TW201120070A - Liquid crystal alignment agent, liquid crystal display device and polyorganosiloxane compounds - Google Patents

Abstract

The present invention provides liquid crystal alignment, liquid crystal display device, and polyorganosiloxane compounds which are suitable for use as liquid crystal alignment agent. The liquid crystal alignment agent can form the liquid crystal display device realizing high-speed response and having excellent voltage retention, residual image characteristics and other various performances. The liquid crystal display device is equipped with liquid crystal oriented film formed from the liquid crystal alignment agent. The present invention contains [A] polyorganosiloxane compounds. The [A] polyorganosiloxane compound is a liquid crystal alignment agent which have a part derived from polyorganosiloxane having epoxy groups and a part derived from compounds having carboxyl groups represented by formula (1).

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal alignment agent suitable for use as a material for forming an alignment film of a liquid crystal display device (LCD), and a liquid crystal having a liquid crystal alignment film formed of the liquid crystal alignment agent. A display element and a polyorganosiloxane compound suitable for use in a liquid crystal alignment agent. [Prior Art] In recent years, liquid crystal display devices are widely used for large-screen liquid crystal display devices such as mobile phones and the like, from small liquid crystal display devices such as mobile phones to large-screen liquid crystal display devices such as liquid crystal televisions, because of their low power consumption and ease of miniaturization and flat paneling. In terms of the driving mode of the liquid crystal display device, Lieutenant currently has TN (Twisted Nematic), STN (Super Directional IJ Distortion, Super Twisted Nematic) according to changes in the alignment (alignment) state of liquid crystal molecules. ), IPS (In-Plane Switching), VA (Vertical Alignment), etc. In addition, since the VA mode improves the viewing angle by the alignment division, the MVA (Multi Domain Vertical Alignment) method and the PVA (Patterned Vertical Alignment) method are used, and in addition, the optical vertical alignment mode is adopted. , PSA (Polymer Sustained Alignment) method, etc. to improve high-speed responsiveness, panel aperture ratio, and impart a pretilt angle to the liquid crystal. In any of the driving modes, the alignment state of the liquid crystal molecules is directly controlled by the liquid crystal alignment film, and the liquid crystal alignment film occupies a considerable proportion in the appearance and control of the functional properties of the liquid crystal display element. Since the liquid crystal display device is desired to be a moving picture display device such as a mobile phone or a liquid crystal television, the performance required for the liquid crystal display element is required to make the electro-optical effect response time in order to smoothly display the dynamic picture while suppressing image sticking as much as possible. Faster. In response to this demand, a technique of providing a structure for providing dielectric anisotropy by a side chain of a polymer used for a liquid crystal alignment film is disclosed (refer to Japanese Patent Laid-Open Publication No. 2007-521361 and Japanese Special Table 2007- Bulletin No. 521506). However, in this patent document, in addition to the speed of electro-optical response time, there are no electrical properties such as an orientation which is important in practical use, a voltage holding ratio, and an afterimage property. Based on this situation, it has been desired to develop a liquid crystal alignment agent which has a short electro-optical response time while satisfying the so-called electrical properties of the alignment and voltage holding ratio which are generally required for liquid crystal alignment elements. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Publication No. 2007-521361 [Patent Document 2] Japanese Patent Application Publication No. 2007-52 No. 506 (Summary of the Invention) [Problems to be Solved by the Invention] The present invention It is proposed according to the above problems, and an object thereof is to provide a liquid crystal alignment agent which can realize a high-speed response of a liquid crystal element and at the same time can form a liquid crystal display element having excellent performance such as a voltage holding ratio and a residual image property; A liquid crystal display element such as a vertical type having a liquid crystal alignment film formed of the liquid crystal alignment agent, and a polyorganosiloxane compound suitable for use as a liquid crystal alignment agent. [Means for Solving the Problems] The present invention proposed to solve the above problems is a liquid crystal alignment agent containing [A] a polyorganosiloxane compound containing an epoxy group-containing compound. A portion of the polyorganosiloxane and a moiety derived from a compound having a carboxyl group represented by the following formula (1) (hereinafter sometimes referred to as "specific carboxylic acid"). R4R2tRl_pOH (1) 0 (In the formula (1), R1 is a methylene group or an alkylene group having 2 to 30 carbon atoms, a phenyl group or a cyclohexylene group. These groups may have a substituent. R2 is a double bond, a linking group of any of a triple bond, an ether bond, an ester bond, and an oxygen atom. R3 is a group having at least two monocyclic structures. a is an integer of 0 to 1.) The liquid crystal alignment agent contains polyorganoquinone Since the oxane compound has a liquid crystal display element using a liquid crystal alignment film formed of the liquid crystal alignment agent, it has excellent alignment property, high voltage holding property, excellent afterimage properties, and shortens response time (starting time). Further, by having an epoxy group, the liquid crystal alignment agent can further improve the so-called electrical properties of the alignment property and the voltage holding ratio. Further, the liquid crystal alignment agent can introduce a structure having dielectric anisotropy in a side chain by having a specific structural unit, and a liquid crystal display element having a liquid crystal alignment film formed using the liquid crystal alignment agent further improves the nature and the residual of the 201120070 The nature of the film further shortens the response time. Further, by utilizing the reactivity between the epoxy group and the carboxyl group, it is possible to easily introduce a dielectric anisotropy represented by the above formula (1) on the side chain in the polyorganosiloxane of the main chain. structure. R3 in the above formula (1) is preferably a group represented by the following formula (2). R7——R6——R5——R4—— (2) (In the formula (2), R4 and R6 are respectively a phenyl group, a phenyl group, a naphthyl group, a cyclohexylene group, a dicyclohexyl group, and a cyclohexyl group. a phenyl group or a heterocyclic ring which may further have a substituent. R5 is any of an alkylene group, a double bond, a triple bond, an ether bond, an ester bond and a heterocyclic ring having 1 to 10 carbon atoms which may have a substituent. a linking group: R7 is any one of a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group and an alkoxy group, and when R6 has a plurality of substituents, they may be the same. Alternatively, a different group may be combined. b is an integer of 0 to 1. c is an integer of 1 to 9.) The above formula (2) is introduced on the side chain of the polyorganosiloxane compound of the liquid crystal alignment agent. The structure shown can increase the electro-optical response of the obtained liquid crystal alignment element. The above epoxy group is preferably a group represented by the following formula (x^l) or (χ1-).

201120070 (In the formula (XL1), A is an oxygen atom or a single bond. h is an integer of 1 to 3. i is an integer of 0 to 6. Here, when i is 0, A is a single bond. By containing a group represented by the above formula (X^1) or (X1-), it is possible to easily introduce a specific one represented by the above formula (1) in the polyorganosiloxane compound of the liquid crystal alignment agent. a side chain group of a structural compound. The liquid crystal alignment agent preferably further contains at least one polymer selected from the group consisting of [B] polyproline and polyimine (hereinafter sometimes referred to as "[B] polymer"). If a liquid crystal alignment film is produced using such a polymer as described above, a liquid crystal display element which further improves electrical properties can be obtained. The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the liquid crystal alignment agent. As a result, it is possible to obtain an electrooptical display element having excellent electrical properties such as excellent alignment properties, voltage holding ratio, and afterimage properties, and having high speed. In the present invention, it is also suitable to include a liquid crystal display element having a transparent electrode and the above liquid crystal alignment film laminated on the transparent electrode, the liquid crystal alignment mode is vertical, and has two or more regions having different alignment directions. Further, in the case of a means having two or more regions having different alignment directions, it is preferable to use a pattern-formed transparent electrode as a means for applying the alignment electrode or a means for imparting an alignment division function to the liquid crystal alignment film. The liquid crystal display element is suitable for use in driving modes such as TN, STN, IPS' VA (including VA-MVA mode, VA-PVA mode, etc.), and can further improve contrast and further improve high-speed responsiveness. 201120070 In the present invention, it is also suitable to include a liquid crystal alignment agent for forming a liquid crystal alignment film in a liquid crystal display element described below, and the liquid crystal display element has a transparent electrode and a liquid crystal alignment film laminated on the transparent electrode The liquid crystal alignment mode is a vertical type and has two or more regions having different alignment directions; and is characterized by comprising a compound having a group represented by the following formula (3). Further, in the case of a means having two or more regions having different alignment directions, it is preferable to use a patterned transparent electrode or a liquid crystal alignment film having an alignment dividing function. R3-|r2-|-* (3)

Ja (in the formula (3), R2 is a linking group containing a double bond, a triple bond, an ether bond, an ester bond or an oxygen atom. R3 is a group having at least two monocyclic structures. a is 0~ An integer of 1. Indicates a connection key.) In the present invention, it is also suitable to include a liquid crystal display element having a liquid crystal alignment mode of a vertical type and having two or more regions having different alignment directions, characterized in that A liquid crystal alignment film formed of the above liquid crystal alignment agent which is characterized by containing a compound having a group represented by the above formula (3). The polyorganosiloxane compound of the present invention contains a moiety derived from a polyorganosiloxane having an epoxy group, and a compound having a carboxyl group represented by the following formula (1), or R3 of the formula (1) has the following A moiety of a compound of a carboxyl group represented by the formula (2).

2 R1r 3 R R1 ο :o

\n/ 1 /V 201120070 (In the formula (1), 'R1 is a methylene group or an alkyl group having 2 to 30 carbon atoms, a phenyl group or a cyclohexylene group. These groups may have a substituent. R2 is a linking group containing any of a double bond, a triple bond, an ether bond, an ester bond, and an oxygen atom. R3 is a group having at least two monocyclic structures. a is an integer of 0 to 1.) R7·-R6- R5-a R4 - (2)

Jc Jb (in the formula (2), R4 and R6 are respectively a phenylene group, a phenylene group, a naphthyl group, a cyclohexylene group, a dicyclohexyl group, a cyclohexylene group or a heterocyclic ring, which may further have a substituent. R5 is a linking group containing any of an alkylene group, a double bond, a triple bond, an ether bond, an ester bond, and a hetero ring having 1 to 10 carbon atoms which may have a substituent. R7 is a hydrogen atom or a cyano group. Any one of a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group and an alkoxy group, and when R6 has a plurality of substituents, they may be the same or may be combined with different groups. b is 0~ An integer of 1 and C is an integer of 1 to 9.) The polyorganosiloxane compound is suitable for a liquid crystal alignment agent for constituting a liquid crystal display element having various properties such as an alignment property, a high-speed responsiveness, a voltage property, and an afterimage property. Used in. [Effects of the Invention] According to the present invention, it is possible to provide a liquid crystal alignment agent which is excellent in the alignment property and which can respond at high speed and which can form liquid crystal display elements having various properties such as voltage properties and afterimage properties. Therefore, the liquid crystal display is suitable for use in driving modes such as TN, STN, IPS, VA (including VA-MVA mode, VA-PVA mode, etc.). [Embodiment] -10-201120070 <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention contains a [A] polyorganosiloxane compound. Since the liquid crystal alignment agent contains a [A] polyorganosiloxane compound, it has a liquid crystal display element using a liquid crystal alignment film formed of the liquid crystal alignment agent, and has excellent alignment property, high voltage holding property, and excellent afterimage properties. Can shorten the response time. Further, "other polymer" which will be described later, such as [B] polymer, may be contained. Further, other optional components may be contained within a range not impairing the effects of the present invention. Hereinafter, each component will be described in detail. <[A] Polyorganosiloxane compound> [A] The polyorganosiloxane compound comprises a moiety derived from a polyorganosiloxane having an epoxy group, and a specific carboxylic acid represented by the above formula (1) part. The liquid crystal alignment agent can introduce a structure having dielectric anisotropy in a side chain by having a specific structural unit, and a liquid crystal display element having a liquid crystal alignment film formed using the liquid crystal alignment agent can further improve electrical properties and image retention properties. 'And further shorten the response time. Further, by utilizing the reactivity between the epoxy group and the carboxyl group, it is possible to easily introduce a dielectric anisotropy represented by the above formula (1) on the side chain in the polyorganosiloxane of the main chain. structure. The [A] polyorganosiloxane compound is considered to be mainly obtained from a reactant of an epoxy group of a polyorganosiloxane and a carboxyl group of a specific carboxylic acid, but in order to facilitate the subsequent description, it will be derived from The portion of the epoxy group-containing polyorganosiloxane (and its derivative) is separated from the portion derived from the specific carboxylic acid', and the [A] polyorganosiloxane compound contained in the liquid crystal alignment agent is described in -11-201120070. [Part from polyorganosiloxane having an epoxy group] This moiety is in the structure of the [A] polyorganosiloxane compound, and comprises a polyorganosiloxane skeleton as far as the polymer main chain The enthalpy of the epoxy group-containing skeleton of the side chain extended by the main chain of the organic siloxane. As described above, the [A] polyorganosiloxane compound is considered to be a reaction of most of the epoxy groups with a specific carboxylic acid, and the initial structure is not present, but the specific carboxylic acid may be bonded to a moiety other than the epoxy group. Therefore, in the present invention, two forms are included to form "a moiety derived from an organooxane compound having an epoxy group". [A] Polyorganosiloxane compound by an epoxy group having a group including a glycidyl group, an oxidized glycidyl group, or an epoxycyclohexyl group, the liquid crystal alignment agent can further improve the alignment property and the voltage retention ratio, so-called electricity nature. The epoxy group is preferably a group represented by the above formula (X^1) or (X1·). By containing a group represented by the above formula (XM) or (X1-) in the polyorganosiloxane having the structural unit represented by the above formula (1), polyorganooxime which can be used in the liquid crystal alignment agent In the alkane compound, a side chain group derived from a compound having a specific structure represented by the above formula (1) is easily introduced. In the above formula (X1-!) or (X1-2), a group represented by the following formula is preferred.

氺

-12- 201120070 Polyorganosiloxane having an epoxy group The polystyrene-equivalent weight average molecular weight measured by gel permeation is more than '100,000, more preferably 1,000 to 50,000, especially preferably 1, 〇〇〇' [Synthesis method of polyorganosiloxane having epoxy group] The polyorganosiloxane having an epoxy group is preferably a mixture of a decane compound or a decane compound having an epoxy group, preferably It is synthesized by hydrolysis, hydrolysis or condensation in the presence of a suitable organic solvent or water. With respect to the above decane compound having an epoxy group, it may be, for example, 3-oxyglycidylpropyltrimethoxydecane, 3-oxypropyltriethoxydecane, 3-oxyglycidylpropyl decane, 3- oxidized glycidyl propyl methyl diethoxylated glycidyl propyl dimethyl methoxy decane, 3- ethoxypropyl dimethyl ethoxy decane, 2-oxyglycidyl ethane hexane, 2-oxyglycidylethyltriethoxydecane, glycerylethylmethyldimethoxydecane, 2-oxo-glycolyldiethoxydecane, 2-oxyglycidylethyldimethane' 2 · Oxidized glycidyl ethyl dimethyl ethoxy decane. Hydroglycidyl butyl trimethoxy decane, 4-oxyglyoxy methoxy decane, 4- oxidized glycidyl butyl methyl dioxy oxy glycidyl butyl group Diethoxy decane, 4-methoxybutyldimethylmethoxydecane, 4-ethoxyglycidyl ethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy] Chromatography (GPC) 圭 Gui is 5 〇〇 ~ ~ 20, 〇〇〇. Examples of epoxy groups and other decanes and catalysts include exemplified glycidyl methyl dimethoxy decane, 3-oxo glycidyl trimethoxy 2- oxidized condensed ethyl methoxy methoxy hydrazine, 4 - butyl butyl diethyl decane, 4-glycidyl butyl dimethyl oxime, 2-(3,4- -13-201120070 epoxycyclohexyl)ethyltriethoxy decane, 3 -(3,4-epoxycyclohexyl)propyltrimethoxydecane, 3-(3,4-epoxycyclohexyl)propyltriethoxylate or the like. They can be used alone or in combination of two or more. Examples of the other decane compound mentioned above include tetrachlorosane, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy oxalate, tetraisopropoxy decane, and tetra-n-butoxy decane. , four or three grades of butoxy@"Complete" trichlorodecane, trimethoxydecane, triethoxydecane, tri-n-propoxylated samarium, triisopropoxy decane, tri-n-butoxy decane, three-three Grade butoxylate, fluorotrichloromethane, fluorotrimethoxydecane, fluorotriethoxy sand, fluorotri-n-propoxy decane, fluorotriisopropoxy decane, fluorotri-n-butoxy sand 'Fluorine tris-butoxybutane' methyltrichlorodecane, methyltrimethoxy sand, methyltriethoxydecane, methyltri-n-propoxydecane, methyltriisopropoxydecane, Methyl tri-n-butoxy decane, methyl tri-tertiary butoxylate, 2-(trifluoromethyl)ethyltrichlorodecane, 2-(trifluoromethyl)ethyltrimethoxy sane, 2-(Trifluoromethyl)ethyltriethoxydecane, 2-(trifluoromethyl)ethyltri-n-propoxydecane, 2-(trifluoromethyl)ethyltriisopropoxydecane, 2-(trifluoromethyl Ethyltri-n-butoxydecane' 2-(trifluoromethyl)ethyltris-tert-butoxydecane, 2-(perfluoro-n-hexyl)ethyltrichlorodecane, 2-(perfluoro-n-hexyl) Trimethoxy decane, 2-(perfluoro-n-hexyl)ethyltriethoxy decane, 2-(perfluoro-n-hexyl)ethyltri-n-propoxy decane, 2-(perfluoro-n-hexyl)ethyl Isopropoxydecane, 2-(perfluoro-n-hexyl)ethyltri-n-butoxydecane, 2-(perfluoro-n-hexyl)ethyltris-butoxypropane, 2-(perfluoro-n-octyl) Ethyltrichloromethane, 2-(perfluoro-n-octyl)ethyltrimethoxydecane, 2-(perfluoro-14-201120070 n-octyl)ethyltriethoxydecane, 2-(perfluoro-n-octane Ethyl tri-n-propoxy decane, 2-(perfluoro-n-octyl)ethyltriisopropoxy decane, 2-(perfluoro-n-octyl)ethyltri-n-butoxy decane, 2-( Perfluoro-n-octyl)ethyltris-tert-butoxydecane, hydroxymethyltrichlorodecane, hydroxymethyltrimethoxydecane, hydroxyethyltrimethoxydecane, hydroxymethyltri-n-propoxydecane, hydroxy Methyl triisopropoxy decane, hydroxymethyl tri-n-butoxy decane, Methyl tri-tertiary butoxy decane, 3-(methyl) propylene methoxy propyl trichloro decane, 3-(methyl) propylene methoxy propyl trimethoxy decane, 3-(methyl) Propylene methoxy propyl triethoxy decane, 3-(methyl) propylene methoxy propyl tri-n-propoxy decane, 3-(methyl) propylene methoxy propyl triisopropoxy decane, 3-(Methyl)propenyloxypropyltri-n-butoxydecane, 3-(methyl)propenyloxypropyltris-tert-butoxydecane, 3-mercaptopropyltrichlorodecane, 3 - mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, 3-mercaptopropyltri-n-propoxyoxydecane, 3-mercaptopropyltriisopropoxydecane, 3-indole Propyl tri-n-butoxy decane, 3-mercaptopropyltris-tert-butoxy decane, decylmethyltrimethoxydecane, decylmethyltriethoxydecane, vinyltrichlorodecane, ethylene Trimethoxy decane, vinyl triethoxy decane, vinyl tri-n-propoxy decane, vinyl triisopropoxy decane, vinyl tri-n-butoxy decane, vinyl tri- tertiary butoxy decane Allyl trichloropurine Alkane, propyl trimethoxy decane, allyl triethoxy decane, allyl tri-n-propoxy decane, allyl triisopropoxy decane, allyl tri-n-butoxy decane, olefin Propyl tris-butoxybutane, phenyltrichlorodecane, phenyltrimethoxydecane, phenyltriethoxydecane, phenyltri-n-propoxydecane, phenyl tri-15-201120070 isopropoxy Base decane, phenyl tri-n-butoxy decane, phenyl tri-tert-butoxy decane, methyl dichlorodecane, methyl dimethoxy decane, methyl diethoxy decane, methyl di-n-propoxy Base decane, methyl diisopropoxy decane, methyl di-n-butoxy decane, methyl di-tert-butoxy decane, dimethyl dichloro decane, dimethyl dimethoxy decane, dimethyl Diethoxydecane, dimethyldi-n-propoxyoxydecane, dimethyldiisopropoxydecane, dimethyldi-n-butoxydecane, dimethylditributoxybutane, (methyl ) 2-(Perfluoro-n-octyl)ethyl]dichlorodecane, (methyl)[2-(perfluoro-n-octyl)ethyl]dimethoxydecane, (methyl) [2-(all) Fluorine Ethyl]diethoxy decane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-n-propoxy decane, (methyl) [2-(perfluoro-n-octyl) Diisopropoxy decane, (methyl) [2-(perfluoro-n-octyl)ethyl]di-n-butoxy decane, (methyl) [2-(perfluoro-n-octyl)ethyl] Di-tert-butoxybutane, (methyl)(3-mercaptopropyl)dichlorodecane, (methyl)(3-mercaptopropyl)dimethoxydecane, (methyl)(3-锍Propyl)diethoxydecane, (methyl)(3-mercaptopropyl)di-n-propoxydecane, (methyl)(3-mercaptopropyl)diisopropoxydecane, (A) (3-mercaptopropyl)di-n-butoxydecane, (methyl)(3-mercaptopropyl)di-tert-butoxydecane, (methyl)(vinyl)dichlorodecane, (A) (vinyl)dimethoxydecane, (meth)(vinyl)diethoxydecane, (methyl)(vinyl)di-n-propoxydecane, (methyl)(vinyl) Isopropoxydecane '(methyl)(vinyl)di-n-butoxydecane, (A (vinyl) di-tertiary butoxy decane, divinyl dichlorodecane, divinyl dimethoxy decane, divinyl diethoxy decane, divinyl di-n-propoxy decane, two Vinyl diisopropoxy decane, -16 - 201120070 divinyl di-n-butoxy decane, divinyl di-n-butoxy decane 'diphenyl dichloro decane, diphenyl dimethoxy decane, Diphenyldiethoxydecane, diphenyldi-n-propoxy decane, diphenyldiisopropoxydecane 'diphenyldi-n-butoxy decane, diphenyl di-tertiary butoxy decane' Chlorodimethyl decane, methoxy dimethyl decane, ethoxy dimethyl decane, chlorotrimethyl sane, bromotrimethyl decane, iodine trimethyl decane, methoxy trimethyl decane, B Oxylic trimethyl decane, n-propoxy trimethyl decane, isopropoxy trimethyl decane, n-butoxy trimethyl decane, tertiary butoxy trimethyl decane, secondary butoxy 3 Methyl decane, (chloro) (vinyl) dimethyl decane, (methoxy) (vinyl) dimethyl decane, (ethoxy) (vinyl) a decane having one ruthenium atom such as decane, (chloro)(methyl)diphenyl decane, (methoxy)(methyl)diphenyl decane or (ethoxy)(methyl)diphenyl decane Compound. As for the commercially available products, for example, KC-89, KC-89S 'X-21-3153' X-21-5841' X-21-5842' X-21-5843, X-2 Bu 5844, X-21-5845, X-21-5846, X-21-5847, X-21-5 848, X- 22- 1 60AS, X- 22- 1 70B, X- 22- 1 7 0BX, X-22 - 1 70D ' X- 22- 1 70DX , X - 2 2 · 1 7 6 B , X - 2 2 - 1 7 6 D , 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-41-1805' X-41-1810' KF6001' KF6002, KF6003, KR212, KR-213, KR -217, KR220L, KR242A, KR27, KR282, KR300, KR31, KR401N, KR500, -17- 201120070 KR5 10, KR5 206, KR5 230, KR5235, KR92 1 8, KR9 7 06 (above, Shin-Etsu Chemical Co., Ltd.);

Class Resin (Showa Denko); SH804 'SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR24U, SR2416, SR2420 (above, TORAY · CORNING); FZ3711, FZ3722 (above, Nippon Unicar ^ W ]); DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45 ' DMS-S5 1, DMS-227, PSD-03 3 2, PDS-1615, PDS- 9 9 3 1, XMS-5025 (above, Chisso);

Methyl silicate MS51, Methyl silicate MS56 (above, Mitsubishi Chemical Corporation);

Ethyl silicate 28 'Ethyl silicate 40, Ethyl silicate 48 (above, Colcoat); GR100, GR650, GR908 'GR950 (above, Showa Denko) and other partial condensates. Among these other decane compounds, tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, and methyl triethyl are preferable from the viewpoints of the alignment property and storage stability of the obtained liquid crystal display element. Oxydecane, 3-(meth)acryloxypropyltrimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, vinyltrimethoxydecane, vinyl triethyl Oxydecane, allyltrimethoxydecane, allyltriethoxydecane' -18- 201120070 Phenyltrimethoxydecane, phenyltriethoxydecane, 3-mercaptopropyltrimethoxydecane And 3-mercaptopropyltriethoxydecane, mercaptomethyltrimethoxydecane, mercaptomethyltriethoxydecane, dimethyldimethoxydecane, dimethyldiethoxydecane. The polyorganosiloxane having an epoxy group preferably used in the present invention has a solvent equivalent of 100 to 10,000 g/mol, more preferably 100 to 10,000 g/mol, because a sufficient amount of a side chain having dielectric anisotropy is introduced. 150~l,000g/mol, particularly preferably 150~300g/mol. Therefore, in the synthesis of the polyorganosiloxane precursor having an epoxy group, it is preferred to set the use ratio of the decane compound and the other decane compound so that the epoxy equivalent of the obtained polyorganosiloxane having an epoxy group is obtained. For the above range. In the synthesis of the polyorganosiloxane having an epoxy group used in the present invention, it is more preferred to use only a decane compound and no other decane compound. The organic solvent to be used in the synthesis of the polyorganosiloxane having an epoxy group may, for example, be a hydrocarbon compound, a ketone compound, an ester compound, an ether compound or an alcohol compound. Examples of the hydrocarbon include, for example, toluene and xylene; and examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, and diethyl ketone. And cyclohexanone, etc.; as the above ester, 'e.g. ethyl acetate, n-butyl acetate, isoamyl acetate 'propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate And ethyl lactate, etc.; as the above-mentioned ether, for example, ethylene glycol dimethyl ether, ethyl alcohol diethyl ether, tetrahydrofuran, dioxane, etc.; for the above alcohol, it can be listed as -19-201120070 For example, I-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether 'ethylene glycol mono-n-butyl Ether, propylene glycol monomethyl ether 'propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. Among them, those which are not water-soluble are preferred. These organic solvents may be used singly or in combination of two or more. The organic solvent is preferably used in an amount of 10 to 10,000 parts by mass, more preferably 50 to 1, by mass based on 100 parts by mass of the total of the decane compound. When the polyorganosiloxane having an epoxy group is produced, the amount of water is preferably from 0.5 to 100 moles, more preferably from 1 to 30 moles per mole of the total decane compound. As the above catalyst, for example, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound or the like can be used. The alkali metal compound may, for example, be sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide or potassium ethoxide. The above organic base may, for example, be a primary or tertiary organic amine such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine or pyrrole; triethylamine, tri-n-propylamine, and tri-n-butyl a secondary organic amine such as a amide, a pyridine, a 4-dimethylaminopyridinium or a dinonylcycloundecene; a new organic amine such as tetramethylammonium hydroxide; and the like. Among these organic bases, a secondary organic amine such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine or 4-dimethylaminopyridine is preferred in view of stable reaction. New organic amines such as tetramethylammonium. In the case of producing a polyorganosiloxane having an epoxy group, an alkali metal compound or an organic base is preferred. By using an alkali metal or an organic base-20-201120070, the catalyst "can not produce a ring-opening reaction such as ring opening, and can obtain a desired polyorganosiloxane with a high hydrolysis 'condensation rate', so that the production stability is excellent. 'The system is better. Further, the liquid crystal alignment agent containing a reaction product of an epoxy group-containing polyorganosiloxane and a specific carboxylic acid synthesized using an alkali metal compound or an organic base as a catalyst is extremely excellent in storage stability. The reason is as pointed out in Chemical Reviews, Vol. 95, pl 409 (1995). 'It is speculated that if an alkali metal compound or an organic base is used as a catalyst in the hydrolysis or condensation reaction, a random structure, a ladder structure, and a cage are formed. The structure is such that a polyorganosiloxane having a small content of a stanol group cannot be obtained. It is presumed that the condensation reaction between the stanol groups is suppressed by the small content ratio of the stanol group, and the condensation reaction between the stanol group and the other polymer is suppressed when the liquid crystal alignment agent contains another polymer described later. Excellent storage stability. In terms of the catalyst, an organic base is particularly preferred. The amount of the organic base to be used should be appropriately determined depending on the kind of the organic base, the reaction conditions, and the like, and is appropriately set. For example, it is preferably 1 to 3 moles, more preferably 0.05 to 1 times, based on the total of the decane compound. Moor. Hydrolysis or hydrolysis in the production of polyorganosiloxane having an epoxy group. The condensation reaction is carried out by dissolving a decane compound having an epoxy group and other decane compounds used as needed in an organic solvent, and the solution and the organic base. It is preferably mixed with water and heated by, for example, an oil bath. In the hydrolysis and condensation reaction, the heating temperature of the ideal oil bath is preferably 丨3 〇 ° C or less, more preferably 40 0 to 1 0 0 ° C, preferably heating 0 · 5 ~ 12 hours, more preferably - 21 - 201120070 Hot 1 to 8 hours. When heating, the mixture may be stirred or refluxed. After completion of the reaction, it is preferred to wash the organic layer separated from the reaction liquid with water. At the time of the washing, it is preferably washed by water containing a small amount of salt, for example, a 0. 2 hydrazine aqueous solution or the like. The washing is carried out until the aqueous layer after washing is neutral, and then dried as a drying agent such as calcium sulfate or molecular sieve as needed, and then the solvent is removed to obtain a polyorganosiloxane having an epoxy group as a target. In the present invention, a commercially available one is used for a polyorganosiloxane having an epoxy group. Examples of such commercially available products include DMS-ECH, DMS-E12, DMS-E21, and EMS-32 (above, Chisso: etc. [A] polyorganosiloxane compound may contain an epoxy group. a portion of the hydrolyzate formed by hydrolysis of the organic oxirane itself, and a polyorganomethoxy oxane derived from an epoxy group to form a hydrolysis condensate component. These hydrolyzates of the constituent materials of the portion are hydrolyzed and condensed with The hydrolysis and condensation conditions of the epoxy group-containing polyorganooxane are the same as those prepared. [Parts derived from a specific carboxylic acid] This portion which is not in the above formula (1) corresponds to the polyorganism of the [A] component in the liquid crystal alignment agent. In the structure of the oxoxane compound, the structure derived from the residue mainly corresponding to the structure of the epoxy group derived from the main chain of the polyorganosiloxane is a starting point side bond structure. However, in the present invention, the machine is introduced. The part which is dissolved in the case where the solvent is dissolved in the vicinity of the specific carboxylic acid and the epoxy group is also included in the case of the connection of j, -22-201120070. Part of a specific carboxylic acid R1 of the above formula (1) is a methylene group or a carbon atom having 2 to 3 fluorenyl groups, a phenyl group or a cyclohexyl group, which may further have a substituted alkyl group having 2 to 30 carbon atoms. Further, examples thereof include a propyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a decyl group, an extensin group, an undecyl group, a dodecyl group, a tetradecyl group, an alkyl group. , octadecyl, hexadecyl, eicosyl, alkyl, tetracosyl, tetracosyl, hexadecane, fifteen Ten yards, twenty-seven yards, one base, twenty-nine alkyl and tenthylene, etc. Among them, liquid crystal alignment appears, preferably octyl, thiol, Extending an alkylene group such as undecyl, an extended dodecyl group, a tetradecyl group, a hexadecyl octadecyl group, a hexadecane group, and an eicosyl group. R 2 is a linking group containing a double bond, a triple bond, an ether bond, an ester bond, and an oxygen atom. Further, R 2 may contain any of the above bonds to contain each bond in combination. Further, R 1 is a phenyl group or a stretch. Cyclohexyl R2 preferably contains an alkylene group having 1 to 30 carbon atoms in view of the alignment property of the formed alignment film and solubility in a solvent. $ is an integer of 0 to 1. R3 has at least two single ring structures. The group 'is preferably a dominant or negative dielectric anisotropy. The single ring structure is a ring-junction in the "extended alkyl group." Out of the Ethylene base, the extension of the sixteen twenty-one base, the extension of the eighteenth courtyard, the stability base, the extension, the extension of more than ten, can also be, from the point of view of the 8th, a shows the normal structure and its 23- 201120070 The structure of the ring structure is independent of 'the bond of a ring structure and the other ring structure, the structure of the so-called condensed ring structure. Further, the monocyclic structure may be any of an alicyclic structure, an aromatic ring structure or a heterocyclic structure, or may be formed by combining them. R3 is not particularly limited as long as it has a group having at least two or more monocyclic structures. Representatively, R3 is preferably a group represented by the above formula (2). By introducing the structure represented by the above formula (2) into the side chain of the polyorganosiloxane compound of the liquid crystal alignment agent, the electrooptic response of the obtained liquid crystal alignment element can be increased. In the formula (2), R4 and R6 are each independently a phenyl group, a biphenyl group, a naphthyl group, a cyclohexylene group, a dicyclohexyl group, a cyclohexylene group or a heterocyclic ring. Examples of the heterocyclic ring include a pyridine ring, a hydrazine ring, a pyrimidine ring and the like. In the above formula (2), R5 includes any of an alkylene group, a double bond, a triple bond, an ether bond, an ester bond and a hetero ring having 1 to 10 carbon atoms which may have a substituent, and is a combination of R4 and R6. The linking group can be appropriately selected depending on the alignment property and dielectric anisotropy necessary for the polyorganosiloxane compound. Further, since b is an integer of 0 or 1, when designing the side chain structure, R5' may or may not be contained. In the above formula (2), R7 is any one of a hydrogen atom, a cyano group, a fluorine atom 'trifluoromethyl group, an alkoxycarbonyl group, an alkyl group and an alkoxy group. In the case of the alkoxycarbonyl group, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group or the like can be mentioned, and examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. a linear or branched alkyl group having a carbon number of 1 to 20, such as a n-butyl group or an isobutyl group, is an alkyl group having a molecular weight of 1 to 20, and the like. Examples of the alkoxy group include a methoxy group and an ethoxy group. Propoxy and the like. In the above formula (2), when R6 has a plurality of substituents (R7), it can be used in groups having different groups. In order to stably exhibit a desired dielectric anisotropy, in the case where R6 has a plurality of substituents, a combination of a fluorine atom and a cyano group, a combination of a fluorine atom and an alkyl group, a cyano group and an alkyl group are preferred. The combination. In addition, eΛ c疋 is an integer of 0 to 9. The compound having a carboxyl group shown may, for example, be a compound represented by the following formula m, (D '1) to (D - 2 5 ). -25- 201120070 rHch^cooh (D-1) r3-{ch2)^-〇-5-^Kcooh (D-16) R3-〇4ch2-)^-COOH (D-2) ,", S /= \ 〇R 〇~tCH Seven. A 11^ J>—COOH (D-17) R3—〇”L_^ch7c〇〇h (4) O 〇 _ R3-. 'CH2"t~C00H (°-4) R3 R ===~~^CH2")^-COOH (D-5> R3-(cH2t^^ COOH (D-6) R3 R3 •COOH (D- 18) COOH (D-19) 卜卜七 L〇-〇^c( °~^CH2V^^—COOH (D-7) R3—0-fcH2-)^0—(^^-C R3^c^ Tr0^〇~( CH2')t~/~COOH (D-9) R3 —V . . /==\ ^"fcH2)^-〇—^ ^~COOH (D-23) R3 —- R3— 〇-Λ CH·

COOH (D-8) -COOH (D-22)

R3-

:CK

COOH (D-9) COOH (D-10) , -hQ~ rHch2)JL〇_^_COOH (D-11)«3-〇-4〇η2)Λ_0_^_COOH (DR 〇—^~~(ch2) j—U—〇—(^ ^-ΟΟΟΗ (D-13) ~^ch2)J-0_^ COOH (D-14) R ~~===~~^CH2·)^—〇—(^ COOH ( D-15) (In the formula (D·1) to (D-25), R3 is the same as defined in the above formula (1). m is an integer of 1 to 30.) With respect to the group represented by the above formula (2) For example, a group represented by the following formulas (E-1) to (E-58) can be cited. R3, •ch7 COOH (D-25) -26- 201120070

-27- 201120070

F

(E-22) F

(E-31)

F

(E-23) F

F3C

(E-24)

(E-32) (Ε·33) (E-34) (Ε·35) -28- 201120070

-29- 201120070

CM

(E-51)

R

R

(^-52) F F

(In the formula (E 1) (E 58), 'R is an alkyl group having a uo number of carbon atoms (methyl S-ethyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group, etc.) or alkoxy group (Methoxy, ethoxy, any ?m propoxy, isopropoxy, butoxy, etc.).) [Synthesis of a specific carboxylic acid & j There is no particular limitation on the synthesis procedure of a specific citric acid. It can be combined with a well-known method. With respect to a representative synthetic step, for example, (1) a compound having a benzene-based skeleton and a compound in which an alkyl chain portion of a higher fatty acid ester is substituted with a halogen can be exemplified under basic conditions, a hydroxyl group and a halogen of a phenol skeleton. a method in which a substituted carbon forms a bond, and then an ester is reduced to form a specific carboxylic acid; (2) a compound having a phenol skeleton and a carbonic acid are formed to form a compound having an alcohol at the end, and the hydroxyl group and the benzene are expanded to activate chlorine. Thereafter, the activated portion and the hydroxy-containing benzamidine vinegar are reacted ' -30- 201120070. The sulfonyl group is partially detached, and the hydroxyl group of the terminal alcohol compound and the hydroxyl group of the methyl benzoate having a hydroxyl group as a substituent form a bond, and then A method of reducing an ester, forming a specific carboxylic acid, or the like. However, the order of synthesis of the specific carboxylic acid is not limited thereto. <Method for synthesizing polyorganotoxioxane compound> The method for synthesizing the [A] polyorganosiloxane compound is not particularly limited, and it can be synthesized by a generally known method. The synthesis method of the [A] polyorganosiloxane compound having an epoxy group can be preferably synthesized by reacting a polyorganosiloxane having an epoxy group and a specific carboxylic acid ' in the presence of a catalyst. Among them, the specific acid is preferably 0.001 to 1 〇mol', more preferably 0.01 to 5 mol, still more preferably 0.05 to 2 mol, based on the epoxy group of the lmol polyorganic sand treatment. In the present invention, a part of the specific carboxylic acid may be used in place of a compound represented by the following formula (5) within a range not impairing the effects of the present invention. At this time, the synthesis of the [A] polyorganosiloxane compound can be carried out by reacting a polyorganosiloxane having an epoxy group with a mixture of a specific carboxylic acid and a compound represented by the following formula (4). A1-L°——L1-Z (4) In the above formula (4), A1 is a linear or branched alkyl group having 1 to 30 carbon atoms and may be 1 to 20 carbon atoms. The alkyl group or the alkoxy group has a cycloalkyl group having 3 to 10 carbon atoms or a hydrocarbon group having a steroidal skeleton of 17 to 51 -31 to 201120070. Here, the ?-portion or the whole of the hydrogen atom of the above-mentioned alkyl group and alkoxy group may be substituted with a substituent such as a cyano group, a fluorine atom or a trifluoromethyl group. L. It is a single button, *-〇-, .-COO- or ¥-〇CO-. The connection key with the connection is A 1 . L1 is a single bond, an alkyl group having a carbon number of 20, a phenyl group, a phenyl group, a cyclohexylene group, a cyclohexyl group or a formula (1^-1) or (Li-2) Group. Z is a monovalent organic group capable of forming a linking group by reacting with an epoxy group in the [A] polyorganosiloxane compound. Where U is a single bond, 1 is a single bond.

In the above formula (LM) or (L, 2), the linking bond with "each is bonded to Z. Z is preferably a carboxyl group. In the above formula (4), the number of carbon atoms represented by Αι is 1 to 30. The chain or branched alkyl group may, for example, be methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, secondary butyl, n-pentyl or 3-methyl. Butyl, 2-methylbutyl, hydrazine-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 4-methylpentyl, 3-methylpentyl, 2.methylpentyl , m-methylpentyl, 3,3-dimethylbutyl ' 2,3-dimethylbutyl, 1,3-dimethylbutyl, 2,2·dimethyl-32- 201120070 butyl, 1 ,2-dimethylbutyl, 1,2-dimethylbutyl, 1,1-dimethylbutyl, n-heptyl, 5-methylhexyl, 4-methylhexyl, 3-methylhexyl , 2-methylhexyl, 1-methylhexyl, 4,4-dimethylpentyl, 3,4-dimethylpentyl, 2,4-dimethylpentyl, 1,4-dimethyl Pentyl, 3,3-dimethylpentyl, 2,3-dimethylpentyl, 1,3-dimethylpentyl' 2,2-dimethylpentyl, 1,2-dimethyl Butyl, 1,1-dimethylpentyl, 2,3,3-trimethylbutyl, 1,3 3-trimethylbutyl, 1,2,3-trimethylbutyl, n-octyl, 6-methylheptyl, 5-methylheptyl, 4-methylheptyl, 3-methylheptyl Base, 2-methylheptyl, 1-methylheptyl, 2-ethylhexyl, n-decyl 'n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-ten Tetraalkyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, etc. It can be an alkyl or alkane having 1 to 20 carbon atoms. The cycloalkyl group having 3 to 10 carbon atoms substituted by an oxy group may, for example, be a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a cyclodecyl group or a cyclododecyl group. The hydrocarbon group having a steroidal steroid skeleton having a carbon number of from 17 to 5 1 may, for example, be a group represented by the following formulas (A-1) to (A-3). -33- 201120070

Or a fluoroalkyl group having 1 to 20 carbon atoms and a group selected from the above formula (A-1) or (A-3). The compound represented by the above formula (4) is preferably a compound represented by any one of the following formulas (4-1) to (4-6). -34- 201120070

CuF2u+1-CvH2v——COOH (4-1)

CwH2w+1—COOH (4-2)

CwH2w-M~f COOH (4-3)

CkH2k+1-fcF2^-(-CH2^-f〇^^^^COOH (4-4)

(4-5)

o—C-fcH2^—COOH O

-COOH (4-6) ^w^2w+1 In the above formula (4-l) to (4-6), u is an integer of 1 to 5. v is an integer from 1 to 18. w is an integer from 1 to 20. k is an integer of Bu 5. p is 0 or l〇q is an integer from 0 to 18. r is an integer from 0 to 18. s and t are each independently an integer of 0 to 2. Among these compounds, a compound represented by the following formula (5 -1) to (5 - 7 ) is more preferably 0 - 35 - 201120070 C17H35-COO Η (5-1) f3c-o-^_ COOH (5-2 F3C—C3H6—0—~^)-COOH (5-3) C2F5—C3H6—-〇{ /)—COOH (5-4)

C8H17——O

COOH

(5-6) (5-7) (5-5) C5H11

The compound represented by the above formula (4) is a compound obtained by reacting a specific carboxylic acid and a polyorganosiloxane having an epoxy group, and imparting a pretilt-developing site to the obtained liquid crystal alignment film. In the present specification, the compound represented by the above formula (4) is sometimes referred to as "other pretilt angle king compound". In the present invention, 'when a specific carboxylic acid is used together with other pretilt-developing compounds, the total use ratio of the specific carboxylic acid and other pretilt-developing compounds is relative to the epoxy group of 1 mol of the polyorganosiloxane. Preferably, it is -36-201120070 0.001~1.5mol, more preferably 0.01~lmol, further preferably 0.05~0.9m ο1. In this case, the other pretilt-developing compound is preferably used in an amount of 7 5 m ο 1 % or less, more preferably 50 ο % or less, relative to the total amount of the specific carboxylic acid. If the ratio of other pretilt angle developing compounds exceeds 7 5 m ο 1 %, it may adversely affect the high-speed response of the liquid crystal. For the catalyst used in the reaction of the epoxy group in the polyorganosiloxane and the residue-containing compound represented by the above formula (4) and other pretilt-developing compounds, an organic base or an epoxy can be used. A compound known as a so-called curing accelerator for reacting a compound with an acid anhydride. The above-mentioned organic base may be exemplified by a primary- tertiary organic amine such as ethylamine, diethylamine, piperidine, piperidine, pyrrolidine or pyrrole; triethylamine, tri-n-propylamine, tri-n-butyl a secondary organic amine such as an amine, a pyridine, a 4-dimethylaminopyridine or a dinonylcycloundecene; a new organic amine such as tetramethylammonium hydroxide; and the like. Among these organic bases, 'triethylamine' tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine or tetramethylammonium hydroxide are preferred. The curing accelerator may, for example, be a secondary compound such as benzyldimethylamine, 2,4,6-gin (dimethylaminomethyl)phenol, cyclohexyldimethylamine or triethanolamine. Amine; 2-methylimidazole, 2-n-heptyl imidazole ' 2 -n-indole-alkylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, ι-benzyl-2-yl Imidazole, ι_pyringyl-2-phenylimidazole, 1,2-dimethylimidazolium 2·ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-methylimidazole Bismuth, 1-(2-cyanoethyl)-2-n-undecyl------------------------------ Benzyl)-2-ethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-(hydroxymethyl)imidazole, 1-(2-cyanoethyl) 2-phenyl-4,5-bis[(2'-cyanooxy)methyl]imidazole, 1-(2-cyanoethyl)-2-n-i-alkyl-imidazole Salt, 1-(2-cyanoethyl)-2-phenylimidazolium pyrogallate, cyanoethyl)-2-ethyl-4-methylimidazole gun benzoate, 2, 4-di-6-[2'-methylimidazolyl-(1')]ethyl-s-tripper, 2,4-di-6-(2'-n-^-alkane Imidazolyl)ethyl-s-tripper, 2,4-di-6-[2'-ethyl-4'-methylimidazolyl-(1')]ethyl-s-trisole, 2 - Isoformyl adduct of thiazole, isomeric cyanuric acid of 2-phenylimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]B Imidazole compound such as bis-s-tri-trap cyanuric acid adduct; organic phosphorus such as diphenylphosphine, triphenylphosphine, triphenyl phosphite; benzyltriphenyl chloride, bromide n-Butyl scale, methyl bromide, ethyltriphenylphosphonium bromide, n-butyltriphenyl bromide, bromophenyliron, ethyltriphenylphosphonium iodide, ethyltriphenyl Iron acetate, butyl iron 0,0-diethylphosphonium disulfide, tetra-n-butyl benzophenone, tetra-n-butyl iron tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate a new iron salt such as phenylphosphonium tetraphenylborate; 1,8-diazobicyclo[5.4.0]undecene-7 and its organic acid salt, etc.; zinc octoate, tin octoate, and Organometallics such as acetonide aluminum complex; K -4- 5-diethylethylbenzene 1-(2-

Synthetic triphenylated tetra-tetra-n-three-salt salt, di-coupled-38- 201120070 tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butyl chloride New ammonium salts such as ammonium chloride; boron compounds such as boron trifluoride and triphenyl borate; metal halides such as zinc chloride and tin chloride; dicyanoguanamine and adducts of amines and epoxy resins, etc. a high-melting-point-dispersion latent curing accelerator such as an amine addition accelerator; a microcapsule-type latent curing accelerator formed by covering a surface of a curing accelerator such as an imidazole compound, an organic phosphorus compound or a neo-square salt; Type of latent curing accelerator; latent curing accelerator such as high temperature decomposing thermal cationic polymerization type latent curing accelerator such as Lewis acid salt and Bronsted acid salt, etc. New ammonium salts such as ammonium amide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride. The catalyst is preferably 100 parts by mass or less, more preferably 〇.〇1 to 1 〇〇 parts by mass relative to 100 parts by mass of the polyorganosiloxane having an epoxy group. The step is preferably 0.1 to 20 mass. The amount used is used. The reaction temperature is preferably from 0 to 200 ° C, more preferably from 50 to 150 t. The reaction time is preferably from 0 to 1 to 50 hours, more preferably from 5 to 20 hours. The synthesis reaction of the [A] polyorganosiloxane compound can be carried out in the presence of an organic solvent as needed. The organic solvent may, for example, be a hydrocarbon compound, an ether compound, an ester compound 'ketone compound, a guanamine compound, an alcohol compound or the like. Among them, an ether compound, an ester compound, and a ketone-39-201120070 compound are preferable from the viewpoints of solubility of a raw material and a product, and ease of purification of the product. The solvent has a solid content concentration (the ratio of the mass of the component other than the solvent in the reaction solution to the total mass of the solution) is preferably 质量.% by mass or more, 70% by mass or less, more preferably 5% by mass or more, and 50% by mass. % below the amount used. The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of the obtained [A] polyorganosiloxane compound is not particularly limited, and is preferably 1, 〇〇〇 200,000, more preferably 2,000. ~20,000. By this molecular weight range, it is possible to ensure good alignment and stability of the liquid crystal display element. The [A] polyorganosiloxane compound of the present invention is subjected to ring-opening addition of an epoxy group to a carboxyl group of a specific carboxylic acid, and is introduced from a specific carboxylic acid in a polyorganosiloxane having an epoxy group. Structure. This production method is simple and is an extremely suitable method in terms of an introduction rate of a structure derived from a specific carboxylic acid. <Optional Component> The liquid crystal alignment agent may contain other components other than the above [A] polyorganosiloxane compound, as long as the effect of the present invention is not impaired, for example, other than the [A] polyorganosiloxane compound. A polymer (hereinafter sometimes referred to as "other polymer"), a curing agent, a curing catalyst, and a curing accelerator 'a compound having at least one epoxy group in the molecule (hereinafter, referred to as "epoxy compound" functional decane) Compounds, surfactants, etc. [Other polymers] -40- 201120070 Other polymers can be used to further improve the solution properties of the liquid crystal alignment agent and the electrical properties of the resulting liquid crystal alignment elements. For example, at least one polymer selected from the group consisting of polylysine and polyimine ([B] polymer); a polyorganosiloxane selected from the following formula (5), and a hydrolyzate thereof At least one of the group consisting of condensates of hydrolyzates thereof (hereinafter, sometimes referred to as "other polyorganosiloxanes"); polyphthalamides, polyesters, polyamines, cellulose derivatives Condensation awake, polystyrene derivatives, poly (styrene reservoir - two lean phenyl butadiene acyl imine) derivatives' poly (meth) acrylate.

In the formula (5), X1 is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms. Y1 is a hydroxyl group or an alkoxy group having 1 to 1 carbon atom.) <[B] Polymer> [B] The polymer is at least one selected from the group consisting of polyproline and polyimine. polymer. Hereinafter, polylysine and polyimine are described in detail. [Polyuric acid] Polylysine can be obtained by reacting tetracarboxylic dianhydride with a diamine compound. Examples of the tetracarboxylic dianhydride which can be used for the synthesis of polyamic acid include, for example, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, butane tetracarboxylic dianhydride, -41 - 201120070 1,2 , 3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutyric acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,5,6-tricarboxy-norborn acetic anhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,33,4,hydro-5-(tetrahydro-2,5-dioxo -3 -furyl)-naphtho[1,2-c]-furanone, 1,3,33,4,5,91)-hexahydro-5-(tetrahydro-2,5-dioxo-3 -furyl)-naphtho[l,2-c]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuranyl-1-ylcyclohexene-1,2- Dicarboxylic anhydride, bicyclo[2.2.2]-oct-7-ene-2,2 formic acid dianhydride, tetracarboxylic acid difatty steroid tetracarboxylic acid represented by the following formulas (F-1) to (F-14) Anhydride and alicyclic tetracarboxylic dianhydride; alkanetetramethane-2-5,9b-hexa-1,3-di-8-methyln-3-carboxamidine, 5,6-tetrahydride and the like - 42- 201120070

(F-1) 〇 ο

(F-2) (F-3)

(F-4)

(F-8) (F-9) (F-10) (F-11)

(F-5)

(F-12)

Acid dianhydride, 3', 4,4' - -43- 201120070 biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenyl decane tetracarboxylic dianhydride, 3,3 ',4,4'-Tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl Thioether dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane Dihydride, 3,3',4,4'-perfluoroisopropylidenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenyl Phosphine dianhydride, p-phenyl-bis(m-phenylphthalic acid) dianhydride, meta-phenyl-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid) _4,4'-diphenylmethane dianhydride, the following formula (F-15)~(F-18) respectively An aromatic steroid tetracarboxylic dianhydride such as tetracarboxylic dianhydride. -44- 201120070

(F-15)

〇

Among them, preferred are 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c ]-furan-1,3-dione, 1,3,33,4,5,913-hexahydro-45- 201120070 -5-(tetrahydro-2,5-dioxo-3-furanyl)-8- Benzyl-naphtho[1,24]-furan-1,3-dione, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, butane tetracarboxylic dianhydride 1,3-dimethyl-1 , 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-biphenyl Terpene tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic acid Dicarboxylic anhydride and tetracarboxylic dianhydride represented by the above formulas (F-1), (F-2), (F-15) to (F-18). These tetracarboxylic dianhydrides may be used singly or in combination of two or more. Examples of the diamine compound which can be used for the synthesis of polyamic acid include, for example, p-phenylenediamine, meta-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4. '-Diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3,3'-dimethyl- 4,4 '-Diaminobiphenyl, 4,4'-diaminophenyl benzophenone, 4,4'-diaminodiphenyl ether, 4,4'-diamino-2,2'-dimethyl Biphenyl, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 5-amino-1-(4'-aminophenyl)-1 , 3,3-trimethylindoline, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindoline, 3,4'-diamino Diphenyl ether '2,2-bis(4-aminophenoxy)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4 -(4-Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy) Phenyl]anthracene, 1,4.bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene' 1,3-bis(3-aminophenoxyl) Benzo, 9,9-bis (4-amino group) Base)-10-hydroquinone, 2,7-diaminopurine, 9,9-bis(4-aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline), 2 ,2',5,5'-tetrachloro-4,4'-diaminol-46 - 201120070 Benzene, 2,2'-dichloro-4,4'-diamino- 5,5'- Methoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-(p-phenylene isopropylidene) bis(aniline), 4,4 '-(Inter)phenyl isopropylidene bis(aniline), 2,2-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4, 4'-Diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluoro Benzene, 6-(4-chalconeoxy)hexyloxy (2,4-diaminobenzene), 6-(4'-fluoro-4-chalconeoxy)hexyloxy (2) , 4-diaminobenzene), 8-(4-chalconeoxy)octyloxy (2,4-diaminobenzene), 8-(4'-fluoro-4-chalconeoxyl) Octyloxy (2,4-diaminobenzene), 1-dodecyloxy-2,4-diaminobenzene, 1-tetradecyloxy-2,4-diaminobenzene, 1-pentadecanyloxy-2,4-diaminobenzene, 1-hexadecyloxy-2,4- Diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene, 1-cholestyloxy-2,4-diaminobenzene, 1-cholestyloxy-2,4- Diaminobenzene, dodecyloxy (3,5-diaminobenzimidamide), tetradecyloxy (3,5-diaminobenzimidamide), pentadecyloxy (3,5) -diaminobenzimidamide),hexadecaneoxy (3,5-diaminobenzimidamide), octadecyloxy (3,5-diaminobenzimidamide), cholesteryloxy ( 3,5-diaminobenzimidamide), cholestyloxy (3,5-diaminobenzimidamide), (2,4-diaminophenoxy) palmitate, (2, 4-diaminophenoxy)stearyl quinone, (2,4-diaminophenoxy)-4-trifluoromethylbenzoate, represented by the following formula (G1) to (G-7) Aromatic steroid diamines such as diamine compounds; -47- 201120070

/CH3 CH, CH3

(G-3) (G-4)

(G-5) (G-6)

H2N

Nh2 (G-7)

Aromatic steroid diamine having a hetero atom such as a C5H" diaminotetraphenylthiophene; m-xylenediamine, 1,3-propylenediamine, butanediamine, pentamethylenediamine, hexamethylenediamine, heptanediamine, octyl Diamine, decanediamine, 4,4-diaminoheptyldiamine, 1,4-diaminocyclohexane, cyclohexanebis(methylamine), isophoronediamine, tetrahydropyrene环-48- 201120070 pentylene monoamine, hexahydro-4,7-extension formazan (11^]^110丨11(^11川(^1^) dimethylene diamine, subtricyclic [6.2 .1.02,7]undecene dimethyldiamine, 4,4, methylene bis(cyclohexylamine) and other fatty steroids or alicyclic diamines; diamino hexamethyldioxane and the like Amino-based organooxane, etc. Among them, 'preferably, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4'4'-diamino-2,2'-di Methylbiphenyl 'cyclohexane bis(methylamine), 1,5-diaminonaphthalene, 2,7-diaminostilbene '4,4'-diaminodiphenyl ether, 4,4' _(p-phenylene isopropylidene) bis(aniline), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4:amino group Phenyl) hexafluoropropane, 2,2-bis(4-amine Phenylphenyl)hexafluoropropane, 2,2-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2, 2' · bis(trifluoromethyl)biphenyl, 4,4-bis[(4-fecyl-2-difluoromethyl)phenoxy]-octafluorobiphenyl, hexagram gas base-2, 4 - an I female basic, 1-octadecyloxy-2,4-diaminobenzene, 1-cholesteryl-2,4-aminoamine, 1-biliary oxy-2,4 -diaminobenzene, hexadecanthoxy (3,5-diaminobenzimidamide), octadecyloxy (3,5-diaminobenzimidamide), cholesteryloxy (3,5 -diaminobenzimidamide)'cholyloxy (3,5-diaminobenzimidamide) and a diamine represented by the above formula (G1) to (G-7). These diamines may be used singly or Two or more types are used. The use ratio of the tetracarboxylic dianhydride and the diamine compound used for the synthesis reaction of polylysine is preferably based on the amine group contained in one equivalent of the diamine compound, and the acid anhydride group of the tetracarboxylic dianhydride is preferably a ratio of 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equivalents.

The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at -0 0 ° C -49 - 201120070 -1 50 ° C 'better at 0 ° C ~ 1 0 0 ° C, Preferably, it is carried out for 5 to 2 hours, preferably for 2 to 10 hours. In addition, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid, and examples thereof include N-methyl-2-pyrrolidone and N,N-dimethylacetamide.非, Ν-dimethylformamide, hydrazine, hydrazine - dimethyl hydrazine π ketal, dimethyl hydrazine, butyl vinegar, tetramethyl urea, hexamethyl sulphide and other aprotic Polar solvent; phenolic solvent such as m-cresol, xylenol, phenol, or halophenol. The amount of the organic solvent (a) is preferably such that the total amount of the tetracarboxylic dianhydride and the diamine compound (b) is 0.1 to 50% by mass, more preferably 5 to 30% by mass based on the total amount of the reaction solution (a + b). The amount of %. Further, the organic solvent may be used together with an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon or the like in a poor solvent of polyproline in a range in which the produced polyamine is not precipitated. Examples of the poor solvent include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, diacetone alcohol, and ethylene glycol. Methyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl Ethoxypropionate, propylene carbonate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, B Glycol isopropyl ether, ethylene glycol monobutyl ether (ethyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, two Ethylene glycol diethyl ether 'diethylene glycol monomethyl ether, diethylene glycol monoethyl ether 'diethylene glycol monomethyl ether acetate' diethylene glycol monoethyl ether acetate, Tetrahydrofuran, dichloromethane '1,2-dichloroethane, 1,4-dichlorobutane, -50- 201120070 trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, Benzene, toluene, xylene, etc. These poor solvents may be used singly or in combination of two or more. As described above, a reaction solution in which polylysine is dissolved can be obtained. The reaction solution can be directly used for preparing a liquid crystal alignment agent, or can be used for preparing a liquid crystal alignment agent after separating the polyamic acid contained in the reaction solution, or purifying the separated polyamic acid to prepare a liquid crystal alignment. Agent. The separation of the polyamic acid can be carried out by injecting the above reaction solution into a large amount of a poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure; or by distilling off the reaction solution by an evaporator under reduced pressure. Alternatively, the polypyridic acid may be re-dissolved in an organic solvent and then precipitated in a poor solvent; or the method may be repeated by repeating the step of distilling off one or more times with an evaporator under reduced pressure. Proline. [Polyimide] The above polyiminoimine can be produced by dehydration ring closure of the glycine structure of the polyamic acid obtained as described above. At this time, the proline structure can be completely dehydrated and closed to a complete hydrazine imidization; or a part of the valeric acid structure can be dehydrated and closed, and a part of the guanidine structure and the quinone ring structure can be formed. Amine. The dehydration ring closure of polylysine is preferably (1) by heating the polyamic acid, or (ii) dissolving the polyaminic acid in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution. It is carried out according to the method of heating as needed. The reaction temperature in the method for heating poly-proline in the above (i) is preferably -51 - 201120070 50 to 20 (TC, more preferably 60 to 17 (TC. by allowing the reaction temperature to be 50 ° C or higher) The dehydration ring closure reaction is carried out, and the decrease in the molecular weight of the obtained quinone imidized polymer can be suppressed by setting the reaction temperature to 200 ° C or lower. The reaction time in the method of heating the polyproline is preferably 〇· 5 to 4 8 hours' is more preferably 2 to 20 hours. On the other hand, in the above method of adding a dehydrating agent and a dehydration ring-closing catalyst to a polyaminic acid solution, for example, acetic anhydride may be used in the case of a dehydrating agent. An acid anhydride such as propionic anhydride or trifluoroacetic anhydride, and the amount of the dehydrating agent is preferably 20 mol with respect to 1 mol of the polyamic acid structural unit. Further, 'for the dehydration ring-closing catalyst', for example, pyridine 'three a secondary amine such as methylpyridine, lutidine or triethylamine, but 'not limited thereto. The amount of the dehydration ring-closing catalyst is preferably 0.01 to 1 0 m ο 1 relative to 1 mol of the dehydrating agent used. The organic solvent used in the dehydration ring closure reaction The organic solvent exemplified as the solvent used for the synthesis of the polyamic acid may be exemplified. The reaction temperature of the dehydration ring-closure reaction is preferably from 〇 to 180 ° C, more preferably from 10 to 150 ° C. The reaction time is preferably from 0.5 to 〜 20 hours, more preferably 1 to 8 hours. In the method (ii), as described above, a reaction solution containing polyiminoimine can be obtained. The reaction solution can be directly used for preparing a liquid crystal alignment agent, or After the reaction solution removes the dehydrating agent and the dehydration ring-closing catalyst, it is used for preparing a liquid crystal alignment agent; after separating the polyimine, it is used for preparing a liquid crystal alignment agent; or after separating the separated polyimine, for preparing a liquid crystal alignment In order to remove the dehydrating agent and the dehydration ring-closure catalyst from the reaction solution, for example, a method such as solvent replacement is suitably used. The separation of the polyimine is '------200200 201120070 by the same method as the separation and purification method of poly-proline π [Other polyorganosiloxanes] The liquid crystal alignment agent may contain other polyorganosiloxanes in addition to [A] polyorganosiloxane. Other polyorganic sands are preferably selected from At least one of the group consisting of the polyorganosiloxane of the above formula (5) and the condensate of the hydrolyzed hydrolyzate thereof. In addition, when the agent contains other polyorganosiloxane, other polyorganooxane It may exist independently of the [A] polyorganosiloxane compound, and one of them exists as a condensate formed as [A] polyorganosiloxane. In X1 and Y1 in the above formula (5), the number of carbon atoms is Examples of the alkyl group of 1 to 20 include a group, an ethyl group, an n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-octyl group, a n-decyl group, a n-decyl group, a n-lauric group, and a positive group. Dodecyl second courtyard base, positive fourteen courtyard base, positive fifteen courtyard base, positive sixteen courtyard base, alkyl, n-octadecyl, n-nonadecyl, n-icosyl, etc.; Examples of the alkoxy group having 1 to 16 atoms include an oxy group and an ethoxy group; and examples of the aryl group having 6 to 20 carbon atoms include exemplified examples. The other polyorganosiloxane may be at least suitable for use by, for example, at least an anthraquinone selected from the group consisting of an alkoxylation compound and a halogenated decane compound (hereinafter also referred to as "raw material decane compound"). In the solvent, hydrolysis or hydrolysis is carried out in the presence of water and a catalyst. The oxyalkylene complex and most of the liquid crystal complexes thereof may be, for example, a methylheptyl group, a positive ten-negative group, for example, a group such as a phenyl decane alkane compound, and a combination of -53-201120070. The raw material of the sand 垸 compound can be used here, w, μ_ for example, tetramethoxy sand yard, tetraethoxy sand yard, tetra-n-propoxy sand yard, tetraisopropoxy sand yard, tetra-n-butoxy Base sands 'four or three grades of butoxy oxime' four-stage butoxy decane, tetrachloro decane; methyl trimethoxy decane, methyl triethoxy sand, methyl tri-n-propoxy decane Methyl triisopropoxy sulphate, methyl tri-n-butoxy decane, methyl tri-tertiary butoxy decane, methyl tri- or 2-butoxylate, methyl triphenyloxydecane, methyl Triclosan, ethyl trimethoxy sand, ethyl triethoxy decane, ethyl tri-n-propoxy decane, ethyl triisopropoxy decane, ethyl tri-n-butoxy fluorene, B Base three or three-stage butoxy decane, ethyl three-dimensional butoxy decane, ethyl chlorosilane, phenyl trimethoxy decane, phenyl triethoxy decane, phenyl trichloro sane; Dimethoxy decane, dimethyl diethoxy decane, dimethyl dichloro decane; trimethyl methoxy decane, trimethyl ethoxy sand, trimethyl chloride sand, and the like. Among these, tetramethoxy sand, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane are preferred. , dimethyl dimethoxy fluorene, dimethyl diethoxy fluorene, trimethyl methoxy sand and trimethyl ethoxy sane. In the case of synthesizing another polyorganosiloxane, the organic solvent which can be used arbitrarily may, for example, be an alcohol compound, a ketone compound, a guanamine compound, an ester compound or other aprotic compound. They can be used alone or in combination of two or more. -54- 201120070 As the alcohol compound, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tertiary butanol, secondary butanol, n-pentanol, isoprene may be mentioned. Alcohol, 2-methylbutanol, tertiary pentanol, secondary pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, tertiary hexanol, 2-ethylbutanol, three Heptanol, hept-3-ol, n-octanol, 2-ethylhexanol, trioctyl octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-nonanol, tertiary ten Monoalkanol, trimethylnonanol, tertiary tetradecyl alcohol, tertiary heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl Monohydric alcohol compounds such as alcohol and diacetone alcohol; ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2 a polyol compound such as 5-hexanediol '2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol or tripropylene glycol; Alcohol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl , ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, Diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl A partial ether or the like of a polyol compound such as a group ether. These alcohol compounds may be used singly or in combination of two or more. Examples of the ketone compound include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, -55-201120070 diethyl ketone, methyl isobutyl ketone, and methyl group. N-pentyl ketone, ethyl n-butyl ketone 'methyl n-hexyl ketone, diisobutyl ketone, trimethyl fluorenone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentyl Monoketone compounds such as diketone, acetonylacetone, acetophenone, fenchone; etidylacetone, 2,4-hexanedione, 2,4 heptanedione, 3,5•heptanedion, 2 , 4-octanedione, 3,5-octanone, 2,4, anthraquinone, 3,5-nonanedione, L-methyl-2,4-hexanedione, 2,2,6,6 - Tetramethyl.3,5-heptanedione, hexafluoro-2,4-heptanedione, etc., ketone compound, and the like. These ketone compounds may be used singly or in combination of two or more. As the above guanamine compound, for example, formamide, N-methylformamide, N,N-dimethylformamide, N-ethylformamide, N,N-diethyl group can be mentioned. Formamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide, N-methyl Propylamine, N-methylpyrrolidone, N-methylmercaptoline, N-methylmercaptopiperidine, N-methylmercaptopyridine, N-ethylmercaptoporphyrin, N-ethylidene Piperidine, N-acetyl group, and the like. These guanamine compounds may be used singly or in combination of two or more. Examples of the ester compound include diethyl carbonate, ethyl carbonate, propylene carbonate, diethyl carbonate, methyl acetate, and ethyl acetate. R-butyl vinegar... pentane vinegar, acetic acid n-propyl vinegar, isopropyl acetate, n-butyl vinegar acetate, isobutyl vinegar acetate, citric acid tertiary vinegar, acetic acid n-pentyl vinegar, acetic acid tertiary pentane vinegar, B 353 - methoxy butyl, acetic acid methyl vinegar, 2-ethyl butyl vine acetate, 2-ethylhexyl acetate, acetoxyacetate, cyclohexyl acetate, methylcyclohexyl acetate 'n-decyl acetate Ethylacetate, ethyl acetate, -56- 201120070 ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate 'diethylene glycol monomethyl ether acetate 'Diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Acid ester, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diacetic acid Ester, methoxytriethylene glycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate 'lactic acid N-butyl ester 'n-pentyl lactate, diethyl malonate dimethyl phthalate, diethyl phthalate and the like. These ester compounds may be used singly or in combination of two or more. As the other aprotic compound, for example, acetonitrile, dimethyl hydrazine, hydrazine, hydrazine, hydrazine, Ν'tetrakisylsulfonamide, trimethylamine hexamethylamine, hydrazine-methyl group can be exemplified. Zylinone, Ν-methylpyrrole, Ν-ethylpyrrole, Ν-methyl-Δ3 -dihydropyrrole, Ν-methylpiperidine' Ν-ethylpiperidine, hydrazine, hydrazine-dimethylper Tillage, hydrazine-methylimidazole, hydrazine-methyl-4-piperidone Ν-methyl-2-piperidone, Ν-methyl-2-pyrrolidone, 1,3-dimethyl-2 - Imidazolidinone, 1,3 - dimethyltetrahydro-2(1 fluorene)-pyrimidinone, and the like. Among these solvents, a polyhydric alcohol compound, a partial ether or an ester compound of a polyhydric alcohol compound is particularly preferred. The amount of water used in the synthesis of the other polyorganosiloxane is 1 mol, more preferably 0 to 01 to 100 mol, more preferably 〇.l, based on the total amount of the alkoxy group and the halogen atom of the starting decane compound. ~30mol, further preferably 1 to 1. 5 m ο 1 ratio. A catalyst which can be used in the synthesis of another polyorganosiloxane, and - for example, a metal chelate compound, an organic acid, an inorganic acid, an organic base, ammonia, an alkali metal compound or the like can be mentioned. The above metal chelate compound may, for example, be triethoxy-mono(ethylmercaptoacetonate) titanium, tri-n-propoxy-mono(ethylmercaptoacetoate) titanium, triisopropoxy group. Mono (acetylpyruvate) titanium, tri-n-butoxy-mono(ethylidenepyruvate) titanium, tri-tertiary butoxy-mono(ethylmercaptopyruvate) titanium, tri- or di-butyl Oxy-mono(ethylmercaptoacetoate) titanium, diethoxy bis(ethyl phthalate) titanium, di-n-propoxy bis(ethyl phthalate) titanium, diisopropyl Oxy-bis(ethylmercaptoacetoate) titanium, di-n-butoxy-bis(acetylsulfonate) titanium, di-tertiary butoxy-bis(ethylmercaptoacetoate) titanium, two Second-order butoxy-bis(ethylmercaptopyruvate) titanium, monoethoxy-parade (ethionylpyruvate) titanium 'mono-n-propoxy-parade (ethionyl pyruvate) titanium, Monoisopropoxy-paraxyl (ethyl acetoacetate) titanium, mono-n-butoxy- cis (ethionyl pyruvate) titanium, mono-tertiary butoxy-glycolate Titanium, single-stage butoxy-paraxyl (acetylthiopyruvate) Titanium, lanthanum (ethionyl pyruvate) titanium, triethoxy-mono(ethyl acetonitrile) titanium, tri-n-propoxy-mono(ethyl acetonitrile) titanium, triisopropoxy -mono(acetonitrile ethyl acetate) titanium, tri-n-butoxy-mono(acetonitrile ethyl acetate) titanium, tri-tertiary butoxy-mono(acetic acid ethyl acetate) titanium, tri- or two-butoxy -mono(acetonitrile ethyl acetate) titanium 'diethoxy-bis(acetic acid ethyl acetate) titanium, di-n-propoxy-bis(acetic acid ethyl acetate) titanium, diisopropoxy-bis ( Acetate ethyl acetate) Titanium 'di-n-butoxy-bis(acetic acid ethyl acetate) titanium, di-tertiary butoxy-bis(acetonitrile ethyl acetate) titanium 'di- or di-butoxy-bis( Acetate ethyl acetate) titanium, monoethoxy-para (acetonitrile ethyl acetate) titanium, mono-n-propoxy-para-58- 201120070 (acetic acid ethyl acetate) titanium, monoisopropoxy-para (acetonitrile ethyl acetate) titanium, mono-n-butoxy-parade (acetonitrile ethyl acetate) titanium, mono-tertiary butoxy-parade (acetic acid ethyl acetate) titanium, single-stage butoxy-para (acetate ethyl acetate) titanium, bismuth (acetic acid ethyl acetate) titanium, single Ethyl pyruvate) ginseng (acetic acid ethyl acetate) titanium, bis(ethyl phthalate) bis(acetic acid ethyl acetate) titanium, ginseng (ethyl acetonate) monoacetate Ethyl ester) titanium chelate compound such as titanium; triethoxy-mono(ethylmercaptopyruvate) zirconium, tri-n-propoxy-mono(ethylmercaptopyruvate) zirconium, triisopropoxy-single (Ethyl pyruvate) zirconium, tri-n-butoxy-mono(ethylmercaptopyruvate) zirconium, tri-tertiary butoxy-mono(ethylmercaptopyruvate) zirconium, three-stage butadiene Base-mono(ethylmercaptoacetate) zirconium, diethoxy bis(ethyl phthalate) oxime, di-n-propoxy bis(ethyl phthalate) pin, diisopropoxy double (Ethyl pyruvate) zirconium, zirconium di-n-butoxy bis(ethyl decyl pyruvate), di-tertiary butoxy bis(ethyl phthalate) zirconium, di- or two-butoxy (Ethyl acetonyl pyruvate) zirconium, monoethoxy oxy (acetoxypyruvate) pin, mono-n-propoxy sulphate (ethionyl pyruvate) zirconium, monoisopropoxy ginseng (acetamidine) Pyruvate) Oxymethylene (ethyl acetonyl pyruvate) ruthenium, mono-tertiary butoxy-oxymethane (ethyl acetonate pyruvate) zirconium, mono- or two-butoxysyl (ethyl acetonate) chrome, bismuth (B Mercapto pyruvate) zirconium, triethoxy-mono(acetic acid ethyl acetate) pin, tri-n-propoxy-mono(acetic acid ethyl acetate) zirconium, triisopropoxy-mono(acetonitrile) Ethyl ester] zirconium tri-n-butoxy-mono(acetonitrile ethyl acetate) zirconium, tri-tertiary butoxy-mono(acetonitrile ethyl acetate) zirconium, tri- or two-butoxy-mono(acetonitrile) Ethyl ester, zirconium, diethoxy bis(acetic acid ethyl acetate) zirconium, di-n-propoxy bis(acetic acid ethyl acetate) pin, diisopropoxy bis-59- 201120070 (ethyl acetate) Zirconium, di-n-butoxy bis(acetic acid ethyl acetate) chromium, di-terternary butoxy bis(acetic acid ethyl acetate) zirconium, di- or two-butoxy bis(acetic acid ethyl acetate) hydrazine, Monoethoxylated oxime (acetic acid ethyl acetate) zirconium, mono-n-propoxyoxyl (ethyl acetate) zirconium, monoisopropoxy oxyethylene (acetic acid ethyl acetate) zirconium, mono-n-butoxy (acetonitrile ethyl acetate) chromium, single tertiary butoxide Base ginseng (acetic acid ethyl acetate) zirconium 'single-stage butoxyl (ethyl acetate) zirconium, lanthanum (acetic acid ethyl acetate) zirconium, mono(ethyl phthalate) Ethyl zirconate, zirconium chelating compound such as zirconium, bis(ethyl decyl pyruvate) bis(acetic acid ethyl acetate) zirconium, ginsyl (acetate pyruvate) mono(acetic acid ethyl acetate) zirconium; (Ethyl acetonyl pyruvate) aluminum chelate compound such as aluminum, ginseng (acetic acid ethyl acetate) aluminum or the like. Examples of the organic acid include acetic acid, propionic acid 'butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, oxalic acid, maleic acid 'methylmalonic acid, Adipic acid, azelaic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, water Salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid 'sulfonic acid, phthalic acid , fumaric acid, citric acid, tartaric acid, and the like. The inorganic acid may, for example, be hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid or phosphoric acid. The organic base may, for example, be pyridine, pyrrole, pipe trap, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanol-60-201120070 amine, diethanolamine, dimethyl group. Monoethanolamine, monomethyldiethanolamine, triethanolamine, dicyclobicyclooctane, dioxodicyclodecane, dinonylcycloundecene, tetramethylammonium hydroxide, and the like. The alkali metal compound may, for example, be sodium hydroxide, potassium hydroxide, barium hydroxide or calcium hydroxide. These catalysts may be used singly or in combination of two or more. Among these catalysts, a metal chelate compound, an organic acid or an inorganic acid is preferred. In the case of a metal chelate compound, a titanium chelate compound is more preferred. The amount of the catalyst to be used is preferably 0.001 to 10 parts by mass, more preferably 0.001 to 1 part by mass, per 100 parts by mass of the starting decane compound. The catalyst may be previously added to the solution of the decane compound as the raw material or the decane compound dissolved in the organic solvent, or may be dissolved or dispersed in the added water. The water added in the synthesis of the other polyorganosiloxane may be added intermittently or continuously to the decane compound as a raw material or the decane compound dissolved in a solution formed by an organic solvent. The reaction temperature at the time of synthesizing other polyorganosiloxanes is preferably from 0 to 100 ° C, more preferably from 1 5 to 80 ° C. The reaction time is preferably from 0.5 to 2 4 hours, more preferably from 1 to 8 hours. When the liquid crystal alignment agent contains the [A] polyorganosiloxane compound and further contains other polymers, the content of the other polymer is relative to 1 part by mass of the [A] polyorganosiloxane compound, preferably ι. 〇, 00〇 parts by mass or less. The better content of other polymers will vary depending on the type of other polymer. ~ 61 - 201120070 The liquid crystal alignment agent in the case of containing [A] polyorganosiloxane compound and [B] polymer, the preferred ratio of use is relative to 1 part by mass of [A] polyorganooxane The total amount of the compound '[B] polymer is preferably from ι to 5,000 parts by mass, more preferably from 200 to 3,000 parts by mass. On the other hand, when the liquid crystal alignment agent contains the [A] polyorganosiloxane compound and other polyorganosiloxane, the preferred ratio of use is relative to 100 parts by mass of the [A] polyorganosiloxane compound. The amount of other polyorganosiloxane is 100 to 2,000 parts by mass. When the liquid crystal alignment agent contains both the [A] polyorganosiloxane compound and other polymers, it is preferably a [B] polymer or other polyorganosiloxane. [Curing Agent' Curing Catalyst and Curing Accelerator] The curing agent and the curing catalyst may be contained in the liquid crystal alignment agent for the purpose of making the crosslinking reaction of the [A] polyorganosiloxane compound stronger. The curing accelerator may be contained in the liquid crystal alignment agent for the purpose of promoting the curing reaction by the curing agent. As the curing agent, a curing agent which is cured by using a curable composition containing a curable compound having an epoxy group or a compound having an epoxy group can be used. As such a curing agent, for example, a polyamine, a polycarboxylic anhydride, or a polycarboxylic acid can be listed. The polycarboxylic acid anhydride can be exemplified by, for example, an acid anhydride of a cycloheximide tricarboxylic acid and other polybasic acid anhydrides. In the case of cyclohexane tricarboxylic anhydride, for example, cyclohexane-62-201120070-1, 3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylate can be exemplified. Acid-3,5-anhydride, cyclohexane-1,2,3-tricarboxylic acid-2,3-anhydride, and the like. As the other polycarboxylic acid anhydride, for example, 4-methyltetrahydrophthalic anhydride or methyl nadic anhydride may be mentioned.

Maleic anhydride, phthalic anhydride, trimellitic anhydride, a compound represented by the following formula (6), tetracarboxylic dianhydride generally used in the synthesis of polylysine, and α-p-capadiene, a Diels-Alder reaction product of an alicyclic compound having a conjugated double bond and a maleic anhydride such as a blister, and a hydride thereof.

(In the formula (6), X is an integer of 1 to 20.) For the curing catalyst, for example, a ruthenium hexafluoride compound, a phosphorus hexafluoride compound, a ginseng acetonide acetonide or the like can be used. These catalysts can be polymerized by heating to catalyze the cation of the epoxy group. Examples of the above curing accelerator include, for example, an imidazole compound; a neophosphorus compound; a neoamine compound; 1,8-dioxabicyclo[5 · 4 _ 0 ] eleven-sinter-7 and an organic acid salt thereof. Anthraquinone; an organic metal compound such as zinc octoate, tin octylate, aluminum acetamacetone complex; boron compound such as boron trifluoride or boric acid triphenyl vinegar; metal halide such as zinc chloride or tin chloride; High-melting-point dispersion type such as an amine addition promoter such as an amine amide, an amine and an epoxy resin, etc. -63- 201120070 Potential curing accelerator; covering the surface with a new scale salt with a polymer to form a capsule type latent curing Promoter; amine salt type latent curing accelerator, such as a high temperature decomposition type thermal cationic polymerization type latent curing accelerator such as a salt of a salt or a sulphate. [Epoxy compound] From the viewpoint of further improving the adhesion of the formed liquid crystal alignment film sheet, the epoxy compound may be preferably an ethylene glycol condensate in the liquid crystal alignment agent. Glycidyl ether glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diacetate, 1,6-hexanediol diglycidyl ether , glycerol diglycidyl ether, dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl hexanediol, hydrazine, hydrazine, Ν', Ν'-tetraglycidyl- M-xylylenediamine, bis(indenyl, hydrazine-diglycidylaminomethyl)cyclohexane, hydrazine, hydrazine, hydrazine, Ν'-hydroglycosyl-4,4'-diaminodiphenyl Methane, hydrazine, hydrazine-diglycidyl 3-amine, hydrazine, hydrazine-diglycidyl-aminomethylcyclohexane, and the like. When the liquid crystal alignment agent contains an epoxy compound, it contains a ratio of '100% by mass relative to the above [A] polyorganosiloxane and any other polymerization used arbitrarily, preferably 0 · 0 1 to 4 0 The mass portion is more preferably 0 parts by mass. Further, when the liquid crystal alignment agent contains an epoxy compound, it can be used together with a catalyst such as 1-benzyl-2-methylimidazole for the purpose of generating the crosslinking reaction. The micro: the road is in the sex pair. , Polyol dihydrate, 2,2--2,4-1,3-tetraketyl-benzyl exemplified, 1-30 effective alkaline-64 - 201120070 [functional decane compound] functional sand yard The compound can be used for the purpose of further improving the adhesion to the substrate of the obtained liquid crystal alignment film. Examples of the functional sand compound include, for example, 3-aminopropyltrimethoxyphthalate, 3-aminopropyltriethoxy-5, and 2-aminopropyltrimethoxy sand. , 2-aminopropyltriethoxydecane 'N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-amino Propylmethyldimethoxydecane, 3-guanidinopropyltrimethoxydecane, 3-guanidinopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane , N-ethoxycarbonylaminopropyltriethoxydecane, N-triethoxydecylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10- Trimethoxydecyl-1,4,7-trioxane, 10-triethoxyindolyl-1,4,7-trioxane, 9-trimethoxyindolyl-3,6-di Mercaptoacetate, 9-triethoxyindolyl-3,6-dimercaptoacetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3 -Aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyethylene) )·3-Amino Trimethoxy decane, fluorene-bis(oxyethylene)-3-aminopropyltriethoxy decane, 3-oxyglycidylpropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl Further, a reaction product of tetracarboxylic dianhydride and a decane compound having an amine group described in JP-A-63-291922, etc., may be mentioned. When the liquid crystal alignment agent contains a functional decane compound, it is preferably 100 parts by mass based on the above-mentioned [A] polyorganosiloxane compound and any other polymer of -65-201120070, preferably in terms of its content ratio. 50 parts by mass or less, more preferably 20 parts by mass or less. [Interacting Agent] Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, organic quinone surfactants, and polyalkylene oxides. Surfactant, fluorine-containing surfactant, and the like. When the liquid crystal alignment agent contains a surfactant, the content of the liquid crystal alignment agent is preferably 10 parts by mass or less, more preferably 1 part by mass or less based on 100 parts by mass of the total of the liquid crystal alignment agent. &lt;Preparation method of liquid crystal alignment agent&gt; The liquid crystal alignment agent contains the [A] polyorganosiloxane compound as an essential component, and may contain other optional components as needed, and it is preferred to dissolve the components into an organic solvent. In the composition, it is formulated as a solution. In the case of an organic solvent which can be used for formulating the liquid crystal alignment agent, it is preferred to dissolve a specific polyorganosiloxane and other components which are used arbitrarily without reacting with them. The organic solvent which can be preferably used in the liquid crystal alignment agent varies depending on the type of other polymer to be added. When the liquid crystal alignment agent contains the [A] polyorganosiloxane compound and the [B] polymer, a preferred organic solvent is exemplified by the solvent used in the synthesis of the polyamic acid. Solvent. At this time, it can also be used together with the poor solvent exemplified as the organic solvent used in the synthesis of the polyamic acid of the present invention. These organic solvents may be used alone or in combination of -66 to 201120070. On the other hand, the liquid crystal alignment agent is preferably organic when it contains only [A] polyorganosiloxane compound as a polymer, or [A] polyorganosiloxane compound and other polyorganosiloxane. The solvent may, for example, be 1-ethoxy-2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, or the like. Propylene 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 Ester, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, n-propyl acetate, isopropyl acetate, n-butyl acetate, acetic acid Butyl ester, tertiary butyl acetate, n-amyl acetate, tertiary amyl acetate '3-methoxybutyl acetate, methyl amyl acetate, acetic acid 2 - Butyl acetate, 2 - ethyl hexyl acetate, benzyl acetate, hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, amyl acetate, isobutyl acetate and the like. Among them, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, tertiary butyl acetate, n-butyl acetate, and amyl acetate are preferred. A preferred solvent to be used in the preparation of the liquid crystal alignment agent can be obtained by combining the above-mentioned organic solvents with or without other polymers and their types. This solvent does not enrich the components contained in the liquid crystal alignment agent at a preferred solid concentration T of the following, and the surface of the liquid crystal alignment agent is in the range of 25 to 40 mN/m. The solid content concentration of the liquid crystal alignment agent of the present invention, that is, the ratio of the total weight of the liquid crystal alignment agent to the total weight of all components other than the solvent in the liquid crystal alignment agent is selected in consideration of viscosity, volatility, etc., preferably 1 to ~ 1 0% by mass range. The liquid crystal alignment agent is applied to the surface of the substrate to form a coating film formed of a liquid crystal alignment film. However, when the solid content concentration is 1% by mass or more, the film thickness of the coating film is not too small, and a favorable liquid crystal alignment film can be obtained. On the other hand, when the solid content concentration is 10% by mass or less, the film thickness of the coating film can be suppressed from being excessively large, and a favorable liquid crystal alignment film can be obtained, and the viscosity of the liquid crystal alignment agent can be prevented from increasing, and the coating property is good. The range of the particularly preferable solid content concentration varies depending on the method used when the liquid crystal alignment agent is applied onto the substrate. For example, when the spin coating method is used, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by mass. When the printing method is used, the solid content concentration is in the range of 3 to 9 mass%, whereby the solution viscosity is particularly preferably in the range of i2 to 50 mPa·s. When the inkjet method is used, the solid content concentration is in the range of 1 to 5 mass%, whereby the solution viscosity is particularly preferably in the range of 3 to 15 mPa·s. The temperature at which the liquid crystal alignment agent is prepared is preferably from 0 ° C to 200 ° C, more preferably (TC to 40 〇 C. <Liquid crystal display element> The driving method of the liquid crystal display element of the present invention is not particularly limited. The present technology can be used in various known methods such as TN, STN, IPS 'VA (including VA-MVA method, VA-PVA method, etc.), and has the liquid crystal alignment film formed of the liquid crystal alignment agent. In general, liquid crystal The display element-68-201120070 has an inner side of the pair of substrates on which the transparent electrode and the liquid crystal alignment film are laminated in this order, and is sealed with a sealant around the pair of substrates. <Method for Manufacturing Liquid Crystal Display Element> The liquid crystal display element formed using the liquid crystal alignment agent is produced by using the liquid crystal display element used in the present invention. The liquid crystal alignment film used in the present invention is formed on the substrate by heating the coated surface on the substrate, and the Portuguese can be used, for example, by float glass. Glass such as soda glass; transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate 'polyether oxime, polycarbon polyolefin. Prepare two substrates such as alignment film. The liquid crystal cell is disposed between the two substrates. When manufacturing the liquid crystal cell, for example, the following two methods are known. First, the film is disposed opposite to each other by a gap (cell) Gap), two configurations, using a sealant, injecting the surface of the peripheral portion of the two substrates and the interstitial space of the sealant into the liquid crystal inlet hole, the liquid crystal cell can be manufactured. The second method is called ODF ( 〇Ne Drop Fill, drop method. Applying, for example, a UV-curable sealing material to one of the two substrates forming the liquid crystal alignment film, and dropping the liquid crystal on the alignment film surface, bonding the other substrate and Opposite, then, the entire surface of the substrate is irradiated with ultraviolet light to make a liquid crystal cell. A pair of substrates, which are filled with liquid crystal, can be coated on the terephthalate or the alicyclic ring as follows. A method of forming a liquid crystal and manufacturing a liquid crystal. The liquid crystal alignment block substrate is opposed to each other, and the gauge on the I substrate in the form of a base after sealing method is then cured in a liquid crystal: liquid crystal alignment film: a sealing agent. -69- 201120070 In the case of any method, after the heat to the isotropic temperature, the slow flow alignment is ideal. Then, the polarizing plate can be obtained, and the present invention can be used for the aforementioned sealant, the aluminum ball and the curing agent. In the case of the above-mentioned liquid crystal, an epoxy resin or the like may be crystallized, etc. In the case of a positive TN type liquid crystal cell or a nematic liquid crystal, for example, a biphenyl liquid crystal, a terphenyl liquid crystal, or a biphenyl may be used. 3 Dioxane liquid crystal, bicyclooctane: In the above liquid crystal, further mercapto phthalate, cholesteryl carbonate € CB-15 (manufactured by Merck) can be sold to amino-2-methylbutyl group. Cinnamon vinegar, on the other hand, in the negative dielectric direction of the vertical alignment nematic liquid crystal, for example, a dicyanobenzene liquid crystal, an azo azo liquid crystal, or a biphenyl is used for the outer side of the liquid crystal cell. The liquid crystal display element which is attached to the outer surface of the liquid crystal cell by absorbing the iodine is sandwiched between the polyethylene virgin protective film and the liquid crystal of the liquid crystal cell. In the case of using, for example, a nematic liquid crystal or a dish type STN type liquid crystal cell containing ruthenium oxide as a spacer, it is preferable to have an anisotropic property. Such a liquid crystal is a crystal, a phenylcyclohexane liquid crystal, an ester I cyclohexane liquid crystal, a pyrimidine liquid crystal, a night crystal, a cubic liquid crystal or the like. Further, for example, a chlorinated cholesterol, a cholesteric liquid crystal, a chiral reagent having a trade name of C -15, a p-oxybenzylidene-based or the like, and a ferroelectric liquid crystal are used. In the case of a liquid crystal cell, it is preferred to form an opposite polarity. Such a liquid crystal may be a well-type liquid crystal, a Schiff base liquid crystal liquid crystal, a phenylcyclohexane liquid crystal or the like. 3 For the polarizing plate, there is no specific alcohol film extending direction, and a polarizing film made of acetic acid fiber as a "ruthenium film" is used as a polarizing film of -70-201120070 or a polarizing plate formed by the ruthenium film itself. The liquid crystal display element of the present invention produced by the present invention is excellent in various properties such as the alignment property, the voltage holding ratio, and the afterimage in addition to the liquid crystallinity and display properties. &lt;Liquid crystal device having two or more regions having different alignment directions&gt; The liquid crystal alignment mode of the liquid crystal display element is a vertical type, and two or more regions having different alignment directions have the same basic structure as the above-described elements. The two or more means having the different alignment methods are not particularly limited, and examples thereof include a means for using a transparent electrode and a means for dividing the liquid crystal alignment film by alignment. The liquid crystal display is suitable for use in flooding, IPS, VA (including VA-MVA mode, VA-PVA mode, etc.), and can further improve contrast and further improve responsiveness. In the method for producing the patterned transparent electrode, the liquid crystal alignment agent is formed by offset prting, spin coating or inkjet printing, and then the side of the coated substrate is formed by heating each coated surface. For the transparent conductive film to be provided, an NEOA film formed of (Sn〇2) (registered trademark of PPG, USA) or indium-tin oxide (In2〇3-Sn〇2) can be used. Next, for example, when a transparent conductive film is formed by photolithography after forming a transparent conductive film without a pattern, a display element such as a square response speed property of a photomask having a desired pattern is used, and a pattern of a liquid crystal display region is formed. Wipe treatment STN, dynamic mode high speed and better system, coating. In the case of tin oxide, a pattern is formed by oxidation, form, formation, etc., -71 - 201120070. The specific pattern-forming transparent electrode can be exemplified in the first to third figures. The patterned transparent electrode will be described with reference to Fig. 1 . Referring to Fig. 1(b), the transparent substrate 3 has an ITO film 1 divided into a plurality of regions, and a plurality of slits 2 are formed to form a pattern. The width wi of the slit 2 is, for example, about 10 μm; and the distance w 2 between the slits 2 is, for example, about 3 5 // m. In this case, the ITO line wi shown in Fig. 1(a) is 9 mm (width 3 5 // m '200). As the material of the transparent substrate, for example, glass or the like can be cited. Further, when a liquid crystal display element is manufactured using the patterned transparent electrode shown in Fig. 1, two substrates having the patterned transparent electrode are prepared, and when the two substrates are opposed to each other, the slit 2 must be formed. They are arranged without overlapping each other (the slits 2 are staggered from each other and are in contact with the IT0 membrane). In the same manner as the above-described "method for manufacturing a liquid crystal display device", a pair of (two sheets) substrates having a liquid crystal alignment film are produced, and rubbing is performed by a photomask. A region method of treating two or more different alignment orientations in one pixel of these substrates. As for the form of the reticle, an array in which one pixel having a hole corresponding to the size of one region is divided into four (a pixel-sized array of 1 Μ) is provided, and a hole is provided one by one. Diagonal juxtaposed reticle).

The liquid crystal alignment agent used in the liquid crystal display element of the present invention having two or more regions having different alignment directions is preferably a compound D-72-201120070 having a group not represented by the above formula (3). R2 is a linking group containing any of a double bond, a triple bond, an ether bond, an ester bond, or an oxygen atom. R3 is a group having at least two single ring structures. a is an integer from 0 to 1. The detailed description of these symbols is omitted here since it has been carried out in the description of the [A] polyorganosiloxane compound. &lt;Polyorganomethoxy oxane compound&gt; The polyorganosiloxane compound of the present invention contains a moiety derived from a polyorganosiloxane having an epoxy group, and a compound having a carboxyl group represented by the following formula (1), Or a part of the compound of the formula (1) wherein R3 has a carboxyl group represented by the following formula (2). The detailed description of the polyorganosiloxane compound has been carried out in the description of the [A] polyorganosiloxane compound contained in the liquid crystal alignment agent, and thus is omitted here. The polyorganosiloxane compound is suitably used in a liquid crystal alignment agent for constituting a liquid crystal display element having various properties such as an alignment property, a high-speed responsiveness, a voltage property, and an afterimage property. [Examples] Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited by the examples. The polyorganosiloxane having an epoxy group obtained in the following examples and the weight average molecular weight (Mw) of the [A] polyorganosiloxane compound are polystyrene-converted oxime measured by GPC in the following manner.

Pipe column: Tosoh Corporation, TSKgelGRCXLII Solvent: Tetrahydrofuran

Temperature: 40°C-73-201120070 Pressure: 68kgf/cm2 Further, the synthesis of the raw material compound and the polymer at the synthesis scale shown in the following synthesis example is repeated as necessary to ensure the raw materials used in the following examples. The necessary amount of compound and polymer. &lt;Synthesis of polyorganosiloxane having epoxy group&gt; [Synthesis Example 1] In a reaction vessel having a stirrer, a thermometer's dropping funnel and a reflux condenser, a 2-(3, 4-epoxycyclohexyl)ethyltrimethoxydecane (ECETS), 500 g of methyl isobutyl ketone, and i.g. triethylamine were mixed at room temperature. Next, 100 g of deionized water was added dropwise from the dropping funnel for 30 minutes, and the mixture was reacted under reflux for 6 hours while being mixed under reflux. After the completion of the reaction, the organic layer was taken out and washed with a 2% by mass aqueous solution of ammonium nitrate until the water after washing was neutral, and then the solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane having an epoxy group. It is a viscous transparent liquid. The lH-NMR analysis of the polyorganosiloxane having an epoxy group gave an epoxy group-based peak such as theoretical strength in the vicinity of a chemical shift (&lt;5) = 3.2 ppm, confirming that no epoxy group was produced in the reaction. reaction. [Synthesis Examples 2 to 3] The polyorganosiloxane having an epoxy group was obtained as a viscous transparent liquid, except that the raw materials to be added were the same as in Synthesis Example 1 except that the materials to be added were as shown in the following Table 1. The Mw and epoxy equivalent of the polyorganosiloxane having an epoxy group obtained in Synthesis Examples 1 to 3 are shown in Table 1. Further, the abbreviation of the raw material decane compound in Table 1 has the following meanings. -74- 201120070 ECETS: 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane MTMS: methyltrimethoxydecane PTMS: phenyltrimethoxydecane [Table 1] Raw material decane compound (g) Mw Epoxy equivalent ECETS MTMS PTMS (g/mol) Synthesis Example 1 100 0 0 2,200 186 Synthesis Example 2 80 20 0 2,500 210 Synthesis Example 3 80 0 20 2,000 228 &lt;Synthesis of a specific carboxylic acid&gt;

Synthesis of a specific carboxylic acid 1 NC according to the following reaction route

/ \ K2CO3 OH + Br-fCHpl—COOMe ---- x 71〇 DMF

Compound 1, , LiOH-HoO 0(CH2) COOMe -►

MeOH / H20

NC 〇~0~〇icH2)

COOH-specific carboxylic acid 1 [Synthesis Example 4] 6.3 g of 4-cyano-4'-hydroxybiphenyl and 10 g of 11-bromo-quot; 1--acid methyl ester were added to a 500 mL three-necked flask equipped with a condenser. 14.2 g of potassium carbonate, 200 mL of hydrazine, hydrazine-dimethylformamide, and heating and stirring at 160 ° C for 5 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature -75 - 201120070. The reaction solution was poured into 500 ml of water 'mixed and stirred. The precipitated white solid was filtered and washed with water. The obtained solid was vacuum dried at 80 ° C to give 11 g of Compound 1. [Synthesis Example 5] Next, 10 g of the compound 1, 1.6 g of lithium hydroxide·1 hydrate, 30 mL of methanol, and 15 mL of water were placed in a 200 mL three-necked flask having a condenser, and the mixture was stirred under heating at 80 ° C for 4 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. Dilute hydrochloric acid was slowly added dropwise to the reaction solution while the reaction solution was stirred. The solid was separated by filtration and washed successively with water and ethanol. The solid obtained was dried under vacuum at 80 ° C to give 8 g of the desired residue. The specific carboxylic acid 2 was synthesized according to the following reaction route.

also

TBAB

0H

〇' '〇 ► NC

\__/ DMF Compound 2

〇Η2α2

〇iCH2)2〇-f-〇-

CI Compound 3

COOMe Compound 4

COOH COOMe K2C03

DMF UOH-H2〇

MeOH/THF/H20 specific carboxylic acid 2 [Synthesis Example 6] -76- 201120070 15 g of 4-cyano-4'-hydroxybiphenyl and 13.5 g of ethylene carbonate were placed in a 500 mL three-necked flask equipped with a condenser. 2.5 g of tetrabutylammonium bromide (TBAB), 300 mL of hydrazine, hydrazine-dimethylformamide, and heating and stirring at 150 ° C for 9 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was washed with a mixed solution of 300 mL of ethyl acetate and 1 mL of a 1N aqueous sodium hydroxide solution. After extracting the organic layer, it was washed with 100 mL of 1 N aqueous sodium hydroxide solution and 1 mL of water. The organic layer was dried over magnesium sulfate, and then the organic solvent was evaporated. The obtained solid was dried under vacuum and then recrystallized from 100 mL of ethanol / 250 mL of hexane to afford 13.1 g of Compound 2. [Synthesis Example 7] In a 200 mL three-necked flask equipped with a condenser and a dropping funnel, 12 g of the compound 2, 12.7 g of 4-chlorobenzenesulfonium chloride, and 60 mL of dehydrated methylene chloride were added. In the state where the reaction solution was cooled in an ice bath, 6 6 g of triethylamine in 1 〇 m L of dehydrated dichloromethane was added dropwise over 1 Torr. The mixture was kept in an ice bath, stirred for 30 minutes, returned to room temperature and stirred for another 6 hours. 150 mL of chloroform was added to the reaction solution, and the mixture was washed 4 times with 1 mL of a water solution. The extracted organic layer was dried with magnesium sulfate to distill off the organic solvent. The obtained solid was washed with ethanol to give 16.1 g of Compound 3. [Synthesis Example 8] In a 300 mL three-necked flask having a condenser, 15 g of Compound 3, llg of methyl 4-hydroxybenzoate, i2.5 g of potassium carbonate, and 18 mL of N,N-dimethylformamidine were placed. The amine was stirred with heating at 80 ° C for 9 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was poured into -77-201120070 500 mL of water and mixed and stirred. The precipitated white solid was filtered and washed with ethanol. The obtained solid was vacuum dried at 80 ° C to obtain i 〇 g compound 4. [Synthesis Example 9] In a 100 mL three-necked flask equipped with a condenser, 9.5 g of Compound 4, 1.6 g of lithium hydroxide·1 hydrate, 30 mL of methanol, 15 mL of tetrahydrofuran, and 15 mL of water were added, and the mixture was heated and stirred at 80 ° C for 4 hours. . After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. Dilute hydrochloric acid was slowly added dropwise to the reaction solution while the reaction solution was stirred. The solid was separated by filtration and washed successively with water and ethanol. The obtained solid was vacuum dried at 8 (TC) to give 9 g of the specific carboxylic acid 2. The specific carboxylic acid 3 was synthesized according to the reaction path described below.

K2C〇3

DMF

Specific carboxylic acid 3 -78- 201120070 [Synthesis Example 1] By using, in Synthesis Example 4, 10.7 g of 2,3,5,6-tetrafluoro-4-(pentafluorophenyl)phenol was used instead of 4-cyano Base-4'-hydroxybiphenyl, 13.7 g of a compound was obtained [Synthesis Example 1 1] By substituting 1,3 g of Compound 5 for Compound 1 in Synthesis Example 5, 11.2 g of a specific carboxylic acid 3 was obtained. Synthesis of specific carboxylic acids according to the following reaction pathway

TBAB DMF

o(ch2) OH

Cl 〇

Et3N CH2CI2

HO

COOMe

K2C〇3 DMF

Me〇H/THF/H2〇 F F F F Compound 6 Li〇H.H2〇 -&gt;

Specific carboxylic acid 4 [Synthesis Example 12] -79-201120070 By using, in Synthesis Example 6, 25.5 g of 2,3,5,6-tetrafluoro-4-(pentafluorophenyl)phenol was used instead of 4-cyano group. -4'-Hydroxybiphenyl to give 23.lg compound [Synthesis Example 13] In Synthesis Example 7, 18.9 g of Compound 6 was used instead of Compound 2 to obtain 24.1 g of Compound 7. [Synthesis Example 14] By using 20 g of Compound 7 in place of Compound 3 in Synthesis Example 8, 15.4 g of Compound 8 was obtained. [Synthesis Example 15] By using, in Synthesis Example 9, 13 g of Compound 8 was used instead of Compound 4, 11.4 g of the specific carboxylic acid 4 was obtained. The specific carboxylic acid 5 was synthesized according to the following reaction route.

NC

Br—(όΗ2·)^~COOMe

K2C〇3 DMF

LiOH H2〇 MeOH / H20

NC

Similarly to the synthesis of the specific carboxylic acid 1, the number of methylene groups was changed from 10 to 5, and 15 g of the specific carboxylic acid 5 was synthesized. -80-201120070 &lt;Synthesis of [A] polyorganomethoxy oxane compound&gt; [Example 1] 9.8 g of the polyorganosiloxane having an epoxy group obtained in the above Synthesis Example 1 was added to a 100 mL three-necked flask. 28 g of methyl isobutyl ketone, 5. The specific carboxylic acid obtained in the above Synthesis Example 5, and 3.3 g of the compound represented by the formula (5-5) of the compound represented by the above formula (5) 0.20 g of octyloxybenzoic acid UCAT 18X (new ammonium salt of San-apro Co., Ltd.) was stirred at 80 ° C for 12 hours. After completion of the reaction, the precipitate was again precipitated with methanol, and the precipitate was dissolved in ethyl acetate to give a solution. After washing the mixture three times, the solvent was distilled off to give 14.5 g of [A] polyorganoxane compound A-1 as white. powder. The molecular weight of the [A] polyoxyalkylene compound A-1 was 6,500. [Example 2] A white powder of 1,2.8 g of [A] polyorganodecane compound A-2 was obtained in the same manner as in Example 1 except that 4 g of the specific carboxylic acid 2 obtained in Synthesis Example 9 was used instead of the specific carboxy group. Mw of A-2 is 6,000» [Example 3] 丨4.7 g [A] was obtained in the same manner as in Example 1 except that 6 g of the specific carboxylic acid 3 obtained in Synthesis Example 1 was used instead of the specific carboxylic acid 1. A white powder of a polyoxyalkylene compound A-3. The Mw of a-3 is 8,100. [Example 4] A [A] polyorganosiloxane compound was synthesized in the same manner as in Example 1 except that 5 6 g of the specific carboxylic acid 4 obtained in Synthesis Example 15 was used instead of the residual acid 1. As a result, 15.0 g of [A] polyorganooxy siloxane compound A-4 was obtained from white to yg and acid was added to acid-oxygen to give a color of -81 - 201120070 powder. The Mw of A-4 is 7,500. [Example 5] 9.8 g of the polyorganosiloxane having an epoxy group obtained in the above Synthesis Example 1, 28 g of methyl isobutyl ketone, and 10 g of the specific composition obtained in the above Synthesis Example 5 were placed in a 100 mL three-necked flask. Carboxylic acid 1 and 0.20 g of UCAT 18X (new ammonium salt of San-apro Co., Ltd.) were stirred at 80 ° C for 12 hours. After completion of the reaction, the precipitate was reprecipitated with methanol, and the precipitate was dissolved in ethyl acetate. After the mixture was washed three times with water, the solvent was evaporated to give 16.0 g of [A] polyorganoxane compound A-5 as a white powder. The Mw of A-5 is 8,500. [Example 6] 12.4 g of [A] polyorganosiloxane compound A- was obtained in the same manner as in Example 1 except that 4 g of the specific carboxylic acid 5 obtained in Synthesis Example 16 was used instead of the specific carboxylic acid 1. 6 white powder. The Mw of A-6 is 6,200. [Example 7] In place of 4-octyloxy group, 4-(4-pentylcyclohexyl)benzoic acid represented by the formula (5-7), which is an exemplary compound of the above formula (5), was used in an amount of 3.6 g. A white powder of 13.4 g of [A] polyorganosiloxane compound A-7 was obtained in the same manner as in Example 1 except for the benzoic acid. The Mw of A-7 is 7,900. [Example 8] 9.8 g of the polyorganosiloxane having an epoxy group obtained in the above Synthesis Example 1, 28 g of methyl isobutyl ketone, and 8. g of the above Synthesis Example 5 were added to a 100 mL three-necked flask. Specific carboxylic acid 1, 1.4 g of 4-(4-pentylcyclohexyl)benzoic acid represented by the above formula (5-7) and 0.20 g of UCAT 18X (san-apro-82-201120070 new ammonium salt) Stir at 80 ° C for 12 hours. The counter-precipitated 'precipitate was dissolved in ethyl acetate, and the solvent was saturated to give 13.9 g of [A] polyorganofluorene white powder. The Mw of the A-8 is 8,900. [Example 9] In a 100 mL three-necked flask, 9.8 g of a polyorganosiloxane having an epoxy group, and 28 g of a specific carboxylic acid obtained in the above Synthesis Example 5, 5.8 g of a 4-(4-pentyl ring) were added. The hexyl)benzoic acid and 新.2〇g UCAT new ammonium salt) were stirred at 8Ot for 12 hours. The precipitate was again dissolved in ethyl acetate, and after washing three times, the solvent was distilled off to give 3.4 g of [A] poly A-9' as a white powder. The Mw of a-9 is 7,600. [Example 1 0] 9.8 g of a polyorganosiloxane having an epoxy group, 28 g of a specific carboxylic acid obtained in the above Synthesis Example 1, 1, 2.6 g of a carboxylic acid derivative, and 0.20 g were placed in a 100 mL three-necked flask. UCAT 18X (san-api-o was stirred at 120 ° C for 12 hours. After the reaction was completed, the product was dissolved in ethyl acetate, and the solution was washed 3 times with water after 15.5 g of [A] polyorganosiloxane compound. A-10, Mw is 9,200. [Comparative Synthesis Example 1] After completion of the washing with methanol solution for 3 times, the alkane compound A-8 is obtained as the above-mentioned Synthesis Example 1 'isobutyl ketone' 2.0 g (8-7) 1 8X (San-apro company should be finished, using methanol to the solution, the solution water organic oxoxane compound. The above synthesis example 1 gave ketobutyl ketone, 8.Og above formula (5 -6) The new ammonium salt of the company shown) was precipitated again in the alcohol, and the solvent was distilled off to obtain a white powder. A - 1 0 -83 - 201120070 In a 100 mL three-necked flask, 9.8 g of the above synthesis example was added. 1 obtained polyorganosiloxane having epoxy group, 28 g of methyl isobutyl hydrazine, 3.3 g of 4-octyloxybenzoic acid and 0.10 g of UCAT 18X (san-apro) The new salt was stirred at 80 ° C for 12 hours. After the reaction was completed, it was reprecipitated with methanol, and the precipitate was dissolved in ethyl acetate. After washing the solution three times, the solvent was distilled off to obtain 9.6 g of [ A] The polyorganosiloxane compound CA-1 'is a white powder. The Mw of CA-1 is 6,000. &lt;Synthesis of poly-proline&gt; [Synthesis Example 1 7] 19.61 g (0.1 mol) of 1, 2,3,4-cyclobutane tetracarboxylic dianhydride and 21.23 g (0. 丨mol) 4,4'-diamino-2,2'-dimethylbiphenyl dissolved in 367-6 g of N-methyl- In 2-pyrrolidone, the reaction was carried out for 6 hours at room temperature. Then, 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 5 hours. , 35 g of polyaminic acid PA-1 was obtained. [Synthesis Example 1 8 ]

14.23 g (0.1 mol) of cyclohexane bis(methylamine) was dissolved in 3 29 32 of N-methyl-2-pyridinone and reacted at 6 CTC for 6 hours. The reaction product was subjected to a forging and purification in a large excess of methanol, and dried under reduced pressure at 40 ° C for 15 hours. Next, the reactants were injected. The precipitate was washed with methanol (32 g) of polyaminic acid PA-2. &lt;Synthesis of Polyimine&gt; [Synthesis Example 1 9] -84- 201120070 1 7.5 g of the polylysine PA-2 obtained in the above Synthesis Example 18 was taken out, and 2 3 2.5 g of N-A was added thereto. The benzyl-2-pyrrolidone, 3.8 g of pyridine and 4.9 g of acetic anhydride were reacted at 120 ° C for 4 hours to carry out oxime imidization. Next, 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 for 15 hours to obtain 15 g of polyimine. [Synthesis Example 20] 19.88 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride for tetracarboxylic dianhydride, 6.83 g of p-phenylenediamine as a diamine compound, and 358 g of diaminodiphenyl Methane and 4.72 g of diamine represented by the above formula (G-4) were dissolved in i4 〇g of N-methyl-2-pyrrolidone to react at 60 ° C for 4 hours. Next, the reaction solution was poured into a large excess of methanol to precipitate a reaction product. Thereafter, it was washed with methanol to reduce the pressure and dried at 40 ° C for 24 hours to obtain 3 2.8 g of polylysine. 30 g of the obtained polylysine was dissolved in 4 g of N-methyl-2-pyrrolidone. Add i2. 〇g卩 ratio steep and i5.5 g of acetic acid at 11 Torr. The underarm dehydration ring closed for 4 hours' was precipitated, washed, and dried under reduced pressure in the same manner as above to obtain 25 y = 92,000, 1^/1^ = 4.19' yttrium imineization rate of 79% polyimine PI-2 . &lt;Preparation of Liquid Crystal Alignment Agent&gt; [Example 11] A solution containing polyglycine ρΑ_ι obtained in Synthesis Example 17 was selected, and the polyglycine PAj contained therein was equivalent to 1 part by mass. Add [A] polyorganosiloxane compound A_1 (1 part by mass), then add -85-201120070 to N-methyl-2-pyrrolidone and butyl cellosolve to form solvent composition N-A Base-2 - pyrrole oxylactone: a solution of butyl cellosolve = 5 0 : 5 0 (mass ratio) and a solid concentration of 3.0% by mass. This solution was filtered using a filter having a pore size of 10.2 / / m to prepare a liquid crystal alignment agent S -1. [Examples 12 to 24 and Comparative Example 1] The combination of the polyamido acid or the polyamidino compound of the [B] polymer and the polyorganosiloxane compound of the [A] component are as shown in Table 2, and Example 1 1 In the same manner, liquid crystal alignment agents S-2 to S-14 and CS-1 were prepared. [Comparative Example 2] N-methyl-2-pyrrolidone and butyl cellosolve were respectively added to the polyimine imine PI-2 obtained in the above Synthesis Example 20, and the solvent was composed of N-methyl-2-pyrrolidine. Ketone: butyl cellosolve = 70: 30 (mass ratio), and a solution having a solid concentration of 3.0% by mass was formed. This solution was filtered using a filter of pore size 〇. 2 v m to prepare a liquid crystal alignment agent CS-2. In the table, "the component is not used. &lt;Production of liquid crystal display device&gt;" The above embodiment was applied by a spin coating method on a transparent electrode surface of a glass substrate having a transparent electrode formed of an ITO film. The prepared liquid crystal alignment agent s -1 ' was prebaked on a hot plate at 80 ° C for 1 minute, and then heated in a nitrogen replacement oven at 2 ° C for 1 hour to remove the solvent to form a film. A coating film (liquid crystal alignment film) having a thickness of 0.08 #m. This operation is repeated to manufacture a pair of (two sheets) substrates having a liquid crystal alignment film. On the outer periphery of a surface of the substrate having a liquid crystal alignment film, -86- 201120070 After coating an epoxy resin adhesive having a diameter of 3.5 // m alumina ball by screen printing, the liquid crystal alignment film of a pair of substrates is faced facing each other and overlapped and crimped at 150 The adhesive was thermally cured at a temperature of 1 ° C. Then, a liquid crystal injection port was used to fill a negative liquid crystal (manufactured by Merck, MLC-6608) in a gap between the substrates, and then sealed with an epoxy-based adhesive. Liquid crystal injection port; then to remove The flow alignment at the time of crystal injection is heated at 150 ° C for 10 minutes, and then slowly cooled to room temperature. Further, on the outer side of the substrate, the polarizing plate is bonded to the polarizing plate and the polarizing directions of the two polarizing plates are made. The liquid crystal display elements were produced by orthogonal to each other, and the liquid crystal display elements were produced in the same manner as in the liquid crystal alignment agents prepared in Examples 1 to 24 and Comparative Examples 1 to 2. <There are two or more regions having different alignment directions. [Liquid crystal display device] [Example 25] A liquid crystal having two or more regions having different alignment directions was produced in the same manner as the above-described liquid crystal display device except that the transparent electrode for pattern formation shown in Fig. 1 was used. Display element. [Example 26] The liquid crystal alignment agent A-1 prepared in the above Example 11 was coated on a substrate on which a transparent electrode was provided, and then prebaked on a hot plate at 80 ° C for 1 minute, in a nitrogen replacement oven. After heating at 200 ° C for 1 hour, the solvent was removed to form a coating film (liquid crystal alignment film) having a film thickness of 〇 8 m. This operation was repeated to manufacture a pair of (two sheets) substrates having a liquid crystal alignment film. These substrates are subjected to rubbing treatment by dividing one pixel into 4 - 87 - 201120070 parts of the mask. Thus, in addition to the rubbing treatment, in the case where one pixel has two or more regions having different alignments, and the above vertical type The liquid crystal display element was manufactured in the same manner, and liquid crystal display elements having two or more regions having different alignment directions were produced. <Evaluation> The manufactured liquid crystal display elements were evaluated as follows. The results are summarized in Table 2. [Orientation] In the liquid crystal display device manufactured as described above, it is visually observed whether there is light transmission or misalignment in a state where no voltage is applied under backlight illumination, and there is no light transmission or misalignment, and a part of the light is transmitted and aligned. The disorder is "△", and the vertical alignment state is not "X". [Voltage retention rate] After applying a voltage of 5 V to the liquid crystal display element manufactured above, with an application time of 60 microseconds and an interval of 167 milliseconds, The voltage holding ratio (%) after the release of the application to 1 67 ms was measured. The measuring device uses VHR-1 of TOYO TECHNICA. [Residual property] A liquid crystal display device produced in the same manner as described above was applied at a temperature of 1 Torr for 20 hours at a voltage of 1 to 7 V, and was subjected to a flash elimination method to obtain a liquid crystal cell after the DC voltage was cut off. Internal voltage (residual D c voltage). [Response speed (electro-optical response at the beginning)] -88- 201120070 The start time of the liquid crystal response was measured in a device including a polarizing microscope, a photodetector, and a pulse generator. The liquid crystal response speed as used herein refers to the time required from the state where no voltage is applied in the produced liquid crystal display element to the maximum application of 5 V for 1 second, from the transmittance of 1% to the transmittance of 9%. (msec.). [Contrast] The liquid crystal display elements manufactured in Example 1 1 and the liquid crystal display elements manufactured in Examples 2 5 and 2 and having two or more regions having different alignment directions were evaluated for contrast. The liquid crystal cell fabricated as above was placed between the two polarizing plates to be fixed to the light box. A piece of polarizing plate was rotated, and the minimum intensity of transmitted light was measured to obtain a minimum transmittance. Further, the same polarizing plate was rotated, and the maximum intensity of the transmitted light was measured to obtain the maximum transmittance. The maximum transmittance-minimum transmittance is defined as the relative transmittance, and the relative transmittance is used as a substitute indicator. When the relative transmittance is 40 or more, it can be judged to be good. As a result, the relative transmittance of the liquid crystal display element produced in Example 11 was 20. The relative transmittance of the liquid crystal display element produced in Examples 25 and 26 having two or more regions having different alignment directions was 4 9 . Further, when liquid crystal display elements having two or more regions having different alignment directions are produced by using the pattern-formed transparent electrodes shown in FIGS. 2 and 3, the same relative transmittances are obtained respectively -89-201120070 [Table 2 ] Liquid crystal alignment agent [A Cheng Cheng [Β] into distribution directional voltage retention rate (%) Afterimage property (mV) Response speed (msec.) Example 11 S-1 A-1 ΡΑ-1 〇99 200 10 夤Example 12 S-2 A-2 ΡΑΊ 150 99 150 15 Example 13 S-3 A-3 ΡΑΊ 〇 98 100 10 Example 14 S-4 A-4 ΡΑΊ 〇 98 100 12 Example 15 S-5 A-5 ΡΙ-2 〇99 200 29 Example 16 S-6 A-6 ΡΑ-1 〇98 200 17 Example 17 S-7 A-7 ΡΑ-1 〇99 150 11 Example 18 S-8 A-8 ΡΑΊ Δ 98 150 9 Example 19 S-9 A-9 ΡΑ-1 〇99 "170 22 Example 20 S-10 A-10 ΡΑ-1 〇99 170 13 Example 21 S-11 Α·7 ΡΑ-2 〇98 200 12 kExample 22 S-12 Α-7 ΡΙ-1 〇99 250 11 Example 23 S-13 Α-7 ΡΙ-2 〇99 240 38 Example 24 S-14 Α-8 ΡΙ-2 〇99 210 34 Comparative Example 1 CS-1 CA-1 ΡΑ-1 〇98 250 50 Comparative Example 2 CS-2 - ΡΙ-2 〇98 550 55 As the results of Table 2, it is revealed that a liquid crystal display element having a liquid crystal alignment film produced using the liquid crystal alignment agents of Examples 1 to 24 has a generally required alignment property, voltage holding ratio, and afterimage property. It is understood that the speed is also increased by about 24% or more compared with the liquid crystal display element of Comparative Example 1 from the worst case. Further, it is known that two of the alignment directions are different using the composition. In view of the above, it is possible to provide a liquid crystal display element having excellent compatibility, high-speed response, and capable of forming various liquid crystal display elements having excellent properties such as voltage properties and image sticking properties. Therefore, the liquid crystal display element is suitable for use in driving modes such as TN, STN, IPS, VA (including MVA 'PVA, optical vertical alignment, PSA, etc.) [Simplified illustration] -90- 201120070 [第1] (a) A plan view of one state of a patterned transparent electrode used in the present invention. (b) An enlarged X-X' sectional view in the above plan view. [Fig. 2] A plan view showing one state of a patterned transparent electrode used in the present invention. [Fig. 3] A plan view of one state of a patterned transparent electrode used in the present invention. [Main component symbol description] 1 IT 0 film 2 slit 3 transparent substrate -91 -

Claims (1)

201120070 VII. Patent application scope: 1. A liquid crystal alignment agent containing [A] polyorganosiloxane compound, the [A] polyorganosiloxane compound comprising polyorganosiloxane having an epoxy group. a part, and a moiety derived from a compound having a carboxyl group represented by the following formula (1), R3 - R2 - R1 - π - OH ... a II (1) Ο In the formula (1), R1 is a methylene group or a carbon atom It is a stretching base of 2 to 30, a phenyl group or a cyclohexyl group, and these groups may have a substituent, and R2 is a linking group containing any of a double bond, a triple bond, an ether bond, an ester bond, and an oxygen atom. R3 is a group having at least two single ring structures, and a is an integer of 〇~1. 2. The liquid crystal alignment agent of claim 1, wherein R3 in the above formula (丨) is a group represented by the following formula (2), R7 - R6 - - R 7 R4 - (2) Formula (2) Wherein R4 and R6 are respectively a phenyl group, a phenyl group, a phenyl group, a cyclohexylene group, a dicyclohexyl group, a cyclohexylene group or a heterocyclic ring, which may further have a substituent, and the R5 may have a linking group of any one of a substituent alkyl group having 1 to 10 carbon atoms, a double bond, a triple bond, an ether bond, an aceton bond, and a hetero ring, and R 7 is a hydrogen atom, a cyano group, a fluorine atom, or a trifluoro group. Any one of a methyl group, an alkoxycarbonyl group, an alkyl group and an alkoxy group may be the same in a plurality of substituents, or may be an ancestor _ + stomach@ group, and b is an integer of 0 to 1, (; It is an integer of 1 to 9. 3. The liquid crystal alignment agent of claim 1, wherein the upper stomach stomach is a group represented by the following formula (XM) or (Χ·-2), Λ In the formula (ΧΜ), Α is an oxygen atom or a single bond, h is an integer of 1 to 3, and 1 is an integer of 0 to 6, wherein, when 丨 is 〇, a is a single bond and represents a linkage. 4. The liquid crystal alignment agent of claim 1, 2 or 3, which further comprises at least one polymer selected from the group consisting of poly-proline and polyimine. A liquid crystal display element having a liquid crystal alignment film formed of the liquid crystal alignment agent according to any one of claims 1 to 4. 6. The liquid crystal display element of claim 5, comprising a transparent electrode and the liquid crystal alignment film laminated on the transparent electrode, wherein the liquid crystal alignment mode is vertical and has two or more regions having different alignment directions. . 7. The liquid crystal display element of claim 6, wherein the means for having two or more regions having different alignment directions is a means for using the patterned transparent electrode as the transparent electrode or imparting alignment to the liquid crystal alignment film A means of a liquid crystal alignment agent which is a liquid crystal alignment agent for forming a liquid crystal alignment element in a liquid crystal display element, wherein the liquid crystal display element has a transparent electrode and a liquid crystal laminated on the transparent electrode. The alignment film, the liquid crystal alignment mode is a vertical type, and has two or more regions having different orientation directions; characterized by: a compound containing a group represented by the following formula (3); R3-(-R2)-* (3) In the formula (3), R2 is a linking group containing any of a double bond, a triple bond, an ether bond, an ester bond or an oxygen atom, and R3 is a group having at least two monocyclic structures, a is An integer of 0 to 1 indicates a connection key. 9. A liquid crystal alignment agent according to item 8 of the patent application, wherein a means for forming a pattern having two or more regions having different alignment directions is used Transparent electrode or liquid crystal alignment film having alignment splitting function. 10. A liquid crystal display element whose liquid crystal alignment mode is vertical and has two or more regions having different alignment directions, and is characterized by having A liquid crystal alignment film formed by a liquid crystal alignment agent of claim 8 or 9. 11. A polyorganosiloxane compound having a moiety derived from a polyorganosiloxane having an epoxy group and from the following formula ( 1) The compound having a carboxyl group or R3 of the formula (1) is a moiety of a compound having a carboxyl group represented by the following formula (2), R3-4r2-|-R1—Π—OH M, Ja I (1) 0 In the formula (1), R1 is a methylene group or a mercapto group having 2 to 30 carbon atoms, a phenyl group or a cyclohexyl group, and these groups may have a substituent, and R2 is a bond containing -94-201120070, a linking group of any of a triple bond, an ether bond, an ester bond, and an oxygen atom, R 3 is a group having at least two monocyclic structures, a is an integer of 0 to 1; R 7 — R 6 —^R 5 —) — R4——(2) JC Jb In the formula (2), R4 and R6 are respectively a phenyl group, a phenyl group, a naphthyl group, a cyclohexyl group, a dicyclohexyl group, a cyclohexylphenyl group or a heterocyclic ring which may further have a substituent, and R5 is an alkyl group having a carbon number of from 1 to 10 which may have a substituent, a double bond, a triple bond a linking group of any of an ether bond, an ester bond and a hetero ring, and R7 is any one of a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group and an alkoxy group, and R6 has When a plurality of substituents are used, they may be the same or different groups may be combined, b is an integer of 0 to 1, and c is an integer of 1 to 9. -95-