TW201031689A - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent showing good liquid crystal alignment capacity through photo-alignment method with few exposure amounts and capable of forming liquid crystal film with excellent performances such electrical property. The above-mentioned liquid crystal alignment agent comprises radio-sensitive polyorganosiloxane having the specific group represented by the following formula: (wherein, ''*'' represents a binding bond). The liquid crystal alignment agent of the present invention preferably can be used in a liquid crystal element having liquid crystal cell of TN type, STN type or IPS type, especially a transverse electric field liquid crystal element having liquid crystal cell of IPS type.

Description

201031689 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, 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 Continuously twisting T~3 60° TN type (twisted nematic) and STN (super twisted nematic) type, IPS (in-plane switching) in which an electrode is formed only on one side of the substrate and an electric field is applied in a direction parallel to the substrate A liquid crystal display element of various liquid crystal cells such as a VA (vertical alignment) type having nematic liquid crystal having negative dielectric anisotropy (see Patent Documents 1 to 4). Among the above, a liquid crystal display element having an IPS type liquid crystal cell is known as a liquid crystal display element of a lateral electric field type. In such a liquid crystal cell, in order to align liquid crystal molecules in a certain direction with respect to the substrate surface, it is necessary to provide a liquid crystal alignment film on the surface of the substrate. Such an e-liquid crystal alignment film is usually formed by a method (grinding method) of rubbing a surface of an organic film formed on a surface of a substrate in a certain direction with a fabric such as rayon, in a TN type, an STN type, or an IPS type liquid crystal cell. However, when the formation of the liquid crystal alignment film is performed by the rubbing treatment, there is a problem in that dust and static electricity are easily generated in the polishing process, and dust adheres to the surface of the alignment film, which causes a display failure, and the TFT is provided. In the case of the substrate of the (thin film transistor) element, there is a problem that the generated static electricity causes damage to the TFT element circuit, which causes a decrease in product yield. Further, in the liquid crystal display element which is in the trend of increasing precision in the future, the unevenness which is inevitably generated on the surface of the substrate due to the high density of the pixels in the case of the high density of the pixels, so that the polishing process is performed uniformly It is getting harder and harder. Then, as another method of aligning the liquid crystal in the liquid crystal cell, a photo-alignment method in which a photosensitive organic thin film formed on the surface of the substrate is irradiated with a polarized or non-polarized ray to generate a liquid crystal alignment energy has been proposed (see Patent Document 5 to 15). It is said that if this method is employed, static electricity and powder dust are not generated, and uniform liquid crystal alignment can be achieved. This technology can be applied to VA type liquid crystal cells in addition to TN type, STN type, and IPS type liquid crystal cells. In recent years, it has been reported that a liquid crystal alignment film having good electrical properties can be obtained by a photo-alignment method by using a specific azo compound in a liquid crystal alignment agent used in a TN type liquid crystal cell (Patent Document 16). However, according to this technique, in order to form a liquid crystal alignment film, a high cumulative exposure amount of 10000 J/m 2 or more is required, and the degree of damage of the exposure apparatus with time is large, and the manufacturing cost of the liquid crystal alignment film is greatly increased. problem. On the other hand, it has been reported that a liquid crystal alignment agent containing a polymer having a specific long-chain structure or a cyclic structure Q can form a liquid crystal alignment film excellent in liquid crystal alignment and electrical properties by a photo-alignment method having a small exposure amount (patent Documents 17 to 19). This technique, when applied to a liquid crystal display element having a VA type liquid crystal cell, is an excellent technique capable of easily and inexpensively forming a liquid crystal alignment film having desired properties, but when applied to a TN type, an STN type, or an IPS type When the liquid crystal display element of the liquid crystal cell is used, the liquid crystal alignment property is not necessarily sufficiently good. When applied to a liquid crystal display element having a TN type, STN type or IPS type liquid crystal cell, in particular, an IPS type liquid crystal display element, a liquid crystal alignment film excellent in liquid crystal alignment and electrical properties can be formed by an optical irradiation method with a small exposure amount of 201031689. Liquid crystal alignment agent is still unknown. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. s. Japanese Laid-Open Patent Publication No. 2000- 1441 No. PCT Publication No. JP-A No. 2000-A No. PCT Publication No. JP-A No. 2000-281724 Japanese Laid-Open Patent Publication No. 2004-163646, Japanese Patent Application Laid-Open No. Hei. Patent Document 17 International Publication No. 2009/0 25385 pamphlet Patent Document 18 International Publication No. 2009/025386 pamphlet Patent Document 19 International Publication No. 2009/025 3 8 8 pamphlet patent document Japanese Patent Application Laid-Open No. SHO-63-119 No. 922 Publication No. 201031689 Non-Patent Document Non-Patent Document IChemical Reviews, 95, P1409 (1995) SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The present invention has been made in view of the above circumstances. The purpose of the present invention is to provide a liquid crystal display element having a TN type, an STN type or an IPS type liquid crystal cell, and a light alignment method having a small exposure amount, which can form a liquid crystal with good display performance and excellent electrical properties. A liquid crystal alignment agent for a liquid crystal alignment film. Another object of the present invention is to provide a liquid crystal alignment film and a liquid crystal display element having excellent properties as described above. Other objects and advantages of the invention will be apparent from the description which follows. Means for Solving the Problems According to the present invention, the above objects and advantages of the present invention, first, are achieved by a φ liquid crystal alignment agent containing a respective expression selected from the following formulas (A1') and (A2') a radiation-sensitive polyorganosiloxane having at least one group in the group consisting of groups,

201031689 (In the formula (A 1 '), R is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluorine atom or a cyano group, and R1 is a stretching phenyl group or a cyclohexylene group, wherein the above stretching phenyl group or a stretching ring A part or all of a hydrogen atom of a hexyl group may be substituted by a fluorine atom or a cyano group, and R 2 is a single bond, a methylene group, an alkylene group having 2 or 3 carbon atoms, an oxygen atom, a sulfur atom, -CH=CH· or -NH-, a is an integer of 0 to 3. When a is 2 or 3, a plurality of R1 and R2 may be the same or different, R3 is a fluorine atom or a cyano group, and b is an integer of 0 to 4. , in the formula (A2'), R' is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluorine atom or a cyano group, and R4 is a phenyl group or a cyclohexyl group, wherein the above phenyl group Or a part or all of the hydrogen atom of the cyclohexyl group may be substituted by a fluorine atom or a cyano group, and R5 is a single bond, a methylene group, an alkylene group having 2 or 3 carbon atoms, an oxygen atom, a sulfur atom or -NH- , c is an integer of 1 to 3 'When c is 2 or 3, a plurality of R 4 and R 5 may be the same 'may be different' R 6 is a fluorine atom or a cyano group, and d is an integer of 0 to 4 ' R 7 is Oxygen atom , -coo_ + or -〇CO- + (where 'the above linkage with "+" is linked to R8). R8 is a divalent aromatic group, a divalent alicyclic group, a divalent hetero A cyclic group or a divalent fused ring group 'R9 is a single bond, +-OCO-(CH〇f- or +-CMCH2), -(wherein the above-mentioned linkage with "+" is located at - (R7 -R8)e - side '[and 2 are integers of 1 to ίο, respectively), and e is an integer '0' and represents a connection key). The above objects and advantages of the present invention, and secondly, are achieved by a liquid crystal alignment film formed of the above liquid crystal alignment agent. Third, it is achieved by a liquid crystal display element having the above liquid crystal alignment film. 201031689 Effect of the Invention The liquid crystal alignment agent of the present invention is applied to a liquid crystal display element having a TN type, STN type or IPS type liquid crystal cell, particularly a horizontal electric field type liquid crystal display element having an IPS type liquid crystal cell, and has a small exposure amount. The photo-alignment method can form a liquid crystal alignment film which exhibits excellent liquid crystal alignment energy and excellent electrical properties and the like. The liquid crystal display element of the present invention having the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention can be effectively applied as various display devices because it can realize high-quality display and is inexpensive. [Embodiment] The liquid crystal alignment agent of the present invention contains a radiation-sensitive polyorganosiloxane having at least one group selected from the group represented by the above formulas (A1') and (A2'). alkyl. <Rain-sensitive linear polyorganosiloxane> The radiation-sensitive polyorganosiloxane having a liquid crystal alignment agent of the present invention has a group selected from the group consisting of the above formulas (A1') and (A2'). At least one group in the group. The alkyl group having 1 to 3 carbon atoms in R in the above formula (A1') and R' in the above formula (A2') is preferably a methyl group, an ethyl group or a n-propyl group. The phenyl and cyclylene groups of R1 in the above formula (A1') and R4 in the above formula (A2') are preferably each a 1,4-phenylene group or a 1,4-cyclohexylene group. R2 in the above formula (A1') is preferably a single bond, an oxygen atom or _ch = CH-. Examples of the divalent aromatic group of R* in the above formula (A2') include 201031689, for example, 1,4 _phenylene or 4,4 '-biphenyl, etc.; as a divalent alicyclic group The group may, for example, be a 1,4-cyclohexylene group, a 4,4'-dicyclohexyl group or the like; and as the divalent heterocyclic group, for example, furan-2,5-diyl, thiophene-2,5 -diyl, 2,2'-dithiophene-5,5-diyl, etc.; as a divalent fused ring group, for example, anthracene-2,6-diyl, naphthalene-1,4-diyl , naphthalene-1,5-diyl, naphthalene-2,6-diyl, naphthalene 2,7-diyl, fluoren-9,10-diyl, carbazole-3,6-diyl, dibenzothiophene -2,8-diyl, etc. The e in the above formula (A2') is preferably 0. Specific examples of the group of the radiation-sensitive polyorganosiloxane which are contained in the liquid crystal alignment agent of the present invention, as the group represented by the above formula (A1'), for example, a group represented by the following formula ; -10- 201031689

-11- 201031689

-12- 201031689 ο

-13- 201031689

-14- 201031689

-15- 201031689

〇—*

ο

-16- 201031689 ο

-17- 201031689

-18- 201031689

-19- 201031689

-20- 201031689 ο

-21 - 201031689 〇—*

-22- 201031689

(The above is a "link"). The group represented by the above formula (A2') may, for example, be a group represented by the following formula.

-23- 201031689 ο

-24- 201031689

-25- 201031689

-26-

-27- 201031689

Coo—*

Coo—*

Coo—*

Coo—*

Coo—*

Coo—*

Coo—*

Coo-氺

Coo—* -28- 201031689

-29- 201031689

201031689

-31 - 201031689 ❹

-32- 201031689 〇

Coo—*

-33- 201031689

(wherein the above "represents a bonding bond". In the radiation-induced linear narrowing contained in the liquid crystal alignment agent of the present invention, at least one group selected from the group domains represented by the above formulas (A1') and (A2') The content ratio is preferably 0.2 to 6 millimolar, more preferably 0.3 to 5 millimoles per gram of the polymer. The radiation-sensitive linear polyalkane contained in the liquid crystal alignment agent of the present invention is preferably selected from the above formula. (A1') and (A2') each have at least one group other than the group of β, and further have an epoxy group equivalent of an epoxy sensitizing radiopolyorganosiloxane, preferably more than 200 Å. ～1 0000 g/mol, more preferably 200 Å. Since the epoxy equivalent of the radiation-based oxoxane is used in this ratio, the liquid crystal alignment agent of the present invention can be used without impairing the storage stability of the agent. In this case, the liquid crystal alignment is more in the group of the organic siloxanes S; the ear/g polymerizes the organic oxime J group to form a base. At this time, 150 g/mole, 2000 g/mole polyorganic F liquid crystal alignment丨Excellent, residual -34- 201031689 Like a liquid crystal alignment film with excellent performance, it is Preferably, the weight average molecular weight of the polyphenylene styrene converted by the gel permeation chromatography is preferably 1000 to 200,000, more preferably, the radiation-sensitive polyorganophthalide contained in the liquid crystal alignment agent of the present invention. It is 2,000 to 10,000, particularly preferably 3,000 to 30,000. <Synthesis of Radiation-Tensored Polyorganooxane> The radiation-sensitive polyorganosiloxane contained in the liquid crystal alignment agent of the present invention is as described above. The radiation-sensitive polyorganosiloxane may be a radiation-sensitive polyorganosiloxane synthesized by any method. As a method for synthesizing the radiation-sensitive polyorganosiloxane contained in the liquid crystal alignment agent of the present invention, For example, a hydrolyzable decane compound having at least one group selected from the group consisting of a group represented by the above formula and (A2,) or a mixture of the hydrolyzable decane compound and another hydrolyzable decane compound a method of performing hydrolysis and condensation; forming a polyorgano oxane having an epoxy group with a compound selected from the group consisting of compounds represented by the following formulas (A1) and (A2) A method in one reaction.

(R, Ri, R2, R3, a and b in the formula (A1) are each the same as defined in the above formula (A1,); -35- 201031689 R', R4, R5, R6 in the formula (A2), R8, R9, c, d and e are each the same as defined in the above formula (A2'); wherein the latter method is preferably employed from the viewpoints of easiness of synthesis of the raw material compound, ease of reaction, and the like. Hereinafter, a polyorganosiloxane having an epoxy group and a method selected from the above formulas (A1) and (A2) are preferred as a preferred method for synthesizing a radiation-sensitive polyorganosiloxane contained in the liquid crystal alignment agent of the present invention. A method of at least one reaction in a group consisting of the respective compounds will be described. ® [Polyorganosiloxane having an epoxy group] The epoxy group in the polyorganosiloxane having an epoxy group, preferably contained in an ethylene oxide skeleton or a 1,2-epoxycycloalkane skeleton The form in the group (the group having an epoxy group) attached to the ruthenium atom directly or through an alkyl group interrupted by an oxygen atom is present in the polyorganooxane. The group having such an epoxy group may, for example, be a group represented by the following formula (EP-1) or (EP-2).

(In the formulae (EP-1) and (EP-2), the epoxy equivalent of the polyorganosiloxane having the epoxy group having the epoxy group is preferably from 1 10000 to 10,000 g/mole, more preferably 150~l〇〇〇g/mole. The polyorganosiloxane having an epoxy group is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography, preferably 500 to -36 to 201031689 100000. More preferably, it is from 1000 to 10000', particularly preferably from 1,000 to 5,000. The polyorganosiloxane having an epoxy group can be, for example, a decane compound having an epoxy group or a decane compound having an epoxy group and other decane compounds. The mixture is preferably synthesized by hydrolysis and condensation in the presence of a suitable organic solvent, water and a catalyst. As the above-mentioned decane compound having an epoxy group, for example, 3-glycidoxypropyltrimethoxydecane may be mentioned. , 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-epoxypropoxy methoxypropylmethyldiethoxydecane , 3-glycidoxypropyl dimethyl methoxy decane, 3-epoxypropoxy Dimethyl ethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltriethoxy decane, etc. Examples of the other decane compound include tetrachloromethane, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, tetra-n-butoxy decane, and fourth. Butoxy decane, trichloro decane, trimethoxy decane, triethoxy decane, tri-n-propoxy decane, triisopropoxy decane, tri-n-butoxy decane, tri-butoxy decane , fluorotrichloroguana, fluorotrimethoxydecane, fluorotriethoxydecane, fluorodi-n-propoxy decane, fluorotriisopropoxy decane, fluorotri-n-butoxysilane , fluorotrisium second butoxy decane, methyltrichlorodecane, methyltrimethoxy sand, methyltriethoxydecane, methyltri-n-propoxydecane, methyltriisopropoxydecane , methyl tri-n-butoxy decane, methyl tri-butoxylate, 2-(trifluoromethyl)ethyltrichlorodecane, 2-(trifluoromethyl)ethyltrimethoxy Alkane, 2-(trifluoromethyl)ethyltriethoxydecane, 2_(tri-37-201031689 fluoromethyl)ethyltri-n-propoxydecane, 2-(trifluoromethyl)ethyltriiso Propoxy decane, 2-(trifluoromethyl)ethyltri-n-butoxy decane, 2-(trifluoromethyl)ethyltri-n-butoxy decane, 2-(perfluorodecylhexyl)ethyl Trichlorodecane, 2-(perfluoro-n-hexyl)ethyltrimethoxydecane, 2-(perfluoro-n-hexyl)ethyltriethoxydecane, 2-(perfluoro-n-hexyl)ethyltri-n-propoxy Decane, 2-(perfluoro-n-hexyl)ethyltriisopropoxydecane, 2-(perfluoro-n-hexyl)ethyltri-n-butoxydecane, 2-(perfluoro-n-hexyl)ethyltri-second Oxydecane, 2-(perfluoro-n-octyl)ethyltrichlorodecane, 2-(perfluoro-n-octyl)ethyltrimethoxynonane, 2-(perfluoro-n-octyl)ethyltriethyl Oxydecane, 2-(perfluoro-n-octyl)ethyltri-n-propoxydecane, 2-(perfluoro-n-octyl)ethyltriisopropoxydecane, 2-(perfluoro-n-octyl) Tri-n-butoxy decane, 2-(perfluoro-n-octyl)ethyltri-n-butoxy decane, hydroxymethyltrichlorodecane, hydroxymethyl Methoxy decane, hydroxyethyl trimethoxy decane, methylol tri-n-propoxy decane, hydroxymethyl triisopropoxy decane, hydroxymethyl tri-n-butoxy decane, hydroxymethyl three second Oxydecane, 3-(meth)acryloxypropyltrichlorodecane, 3-(methylpyridyl)propenyloxypropyltrimethoxydecane, 3-(methyl)propenyloxypropyl Triethoxydecane, 3-(methyl)propenyloxypropyltri-n-propoxyoxydecane, 3-(methyl)propenyloxypropyltriethylisopropoxydecane, 3-(methyl Propylene methoxy propyl tri-n-butoxy decane, 3-(methyl) propylene methoxy propyl tri-tert-butoxy decane, 3-mercaptopropyl trichloro decane, 3-mercaptopropyl methacrylate Oxydecane, 3-mercaptopropyltriethoxydecane, 3-mercaptopropyltri-n-propoxyoxydecane, 3-mercaptopropyltriisopropoxydecane, 3-mercaptopropyltriazine Butoxy decane, 3-mercaptopropyltriamine tert-butoxydecane, decylmethyltrimethoxydecane, decylmethyltriethoxydecane, vinyltrichloromethane, -38- 201031689 vinyl trimethyl Oxydecane, vinyl triethoxy Base decane, vinyl tri-n-propoxy decane, vinyl triisopropoxy decane, vinyl tri-n-butoxy decane, vinyl tri-second butoxy decane, allyl trichloro decane, allyl Trimethoxy decane, allyl triethoxy decane, allyl tri-n-propoxy decane, allyl triisopropoxy decane, allyl tri-n-butoxy decane, allyl tri-second Butoxy decane, phenyl trichloro decane, phenyl trimethoxy decane, phenyl triethoxy decane, phenyl tri-n-propoxy decane, phenyl triisopropoxy decane, phenyl tri-n-butoxy Base decane, phenyl tri-tert-butoxy v-decane, methyl dichlorodecane, methyl dimethoxy decane, methyl diethoxy decane, methyl di-n-propoxy decane, methyl diisopropyl Oxy decane, methyl di-n-butoxy decane, methyl di-butoxy decane, dimethyl dichloro decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, dimethyl Di-n-propoxy decane, dimethyl diisopropoxy decane, dimethyl di-n-butoxy decane, dimethyl di-butoxy decane, [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-octane) Ethyl]di-butoxybutane, (methyl)(3-mercaptopropyl)dichlorodecane, (methyl)(3-mercaptopropyl)dimethoxydecane, (methyl) (3-mercaptopropyl)diethoxydecane, (methyl)(3-mercaptopropyl)di-n-propoxydecane, (methyl K3-mercaptopropyl)diisopropoxydecane , (methyl) (3-mercaptopropyl) di-n-butoxydecane, (methyl) (3-mercaptopropyl) di-butoxy decane, (methyl-39- 201031689) (ethylene (di) chlorodecane, (methyl) (vinyl) dimethoxy decane, (methyl) (vinyl) diethoxy decane, (methyl) (B) Di-n-propoxy decane, (methyl) (vinyl) diisopropoxy decane, (methyl) (vinyl) di-n-butoxy decane, (methyl) (vinyl) bis Butoxy decane, divinyl chlorodecane, divinyl dimethoxy decane, divinyl diethoxy decane, divinyl di-n-propoxy decane, divinyl diisopropoxy decane, Divinyldi-n-butoxydecane, divinyldi-butoxybutane, diphenyldichlorodecane, diphenyldimethoxydecane, diphenyldiethoxy® decane, diphenyl Di-n-propoxy decane, diphenyl diisopropoxy decane, diphenyl di-n-butoxy decane, diphenyl bis second butoxy decane, chlorodimethyl decane, methoxy dimethyl Base decane, ethoxy dimethyl decane, chlorotrimethyl decane, bromotrimethyl decane, iodotrimethyl decane, methoxy trimethyl decane, ethoxy trimethyl decane, n-propyl Oxy trimethyl decane, isopropoxy trimethyl decane, n-butoxy trimethyl decane, second butoxy trimethyl decane, third butyl Trimethyl decane, (chloro) (vinyl) dimethyl Φ decane, (methoxy) (vinyl) dimethyl decane, (ethoxy) (vinyl) dimethyl decane, (chlorine) a decane compound having one ruthenium atom such as (methyl)diphenyl decane, (methoxy) (methyl) diphenyl decane or (ethoxy) (methyl) diphenyl decane, and Also listed are trade names such as KC-89, KC-89S, X-213-1153, X-21- 5841, X-21- 5842, X-21- 5843, X-21- 5844, X-21-8455 , X - 21 - 5846, X - 21 - 5847, X - 21 - 5848, X - 22 - 160AS, X - 22 - 170B, X - 22 - 170BX, X - 22 - 170D, X - 22 - 170DX, X - 22 - 1 76B, X- 22- 176D, -40- 201031689 X - 22 - 176DX, X - 22 - 176F, X - 40 - 2308, X - 40 - 2651, 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 - 4 1 - 1 805 ' X - 41 - 1810 , KF600 1 ' KF 6002 , KF 6003 , KR212, KR-213, KR-217 'KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (above produced by Shin-Etsu Chemical Co., Ltd.); glass Resin (produced by Showa Denko Co., Ltd.); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above produced by D ow C or ni ng Tor ay) ; FZ3711, FZ3722 (above, produced by Unicar, Japan), 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-9931, XMS-5025 (above produced by Chisso); methyl decanoate MS51, 矽Methyl ester MS 56 (produced by Mitsubishi Chemical Co., Ltd.): Ethyl citrate 28, Ethyl citrate 40, Ethyl citrate 48 (above produced by Colcoat); GR100, GR65 0, GR908, A partial condensate such as GR950 (produced by Showa Denko Co., Ltd.). More than one of them can be used. As the other decane compound, among the above, it is preferably selected from the group consisting of tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, and 3-(methyl) propylene fluorenyloxy group. Propyltrimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, vinyltrimethoxydecane, -41 - 201031689 vinyltriethoxydecane, allyltrimethoxy Decane, allyloxydecane, phenyltrimethoxydecane, phenyltriethoxydecylpropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, 1,3-trimethoxydecane, fluorenyl One of the group consisting of triethoxy decane, dimethyl decane and dimethyl diethoxy decane. The synthesis of polyorganosiloxane having an epoxy group in the present invention is epoxy-based. The use ratio of the decane compound to other decane compounds is preferably adjusted so that the epoxy equivalent of the obtained polyorganosiloxane is adjusted to the range of upper v. In the case of synthesizing a polyorganosiloxane having an epoxy group, the organic solvent may be, for example, a hydrocarbon, a ketone, an ester, an ether or an alcohol, and examples thereof include the above-mentioned hydrocarbons, and examples thereof include the above-mentioned ketones such as toluene and xylene. For example, methyl ethyl ketone, methyl isobutyl sulfanyl ketone, diethyl ketone, cyclohexanone, etc. may be mentioned. Examples of the above esters include ethyl acetate and n-amyl acetate. And propylene glycol monomethyl ether acetate, 3-methoxybutyl ethyl lactate, etc.; as the ether, for example, ethylene glycol dimethyl ether, diethyl ether, tetrahydrofuran, dioxane, etc.; The class may, for example, be 1-hexanol, 4-methyl-2 ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , propylene glycol 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. Base triethyl, 3-anthracene thiol dimethylox or higher. In the case of, for example, there are classes and the like which are preferably used. As a ketone, a: butyl ester, an acid ester, an ethylene glycol-pentanol, an ethylene glycol mono-n-propyl-42-201031689 amount of an organic solvent's relative to 100 parts by weight of a total amount of a decane compound (refers to having an epoxy The total amount of the decane compound of the base and the other sandane compound to be used, the same applies hereinafter, preferably from 10 to 10,000 parts by weight, more preferably from 50 to 1,000 parts by weight. The amount of water used in the synthesis of the polyorganosiloxane having an epoxy group is preferably from 0.5 to 100 moles, more preferably from 1 to 30 moles, based on the total amount of the 1 moles of the compound. As the above catalyst, for example, an acid, an alkali metal compound, an organic base, a titanium compound, a chromium 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 a 1 to 2 amine such as ethylamine, diethylamine, piperidine, piperidine, pyrrolidine or pyrrole; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine or 4-di A tertiary organic amine such as methylaminopyridine or diazabicycloundecene or a 4-grade organic amine such as tetramethylammonium hydroxide. Among these organic bases, a tertiary amine such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine or 4-dimethylaminopyridine, or a tertiary amine such as tetramethylammonium hydroxide is preferred. As the catalyst for synthesizing the polyorganosiloxane having an epoxy group, an alkali metal compound or an organic base is preferred. By using an alkali metal compound or an organic base, side reactions such as ring opening of an epoxy group do not occur, and the desired polyorganosiloxane can be obtained at a rapid hydrolysis and condensation rate, so that the production stability is excellent, and thus it is Good. Further, the liquid crystal alignment agent of the present invention containing a reaction product of an epoxy group-containing polyorganosiloxane and a meat-43-201031689 cinnamic acid derivative synthesized using an alkali metal compound or an organic base as a catalyst is very stable in storage stability. Excellent, so it is very convenient. The reason for this is presumably, as described in Non-Patent Document 1 (Chemical Reviews, Vol. 95, pl 409 (1995)), because an alkali 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, thereby obtaining a polyorganosiloxane having a small content ratio of sterol groups. It is presumed that since the sterol group content ratio is small, the condensation reaction between the sterol groups can be suppressed, and when the liquid crystal alignment agent of the present invention further contains other polymers described below, the sterol group can be inhibited. The condensation reaction of other polymers gives a result of excellent storage stability. 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, the total amount of the 1 molar solvent is preferably 0.01 to 3 mol, more preferably 0.05 to 0.05. 1 mole. Hydrolysis and condensation reaction φ when synthesizing polyorganosiloxane having an epoxy group, preferably by dissolving a decane compound having an epoxy group and other decane compounds as needed in an organic solvent, the solution and the organic base Mixing with water is carried out by heating with a suitable heating device such as an oil bath. In the hydrolysis and condensation reaction, the heating temperature is preferably 130 ° C or lower, more preferably 40 to 100 ° C, preferably 0.5 to 12 hours, more preferably 1 to 8 hours. During the heating, the mixture may or may not be stirred, or the mixture may be placed under reflux. After completion of the reaction, it is preferred to wash the organic solvent layer separated from the reaction mixture with water. At the time of the washing, it is preferable to use a water containing a small amount of salt, for example, an aqueous solution containing 0.2% by weight of ammonium nitrate or the like, from the viewpoint of facilitating the washing operation at an angle of -44 - 201031689. The washing is carried out until the aqueous layer after washing is made 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-E01, DMS-E12, DMS-E21, and EMS-32 (the above are produced by Chisso Co., Ltd.). [Compound represented by each of the above formulas (A1) and (A2)] Specific examples of the compounds represented by the above formulas (A1) and (A2) are exemplified as the above formulas (A1') and (A2'). The carboxylic acid obtained by linking a hydrogen atom to the linkage of the group exemplified as the group. [Synthesis of Radiation-Tensible Polyorganosiloxane] The radiation-sensitive polyorganooxirane contained in the liquid crystal alignment agent of the present invention is preferably selected from the above-mentioned polyorganosiloxane having an epoxy group. At least one of the groups consisting of the compounds represented by the above formulas (A1) and (A2) is preferably reacted in the presence of a catalyst and an organic solvent, and can be easily produced. Wherein at least one selected from the group consisting of the compounds represented by the above formulas (A1) and (A2), and the total amount thereof is preferably 0.001 with respect to the one-mole earring group of the polyorganosiloxane. ~ 10 Moar, better 0 01 ~ 5 Mo Er, and even better 〇. 〇 5 ~ 2 Mo Er, Tejia 0.05 ~ 0.8 Moer ratio used. -45-201031689 As the above catalyst, a compound known as a so-called hardening accelerator which reacts with an organic hydrazine or an epoxy group compound and an acid anhydride can be used. The organic base may, for example, be a 1 to 2 amine such as ethylamine, diethylamine, pipe trap, piperidine, pyrrolidine or pyrrole; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-di a tertiary organic amine such as methylaminopyridine or diazabicycloundecene; a 4-grade organic amine such as tetramethylammonium hydroxide. Among these organic bases, a tertiary organic amine such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine or 4-dimethylaminopyridine; and a 4-grade organic amine such as tetramethylammonium hydroxide are preferred. Examples of the hardening accelerator include a tertiary amine such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, cyclohexyldimethylamine, and triethanolamine; Imidazole, 2-n-heptyl imidazole, 2-undecylimidazole, 2-phenyl φ imi, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1- Benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-(2·cyanoethyl)-2-methylimidazole, ι_(2- Cyanoethyl)-2-n-undecylimidazole, 1-(2-cyanoethyl)_2-phenylimidazole, ι_(2-cyanoethyl)-2-ethyl-4-methyl Dimethoate, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis(hydroxymethyl)imidazole, 1-(2-cyanoethyl)_2-benzene 4-,5-bis[(2'-cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl)_2-n-undecylimidazole key trimellitate, 1- (2-cyanoethyl)_2-phenylimidazole gun trimellitate, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazolium pyromellitate, 2, 4-diamino-6-[2,-methyl-46- 201031689 imidazolium _(1')]ethyl-s_tripper, 2,4-diamino-6-(2'-positive Monoalkylimidazolium)ethyl-s-trinyl, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolium-(indenyl)]ethyl-s-trisole, 2 - an isocyanuric acid addition product of methylimidazole, an isocyanuric acid addition product of 2-phenylimidazole, 2,4-diamino-6-[2'-methylimidazolium (oxime)]ethyl-s - an imidazole compound such as a three-pilled isocyanuric acid adduct; an organophosphorus compound such as diphenylphosphine, triphenylphosphine or triphenylphosphite; benzyltriphenyl chloride, tetra-n-butyl bromide Scale, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenyl bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltri Phenyl sulphate, tetrabutyl sulphate, ruthenium, osmium-diethyl dithiophosphate, tetra-n-butyl benzotriazole complex, tetra-n-butyl fluorene tetrafluoroborate, tetra-n-butyl 4-grade iron salt such as iron tetraphenylborate or tetraphenyltriphenylborate; 1,8-diazabicyclo[5.4.0]undec-7-ene, organic acid salt thereof, etc. Azabicycloalkenes; organic ruthenium complexes such as zinc octoate, tin octoate, acetonitrile aluminum complex; tetraethylammonium bromide, bromide a 4-grade ammonium salt such as n-butylammonium, 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; High-melting-point-dispersion latent curing accelerator such as dicyandiamide or an amine-forming accelerator such as an amine or an epoxy resin; and hardening promotion such as the above-mentioned imidazole compound, organic phosphine compound, or quaternary salt The surface of the agent is coated with a polymer-coated microcapsule type of latent hardening-47-201031689; amine salt type latent hardening accelerator; high temperature degradable thermal cationic polymerization type such as Lewis acid salt, Bronsted acid salt A latent hardening accelerator such as a hardening accelerator. Among them, a 4-grade ammonium salt such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetraethylammonium chloride or tetra-n-butylammonium chloride is preferred. The catalyst is used in a ratio of preferably 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, per 100 parts by weight of the polyorganooxime oxyalkylene having an epoxy group. The reaction of at least one of the polyorganosiloxane having an epoxy group and at least one selected from the group consisting of the compounds represented by the above formulas (A1) and (A2) can be carried out in the presence of an organic solvent, if necessary. Examples of such an organic solvent include hydrocarbon compounds, ethers, esters, ketones, guanamines, alcohols, and the like. Among them, ethers, esters or ketones are preferred from the viewpoints of solubility of raw materials and products and ease of refining of products. The solvent is preferably used in a ratio of the solid content φ concentration (the ratio of the weight of the component other than the solvent in the reaction solution to the total weight of the solution) of 0.1% by weight or more, more preferably 5 to 50% by weight. The reaction temperature is preferably from 0 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 synthesis of the radiation-sensitive polyorganosiloxane described above is carried out by a ring-opening addition of an epoxy group of a polyorganosiloxane having an epoxy group, and is selected from the above formula (A1') and A2') A method of at least one of the group -48-201031689 of the group represented by each group. This synthesis method is very simple, and is a very suitable method in terms of an introduction rate of at least one group selected from the group consisting of groups represented by the above formulas (A1') and (A2'). . <Other Components> The liquid crystal alignment agent of the present invention contains the radiation sensitive polyorganosiloxane described above. The liquid crystal alignment agent of the present invention may further contain other components in addition to the radiation-sensitive polyorgano V oxane 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 (excluding a radiation-sensitive polyorganosiloxane, hereinafter referred to as an "epoxy compound"), a functional decane compound (excluding a radiation-sensitive polyorganosiloxane), and a surfactant φ agent and so on. [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. Examples of such other polymers include at least one polymer selected from the group consisting of polylysine and polyimine, and polyorganosiloxanes other than the above-mentioned radiation-sensitive polyorganosiloxane (hereinafter Known as "other polyorganosiloxanes"), polyphthalates, polyesters, polyamines, cellulose derivatives, polyacetals, polystyrene derivatives, poly(styrene-phenyl malazone) Imine) derivative -49- 201031689 Bio, poly (meth) acrylate, etc. [Polyuric acid] The above polylysine can be produced by reacting a tetracarboxylic dianhydride with a diamine to prepare a tetracarboxylic dianhydride which can be used for the synthesis of the polyamic acid in the present invention, and examples thereof include aliphatic Tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, and the like. Specific examples of the aliphatic tetracarboxylic dianhydride include butane tetracarboxylic dianhydride and the like. Ο As the alicyclic tetracarboxylic dianhydride, for example, 1, 2, 3, 4 may be mentioned. - cyclobutane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3&,4,5,95-hexahydro-5-(tetrahydro-2,5 -dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, i,3,3a,4,5,9b-hexahydro-8-formam-5 -(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [i,2-c]-furan-1,3-dione, 3-oxabicyclo[3.2.1]octane- 2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)_3_methyl- 3-cyclohexene-1,2-dicarboxylic acid φ anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, 2,4,6 , 8-tetracarboxybicyclo[3.3.0]octane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3_1_0 2 6 ]undecane-3,5,8 In the above-mentioned aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride or the like can be mentioned. In addition to the above, tetracarboxylic dianhydrides listed in Patent Documents 丨 7 to 19 can also be used. As the tetracarboxylic dianhydride which can be used for the synthesis of the above polyamic acid, it is preferably a tetracarboxylic dianhydride containing an alicyclic tetracarboxylic dianhydride, and more preferably contains a selected from 2, 3, 5 - At least one tetracarboxylic dianhydride in the group consisting of tricarboxycyclopentyl acetic acid dianhydride and 12,3,4-cyclobutane tetra-50-201031689 carboxylic acid dianhydride, particularly preferably containing 2,3,5 a tetracarboxylic dianhydride of tricarboxycyclopentyl acetic acid dianhydride. As the tetracarboxylic dianhydride which can be used for the synthesis of the above polyamic acid, it is preferably contained in an amount of 10 mol% or more selected from 2,3,5-tricarboxycyclopentyl acetic acid dianhydride with respect to all of the tetracarboxylic dianhydride. And at least one tetracarboxylic dianhydride in the group consisting of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, more preferably 20 mol% or more, and most preferably only selected from 2, 3, At least one selected from the group consisting of 5-tricarboxycyclopentyl acetic acid dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride. ❹ As the diamine which can be used for the synthesis of poly-proline, for example, an aliphatic diamine, an alicyclic diamine, an aromatic diamine, a diamine organic oxime, or the like can be cited as a specific example, as an aliphatic group. Examples of the diamine include 1,1-m-xylylenediamine, 1,3-propanediamine, butanediamine, pentanediamine, hexamethylenediamine, and the like; as the alicyclic diamine, for example, 1, 4 -diaminocyclohexyl, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, etc.; as the aromatic diamine, for example, p-benzene Diamine, 4,4'-diamine φ-diphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4 , 4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,7-diaminopurine, 4,4'-diamine Diphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-di[4- (4-Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylene diisopropylidene) Aniline, 4,4'-(interphenylene) Isopropyl)diphenylamine, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine , 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminotrim, 3,6-diaminocarbazole, N-methyl-3,6--51 - 201031689 Diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, ΝΑ'-bis(4-aminophenyl) Benzidine, anthracene, Ν'·bis(4-aminophenyl)-indole, Ν'-dimethylbenzidine, 1,4-bis-(4-aminophenyl)-piperazine, 3,5 -diaminobenzoic acid, dodecyloxy-2,4-diaminobenzene, tetradecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diamino Benzene, cetyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene 'tetradecane Oxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, cetyloxy-2,5-diaminobenzene, octadecyloxy-2, 5-diamine benzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-2,4-diamino Benzene, cholesteryl-2,4-diaminobenzene, 3,5-di Cholesteryl benzoate, cholesteryl 3,5-diaminobenzoate, lanosteryl 3,5-diaminobenzoic acid, 3,6-bis(4-aminobenzoic acid)醯oxy)cholinane, 3,6-bis(4-aminophenoxy)cholestane, 4-(4'-trifluoromethoxybenzylideneoxy)cyclohexyl-3,5_ Diaminobenzoate, 4-(4,trifluoromethylbenzyloxy)cyclohexyl-3,5-diaminobenzoate, 1,1-di(4-((aminophenyl) φ))methyl)phenyl)-4-butylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-heptylcyclohexane, 1, 1_bis(4-((aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl) -4-(4-heptylcyclohexyl)cyclohexane and a compound represented by the following formula (D-1),

(In the formula (D-1), XI is an alkyl group having 1 to 3 carbon atoms, *_〇·, *-COO- or *-〇C〇· (with a bond and diaminobenzene) The base phase is connected), h is 0 or i'i is an integer of 〇~2, and j is an integer of 1 to 2〇); -52- 201031689 As the diamine-based organodecane, for example, 1,3-two In addition to the (3-aminopropyl)-tetramethyldioxane, the diamines described in Patent Documents 17 to 19 can also be used. X1 in the above formula (D-1) is preferably an alkyl group having 1 to 3 carbon atoms, *-0- or *_COO- (wherein the linking bond is bonded to the diaminophenyl group). Specific examples of the group (: 汨 2 +1 +1) include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and n-decyl group. , n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nine An alkyl group, n-icosyl group, etc. The two amine groups on the diaminophenyl group are preferably a 2,4-position or a 3,5-position relative to the other groups. As the above formula (D-1) Specific examples of the compound to be represented include, for example, a compound represented by each of the following formulas (D-1 to 1) to (D-1 to 4).

C5Hh (D-1-1)

D-1-3) C5Hh (CM-2)

Ό 1 (CH2) 17〇H3 (D-1-4) 53- 201031689 In the above formula (D-1), h and i are not 0 at the same time. These diamines may be used alone or in combination of two or more. The ratio of the tetracarboxylic dianhydride to the polyaminic acid synthesis reaction is preferably 0.2 to 2 equivalents based on the acid anhydride group of the equivalent of the amine dianhydride contained in the diamine compound, more preferably equivalent. ratio. The synthesis reaction of poly-proline is preferably carried out in an organic solvent at a temperature of from -150 ° C, more preferably from 0 to 100 ° C, more preferably for 24 hours, more preferably from 2 to 10 hours. Here, as a solvent which is capable of dissolving the synthesized polyaminic acid, it is not mentioned, and examples thereof include N-methyl-2-pyrrolidone, N,N-amine, hydrazine, hydrazine-dimethylformamide, and N. , N-dimethyl quinazolinone maple, r-butyrolactone, tetramethyl urea, hexamethylphosphonium triamine and other solvents; m-methylphenol, xylenol, phenol, halogenated benzene agent. The amount of the organic solvent used is such that the amount of the tetracarboxylic dianhydride and the total amount (b) relative to the total amount of the reaction solution (a + b) is preferably C%, more preferably 5 to 30% by weight. As described above, the reaction solution in which the polylysine is dissolved can be directly supplied to the liquid crystal alignment agent, or the polyamic acid contained in the liquid can be separated and supplied to the liquid crystal alignment or the separated polymerization can be obtained. Modulation of supply of proline after purification. When the polyglycine is dehydrated and closed to form a polyimine, the liquid can be directly supplied to the dehydration ring-closure reaction, and the reaction can be preferably carried out. The ratio of use of the amine is such that the tetracarboxylic acid is 0.3 to 1.2, preferably -2 0 I is carried out in a 0.5~ machine solvent, and only special phenolic solvents such as dimethyl hydrazine and dimethyl aprotic phenol are dissolved. 1.1 to 50 parts by weight of the amine compound. The reaction is carried out by dissolving the reaction solvent, the poly-proline acid contained in the above-mentioned reaction solution of the liquid crystal alignment agent, and then supplying the dehydration ring-closure reaction, or the separated polyamic acid may be refined. Supply dehydration ring closure reaction. The separation of the polyamic acid can be carried out by adding the above reaction solution to a poor amount of solvent to obtain a precipitate, and then drying the precipitate under reduced pressure, or steaming the organic solvent in the reaction solution with an evaporator under reduced pressure. The removal method is carried out. Further, the poly-proline can be purified by re-dissolving the polylysine in an organic solvent, and then precipitating it with a poor solvent, or by subjecting it to a vacuum distillation process using an evaporator or the like. . [Polyimide] The above polyimine can be synthesized by subjecting a proline structure having a polyamic acid obtained as described above to dehydration ring closure. In this case, the amine acid structure may be completely dehydrated and closed to be completely imidized, or a part of the quinone imide compound in which a part of the proline structure is dehydrated and closed, and the proline structure and the guanamine structure coexist may be used. Q polyhydrazide dehydration ring closure, either (1) by heating poly-proline, or (ii) by dissolving poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution and heating as needed The way to do it. The reaction temperature in the method for heating poly-proline in the above (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 °C, the dehydration ring-closure reaction may not proceed sufficiently. When the reaction temperature exceeds 200 °C, the molecular weight of the obtained polyimine may decrease. The reaction time in the method of heating the polyamine is preferably from 0.5 to 48 hours, more preferably from 2 to 2 minutes, and only from the sub-group, the acid is -55 to 20, 201031689 hours. On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the polyamic acid solution of the above (u), as the dehydrating agent, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount 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 amount of the closed-loop catalyst for dehydration is preferably 〇. 1 to 1 0 mol with respect to the dehydrating agent used for 1 mol. The organic solvent used in the dehydration ring-closure reaction may, for example, be an organic solvent exemplified as an organic solvent used in the synthesis of polyglycine. The reaction temperature of the dehydration ring-closure reaction is preferably from ～1 to 80 ° 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 obtained by refining the obtained polyimine and then supplying it 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 prepared by supplying a liquid crystal alignment agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, or may be separated from the polyimine and then supplied to the liquid crystal alignment agent. The preparation may be carried out by refining the separated polyimine and then supplying it to the liquid crystal alignment agent. 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. Separation and purification of the polyimine can be carried out in the same manner as described above for the separation and purification of polyamic acid. From -56 to 201031689. [Other polyorganosiloxanes] The other polyorganosiloxanes in the present invention are polyorganoles other than the above-mentioned radiation-sensitive polyorganisms. As such other polyorganosiloxane, at least one decane compound (hereinafter referred to as a raw material compound) which is, for example, selected from the group consisting of an alkoxydecane compound and a halogenated decane compound can be preferably used. In the organic solvent, hydrolysis and condensation are carried out in the presence of water and a catalyst to synthesize. ® As a raw material decane compound which can be used here, for example, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, tetra-n-butoxy decane, and tetra-second butyl can be mentioned. Oxydecane, tetra-tert-butoxydecane, tetrachlorodecane; methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane, methyltriisopropoxydecane, A , s-tri-n-butoxy decane, methyl tri-tert-butoxy decane, methyl tri-tert-butoxy decane, methyltriphenyloxydecane, methyltrichlorodecane, ethyltrimethyl methoxy Decane, ethyltriethoxydecane, ethyltri-n-propoxydecane, ethyltriisopropoxydecane, ethyltri-n-butoxydecane, ethyltri-t-butoxydecane, ethyltri Third 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, etc. It is preferred to use one or more of them, and it is particularly preferred to use a compound selected from the group consisting of tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, phenyl trimethoxy decane, and benzene. Group consisting of triethoxy decane, bis-57-201031689 methyl dimethoxy decane, dimethyl diethoxy decane, trimethyl methoxy sand and dimethyl ethoxy sand At least one of them. The other polyorganosiloxane in the present invention can be synthesized in the same manner as the above-described method of synthesizing a polyorganosiloxane having an epoxy group, except that the above-mentioned raw material decane compound is used. For other polyorganosiloxanes, the polystyrene-reduced weight average molecular weight measured by gel permeation chromatography is preferably from 1,000 to 100,000, more preferably from 5,000 to 50,000. {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 preferably relative to 100 parts by weight of radiation. Polyorganosiloxane is!重量 Below the weight. The better use ratio of other polymers varies depending on the type of other polymers. 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, a better use ratio of the two is relative to The total amount of the 100 parts by weight of the radiation-sensitive polyorganosiloxane, the polyamic acid and the polyimine is from 1 to 5 000 parts by weight, more preferably from 200 to 2000 parts by weight. 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 amount of the polyorganosiloxane is 100 to 2000 parts by weight. When the liquid crystal alignment agent of the present invention contains both a radiation-sensitive polyorgano-58-201031689 oxane and other polymers, it is used as a polyorganophthalic acid and a polyamidolimine or other [hardener]. And a hardening catalyst] The above-mentioned hardening agent and the crystallizing agent of the hardening-radio-radiopolyorganosiloxane, as the hardening agent for the purpose of the hardening-promoting hardening reaction, may be a compound or a hardening which is usually used for epoxidation. Agent, anhydride, polycarboxylic acid. As the above polyvalent carboxylic anhydride anhydride and other polycarboxylic acid anhydrides as cyclohexane tricarboxylic acid, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,2,3-tri The carboxylic anhydride may, for example, be a mixture of 4-methylenedicarboxylic anhydride, dodecene anhydride, phthalic anhydride, a partial benzene compound, and polyglycine, and is preferably selected from other polymers. At least one polymer or both of the groups. The agent may be included in the liquid crystal alignment agent of the present invention for the purpose of further enhancing the crosslinking reaction. The hardening composition of the compound which is a compound having a curing group having an epoxy group may, for example, be a polyamine or a polyvalent carboxylic acid, and examples thereof include a specific example of phthalic anhydride of cyclohexanetricarboxylic acid, and examples thereof include an acid anhydride. Cyclohexane-1,3,5-tricarboxylic acid-3,5-acid-2,3-anhydride, etc., as other polyvalent carboxytetrahydrophthalic anhydride, methylnorbornyl succinic anhydride, succinic anhydride , maleic acid trianhydride, tetracarboxylic dianhydride commonly used in the formation of the following formula (CA-1), -59- 201031689

(in the formula (CA-1), k is an integer of 1 to 20), and examples thereof include an alicyclic compound having a conjugated double bond such as α-terpinene and allo-ocimene, and maleic anhydride. Diels-Alder reaction product and its hydrogenated product. ® As the above-mentioned curing catalyst, for example, a ruthenium hexafluoride compound, a 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 an imidazole compound; a 4-stage phosphorus compound; a 4-grade amine compound; 1,8-diazabicyclo[5.4.0]undec-7-ene and an organic salt thereof. @heterobicycloolefin; organometallic compound such as zinc octoate, tin octoate, acetoacetate aluminum complex; boron compound such as boron trifluoride or triphenyl borate; metal halide such as chlorinated chloride and tin chloride; Amine-forming accelerator such as an amine, an amine, and an epoxy resin, and a latent curing accelerator for stomach and stomach melting. · A microcapsule-based latent curing accelerator coated with a polymer such as a 4-stage phosphorus salt. -60- 201031689 Amine salt type latent hardening accelerator; Luminic acid salt, Bronsted acid salt and other high temperature degradable thermal cation polymerization type latent hardening accelerator. [Epoxy group] The above epoxy group compound can be contained in the alignment agent of the present invention from the viewpoint of further improving the adhesion of the formed alignment film to the surface of the substrate. As such an epoxy compound, for example, ethylene diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether pentanediol 2 is preferable. Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-glycidyl-2, 4-hexanediol, N,N,N',N'-tetraglycidyl-m-aniline, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N, N,N tetraglycidyl-4,4'-diaminodiphenylmethane, anthracene, fluorene-di-glycidyl-benzylamine, hydrazine, hydrazine-diglycidyl-aminomethylcyclohexane, and the like. When the liquid crystal alignment agent of the present invention contains an epoxy compound, the content ratio is preferably 40% by weight based on 100 parts by weight of the total amount of the above radiation-sensitive polyorganoalkane and optionally other polymers. Preferably, it is 0.1 to 30 parts by weight. Further, the liquid crystal alignment agent of the present invention contains an epoxy group compound for the purpose of efficiently performing the crosslinking reaction, and may be used in combination with a basic catalyst such as 1.-2-methylimidazole. [Functional decane compound] ionic liquid crystal liquid crystal alcohol diglycerin, neoditetramethyl condensate, hydrazine, - oil base is its sand oxygen component, -benzyl group -61 - 201031689 The above functional decane compound may be It is used for the purpose of improving the adhesion between the obtained liquid crystal alignment film and the substrate. The functional decane compound may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane or 2-aminopropyltri Ethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Decane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3- Aminopropyltriethoxy decane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxydecane Base-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diaza Mercaptoacetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3 -Aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-di(oxyethylene) φ base 3-aminopropyltrimethoxydecane, N-bis(oxyvinyl)-3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 2-( And a tetracarboxylic dianhydride as described in the patent document 20 (JP-A-63-291) A reaction product of an amine-based decane compound or the like. When the liquid crystal alignment agent of the present invention contains a functional decane compound, the total content thereof is preferably a total amount of the above-mentioned radiation-sensitive polyorganosiloxane and optionally other polymers, based on 1 part by weight. 50 parts by weight or less, more preferably 20 parts by weight or less. -62- 201031689 [Surfactant] Examples of the above surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a polyfluorene ketone surfactant, and a polyalkylene oxide. Surfactant, fluorine-containing surfactant, and the like. When the liquid crystal alignment agent of the present invention contains a surfactant, the content thereof is preferably 10 parts by weight or less, more preferably 1 part by weight or less based on 100 parts by weight of the total amount of the liquid crystal alignment agent. <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention contains a radiation-sensitive polyorganosiloxane as an essential component as described above, and further contains other components as needed, and is preferably prepared so that the components are soluble. A solution-like composition in an organic solvent. As the organic solvent which can be used for preparing the liquid crystal alignment agent of the present invention, a solvent which is capable of dissolving the radiation-sensitive polyorganosiloxane and other components which are optionally used, and which does not react with them, is preferred. The organic solvent which can be preferably used in the liquid crystal alignment agent of the present invention differs depending on the kind of other polymer which is optionally added. 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 polylysine and polyimine, and in addition to a radiation-sensitive polyorganosiloxane When at least one polymer selected from the group consisting of polylysine and polyimine contains other polyorganosiloxanes, a preferred organic solvent is exemplified as the synthesis of polyamic acid. The organic solvent exemplified as the solvent used. At this time, -63 to 201031689 may be used in combination as a solvent exemplified as the poor solvent which can be used in the synthesis of the polyamic acid of the present invention. These organic solvents may be used singly or in combination of two or more. In addition, when the liquid crystal alignment agent of the present invention contains only a radiation-sensitive polyorganosiloxane as a polymer, or when it contains a radiation-sensitive polyorganosiloxane and other polyorganosiloxane, it is not selected from polyamine. In the case of at least one polymer selected from the group consisting of an acid and a polyimine, examples of preferred organic solvents include 1-ethoxy-2-propanol, propylene glycol monoethyl ether, and propylene glycol monopropyl ether. , propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl Ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monopentyl ether, ethylene glycol monohexyl ether, diethylene glycol, methyl cellosolve acetate, ethyl cellosolve acetate, Propyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, n-propyl acetate, isopropyl acetate, Orthobutyl phthalate acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, second amyl acetate 3-methoxybutyl acetate, methyl amyl acetate, 2-ethyl butyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate, pentane acetate Ester, isoamyl acetate, and the like. Among them, preferred are n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, and second amyl acetate. The solvent which can be used for preparation of the liquid crystal alignment agent of the present invention is a solvent obtained by combining one or two or more kinds of the above organic solvents depending on whether or not another polymer and its kind are used, and is preferably a solid content as described below. -64 - 201031689 At the concentration, the components contained in the liquid crystal alignment agent are not precipitated, and the surface tension of the liquid crystal alignment agent is dropped to 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 ratio of the weight of all components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent, is selected in consideration of viscosity, volatility, etc., preferably 1 to 10 parts by weight. The range of %. The liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a coating film as a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the thickness of the coating film is too small to obtain a good liquid crystal alignment film. Happening. 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 to apply the liquid crystal alignment agent 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% 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·φ 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 0 ° C to 200 ° C, more preferably 0 ° C. <Method of Forming Liquid Crystal Alignment Film> 'The liquid crystal alignment agent of the present invention can be suitably used for forming a liquid crystal alignment film by a photo-alignment method, a liquid crystal display element having a TN-type or STN-type liquid crystal cell, or a cross-section having an IPS type liquid crystal cell. Liquid-65-201031689 crystal alignment film used in electric field type liquid crystal display elements. The liquid crystal alignment agent of the present invention, when applied to a liquid crystal display element having an IPS cell, can maximize the effects of the present invention and is therefore preferable. The liquid crystal alignment film of the present invention is used to form a liquid crystal alignment film, and the liquid crystal alignment agent of the present invention can be applied to a substrate to form a coating film, and the coating film can be irradiated with radiation. Here, when the liquid crystal alignment agent of the present invention is applied to a liquid crystal display element having a TN STN type liquid crystal cell, two substrates provided with a transparent conductive film are provided as a pair, and a transparent guide surface is formed on each of them. The liquid crystal alignment agent of the present invention is applied to form a coating film. Further, when the liquid crystal alignment agent of the present invention is applied to a liquid display element having an IPS type liquid crystal cell, a substrate having an electrode formed by patterning a transparent conductive film or a metal film on one side and a counter base having no electrode provided thereon In a pair, the liquid crystal alignment agent of the present invention is applied to each of the surface on which the comb-shaped electrode is formed and the opposite surface of the substrate to form a coating film. In either case, as the substrate, for example, glass such as float glass or soda lime glass; polyethylene transparent to polyethylene terephthalate, polybutylene terephthalate, polyether oxime or polycarbonate can be used. For the transparent conductive film, for example, a film made of Iri 2 〇 3 - SnCh, a NESA (registered trademark) film made of SnCh, or the like can be used. As the metal film, a film made of a metal such as chromium is used. For the formation of the transparent conductive film and the metal film, for example, a method of forming a pattern by forming a transparent conductive film without a pattern, a method of forming a pattern by a sputtering method, or the like, or a method of forming a mask having a desired pattern in forming a transparent conductive film can be employed. Wait. The effect of the type of liquid is on the electric film of the type or the case, when the crystal comb is used, the method is benzene, and the like. ITO, when patterning over-lighting -66 - 201031689 When applying a liquid crystal alignment agent to a substrate, in order to further improve the adhesion of the conductive film or the electrode to the coating film, a functional decane compound, titanate, etc. may be preliminarily coated on the substrate. . The liquid crystal alignment agent is applied onto the substrate, and a suitable coating method such as a spin coating method, a roll coating method, or an inkjet printing method is preferably applied, and then the coated surface is preheated (prebaked) and then fired to form a coating film. The prebaking conditions are, for example, 40 to 12 minutes (TC minutes, post-baking conditions: preferably 120 to 300 ° C, more preferably ° ° C, preferably 5 to 200 minutes, more preferably 10 to 1 minute) The thickness of the subsequent coating film is preferably 0.001 to 1/m, more preferably 0.5 m. By irradiating the coating film thus formed with linear polarized light or partial or non-polarizing rays, the liquid crystal alignment energy is generated. For example, a violet light having a wavelength of 150 to 800 nm may be used, and when the ultraviolet Q beam having a wavelength of 300 to 400 nm is preferably linearly polarized or partially polarized, the irradiation may be performed from a vertical direction or may be generated in advance. The tilt angles are from the line, and they can also be combined. When the non-bias illumination direction is irradiated, it must be an oblique direction. As the light source used, for example, a low-pressure mercury lamp, a xenon lamp, a gold halide lamp, an argon resonance lamp can be used. The ultraviolet light of the above-mentioned preferred wavelength range of the xenon lamp and the excimer can be obtained by means of a combination of the above-mentioned optical device, diffraction grating, etc. The irradiation amount of the radiation is preferably 1]/m2 or more, and the substrate is improved. Board and electricity The upper printing method and the method are carried out, and then (post-baking) is carried out for 0.1 to 5 good 1 5 0 to 2 5 0. The post-baking is 0.005 to the partial polarized shot, as the outside line and visible. When used straight to When the substrate is inclined in the direction of the i-ray, > high pressure mercury lamp, laser, etc. The source and the filter are, for example, less than 10000 -67 - 201031689 J/m2, more preferably 10 to 3000 J/m2. When a liquid crystal alignment energy is generated by a photo-alignment method to form a coating film formed of a conventionally known liquid crystal alignment agent, a radiation irradiation amount of 10000 J/m 2 or more is required. However, when the liquid crystal alignment agent of the present invention is used, optical alignment is employed. When the amount of radiation of the method is 3000 J/m 2 or less, or even 1000 J/m 2 or less, good liquid crystal alignment energy can be generated, which is advantageous for improving the productivity of the liquid crystal display element and reducing the manufacturing cost. Manufacturing Method > φ The liquid crystal display element formed using the liquid crystal alignment agent of the present invention can be produced, for example, as follows: First, a pair of substrates on which a liquid crystal alignment film is formed as described above is prefabricated, and a liquid is interposed between the pair of substrates. The liquid crystal cell of the structure. The production of the liquid crystal cell can be exemplified by the following two methods. The first method is a previously known method. First, by placing two substrates relatively through a gap (cell gap), the respective The liquid crystal alignment film phase φ is opposed to each other, and the peripheral portions of the two substrates are bonded together with a sealant, and liquid crystal cells are filled into the cell gap surrounded by the substrate surface and the sealant, and then the injection holes are closed to obtain a liquid crystal cell. The second method is a method called a DropDF (One Drop Fill) method in which a predetermined portion on one of the two substrates forming the liquid crystal alignment film is coated with, for example, an ultraviolet curable sealant material, and then in a liquid crystal. After the liquid crystal is dropped on the alignment film surface, the other substrate is bonded to face the liquid crystal alignment film, and then the entire surface of the substrate is irradiated with ultraviolet rays to harden the sealing agent to obtain a liquid crystal cell. -68- 201031689 In the case of any of the methods, it is necessary to remove the flow alignment at the time of liquid crystal charging by heating the liquid crystal cell to a temperature at which the liquid crystal used is in an isotropic phase and then slowly cooling to room temperature. Then, the liquid crystal display element of the present invention can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell. Here, a desired liquid crystal display element can be obtained by appropriately adjusting the angle formed by the polarization direction of the linearly polarized ray irradiated on the two substrates on which the liquid crystal alignment film is formed and the angle between each substrate and the polarizing plate. 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 or a dish-shaped liquid crystal can be used. A liquid crystal having positive dielectric anisotropy of a nematic liquid crystal is preferably used, and for example, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, or a biphenyl cyclohexane can be used. Liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubic liquid crystal, and the like. Further, a cholesteric liquid crystal such as cholesteryl cholesteryl, cholesteryl phthalate or cholesteryl carbonate may be further added to the liquid crystal, and the trade names "C-1 5" and "CB-15" (above by Merck) The chiral agent sold by the company is used for ferroelectric liquid crystals such as decyloxybenzylidene-p-amino-2-methylbutyl cinnamate. The polarizing plate used for the outer side of the liquid crystal cell may be a polarizing plate obtained by sandwiching a polarizing film called "H film" obtained by stretching and dispersing polyvinyl alcohol and absorbing iodine, in a cellulose acetate protective film, or a film made by itself. A polarizing plate, etc. -69- 201031689 The liquid crystal display element of the present invention thus produced is excellent in various properties such as display performance, electrical properties, and performance. EXAMPLES Hereinafter, the present invention will be more specifically described by examples, but the present invention is not limited to the examples. The weight average molecular weight in the following synthesis examples is a polystyrene-converted enthalpy measured by gel permeation chromatography under the following conditions.

Pipe column: manufactured by Tosoh, TSK gel GRCXL II 溶剂 Solvent: tetrahydrofuran

Temperature: 40 ° C Pressure: 68 kg f/cm 2 In addition, in the following synthesis examples, 'the synthesis of the starting compound and the polymer was repeated by the following synthesis route and as needed to ensure the required in the subsequent examples. the amount. <Synthesis Example of Polyorganooxane having an epoxy group> Q Synthesis Example ES 1 To a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 2-(3,4-) was added. Epoxycyclohexyl)ethyltrimethoxydecane 100.Og, methyl isobutyl ketone 500 g and triethylamine 10 g were mixed at room temperature. Then, 10 g of deionized water was added dropwise via a dropping funnel for 30 minutes, and then 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 2% by weight aqueous solution of ammonium nitrate until the washed water was neutral, and then the solvent was distilled off under reduced pressure and -70-201031689 water was obtained to have an epoxy resin. A viscous, transparent liquid of a polyorganosiloxane (ES-1). 1 H-NMR analysis of the polyorganosiloxane having an epoxy group, and an epoxy group-based peak having a theoretical strength was obtained in the vicinity of the chemical shift (5 ) = 3.2 ppm, and it was confirmed that the epoxy group was not present in the reaction. reaction. The viscosity, Mw and epoxy equivalent of the polyorganooxynonane (ES-1) having an epoxy group are shown in Table 1. Synthesis Examples ES2 to 3 In the same manner as in Synthesis Example 1, except that the raw materials to be charged were as shown in Table 1, the polyorganosiloxane (ES-2) and (ES-3) having an epoxy group were obtained. Transparent liquid. The Mw and epoxy equivalents of these polyorganosiloxanes having an epoxy group are shown in Table 1. Further, in Table 1, the abbreviations of the raw material decane compounds have the following meanings. φ ECETS : 2-(3,4-Epoxycyclohexyl)ethyltrimethoxydecane MTMS : Methyltrimethoxydecane PTMS : Phenyltrimethoxydecane Table 1 Raw Materials] Shatanic Compound (g) Poly 5 & oxyalkylene ECETS MTMS PTMS name Mw epoxy equivalent (green ear) Synthesis Example ESI 100 0 0 ES-1 2200 186 Synthesis Example ES2 80 20 0 ES-2 2500 210 Synthesis Example ES3 80 0 20 ES-3 2000 228-71-201031689 <Synthesis Example of Compound represented by the above formula (A1)> The following formula (A1 to 1) to (A1 - 4) were synthesized as described in the following Synthesis Examples A1-1 to A1-4. Each of the compounds (hereinafter referred to as "compound (A1 - 1)", "compound (A1 - 2)", "compound (A1-3)" and "compound (A1 - 4)", respectively.

Synthesis Example A 1 - 1 To a 500 ml three-necked flask equipped with a condenser, 20 g of 4-bromodiphenyl ether, 0.18 g of palladium acetate, 0.98 g of tris(2-tolyl)phosphine, 32.4 g of triethylamine and 135 ml of dimethylacetamide was mixed and formulated into a solution. Then, 7 g of acrylic acid was added to the above solution with a syringe and stirred, and the mixture was stirred at 120 ° C for 3 hours to carry out a reaction. After confirming completion of the reaction by thin layer chromatography (TLC), the reaction solution was cooled to room temperature. After filtering the insoluble matter, the filtrate was poured into 300 ml of 1N hydrochloric acid to recover a precipitate. The precipitate was recrystallized from a mixed solvent of ethyl acetate and hexane (ethyl acetate:hexane = 1:1 (volume: 72 - 201031 689)) to give 8.4 g of the compound (Α1 ι). Synthesis Example A 1 - 2 To a 300 ml three-necked flask equipped with a condenser, 6.5 g of 4-oxyphenylboronic acid, 10 g of 4-bromocinnamic acid, 2.7 g of tetrakis(triphenylphosphine), 4 g of sodium carbonate, and 80 ml were added. Tetrahydrofuran and 39 ml of pure water were mixed, and then stirred at 80 t for 8 hours to carry out a reaction. After confirming completion of the reaction by TLC, the reaction mixture was cooled to room temperature. The cooled reaction mixture was poured into 200 ml of 1N hydrochloric acid, and the precipitate was collected. The solution obtained by dissolving the obtained precipitate in ethyl acetate was washed successively with 100 ml of 1N hydrochloric acid, 100 ml of purified water and 1 ml of saturated brine, and dried over anhydrous magnesium sulfate. The obtained solid was vacuum dried to give 9 g of Compound (A1-2). Synthesis Example A 1 - 3 To a 200 ml three-necked flask equipped with a condenser, 3.6 g of 4-fluorostyrene, 6 g of 4-bromocinnamic acid, ruthenium, 5,9 g of palladium acetate, and 0.32 g of tris(2-tolyl) were added. Phosphine, llg of triethylamine and 50 ml of dimethylacetamide were mixed and made into a solution. The solution was stirred at 120 ° C for 3 hours to carry out a reaction. After confirming the completion of the reaction by TLC, the reaction mixture was cooled to room temperature, and the insoluble material was filtered off. Then, the filtrate was poured into 300 ml of 1N hydrochloric acid, and the precipitate was collected. The precipitate was recrystallized from ethyl acetate to give 4. lg compound (A1 - 3). Synthesis Example A 1 - 4

To a 200 ml three-necked flask equipped with a condenser, 9_5 g of 4-vinylbiphenyl '10 g of 4-bromocinnamic acid, 〇.〇9 9 g of palladium acetate, 〇.54 g of tris(2-tolyl)phosphine, and 18 g were added. Triethylamine and 80 ml of dimethylacetamide were mixed and made into a solution. The solution was stirred at 120 ° C for 3 hours to carry out a reaction. After confirming the completion of the reaction by TLC-73-201031689, after cooling the reaction mixture to the chamber, the filtrate was poured into 500 ml of 1N hydrochloric acid, and the recovered product was a mixture of dimethylamine and ethanol: ethanol = Recrystallization (A1 - 4) was carried out in 1: 1 (volume ratio). <Synthesis Example of Compound represented by the above formula (A2)> A compound represented by each of (A2 - 1) and (A2 - 4) as described in Synthesis Examples A2 - 1 and A2 - 2 (hereinafter, A 2 - 1)" and "compound (A 2 - 2)"). The precipitates of insoluble matter were filtered off at a temperature. The r-solvent (dimethyl b, which gave 11 g of the synthesis example) was hereinafter referred to as " Compound

Synthesis Example A2 _ 1 In a 200 ml three-necked flask equipped with a condenser, 'phenyl ester, 11.3 g of 4-bromobenzoic acid, 0.13 g of palladium acetate, phosphine, 23 g of triethylamine and 100 ml of dimethylacetamide. Solution. The solution was stirred at 120 T: for 3 hours. After the completion of the reaction by TLC, the reaction mixture was cooled to dissolve, and then the filtrate was poured into 500 ml of 1N hydrochloric acid. The precipitate was recrystallized from ethyl acetate to give -1. Synthesis Example A 2 - 2 A solution of 0.6 g of tris(2-toluene) was mixed with 1 g of acrylic acid, and the reaction was carried out. The mixture was filtered off to room temperature, and the precipitate was not recovered. 9.3 g of the compound (A2 - 74 - 201031689) In a 200 ml three-necked flask equipped with a dropping funnel, 10 g of 4·cyclohexylphenol, 6.3 g of triethylamine and 80 ml of dehydrated tetrahydrofuran were added and mixed. The mixture was cooled in an ice bath and added dropwise by a dropping funnel from 5.7 g. A solution consisting of acrylonitrile chloride and 40 ml of dehydrated tetrahydrofuran. After completion of the dropwise addition, the mixture was further stirred in an ice bath for 1 hour, then allowed to warm to room temperature, and further stirred for 2 hours to carry out a reaction. After the reaction was completed, the reaction mixture was filtered to remove the product. Ethyl acetate was added to the filtrate, and the obtained organic layer was washed with water, and the solvent was removed under reduced pressure, and then dehydrated to obtain 12.3 g of intermediate 4-cyclohexanyl methacrylate. In a 100 ml three-necked flask of a condenser, 6 g of 4-cyclohexyl phenyl acrylate obtained, 5-7 g of 2-fluoro-4-bromobenzoate, 0.06 g of palladium acetate, and 0.32 g of tris(2-methylphenyl) were added. Phosphine, triethylamine llg and dimethyl 50 ml of guanamine was mixed and mixed to prepare a solution. The solution was stirred at 120 ° C for 3 hours to carry out a reaction. After confirming completion of the reaction by TLC, the reaction mixture was cooled to room temperature, and the insoluble matter was filtered off, and then the filtrate was poured into 300 ml. In the Q IN hydrochloric acid, the formed precipitate was recovered. The precipitate was recrystallized from ethyl acetate to give 3.4 g of the compound (A2-2). <Comparative Synthesis Example of Carboxylic Acid> Synthesis Example RA 1 to 200 ml Into a three-necked flask, 11.21 g of 4-hydroxychalcone, 8.35 g of ethyl bromoacetate, i3.8 g of potassium carbonate and 100 ml of dimethylacetamide were added and mixed, and the mixture was stirred at 12 CTC for 7 hours to carry out a reaction. After the reaction was completed, the reaction mixture was cooled to room temperature, and then 100 ml of ethyl acetate was added thereto, and the obtained organic layer was washed. From the obtained organic layer, the solvent was removed under reduced pressure from -75 to 201031, and dried. A mixed solvent of ethanol and water (ethanol: water = 4:1 (volume ratio)) was recrystallized to obtain 11.4 g of an intermediate of the organic chalcone oxyacetate. To a 500 ml three-necked flask equipped with a condenser , adding the chalcone oxygen produced above 6.2 g of ethyl acetate, 2 g of sodium hydroxide, 200 ml of ethanol and 50 ml of water were mixed, and the reaction was carried out under reflux for 3 hours. After the reaction was completed, the reaction mixture was cooled, and then diluted with hydrochloric acid was added to adjust the acidity. 5 00 ml of ethyl acetate was extracted. After the obtained organic layer was washed with water, the solvent was removed under reduced pressure to obtain a compound represented by the following formula (RA - 丨) (Compound (RA-1) ).

(RA-1) <Synthesis Example of Radiation-Radio Polyorganooxane> Synthesis Example S 1 To a 100 ml three-necked flask, 9.3 g of a polyorganofluorene having an epoxy group obtained in the above Synthesis Example ESI was added. Oxystane (ES-1), 26 g of methyl isobutyl ketone, 3 g of the compound (Al-1) obtained in the above Synthesis Example A1-1, and 〇.l〇g UCAT 18X trade name '(San-Apro) The produced 4-grade amine salt) was stirred at 80 ° C for 12 hours to carry out a reaction. After the completion of the reaction, the reaction mixture was poured into methanol, and the resulting sinker was recovered, dissolved in ethyl acetate to prepare a solution, and the solution was washed with water three times, and then the solvent was distilled off to obtain 6.3 g of a radiation-sensitive polyorganism. A siloxane (S-1) white powder. The radiation-sensitive linear polyorganosiloxane (S-1) had a weight average molecular weight Mw of 35 00. -76-201031689 Synthesis Example S 2 In the synthesis example S1, the same procedure as in the above Synthesis Example S1 was carried out, except that 3 g of the compound (A1 - 2) obtained in the above Synthesis Example Al-2 was used instead of the compound (A1 - 1). A white powder of 7.0 g of a radiation-sensitive polyorganosiloxane (S-2) was obtained. The radiation-sensitive polyorganosiloxane (S-2) had a weight average molecular weight Mw of 4,900. Synthesis Example S 3 In the same manner as in the above Synthesis Example S1, except that 4 g of the compound (A1 - 3) obtained in the above Synthesis Example A1-3 was used instead of the compound (A1 - 1), L〇g A white powder of a radioactive linear polyorganosiloxane (S-3). The radiation-sensitive polyorganosiloxane (S-3) had a weight average molecular weight Mw of 5,000. Synthesis Example S4 In the synthesis example S1, except that 4 g of the compound (A1 - 4) obtained in the above Synthesis Example A1-4 was used instead of the compound (Al to 1), the same procedure as in the above Synthesis Example φ S1 was carried out. L〇g A white powder of a radioactive linear polyorganosiloxane (S-4). The radiation-sensitive polyorganosiloxane (S-4) had a weight average molecular weight Mw of 4,200. Synthesis Example S5 In Synthesis Example S1, except that 10.5 g of the polyorganosiloxane (ES-2) having an epoxy group obtained in the above Synthesis Example ES2 was used instead of the polyorganosiloxane having an epoxy group (ES) -1), 3.35 g of the compound (A2 - 1) obtained in the above Synthesis Example A2 - 1 was used in the same manner as in the above Synthesis Example S1 except for the compound (Al-1) to obtain 7.0 g of a radiation-sensitive polyorganoindene. White powder of oxyalkylene (S_5) -77- 201031689. The radiation-sensitive polyorganosiloxane (S-5) had a weight average molecular weight Mw of 5,500. Synthesis Example S6 In Synthesis Example S1, except that 11.4 g of the polyorganooxyalkylene having an epoxy group (ES-3) obtained in the above Synthesis Example ES3 was used instead of the polyorganosiloxane having an epoxy group (£ 3-1), 4.62 The compound (A2-2) obtained in the above Synthesis Example VIII 2_2 was used in the same manner as in the above Synthesis Example S1 except for the compound (Al-1) to obtain 9.6 g of a radiation-sensitive linear polyorganosiloxane. A white powder of alkane (s-6). The radiation-sensitive polyorganosiloxane (S-6) had a weight average molecular weight Mw of 7,400. <Comparative Synthesis Example of Radiation-Radio Polyorganooxane> Synthesis Example RS1 In Synthesis Example S-1, a method described in Patent Document 17 (International Publication No. 2009/025385 pamphlet) was used in addition to 4.4 g. A compound represented by the following formula was used in the same manner as in the above Synthesis Example si φ in place of the compound (Al-1) to obtain a white powder of 7.2 g of a radiation-sensitive polyorganosiloxane (rs _ 1). The radiation-sensitive linear polyorganosiloxane (RS-1) had a weight average molecular weight Mw of 9,400.

CsHiiO^VcOO-^Vv Synthesis Example RS2 In the synthesis example S1, the same procedure as in the above Synthesis Example S1 was carried out except that 3.52 g of the compound (RA-1) obtained in the above Synthesis Example RA1 was used instead of the compound (A1-1). Operation, a white powder of 9.1 g of a radiation-sensitive polyorganosiloxane (RS--78-201031689 2) was obtained. The radiation-sensitive linear polyorganosiloxane (RS-2) had a weight average molecular weight Mw of 6,900. <Synthesis Example of Other Polymer> [Synthesis Example of Polylysine] Synthesis Example P a 1 19.61 g (〇.l mole) cyclobutane tetracarboxylic dianhydride and 21.23 g (0.1 mol) 4,4'-Diamino-2,2'-dimethylbiphenyl was dissolved in 367.6 g of N-methyl-2-pyrrolidone and allowed to react at room temperature for 6 hours. The reaction mixture was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol, and dried at 40 ° C for 15 hours under reduced pressure to give 35 g of polyamine (p-1). Synthesis Example pa2 22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 14.23 g (0.1 mol) of cyclohexane bis(methylamine) were dissolved in 329.3 g of N-methyl-2. In the pyrrolidone, the reaction was carried out at 60 ° C for 6 hours. The reaction mixture was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol, and dried under reduced pressure at 40 ° C for 15 hours to obtain 32 g of polyamine (pa-2). [Synthesis Example of Polyimine] Synthesis Example P i-1 17.5 g of the poly-proline acid pa-2 obtained in the above Synthesis Example pa-2 was dissolved in 232.5 g of N-methyl-2. Further, 3.8 g of pyridine and 4.9 g of acetic anhydride were added to the pyrrolidone, and a dehydration ring-closure reaction was carried out at 120 ° C for 4 hours. After completion of the reaction, the reaction mixture was poured into a large excess of methanol to precipitate a product of the anti-79-201031689 product. The precipitate was recovered and washed with methanol for 15 hours to obtain 15 g of polyimine (pi-1). [Synthesis Example of Other Polyorganooxane] Synthesis Example S1 In Synthesis Example S1, except that 5 g of lauric acid was used, A white powder of decane (s-1) was produced in the same manner as in the above Synthesis Example S1. The other aggregated has an average molecular weight Mw of 6000. <Preparation of Liquid Crystal Aligning Agent> 100 parts by weight of the above-mentioned synthesis example pa-amino acid (pa_l) which is a radiation-sensitive linear dispersion of the radiation-sensitive polyorganoprene component obtained in the example S1 as another polymer Mixing, adding N-methyl 3 -based cellosolve to the solvent composition of N-methyl-2-pyrazine = 50: 50 (weight ratio), solid content concentration of 2, using the pore size of the solution The //m filter is over-expanded. <Production of Liquid Crystal Display Element> A chrome substrate having a comb-tooth pattern on one surface and an electrode-coated surface on which a counter-glass substrate having no electrode is provided and a coating machine facing the glass substrate are coated. The liquid crystal alignment agent (LA-1: after pre-baking for 1 minute, after the strip is replaced by nitrogen in the chamber, the compound (A 1 - 1) is dried under reduced pressure to obtain 11 g of other polyorganism: sand oxygen chamber (s-1) heavy oxirane of the above-mentioned alkane (s-1) and 1000-1 produced polyfluorene S-2-pyrrolidone and butyrrolidone: butylcellulose ί. 0% by weight solution I: The glass of the liquid crystal alignment metal electrode is prepared as a pair, and the glass substrate is respectively rotated, and the heating plate at 80 ° C is in the air oven at 200-80-201031689 °C. The film was heated for 1 hour (post-baking) to form a film having a film thickness of 0.1/zm, and then the surface of the film was irradiated with 300 J/m2 from the substrate normal direction by using an Hg-Xe lamp and a Glan-Taylor®, respectively. A polarized ultraviolet ray having a 313 nm bright line is used to obtain a pair of substrates having a liquid crystal alignment film. In the outer periphery of the surface of the liquid crystal alignment film of one of the substrates, an epoxy resin adhesive having a diameter of 5.5 # m is applied by screen printing, and the liquid crystal alignment film faces of the pair of substrates are opposed to each other. The directions of the respective substrates irradiated with the polarized ultraviolet rays are reversed to each other, and the pressure is combined and pressed, and the adhesive is thermally cured at 150 ° C for 1 hour. Then, the liquid crystal injection port is filled with Merck to the gap between the substrates. After the liquid crystal MLC-7 028 produced by the company, the liquid crystal injection port was closed with an epoxy-based adhesive, and 'to eliminate the flow alignment during liquid crystal injection, it was heated at 150 ° C and then slowly cooled to room temperature. Then, the polarizing plates are bonded to the outer surfaces of the substrate so that the polarization directions thereof are perpendicular to each other, and the ultraviolet light axis of the liquid crystal alignment film is perpendicular to the projection direction of the substrate surface, thereby producing a liquid crystal display element. Method> The liquid crystal display element produced above was evaluated by the following method. The evaluation results are shown in Table 2. (1) Evaluation of liquid crystal alignment property For the liquid crystal display manufactured above When the 5V voltage was turned on (applied/released) by an optical microscope, the presence or absence of an abnormal region was observed in the light and dark change. When no abnormal region was observed, the liquid crystal alignment property was evaluated as "good", and when the abnormal region was observed, the liquid crystal alignment evaluation was performed. "Bad". (2) Evaluation of voltage holding ratio -81 - 201031689 Applying a voltage of 5 V to the above-made liquid crystal display element at 60 ° C for a period of 167 msec, the application time is 60 μs. Then, the voltage holding ratio from the voltage release to 167 milliseconds was measured. The measuring device used VHR-1 manufactured by Toyo Technica. Examples 2 to 12 and Comparative Examples 1 and 2 In Example 1, except that the types and amounts of the polymers listed in Table 2 were used as the radiation-sensitive polyorganosiloxane and the other polymers, respectively, In the same manner as in the above-described Example 1, a liquid crystal display element was produced and evaluated in the same manner as in the above-described Example 1, except that the amount of the polarized ultraviolet light irradiated at the time of formation of the liquid crystal® alignment film was as shown in Table 1. The evaluation results are shown in Table 2, respectively. Further, in Example 7, when the liquid crystal alignment agent was prepared, the two polymers were used in combination as another polymer. -82 - 201031689

Table 2 Composition of Liquid Crystal Aligning Agent Polarized Ultraviolet Irradiation (J/m2) Evaluation Results of Liquid Crystal Display Element Radiation-based Polyorganophosphonium Oxide Other Kinds (Parts by Weight) Type (Part by Weight) Liquid Crystal Alignment Voltage Retention Rate (%) Example 1 S-1 100 pa-1 1000 300 Good 99 Example 2 S-2 100 pa-1 1000 300 Good 99 Example 3 S-3 100 pa-1 1000 300 Good 99 Example 4 S- 4 100 pa—1 1000 300 Good 99 Example 5 S-4 100 pa—2 1000 300 Good 99 Example 6 S-4 100 pi—1 1000 300 Good 99 Example 7 S-1 50 pa—1 1000 300 Good 99 s - 1 50 Example 8 S-5 100 pa - 1 1000 300 Good 99 Example 9 S-6 100 pa - 1 1000 300 Good 99 Example 10 S-5 100 pa - 1 2000 300 Good 99 Example 11 S-5 100 pa—1 500 300 Good 99 Example 12 S-6 100 pa—1 500 300 Good 99 Comparative Example 1 RS-1 100 pa—1 1000 1000 Bad 98 Comparative Example 2 RS-2 100 pa—1 1000 1000 Bad 96 Schematic description] Dirty J\ \\ [Main component symbol description] Μ 〇-83-

Claims (1)

201031689 VII. Patent application scope: 1. A liquid crystal alignment agent characterized by containing at least one group having a group selected from the group represented by the following formulas (A1') and (A2') Radioactive polyorganosiloxane, (In the formula (A1'), R is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluorine atom or a cyano group, and R1 is a stretching phenyl group or a cyclohexylene group, wherein the above-mentioned phenyl group or cyclohexylene group is present. A part or all of a hydrogen atom may be substituted by a fluorine atom or a cyano group, and R2 is a single bond, a methylene group, an alkylene group having 2 or 3 carbon atoms, an oxygen atom, a sulfur atom, -CH=CH- or -NH -, a is an integer φ of 0 to 3. When a is 2 or 3, a plurality of R1 and R2 present may be the same 'may be different, R3 is a fluorine atom or a cyano group, and b is an integer of 0 to 4. , " " represents a linkage; in the formula (A2'), R' is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluorine atom or a cyano group, and R4 is a stretching phenyl group or a cyclohexyl group, wherein the above extension A part or all of a hydrogen atom of a phenyl$cyclohexyl group may be substituted by a fluorine atom or a cyano group, and R5 is a single bond, a methylene group, an alkylene group having 2 or 3 carbon atoms, an oxygen atom, a sulfur atom or NH-, c is an integer of 1 to 3. When c is 2 or 3, a plurality of R4 and R5 may be the same, or -84-201031689 different 'R6 is a fluorine atom or a cyano group, and d is 〇~ 4 of the whole R7 is an oxygen atom, -C00- + or ·〇(:〇· + (wherein the above bond with "+" is bonded to R8, R8 is a divalent aromatic group, and a divalent alicyclic ring) a group, a divalent heterocyclic group or a divalent fused ring group, R9 is a single bond, + -OCO-(CH2)f- or +-〇-(CH〇e- (wherein The "+" connection key is located at the - (R7-R8)e-side, f and g are each an integer of 1 to 10), e is an integer of 0 to 3, and represents a connection key. The liquid crystal alignment agent of the first aspect, wherein the sensible radiation Wjk linear polyorganosiloxane is a group of a polyorganosiloxane having an epoxy group and a compound selected from the group consisting of the following formulas (A1) and (A2) a reaction product of at least one of the groups, (R, R1, R2, R3, a and b in the formula (A1) are each the same as defined in the above formula (A1'); R', R4, R5, R6, R8, R9 in the formula (A2), c, d and e are each the same as defined in the above formula (A2')). 3. The liquid crystal alignment agent of claim 1 or 2, which further comprises at least one polymer selected from the group consisting of polylysine and polyimine. The liquid crystal alignment agent of claim 1 or 2, further comprising a polyorganosiloxane such as the above-mentioned radiation-sensitive polyorganosiloxane. A method of forming a liquid crystal alignment film, which comprises coating a liquid crystal alignment agent according to any one of claims 1 to 4 on a substrate to form a coating film, and irradiating the coating film with radiation. A liquid crystal display element characterized by having a liquid crystal alignment film formed of the liquid crystal alignment agent according to any one of claims 1 to 4. 7. The liquid crystal display element of claim 6 is a transverse electric field type. A polyorganosiloxane which is characterized by having at least one group selected from the group consisting of groups represented by the above formulas (a 1') and (A2'). ❹ 201031689 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Sister. ^\\\ V. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: