TW201033253A - Liquid crystal alignment agent, polyorgano siloxane, liquid crystal alignment film and method for forming the same as well as liquid crystal display element - Google Patents

Abstract

Provided is a liquid crystal alignment agent which is capable of providing a pretilt-angle by photo-alignment-method and providing a liquid crystal alignment with excellent ageing-stability of the pretilt-angle. The said liquid crystal alignment agent comprises a radiation-sensitive polyorgano siloxane obtained from reacting specific polyorgano siloxane having epoxy group and (A) cinnamic acid derivate with (B) specific compound having photosensitizing structure selected from preferable acetophenone structure, benzophenone structure, anthraquinone structure, biphenyl structure, carbazole structure, nitro-aryl structure, fluorene structure, naphthalene structure, anthracene structure, acridine structure and indole structure.

Description

201033253 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment agent, a polyorganosiloxane, a liquid crystal alignment film, a method for forming the same, and a liquid crystal display element. [Prior Art] Heretofore, it has been known to form a sandwich structure in which a nematic liquid crystal having positive dielectric anisotropy is formed in a substrate having a transparent electrode having a liquid crystal alignment film, and to have a long axis of liquid crystal molecules on a substrate as needed Between the TN type (twisted nematic) and the STN (super twisted nematic) type, which are 0 to 3 60°, and the IPS (in-plane switching) type in which the long axis of the liquid crystal molecules is aligned with respect to the substrate in the horizontal direction. Liquid crystal display element of liquid crystal cell (refer to Patent Documents 1 to 4). In such a liquid crystal cell, as a means for aligning the liquid crystal, an organic film is formed on the surface of the substrate, and then the surface of the organic film is rubbed in a certain direction by a cloth such as rayon to cause liquid crystal alignment energy to be used as a liquid crystal cell. A method of liquid crystal alignment film (method of performing rubbing treatment), a method of obliquely smashing ruthenium oxide on the surface of a substrate, or a method of forming a monomolecular film having a long-chain alkyl group by the Langmuir-Blodgett method (LB method)@. Among them, from the viewpoint of substrate size, liquid crystal alignment uniformity, processing time, and processing cost, liquid crystal alignment energy is usually generated by rubbing treatment. However, when the alignment of the liquid crystal is carried out by the rubbing treatment, there is a problem that powdery dust and static electricity are likely to be generated in the process, and dust adheres to the surface of the alignment film, which causes a display failure. In particular, in the case of using a substrate having a TFT (Thin Film Transistor) element, there is a problem that the generated static electricity 201033253 causes damage to the TFT element circuit and causes a decrease in yield. Further, in the liquid crystal display device which is highly purified in the future, as the density of the pixels is increased, unevenness of the surface of the substrate is inevitably caused, so that it is increasingly difficult to uniformly perform the rubbing treatment. As another method of imparting liquid crystal alignment energy to a liquid crystal alignment film in a liquid crystal cell, it is known that a photosensitive film such as polyethylene cinnamate or polyimide which is formed on the surface of a substrate is irradiated with polarized or non-polarized radiation. The photo-alignment method in which the liquid crystal alignment energy is generated. According to this method, static electricity and dust are not generated, and uniform liquid crystal alignment can be achieved (refer to Patent Documents 6 to 16 and 1 9 to 2 1). However, in the TN type (twisted nematic), STN (super twisted direction) In the liquid crystal cell of the column type or the like, the liquid crystal alignment film must have the liquid crystal molecules obliquely aligned at a predetermined angle (pretilt angle) with respect to the substrate surface (refer to Patent Document 2). In the case where the liquid crystal alignment film is formed by the photoalignment method, The pretilt angle is usually generated by irradiating the substrate surface with radiation inclined from the substrate normal to the incident direction (refer to φ Patent Document 6). On the other hand, the operation mode of the liquid crystal display element other than the above is also known to have a negative A homeotropic alignment mode in which dielectric anisotropic liquid crystal molecules are vertically aligned between substrates. In this mode of operation, when a voltage is applied between the substrates to tilt the liquid crystal molecules in a direction parallel to the substrate, the liquid crystal molecules must be removed from the liquid crystal molecules. The normal direction of the substrate is inclined in one direction in the plane of the substrate. As a means for achieving this purpose, it has been proposed, for example, to provide protrusions on the surface of the substrate. Method, method of providing a strip on a transparent electrode, 201033253 A method of using a rubbing alignment film to slightly tilt (pretilt) liquid crystal molecules from a normal direction of a substrate to one direction in a substrate surface (refer to Patent Document 5 and Non-Patent Documents 1 to 3) The above-described photo-alignment method is also known as a method for controlling the tilt direction of liquid crystal molecules in a liquid crystal display device of a vertical alignment mode (refer to Patent Documents 15 to 21). The liquid crystal alignment film produced by the photo-alignment method can be effectively applied to a liquid crystal display element. However, the liquid crystal alignment film manufactured by the prior photo-alignment method has an unstable pretilt angle, that is, even when the liquid crystal alignment film is just formed In the case of a good pretilt performance, there is a problem that the pretilt performance is degraded with the lapse of time. [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei-4-153322 [Patent Document 2] JP-A-56-91277 [Patent Document 4] US Patent No. 5,958,333 [Patents] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei. No. 2000-144136 (Patent Document No. 1). Japanese Laid-Open Patent Publication No. Hei. No. 2003-307736 (Patent Document No. JP-A-2003-307736) [Patent Document 16] JP-A-2004 Japanese Laid-Open Patent Publication No. JP-A-2006-171304 (Patent Document No. JP-A-2006-171304) [Patent Document No. 2006-171304] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Literature] [Non-Patent Document 1] "Liquid Crystal", Volume 3 The second phase, p 1 1 7 (19.9) 〇 [Non-Patent Document 2] "Liquid Crystal", Vol. 3, No. 4, P272 (1999) [Non-Patent Document 3] "Jpn Appl. phys ., Vol. 36, p. 428 (1997) [Non-Patent Document 4] Chemical Review, Vol. 95, pl 409 (1995) [Non-Patent Document 5] TJ Scheffer et al., J. Appl. Phys, Vol. P2013 (1980) 201033253 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a time-lapse capable of forming a pretilt angle by a photo-alignment method and generating a pretilt angle. A liquid crystal alignment agent for a liquid crystal alignment film excellent in stability. Another object of the present invention is to provide a method for forming a liquid crystal alignment film from the above liquid crystal alignment agent. A further object of the present invention is to provide a liquid crystal alignment film and a liquid crystal display element excellent in long-term reliability. Further further objects and advantages of the invention will be apparent from the following description. Means for Solving the Problems According to the present invention, the above objects and advantages of the present invention, firstly, are achieved by a liquid crystal alignment agent comprising a radiation sensitive polyorganosiloxane which is selected from the group consisting of radiation sensitive polyorganosiloxanes At least one of the group consisting of a polyorganosiloxane having a repeating unit represented by the following formula (1), a condensate of the hydrolyzate and the hydrolyzate, and (A) having a carboxyl group, a hydroxyl group, - a cinnamic acid derivative of at least one group of SH, NCO, · NHR (wherein R is a hydrogen atom or a group having 1 to 6 carbon atoms), _ch = ch2 and -S02C1, and (B) Having at least one selected from the group consisting of a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CH = CH2 and -S〇2Cl A compound of a group and a photo-sensitizing structure is inversely produced by (1) (1) 201033253, "X1 Ί

I ——Si—Ο—

I

L Y1 J (In the formula (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 An aryl group having 6 to 20 carbon atoms). The above objects and advantages of the present invention are at least the object of forming a liquid crystal alignment film by applying the liquid crystal alignment agent onto a substrate to form a coating film, and irradiating the coating film with polarized or non-polarized radiation. The above objects and advantages of the present invention are attained by a liquid crystal alignment film formed of the above liquid crystal alignment agent, and fourth, by a liquid crystal display element having the above liquid crystal alignment film. EFFECTS OF THE INVENTION According to the liquid crystal alignment agent of the present invention, a liquid crystal alignment film having excellent temporal stability of a pretilt angle can be formed by a photo-alignment method. The liquid crystal alignment film of the present invention formed of the liquid crystal alignment agent of the present invention can be applied to various liquid crystal display elements. The liquid crystal display element of the present invention having such a liquid crystal alignment film does not deteriorate in display performance even after long-term use. Therefore, the liquid crystal display element of the present invention can be effectively applied to various devices, for example, it can be applied to a timepiece, a portable game machine, a word processor, a notebook personal computer, a car navigation system, a video camera, a portable information terminal, A display device such as a digital camera, a mobile phone, various monitors, and a liquid crystal television. 201033253 [Embodiment] Mode for Carrying Out the Invention Hereinafter, the present invention will be described in detail. The liquid crystal alignment agent of the present invention contains at least one selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the above formula (1), and a condensate of a hydrolyzate and a hydrolyzate (hereinafter referred to as " a polyorganosiloxane having an epoxy group"), and (A) having a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) a cinnamic acid derivative (hereinafter referred to as "cinnamic acid derivative (A)") and (B) having at least one group selected from the group consisting of _CH = CH2 and -S02C1 having a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), at least one group of -CH = CH2 and -S02C1, and a compound of a photo-sensitizing structure (hereinafter A radiation-sensitive polyorganosiloxane which is obtained by a reaction called "photosensitizing compound (B)"). Here, a part of the above cinnamic acid derivative (A) may be replaced by a compound represented by the following formula (5), R15-R16-R17 (5) in the formula (5), insofar as the effects of the present invention are not impaired. R15 is a monovalent organic group having an alicyclic group having 3 to 40 carbon atoms, or an alkyl group or alkoxy group having 4 to 20 carbon atoms, wherein the alkyl group or the alkoxy group is partially Or all of the hydrogen atoms may be substituted by a fluorine atom, R16 is a single bond or a phenyl group, but when R15 is an alkoxy group, R1 6 is a phenyl group, and R17 is selected from a carboxyl group, a hydroxyl group, -SH, -NCO, - At least one group of NHR (wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CH=CH2, and 201033253-S02C1. <Sensory Radiation Polyorganooxane> [Polyorganic Oxide Court having an epoxy group] The X1 group in the above formula (1) is preferably the following formula (X1-) or (x1) -〗)) The group indicated, Λ (X1-1) ❹

(Χ1-2) In the above formula, it is expressed as a connection key. Examples of the alkoxy group having 1 to 10 carbon atoms in the oxime 1 include a methoxy group and an ethoxy group; and examples of the alkyl group having 1 to 20 carbon atoms include a methyl group and an ethyl group. N-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, positive Tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, etc.; as a carbon number of 6 to 20 Examples of the aryl group include a phenyl group; and a polyorganosiloxane having an epoxy group, and the polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) is preferably 500 to 100,000. More preferably, it is from 1000 to 10,000, further preferably from 1,000 to 5,000. «The polyorganosiloxane having an epoxy group may be a decane compound having an epoxy group preferably having -11 to 201033253 or having an epoxy group. a mixture of a decane compound and another decane compound, preferably in the presence of a suitable organic solvent, water and a catalyst Synthesis or hydrolysis or condensation. Examples of the above decane compound having an epoxy group include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and 3-epoxypropoxypropane. Methyldimethoxydecane, 3_glycidoxypropylmethyldiethoxylate, 3-glycidoxypropyldimethylmethoxydecane, 3-glycidoxy Propyl dimethyl ethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane ' 2-(3,4-epoxycyclohexyl)ethyltriethoxy Decane and so on. Examples of the other decane compound include tetrachloroguanidine, tetramethoxy sand, tetraethoxy sand, tetra-n-propoxy lanthanum, tetraisopropoxy decane, and tetra-n-butoxy decane. Tetra- or two-stage butoxy decane, trichloro- stanal, trimethoxy decane, triethoxy decane, tri-n-propoxy oxidant, triisopropoxy sand, di-n-butoxy sand, three two Grade butoxylate, fluorotrichlorodecane, fluorotrimethoxydecane, fluorotriethoxy sand, gas tri-n-propoxy decane, fluorotriisopropoxy decane, fluorinated three n-Butoxydecane, fluorotri- or 2-butoxybutane, methyltrichloroindole, methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxylated samarium, methyl Triisopropoxydecane, methyltri-n-butoxydecane, methyltri- or 2-butoxybutane, 2-(trifluoromethyl)ethyltrichlorodecane, 2-(trifluoromethyl)ethyl Trimethoxydecane, 2-(trifluoromethyl)ethyltriethoxy oxime, 2-(trifluoromethyl)ethyltri-n-propoxydecane, 2-(trifluoromethyl)ethyltriiso Propoxy-12- 201033 253 decane, 2-(trifluoromethyl)ethyltri-n-butoxy decane, 2-(trifluoromethyl)ethyltri-n-butoxy decane, 2-(perfluoro-n-hexyl)ethyltri Chlorodecane, 2-(perfluoro-n-hexyl)ethyltrimethoxydecane, 2-(perfluoro-n-hexyl)ethyltriethoxydecane, 2-(perfluoro-n-hexyl)ethyltri-n-propoxydecane , 2-(perfluoro-n-hexyl)ethyltriisopropoxydecane, 2-(perfluoro-n-hexyl)ethyltri-n-butoxyoxane, 2-(perfluoro-n-hexyl)ethyltri-n-butoxy Baseline, 2-(perfluoro-n-octyl)ethyltrichloromethane, 2-(perfluoro-n-octyl)ethyltrimethoxysulfonium alkane, 2-(perfluoro-n-octyl)ethyltriethoxylate Baseline, 2-(perfluoro-n-octyl)ethylidene tri-n-propoxyoxydecane, 2-(perfluoro-n-octyl)ethyltriisopropoxydecane, 2-(perfluoro-n-octyl) Tri-n-butoxy decane, 2-(perfluoro-n-octyl)ethyl tri- or 2-butoxy decane, hydroxymethyltrichloro decane, hydroxymethyltrimethoxy decane, hydroxyethyltrimethoxy decane, Hydroxymethyl tri-n-propoxy decane, methylol triisopropoxy decane, hydroxymethyl tri-n-butoxy Decane, hydroxymethyl tri- or 2-butoxybutane, 3-(methyl)propenyloxypropyltrichlorodecane, 3-(methyl)propenyloxypropyltrimethoxydecane, 3-(A) Acryloxypropenyltriethoxydecane, 3-(methyl)propenyloxypropyltri-n-propoxyoxydecane, 3-(methyl)acryloxypropyltriisopropyloxy Baseline, 3-(methyl)propenyloxypropyltri-n-butoxydecane, 3-(methyl)propenyloxypropyltri-n-butoxypropane, 3-mercaptopropyltrichloro Decane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, 3-mercaptopropyltri-n-propoxyoxydecane, 3-mercaptopropyltriisopropoxydecane , 3-mercaptopropyltri-n-butoxydecane, 3-mercaptopropyltri-n-butoxybutane, mercaptomethyltrimethoxydecane, sulfomethyltriethoxydecane, vinyl three Chlorodecane, ethylene-13- 201033253 bis trimethoxy decane, vinyl triethoxy decane, vinyl tri-n-propoxy decane, vinyl triisopropoxy decane, vinyl tri-n-butoxy decane, ethylene Tris-butoxybutyrate Alkane, allyltrichlorodecane, allyltrimethoxydecane, allyltriethoxydecane, allyltri-n-propoxydecane, allyltriisopropoxydecane,allyl-3 n-Butoxydecane, allyl tri-n-butoxy decane, phenyl trichloro decane, phenyl trimethoxy decane, phenyl triethoxy decane, phenyl tri-n-propoxy decane, phenyl tri Isopropoxy decane, phenyl tri-n-butoxy decane, phenyl tri-n-butoxy decane, methyl dichloro decane, methyl dimethoxy decane 'methyl diethoxy decane, methyl two N-propoxy decane, methyl diisopropoxy decane, methyl di-n-butoxy decane, methyl di- or 2-butoxy decane, dimethyl dichloro decane, dimethyl dimethoxy decane, Dimethyldiethoxydecane, dimethyldi-n-propoxyoxydecane, dimethyldiisopropoxydecane, dimethyldi-n-butoxydecane, dimethyldi-2-butoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]dichlorodecane, (methyl)[2-(perfluoro-n-octyl)ethyl]dimethoxydecane, (methyl)[2 -(perfluoro-n-octyl Ethyl]diethoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-n-propoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl] Diisopropoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-n-butoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]di Butoxy decane, (methyl) (3-mercaptopropyl) dichlorodecane, (methyl) (3-mercaptopropyl) dimethoxy decane, (methyl) (3-mercaptopropyl propyl) Diethoxy decane, (methyl) (3-mercaptopropyl) di-n-propoxy decane, (methyl) (3-mercaptopropyl) diisopropoxy decane, (methyl) ( 3-mercaptopropyl)di-n-butoxydecane, (methyl)(3_mercaptopropene 201033253)dibasic butoxybutane, (methyl)(vinyl)dichlorodecane, (methyl (vinyl)dimethoxydecane, (meth)(vinyl)diethoxydecane, (meth)(vinyl)di-n-propoxydecane, (methyl)(vinyl) diiso Propoxy decane, (methyl) (vinyl) di-n-butoxy decane, (methyl) (B) Alkenyl) di- or two-butoxybutane, divinyldichlorodecane, divinyldimethoxydecane, divinyldiethoxydecane, divinyldi-n-propoxydecane, divinyldiene Isopropoxydecane, divinyldi-n-butoxydecane, dimethylvinyldi-butoxybutane, diphenyldichlorodecane, diphenyldimethoxydecane, diphenyldiethoxy Base decane, diphenyl di-n-propoxy decane, diphenyl diisopropoxy decane, diphenyl di-n-butoxy decane, diphenyl di-n-butoxy decane, chlorodimethyl decane , methoxy dimethyl decane, ethoxy dimethyl decane, chlorotrimethyl decane, bromotrimethyl decane, iodotrimethyl decane, methoxy trimethyl decane, ethoxy three Methyl decane, n-propoxy trimethyl decane, isopropoxy trimethyl decane, n-butoxy trimethyl decane, secondary butoxy trimethyl decane, tertiary butoxy trimethyl hydrazine Brothel, (chloro) (vinyl) dimethyl decane, (methoxy) (vinyl) dimethyl fluorene, (ethoxy) (vinyl) dimethyl a decane having one ruthenium atom such as decane, (chloro)(methyl)diphenyl decane, (methoxy)(methyl)diphenyl decane or (ethoxy)(methyl)diphenyl decane In addition to the above, the product name is, for example, KC-89, KC-89S, X-21-3153, X-21-5841, X-2 1 -5842, X-2 1 -5 843 U 1 - 5 844, Χ-21·5 84 5, X-2 1 -5 846, X-21-5847, Χ-21-5848, X-22-160AS, X-22-170B, X-22- 1 70BX, X_22- 1 70D, X-22- 1 70DX, X-22- 1 76B, -15- 201033253 X-22-17 6D, X-22-1 76DX 'X-22-1 76F, X-40-2308, X-40-265 1, X-40-2655A 'X-40-2671, 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 , KR2 1 2 , KR-2 1 3, KR-2 1 7, KR22 0 L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR523 5, KR9218, KR9706 (above by Shin-Etsu Chemical Industry ( Stock) production); Glass Resin (produced by Showa Denko (share)) SH804, SH805, SH806A, SH840, SR2400, SR2 402, SR2405 'SR2406, SR2410, SR2411, SR2416, SR2420 (above produced by Toray Dow Corning (share)); FZ3711, FZ3722 (above, by 曰本Unicar(股) Production), DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45 ' DMS-S51 , DMS-227, PSD-0332, PDS-1615, PDS-993 1, XMS-5025 (above produced by Chisso); methyl phthalate MS51, methyl phthalate MS56 (by _ on by Mitsubishi Chemical (stock) production); ethyl phthalate 28, ethyl phthalate 40, ethyl phthalate 48 (above produced by Colcoat); GR100'GR650, GR90 8, GR95 0 (above by Showa A partial condensate such as an electrician (produced). Among these other decane compounds, preferred are tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, 3-(methyl) propylene methoxy propyl trimethoxy. Baseline, 3-(meth)acryloxypropyltriethoxydecane, vinyltrimethoxydecane, vinyltriethoxy-16-201033253 decane, allyltrimethoxydecane, allyl Triethoxy methoxy trimethoxy decane, phenyl triethoxy decane, 3-mercaptopropyl decane, 3-mercaptopropyl triethoxy decane, decyl methyl trimethoxy decyl methyl triethyl Oxydecane, dimethyldimethoxydecane or ethoxydecane. The polyorganosiloxane base equivalent having an epoxy group used in the present invention is preferably from 100 to 100 g/mole, more preferably from 150 to ^ ears, particularly preferably from 150 to 30,000 g/mole. Therefore, in the case of synthesizing a polyorganosiloxane, the use ratio of the decane compound having an epoxy group to the compound thereof is preferably set so that the obtained polyorganofluorene group equivalent is adjusted within the above range. In the synthesis of the polyorganosiloxane having an oxy group in the present invention, it is preferred to use only an epoxy compound without using other decane compounds. The polyorganosiloxane having an epoxy group may be an organic solvent, and examples thereof include a hydrocarbon, a ketone, an ester, an ether, and hydrazine, and the ketone may be, for example, toluene or xylene. For example, methyl ethyl ketone, methyl isobutyl n-pentyl ketone, diethyl ketone, cyclohexanone, etc. are listed; as the above ester, for example, ethyl acetate, n-butyl acetate, isoamyl acetate, methyl ether B are listed. Examples of the ether such as an acid ester, 3-methoxybutyl acetate, and ethyl lactate include ethylene glycol dimethyl ether, ethylene glycol dihydrofuran, and dioxane. For example, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, alkane, phenyltrimethoxydecane, dimethyl di, epoxy 1 000 g / molyblyoxy The decane having a ring group of an epoxy group of an alkylene oxide is an alcohol or the like. Ethen, as a ketone, a class, can be propylene glycol, as the upper ether, tetra-I 1-hexanol, ethylene glycol single 201033253 n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol mono-n-propyl ether and the like. Among them, a water-insoluble solvent is preferred. These organic solvents may be used singly or in combination of two or more. The amount of the organic solvent is preferably from 10 to 10,000 parts by weight, more preferably from 50 to 1,000 parts by weight, per 100 parts by weight of the total of the decane compound. The amount of water used in the preparation of the polyorganosiloxane having an epoxy group is preferably from 0.5 to 100 moles, more preferably from 1 to 30 moles per mole of the total decane compound. m As the above catalyst, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound or the like can be used. Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide. The organic base may, for example, be an organic primary or secondary amine such as ethylamine, diethylamine, pipe trap, piperidine, pyrrolidine or pyrrole; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4- An organic tertiary amine such as dimethylaminopyridine or diazabicycloundecene or an organic quaternary ammonium ammonium such as tetramethylammonium hydroxide. Among these organic bases, organic tertiary amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, and organic quaternary ammonium hydroxide such as tetramethylammonium hydroxide are preferable. As the catalyst for preparing the polyorganosiloxane having an epoxy group, an alkali metal compound or an organic base is preferred. Since the use of an alkali metal compound or an organic base as a catalyst does not cause a side reaction such as ring opening of an epoxy group, the desired polyorganosiloxane can be obtained at a rapid hydrolysis and condensation rate, so -18-201033253 production It is excellent in stability and is therefore preferred. Further, the liquid crystal alignment agent of the present invention containing a reaction product of an epoxy group-containing polyorganosiloxane and a cinnamic acid derivative synthesized using an alkali metal compound or an organic base as a catalyst is excellent in storage stability, so it is convenient . The reason 'is supposed to be as described in Non-Patent Document 4 (Chemical Reviews' 95, pl 409 (1995)), because if a base metal compound or an organic base is used as a catalyst in the hydrolysis or condensation reaction, A random structure, a trapezoidal structure, or a cage structure is formed, thereby obtaining a polyorganosiloxane having a small content ratio of sterol groups. That is, it is presumed that such a polyorganosiloxane has a small content ratio of sterol groups, thereby suppressing a condensation reaction between sterol groups, and when the liquid crystal alignment agent of the present invention further contains the following other In the case of a polymer, a condensation reaction of a sterol group with another polymer can be suppressed, and thus a result of excellent storage stability is obtained. As the catalyst, an organic base is particularly preferred. The amount of the organic base to be used varies depending on the type of the organic base, the reaction conditions, and the like, and should be appropriately set. For example, it is preferably 0.01 to 3. mM, more preferably 0.05 to 1 times, based on the total of the decane compound. ear. The hydrolysis or hydrolysis, condensation reaction in the preparation of the polyorganosiloxane having an epoxy group, preferably by dissolving the decane compound having an epoxy group and other decane compounds as needed in an organic solvent, The organic base is mixed with water and heated by, for example, an oil bath. In the hydrolysis and condensation reaction, the heating temperature is preferably 1 30 ° C or less, more preferably 40 to 100 ° C, preferably 0.5 to 12 hours, more preferably 1 to -19 - 201033253 8 hours. . The mixture may be stirred during heating or under reflux. After completion of the reaction, it is preferred to wash the organic solvent layer separated from the reaction liquid with water. At the time of the washing, it is preferable to wash the water containing a small amount of salt, for example, an aqueous solution containing about 0.2% by weight of ammonium nitrate, from the viewpoint of facilitating the washing operation. The washing is carried out until the aqueous layer after washing is neutral, and then the organic solvent layer is dried with an appropriate desiccant such as anhydrous calcium sulfate or molecular sieve as necessary, and then the solvent is removed to obtain an epoxy group as a target. Polyorganosiloxane. In the present invention, a commercially available product can also be used as the polyorganosiloxane having an epoxy group. Examples of such a commercially available product include DMS-E0 1, DMS-E12, DMS-E21, and EMS-32 (manufactured by Chisso Co., Ltd.). [Cinnamic acid derivative (A)] The cinnamic acid derivative (A) which can be used in the present invention has a member selected from the group consisting of a carboxyl group, a hydroxyl group, -SH, -NCO, and -NHR (wherein R is a hydrogen atom or a carbon number of 1) A cinnamic acid derivative of at least one group of the group consisting of ～6 alkyl), —CH=CH2 and —S02C1. The cinnamic acid derivative (A) ' is preferably a compound represented by the following formula (2) or a compound represented by the following formula (3), R1 - R2 - (R3 - R4)

CH=CH- Ο R5—R6 (2) (In the formula (2), R1 is a monovalent organic group having an alicyclic group having 3 to 4〇201033253, or a carbon number of 1 An alkyl group of 〜40, wherein some or all of the hydrogen atoms of the above alkyl group may be substituted by a fluorine atom, R2 is a single bond, an oxygen atom, -COO- or -OCO-, R3 is a divalent aromatic group, and divalent An alicyclic group, a divalent heterocyclic group or a divalent fused ring group, R4 is a single bond, an oxygen atom, -COO- or -OCO-, and R5 is a single bond, an oxygen atom, sulfur An atom, a methylene group, an alkylene group having 2 to 10 carbon atoms or a divalent aromatic group. When R5 is a single bond, t is 1, and R6 is a hydrogen atom, ❹ when R5 is a methylene group. And an alkyl group or a divalent aromatic group, t is 0 or 1, and R6 is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR, -CH=CH2 or -so2cn, wherein the above R is a hydrogen atom Or an alkyl group having 1 to 6 carbon atoms, R7 is a fluorine atom or a cyano group, and a is an integer of 0 to 3 'b is an integer of 0 to 4)'

:CH

=\^R10-R11-^-R12~R13, (R14)d (3) R8_R9_C—CH:

II 0 (in the formula (3), R8 is a monovalent organic group having an alicyclic group having 3 to 40 carbon atoms, or a group having 1 to 40 carbon atoms, wherein the alkyl group is Some or all of the hydrogen atoms may be optionally substituted by a fluorine atom, 'R9 is an oxygen atom or a divalent aromatic group, R1() is an oxygen atom, -COO- or -OCO_, and R11 is a divalent aromatic group, a divalent heterocyclic group or a divalent fused ring group, R12 is a single bond, -〇C〇-(CH2)e-* or -0-(CH2)g-*, wherein the above 6 and g Each is an integer from 1 to 10, each of which represents a linkage with it and is linked to R13 'Rl3 is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR, -CH=CH2 or -S02C1' wherein R is a hydrogen atom or An alkyl group having 1 to 6 carbon atoms, R14 is a fluorine atom or a cyano group 'c•厶丄·201033253 is an integer of 0 to 3, and d is an integer of 0 to 4). The monovalent organic group having an alicyclic group-containing carbon atom having 3 to 40 carbon atoms in the above formula (2), for example, a cholesteryl group, a cholesteryl group, an adamantyl group or the like can be given. The alkyl group having 1 to 40 carbon atoms as R1 is preferably an alkyl group having 1 to 20 carbon atoms, for example, a part or all of hydrogen atoms of the alkyl group may be substituted by a fluorine atom. Examples of such an alkyl group include n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecane. Base, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, 4,4,4- Trifluorobutyl, 4,4,5,5,5-pentafluoropentyl, 4,4,5,5,6,6,6-heptafluorohexyl, 3,3,4,4,5,5, 5-heptafluoropentyl, 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2-(perfluorobutyl)ethyl, 2-(perfluorooctyl) Ethyl, 2-(perfluorodecyl)ethyl and the like. Examples of the divalent aromatic group of R3 and R5 include a 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, a 3-fluoro-1,4-phenylene group, and 2,3. , 5,6-tetrafluoro-1,4-phenylene, etc.; as the divalent heterocyclic group of r3, for example, @1,4-1,4-pyridyl, 2,5-extended pyridyl, 1,4 - a ketone group or the like; and as the divalent condensed ring group of R3, for example, a naphthyl group or the like can be mentioned. Examples of the alicyclic group of R3 include hydrazine, 4-cyclohexylene, and the like. The compound represented by the above formula (2) is preferably a compound in the above formula (2) wherein R 5 is a single bond 't is 1' and Re is a hydrogen atom, or R 5 is a methylene group, a stretching group or a divalent group. An aromatic group, hydrazine or a compound wherein R6 is a carboxyl group. -22-201033253 A preferred example of the compound represented by the above formula (2) is a compound represented by each of the following formulas (2-1) to (2-35).

R1h( V-CH=CH—COOH

Nf (2-1) R10

CH=CH—COOH (2-2)

COO CH=CH—COOH (2-3) (2-4)

R1COQ-^~~^-COO CH=CH—COOH (2-5)

CH=CH—COOH (2-6) ❿

CH=CH—COOH (2-7) -23 201033253 (2-8) R1. . . <y CH=CH—COOH (2-9)

R

CH=CH~C0Q-(CH2)-0H (2-10)

R10—CH=CH~COQ-(CH2)-〇H

R1COO (2-11) CH=CH—CO〇-(CH2)-〇H (2-12)

R 丨-^~^~CH=CH—C00-(CH2)“C00H (2-13) R10 CH=CH~C00-(CH2)-C00H (2-14)

-24 201033253

R1COQ—CH=CH~CQ〇-(CH2)-COOH (2-15)

COQ-^~~^-CH=CH—C0Q-(CH2)-0H (2-16)

COO CH=CH—C00-(CH2)-0H (2-17)

R1COQ—CH=CH~C00-(CH2)-0H Ο (2-18)

COO—CH=CH—CQ0-(CH2)-C00H (2-19)

R1〇-^~y~COQ-^~^—CH=CH~CQ0-(CH2)-C00H (2-20)

R1COQ-^~^—COO~^~~^—CH=CH—CQ〇-(CH2)-COOH (2-21) -25- 201033253 R10 ^〇~c〇〇-h〇~ CH=CH—COOH (2-22) -o —coo o CH=CH—COOH (2-23)

°~o^'J\JT

R1~COO

CH=CH—CO

CH=CH—CO *〇 COOH (2-24) COOH (2-25)

Oir

CH=CH—CO COOH (2-26) coo <y CH=CH—CO ~^JT COOH (2-27) R1-COQ-^~~^~COO CH=CH—CO ·〇COOH (2- 28) -coo CH=CH—CO O~ COOH (2-29) (2-30) ❹

R1-^ ^-COO—CH=CH—CO—^~^>-COOH -26- 201033253 R1

CH=CH—COOH (2-31) R10

CH II CH-COOH (2-32)

CH=CH—COOH (2-35) (wherein R1 is the same as defined in the above formula (2), and f is each an integer of 1 to 10). The monovalent organic group having an alicyclic group-containing carbon atom number Ο of 3 to 40 in the above formula (3), for example, a cholesteryl group, a cholesteryl group, an adamantyl group or the like can be given. The alkyl group having 1 to 40 carbon atoms as R8 is preferably, for example, an alkyl group having 1 to 20 carbon atoms, wherein a part or all of the hydrogen atoms of the alkyl group may be optionally substituted by a fluorine atom. As an example of such an alkyl group, for example, a group exemplified as the alkyl group of R1 in the above formula (2) can be mentioned. The divalent aromatic group, the heterocyclic group or the fused ring group of R9 and R11 may, for example, be a divalent aromatic group, a heterocyclic group or a thick group as R3 and R5 in the above formula (2). The groups listed separately for the ring group. 201033253 As R13, a carboxyl group is preferred. Preferable examples of the compound represented by the above formula (3) include compounds represented by the following formulas (3-1) to (3-11), and R80C0-CH=CH-^~~^-OH (3) -1)

R8OC〇-CH=CH-^~y~OCO OH (3-2)

R8co-ch=ch-^~~^—oco OH ❿ (3-3)

R8oco-ch=ch 0C0-^~^-00C-(CH2) -COOH (3-4)

R8co-ch=ch oco -Qjr OOC—(CH2):〇H (3-5)

R8co-ch=ch—oco OOC-(CH2)-COOH (3-6) r8-oco-ch=ch -Or oco—(CH2)u-COOH (3-7) ❿•COOH (3-8) CO —CH=CH ( R80"^~^"C0-CH=CH—^广广OHOH (3-9) R8 ~Qr CO—CH=CH oco—(CH2)u-COOH (3-10) CO—CH =CH—^~^-0 CO - (C H2)u- CO OH (3-11) -28- 201033253 wherein R8 is the same as defined in the above formula (3), and each of u is 1 to 1 0 The cinnamic acid derivative (A) can be synthesized by appropriately combining the information of organic synthesis. The synthetic route and reaction conditions are easily set by the skill of the artist and a small amount of preliminary tests. [Photosensitizing Compound (B)] The photosensitizing compound (B) in the present invention has a member selected from the group consisting of a carboxyl group, a hydroxyl group, -SH, -NCO, and -NHR (wherein R is a hydrogen atom or the number of carbon atoms is At least one group and a photo-sensitizing structure compound of the group consisting of 1 to ◎ 6 alkyl groups, -CH = CH2 and -S02C1, by using the above-mentioned epoxy group-containing polyorganosiloxane and cinnamic acid A mixture of the derivative (A) and the photosensitizing compound (B) is reacted to make the liquid crystal alignment agent of the present invention The radiation-sensitive polyorganosiloxane containing both a photosensitive structure derived from the cinnamic acid derivative (A) (cinnamic acid structure) and a light-sensitizing structure derived from the light-sensitizing compound (B) The sensitizing structure has a function of exciting by irradiating radiation and imparting the excitation energy to an adjacent photosensitive structure in the ruthenium polymer. The excited state can be either a double excitation or a triple excitation, and the lifetime is long and efficient. From the viewpoint of transferring energy, triple excitation is preferred. The radiation absorbed by the light-sensitizing structure is preferably ultraviolet or visible light having a wavelength in the range of 150 to 600 nm, and the wavelength is shorter than the radiation. It is processed by a normal optical system, and thus cannot be applied to a photo-alignment method. In the other aspect, radiation having a longer wavelength is less likely to cause an excitation state of the above-described light-sensitizing structure due to low energy. -29- 201033253 The photosensitizing structure may, for example, be an acetophenone structure, a benzophenone structure, an anthracene structure, a biphenyl structure, a carbazole structure, a nitroaryl structure, The fluorene structure, the naphthalene structure, the fluorene structure, the acridine structure, the fluorene structure, etc. may be at least one of them. These structures are respectively derived from benzophenone, acetophenone, anthracene, biphenyl, carbazole, and nitrate. a structure consisting of a structure obtained by removing 1 to 4 hydrogen atoms in a benzene or a dinitrobenzene, naphthalene, anthracene, anthracene, acridine or an anthracene. Here, the acetophenone structure, the carbazole structure and the fluorene structure are respectively It is preferably a structure composed of a group obtained by removing 1 to 4 of the hydrogen atoms of the benzene ring of acetophenone, carbazole or anthracene. As the light-sensitizing structure, among them, it is preferably selected from the group consisting of an acetophenone structure, a benzophenone structure, a fluorene structure, a biphenyl structure, a carbazole structure, a nitroaryl structure, and a naphthalene structure. At least one of them is particularly preferably at least one selected from the group consisting of an acetophenone structure, a benzophenone structure, and a nitroaryl structure. The photo-sensitizing compound (B) is preferably a compound having a carboxyl group and a photo-sensitizing structure. Examples of a more preferable compound include those represented by the following formulas 0 (B-1) to (B-42). Compound, -30- 201033253

Ch3

C-COOH (B-6)

201033253

Ch2-cooh (B-11)

CH3—(CH2)q—0

CH3

(B-16)

COOH

CH3—(CH2)r

CH3 ch3

(B-22) -32- 201033253

(B-24) Cl

;OOH V^N〇2 (B-26)

COOH

02N

02N v N02 (B-27) (B-28) (B-29)

Cj)OOH CH2

N〇2 N〇2 (B-30)

CpOOH COOH jfj XI if ^L/N〇2 〇2N^y , N02 / r1 Cl (B-31) ch3 〇, ch3 (B-32)

CH

(B-34)

OOH ^N〇2 (B-35) 201033253 COO Η

HO ^Ν〇2 (B-36)

CH30 [//N〇2 (B-38)

(CH2)s-C00H CH2-COOH ❹ (B-42) (In the above formula, 'P, q, 1 and s are each an integer of 1 to 6). The radiation-sensitive polyorganosiloxane of the present invention can be preferably obtained by using the polyorganosiloxane having an epoxy group as described above, the cinnamic acid derivative (A) and the photosensitizing compound (B). It is synthesized in the presence of a catalyst, preferably in an organic solvent. Here, the 'cinnamic acid derivative (A) is preferably a mole, more preferably 0.1 to 1 mole, relative to 1 mole of the polyorganosiloxane having an epoxy group, more preferably Use a range of 0.2 to 0.9 moles. The photo-sensitizing compound (B)' is preferably 〇〇〇〇1 to 〇5 mol, more preferably 0·0005~ relative to the 1 moler atom of the polyorganosiloxane having an epoxy group. The 〇·2 moule and the step are preferably used in the range of 0.001 to 0.1 mol. In the present invention, a part of the above-mentioned cinnamic acid derivative may be used in place of the compound represented by the above formula (5) in the range of -34 to 201033253, insofar as the effects of the present invention are not impaired. In this case, the synthesis of the radiation-sensitive polyorganosiloxane is carried out by using a polyorganosiloxane having an epoxy group, a compound represented by the cinnamic acid derivative (A) and the above formula (5), and photosensitizing property. The mixture of the compound (B) is reacted. R15 in the above formula (5) is preferably an alkyl group or alkoxy group having 8 to 20 carbon atoms or a fluoroalkyl group or a fluoroalkoxy group having 4 to 21 carbon atoms as Ri6. Preferably, it is a single bond, a compound, a 4-cyclohexyl group or an i,4-phenylene group, as R17, preferably a carboxyl group. Preferred examples of the compound represented by the above formula (5) include compounds represented by the following formulas (5_1) to (5-4), chF2h+i'--CjHa-COOH (5-1)

CjH2j+iΟ^ /-COOH (5-2)

e (in the above formula, 'h is an integer from 1 to 3, 1 is an integer from 3 to 18, j is an integer from 5 to 20, and is an integer from 1 to 3, m is an integer from 〇 to 18, and η is 1 to (Integer of 18) ' As a more preferable example, the compound represented by the following formula (5-3-1) - (5-3-3) in the above formula is mentioned. 201033253 cf3—〇 Ό~ COOH (5-3-1) cf3-C3H6—~〇

COOH (5-3-2) c2f5-C3H6—〇

COOH (5-3-3) The compound represented by the above formula (5) is such that the above cinnamic acid derivative (A) and the photosensitizing compound (B) react with a polyorganosiloxane having an epoxy group. Further, a compound which gives a portion of the obtained liquid crystal alignment film which produces a pretilt angle expression is introduced. In the present specification, the compound represented by the above formula (5) is hereinafter referred to as "other pretilt expression compound". In the present invention, the cinnamic acid derivative (A), the photosensitizing compound (B) and other pretilt angle expressions are used when a part of the above cinnamic acid derivative (A) is replaced by another pretilt angle expressing compound. The total use ratio of the compound is preferably 0.001 to 1 mol with respect to 1 mol of the polyorganosiloxane having an epoxy group, more preferably 1 to 1 mol, and further preferably. 0_2~0.9 Moer. In this case, the other pretilt angle-expressing compound is preferably used in a range of 50 mol% or less, more preferably 25 mol% or less, based on the total amount of the cinnamic acid derivative (A). If the usage ratio of other pretilt-exhibiting compounds exceeds 50 mol%, an unfavorable situation occurs in which an abnormal region occurs when the liquid crystal display element is turned ON. As the catalyst, an organic base or a known compound called a hardening accelerator which promotes the reaction of an epoxy compound with an acid anhydride can be used. Examples of the organic base include organic-grade and secondary amines such as ethylamine, diethylamine, pipe trap, piperidine, pyrrolidine, and pyrrole; triethylamine, tri-n-36-201033253 propylamine, and tri-n-butylamine. , an organic tertiary amine such as pyridine, 4-dimethylaminopyridine or diazabicycloundecene; an organic quaternary ammonium salt such as tetramethylammonium hydroxide or the like. Among these organic bases, triethylamine is preferred. An organic tertiary amine such as tri-n-propylamine, tri-n-butylamine, pyridine or 4-dimethylaminopyridine; or an organic quaternary ammonium salt such as tetramethylammonium hydroxide. Examples of the hardening accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, cyclohexyldimethylamine, and triethanolamine; Imidazole, 2-n-heptyl imidazole, 2-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl 2-Phenyl imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-methylimidazole, 1-(2-cyanide Benzyl)-2-n-undecylimidazole, 1-(2-aminoethyl)_2-phenyl miso, 1-(2-aminoethyl)-2-ethyl-4-yl Imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis(hydroxymethyl)imidazole, 1-(2-cyanoethyl)-2- Phenyl-4,5-bis[(2'-cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl)-2-n-undecylimidazolium trimellitate, 1-(2-cyanoethyl)_2·phenylimidazolium pyromellitate, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole gun trimellitate, 2,4-Diamino-6-[2,-Methylammonium-(1')]ethyl-s-triterpene, 2,4-diamino- 6- (2 正十一院基咪Ethyl-s-triterpene, 2,4-diamino-6-[2'-ethyl-4'-methylamido-(1,)]ethyl-s-trisole, 2-methyl Alizarin uric acid adduct of Gimami, isocyanuric acid addition of 2-phenylimidazole, 2,4-diamino-6-[2'-methylimidazolium (1,)] ethyl-s - an organic phosphorus compound such as diphenylphosphine, 201033253 triphenyl o- or triphenyl phosphite; benzyl triphenyl chloride scale, tetra-n-butyl Brominated scale, methyltriphenyl bromide scale, ethyltriphenylphosphonium bromide, n-butyltriphenyl bromide, tetraphenyl bromide scale, ethyltriphenyl iodide scale, ethyl Triphenyl sulphate acetate, tetrabutyl hydrazine, 0,0-diethyl dithiophosphate, tetra-n-butyl benzotriazole, tetra-n-butyl hydroxytetrafluoroborate, tetra-n-butyl rust a tetrabasic scale salt such as tetraphenylborate or tetraphenylphosphonium tetraphenylborate; 1,8-diazabicyclo[5.4.0]undec-7-ene, an organic acid salt thereof and the like Heterobicycloolefin; organometallic compound such as zinc octoate, tin octoate, acetonitrile aluminum complex; tetraethylammonium bromide, tetra-n-butylammonium bromide a quaternary ammonium salt such as tetraethylammonium chloride or tetra-n-butylammonium chloride; a boron compound such as boron trifluoride or triphenyl borate; a metal halide such as zinc chloride or tin chloride; or a cyanoguanidine or a high-melting-point-distribution latent curing accelerator such as an amine addition accelerator such as an amine or an epoxy resin; and a surface of a hardening accelerator such as an imidazole compound, an organic phosphine compound or a quaternary phosphonium salt coated with a polymer Miniature capsule type latent hardening accelerator; amine salt type latent hardening accelerator; latent hardening accelerator such as high temperature degradable thermal cationic polymerization latent hardening accelerator such as Lewis acid salt and Bronsted acid salt . Among these, a tetra-ammonium salt such as tetraethylammonium bromide, tetra-n-butylammonium bromide, -38-201033253 tetraethylammonium chloride or tetra-n-butylammonium chloride is preferred. 100 parts by weight of the polyorganosiloxane having an epoxy group is preferably used in a ratio of 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, still more preferably 0.1 to 20 parts by weight. The reaction temperature is preferably from 〇 to 200 ° C, more preferably from 50 to 150 ° C. The reaction time is preferably from 0.1 to 50 hours, more preferably from 0.5 to 20 hours. The organic solvent which can be used in the synthesis of the radiation-sensitive polyorganosiloxane is, for example, a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, a guanamine compound, or an alcohol compound. Among them, an ether compound, an ester compound, and a ketone compound are preferred from the viewpoints of solubility of the raw material and the product and ease of refining of the product. The solvent is used in an amount such that the 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, more preferably 5 to 50% by weight. The radiation-sensitive polyorganosiloxane which is contained in the liquid crystal alignment agent of the present invention is obtained by using a polyorganosiloxane having an epoxy group as a raw material, and is introduced into a cinnamic acid derivative by ring-opening addition of an epoxy group thereof. (A) and the structure of the photo-sensitizing compound (B). This preparation method is simple. Further, in particular, it is a very suitable method for improving the introduction rate of the cinnamic acid structure derived from the cinnamic acid derivative (A). In addition, since the photo-sensitizing structure derived from the photo-sensitizing compound (B) is chemically bonded on the radiation-sensitive polyorganosiloxane, it can be efficiently present in the radiation-sensitive polyorganosiloxane. The cinnamic acid structure derived from the cinnamic acid derivative (A) in the vicinity is supplied with the excitation energy generated by the irradiation of the radiation in the photo-alignment method. Thus, a sufficient amount of the liquid crystal alignment can be obtained by a small amount of radiation irradiation of .39-201033253. Sex and showing a pretilt angle. Further, since the light-sensitizing structure is chemically bonded in the matrix polymer, sublimation at the time of post-baking can be prevented when forming a coating film as a liquid crystal alignment film. [Other Components] The liquid crystal alignment agent of the present invention contains a radiation-sensitive polyorganosiloxane as described above. The liquid crystal alignment agent of the present invention may further contain other components in addition to the radiation sensitive polyoxane as described above, without impairing the effects of the present invention. Examples of such other components include a polymer other than a radiation-sensitive polyorganosiloxane (hereinafter referred to as "another polymer"), a curing agent, a curing catalyst, a curing accelerator, and at least one epoxy group in the molecule. A compound (hereinafter referred to as "epoxy compound"), a functional decane compound, a surfactant, a photosensitizer, and the like. [Other Polymers] The above other polymers may be used in order to further improve the solution properties of the liquid crystal alignment agent of the present invention and the electrical properties of the resulting liquid crystal alignment film. As such another polymer, for example, at least one polymer selected from the group consisting of polylysine and polyimine, a polyorganosiloxane selected from the following formula (4), and hydrolysis thereof may be mentioned. At least one of a group consisting of a condensate of a substance and a hydrolyzate (hereinafter referred to as "other polyorganosiloxane"), a polyphthalate, a polyester, a polyamide, a cellulose derivative, a polyacetal , polyphenylene derivative, poly(styrene-phenylmaleimide) derivative, poly(methyl)propene (4) 201033253 enoate, etc.

X2 I - Si - Ο - .Y2 (In the formula (4), 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 a carbon atom An aryl group of 6 to 20, Υ 2 is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms.) [Polyproline] The above polylysine can be reacted with a diamine compound by reacting a tetracarboxylic dianhydride with a diamine compound. And made. Examples of the tetracarboxylic dianhydride which can be used in the synthesis of polylysine include, for example, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, butane tetracarboxylic dianhydride, and cyclobutane tetracarboxylic acid Anhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,5,6- Tricarboxynorbornane·2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, UjaJJJb-hexahydro-5·(tetrahydro-2,5-dioxo-3-furanyl )-naphthalene [l,2-c]-furan·13-dione, ^,^,々^,"-hexahydropyrene tetrahydro-mono-dioxo-3-furanyl-8-A -naphthalene [1,2-c]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-di Carboxylic anhydride, bicyclo[2·2·2]_oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, four of the following formulas (T-1) to (T-14) Aliphatic tetracarboxylic dianhydride such as carboxylic acid dianhydride and alicyclic tetracarboxylic dianhydride; -41- 201033253

σ-D

Σ-8) σ-2) σ-3) OCF,

Σ-4) σ-5)

Q

(Τ-10) (Τ-11) σ-9)

H3c ^ (Τ-12)

Σ-6)

Ο

σ·ΐ3)

Σ-7)

〇U (Τ-14) 3,3,,4,4,-diphenyl maple tetracarboxylic dianhydride-42- 201033253 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6 , 7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonanetetracarboxylic acid Dihydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-di(3,4-di Carboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4'-bis(3,4-dicarboxyl Phenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride , bis(phthalic acid) phenylphosphine oxide _ dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, meta-phenyl- bis(triphenylphthalic acid) Dihydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, the following An aromatic tetracarboxylic dianhydride such as tetracarboxylic dianhydride represented by each of the formulae (T-15) to (T-18).

-43- 201033253

Preferred tetracarboxylic dianhydrides among these include 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl). -Naphthalene [1,2-. ]-furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-8- Methyl-naphthalene [1,2-c]-furan-1,3-dione, 2,3,5-tri-44- 201033253 fluorenylcyclopentyl thioacetic acid dianhydride, butane tetracarboxylic dianhydride 1,3_Dimethyl-1,2,3,4-cyclobutene% ^ hospital tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride,

Pyromellitic acid - "P-leaf, 3,3,,4,4, diphenyl-tetracarboxylic dianhydride, 1,4,5,8_ Cai Siic acid Er Xuan' 2,3,6,7 - naphthalene tetraphthalic acid dianhydride, 3,3', 4,4, diphenyl ether tetraresidic acid - Xuan or the above formula (Τ·1), (Τ·2) and (Τ·15)~(T_18 ) each represented a tetracarboxylic dianhydride. These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

Examples of the diamine compound which can be used in the synthesis of polylysine include, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-aminodiphenylmethane, and 4,4,-diaminodi Phenylphenyl, 4,4'-monoamine-based thioether, 4,4'-monoaminodiphenyl maple, 3,3'-dimethyl-4,4'-diamine Benzene, 4,4'-diaminobenzimidamide, 4,4,-diaminodiphenyl ugly, anthracene, 5-diaminocaxene, 5-amino-1·(4,-aminophenyl) )-1,3,3-trimethylindoline, 6-aminoaminophenyl)-13,3-trimethylindoline, 3,4'-diaminodiphenyl ether, 2 ,2-bis(4-aminophenoxy)propane, 2,2-di[4-(4-aminophenoxy)phenyl]propane, 2,2-di[4-(4-amine Benzophenoxy)phenyl]hexafluoropropanoid, 2,2-di(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl] mill , 丨, 4 · bis(4-aminophenoxy)benzene,! ,3-di(4-aminophenoxy)benzene, indole-di(mono)-aminophenoxy)benzene, 9,9-di(4-amine basic)_1〇_nitrogen, 2,7 --aminopurine, 9,9-bis(4-aminophenyl)anthracene, 4,4-methylene-bis(2-chloroaniline), 2,2,5,5,-tetrachloro 4,4,-Diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5,-dimethoxybiphenyl, 3,3,-dimethoxy_ 4,4'-diaminobiphenyl, 4,4,-(p-phenylisopropylene)diphenylamine, 4,4'-(meta-phenylisopropylene)-45- 201033253 diphenylamine 2,2-bis[4-(4-Amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-di(trifluoro Methyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 6-(4-chalconeoxy)hexyloxy (2,4-diaminobenzene), 6-(4'-fluoro-4-chalconeoxy)hexyloxy (2,4-diaminobenzene), 8-(4-chalconeoxyl) Octyloxy (2,4-diaminobenzene), 8-(4'-fluoro-4-chalconeoxy)octyloxy (2,4-diaminobenzene), 1-decyloxy -2,4-diaminobenzene, 1-tetradecyloxy-2,4-diaminobenzene, 1-pentadecyloxy-2, 4-diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy-2,4-decyldiaminobenzene, 1-cholesteryloxy- 2,4-Diaminobenzene, 1-cholestyloxy-2,4-diaminobenzene, dodecyloxy (3,5-diaminobenzimidamide), tetradecyloxy ( 3, 5-diaminobenzimidamide, pentadecyloxy (3, 5-diaminobenzimidamide), hexadecanyloxy (3,5-diaminobenzamide), eighteen Alkoxy (3,5-diaminobenzimidamide), cholesteryloxy (3,5-diaminobenzimidamide), cholestyloxy (3,5-diaminobenzimidamide) , (2,4-diaminophenoxy)palmitate, (2,4-diaminophenoxy)stearate, (2,4-diaminophenoxy)-4- Trifluoromethyl benzoate, an aromatic diamine such as a diamine compound represented by each of the following formulas (D-1) to (D-5); -46- 201033253

An aromatic diamine having a hetero atom such as diaminotetraphenylthiophene; m-xylylenediamine, 1,3-propanediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, and octanediamine , hydrazine diamine, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene diamine, hexahydro-4,7-methylene dimethylene diamine, Alicyclic diamines and alicyclic diamines such as tricyclo[6.2.1.02'7]-undecylenedimethyldiamine, 4,4'-methylenebis(cyclohexylamine); diamine A diamine-based organooxane such as hexamethyldioxane. -47- 201033253 Among them, preferred are diphenylamine, 4,4,-diaminodiphenylmethane, U5-diaminonaphthalene, 2,7-diaminopurine, 4 , 4,-Diaminodiphenyl ether, 4,4'·(p-phenylisopropylene)diphenylamine, 2,2-bis[4-(4.aminophenoxy)phenyl] Hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoro Propane, 4,4,-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4,_bis[(4-amino-2-trifluoromethyl)phenoxy] - octafluorobiphenyl, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene, 1-cholesteryloxy-2, 4-diaminobenzene, 1-cholestyloxy-2,4-diaminobenzene, hexadecyloxy (3,5-di-aminobenzamide) octadecyloxy (3 , 5-diaminobenzimidamide), cholesteryloxy (3,5-diaminobenzimidamide), cholestyloxy (3,5-diaminobenzimidamide) and the above formula ( D-1) to (D-5) each represents a diamine compound. These diamine compounds may be used singly or in combination of two or more. The ratio of use of the tetracarboxylic dianhydride to the diamine compound to be supplied to the polyaminic acid synthesis reaction is preferably from 0.2 to 2 equivalents based on 1 equivalent of the amine group contained in the diamine compound. The ratio is better to make it a ratio of 〇.3 〜 ~1.2 equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at a temperature of from -20 to 150 ° C, more preferably from 0 to 100 ° C, preferably from 0.5 to 24 hours, more preferably 2 ~10 hours. Here, the organic solvent is not particularly limited as long as it is a solvent capable of dissolving the synthesized polylysine, and examples thereof include N-methyl-2-pyrrolidone and N,N-dimethylacetamide. N,N-dimethylformamide, N,N-dimethylimidazolidinone, dimethyl sub-48- 201033253 Maple, r-butyrolactone, tetramethylurea, hexamethylphosphonium triamine An aprotic polar solvent; a phenolic solvent such as m-methylphenol, xylenol, phenol or halogenated phenol. The amount (a) of the organic solvent is such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is preferably 0.1 to 50% by weight, more preferably 5, based on the total amount of the reaction solution (a+b). ~30% by weight of the amount. As described above, a reaction solution obtained by dissolving polyamic acid was obtained. The reaction solution may be directly supplied to the liquid crystal alignment agent, or may be separated from the poly-proline contained in the reaction solution, and then supplied to the liquid crystal alignment agent, or the separated polylysine may be used. After the purification, the preparation of the liquid crystal alignment agent is supplied. When the polylysine is dehydrated and closed into a polyimine, the reaction solution may be directly supplied to the dehydration ring-closure reaction, or the poly-proline contained in the reaction solution may be separated and then supplied to the dehydration ring-closure reaction, or may be The separated polyamic acid is refined and then supplied to a dehydration ring closure reaction. The separation of the polyamic acid can be carried out by adding the above reaction solution to a large amount of a poor solvent to obtain a precipitate, and then drying the precipitate enthalpy under reduced pressure, or reducing the organic solvent in the reaction solution by an evaporator. This is carried out by a method of pressure distillation removal. Further, the polylysine can be purified by re-dissolving the polylysine in an organic solvent, then precipitating it with a poor solvent, or by performing a process of distilling off one or several times with an evaporator under reduced pressure. . [Polyimide] The above polyimine can be produced by subjecting a proline structure having a polyamic acid obtained as described above to dehydration ring closure to ruthenium. At this time, -49- 201033253 may be a complete dehydration ring closure of the proline structure, or may be a part of the proline structure dehydration ring closure, the proline structure and the quinone imine structure coexist. Compound. The polyimine in the present invention has a ruthenium iodide ratio of preferably 30% or more, more preferably 40 to 95%» a dehydration ring closure of poly-proline, which can (i) a method of heating poly-proline Or (Π) by dissolving polylysine in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and heating as needed. The reaction temperature in the method for heating poly-proline in the above (1) is preferably @50 to 2 00t:, more preferably 60 to 170 °C. When the reaction temperature is less than 50 ° C, the dehydration ring-closure reaction cannot be sufficiently carried out. When the reaction temperature exceeds 200 ° C, the molecular weight of the obtained ruthenium-imided polymer may be lowered. The reaction time of the method of heating the polyamic acid is preferably from 0.5 to 48 hours, more preferably from 2 to 20 hours. On the other hand, in the above method of adding a dehydrating agent and a dehydration ring-closure catalyst to a polyamic acid solution, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used as the dehydrating agent. The use ratio of the dehydrating agent is preferably 0.01 to 20 moles per 1 mole of the polyamic acid structural unit. Further, as the dehydration ring-closure catalyst, a tertiary amine such as pyridine, trimethylpyridine, dimethylpyridine or triethylamine can be used. However, it is not limited to these. The use ratio of the dehydration ring-closing catalyst is preferably 0.01 to 10 moles per 100 parts of the dehydrating agent used. The organic solvent to be used in the dehydration ring-closure reaction is exemplified by the -50-201033253 organic solvent exemplified as the organic solvent used in the synthesis of polyglycine. The reaction temperature of the dehydration ring closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C, and the reaction time is preferably from 0.5 to 20 hours, more preferably from 1 to 8 hours. The polyimine obtained in the above method (i) may be directly supplied to a liquid crystal alignment agent, or may be purified and then supplied to a liquid crystal alignment agent. On the other hand, in the above method (ii), a reaction solution containing polyienimine is obtained. The reaction solution may be directly supplied to the liquid crystal alignment agent, or may be supplied from the reaction solution to remove the dehydrating agent and the dehydration ring-closing catalytic agent, and then supplied to the liquid crystal alignment agent, and the polyimine may be separated and supplied. The preparation of the liquid crystal alignment agent or the preparation of the liquid crystal alignment agent may be carried out after the separated polyimine is refined. The dehydrating agent and the dehydration ring-closure catalyst are removed from the reaction solution, and a method such as solvent replacement can be employed. The separation and purification of the polyimine can be carried out in the same manner as described above for the separation and purification of polylysine. [Other polyorganosiloxanes] The other polyorganosiloxanes in the present invention are selected from the group consisting of polyorganosiloxanes represented by the above formula (4), condensates of hydrolyzates and hydrolyzates thereof. At least one of them. For other polyorganosiloxanes, the polystyrene-equivalent weight average molecular weight measured by GPC is preferably from 500 to 100,000, more preferably from 500 to 10,000. Such a polyorganosiloxane may, for example, be preferably at least one decane compound (hereinafter also referred to as "raw material decane compound") selected from the group consisting of an alkoxy decane compound and a halogenated decane compound. .51 - 201033253 In an organic solvent, it is synthesized by hydrolysis, hydrolysis or condensation in the presence of water and a catalyst. As the raw material sand compound which can be used here, for example, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, tetra-n-butoxy decane, and tetra-di-butyl can be mentioned. Oxydecane, tetra-tertiary butoxydecane, tetrachlorodecane, etc.; methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane, methyltriisopropoxydecane, Methyl tri-n-butoxy decane, methyl di-first-butoxylate, methyl tri-tertiary butoxylate, methyltriphenyloxydecane, methyltrichlorodecane, ethyltrimethoxy Decane, ethyltriethoxydecane, ethyltri-n-propoxydecane, ethyltriisopropoxydecane, ethyltri-n-butoxydecane, ethyltri-n-butoxydecane, ethyltri Tertiary butoxy decane, ethyl trichloro decane, phenyl trimethoxy decane, phenyl triethoxy decane, phenyl trichloro decane; dimethyl dimethoxy decane, dimethyl diethoxy Decane, dimethyldichlorodecane; trimethyl methoxy decane, trimethyl ethoxy decane, trimethyl chloro decane, and the like. Among them, preferred are tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, and dimethyl group. Methoxydecane, dimethyldiethoxydecane, trimethylmethoxydecane or trimethylethoxydecane. In the synthesis of other polyorganosiloxanes, as the solvent which may be optionally used, for example, an alcohol compound, a ketone compound, a guanamine compound or an ester compound or other aprotic compound may be mentioned. They may be used alone or in combination of two or more. Examples of the above alcohol compound include methanol, ethanol, IH • methanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, isoamyl alcohol, and 2-methylbutyl. Alcohol, secondary pentanol, tertiary pentyl alcohol, 3 alcohol, oxybutanol, n-hexanol, 2-methylpentanol, secondary hexanol, 2-ethyl hydrazine

IH alpha-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, secondary octanol, decyl alcohol, 2,6-dimethyl-4-heptanol, n-nonanol, secondary Undecyl alcohol, = *>. decyl alcohol, secondary tetradecyl alcohol, secondary heptadecyl alcohol, phenol, cyclohexanol methylcyclohexanol, 3,3,5-trimethylcyclohexane Alcohol, benzyl alcohol, diacetone alcohol and other alcohol compounds; 2 - ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,4-pentanediol, yl-2,4-pentane Polyols such as alcohol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1>3-alcohol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol; Methyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, && glycol diglycol monomethyl _ polyhydric hydrazinol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monobenzene Ether, mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, C::: ether , propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropionic acid Part ether compound. These alcohol compounds may be used in combination of one type or from 2 to 53 to 201033253. Examples of the ketone compound include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, and B. N-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethyl fluorenone, cyclohexanone, 2-hexanone, methyl cyclohexanone, 2,4-pentanedione, acetone acetone a monoketone compound such as acetophenone or anthrone; acetamidine, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3, 5-octanedione, 2,4-dione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl·3,5 a diketone compound such as heptanedione or 1,1,1,5,5,5-hexafluoro-2,4-heptanedione or the like. These ketone compounds may be used alone or in combination of two or more. The above guanamine compound may, for example, bemethantamine, hydrazine-methylformamide, hydrazine, hydrazine-dimethylformamide, hydrazine-ethylformamide, hydrazine, hydrazine-diethylformamide , acetamide, hydrazine-methyl acetamide, hydrazine, hydrazine-dimethylacetamide, hydrazine-ethyl acetamide, hydrazine, hydrazine-diethyl acetamide, hydrazine-methyl propyl amide 'Ν_Methylpyrrolidone, Ν-methylmercaptomorpholine, Ν·methylmercaptopiperidine, Ν-methylpyridyl pyridine, Ν-ethinylmorpholine, Ν-ethinylpiperidine, Ν- Ethyl pyrrolidine and the like. These guanamine compounds may be used alone or in combination of two or more. Examples of the ester compound' include diethyl carbonate, carbon ethylene glycol, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, r-butyrolactone, r-valerolactone, and acetic acid. N-propyl ester, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-butyl acetate, n-amyl acetate, diamyl acetate '3-methoxybutyl acetate, methyl amyl acetate , acetic acid-54- 201033253 butyl ketone '2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-decyl acetate, methyl acetate, ethyl acetate Ester, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl acetate, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol acetate Monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, ethylene glycol diacetate, methoxy triethylene glycol acetate, propionic acid • ethyl ester , n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate Methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, and the like. These ester compounds may be used alone or in combination of two or more. Examples of the other aprotic compound include acetonitrile, dimethyl hydrazide 'N, N, N, N, -tetraethyl sulfonamide, trimethylamine hexamethyl phosphate, N-methylmorpholine, and N. -methylpyrrole, N-ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N,N-dimethylpiper well, N-methyl Imidazole, © N-methyl-4-piperidone, N-methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 13- Dimethyltetrahydropyrimidinone and the like. Among these solvents, a polyhydric alcohol compound or a partial ether or ester compound of a polyhydric alcohol compound is particularly preferred. The amount of water used for the synthesis of the other polyorganosiloxane is preferably 0.01 to 100 moles, more preferably 0.01 to 100 moles, based on the total amount of the alkoxy group and the halogen atom which the raw material sand compound has. It is 01 to 30 m, and further preferably 1 to 1.5 m. 201033253 Examples of the catalyst which can be used in the synthesis of another polyorganosiloxane are, for example, a metal chelate compound, an organic acid, an inorganic acid, an organic hydrazine, an ammonia, a ruthenium metal compound, or an alkaline earth ruthenium compound. The metal chelate compound may, for example, be triethoxy-mono(acetonitrile) titanium, tri-n-propoxy-mono(acetonitrile) titanium, triisopropoxy-mono(acetonitrile) titanium. , tri-n-butoxy. mono (acetonitrile) titanium, tri- or two-butoxy-single (acetylacetone) titanium, tris-tertiary butoxy-single (acetonitrile) titanium, diethoxy · Di(acetonitrile) titanium, di-n-propoxy-bis(acetonitrile) titanium, diisopropoxy. bis(acetoxime) titanium, di-n-butoxy-bis(acetonitrile) titanium 'Di-secondary butoxy-bis(acetonitrile) titanium, di-tertiary butoxy-bis(acetamidine) titanium, monoethoxy-tris(acetonitrile) titanium, mono-n-propoxy Base · tris(acetonitrile) titanium, monoisopropoxy tris(acetonitrile) titanium, mono-n-butoxyg (ethyl acetate) titanium, single-stage butoxy. tris(acetonitrile) Titanium, mono-tertiary butoxy-tris(acetonitrile) titanium, tetrakis(acetonitrile)titanium, triethoxy-mono(acetic acid ethyl acetate) titanium, tri-n-propoxy-single Ethyl acetate) titanium, triisopropoxy (acetonitrile ethyl acetate) titanium, tri-n-butoxy. mono (acetonitrile ethyl acetate) titanium, ginseng-tertiary butoxy. mono (acetic acid ethyl acetate) titanium, tri- or tertiary-butoxy Base·(Ethyl acetate) titanium, diethoxy. Di(acetonitrile ethyl acetate) titanium, di-n-propoxy. Di(acetonitrile ethyl acetate) titanium, diisopropoxy. (acetic acid ethyl acetate) titanium, di-n-butoxy-bis (ethyl acetate) titanium, di- or 2-butoxy. di(acetonitrile ethyl acetate) titanium, di-tertiary butoxy · Di(acetonitrile ethyl acetate) titanium, monoethoxy tris(ethyl acetate) titanium, mono-n-propoxy-tris(ethyl acetate) titanium, monoisopropoxy. Acetate ethyl acetate) titanium, mono-n-butoxy-tris(B-56-201033253 醯 ethyl acetate) titanium, single-stage butoxy-tris(ethyl acetate) titanium, single-stage butoxide Base · triacetate ethyl acetate titanium, tetrakis(acetonitrile ethyl acetate) titanium, mono (acetonitrile) tris(ethyl acetate) titanium, di(acetonitrile) diacetate Ester) titanium, tris(acetonitrile) single Ethyl ester) Titanium coordination compound such as titanium; Triethoxy mono(acetonitrile) cone, tri-n-propoxy-mono(acetonitrile) Chromium, triisopropoxy. Mono(acetonitrile) zirconium , tri-n-butoxy-mono (acetonitrile) zirconium, tri- or 2-butoxy-single (acetylacetone) zirconium, tris-tertiary butoxy ❹ singly (acetamidine), two Oxy-bis(acetonitrile)zirconium, di-n-propoxy-bis(acetonitrile)zirconium, diisopropoxy-bis(acetamidineacetone), di-n-butoxy-bis(acetonitrile) ) cone, di- or two-stage butoxy-bis(acetonitrile) chromium, di-tertiary butoxy-bis(acetonitrile)zirconium, monoethoxy-tris(acetonitrile)chromate, single positive Propyloxy-tris(acetonitrile)zirconium, monoisopropoxy-tris(acetonitrile)zirconium, mono-n-butoxy-tris(acetonitrile)zirconium, single-stage butoxy-three (B)醯 acetone) zirconium, mono-tertiary butoxy-tris(acetonitrile) zirconium, tetrakis(acetonitrile) φ zirconium, triethoxy. mono(ethyl acetate) zirconium, tri-n-propoxy. Mono(acetonitrile ethyl acetate) zirconium, triisopropoxy group (acetic acid ethyl acetate) zirconium, tri-n-butoxy-mono(acetic acid ethyl acetate) zirconium, tri- or two-butoxy. mono(ethyl acetate) zirconium, tri-tertiary butoxy Mono(acetic acid ethyl acetate) chromium, diethoxy. bis(acetic acid ethyl acetate) chromium, di-n-propoxy bis(ethyl acetonitrile) hydrazine, diisopropoxy bis (B) Ethyl acetate, zirconium, di-n-butoxy-bis(acetic acid ethyl acetate) zirconium, di- or di-butoxy-bis(acetic acid ethyl acetate) chromium, di-tertiary butoxy (acetic acid ethyl acetate) zirconium, monoethoxy. tris(ethyl acetate) hydrazine, mono-57-201033253 n-propoxy. tris(ethyl acetate) zirconium, monoisopropoxy Tris(acetonitrile ethyl acetate) zirconium, mono-n-butoxy-tris(ethyl acetate) chromium, mono-butoxy-butoxy. tris(ethyl acetate) zirconium, mono-tertiary butoxy. Tris(acetate ethyl acetate) zirconium, tetrakis(acetate ethyl acetate) ruthenium, mono(acetonitrile)acetate (ethyl acetate) zirconium, di(acetonitrile)acetate (acetic acid ethyl acetate) Zirconium, tris(acetonitrile) monoacetate Zirconium coordination compound such as chromium; aluminum complex compound such as tris(acetonitrile)aluminum, tris(acetonitrileacetate)aluminum, etc. ❿ As the organic acid, for example, acetic acid, propionic acid, butyric acid, Valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid 'oxalic acid' maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, mellitic acid, peanut four Alkenoic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid , monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, and the like. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid. Examples of the organic base include pyridine, pyrrole, piperidine 'pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, and monomethyldiethanolamine. Triethanolamine 'diazabicyclooctane, diazabicyclononane, diazabicyclo-decene, tetramethylammonium hydroxide, and the like. -58-201033253 The above-mentioned base metal compound may, for example, be sodium hydroxide or potassium hydroxide; and the alkaline earth metal compound may, for example, be cerium hydroxide or calcium hydroxide. These catalysts may be used alone or in combination of two or more. Among these catalysts, preferred are metal chelate compounds, organic acids or inorganic acids, more preferably titanium complex compounds or organic acids. The use ratio of the catalyst is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 1 part by weight, per 100 parts by weight of the raw material decane compound.水 The water added in the synthesis of the other polyorganosiloxane may be added to the raw material decane compound or the solvent obtained by dissolving the decane compound in an organic solvent intermittently or continuously. The catalyst may be previously added to the raw material decane compound or the solvent obtained by dissolving the decane compound in an organic solvent, or may be dissolved or dispersed in the added water. The reaction temperature at the time of synthesis of the other polyorganosiloxane is preferably from 〇 to 100 ° C, more preferably from 15 to 80 ° C. The reaction time is preferably from 0.5 to 24 hours, and φ is more preferably from 1 to 8 hours. [Use Ratio of Other Polymers] When the liquid crystal alignment agent of the present invention contains the above-mentioned radiation-sensitive polyorganosiloxane and other polymers, the ratio of use of other polymers is relative to 100 parts by weight of the radiation-sensitive polyorganoindene The oxane is preferably 10,000 parts by weight or less. The better use ratio of other polymers varies depending on the type of other polymers. The liquid crystal alignment agent of the present invention preferably contains at least one of the above-mentioned radiation-sensitive polyorganofluorene-59-201033253 oxane and at least one polymer selected from the group consisting of polyglycine and polyimine. The use ratio is 100 to 5000 parts by weight, more preferably 200 to 2000 parts by weight, based on 100 parts by weight of the radiation-sensitive polyorganosiloxane, the total amount of the polyamic acid and the polyimide. In addition, when the liquid crystal alignment agent of the present invention contains a radiation sensitive polyorganosiloxane and other polyorganosiloxanes, a better use ratio of the two is compared with 100 parts by weight of the radiation-sensitive polyorganosiloxane, and the like. The polyorganosiloxane is 100 to 2000 parts by weight. The liquid crystal alignment agent of the present invention, when containing both a radiation-sensitive polyorganosiloxane and other polymers, is preferably a group selected from the group consisting of polylysine and polyimine. At least one polymer, or other polyorganic sands. [Reinforcing agent, curing catalyst, and curing accelerator] The curing agent and the curing catalyst may be contained in the liquid crystal alignment agent for the purpose of further enhancing the crosslinking reaction of the radiation-sensitive polyorganosiloxane, and the curing accelerator may be It may be contained in the liquid crystal alignment agent of the present invention for the purpose of promoting the φ curing reaction in which the hardener participates. As the curing agent, a curing agent which is usually used as a curable compound having an epoxy group or a curable composition containing a compound having an epoxy group can be used, and examples thereof include a polyamine, a polycarboxylic acid anhydride, and a polycarboxylic acid. Acid, etc. The polyvalent carboxylic acid anhydride may, for example, be an acid anhydride of cyclohexanetricarboxylic acid or another polyvalent carboxylic acid anhydride. -60- 201033253 As a specific example of the acid anhydride of cyclohexanil diterpenic acid, for example, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-tridecanoic acid can be used. 3,5· Anhydride, cyclohexane-1,2,3-tricarboxylic acid-2,3-anhydride, etc., as another polyvalent carboxylic acid anhydride, for example, 4-methyltetrahydrophthalic anhydride, methyl group Commonly used in the synthesis of norfloxadicarboxylic anhydride, dodecenyl succinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, a compound represented by the following formula (6), and polyglycine Tetracarboxylic dianhydride,

(In the formula (6), p is an integer of 1 to 20)" In addition, examples thereof include an alicyclic compound having a conjugated diene bond such as terpinene or an allo-ocimene, and a disulfide of maleic anhydride. - Adel reaction product and its hydrogenated product, and the like. As the hardening catalyst, for example, ruthenium hexafluoride compound Φ, phosphorus hexafluoride compound, aluminum acetonate or the like can be used. These catalysts can catalyze the cationic polymerization of epoxy groups by heating. Examples of the hardening accelerator include, for example, an imidazole compound; a quaternary scaly compound; a quaternary ammonium compound; 1,8-aza-aza [5.4.0]~ (carbon-7- diaza and an organic salt thereof; Bicyclic olefin; organometallic compound such as zinc octoate, tin octoate, acetonitrile aluminum complex; -61 - 201033253 Boron compound such as boron trifluoride or triphenyl borate; High-melting-point-dispersion latent hardening accelerator such as cyanoguanidine, an amine and an epoxy resin addition product; and a microcapsule-type potential coated with a polymer such as a quaternary iron salt Hardening accelerator; amine salt type latent hardening accelerator; high temperature degradable thermal cationic polymerization latent hardening accelerator such as Lewis acid salt, Bronsted acid salt, etc. The use ratio of the hardener in the present invention is relatively 100 parts by weight of the radiation-sensitive polyorganosiloxane, preferably 1 part by weight or less. The use ratio of the hardening catalyst is preferably 2 with respect to 1 part by weight of the radiation-sensitive polyorganosiloxane. Parts by weight or less. The use ratio of the chemical accelerator is preferably 10 parts by weight or less based on 100 parts by weight of the radiation-sensitive polyorganosiloxane. [Epoxy compound] The above epoxy compound is further improved from the formed liquid crystal alignment film. The liquid crystal alignment agent of the present invention can be contained in the liquid crystal alignment agent of the present invention. Examples of such an epoxy compound include ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether. , propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2, 2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6- 201033253 tetraglycidyl-2,4-hexanediol, N,N,N,,N,-tetraglycidyl 3 Methylamine, 1,3-bis(N,N-diglycidylaminomethyl) ring >1,>1,:^',>1'-tetraglycidyl-4,4,- Diaminodiphenylmethane, glycidyl-benzylamine, N,N-diglycidyl-aminomethylcyclohexene as the liquid crystal of the present invention When the agent contains an epoxy compound, the content ratio is preferably 40% by weight or less, more preferably 0.1 to 30%, based on 100 parts by weight of the total amount of the above-mentioned radiation-sensitive polyalkane and optionally other polymers. In addition, the liquid crystal alignment agent of the present invention contains an epoxy group compound for the purpose of efficiently carrying out a crosslinking reaction, and may be used together with an inert catalyst such as 1-: methylimidazole. The catalyst ratio is preferably 10 parts by weight, more preferably 0 to 2 parts by weight, per 100 parts by weight of the epoxy compound. [Functional decane compound] The above functional decane compound may be used to increase the obtained ruthenium film. It is used for the purpose of adhesion to a substrate. Examples of the functional oxime include 3-aminopropyltrimethoxydecane, 3-aminetriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminoethoxy decane, and N. -(2-Aminoethyl)-3-aminopropyltrimethoxy N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-yltrimethoxy Decane, 3-ureidopropyltriethoxydecane, N-ethyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl decane, N-triethoxy矽-propyl propyl triethylene triamine, N. ses-m-phenyl hexane, N, N-di^, etc. As a part of the oxygen content of the machine, it is a long base-2-use ratio of the liquid crystal with alkane propyl propyl trisole, ureidopropoxycarbonyl triethoxytrimethoxy 201033253 sulfonyl propyl triamide Ethyltriamine, 10-trimethoxydecyl-H 7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl -3,6-diazepine acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxy Brothel, N-nodal-3-aminopropyltriethoxy chopping, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethyl Oxydecane, N-bis(oxyvinyl)-3-aminopropyltrimethoxydecane, N-bis(oxyvinyl)-3-aminopropyltriethoxydecane, 3-epoxypropane Oxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, etc., and can also be listed as Patent Document 23 (Japanese Patent Laid-Open No. 63-291 922) The reaction product of the tetracarboxylic dianhydride and the decane compound having an amine group described in the publication). When the liquid crystal alignment agent of the present invention contains a functional decane compound, the content ratio thereof is preferably 50% by weight based on 100 parts by weight of the total amount of the above radiation-sensitive polyorganosiloxane and optionally other polymers. The remainder is more preferably 20 parts by weight or less. [Surfactant] _ As the above surfactant, for example, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a polyoxyxyl surfactant, a polyalkylene oxide surfactant may be mentioned. , fluorine-containing surfactants, and the like. 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 1 part by weight or less based on the total amount of the liquid crystal alignment agent per part by weight. -64-201033253 [Photosensitizer] Examples of the photosensitizer include tetraphenylbutanone, phenylacetone, acetophenone, anthrone, 4-methoxyoxyacetophenone, anthrone, and benzene. Formaldehyde, 4,4'-dimethoxyketone, anthracene, 9,10-benzophenanthrene, biphenyl, thioxanthone, ethylamino)benzophenone, phenanthrene, naphthalene, 4-phenylacetophenone , 2-iodonaphthalene, anthracene, 2-naphthonitrile, 1-iodophthalene, 1-naphthonitrile, fluoranthene, anthracene, 1,2-benzopyrene, acridine, anthracene, sulphate, 1, 4-Dicyanophthalene, 9-fluoroanthrene, 9,10-dicyanotetracyanoguanidine, and the like. When the liquid crystal aligning agent of the present invention contains a photosensitizer ratio, it is 20 parts by weight or less, more preferably 10 parts by weight or less based on 100 parts by weight of the sensitizing agent. <Liquid Crystal Aligning Agent> The liquid crystal aligning agent of the present invention As described above, the φ-containing organic siloxane is an essential component, and the other components are preferably prepared so that the components are dissolved in an organic solvent. The preparation for the liquid crystal alignment agent of the present invention is preferably a solvent which is capable of dissolving other components of the radiation-sensitive polyorganofluorene and which does not react with them. The liquid crystal alignment agent of the present invention preferably uses different types of other polymers which are preferably used. Methylbenzene, benzonitrile, acetophenone, 3-methylbenzophenone, diphenyl[醌, 4,4'-bis(di-4-phenylbenzophenone, hydrazine, hydrazine, benzotetraphenyl) Or 2-methoxy oxime, 2,6,9,10-, as the organic oxime-containing gas, preferably having a sensible radial polymerization, further comprising an organic dissolved oxygen alkane used in combination in solution Optionally using an organic solvent, according to any of -65-201033253 when 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 polyamic acid and polyimine In the case of a preferred organic solvent, a solvent exemplified as a solvent used in the synthesis of polyamic acid may be used. These organic solvents may be used singly or in combination of two or more. Further, the liquid crystal alignment agent of the present invention contains only When a radiation-sensitive polyorganosiloxane is used as a polymer or a radiation-sensitive polyorganosiloxane and other polyorganosiloxane, a preferred organic solvent is, for example, 1-ethoxy-2. Propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ® propylene glycol Butyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ether, dipropylene glycol propyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, B Glycol monobutyl ether (butyl cellosolve), ethylene glycol monopentyl ether, ethylene glycol monohexyl ether, diethylene glycol, methyl cellosolve acetate, ethyl cellosolve acetate propyl solution Fibrin acetate, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, n-propyl acetate, isopropyl acetate, n-butyl acetate Ester 'acetate@isobutyl ester, n-butyl acetate, n-amyl acetate, diethyl amyl acetate, 3-methoxybutyl acetate, methyl amyl acetate '2-ethyl butyl acetate, acetic acid 2 -ethylhexyl ester, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate, etc. Among them, preferred are n-propyl acetate, isopropyl acetate, and acetic acid. N-butyl ester, isobutyl acetate, 2-butyl acetate, n-amyl acetate, diethyl amyl acetate, etc. Preparation of liquid crystal alignment agent of the present invention The preferred solvent to be used is -66 - 201033253. The solvent obtained by combining i or two or more of the above organic solvents according to whether or not another polymer or the type thereof is used is a liquid crystal at a preferred solid content concentration as described below. The components contained in the alignment agent are not precipitated, and the surface tension of the liquid crystal alignment agent is dropped in a solvent in the range of 25 to 40 mN/m. The solid content concentration in the liquid crystal alignment agent of the present invention, that is, the solvent in the liquid crystal alignment agent The ratio of the weight of all the components to the total weight of the liquid crystal alignment agent is selected in consideration of viscosity, volatility, etc., preferably in the range of 1 to 10% by weight. The liquid crystal alignment agent of the present invention is applied to the surface of the substrate. When the coating film which is a liquid crystal alignment film is formed, 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 favorable liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the coating film thickness is too thick to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent is increased to cause insufficient coatability. The particularly preferable solid content concentration range differs depending on the method used when the liquid crystal alignment agent is applied to the substrate. For example, when the spin coating method is employed, it is particularly preferably in the range of 1.5 to 4.5 φ% by weight. When the printing method is employed, it is particularly preferable that the solid content concentration is in the range of 3 to 9 wt%, so that the solution viscosity can be made to fall within the range of 12 to 50 mPa·s. When the ink jet method is employed, it is particularly preferable that the solid content concentration is in the range of 1 to 5 % by weight, so that the solution viscosity can be made to fall within the range of 3 to 15 mPa 's. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably 〜200 ° C, more preferably 10 to 60 ° C. <Method of Forming Liquid Crystal Alignment Film> 201033253 The liquid crystal alignment agent of the present invention can be suitably used to form a liquid crystal alignment film by a photo-alignment method. The method for forming the liquid crystal alignment film may, for example, be a method in which a liquid crystal alignment agent of the present invention is applied onto a substrate to form a coating film, and then the coating film is irradiated with polarized light or non-polarized radiation to generate liquid crystal alignment energy. First, the liquid crystal alignment agent of the present invention is applied to the transparent conductive film side of the substrate on which the pattern-shaped transparent conductive film is provided by an appropriate coating method such as a roll coating method, a spin coating method, a printing method, or an inkjet method. Then, the coated surface is preheated (prebaked), followed by firing (post-baking) to form a coating film. The prebaking conditions are, for example, 0.1 to 5 minutes at 40 to 120 ° C, and the post-baking conditions are preferably 120 to 300 ° C, more preferably 150 to 250 ° C, and preferably 5 to 200 minutes. Better to carry out 10 to 100 minutes. The thickness of the coating film after the post-baking is preferably 0.001 to Ιμηη, more preferably 0.005 to 0 · 5 μιη 0. As the substrate, for example, glass such as float glass or soda lime glass; polyethylene terephthalate can be used; A transparent substrate made of plastic such as glycol ester, polybutylene terephthalate, polyether oxime or polycarbonate. As the transparent conductive film, a pattern of these transparent conductive films, such as a NESA film made of Sn02, an ITO film made of In203-Sn02, or the like, can be used, and a lithography lithography method or a method of using a photomask when a transparent conductive film is formed can be used. Wait. In the application of the liquid crystal alignment agent, in order to further improve the adhesion of the substrate or the transparent conductive film to the coating film, it is also possible to apply a functional decane compound or a titanate compound to the substrate and the transparent conductive film in advance-68-201033253. Wait. Next, the coating film is irradiated with a linearly polarized or partially polarized radiation or non-polarized radiation to generate a liquid crystal alignment energy. Here, as the radiation, for example, ultraviolet rays and visible rays having a wavelength of 150 to 800 nm, and ultraviolet rays having a wavelength of 300 to 40 Onm wavelength can be used. When the radiation used is linearly polarized or partially polarized, the irradiation may be performed from the direction perpendicular to the substrate surface, or may be performed from the oblique _ direction in order to generate the pretilt angle, and they may be combined. When illuminating non-polarized ❹ radiation, the direction of illumination must be oblique. As the light source used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. The ultraviolet light of the above preferred wavelength range can be obtained by a means for applying the above-mentioned light source to, for example, a filter or a diffraction grating. The irradiation amount of the radiation is preferably 1 J/m2 or more and less than 10,000 J/m2, more preferably 10 to 3000 J/m2. Further, when liquid crystal alignment energy is generated by a liquid alignment method which is formed by a conventional liquid crystal alignment agent by a photo-alignment method, a radiation irradiation amount of 1 0000 J/m 2 or more is required. However, when the liquid crystal alignment agent of the present invention is used, when the amount of radiation irradiation in the photo-alignment method is 3,000 J/m 2 or less, or even 1 〇〇〇 J/m 2 or less, good liquid crystal alignment energy can be produced, which is advantageous. To reduce the manufacturing cost of the liquid crystal display element. Further, the "pretilt angle" in the present invention means an angle at which liquid crystal molecules are inclined from a direction parallel to the substrate surface. 201033253 <Liquid Crystal Alignment Film> The liquid crystal alignment film of the present invention formed by the liquid crystal alignment agent of the present invention, the pretilt angle thereof Excellent stability over time. In order to reveal the reason why such an unexpected excellent effect is exhibited, the present inventors conducted intensive studies, and as a result, it was found that the liquid crystal alignment film of the present invention has a special film as compared with the previously known liquid crystal alignment film. structure. That is, in the liquid crystal alignment film of the present invention, the existence distribution of the group derived from the above (A) cinnamic acid derivative in the thickness direction was investigated, and it was unexpectedly found that in the liquid crystal alignment film of the present invention, it was derived from (A) cinnamon. The group of the acid-derived material is biased within 30% of the thickness from the surface of the film, even within the range of 25%, especially 20%. Further, the concentration of the group derived from the (A) cinnamic acid derivative has the largest enthalpy on the surface of the liquid crystal alignment film. It is presumed that such a photosensitive group is biased in a narrow range in the vicinity of the surface of the film, and is one of the causes of being able to produce a pretilt angle excellent in stability with time with a small amount of exposure.

Further, it has been found that such a special film structure can be surely obtained particularly when the liquid crystal alignment agent of the present invention contains the above-mentioned radiation-sensitive polyorganosiloxane and other polymers at the above-mentioned preferable content ratio. The distribution of the group derived from the (A) cinnamic acid derivative in the liquid crystal alignment film in the film thickness direction can be known by, for example, ToF-S IMS analysis (time-of-flight secondary ion quality analysis). More specifically, a liquid crystal alignment film formed on a transparent conductive film of a substrate having a transparent conductive film is a Tow-SIMS measuring device using a Bi3 + + ion cluster having an acceleration voltage of -70 to 201033253 of 25 kV as an ion source. C6D sputtering and ToF-SIMS analysis were repeated on the liquid crystal alignment film under the conditions of 〇·〇5ρΑ, measurement field of view of 100 μm, and measurement quality range of 0 to 1 8 5 5 amu. The atomic species (for example, indium ions) from the transparent conductive film of IT 0. It is considered that the deepest portion of the film has been reached at the time when the atomic species originating from the transparent conductive film is detected. Therefore, the measurement is started as the film thickness range of the liquid crystal alignment film from the start of the measurement, and the investigation is equivalent to the source (A). The number of counts of the fragments of the group of the cinnamic acid derivative is distributed upward in the film thickness. Moreover, in order to eliminate the influence of measurement noise, the number of counts of each depth of the film (depth from the film surface) is divided by the minimum number of counts (measurement noise level) in the film thickness range. Thus, the distribution of the group derived from the (A) cinnamic acid derivative in the film thickness direction is known. Further, the group derived from the (A) cinnamic acid derivative is disposed within a range of 30% of the thickness from the surface of the film, and means that in the above-mentioned corrected distribution, from the surface of the liquid φ crystal to the surface of the film to 30% The concentration of the group derived from the (A) cinnamic acid derivative within the range is more than 95% of the entire concentration in the film thickness range. <Manufacturing Method of Liquid Crystal Display Element> The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention. The liquid crystal display element of the present invention can be produced, for example, as follows. Two substrates on which the liquid crystal alignment film was formed as described above were prepared, and liquid crystal cells were fabricated by arranging liquid crystals between the two substrates. For the manufacture of liquid crystal cells, the following two methods can be listed. -71 - 201033253 The first method' is a previously known method. First, the two substrates are opposed to each other with a gap (box gap) interposed therebetween, and the respective liquid crystal alignment films are bonded to each other with a sealant to the peripheral portion of the two substrates, and the gap between the substrate and the sealant is closed. After filling the liquid crystal with the internal injection, the liquid crystal cell can be obtained by closing and filling the hole. The second method is called the 〇DF (〇ne Drop Fill) method. Applying, for example, an ultraviolet curable sealant material to a predetermined portion of one of the two substrates forming the liquid crystal alignment film, and then dropping the liquid crystal on the liquid crystal alignment film surface, and bonding the other substrate to make the liquid crystal alignment film phase ® Opposite, then irradiate the entire surface of the substrate with UV rays to cure the sealant to produce a liquid crystal cell. In either method, it is necessary to subsequently heat the liquid crystal cell until the liquid crystal used is at an isotropic phase temperature, and then slowly cool to room temperature to eliminate the liquid alignment during liquid crystal charging. Then, the liquid crystal display element of the present invention can be obtained by laminating a polarizer on the outer surface of the liquid crystal cell. Here, when the liquid crystal alignment film is level-aligned, it is possible to adjust the angle formed by the polarization direction of the irradiated linearly polarized radiation in the two substrates on which the liquid crystal alignment film is formed and the angle between each substrate and the polarizer. A liquid crystal display element having a TN type or STN type liquid crystal cell. On the other hand, when the liquid crystal alignment film is vertically aligned, the liquid crystal cells are formed by making the directions of the easy alignment axes of the two substrates on which the liquid crystal alignment film are formed parallel, and the polarizing plate is formed in the polarization direction and the easy alignment axis. A -72-201033253 liquid crystal display element having a vertically aligned liquid crystal cell can be obtained by bonding it at a 45 degree angle. As the above-mentioned sealant, for example, an epoxy resin containing an alumina sphere as a separator and a curing agent can be used. As the liquid crystal, for example, a nematic liquid crystal, a dish-shaped liquid crystal or the like is preferably used. When it is a TN type liquid crystal cell or an STN type liquid crystal cell, a nematic liquid crystal having a positive dielectric anisotropy is preferable, and for example, a biphenyl liquid crystal, a benzene A cyclohexane liquid crystal, an ester liquid crystal, or a linking can be used. A triphenyl 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, a cholesteric liquid crystal such as cholesteryl chloride, cholesteryl phthalate or cholesteryl carbonate may be further added to the liquid crystal; and the trade names "C-15" and "CB-1 5" (manufactured by Merck) Hand-skins for sale; for use in ferroelectric liquid crystals such as decyloxybenzylidene-p-amino-2-methylbutyl cinnamate, etc. On the other hand, when it is a vertically aligned liquid crystal cell Preferably, a nematic liquid crystal having a negative dielectric anisotropy is used, for example, a diamine benzene liquid crystal, a ruthenium-like liquid crystal, a Schiff base liquid crystal, an azo-based liquid crystal, or a biphenyl liquid crystal can be used. , phenylcyclohexane liquid crystal, and the like. The polarizer used for the outer side of the liquid crystal cell is a polarizer obtained by sandwiching a polarizing film called "H film" in which polyvinyl alcohol is extended and absorbing iodine, and is made of a cellulose acetate protective film, or a ruthenium film itself. Polarizers, etc. The liquid crystal display element of the present invention thus produced is excellent in various properties such as display performance and long-term reliability of 201033253. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples.

The weight average molecular weight M w in the following examples is a polystyrene-converted oxime measured by a gel permeation chromatography (GPC) under the following conditions. Column: manufactured by Tosoh (stock), TSK gel GRCXL II Solvent: tetrahydrofuran temperature: 40 ° C Pressure: 6 8 kg f / cm 2 Epoxy equivalent is determined according to JIS C 2105 "hydrochloric acid - methyl ethyl ketone method" of. The solution viscosity of the polymer solution was determined by measuring the polymer solution described in each of the synthesis examples using an E-type viscometer at 25 °C.

Further, in the following, the synthesis of the starting compound and the polymer is repeated as needed according to the following synthetic route to ensure the necessary amount used in the next synthesis. <Synthesis of Polyorganic Oxygen Court with Epoxy Group> Synthesis Example E-1 To a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 2-(3,4_ ring was added) Oxycyclohexyl)ethyltrimethoxydecane 100.Og, methyl isobutyl ketone 50 〇g and triethylamine 1 〇〇g' were mixed at room temperature. Then, by adding dropwise 1 〇g deionized -74 to 201033253 water through a dropping funnel for 3 minutes, it was mixed under reflux while allowing to react at 80 ° C for 6 hours. After completion of the reaction, the organic layer was taken out and washed with a 0.2% by weight aqueous solution of ammonium nitrate until the water after washing was neutral, and then the solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane having an epoxy group. (EPS-1) viscous transparent liquid

Bite body. 1H-NMR analysis of the epoxy group-containing polyorganosiloxane (EPS-1) gave a theoretical strength based on the epoxy group near the chemical shift (5) = 3.2 ppm, confirming that no ring occurred in the reaction. A side reaction of an oxy group. The polyorganooxynonane (EPS-1) having an epoxy group had a weight average molecular weight Mw of 2,200 and an epoxy equivalent of 186 g/mole. <Synthesis of cinnamic acid derivative (A)> Synthesis Example C-1 A cinnamic acid derivative (2-4-1) was synthesized according to the following Scheme 1.

HO C5H”Br Na0H/H20 -(Q>-cooch3 -► -► CgHn-o-^-

COOH K2C〇3 (2-4-1-1) SOCI〇

HO

CH=CH a COOH K2C〇3

CH=CH-COOH C5H11-0 coo (2-4-1) Synthesis Route 1 201033253 To a 1 L eggplant-shaped flask was charged 91.3 g of methyl 4-hydroxybenzoate, 182.4 g of potassium carbonate and 320 ml of N-methyl- 2-pyrrolidone, after stirring at room temperature for 1 hour, 99.7 g of 1-bromopentane was added, and the mixture was stirred for 5 hours under TC. After the reaction was completed, reprecipitation was carried out with water. Then, 48 g of the precipitate was added. Sodium hydroxide and 400 ml of water were refluxed for 3 hours to carry out a hydrolysis reaction. After the completion of the reaction, neutralization with hydrochloric acid was carried out. The resulting precipitate was recrystallized from ethanol to obtain 1 g of a compound (2-4-1-1). Crystals. Take 41.g of the compound (2-4-1-1) into a reaction vessel, and add 100 ml of sulfinium chloride and 77 μί, Ν-dimethylformamide at 80 °C. The mixture was stirred for 1 hour, and then 'distilled to remove sulfinium chloride under reduced pressure', added to dichloromethane, washed with an aqueous solution of sodium hydrogencarbonate, dried over magnesium sulfate, concentrated, and then added to a solution of tetrahydrofuran. To a 500 mL three-necked flask other than the above, 7.39 g of 4-hydroxycinnamic acid, 13.82 g of potassium carbonate, and 48.48 g of four were added. Potassium bromoammonium bromide, 50 ml of tetrahydrofuran and 10 ml of water. The aqueous solution was cooled with ice, and the above tetrahydrofuran solution was slowly added dropwise, and the reaction was further carried out for 2 hours under stirring. After the reaction was completed, hydrochloric acid was added for neutralization with acetic acid. After ethyl acetate was extracted, it was dried over magnesium sulfate, concentrated, and recrystallized from ethanol to obtain white crystals of 9·0 g of cinnamic acid derivative (2-4-1). Synthesis Example C-2 In the above synthesis example In the same manner as in the synthesis example C-1 except that 1 -bromopentane was replaced by ll 〇.9 g of 1-iodo-4,4,4-trifluorobutane, 9.2 g of the following formula was obtained. 2-4-2) A compound of the formula (cinnamic acid derivative (2-4-2)) of 201033253 white crystals.

CF3C3H6O O~c〇〇-〇-

CH=CH—COOH (2-4-2) Synthesis Example C-3 In the above Synthesis Example C1, except for the intermediate, 9.91 g of 4-pentyl-trans-cyclohexylcarboxylic acid was used instead of the compound which was synthesized and used (2) In the same manner as in the synthesis example C-1, white crystals of the compound (cinnamic acid derivative (2-23-1)) represented by the following formula (2-23-1) were obtained. .

C5Hn Ο COO COOH (2-23-1) Synthesis Example C-4 A cinnamic acid derivative (2-31-1) was synthesized according to the following Scheme 2.

C5Hn

CH=CH-COOH (2-31-1) Synthetic route 2 To a 500-neck three-necked flask equipped with a reflux tube, a thermometer and a nitrogen introduction tube, 31 g of a compound (2-31-b 1), 〇.23 g were added. Palladium acetate, 1.2 g of tris(o-tolyl)phosphine, 56 ml of triethylamine, 8.2 ml of acrylic acid and 200 ml of N,N-.11 - « « 201033253 dimethylacetamide' was stirred at 120 ° C for 3 hours. . After the completion of the reaction, the reaction mixture was filtered, and 1 L of ethyl acetate was added to the obtained filtrate. The obtained organic layer was washed twice with dilute hydrochloric acid, washed three times with water, dried over magnesium sulfate, and then evaporated. The obtained solid was recrystallized from a mixed solvent of ethyl acetate and tetrahydrofuran to obtain crystals of 15 g of cinnamic acid derivative (2-31-1). Synthesis Example C - 5

In the above-mentioned Synthesis Example C-4, except that the compound represented by the following formula (2-32-1-1) was used instead of the compound (2_3 1 -1 -1 ), the same procedure as in the synthesis example C-4 was carried out. 16 g of a compound represented by the following formula (2-3 2-1) (cinnamic acid derivative (2-32-1>> CF3C3H6-0)

(2-32-1-1) CF3C3H6—0

CH II CH-COOH (2-32-1)

Synthesis Example C-6 A cinnamic acid derivative (2-35-1) was synthesized according to the following Scheme 3. -78- 201033253 C5Hn

COOH (2-35-1-1) o C5H11

K2C03 C5H11

COCI (2-35-1-2) HO

CH 2 CH—COOH coo~〇^ CH=CH-COOH (2-35-1) Synthetic route 3 To a 300 ml eggplant-shaped flask equipped with a reflux tube and a nitrogen introduction tube, 21 g of a compound (2-35-1) was added. -1), 80 ml of sulfinium chloride and 0.1 mL of N,N-dimethylcartoamine' were stirred at 80 ° C for 1 hour to carry out a reaction. After the end of the reaction, the thioanisole chloride was distilled off from the reaction mixture, and then the organic layer was washed three times with water by adding 150 ml of dichloromethane. After the organic layer was dried over magnesium sulfate, the solvent was removed under reduced pressure, and 400 ml of tetrahydrofuran (as a solution) was added to the obtained solid (compound (1-35-1-2)). In addition, to a 1 L three-necked flask equipped with a dropping funnel and a thermometer, 16 g of p-hydroxycinnamic acid, 24 g of potassium carbonate, 〇.87 g of tetrabutylammonium bromide, 200 ml of water and 100 ml of tetrahydrofuran were added and cooled to ice. Below 5 °C. The above A solution was added dropwise thereto over 3 hours, and further reacted for 1 hour with stirring. After completion of the reaction, dilute hydrochloric acid was added to the reaction mixture to adjust the pH to 4 or less, and then 3 L of toluene and 1 L of tetrahydrofuran were added, and the obtained organic layer was washed with water three times. After the organic layer was dried over magnesium sulfate, -79-201033253 solvent was removed under reduced pressure, and the obtained solid was recrystallized from a mixed solvent of ethanol and tetrahydrofuran to obtain 21 g of a cinnamic acid derivative (2-354). <Synthesis of Radiation-Radio Polyorganooxane> Example S-1 A polyorganosiloxane having an epoxy group obtained by adding 5.0 g of the above-mentioned Synthesis Example E into a 200 ml three-necked flask ( EPS-1), 464 g of methyl isobutyl ketone, 4.76 g of the compound (2-4-1) obtained in the above Synthesis Example C1 as the cinnamic acid derivative (A) (relative to the ruthenium atom of EPS-1) (equivalent to 50 mol%), l_0 8 g as the photosensitizing compound (B), the compound represented by the following formula (Bqq) © (relative to the ruthenium atom of EPS-1, equivalent to 2 〇 mol%) ),

The reaction was carried out by stirring at 120 ° C for 12 hours with 0.10 g of tetrabutylammonium bromide. After completion of the reaction, reprecipitation was carried out with methanol, and the precipitate was dissolved in ethyl acetate to obtain a solution. The solution was washed three times with water, and then the solvent was evaporated to give 2.8 g of s. 1) White powder. The weight average molecular weight Mw of the radiation-sensitive polyorganosiloxane (S-1) was 12,500°. Examples S-2 to S-55 In the above Example S-1, except for the cinnamic acid derivative (A) and photosensitization The type and amount of the compound (B) were the same as those in the example S-1 except that the type and amount of the compound (B) were respectively the same, and the radiation-sensitive polyorganosiloxane (80-201033253 (S-2) ~ ( S-55). The obtained respective radioactive linear average molecular weights are shown in Table 1. Further, in Examples S-4 9 and S-54, (A), two compounds were respectively used, and in Examples S and S-5 2, other pre-tilt expression compounds were respectively used (A). Used as part of ). The weight of organic decane is a cinnamic acid derivative '31, S-48, S-51% instead of cinnamic acid

-81 - 201033253 Table 1 Name of sensitizing radiopolyorganosiloxane cinnamic acid derivative (A) Photosensitizing compound (B) Other pretilt angle expressive compound Weight average molecular weight Mw Species (mol%) Species amount (% by mole) Type of species (% by mole) Example s-1 S-1 2-4-1 50 B-1-1 20 - 0 12,500 Example S-2 S-2 2-4-1 50 B -1-1 10 - 0 12,000 Example S-3 S-3 2-4-1 50 B-1-1 5 - 0 11,600 Example S-4 S-4 2-4-1 50 B-1-1 1 - 0 11,000 Example S-5 S-5 2-4-1 50 B-1-1 0.2 - 0 10,500 Example S-6 S-6 2-4-1 50 B-2 5 - 0 11,700 Example S-7 S-7 2-4-1 50 B-3 5 - 0 11,700 Example S-8 S-8 2-4-1 50 B-5 20 - 0 12,400 Example S-9 S-9 2- 4-1 50 B-5 10 - 0 11,900 Example S-10 S-10 2-4-1 50 B-5 5 - 0 11,500 Example S-11 S-11 2-4-1 50 B- 5 1 - 0 11,100 Example S-12 S-12 2-4-1 50 B-5 0.2 - 0 10,400 Example S-13 S-13 2-4-1 50 B-11 20 - 0 12,200 Example S -14 S-14 2-4-1 50 B-11 10 - 0 11,900 Example S-15 S-15 2-4-1 50 B-11 5 - 0 11,200 Example S-16 S-16 2-4 -1 50 B-11 1 - 0 10,800 Example S-17 S-17 2-4-1 50 B-11 0.2 - 0 10,000 Example S-18 S-18 2-4-1 50 B-28-1 20 - 0 13,000 Example S-19 S-19 2-4-1 50 B-28-1 10 - 0 12,400 Example S-20 S-20 2-4-1 50 B-28-1 5 - 0 11,900 Example S-21 S-21 2-4- 1 50 B-28-1 1 - 0 11,100 Example S-22 S-22 2-4-1 50 B-28-1 0.2 - 0 10,500 Example S-23 S-23 2-4-1 50 B- 39-I 20 - 0 12,400 Example S-24 S-24 2-4-1 50 B-39-1 10 - 0 11,800 -82- 201033253 Table 1 continued

The name of the radiation-sensitive polyorganosiloxane, cinnamic acid derivative Α, light-sensitizing compound, other pretilt angle, expressive compound, weight average molecular weight, Mw, type (mol%), amount of species (% by mole), amount of species %) Example S-25 S-25 2-4-1 50 Β-39-1 5 - 0 11,300 Example S-26 S-26 2-4-1 50 Β-39-1 1 - 0 10,900 Example S-27 S-27 2-4-1 50 Β-39-1 0.2 - 0 10,100 Example S-28 S-28 2-4-1 50 Β-42-1 5 - 0 10,900 Example S-29 S -29 2-4-1 50 Β-42-2 5 - 0 10,800 Example S-30 S-30 2-4-1 75 Β-28-1 5 - 0 14,300 Example S-31 S-31 2- 4-1 50 Β-28-1 5 5-3-1 20 13,700 Example S-32 S-32 2-4-2 50 Β-1-1 20 - 0 12,400 Example S-33 S-33 2- 4-2 50 Β-1-1 10 - 0 12,000 Example S-34 S-34 2-4-2 50 Β-1-1 5 - 0 11,200 Example S-35 S-35 2-4-2 50 Β-1-1 1 - 0 10,900 Example S-36 S-36 2-4-2 50 Β-1-1 0.2 - 0 10,500 Example S-37 S_37 2-4-2 50 Β-5 20 - 0 12,500 Example S-38 S-38 2-4-2 50 Β-5 10 - 0 11,900 Example S-39 S-39 2-4-2 50 Β-5 5 - 0 11,200 Example S-40 S- 40 2-4-2 5 0 Β-5 1 - 0 10,400 Example S-41 S-41 2-4-2 50 Β-5 0.2 - 0 10,000 Example S-42 S-42 2-4-2 50 Β-28-1 20 - 0 13,000 Example S-43 S-43 2-4-2 50 Β-28-1 10 - 0 12,200 Example S-44 S-44 2-4-2 50 Β-28-1 5 - 0 11,500 Example S-45 S-45 2-4-2 50 Β-28-1 1 - 0 11,000 Example S-46 S-46 2-4-2 50 Β-28-1 0.2 0 10,600 Example S-47 S- 47 2-4-2 75 Β-28-1 0.2 0 13,800 Example S-48 S-48 2-4-2 50 Β-28-1 0.2 Stearic acid 20 13,300 201033253 Table 1 Continuation of radiation linear polyorgano Name of oxane cinnamic acid derivative (A) Photosensitizing compound (B) Other pretilt angle expressive compound Weight average molecular weight Mw Species amount (mol%) Species 莫 (mole%) Species amount (mol%%) Example S-49 S-49 2-4-2 25 B-28-1 0.2 - 0 10,000 2-31-1 25 Example S-50 S-50 2-31-1 50 B-28-1 0.2 0 9,500 Example S-51 S-51 2-31-1 50 B-28-1 0.2 Stearic acid 20 12,800 Example S-52 S-52 2-31-1 50 B-28-1 0.2 5-3 -1 20 13,100- Example S-53 S-53 2-32-1 50 B-28-1 0.2 - 0 1 11,500 Example S-54 S-54 2-4-2 40 B-28-1 0 .2 - 0 10,500 2-23-1 10 Example S-55 S-55 2-35-1 25 B-28-1 0.2 - 0 12,000 The cinnamic acid derivative (A) in Table 1, photosensitization The abbreviations of the compound (B) and other pretilt-exhibiting compounds are as follows. <Cinnamic acid derivative (A)> 2-4-1: 2-4-2 produced in the above Synthesis Example C-1: 2-23-1 in the above Synthesis Example C-2: Synthesis Example C- 3 (2-23-1) 2-31-1: Synthesis Example c-4 (2-31-1) 2-32-1: Synthesis Example c-5 (2-32-1) 2-35- 1: Synthesis Example c-6 (2-35-1) <Photosensitizing Compound (B)> B-1-1: The above formula (B-1-l) represents a white cinnamic acid derivative (2-4-1) The cinnamic acid obtained from the cinnamic acid derivative obtained from the cinnamic acid derivative obtained in the cinnamic acid derivative obtained in the obtained cinnamic acid derivative (2-4-2) Derivative J compound-84-201033253 B-2·Compound B-3 represented by the above formula (B-2): Compound B-5 represented by the above formula (B-3): represented by the above formula (B-5) Compound B-11: Compound B-28-1 represented by the above formula (BU): Compound B-39-1 represented by the following formula (Βα^): Compound B-42- represented by the following formula (8-394) 1: Compound B-42-2 represented by the following formula (B-42-1): a compound represented by the following formula (B-42-2) <Other pretilt expression compound> 5-3-1: a compound represented by the following formula (5-3-1)

N〇2 (B_28_1) (B-39-1)

<Synthesis of Other Polymer> [Synthesis of Polylysine] Synthesis Example PA-1 Benzotetracarboxylic dianhydride as tetracarboxylic dianhydride 109 g (05 〇 Moule) and -85-201033253 1, 2,3,4-cyclobutanetetracarboxylic dianhydride 98 g (0.50 mol), 4,4-diaminodiphenyl ether as a diamine compound 200 g (1.0 mol) dissolved in 229 g of N After reacting at ～2-pyrrolidone for 3 hours at 40 ° C, 135 〇g of N-methyl-2-pyrrolidone was added to obtain about 3590 g of a solution containing 10% by weight of polyglycine (pA_1}. The solution viscosity of polylysine solution is 21〇mPa.s ^ Synthetic example PA-2 will be used as 12,3,4-cyclobutanine tetraphthalic acid dianhydride 98g (0-50 moles) and benzene. Tetrahydrous dianhydride i〇9g (0.50 mol), and 4,4,-diaminodiphenylmethane i98g (l. oxime) as a diamine compound are dissolved in ginseng 2290g N-methyl·2 - In pyrroleone, it was allowed to react at 4 Torr for 3 hours, and 1350 g of N-methyl-2-lager was added to obtain a solution containing 1% by weight of polyacrylic acid (PA-2). The solution viscosity of the proline solution is 135 mpa s. Synthesis Example PA-3 ❹ will be used as the tetracarboxylic dianhydride 1 2,3,4-cyclobutanetetracarboxylic acid di-hepatic 1 96 g (1.0 mol)' and 4,4'-diaminodiphenyl acid as a diamine compound 200 g (l. oxime) are soluble 2246 g of N-methyl-2-pyrrolidine copper was allowed to react at 4 ° C for 4 hours, and 1321 g of N-methyl-2-pyrrole was added to obtain 10% by weight of polyglycine (PA_3). The solution has a melt viscosity of 220 mPa·s. Synthesis Example PA-4 i,2,3,4-cyclobutanetetracarboxylic acid dihydrogen 1 96 g as tetracarboxylic dianhydride (1·0 mole), and 2,2,-dimethyl-4,4, diaminobiphenyl as a diamine compound, 2l2g (l. oxime) dissolved in 3 67 〇g N-methyl -2-Pyrrolidone-86-201033253 'Make it react at 40 ° C for 3 hours to obtain a solution containing 1 〇 by weight of polyglycine (ΡΑ-4). The solution viscosity of the polyaminic acid solution 17 〇 inPa.s. Synthesis Example PA-5 224 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, and 4,4 as a diamine compound. , _diaminodiphenyl ether 200g (l. oxime) was dissolved in 24 〇 4g N_methyl-2_pyrrolidone, and allowed to react at 40 ° C for 4 hours, To a solution containing poly-proline (PA-5). ◎ Take a small amount of the poly-proline solution 'Addition of N-methyl-2-pyrrolidone to a solution with a concentration of 10% by weight. The viscosity of the solution is 19〇. mPa.s. [Synthesis of Polyimine] Synthesis Example PI -1 2,3,5-trimethylcyclopentyl acetic acid dianhydride as tetradecanoic dianhydride 11_2 g (0.50 mol) and i, 3, 3a, 4 ,5,9b-hexahydro-8-methyl_5-(tetrahydro-2,5.dioxo-3-furanyl)-naphthalene[l,2-c]-furan-1,3-dione I57g (0.50 mole)' and p-phenylenediamine as a diamine compound 95g (〇.88 mole), 2,2_ Q bis(trifluoromethyl)-4,4-diaminobiphenyl 32g (0.1 0 Moer), 3 6_ bis (4_Aminobenzyloxy) hexanes 6.4g (0_010 mol) and 18th court oxy 2,5 - _amine basic 4_0g (0.015 mol) soluble in 960gN -Methyl 2 - _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The measured solution viscosity was 58 mPa·s. To the obtained polyaminic acid solution, 2740 g of N-methyl-2-pyridinone, 396 g of pyridine and 409 g of acetic anhydride were added, and dehydration was carried out for 4 hours under uot 201033253 ring closure reaction. After the ring closure reaction, the solvent in the system is replaced by a solvent with a new N-methyl-2-pyrrolidone (by the solvent) Operation, removing the pyridine and acetic anhydride used in the dehydration ring-closure reaction to the outside of the system, the same as the following) 'obtaining about 25 OOg of polyethylenimine (PI-1) containing 15% by weight of ruthenium imidization rate of about 95%. A small amount of the polyimine solution was taken, and the solvent was removed under reduced pressure, and then dissolved in γ-butyrolactone to prepare a solution having a polymer concentration of 8.0% by weight, and the measured solution viscosity was 33 mPai. PI-2 will be used as tetracarboxylic dianhydride 2,3,5-tricarboxycyclopentyl acetic acid dianhydride 112g (0.50 mol) and 1,3,3a,4,5,9b-hexahydro-8-A 5- 5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione 157 g (0.50 mol) as a diamine compound P-phenylenediamine 96g (0.89 moles), diaminopropyl tetramethyldioxane 25g (0.10 moles) and 3,6-bis(4-aminobenzylideneoxy)cholestane 13 g (0.020 mol), and 8.1 g of N-octadecylamine as a monoamine (〇.〇30 mol) were dissolved in 960 g of N-methyl-2-pyrrolidone to cause reaction at 60 ° C. 6 hours. Take a small amount of the obtained poly-proline solution and add N-methyl-2-pyrrolidone to form a thick The viscosity of the solution was determined to be 60 mPa.s for a 10% by weight solution. 2700 g of N-methyl-2-pyrrolidone was added to the obtained polyaminic acid solution, and then 396 g of pyridine and 409 g of acetic anhydride were added, at 11 (TC). A 4 hour dehydration ring closure reaction was carried out. After the dehydration ring closure reaction, the solvent in the system is subjected to solvent replacement with a new N-methyl-2-pyrrolidone to obtain a polyamidene containing 15 - 88 - 201033253 % by weight of ruthenium iodide (about 95 %) ( A solution of PI-2). A small amount of the polyimine solution was taken, N-methyl-2-pyrrolidone was added, and the solution was diluted to a concentration of 6.0% by weight, and the solution viscosity was determined to be 18 mP a.s. Synthesis Example PI-3 224 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride as a diamine compound p-phenylenediamine i 7 g (〇.99) Mox) and 3,6-bis(4-aminobenzylideneoxy)cholestane 6.43 g (0.010 mol) were dissolved in 3039 g of N-methyl-2-pyrrolidone to give a weight of 60. (: The reaction was carried out for 6 ◎ hours to obtain a polyaminic acid solution having a solution viscosity of about 260 mP a.s. 2700 g of N-methyl-2-pyrrolidone was added to the obtained polyaminic acid solution, and 396 g of pyridine and 306 g were further added. The acetic anhydride was subjected to a dehydration ring-closure reaction at U 〇 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain a 含有% by weight. A solution of polyimine (pi-3) having an imidization rate of about 89%. A small amount of the polyimine solution is added, N-methyl-2-pyrrolidone is added, and the solution is diluted to a concentration of 5.0% by weight. The measured solution viscosity was 74 mPa·s. Synthesis Example PI - 4 will be used as tetracarboxylic dianhydride 2,3,5-tricarboxycyclopentyl acetic acid dianhydride ^4 (0.50 mol) and 1,3, 3a,4,5,9b-hexahydro-8.methyl-5-(tetrahydro-2,5-oxo-3-furanyl)-naphthalene[l,2-c]-furan-1,3 -dione 157g (〇.5〇莫耳)' p-phenylenediamine as a diamine compound 89g (〇82mol), 2 2,-di(trifluoromethyl)-4,4,-diamino Biphenyl 32g (0.10 mol), ^(3,5·diaminobenzylideneoxy)-4-(4-trifluoro Methylbenzhydryloxy)-cyclohexane 201033253 258 (0.059 mol) and octadecyloxy-2,5-diaminobenzene 4. (^ (0.011 mol) dissolved in 2175 g N-methyl In 2-pyrrolidone, it was reacted at 60 ° C for 6 hours. A small amount of the obtained polyaminic acid solution was added, N-methyl-2-pyrrolidone was added, and a solution having a concentration of 10% by weight was prepared, and the solution viscosity was measured. 1 500 g of the obtained polyaminic acid solution was taken for 110 mP a·s, and 3 000 g of N-methyl-2-pyrrolidone was added thereto, and 221 g of pyridine and 228 g of acetic anhydride were further added thereto, and the mixture was carried out at 110 ° C for 4 hours. Dehydration ring closure reaction. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2·foslacone to obtain a polyfluorene containing 10% by weight of ruthenium iodide of about 92%. a solution of imine (ΡΙ·4). Take a small amount of the polyimine solution, add Ν-methyl-2-pyrrolidone, and dilute to a concentration of 4.5% by weight of the solution, and determine the solution viscosity to be 26 mp a·S ° Synthesis Example PI-5 19.9 g (0.089 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride as p-phenylenediamine of diamine compound 68 g (〇〇63 mol), 4,4'-diaminodiphenylmethane 3.6 g (〇〇18 mol) and the compound represented by the above formula (D-4) 4.7 g (0,0〇9 Mo) The ear was dissolved in 140 g of Ν·methyl-2_ 妣 院 ketone' to react at 6 (TC for 4 hours). A small amount of the obtained poly-limus acid solution was added, and N-methyl-2-pyrrolidone was added to prepare a solution having a solid concentration of 10% by weight. The solution viscosity was 115 mPa·s. Add 3 2 5 g of N_methyl 2 -pyrrolidone to the obtained poly-proline solution, add 14 g of stray and 18 g of acetic anhydride, and carry out 4 small 201033253 dehydration ring closure under 丨i 〇〇c reaction. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain a polyamidene (PI-5) containing 15.4% by weight of ruthenium iodide ratio of about 7 7 %. )The solution. A small amount of the polyimine solution was taken, N-methyl-2-pyrrolidone was added, and the solution was diluted to a concentration of 10% by weight, and the measured solution viscosity was 84 mPa·s. Synthesis Example PI-6 2,3,5-tricarboxycyclopentyl acetic acid dianhydride φ 20.9 g (0.093 mol) as tetracarboxylic dianhydride, p-phenylenediamine 9.2 g (0.085 Mo) as diamine compound The ear and 4.9 g (0.009 mol) of the compound represented by the above formula (D-4) were dissolved in 140 g of N-methyl-2-pyrrolidone, and allowed to react at 60 ° C for 4 hours. A small amount of the obtained polyaminic acid solution was taken, and N-methyl-2-pyrrolidone was added to prepare a solution having a concentration of 10% by weight, and the viscosity of the solution was determined to be 126 mPa·s. To the obtained polyaminic acid solution, 325 g of N-methyl-2-pyrrolidone was added, and 7.4 g of pyridine and 9.5 g of acetic anhydride were further added thereto at 11 Torr. (: The dehydration ring-closure reaction was carried out for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain a content of 16.1% by weight of ruthenium. 4% solution of polyimine (PI-6). Take a small amount of the polyimine solution, add N-methyl-2-pyrrolidone, dilute to a concentration of 10% by weight of the solution, and determine the solution viscosity to 75. mPa.s. Synthesis Example PI-7 18.8 g (0.084 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, and 74 g of p-phenylenediamine as a diamine compound ( 〇〇68 Mohr) and 8.9 g (0.017 mol) of the compound represented by the above formula (D-4) were dissolved in -91 - 201033253 140 g of N-methyl-2-pyrrolidone, and allowed to react at 60 ° C. A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-pyrrolidone was added to prepare a solution having a concentration of 10% by weight, and the measured solution viscosity was 126 mPa's. Addition to the obtained polyaminic acid solution 3 2 5 g of N-methyl-2-pyrrolidone, further adding 6.6 g of pyridine and 8.5 g of acetic anhydride, and performing a dehydration ring-closure reaction at 110 ° C for 4 hours. After the water ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain a polyamidene (PI-7) containing 15.9% by weight of a ruthenium iodide ratio of about 55%. a solution of a small amount of the polyimine solution, added with N-methyl-2-pyrrolidone, diluted to a concentration of 1% by weight of the solution, the measured viscosity of the solution is 75 mPa's. Synthesis of PI-8 will be used as tetracarboxylic acid Acid dianhydride 2,3,5-tricarboxycyclopentyl acetic acid dianhydride 19.1 g (〇.〇85 mol)' as a diamine compound p-phenylenediamine 7.4g (〇.〇69 Mo) and under Description (D - 6)

The indicated compound 8.5 g (〇.〇i7 mol) was dissolved in l40 g of N-methyl-2-pyridinone and allowed to react at 6 (rc for 4 hours). A small amount of the obtained polyaminic acid solution was added and N was added. -Methyl-2-pyrrolidone, prepared in a solution having a concentration of 10% by weight, having a solution viscosity of 206 mPa.s ^ Adding 325 g of N-methyl-2-pyrrolidine 201033253 ketone to the obtained polyaminic acid solution Further, 6.7 g of pyridine and 8.7 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out for 4 hours at no ° C. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain a solvent. A solution containing 15.8% by weight of a polyamidimide (PI-8) having a ruthenium iodide ratio of about 52%. A small amount of the polyimine solution was added to N-methyl-2-pyrrolidone and diluted to a concentration of 10 % by weight solution, the measured solution viscosity was 105 mPa.s ^ Synthesis Example PI - 9 17.3 g (0.077 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 5.2 g of p-phenylenediamine as a diamine compound, 4.1 g of a compound represented by the above formula (D-4), and the above formula (D) -6) The compound represented by 7.7 g (0.016 mol) was dissolved in 140 g of N-methyl-2-pyrrolidone and allowed to react at 60 ° C for 4 hours. A small amount of the obtained polyaminic acid solution was taken and N·A was added. Base-2-pyrrolidone, a solution having a concentration of 1% by weight, and a solution viscosity of 117 mP a. s. Adding 325 g of N-methyl-2-pyrrolidine φ ketone to the obtained polyglycine solution, Further, 6.lg pyridine and 7.9 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent. A solution containing 15.4% by weight of polyamidiamine (PI-9) having a ruthenium iodide ratio of about 55% was obtained. A small amount of the polyimine solution was added, N-methyl-2-pyrrolidone was added, and the concentration was diluted. 10% by weight of solution, the measured solution viscosity is l〇9mPa-s. [Synthesis of other polyorganosiloxanes] Synthesis Example OE-1 201033253 Add 20.8g of tetraethylene to a 200ml three-necked flask equipped with a condenser Oxydecane and 28.2 gl-ethoxy-2-propanol are heated and stirred at 60°., and added to a volume of 20 ml. 0.26 g of maleic anhydride prepared in a flask was dissolved in 10.8 g of aqueous maleic anhydride solution, and further heated and stirred at 60 ° C for 4 hours to carry out the reaction. The solvent was removed from the obtained reaction mixture, and then 1-B was added. Oxy-2-propanol, again concentrated to give a polymer solution containing 10% by weight of other polyorganosiloxane (PS-1). The weight average molecular weight Mw' of the other polyorganosiloxane (PS-1) was measured to be 5 100 ° <Evaluation of preparation and storage stability of liquid crystal alignment agent> Example A-1 [Modulation of liquid crystal alignment agent] 100 parts by weight of the radiation-sensitive polyorganosiloxane (S-1) obtained in the above Example S-1 and the amount of the other polymer in terms of polyamine acid (PA-1) equivalent to 2000 parts by weight The polyglycine (PA-1)-containing solution prepared in the above Synthesis Example PA-1 is mixed, and N-methyl-2-pyrrolidone and butyl cellosolve are added thereto to prepare a solvent composition. N-methyl-2-pyrrolidone: a solution of butyl cellosolve = 50:50 (weight ratio) and a solid content concentration of 3.0% by weight. This solution was filtered through a filter having a pore size of 111 to prepare a liquid crystal alignment agent (A-1). [Evaluation of Storage Stability] This liquid crystal alignment agent (A-1) was stored at -15 ° C for 6 months. The viscosity was measured at 25 °C with an E-type viscometer before and after storage. When the change rate of the solution before and after storage at 201033253 degrees is less than 10%, the storage stability is evaluated as "good", and when it is 1% or more, the storage stability is evaluated as "poor", and the liquid crystal alignment agent (A-ι) The storage stability is "good". Examples A-2 to A-16, A-18 to A-68, A-70 to A-89, and A-91 to A-109 except for the type of radiation-sensitive polyorganosiloxane and other types of polymers The liquid crystal alignment agents (A-2) to (A-16) and (A-18) to © (A-68) were prepared in the same manner as in Example A-1 except that the amounts and amounts were respectively shown in Table 2. ), (A-70) ~ (A-89) and (A-91) ~ (A-109). With respect to these liquid crystal alignment agents, the storage stability was evaluated in the same manner as in Example A-1. The evaluation results are shown in Table 2. Example A - 1 7 Other polyorganosiloxane (PS-1) prepared in the above Synthesis Example OE-1 in an amount equivalent to 2000 parts by weight of other polyorganosiloxane (PS-1) To the solution, 1 part by weight of the sensitized radiopolyorganosiloxane (S-3) prepared in the above Example S-3, and then 1-ethoxy-2-propanol was added thereto. A solution having a solid content concentration of 4.0% by weight. This solution was filtered through a filter having a pore size of Ιμηη to prepare a liquid crystal alignment agent (A-17). The liquid crystal alignment agent (?-17) was evaluated for storage stability in the same manner as in Example 1-1, and the evaluation results are shown in Table 2. Examples Α-69 and Α-90 In the same manner as in Example A-1, except that the kind of the radiation-sensitive polyorganosiloxane used was as shown in Table 2, the liquid crystal 201033253 alignment agent was separately prepared ( A-69) and (A-90). The storage stability of these liquid crystal alignment agents was evaluated in the same manner as in Example A-1, and the evaluation results are shown in Table 2. Table 2 Name of Liquid Crystal Alignment Agent Bianfang Shooting Di Right Shut Other Polymer Preservation Stability Imagine Milk Paper 1 Type and Type of Molybdenum (Parts by Weight) Example A-1 Α·1 S-1 ΡΑ -1 2,000 Good Example A-2 Α-2 S-2 ΡΑ-1 2,000 Good Example A-3 Α-3 S-3 ΡΑ-1 2,000 Good Example A-4 Α-4 S-3 ΡΑ-2 2,000 Good Example A-5 Α-5 S-3 ΡΑ-3 2,000 Good Example A-6 Α-6 S-3 ΡΑ-4 2,000 Good Example A-7 Α-7 S-3 ΡΑ-5 2,000 Good Example A-8 Α-8 S-3 ΡΙ-1 2,000 Good Example A-9 Α-9 S-3 ΡΙ-2 2,000 Good Example A-10 Α-10 S-3 ΡΙ-3 2,000 Good Example A-11 Α-11 S-3 ΡΙ-4 2,000 Good Practice A-12 Α-12 S-3 ΡΙ-5 2,000 Good Practice A-13 Α-13 S-3 ΡΙ-6 2,000 Good Practice A- 14 Α-14 S-3 ΡΙ-7 2,000 Good Practice A-15 Α-15 S-3 ΡΙ-8 2,000 Good Practice A-16 Α-16 S-3 ΡΙ-9 2,000 Good Practice A-17 Α -17 S-3 PS-1 2,000 Good Example A-18 Α-18 S-4 ΡΑ-1 2,000 Good Practice A-19 Α-19 S-5 ΡΑ-1 2,000 Good Practice A -20 Α-20 S-6 ΡΑ-1 2,000 Good Example A-21 Α-21 S-7 ΡΑ-1 2,000 Good Practice A-22 Α-22 S-8 ΡΑ-1 2,000 Good Practice A-23 Α-23 S-9 ΡΑ-1 2,000 Good Practice A-24 Α-24 S-10 ΡΑ-1 2,000 Good Practice A-25 Α-25 S-11 ΡΑ-1 2,000 Good Practice A-26 Α- 26 S-12 ΡΑ-1 2,000 Good Practice A-27 Α-27 S-13 ΡΑ-1 2,000 Good Practice A-28 Α-28 S-14 ΡΑ-1 2,000 Good Practice A-29 Α-29 S -15 ΡΑ-1 2,000 Good Practice A-30 Α-30 S-16 ΡΑ-1 2,000 Good-96- 201033253 Continued on Table 2

Liquid crystal alignment agent name or your opportunity, other polymer storage stability, type of siloxane, amount (parts by weight) Example A-31 Α·31 S-17 ΡΑ-1 2,000 Good example A-32 Α-32 S-18 ΡΑ-1 2,000 Good Example A-33 Α-33 S-19 ΡΑ-1 2,000 Good Practice A-34 Α-34 S-20 ΡΑ-1 2,000 Good Practice A-35 Α- 35 S-21 ΡΑ-1 2,000 Good Practice A-36 Α-36 S-22 ΡΑ-1 2,000 Good Practice A-37 Α-37 S-23 ΡΑ-1 2,000 Good Practice A-38 Α-38 S -24 ΡΑ-1 2,000 Good Example A-39 Α-39 S-25 ΡΑ-1 2,000 Good Practice A-40 Α-40 S-26 ΡΑ-1 2,000 Good Practice A-41 Α-41 S-27 ΡΑ-1 2,000 Good example A-42 Α-42 S-28 ΡΑ-1 2,000 Good example A-43 Α-43 S-29 ΡΑ-1 2,000 Good example A-44 Α-44 S-30 ΡΑ- 1 2,000 Good example A-45 Α-45 S-31 ΡΑ-1 2,000 Good example A-46 Α-46 S-32 ΡΑ-1 2,000 Good example A-47 Α-47 S-33 ΡΑ-1 2,000 Good example A-48 Α-48 S-34 ΡΑ-1 2,000 Good example A-49 Α-49 S-35 ΡΑ-1 2,000 Good Example A-50 Α-50 S-36 ΡΑ-1 2,000 Good Example A-51 Α-51 S-37 ΡΑ-1 2,000 Good Example A-52 Α-52 S-38 ΡΑ-1 2,000 Good Example A-53 Α-53 S-39 ΡΑ-1 2,000 Good Example A-54 Α-54 S-40 ΡΑ-1 2,000 Good Practice A-55 Α-55 S-41 ΡΑ-1 2,000 Good Example A- 56 Α-56 S-41 ΡΑ-2 2,000 Good Practice A-57 Α-57 S-41 ΡΑ-3 2,000 Good Practice A-58 Α-58 S-41 ΡΑ-4 2,000 Good Practice A-59 Α -59 S-41 ΡΑ-5 2,000 Good Example A-60 Α-60 S-41 ΡΜ 2,000 Good-97- 201033253 Table 2 Continuation of Radiation Linear Polyorganic Other Polymer Preservation Stability Liquid Crystal Alignment Agent Name 矽 烷Types and amounts (parts by weight) Example A-61 A-61 S-41 PI-2 2,000 Good example A-62 A-62 S-41 PI-3 2,000 Good example A-63 A-63 S-41 PI-4 2,000 Good Example A-64 A-64 S-41 PI-5 2,000 Good Practice A-65 A-65 S-41 PI-6 2,000 Good Practice A-66 A-66 S-41 PI- 7 2,000 Good Practice A-67 A-67 S-41 PI-8 2,000 Good Practice A-68 A-68 S-41 PI-9 2,000 Good Example A-69 A-69 S-41 PS-1 2,000 Good Example A-70 A-70 S-41 PA-4 500 Good Practice A-71 A-71 S-41 PA-4 1,000 Good Practice A-72 A-72 S-42 PA-1 2,000 Good Practice A-73 A-73 S-43 PA-1 2,000 Good Practice A-74 A-74 S-44 PA-1 2,000 Good Practice A- 75 A-75 S-45 PA-1 2,000 Good Practice A-76 A-76 S-46 PA-1 2,000 Good Practice A-77 A-77 S-46 PA-2 2,000 Good Practice A-78 A -78 S-46 PA-3 2,000 Good Practice A-79 A-79 S-46 PA-4 2,000 Good Practice A-80 A-80 S-46 PA-5 2,000 Good Practice A-81 A-81 S-46 PI-1 2,000 Good Example A-82 A-82 S-46 PI-2 2,000 Good Practice A-83 A-83 S-46 PI-3 2,000 Good Practice A-84 A-84 S- 46 PI-4 2,000 Good Practice A-85 A-85 S-46 PI-5 2,000 Good Practice A-86 A-86 S-46 PI-6 2,000 Good Practice A-87 A-87 S-46 PI -7 2,000 Good Practice A-88 A-88 S-46 ΡΪ-8 2,000 Good Practice A-89 A-89 S-46 PI-9 2,000 Good Practice A-90 A-90 S-46 PS-1 2,000 Good-98- 201033253 Table 2 continued liquid crystal alignment agent name Types of linear polyorganosiloxanes Other polymer storage stability Types (parts by weight) 窨 Example A-91 A-91 S-46 PA-4 500 Good example A-92 A-92 S-46 PA- 4 1,000 Good A-93 A-93 S-47 PA-4 2,000 Good A-94 A-94 S-47 PI-6 2,000 Good Practice A-95 A-95 S-48 PA- 4 2,000 Good Practice A-96 A-96 S-48 ΡΪ-6 2,000 Good Practice A-97 A-97 S-49 PA-4 2,000 Good Practice A-98 A-98 S-49 PI-6 2,000 Good example A-99 A-99 S-50 PA-4 2,000 Good example A-100 A-100 S-50 PI-6 2,000 Good example A-101 A-101 S-51 PA-4 2,000 Good implementation Example A-102 A-102 S-51 ΡΙ·6 2,000 Good Practice A-103 A-103 S-52 PA-4 2,000 Good Practice A-104 A-104 S-52 PI-6 2,000 Good Practice A -105 A-105 S-53 PA-4 2,000 Good Practice A-106 A-106 S-53 PI-6 2,000 Good Practice A-107 A-107 S-54 PA-4 2,000 Good Practice A-108 A-108 S-54 PI-6 2,000 Good Practice A-109 A-109 S-55 PA-4 2,000 Good

<Manufacturing and Evaluation of Liquid Crystal Display Element> Example D-1 [Formation of Liquid Crystal Alignment Film and Production of Liquid Crystal Display Element] 液晶 The liquid crystal alignment agent prepared in the above Example A-1 was applied by a spin coater (A) -1) Coating on a transparent electrode surface of a glass substrate with a transparent electrode made of IT film, pre-baking on a hot plate at 80 ° C for 1 minute, and then performing an atmosphere of nitrogen gas in the chamber The film was heated at 200 ° C for 1 hour to form a film having a film thickness of Ο. ίμιη. Then, by using a Hg-Xe lamp and a Glan-Taylor prism, the surface of the coating film was irradiated with 20 (U/m2 polarized ultraviolet rays containing 313 nm bright lines) in a direction inclined by 40° from the substrate normal line to prepare a liquid crystal alignment film. The operation 'produces a pair of (two pieces) base-99-201033253 plate having a liquid crystal alignment film. On the periphery of the surface of the substrate having the liquid crystal alignment film on the substrate, the diameter is added by screen printing After the epoxy resin binder of the alumina sphere of 5.5 μm, the liquid crystal alignment film faces of the pair of substrates are opposed to each other, and the projection directions of the ultraviolet light axes of the respective substrates on the substrate surface are reversed and pressed together. Further, the adhesive was thermally cured at 150 ° C for 1 hour. Then, a negative liquid crystal (manufactured by Merck, MLC-6608) was charged from the liquid crystal injection port to the gap between the substrates, and an epoxy group was used. The adhesive closes the liquid crystal injection port, and in order to eliminate the flow alignment during liquid crystal injection, it is heated at 150 ° C and then slowly cooled to room temperature. Then, the polarizing plate is attached to both sides of the substrate to be measured. Polarized light The liquid crystal display element was produced to be perpendicular to each other and at an angle of 45° with respect to the projection direction of the ultraviolet light axis of the liquid crystal alignment film on the substrate surface. The liquid crystal display element was evaluated by the following method. Table 3 (1) Evaluation of liquid crystal alignment property The liquid crystal display element manufactured above was observed by an optical microscope when there was an abnormality in the change of brightness and darkness when the voltage of 5 V was ON'OFF (applied and released) at room temperature, and there was no abnormal region. The evaluation was "good." (2) Evaluation of the pretilt angle According to the method described in Non-Patent Document 5 (TJ Scheffer et al., J. Appl. Phys., Vol. 19, 2013 (1980)), by using ^_; The crystal rotation method of the laser was used to measure the pretilt angle -100-201033253 of the liquid crystal display element manufactured above. (3) Evaluation of voltage holding ratio At an ambient temperature of 60 ° C, within a time span of 167 msec, The manufactured liquid crystal cell was applied with a voltage of 5 V for an application time of 60 μsec, and then the voltage holding ratio from the voltage release to 167 msec was measured. The measuring device was "VHR" manufactured by Dongyang Techniker Co., Ltd. -1" type. (4) Evaluation of pretilt stability The liquid crystal display element manufactured above was set at 23. (3 days after storage for 3 days, the pretilt angle was measured again. When the amount of change from the initial flaw was less than 1 °' The pretilt stability was evaluated as "good." Examples D-2 to D-109 In addition to the type of liquid crystal alignment agent used, a liquid crystal alignment film was formed in the same manner as in the stomach example D-1 in Table 3, and a liquid crystal display element was produced. The results are not shown in Table 3. -101 - 201033253 Table 3 Liquid crystal alignment agent type Liquid crystal display element Liquid crystal alignment pretilt angle (°) Voltage retention ratio (%) Pretilt stability Example D1 A-1 Good 89 98 Good Example D-2 A-2 Good 89 98 Good Practice D-3 A-3 Good 88 98 Good Practice D-4 A-4 Good 88 98 Good Practice D-5 A-5 Good 88 98 Good Example D-6 A-6 Good 88 98 Good Example D-7 A-7 Good 88 98 Good Practice D-8 A-8 Good 88 98 Good Practice D-9 A-9 Good 88 98 Good Practice D-10 A-10 Good 88 98 Good Practice Dl 1 A-11 Good 88 98 Good Practice D-12 A-12 Good 88 98 Good Practice D-l3 A-13 Good $8 98 Good Practice D-14 A-14 Good 88 98 Good Practice D-15 A-15 Good 88 98 Good Practice D-l6 A-16 Good 88 98 Good Example D-17 A-17 Good 88 98 Good Practice D-l8 A-18 Good 88 98 Good Practice D-19 A-19 Good 88 98 Good Practice D-20 A-20 Good 88 98 Good Practice Example D-21 A-21 Good 88 98 Good Example D-22 A-22 Good 89 98 Good Practice D-23 A-23 Good 89 98 Good Practice D-24 A-24 Good 88 98 Good Practice D -25 A-25 Good 88 98 Good Example D-26 A-26 Good 88 98 Good Practice D-27 A-27 Good 88 98 Good Practice D-28 A-28 Good 88 98 Good Practice D-29 A-29 Good 88 98 Good Practice D-30 A-30 Good 88 98 Good-102- 201033253 Continued on Table 3

Liquid crystal alignment agent type Liquid crystal display element Liquid crystal alignment pretilt angle (.) Voltage retention ratio (%) Pretilt stability Example D-31 A-31 Good 88 98 Good example D-32 A-32 Good 89 98 Good implementation Example D-33 A-33 Good 89 98 Good Example D-34 A-34 Good 88 98 Good Practice D-35 A-35 Good 88 98 Good Practice D-36 A-36 Good 88 98 Good Practice D -37 A-37 good 89 98 good example D-38 A-38 good 89 98 good example D-39 A-39 good 88 98 good example D-40 A-40 good 88 98 good example D-41 A-41 Good 88 98 Good Example D-42 A-42 Good 88 98 Good Practice D-43 A-43 Good 88 98 Good Practice D-44 A-44 Good 88 98 Good Practice D-45 A- 45 good 88 98 good example D-46 A-46 good 89 99 good example D-47 A-47 good 89 99 good example D-48 A-48 good 88 - 99 good example D-49 A-49 Good 88 99 Good Example D-50 A-50 Good 88 99 Good Practice D-51 A-51 Good 89 99 Good Practice D-52 A-52 Good 89 99 Good Example D-53 A-53 Good 88 99 Good Practice D-54 A-54 Good 88 99 Good Practice D-55 A-55 Good 88 99 Good Practice D-56 A-56 Good 88 99 Good Practice D-57 A-57 Good 88 99 Good Practice D-58 A-58 Good 88 99 Good Practice D-59 A-59 Good 88 99 Good Practice D-60 A-60 Good 88 99 Good.im - 201033253 Table 3 continued liquid crystal display element fixHB 0ul〇J m type liquid crystal alignment pretilt angle (°) voltage retention rate (%) pretilt stability example D-61 A-61 good 88 99 good example D-62 A-62 Good 88 99 Good Practice D-63 A-63 Good 88 99 Good Practice D-64 A-64 Good 88 99 Good Practice D-65 A-65 Good 88 99 Good Practice D-66 A-66 Good 88 99 Good Example D-67 A-67 Good 88 99 Good Practice D-68 A-68 Good 88 99 Good Practice D-69 A-69 Good 88 99 Good Practice D-70 A-70 Good 88 99 Good Example D-71 A-71 Good 88 99 Good Practice D-72 A-72 Good 88 99 Good Practice D-73 A-73 Good 89 99 Good Practice D-74 A-74 Good 89 99 Good example D-75 A-75 Good 88 99 Good example D-76 A-76 Good 88 99 Good example D-77 A-77 Good 88 99 Good example D-78 A-78 Good 88 99 Good Example D-79 A-79 Good 88 99 Good Practice D-80 A-80 Good 88 99 Good Practice D-81 A-81 Good 88 99 Good Practice D-82 A-82 Good 88 99 Good Practice Example D-83 A-83 Good 88 99 Good Practice D-84 A-84 Good 88 99 Good Practice D-85 A-85 Good 88 99 Good Practice D-86 A-86 Good 88 99 Good Practice D -87 Α·87 Good 88 99 Good example D-88 A-88 Good 88 99 Good example D-89 A-89 Good 88 99 Good example D-% A-90 Good 88 99 Good-104- 201033253 Table 3 continued liquid crystal alignment agent type liquid crystal display element liquid crystal alignment pretilt angle (. Voltage holding ratio (%) Pretilt stability Example D-91 A-91 Good 88 99 Good example D-92 A-92 Good 88 99 Good example D-93 Α·93 Good 88 99 Good example D -94 Α-94 good 88 99 good example D-95 Α-95 good 88 99 good example D-96 Α-96 good 88 99 good example D-97 Α-97 good 87 99 good example D-98 Α-98 good 88 99 good example D-99 Α-99 good 87 99 good example D-100 Α-100 good 88 99 good example D-101 Α-101 good 88 99 good example D-102 Α- 102 good 89 99 good example D-103 Α-103 good 87 99 good example D-104 Α-104 good 88 99 good example D-105 Α-105 good 87 99 good example D-106 Α-106 good 88 99 Good Practice D-107 Α-107 Good 88 99 Good Practice D-108 Α-108 Good 88 99 Good Practice D-109 Α-109 Good 88 99 Good

Example T-1 A liquid crystal alignment agent (A-46) prepared in the above Example A-46 was applied onto a transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film by a spin coater at 80 After prebaking for 1 minute on a hot plate of ° C, the film was heated at 210 ° C for 20 minutes in an oven purged with nitrogen gas to form a coating film having a film thickness of 80 nm. The ToF-SIMS measuring device manufactured by ULVAC-PHI Co., Ltd. uses a Bi3 + + ion cluster with an accelerating voltage of 25 kV as an ion source, and the ion field is 0.05 pA, and the field of view is ΙΟΟμιη, and the measurement quality range is 0 to 1850 amu. Next, repeat the C6G sputtering on the coating film formed above and -105 - 201033253

ToF-SIMS analysis was performed until the detection of indium ions from ITO was performed. The time point at which the indium ions were detected was regarded as having reached a depth of 8 〇 nm from the surface of the coating film, and the composition distribution in the thickness direction of the coating film was investigated. At this time, the curves showing the distribution of the segments of m/z = 231 are shown in Fig. 1 (existence distribution) and Fig. 2 (cumulative 値). In addition, the curves shown in these figures are curves obtained by assigning the count number of the segments at each depth to the measurement noise level. The fragment of the above m/z = 231 is considered to correspond to the fragment represented by the following formula derived from the cinnamic acid derivative (2-4-2).

CF3C3H6O Therefore, from the results of Fig. 1, it can be strongly inferred that in the coating film formed in the present embodiment, the group derived from the (A) cinnamic acid derivative exists at the highest concentration at the surface of the coating film, and is biased in the coating film. From the surface to a range of about 20% of the thickness (up to 30%). BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the distribution of the presence of a fragment of m/z = 231 observed by ToF-SIMS in the film thickness direction in Example T-1. Fig. 2 is a graph showing the cumulative enthalpy distribution of the fragments of m/z = 231 observed by ToF-SIMS in the film thickness direction in Example T-1. [Main component symbol description] None. -106-

Claims (1)

201033253 VII. Patent application scope: 1. A liquid crystal alignment agent characterized by containing a radiation sensitive polyorganosiloxane, the radiation linear polyorganosiloxane being selected from the group consisting of the following formula (1) At least one of the group consisting of a polyorganosiloxane of a unit, a hydrolyzate thereof, and a condensate of a hydrolyzate, and (A) having a group consisting of a carboxyl group, a hydroxyl group, -811, -:^(:0, -1^11 (wherein R is a hydrogen atom or a carbon number of 1 to 6), -CH = CH2 and -SO2CI a cinnamic acid derivative of at least one group in the group and (B) having a terminal group selected from a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), CH = CH2 and - S02C1 at least one group in the group and the compound of the photo-sensitizing structure are reacted to obtain X1 · -Si-0 - (1) II Y1 J (in formula (1), X1 a monovalent organic group having an epoxy group, γ1 is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms) 2. The liquid crystal alignment agent of claim 1, wherein the (A) cinnamic acid derivative is a compound represented by the following formula (2) or a compound represented by the following formula (3), r1-r2-( R3-r4)^/= CH=CH——丨Ο R5—R6 (2) (In the formula (2), R1 is a 3-107-201033253 monovalent organic group having an alicyclic group and having a carbon atom number of 3 to 40, or carbon An alkyl group having 1 to 40 atoms, wherein some or all of the hydrogen atoms of the above alkyl group may be substituted by a fluorine atom ' R 2 is a single bond, an oxygen atom, -COO- or - OCO-, and R 3 is a divalent aromatic group. a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group, R 4 is a single bond, an oxygen atom, -COO- or - OCO-, and R 5 is a single bond, An oxygen atom, a sulfur atom, a methylene group, an alkylene group having 2 to 10 carbon atoms or a divalent aromatic group. When R5 is a single bond, t is 1, and R6 is a hydrogen atom, when R5 is When methylene, alkylene or divalent aromatic groups, t is 0 or 1, and R6 is carboxy, hydroxy, -SH, -NCO, -NHR, -CH=CH2 or -S02C1, wherein R Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R7 is a fluorine atom or a cyano group, a is an integer of 0 to 3, and b is an integer of 0 to 4), ^==^R10_R11^_R12_R13 R8_R9_c_ch=ch —/ J c (3) & ^^(R14)d (in equation (3), R8 is contained a cyclic group having a monovalent organic group having 3 to 40 carbon atoms or a group having 1 to 40 carbon atoms, wherein some or all of the hydrogen atoms of the above alkyl group may be substituted by a fluorine atom, and R9 is An oxygen atom or a divalent aromatic group, R1() is an oxygen atom, _OCO-, R11 is a divalent aromatic group, a divalent heterocyclic group fluorene or a divalent fused ring group, R12 Is a single bond, -〇C〇-(CH2)e-* or -〇-(CH2)g-*' wherein each of e and g above is an integer of 1 to 1 ,, each representing a linkage with it and R13 R13 is a fluorenyl group, a hydroxyl group, -SH, -NCO, -NHR, -CH=CH2 or -S02C1, wherein the above R is -108-201033253 hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R14 is A fluorine atom or a cyano group, c is an integer of 0 to 3 'd is an integer of 0 to 4). 3. The liquid crystal alignment agent of the first aspect of the invention, wherein the X1 group in the above formula (1) is a group represented by the following formula (Χ1-^ or (X1 - 2), (X1-2) (in the above formula, it is represented as a connection key). 4. The liquid crystal alignment agent of claim 1, wherein (B) the photo-sensitizing structure in the compound having a photo-sensitizing structure is selected from the group consisting of an acetophenone structure and a benzophenone structure. At least one of the group consisting of a biphenyl structure, a carbazole structure, a nitroaryl structure, an anthracene structure, a naphthalene structure, an anthracene structure, an acridine structure, and an anthracene structure. 5. The liquid crystal alignment agent according to any one of claims 1 to 4, wherein Further, at least one polymer selected from the group consisting of polylysine and polyimine is contained. The liquid crystal alignment agent of any one of Claims 1 to 4 which further consists of a polyorganooxane represented by the following formula (4), a hydrolyzate and a hydrolyzate condensate. At least one of the groups, "X2 - -Si-Ο-- (4) IL γ2 J (in the formula (4), X2 is a radical, a halogen atom, a hospital having a carbon number of 1 to 20 - 109 - 201033253, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms, and Y2 being a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms). A method for forming a liquid crystal alignment agent according to any one of claims 1 to 6 to form a coating film on the substrate, and irradiating the coating film with radiation. 8. A liquid crystal alignment film, It is characterized in that it is formed of a liquid crystal alignment agent according to any one of claims 1 to 6. 9. A liquid crystal alignment film characterized in that the group derived from the (A) cinnamic acid derivative is biased from The surface of the liquid crystal alignment film is in the range of 30% of the thickness. 10. A liquid crystal display element characterized by having A liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of the above items 1 to 6. 11. A radiation sensitive polyorganosiloxane having a repeating unit selected from the group consisting of the above formula (1) At least one of the group consisting of a polyorganosiloxane, a condensate of the hydrolyzate thereof and the hydrolyzate, and (A) having a group selected from the group consisting of a carboxyl group, a hydroxyl group, -SH, -NCO, and -NHR (wherein R is a hydrogen atom) Or a cinnamic acid derivative of at least one group of a group consisting of an alkyl group having 1 to 6 carbon atoms, -CH=CH2 and -S02C1, and (B) having a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), at least one group of -CH = CH2 and -S02C1 reacts with a compound of a photo-sensitizing structure Made. -110-