mixed solvent of ethyl acetate and hexane to obtain white crystals of compound (3-1) (purity 9 8.0 %). ) 1 8 g 〇&lt; Synthesis of Other Polymers &gt; [Synthesis of Polyamide] Synthesis Example PA - 1 Q The pyromellitic dianhydride as tetracarboxylic dianhydride l 9g (0.50 mole equivalent) and 1,2, 3,4-cyclobutanetetracarboxylic dianhydride 98 g (0.50 molar equivalent) and 4,4-diaminodiphenyl ether as a diamine 200 g (1.0 molar equivalent) dissolved in N-methyl-2 - 2,290 g of pyrrolidone, after reacting for 3 hours at 40 ° C, 'addition of N-methyl-2-pyrrolidone 1,350 g to obtain a solution containing 10% by weight of polyglycine (PA-1) of about 4, 0 0 0 g. The solution viscosity of this polyaminic acid solution is 2 1 OmP a * s. 〇 Synthesis Example PA-2 1,2,3,4-cyclobutanetetracarboxylic acid as tetracarboxylic dianhydride 98 g (0.50 molar equivalent) of dianhydride and 109 g (〇.5〇 molar equivalent) of pyromellitic dianhydride and 198 g (1.0 molar equivalent) of 4,4,-diaminodiphenylmethane as diamine Dissolved in N-methyl-2-lahydrofurfurone 2,290 g at 40. (: After 3 hours of reaction, 'addition of N-methyl-2-pyrrolidone 1, 3 50 g to obtain poly-proline (PA- 2) 10% by weight of the solution is about 4, 〇〇〇g. The solution viscosity of the polyaminic acid solution is 135 mPa.s. -81 - 200934859 Synthesis Example PA-3 is used as a tetrahydro acid-hepatic 1,2,3,4 cyclobutane tetracarboxylic dianhydride 196g (l. 〇 耳 耳) and 4,4,-diamine as a monoamine Diphenyl ether 2〇〇g (1. 〇 molar equivalent) is dissolved in N_methyl-2_zzarol ketone 'Μ", after 4 hours of reaction at 4 〇t, additional N_methyl _ 2_pyrrolidone oxime, ^" and obtained a solution containing poly-aracine (PA-3H0% by weight of about 3,95 〇g. The solution viscosity of this polyaminic acid solution was 220 mPa.s. Synthetic example PA-4 was used as tetraterpene acid-hepatic sputum, 2,3, 々-cyclobutanine tetradecanoic acid di-hepatic 196 g (1. 〇 molar equivalent) and 2,2,_dimethyl diamine as diamine 212 g (1.0 molar equivalent) of the base 4,4,-diaminobiphenyl was dissolved in N-methyl 2 -pyrrolidone 4, 〇 5 〇 g, and reacted at 4 ° C for 3 hours to obtain A solution containing 3,700 g of polyhydric acid (pA 4) in an amount of 1% by weight. The solution viscosity of the polyaminic acid solution is i7〇mPa.s 〇 Synthesis Example PA-5 224g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride (l. Equivalent) and 2,404 g of 44-diaminodiphenyl ether as a diamine dissolved in N-methyl-2-pyrrolidone, and reacted at 40 ° C for 4 hours. A solution containing 15% by weight of poly-proline (pa - 5 ) was about 2,800 g. The polyamic acid solution was taken out in small portions, and the solution viscosity of the solution obtained by adding N-methyl-2-pyrrolidone as a polymer concentration of 10% by weight was -82-200934859 190 mPa*s ° [Juyue Fee Synthesis] Synthesis Example PI-1 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetra-residual dianhydride • 112 at 0.50 mol) and 1,3,3&, 4,5,913-hexahydrogen -8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[indenyl]furan-oxime, 3dione oxime 57g (〇5〇莫耳〇) As a diamine, P-phenylenediamine 95g (0.88 moles), 2,2-ditrifluoromethyl-4,4-diaminobiphenyl 32g (〇.1() molar), 36_double ( 4_Aminobenzyloxy) 6.4 g (0.010 mol) and octadecyloxy-2,5-diaminobenzene 4.0 g (0.015 mol) dissolved in Ν_methyl_2_pyrrolidone 960g, reacted at 6 (TC for 9 hours. The solution obtained by taking a small amount of the obtained polyaminic acid solution and adding N-methyl-2-pyrrolidone to a polymer concentration of 1 〇% by weight has a solution viscosity of 58 mP as Adding N 2 -methyl-2-pyrrolidone 6 2,740 g, pyridine 396 g and acetic anhydride 409 g to the obtained polyamic acid solution. 110. (: 4 hours dehydration ring closure reaction. After dehydration ring closure reaction, the solvent is replaced by a new N-methyl-2-pyrrolidone solvent (by this operation, the pyridine and B used in the dehydration ring closure reaction) The acid anhydride is excluded from the system. The following is the same.) 'A polyacetamide (PI-) having a ruthenium iodide ratio of about 95% is obtained, and a solution of 5% by weight is about 2,500 g. A small amount of the amine solution was taken out. The solution viscosity after dissolving the solvent under reduced pressure and dissolved in γ-butyrolactone as a polymer concentration of 8.0% by weight was 33 mPa·s. -83- 200934859 Synthesis Example PI-2 2,3,5-tricarboxycyclopentyl acetic acid dianhydride of carboxylic acid dianhydride 112 § (0.50 旲 ear) and 1,3,3 &, 4,5,91)-six art-8-methyl-5- (tetrahydro-2,5-monooxy-3-furanyl)naphtho[i,2_c]furan·ι,3-dione 157g (0.50 mol) • P-phenylenediamine as a diamine 96g ( 〇.89 moles), bisaminopropyltetramethyldioxane 25g (0.10 mole) and 3,6-bis(4-aminooxy) cholestane 0 13§(〇.〇 2〇莫耳) and N_octadecylamine as a monoamine 8.1g (0.030 mole) Dissolved in 960 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 6 hours. The obtained polyaminic acid solution was taken out in small portions, and N-methyl-2-pyrrolidone was added to have a polymer concentration of 1% by weight. The solution viscosity measured by the solution was 60 mPa.s. Then, 2,700 g of N-methyl-2-pyrrolidone was added to the obtained polyaminic acid solution, and 396 g of pyridine and 409 g of acetic anhydride were added, followed by a dehydration ring-closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the internal solvent is substituted with a new Φ N-methyl-2-pyrrolidone to obtain a solution of 15% by weight of polyimine (Pi-2) having a ruthenium iodide ratio of about 95%. About 2,400g. The polyimine solution was taken in a small amount, and the solution viscosity of the solution of N-methyl-2-pyrrolidone as a polymer concentration of 6.0% by weight was determined to be 1 8 m P a · s. Synthesis Example PI-3 224 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride and P-phenylenediamine 10 g (0.99 mol) as a diamine ) -84 - 200934859 and 3,6-bis(4-aminobenzyloxy)cholestane 643g (〇〇1〇莫耳) dissolved in & methyl-2-pyrrolidone 3, 〇39g, at 6〇 t: A reaction was carried out for 6 hours to obtain a solution containing 10% by weight of polyglycine. The viscosity of the solution of the poly-proline is 2 6 OmP a·s 〇 then 'addition of N_methyl_2_pyrrolidone to the obtained poly-proline solution 2. 2,700g' added 396g and 306g of acetic anhydride at 11〇 . 〇 Perform a 4 hour dehydration ring closure reaction. After the dehydration ring-closing reaction, the solvent in the internal solvent was substituted with a new N-methyl-perfluoroalkanone to obtain a polyimine (Ρΐ-3) 9·0 wt% containing a ruthenium iodide ratio of about 89%. The solution is about 3,500 g. The polyiminoimine solution was taken out in small portions, and the solution viscosity of the solution of N-methyl-2-pyrrolidone as a polymer concentration of 5.0% by weight was 74 mPa·s. Synthesis Example PI-4 2,3,5-tricarboxycyclopentyl acetic acid dianhydride φ 1 12g (0.50 mol) and 1,3,3&amp;, 4,5,91) as tetracarboxylic dianhydride Hexahydro-8-methyl-5(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]-furan-1,3-dione 157 g (0.50 mol) And as a diamine P-phenylenediamine 89g (0_82 mole), 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl 32g (0.10 mole), 1- (3, 5-diaminobenzyloxy)-4-(4-trifluoromethylbenzyloxy)-cyclohexane 25g (0.05 9 moles) and octadecyloxy-2,5-diaminobenzene 4.0 g (0.011 mol) was dissolved in 2,175 g of N-methyl-2-pyrrolidone, and the reaction was carried out at 60 ° C for 6 hours to obtain a polyglycine-containing solution. The obtained polyamic acid solution is taken out in small portions, and the solution viscosity of the solution obtained by adding N-methyl-2·pyrrolidone to a polymer concentration by weight is -85-200934859 is 1 1 OmPa · s. 1,500 g of the proline solution was added 3,000 g of N-methyl-2-pyrrolidone, and 221 g of pyridine and 228 g of acetic anhydride were added, followed by a dehydration ring-closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the internal solvent was replaced with a new N-methyl-2-pyrrolidone to obtain a solution containing 10% by weight of polyamidimide (PI-4) having a ruthenium iodide ratio of about 92%. 4,000g. A small amount of this polyimine solution was taken out, and the solution viscosity of the solution of N-methyl-2-pyrrolidone as a polymer concentration of 4.5% by weight was determined to be 2 8 mP a · s. [Synthesis of Other Polyoxane] Synthesis Example PS-1 20.8 g of tetraethoxysilane and 28.2 g of 1-ethoxy-2-propanol were added to a 200 mL three-necked flask equipped with a cooling tube, and heated to 60°. C and stir. Here, a maleic anhydride aqueous solution prepared by dissolving 0.26 g of maleic acid anhydride in 10.80 g of water, which was prepared in a separate flask having a volume of 20 mL, was further heated at 60 ° C for 4 hours, and stirred to carry out a reaction. The solvent was distilled off from the obtained reaction mixture, and 1-ethoxy-2-propanol was added thereto, followed by concentration again to obtain a polymer solution containing 1% by weight of polyorganooxane PS-1. The weight average molecular weight Mw of PS-1 is 5,100. &lt;Synthesis of Radiation-Radio Polyorganooxane&gt; Example ArIE-1 In a 200 mL 2 three-necked flask equipped with a reflux tube, the polyorganooxyl group having the epoxy group obtained in the above Synthesis Example-86-200934859 1 (1) was added. Alkane EPS-1: 5.0 g, 6.7 g of the compound (2-1-1) obtained in the above Synthesis Example 2 (1) as the cinnamic acid derivative (1) (for the epoxy of the polyorganosiloxane having an epoxy group) The base is equivalent to 50 mol%.) and 0.5 g of tetrabutylammonium bromide, and N,N-dimethylacetamide is added so that the solid content concentration is 20% by weight, and the reaction is carried out at 120 ° C for 1 hour. After completion of the reaction, methanol was added to form a precipitate, and the solution obtained by dissolving the precipitate in ethyl acetate was washed with water three times, and then the solvent was distilled off to obtain a white powder of a sensitized radioactive polyorganosiloxane S-ArIE-indole. 8.4g. The weight average molecular weight Mw of the radiation-sensitive linear polyorganosiloxane S-ArIE-Ι is 28,100 ° Examples ArIE-2 to 1 3 In the above embodiment ArIE-Ι, a polyorganosiloxane having an epoxy group The type and amount of the cinnamic acid derivative (1) and the amount of the cinnamic acid derivative (1) were the same as in the second table, and were synthesized in the same manner as in the example ArIE-Ι, and the synthetic radiation Ο polyorganosiloxane (S-ArIE-2) was synthesized. S-ArIE-13. The weight average molecular weight Mw of these sensitizing radiopolyorganosiloxanes is as shown in Table 2. Further, in the examples ArIE-6 and 7, two types of cinnamic acid derivatives (1) were used. In the second table, the "usage amount" of the cinnamic acid derivative (1) means the ratio of the epoxy group to the polyorganosiloxane having an epoxy group. -87- 200934859 Qό 撇CN濉秘 m 1 丨Mw 1 〇〇CO (N 35,000 | 27,500 1 27,200 I 27,800 | 28,300 〇CN 00 &lt;N 30,000 I 27,600 | 29,900 I 27,000 | 26,500 26,900 | S-ArIE-1 S-ArIE-2 S-ArIE-3 S-ArIE-4 S-ArIE-5 S-ArIE-6 S-ArIE-7 S-ArIE-8 S-ArIE-9 S-ArIE-10 S-ArIE-11 j S-ArIE-12 | S-ArIE-13 i /—S Usage (mol%) JO § om Type 2-1-1 2-1-1 2-1-1 2-1 -1 2-1-1 2-6-1 &lt;N 2-6-1 叮(N 1 m 2-6-1 2-6-1 2-6-1 2-6-1 2-6-1 Ms ig mmm shout EPS-1 EPS-1 EPS-2 EPS-3 EPS-4 EPS-1 EPS-1 EPS-1 EPS-1 EPS-1 EPS-3 EPS-4 | Example ArIE-1 1 EXAMPLES ArIE-2 | EXAMPLES ArIE-3 | EXAMPLES ArIE-4 | EXAMPLES ArIE-5 EXAMPLES ArIE-6 EXAMPLES ArIE-7 | EXAMPLES Ai: IE-8 I EXAMPLES Arffi-9 | EXAMPLES ArIE-10 | EXAMPLES ArIE-11 | EXAMPLES ArIE-12 | EXAMPLES ArIE-13 -88- 200934859 &lt;Evaluation of Modulation and Preservation Stability of Liquid Crystal Aligning Agents&gt; Examples ArIE-14 Mixing the above Examples ArIE-1 obtained radiation-sensitive polyorganosiloxane, S-ArIE-Ι1 part by weight, and In the other polymer, the solution containing the polyamic acid PA-1 obtained in the above-mentioned Synthesis Example PA-1 is added in an amount of about 2,000 parts by weight in terms of PA-1, and N-methyl-2-pyrrolidone and butyl cellosolve are added thereto. The solvent was made into a solution of N-methyl-2-pyrrolidone: butyl-soluble p-fibrid = 50:50 (weight ratio) and a solid concentration of 3.0% by weight. The solution was filtered through a filter having a pore size of 1 μm. The liquid crystal alignment agent A-ArIE-1 was prepared. The liquid crystal alignment agent Α-ArIE-1 was stored at -15 ° C for 6 months, and the viscosity was measured by an E-type viscometer at 25 t before and after storage. If the rate of change before and after the storage of the solution viscosity is less than 1%, the storage stability is "good" or more than 1%, the storage stability is "poor", and the storage stability of the liquid crystal alignment agent A-ArIE-Ι is "good". Φ Examples ArIE-15 to 31 and 33 to 52 In the above-described Example ArIE-14, the types and amounts of the radiation-sensitive polyorganosiloxane and the types and amounts of other polymers were as described in Table 3, respectively. Example ArIE-14 was similarly applied to prepare liquid crystal alignment agents A_ArIE-2 to A-18 and A-ArIE-20 to 39, respectively. The evaluation results of the storage stability investigated in the same manner as in Example ArIE-14 for each liquid crystal alignment agent are shown in Table 3. -89- 200934859 Example ArIE-3 2 The amount of the solution containing the other polyoxyalkylene PS-1 obtained in the above-mentioned Synthesis Example PS-1 was converted to the amount of PS-1 equivalent to 500 parts by weight. The above-mentioned Example Arie-Ι obtained radiation-sensitive polyorganosiloxane S-ArIE-Ι: 100 parts by weight, and further added 1-ethoxy-2-propanol. A solution having a solid concentration of 4.0% by weight was obtained. The liquid crystal alignment agent A-ArlE-1 was prepared by filtering this solution through a filter having a pore size of 1 μm. Q The liquid crystal alignment agent A-ArIE-19 was evaluated in the same manner as in the example ArIE-14, and the evaluation results of the storage stability were as shown in Table 3. EXAMPLES ArIE-53 In the above example ArIE-32, a substituted radiation-sensitive polyorganosiloxane, S-ArIE-oxime, using the radiation-sensitive polyorganosiloxane S-ArIE-9 obtained in the above Example ArIE-9 The liquid crystal alignment agent Α-ΑγΙΕ-40 was prepared in the same manner as in Example ArIE-32 except for 100 parts by weight, and the storage stability was examined. Φ The evaluation results of preservation stability are shown in Table 3. Example ArIE-54 to 57 In the above-described Example ArIE-14, the type and amount of the other polymer are used as described in the third table, and the epoxy compound described in the third table is used in the amount of the third table, and Example ArIE-14 The liquid crystal alignment agents A-ArIE-41 to A-ArIE-44 were separately prepared in the same manner. With respect to these liquid crystal alignment agents, the evaluation results of the storage stability investigated in the same manner as in the example ArlE-1, respectively, are shown in Table 3. Further, in the third table, the abbreviations "E-l" and "E-2" of the epoxy compound are each a compound represented by the following formula (E-1) or (E-2).

Ο 〇

(E — 2) -91 - 200934859 οο 嗽eReserving the stability of the n^ sign ( &lt;Π Usage (parts by weight) 1 1 1 1 1 1 1 t 1 1 1 1 1 1 1 mm Type 1 1 1 1 ) 1 1 1 1 1 1 1 1 1 1 Other polymer usage (parts by weight) 2,000 2,000 2,000 2,000 2,000 500 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 PA-1 PA-2 PA-3 PA-4 PA- 5 PA-4 PA-4 PI-1 PI-2 PI-3 PI-4 PA-4 PA-4 1 PA-4 1 PA-4 Radiation-sensitive polyorganosiloxane species S-ArIE-1 S-ArIE -1 S-ArIE-1 S-ArIE-1 S-ArIE-1 S-ArIE-1 S-ArIE-1 S-ArIE-1 S-ArIE-1 S-ArIE-1 S-ArIE-1 S-ArIE -2 S-ArIE-3 S-ArIE-4 S-ArIE-5 Liquid Crystal Alignment Name A-ArIE-1 A-ArIE-2 A-ArIE-3 A-ArIE-4 A-ArIE-5 A-ArIE- 6 A-ArIE-7 A-ArIE-8 A-ArIE-9 A-ArIE-10 A-ArIE-11 A-ArIE-12 A-ArIE-13 A-ArIE-14 A-ArIE-15 Example ArIE- 14 1 Example ArIE-15 | Example ArIE-16 | Example Arffi-17 | Example ArIE-18 | Example ArIE-19 I Example ArIE-20 | Example ArIE-21 | Example ArIE-22 | EXAMPLES ArIE-23 | EXAMPLES ArIE-24 EXAMPLES ArIE-25 | EXAMPLES ArIE-26 | EXAMPLE A rIE-27 Example ArIE-28 -92- 200934859 ο0 (Drive) 谳£:濉Save stability π^ Thief n^ -23⁄4 •n^ Usage (parts by weight) 1 1 1 1 1 1 1 1 1 1 t 1 1 1 1 Secret m Type 1 1 1 1 1 1 1 t 1 1 1 1 1 I 1 Other polymer usage infringement) 1 2,000 2,000 2,000 〇 2,000 2,000 2,000 2,000 2,000 〇»ri 1,000 2,000 2,000 2,000 2,000 PA-4 PA-4 PA-4 PS-1 PA-1 PA-2 PA-3 PA-4 PA-5 PA-4 PA-4 1 PI-1 1 PI-2 PI-3 PI-4 Discussion! S-ArIE-6 S-ArIE-7 S-ArIE-8 S-ArIE-1 S-ArIE-9 S-ArIE-9 S-ArIE-9 S-ArIE-9 S-ArIE-9 S-ArIE-9 S-ArIE-9 S-ArIE-9 S-ArIE-9 S-ArIE-9 S-ArIE-9 Liquid Crystal Alignment Name A-ArIE-16 A-ArIE-17 A-ArIE-18 A-ArIE-19 A -ArIE-20 A-ArIE-21 A-ArIE-22 A-ArIE-23 A-ArIE-24 A-ArIE-25 A-ArIE-26 A-ArIE-27 A-ArIE-28 A-ArIE-29 A - ArIE-30 Example Arffi-29 | Example Arffi-30 Example ArIE-31 Example ArIE-32 [Example ArIE-33 | Example ArtE-34 | Example ArIE-35 Example Arffi-36 | Implementation Example ArIE-37 "Example ArIE-38 | Example ArIE-39 实施 Example ArIE-4〇 | Example ArIE-41 | Example ArIE-42 | Example ArIE-43 -93- 200934859 οό §撇e Preservation stability {13⁄4 Π2 (loose &lt;Π r^&gt; Usage (parts by weight) 1 1 1 1 1 1 1 t 1 1 200 200 Secret m Type 1 1 1 1 1 1 1 1 1 1 ώ ώ (N ώ (N ώ Other polymer usage (parts by weight) 2,000 2,000 2,000 2,000 i 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 2,000 PI-4 PI-4 PI-4 PI-4 PI-4 PA-4 PA-4 PA-4 PA-4 PS-1 PI-5 PI-5 PI-7 1 PI-7 i iH ; 1 to the 'S-ArIE-9 S-ArIE-9 S-ArIE-9 S-ArIE-9 S-ArIE-9 S-ArIE-10 S-ArIE-11 S-ArIE-12 S-ArIE-13 S-ArIE-9 S-ArIE-9 S-ArIE-9 S-ArIE-9 S-ArIE-9 Liquid crystal alignment agent name A-ArIE-31 A-ArIE-32 A-ArIE-33 A-ArIE-34 A -ArIE-35 A-ArIE-36 A-ArIE-37 A-ArIE-38 A-ArIE-39 A-ArIE-40 A-ArIE-41 A-ArIE-42 A-ArIE-43 A-ArIE-44 Implementation Example ArIE-44 | Example ArIE-45 I Example ArIE-46 | Example ArIE-47 | Example ArIE-48 Example ArIE-49 Example ArIE-50 Example ArIE-51 Example ArIE-52 | Example ArIE-53 | Example ArIE-54 | Example ArIE-55 f Example ArIE-56 Example ArIE-57-94-200934859 Example ArIE-58 &lt;Manufacturing of TN-Aligned Liquid Crystal Display Element&gt; The liquid crystal alignment agent A-ArIE-1 prepared in ArIE-14 was coated on a transparent electrode surface of a transparent electrode glass substrate made of an ITO film by spin coating, and was applied on a hot plate at 80 ° C. 1 minute pre-bake. After baking, a coating film having a film thickness of 1 μm was formed by heating at 180 ° C for 1 hour. On the surface of the coating film, an Hg-Xe lamp and a Glan-Taylor prism were used to impart a liquid crystal alignment by irradiating a polarized ultraviolet light of 313 nm with a polarized ultraviolet light of 1,000 J/m 2 in a direction inclined by 40° from the substrate normal. It can form a liquid crystal alignment film. The same operation as above was repeated to prepare a pair of (two) glass substrates having a liquid crystal alignment film on the surface of the transparent conductive film. The peripheral portion of the liquid crystal alignment film surface is formed on each of the pair of substrates, and the epoxy resin adhesive containing the alumina sphere having a diameter of 5 · 5 μm is applied by screen printing, and then the direction of the polarized ultraviolet light is orthogonal. The substrate was stacked at a weight of 0 and pressed with 'heating at 15 〇t for 1 hour. Then, a positive nematic liquid crystal (manufactured by Merck & Co., Ltd., MLC-622 1, containing a chiral agent) was injected from the liquid crystal injection port, and the liquid crystal injection port was sealed with an epoxy-based adhesive. Further, in order to remove the flow alignment at the time of liquid crystal injection, it was heated at 150 ° C for 10 minutes and then slowly cooled to room temperature. Then, the polarizing plates were bonded to each other on the outer surfaces of the substrate so that the polarizing directions were perpendicular to each other and parallel to the polarizing direction of the liquid crystal alignment film, thereby producing a TN alignment type liquid crystal display device. Regarding these liquid crystal display elements, evaluation was performed by the following method. Commentary -95- 200934859 The results are estimated as shown in Table 4. &lt;Evaluation of liquid crystal display element&gt; (1) Evaluation of liquid crystal alignment property The liquid crystal display element manufactured as described above was observed by an optical microscope, and was abnormally changed in brightness and darkness when ON/OFF (applied/released voltage) was performed at a voltage of 5 V. If there is no area, there is no abnormal area, it is "good". 〇(2) The voltage maintenance rate was evaluated by adding the voltage of 5V and 60 microseconds to the liquid crystal display element manufactured above, and after adding the distance of 167 milliseconds, the voltage was maintained after 167 milliseconds after the applied voltage was released. rate. The measuring device for the voltage maintenance rate was used by VYO-1 manufactured by TOYO Corporation. « (3) Evaluation of the burnt-out liquid crystal display element manufactured by the above, the rectangular wave of 30 Hz and 3 V of overlapping DC of 5 V is applied at an ambient temperature of 60 ° C for 2 hours so that the liquid crystal cell immediately after the DC voltage is cut off The residual voltage is determined by the Flicker minimizing method. (Examples) ArIE-59 to 74 were used as liquid crystal alignment agents, and TN alignment type liquid crystal display elements were produced and evaluated in the same manner as in the above-described Example ArIE-58, as shown in the fourth table. The results are as shown in Table 4. -96- 200934859 Table 4 Liquid crystal alignment agent (name) TN alignment type liquid crystal display element Liquid crystal alignment voltage maintenance ratio (%) Burning (mV) Example ArIE-58 A-ArIE-1 Good 98 12 Example AriE- 59 A-ArIE-2 Good 98 12 Example ArIE-60 A-ArIE-3 Good 98 13 Example ArIE-61 A-ArIE-4 Good 98 12 Example AriE-62 A-ArIE-5 Good 98 12 Example ArIE-63 A-ArIE-6 Good 98 15 Example ArIE-64 Α-ΑγΙΕ-7 Good 98 12 Example ArIE-65 A-ArIE-8 Good 98 12 Example ArIE-66 A-ArIE-9 Good 98 13 EXAMPLES ArIE-67 A-ArIE-10 Good 98 12 Example ArIE-68 Α-ΑγΙΕ-11 Good 98 12 Example ArIE-69 A-ArIE-12 Good 98 14 Example ArIE-70 A-ArIE-13 Good 98 12 EXAMPLES ArIE-71 A-ArIE-14 Good 98 12 Example ArIE-72 A-ArIE-15 Good 98 12 Example ArIE-73 A-ArIE-18 Good 98 15 Example ArIE-74 A-ArIE- 19 good 98 12

EXAMPLES ArIE-75 &lt;Production of Vertical Alignment Type Liquid Crystal Display Element&gt; The liquid crystal alignment agent A-ArIE-16 prepared by the above Example ArIE-29 was transparent to a transparent electrode glass substrate formed by an IT ruthenium film. The electrode surface was coated by spin coating, prebaked on a hot plate at 80 ° C for 1 minute, and then heated at 200 ° C for 1 hour - 97 - 200934859 in an oven substituted with nitrogen in the library (after Baking) 'Forming a film thickness Ο. ίμιη coating film. Next, on the surface of the coating film, a polarized ultraviolet ray of 313 nm was subjected to a tilt of 40 from the substrate normal line using an Hg-Xe lamp and a Glan-Taylor crucible. The direction of the lens is obtained by the liquid crystal alignment film. The same operation was repeated to fabricate a pair of (two) substrates having a liquid crystal alignment film. On the outer periphery of one of the substrates in which the liquid crystal alignment film is provided, the epoxy resin adhesive containing the alumina spheres having a diameter of 5 · 5 μm is coated by screen printing, and then the substrate of the pair is made The liquid crystal alignment film faces, and the projection direction of the substrate surface of the optical axis of the ultraviolet light of each substrate is pressed in antiparallel, and the adhesive is thermally cured at 150 ° C for 1 hour. Then, the liquid crystal injection port was sealed with a negative-type liquid crystal (MLC-6608 manufactured by Merck Co., Ltd.) from the gap between the substrates, and the liquid crystal injection port was sealed with an epoxy-based adhesive. Further, in order to remove the flow alignment at the time of liquid crystal injection, the mixture was heated at 150 ° C for 1 minute and then slowly cooled to room temperature. Next, on the outer surfaces of the substrate, the polarizing plates are perpendicular to each other in the direction of polarization, and the projection direction of the substrate from the ultraviolet light axis of the liquid crystal alignment film is 45. The bonding is performed in an angle manner to manufacture a vertically aligned liquid crystal display element. The liquid crystal alignment property, voltage maintenance ratio, and baking of the vertical alignment type liquid crystal display device were evaluated in the same manner as in the example ArIE-58, and the pretilt angle and heat resistance were evaluated in accordance with the following methods. The overall evaluation results are shown in Table 5. (4) Evaluation of pretilt angle The liquid crystal display element manufactured as described above is used according to the method described in J. Scheffer-98-200934859 et. al. J. Appl. Phys. vol. 19, p2013 (1980). He-Ne laser light was measured by a crystal rotation method to measure the pretilt angle. (5) Evaluation of heat resistance The post-baking temperature at which the liquid crystal alignment film was formed was set to 250 ° C. The formation of a liquid crystal alignment film and the production of a vertical alignment type liquid crystal display element were carried out in the same manner as above. Regarding the obtained liquid crystal display element, those who showed good vertical alignment (displayed as a uniform black display) were "good", and those who had light leakage were "bad J. Example ArIE-76 to 101 as a liquid crystal alignment agent, except for use separately. In the same manner as in the Example ArIE-75, a vertical alignment type liquid crystal display device was produced and evaluated. The results are shown in Table 5. $ φ -99- 200934859 Table 5 Liquid Crystal Alignment Agent (Name) Vertical Alignment Liquid crystal display element liquid crystal alignment pretilt angle (°) Voltage maintenance ratio (%) Burning (mV) Heat resistance Example ArIE-75 A-ArIE-16 Good 89 98 7 Good example ArIE-76 A-ArIE-17 Good 89 98 6 Good example ArIE-77 A-ArIE-20 Good 89 98 7 Good example ArIE-78 A-ArIE-21 Good 89 98 7 Good example ArIE-79 A-ArIE-22 Good 89 98 7 Good EXAMPLES ΑιΊΕ-80 Α-ΑγΙΕ-23 Good 89 98 8 Good Example ArIE-81 A-ArIE-24 Good 89 98 8 Good Example ArIE-82 A-ArIE-25 Good 89 97 7 Good Example ArIE-83 Α-ΑγΙΕ-26 Good 89 97 7 Good implementation inverted J AriE-84 A-ArIE-27 Good 89 98 7 Good example ArIE-85 A-ArIE-28 Good 89 98 7 Good EXAMPLES ArIE-86 A-ArIE-29 Good 89 98 7 Good Example ArIE-87 A-ArIE-30 Good 89 98 8 Good Example ArIE-88 A-ArIE-31 Good 89 98 8 Good Example ArIE-89 A-ArIE-32 good 89 98 7 good example ArIE-90 A-ArIE-33 good 89 98 7 good example 1 ArIE-91 A-ArIE-34 good 89 98 7 good example ArIE-92 A-ArIE- 35 good 89 98 7 good example ArIE-93 A-ArIE-36 good 89 98 7 good example ArIE-94 A-ArIE-37 good 89 98 8 good example ArIE-95 A-ArIE-38 good 89 98 7 Good example ArIE-96 A-ArIE-39 Good 89 98 7 Good example ArIE-97 A-ArIE-40 Good 89 98 7 Good example ArIE-98 A-ArIE-41 Good 89 98 7 Good example ArIE- 99 A-ArIE-42 Good 89 98 8 Good example ArIE-100 A-ArIE-43 Good 89 98 7 Good example ArIE-101 A-ArIE-44 Good 89 98 7 Good

EFFECTS OF THE INVENTION -100-200934859 The liquid crystal alignment agent of the present invention is a liquid crystal alignment agent which is excellent in liquid crystal alignment and electrical properties, and can be used as a liquid crystal alignment agent which is suitable for a photo-alignment method. Further, since the formed liquid crystal alignment film has high heat resistance, the liquid crystal panel can be produced without any discomfort in steps. Further, when the liquid crystal alignment element is used for the liquid crystal display element, the liquid crystal display element can be manufactured at a lower cost than before. The obtained liquid crystal display element is excellent in display performance, reliability, and the like. Moreover, such liquid crystal display elements can be effectively applied to various devices such as desktop computers, watches, clocks, counting display panels, word processing systems, personal computers, liquid crystal televisions and the like. ❾ -101 -

Claims (1)

200934859 X. Patent application scope 1. A liquid crystal alignment agent characterized by the following formula (1) φ (in the formula (!), R1 is a hydrogen atom or a monovalent organic group having a carbon number of 1 to 40, and RII, Rlv and Rv are each independently a hydrogen atom, a methyl group, a cyano group or a fluorine atom, and R1 is a hydrogen atom. When R111 is a monovalent organic group having 1 to 40 carbon atoms, R1 is a carboxyl group when RNi is a carboxyl group, and a compound selected from the following formula (S-1) (S-1) (In the formula (S-1), X1 is a monovalent organic group having an epoxy group, Y1 is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 20 carbon atoms or Radiation-based polyorganosiloxane obtained by reacting at least one of a group of polyorganosiloxanes having a repeating unit and a condensate of a hydrolyzate and a hydrolyzate thereof, represented by an aryl group having 6 to 20 carbon atoms alkyl. 2. The liquid crystal alignment agent of the first aspect of the invention, wherein the compound represented by the above formula (1) is the following formula (2) -102 - 200934859 RVII Ru O :nhQ-CH=CH-COOH (In the formula (2), R11, RIV and Rv are respectively synonymous with the above formula (1), and RVI „ is a single bond, an ether bond, a thioether bond, an ester bond, a thioester bond Or a guanamine bond, Rvn is a compound represented by an alkyl group having 1 to 30 carbon atoms which may be substituted by a fluorine atom or an alicyclic group having a Q carbon number of 3 to 40 which may be substituted by a fluorine atom. A liquid crystal alignment agent according to the above formula (1), wherein the compound represented by the above formula (1) is a formula (3) (In the formula (3), R11, RIV and Rv are the same as those in the above formula (1), and Q RVU1 is an alkyl group having 1 to 30 carbon atoms which may be substituted by a fluorine atom or a carbon number of 3 to 40 which may be substituted by a fluorine atom. The compound represented by the alicyclic group. 4. The liquid crystal alignment agent according to any one of claims 1 to 3, further comprising at least one polymer selected from the group consisting of polyproline and polyimine. 5. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the liquid crystal alignment agent is further selected from the group consisting of the following formula (S-2) - s 〇 - - Ϋ 2 (S-2) -103 - 200934859 (In the formula (s_2), X2 is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having a carbon number of 6 to 20 Y 2 is a trans group or a carbon number of 1 At least one of the polyoxyalkylene represented by the alkoxy group of ～10, the hydrolyzate thereof and the condensate of the hydrolyzate. A method for forming a liquid crystal alignment film, which comprises applying a liquid crystal alignment agent according to any one of claims 1 to 3 on a substrate, and forming a 4 © coating film, and irradiating the coating film with radiation. 7. A liquid crystal display device characterized by comprising a liquid crystal alignment film formed by a liquid crystal alignment agent according to any one of claims 1 to 3, a radiation-sensitive polyorganosiloxane. It is characterized in that a compound represented by the above formula (1) and a condensate of a polyorganosiloxane having a repeating unit represented by the above formula (S-1), a hydrolyzate thereof and a hydrolyzate are selected in groups. At least one of the types obtained by the reaction. ® 9 - a compound represented by the above formula (1). -104- 200934859 VII. Designated representative map: (1) The representative representative of the case is: None (2), the representative symbol of the representative figure is simple: No 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: CH=CH—COOR1 α)