TW201144361A - Liquid crystal alignment agent, liquid crystal alignment film, method for forming liquid crystal alignment film, liquid crystal display element, and polyorganosiloxane compounds - Google Patents

Abstract

The present invention provides a liquid crystal alignment film which fully satisfies that as a liquid crystal display element in the practical aspects requires characteristics such as liquid crystal alignment properties, voltage retention and light resistance, etc.; a method for forming the liquid crystal alignment film; a liquid crystal alignment agent which has excellent storage stability suitable for as a forming material of the liquid crystal alignment film and can adopt the liquid crystal alignment film formed by photoalignment; and a liquid crystal display element having the liquid crystal alignment film. The liquid crystal alignment agent comprises [A] polyorganosiloxane compounds having at least one structure selected from the group consisting of a piperidine structure, a phenol structure and an aniline structure.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal alignment agent suitable as a liquid crystal alignment film forming material, a polyorganosiloxane compound used in the liquid crystal alignment agent, and a liquid crystal alignment agent. A liquid crystal alignment film formed, a method of forming a liquid crystal alignment film, and a liquid crystal display element including the liquid crystal alignment film. [Prior Art] The liquid crystal display element has advantages such as low power consumption and ease of miniaturization and planarization. Therefore, it can be widely used for liquid crystal display devices such as mobile phones and liquid crystal televisions. As a display method of a liquid crystal display device, for example, it has been disclosed in the patent document 丨~4 that it has a twisted nematic type (TN type), a super twisted nematic type (STN type), and a surface according to a change in alignment state of liquid crystal molecules. A liquid crystal display element of a liquid crystal cell such as an internal switching type (IPS type) or a vertical alignment type (VA type). The operating principles of the above various liquid crystal display elements can be roughly classified into a transmissive type and a reflective type. The transmission type is displayed by a backlight from the back of the component. Since the liquid crystal alignment film provided in the transmissive liquid crystal display element is exposed to light from a backlight for a long period of time, when it is irradiated with a backlight having a high irradiation intensity such as a metal halide lamp, there is a rise in temperature. defect. On the other hand, the reflective type does not use a backlight, but is displayed by reflected light from external light such as sunlight. Therefore, it consumes less power than the transmissive type, but it is always exposed to strong ultraviolet rays. Further, in the manufacturing step of the liquid crystal display element, the liquid crystal dropping method "which can be employed" from the viewpoint of the reduction step or the like includes the ultraviolet irradiation step. Therefore, any of the 201144361 liquid crystal display elements requires excellent heat resistance and light resistance. In addition, in recent years, liquid crystal display elements are expected to have excellent electrical characteristics such as liquid crystal alignment property and voltage holding ratio, and do not cause an afterimage problem. Therefore, a technique of forming a liquid crystal alignment film excellent in heat resistance and light resistance by a specific polyoxyalkylene solution has been developed (see Patent Document 5). However, as the manufacturing environment and the use environment have become stricter in recent years, even if the technique is employed, the above-mentioned required performance cannot be satisfied, and the storage stability of the coating liquid is also insufficient, so that it is not convenient to be used in the industry. In view of such a situation, it is desired to develop a liquid crystal display element which satisfies the required characteristics such as liquid crystal alignment property, voltage holding ratio, and light resistance in practical use, and can form a liquid crystal excellent in storage stability of a liquid crystal alignment film by a photo-alignment method. An aligning agent. CITATION LIST Patent Literature Patent Literature 1 Patent Document 2 Patent Document 3 Patent Document 4 Patent Document 5 Patent Document 6 Patent Document 7 Patent Document 8 Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei. U.S. Patent No. 5,928,73, No. 5, 928, No. 3, 928, pp. pp. [Description of the Invention] 201144361 [Problem to be Solved by the Invention] The present invention has been made in view of the above circumstances, and an object thereof is to provide a liquid crystal alignment property and a voltage retention ratio which are sufficiently satisfied as a liquid day display. And a liquid crystal alignment film having characteristics such as light resistance; the method for opening the liquid crystal alignment film is suitable as a liquid crystal alignment agent which is excellent in storage stability of a liquid crystal alignment film forming material and which can form a liquid crystal alignment film by photo-alignment method; A liquid crystal display element of a liquid crystal alignment film. [Means for Solving the Problem] The invention for solving the above problems is a liquid crystal alignment agent containing a [A] polyorganic oxide compound having a piperidine structure, a phenol structure and an aniline structure. The liquid crystal alignment agent is excellent in storage stability, and the liquid crystal alignment film formed of the liquid crystal alignment agent satisfies the characteristics such as liquid crystal alignment property, voltage holding ratio, and light resistance which are required for practical use as a liquid crystal display element. The above piperidine structure is preferably represented by the following formula (A-1'), and the phenol structure is preferably represented by the following formula (A-2'), and the aniline structure is preferably represented by the following formula:

(In the formula (A-1'), R1 is a hydrogen atom, an alkyl group having a carbon number, an aryl group having 6 to 20 201144361, an aralkyl group having 7 to 13 carbon atoms, or 1,3 - two side oxybutyl groups. R2 to R5 are each independently an alkyl group having a carbon number, an aryl group having 6 to 12 carbon atoms, or an aromatic group having 7 to 13 carbon atoms. X1 is a single bond. The carbonyl group or "-CONH-.X2 to X5 are each independently a single bond, a carbonyl group, a **-CH2-CO- or a **-CH2-CH(OH)-» ** linkage and a piperidine ring bond * The indicated bond is bonded to the main or side chain of the polyorganosiloxane skeleton.)

(In the formula (A-2'), R6 is an alkyl group having 1 to 16 carbon atoms. Further, the alkyl group may have an oxygen atom, a sulfur atom, a carbonyl group, an ester group or two of them in the skeleton chain. A group in which the above is combined. η is an integer of 0 to 4. * The bond shown is bonded to the main chain or side chain of the polyorganosiloxane skeleton.) RVR8

(In the formula (Α-3'), R7 and R8 are each independently an alkyl group having 1 to 16 carbon atoms, wherein the alkyl group may have an oxygen atom, a sulfur atom 'carbonyl group, an ester group or the like in the skeleton chain. a group in which two or more of them are combined. * The bond represented by the bond is bonded to the main chain or side chain of the polyorganosiloxane skeleton.) 201144361 In the liquid crystal alignment agent, [A] polyorganic The oxoxane compound preferably contains at least one selected from the group consisting of a polyorganic oxalate having a structural unit represented by the following formula (1), a hydrolyzate thereof, and a condensate of the hydrolyzate. And a part derived from at least one compound selected from the group consisting of compounds represented by the following formula (A-1), formula (A-2) and formula (A-3). ~ Xa -Si-Ο—— (1)

I

Ya (in the formula (l), '^ is an i-valent organic group having an epoxy group. γ3 is a sulfhydryl group, an alkoxy group having 1 to 10 carbon atoms, or a carbon or carbon group of 1 to 20 or a carbon group. An aryl group having an atomic number of 6 to 20.) R1

(A-1)

201144361

(A-3) (In the formula (Al), R to R5 and X1 to X5 are synonymous with the above formula (Al,). In the formula (A-2), R6 is synonymous with the above formula (A-2'). In (A-3), R7 and R8 are synonymous with the above formula (A-3'). In the formula (A-1) to (A-3), Y is a single bond, and an alkane having 1 to 16 carbon atoms And the above-mentioned alkanediyl group may have an oxygen atom, a sulfur atom, a carbonyl 'ester group, a guanamine group or a group combining two or more of them in the structure. Z is a carboxyl group or a hydroxyl group. In the liquid crystal alignment agent, the [A] polyorganosiloxane compound contains a polyorganosiloxane having a structural unit represented by the above formula (1), a hydrolyzate thereof, and a condensate of the hydrolyzate. At least one selected portion of the group 'so that a structure having a radical scavenging ability such as a piperidine structure can be easily introduced into the [A] polyorganosiloxane compound* to improve light resistance. In the liquid crystal alignment agent, χ a in the above formula (丨) is preferably a group represented by the following formula (Xa-1) or formula (Xa-2), and more preferably a formula (χΜ_υ). Or the group represented by (Xa-2-l) 201144361

(Xa-1) CVH2V-*

CsH2s o

(Xa-2) (In the formula (xa-1) and the formula (Xa-2), 's is an integer of 0 to 3. t is an integer of U6. u is an integer of 0 to 2. v is an integer of 0 to 6. * The connection key represented by the * is bonded to the helium atom.)

(The linkage bond represented by '* in the formula (XM-1) and the formula (Xa-2-l) is bonded to a ruthenium atom.) By using the above specific group as the above monovalent organic group having an epoxy group It is easy to introduce a moiety derived from the compound represented by the above formula (Α_υ, formula (A_2) or formula (A_3) into the [A] polyorganosiloxane compound of the liquid crystal alignment agent. In the liquid crystal alignment agent The [A] polyorganosiloxane compound preferably contains a structure having a liquid crystal alignment ability. [A] a polyorganosiloxane compound, which can further improve the liquid crystal alignment ability by including a structure having a liquid crystal alignment ability. The structure of the liquid crystal alignment ability 'preferably has an organic group having a carbon number of 17 to 51 having a sterol skeleton of the type --10-201144361, an alkyl group having 2 to 20 carbon atoms, and a carbon number of 20 a fluoroalkyl group, a cyclohexyl group, an alkoxyaryl group having an alkyl group having 2 to 20 carbon atoms, an alkylcyclohexyl group having an alkyl group having 1 to 20 carbon atoms, and having 1 to 1 carbon atom; a fluoroalkylcyclohexyl group of 20 fluoroalkyl group and a fluorine group having 1 to 20 carbon atoms At least one group selected from the group consisting of fluoroalkylalkoxycyclohexyl groups having a liquid crystal alignment ability, having the above specific group (hereinafter, sometimes referred to as "liquid crystal alignment group) The liquid crystal alignment agent can impart more excellent liquid crystal alignment ability to the liquid crystal alignment agent. The structure having the liquid crystal alignment ability preferably has a structure represented by the following formula (B-1).

(In the formula (B-1), m is an integer of 0 to 4.) Since the structure having the liquid crystal alignment ability has the above specific structure, the liquid crystal alignment film can be formed from the liquid crystal alignment agent even by the photoalignment method. The liquid crystal alignment agent preferably further contains at least one polymer selected from the group consisting of polylysine and polyimine (hereinafter, sometimes referred to as "[B] polymer") . By using a liquid crystal alignment film further containing a [B] polymer, a liquid crystal alignment film can be obtained, whereby a liquid crystal display element having further improved electrical characteristics such as voltage holding ratio can be obtained. The liquid crystal alignment agent preferably further contains [C] a polyorganosiloxane compound having a structural unit represented by the following formula (2)-11 to 201144361 (hereinafter, sometimes referred to as "[c] other polyorganisms) A siloxane compound"). Xb

I --Si—Ο (2 )

Yb _ (In the formula (2), Xb 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. Yb is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms.) The liquid crystal alignment agent can promote the crosslinking of the [A] polyorganosiloxane compound by further containing [C] other polyorganosiloxane compound. In combination, the voltage holding ratio and the like of the obtained liquid crystal display element can be further improved. The method for forming a liquid crystal alignment film of the present invention comprises: (1) a step of coating a liquid crystal alignment agent containing a [A] polyorganosiloxane compound on a substrate to form a coating film, the [A] polyorganosiloxane The compound contains a structure having a liquid crystal alignment ability having the structure represented by the above formula (B-1), and (2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation. By the method of the present invention using the liquid crystal alignment agent, it is possible to form a liquid crystal alignment film which satisfies the required characteristics such as liquid crystal alignment property, voltage holding ratio and light resistance as a liquid crystal display element in practical use. A liquid crystal alignment film formed of the liquid crystal alignment agent and a liquid crystal display element including the liquid crystal alignment film are also suitably included in the present invention. The liquid crystal display element-12-201144361 of the present application having the liquid crystal alignment film formed of the liquid crystal alignment agent can be suitably used for, for example, a timepiece, a portable game machine, a word processor, a notebook computer, a car navigation system, Display devices such as cameras, portable information terminals, digital cameras, mobile phones, various displays, and LCD TVs. Further, the aryl group having 6 to 20 carbon atoms represented by the above R1, the aralkyl group having 7 to 13 carbon atoms, the alkyl group having the carbon number represented by R and R5, and the carbon number of 6~ A part or all of the hydrogen atom of the aryl group of 12 and the aralkyl group having 7 to 13 carbon atoms may be substituted. [Effects of the Invention] According to the present invention, it is possible to provide a liquid crystal alignment film which satisfies the required characteristics such as liquid crystal alignment, voltage holding ratio, and light resistance as a liquid crystal display element, and a method for forming the liquid crystal alignment film. The liquid crystal alignment film forming material is excellent in storage stability, and a liquid crystal alignment agent which forms a liquid crystal alignment film by a photo-alignment method and a liquid crystal display element including a liquid crystal alignment film can be used. The liquid crystal display element of the present application having the liquid crystal alignment film formed of the liquid crystal alignment agent can be suitably used for, for example, a timepiece, a portable game machine, a word processor, a notebook computer, a car navigation system, a video camera, and a portable type. Display devices such as information terminals, digital cameras, mobile phones, various display devices, and LCD TVs. [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, embodiments of the present invention will be described in detail. <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention contains [A] polyorganooxane having at least one structure selected from the group consisting of a piperidine structure, a phenol structure-13-201144361, and an aniline structure. Compound. The liquid crystal alignment agent is excellent in storage stability, and the liquid crystal alignment film formed of the liquid crystal alignment agent satisfies the characteristics such as desired liquid crystal alignment property, voltage holding ratio, and light resistance as a liquid crystal display element. Further, the [A] polyorganosiloxane compound preferably has a structure having a liquid crystal alignment ability, and the liquid crystal alignment agent preferably contains a polymer other than the [A] polyorganosiloxane compound (hereinafter, sometimes referred to as Further, the "liquid crystal alignment agent" may contain an optional component as long as the effect of the present invention is not impaired. Hereinafter, the [A] polyorganosiloxane compound, a structure having a liquid crystal alignment ability, other polymers, and optional components will be described in detail. <[A] Polyorganosiloxane compound> [A] A polyorganosiloxane compound having at least one structure selected from the group consisting of a piperidine structure, a phenol structure, and an aniline structure. Further, the [A] polyorganosiloxane compound preferably contains a polyorganosiloxane having a structural unit represented by the above formula (1) (hereinafter, sometimes referred to as "polyorganofluorene having an epoxy group" a portion of the oxane ") and a portion derived from at least one compound selected from the group consisting of the compounds represented by the above formula (A-1), the formula (A-2), and the formula (A-3). Such a [A] polyorganosiloxane compound can be represented by the polyorganosiloxane having an epoxy group and the above formula (A-1), formula (A-2) or formula (A-3). Obtained by the reaction of the compound. In the liquid crystal alignment agent, '[A] polyorganosiloxane compound' contains a polyorganosiloxane derived from a structural unit represented by the above formula U), a hydrolyzate thereof, and the hydrolyzate of the same -14-11444361 The at least one selected from the group consisting of condensates can easily introduce a structure having a radical scavenging ability such as a piperidine structure into the [A] polyorganosiloxane compound, thereby improving Lightfastness. The polyorganosiloxane having a piperidine structure, a phenol structure, an aniline structure and an epoxy group is described in detail below. [Piperidine structure] The piperidine structure of the [A] polyorganosiloxane compound is preferably a structure represented by the above formula (A-1'). The [A] polyorganosiloxane compound having such a piperidine structure can be obtained by a reaction of a polyorganosiloxane having an epoxy group with a compound represented by the above formula (A-1). The alkyl group having 1 to 6 carbon atoms represented by the above R^R5 may be either linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Heji and so on. The aryl group having 6 to 20 carbon atoms represented by the above R1 may, for example, be a phenyl group, a naphthyl group or an oxybenzoic acid. Further, a part or all of the hydrogen atoms of the aromatic ring of the aryl group are preferably substituted with a fluorenyl group or an alkoxy group having 1 to 4 carbon atoms. The aralkyl group having 7 to 13 carbon atoms represented by the above R1 to R5 may, for example, be a benzyl group or a phenethyl group. Further, a part or all of the hydrogen atoms of the aromatic ring of the aralkyl group are preferably substituted by a fluorenyl group or an alkoxy group having a carbon atom of 1-4. The aryl group having 6 to 12 carbon atoms represented by the above R2 to R5 may be, for example, a phenyl group or a naphthyl group. Further, a part or all of the hydrogen atoms of the aromatic ring of the aryl group are preferably substituted by a fluorenyl group or an alkoxy group having 1 to 4 carbon atoms. The oxy group having 1 to 4 carbon atoms represented by the above R and R5 may, for example, be a methoxy group, an ethoxy group or a n-propoxy group. The Z in the above formula (A-1) is preferably a carboxyl group, and examples of the compound represented by the following formulas (A-1-1) to (A-b 4) are preferably those of the formula (Α_υ). For example.

The ratio of the (A -1 ') structure in the [A] polyorganic oxide compound is preferably from 2 mol% to 80 mol%, more preferably from 5 mol% to 75 mol%, relative to Xa. And especially good for 25 mol% ~ 60 mol%. [酣 structure] The phenol structure of the [A] polyorganosiloxane compound is preferably -16-201144361. The structure represented by the above formula (A-2'). The [A] polyorganosiloxane compound having such a phenol structure can be obtained by a reaction of a polyorganosiloxane having an epoxy group with a compound represented by the above formula (A-2). The alkyl group having 1 to 16 carbon atoms represented by the above R6 may be either linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like. . Z in the above formula (A-2) is preferably a carboxyl group. For example, a compound represented by the following formula (Α-2-1) to (Α_2-7) may be exemplified by the formula (Α·2). Preferably, it is an example. -17- 201144361

OH (A-2-3)

COOH (A-2-4)

H3C OH ^ COOH

OH

H3C COOH

H3CO OH ^ COOH (A-2-5) (A-2-6) (A-2-7) Example, phase F % ~ 80 as [A] polyorganosiloxane compound (A-2') structure The ratio is preferably from 10 mol% to 90 mol%, more preferably 20 mol%, and particularly preferably 25 mol% to 75 mol% for Xa. [Aniline structure] -18- 201144361 The aniline structure of the [A] polyorganosiloxane compound is preferably a structure represented by the above formula (A-3'). The [A] polyorganosiloxane compound having such an aniline structure can be obtained by a reaction of a polyorganosiloxane having an epoxy group with a compound represented by the above formula (A-3). The alkyl group having 1 to 16 carbon atoms represented by the above R7 and R8 may be the same alkyl group as the alkyl group described in the above formula (A-2). The Z in the above formula (A-3) is preferably a carboxyl group. For example, a compound represented by the following formula (Α-3·1) to (Α-3-8) may be exemplified by the formula (A-3). Preferably, it is an example. -19- 201144361 (A-3-1)

COOH

C7H15 \ (A-3-2) (A-3-3) (A-3-4) (A-3-5) (A-3-6) COOH (A·3 - 7) COOH (A-3 - 8) r C7H15

CeH, 7 \

I

The ratio of CeH17 as the structure of the (A_3,) structure in the [A] polyorganosiloxane compound is preferably from 10 mol% to 90 mol%, more preferably from 20 mol% to 80 mol%, relative to Xa'. And especially good for 25 mol% ~ 75 mol%. [Polyorganosiloxane having an epoxy group] The polyorganosiloxane having an epoxy group means a polyorganosiloxane containing a polymer main chain in the structure of the [A] polyorganosiloxane compound.院骨-20- 201144361 Frame 'and the nucleation of the epoxy-containing skeleton as a polymer backbone branched from the polyorganosiloxane. The monovalent organic group having an epoxy group represented by xam in the above formula (1) is not particularly limited as long as it is a monovalent organic group having an epoxy group, and examples thereof include glycidyl group and glycidol. A group of an oxy group, an epoxycyclohexyl group, or the like. Wherein 'xa is preferably a group ' represented by the above formula (Xa-1) or (Xa_2) and more preferably a group represented by the above formula (Xa-1-1) or (Xa-2-l). By using the above specific group as the above monovalent organic group having an epoxy group, the compound represented by the above formula (A-1), formula (A-2) or formula (A-3) can be easily used. A portion is introduced into the [A] polyorganosiloxane compound of the liquid crystal alignment agent. The alkoxy group having 1 to 10 carbon atoms represented by Ya in the above formula (1) may, for example, be a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group or a n-butoxy group. Isobutoxy and the like. The alkyl group having 1 to 20 carbon atoms represented by Ya in the above formula (1) may, for example, be a linear or branched methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. , heptyl, octyl, decyl, decyl, lauryl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl , nonadecyl, eicosyl and the like. The aryl group having 6 to 20 carbon atoms represented by Ya in the above formula (1) may, for example, be a phenyl group or a naphthyl group. [Synthesis method of polyorganosiloxane having an epoxy group] Polyorganosiloxane having an epoxy group can be preferably carried out in the presence of an appropriate organic solvent, water and a catalyst in the appropriate period from 21 to 201144361. A mixture of a decane compound having an epoxy group or a decane compound having an epoxy group and another decane compound is synthesized by hydrolysis or hydrolysis/condensation. Examples of the sand compound having an epoxy group include, for example, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and 3-glycidoxypropylmethyl. Dimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyldimethylmethoxydecane, 3-glycidoxypropyldimethylethyl Oxydecane '2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, and the like. They may be used singly or in combination of two or more. As other decane compounds, for example, tetrachlorodecane, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, tetra-n-butoxy decane, and tetra-second butoxy Base decane, trichloro decane, trimethoxy decane, triethoxy decane, tri-n-propoxy decane, triisopropoxy decane, tri-n-butoxy decane, tri- or 2-butoxy decane, fluorotrichloro Decane, fluorotrimethoxydecane, fluorotriethoxydecane, fluorotri-n-propoxy decane, fluorotriisopropoxy decane, fluorotri-n-butoxy decane, fluorotri-n-butoxy decane, methyl Trichlorodecane, methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane, methyltriisopropoxydecane, methyltri-n-butoxydecane, methyltrimethylene Butoxy decane, 2-(trifluoromethyl)ethyltrichlorodecane, 2·(trifluoromethyl)ethyltrimethoxydecane, 2-(trifluoromethyl)ethyltriethoxydecane 2-(Trifluoromethyl)ethyltri-n-propoxy-22- 201144361 decane, 2-(trifluoromethyl)ethyltriisopropoxydecane, 2 ·(trifluoro Ethyl tri-n-butoxy decane, 2-(trifluoromethyl)ethyl tri-n-butoxy decane, 2-(perfluoro-n-hexyl)ethyltrichloro decane, 2-(perfluoro-n-hexyl) Ethyltrimethoxydecane, 2-(perfluoro-n-hexyl)ethyltriethoxydecane, 2-(perfluoro-n-hexyl)ethyltri-n-propoxydecane, 2-(perfluoro-n-hexyl) Triisopropoxy decane, 2-(perfluoro-n-hexyl)ethyltri-n-butoxy decane, 2-(perfluoro-n-hexyl)ethyltri-n-butoxy oxane, 2-(perfluoro-n-octane Ethyl trichloromethane, 2-(perfluoro-n-octyl)ethyltrimethoxydecane, 2-(perfluoro-n-octyl)ethyltriethoxydecane, 2·(perfluoro-n-octyl) Tri-n-propoxy decane, 2-(perfluoro-n-octyl)ethyltriisopropoxy decane, 2-(perfluoro-n-octyl)ethyltri-n-butoxy decane, 2-(perfluoro-positive Octyl)ethyl tri-n-butoxybutane, hydroxymethyltrichlorodecane, hydroxymethyltrimethoxydecane, hydroxyethyltrimethoxydecane, hydroxymethyltri-n-propoxydecane, hydroxymethyl three Isopropoxydecane, hydroxymethyltri-n-butoxydecane, hydroxy Methyl tri- or 2-butoxy decane, 3-(methyl) propylene methoxy propyl trichloro decane, 3-(methyl) propylene methoxy propyl trimethoxy decane, 3-(methyl) propylene醯oxypropyl triethoxy decane, 3-(methyl) propylene methoxy propyl tri-n-propoxy decane, 3-(methyl) propylene methoxy propyl triisopropoxy decane, 3 -(Meth)acryloxypropyltri-n-butoxydecane, 3-(methyl)propenyloxypropyltri-n-butoxypropane, 3-mercaptopropyltrichlorodecane, 3- Mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, 3-mercaptopropyltri-n-propoxyoxydecane, 3-mercaptopropyltriisopropoxydecane, 3-indole Propyl tri-n-butoxy decane, 3-mercaptopropyl tri-n-butoxy decane, decylmethyltrimethoxy decane, -23- 201144361 decylmethyltriethoxy decane, vinyl trichloride矽, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tri-n-propoxy decane, vinyl triisopropoxy decane, vinyl tri-n-butoxy decane, vinyl tri- or Oxydecane, allyl Chlorodecane, allyltrimethoxydecane, allyltriethoxydecane, allyltri-n-propoxydecane, allyltriisopropoxydecane, allyltri-n-butoxydecane, Allyl tri- or two-butoxy decane, phenyl trichloro decane, phenyl trimethoxy decane, phenyl triethoxy decane, phenyl tri-n-propoxy decane, phenyl triisopropoxy decane, Phenyl tri-n-butoxy decane, phenyl tri-n-butoxy decane, methyl dichlorodecane, methyl dimethoxy decane, methyl diethoxy decane, methyl di-n-propoxy decane, Methyl diisopropoxy decane, methyl di-n-butoxy decane, methyl di- or 2-butoxy decane, dimethyl dichloro decane, dimethyl dimethoxy decane, dimethyl diethoxy Base decane, dimethyldi-n-propoxy decane, dimethyl diisopropoxy decane, dimethyl di-n-butoxy decane, dimethyl di-2-butoxy decane, (methyl) [2 -(perfluoro-n-octyl)ethyl]dichlorodecane, (methyl)[2-(perfluoro-n-octyl)ethyl]dimethoxydecane, (methyl)[2_(perfluoro-n-octyl) Ethyl] two Oxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-n-propoxydecane, (methyl)U-(perfluoro-n-octyl)ethyl]diisopropoxydecane , (methyl) [2-(perfluoro-n-octyl)ethyl]di-n-butoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]di- or 2-butoxybutane, (methyl)(3-mercaptopropyl)dichlorodecane, (methyl)(3-mercaptopropyl)dimethoxydecane, (methyl K3-mercaptopropyl)diethoxydecane, Methyl)(3-mercaptopropyl)di-n-propoxydecane, (methyl)(3-mercaptopropyl)diisopropoxydecane, (methyl-24- 201144361) (3-mercaptopropyl Di-n-butoxy decane, (methyl) (3-mercaptopropyl) di- or 2-butoxy decane '(methyl)(vinyl)dichlorodecane, (methyl)(vinyl) II Methoxy decane, (meth) (vinyl) diethoxy decane, (methyl) (vinyl) di-n-propoxy decane, (methyl) (vinyl) diisopropoxy decane, ( Methyl)(vinyl)di-n-butoxydecane, (methyl)(vinyl) II Grade butoxy decane, divinyl chlorodecane, divinyl dimethoxy decane, divinyl diethoxy decane, divinyl di-n-propoxy decane, divinyl diisopropoxy decane , divinyl di-n-butoxy decane, divinyl di-n-butoxy decane, diphenyl dichloro decane, diphenyl dimethoxy decane, diphenyl diethoxy decane, diphenyl Di-n-propoxy decane, diphenyl diisopropoxy decane, diphenyl di-n-butoxy decane, diphenyl di-n-butoxy decane, chlorodimethyl decane, methoxy dimethyl Decane, ethoxy dimethyl decane, chlorotrimethyl decane, bromotrimethyl decane, iodine trimethyl decane, methoxy trimethyl decane, ethoxy trimethyl decane, n-propoxy trimethyl Base decane, isopropoxy trimethyl decane, n-butoxy trimethyl decane, secondary butoxy trimethyl decane, tertiary butoxy trimethyl decane, (chloro) (vinyl) dimethyl Base decane, (methoxy) (vinyl) dimethyl decane, (ethoxy) (vinyl) dimethyl decane, (chloro) (methyl) Diphenyl Silane, (methoxy) (methyl) diphenyl Silane, (ethoxy) (methyl) diphenyl Silane Silane compounds and the like having a silicon atom and the like. They may be used singly or in combination of two or more. A material which can be used as a commercial item is exemplified by KC-89, KC-89S, X-21-3153 'X-21-5841' X-21-5842' X-21-5843' X, 2 1 - 5 844 ' X-2 1 -5 845 ' X-2 1 -5 846 ' X-2 1 -5 847 ' X-2 1 -5 848 ' -25- 201144361 X-22-1 60AS , X-22- 1 70B , X-22- 1 70BX, X-22- 1 70D, X-22- 1 70DX, X-22- 1 76B, X-22- 1 76D, X-22- 1 76DX, X-22-176F' 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, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (above, Shin-Etsu Chemical Co., Ltd.);

Glass Resin; SH804, SH805, SH806A, SH840, SR2400, SR2402,

I SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, Toray Dow Corning); FZ3711, FZ3722 (above, UNI UNICAR); DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS -S31, DMS-S32, DMS-S33, DMS-S35 'DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS-227, PSD-03 32, PDS-1615, PDS-993 1 ' XMS -5025 (above, chisso); methyl decanoate MS5 methyl benzoate MS56 (above, Mitsubishi Chemical Corporation); ethyl citrate 28, ethyl citrate 40, ethyl citrate 48 (above, Colcoat) ); a partial condensate of GR100, GR650, GR908, GR950 (above, Showa Denko). -26- 201144361 In the pursuit of some other sandane compounds, 'preferably tetramethoxy sand yard' tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, 3 - (methyl) propyl醯 methoxypropyl trimethoxy decane, 3-(meth) propylene methoxy propyl diethoxy decane, vinyl trimethoxy decane, vinyl triethoxy cerium, allyl trimethoxy Decane, allyltriethoxydecane, phenyldimethoxydecane, phenyltriethoxydecane, 3'mercaptopropyltrimethoxysane, 3-mercaptopropyltriethoxydecane , mercaptomethyltrimethoxydecane, sulfomethyltriethoxydecane, dimethyldimethoxydecane or dimethyldiethoxydecane. As the epoxy equivalent of the polyorganic sand oxyalkylene having an epoxy group, it is preferably l〇〇g/mole to 1 0000 g/mole' more preferably 15 〇g/mole~i〇〇〇g/ Moer, and especially good for 150g / Moer ~ 300g / Moh. Therefore, when synthesizing a polyorganosiloxane having an epoxy group, the ratio of use of the decane compound having an epoxy group and other sand compound is preferably set to the epoxy equivalent of the obtained polyorganosiloxane. Reach the above range. The organic solvent which can be used in the synthesis of the polyorganosiloxane having an epoxy group is, for example, a hydrocarbon compound, a ketone compound, an ester compound, an ether compound, an alcohol compound or the like. They may be used singly or in combination of two or more. Examples of the hydrocarbon compound include toluene, xylene, and the like. Examples of the ketone compound include methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentanone 'diethyl ketone, and cyclohexanone. The ester compound may, for example, be ethyl acetate, n-butyl acetate, -27-201144361 isoamyl acetate, propylene glycol monomethyl ether acetate or 3-methoxybutyl lactate. The ether compound may, for example, be ethylene glycol dimethyl ether diethyl ether 'tetrahydrofuran or dioxane. Examples of the alcohol compound include, for example, 1-hexanol, 4-methylglycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether mono-n-butyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. Propylene ether and the like. Among them, a substance which is not water-soluble is preferred. The amount of use as the organic solvent is preferably 10 parts by mass to 10 parts by mass based on 100 parts by mass of the compound, and more parts by weight to 1,000 parts by mass. The water for synthesizing the polyorganosiloxane having an epoxy group is preferably 0.5 times by mole to 100 parts by weight and more preferably 1 time by mole to 30 times by mole relative to the total of the decane compound. The catalyst may, for example, be an acid, an alkali metal base, a titanium compound or a pin compound. They can be used alone in combination. The alkali metal compound may, for example, be potassium hydride, sodium methoxide, potassium methoxide, sodium ethoxide or potassium ethoxide. The organic base may, for example, be an organic primary or secondary amine such as ethylamine, diethylamine, pyridine, pyrrolidine or pyrrole; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine or 4-diacetate. , ethylene glycol 2-pentanol, ethylene glycol mono-n-propyl all decane blue for 50 mass usage, megamol, organic, or two, cesium hydroxide trap, methylphenidamine -28- 201144361 Organic tertiary amine such as pyridine or dioxodicycloundecene; organic quaternary ammonium such as tetramethylammonium hydroxide. As the catalyst for producing the polyorganosiloxane having an epoxy group, an alkali metal compound or an organic base is preferred. By using an alkali metal compound or an organic base as a catalyst, side reactions such as ring opening of an epoxy group are not generated, and polyorganosiloxane can be obtained at a high hydrolysis/condensation rate, so that production stability is excellent. Further, a reaction product of a polyorganosiloxane having an epoxy group synthesized using an alkali metal compound or an organic base as a catalyst and a compound represented by the above formula (Α_υ, formula (A_2) or formula (A-3), respectively The liquid crystal alignment agent is extremely advantageous because it is extremely excellent in storage stability. The reason can be presumed to be 'in the science of sol-gel method (Agune Chengfengshe, 1 988, pages 15 to 161). When an alkali metal compound or an organic base used in the hydrolysis or condensation reaction is used as a catalyst, whether a three-dimensional structure such as a random structure or a cage structure is formed, and a polyorganosiloxane having a small content of a sterol group can be obtained. It is presumed that since the polyorganosiloxane has a small content of a sterol group, it is possible to suppress a condensation reaction between sterol groups. Further, when the liquid crystal alignment agent of the present invention contains other polymers described later' It is also possible to suppress the condensation reaction of the sterol group with other polymers, and thus the result of excellent storage stability is obtained. As the catalyst, it is more preferably an organic base, and is particularly preferable. The organic tertiary amine and the organic quaternary ammonium are used. The amount of the organic base to be used varies depending on the reaction conditions such as the type of the organic base and the temperature. For example, -29 to 201144361 is preferably 0. 01 times. The ear is ~3 times Mo' and more preferably 0.05 times mole to 1 mole. Hydrolysis or hydrolysis when synthesizing polyorganosiloxane having an epoxy group. The condensation reaction is preferably by having an epoxy The base decane compound and other sand compound compounds as needed are dissolved in an organic solvent, and the solution is mixed with an organic base and water' and heated by, for example, an oil bath. The oil bath is used as a hydrolysis/condensation reaction. The heating temperature is preferably 1 30 ° C or lower and more preferably 40 ° C to 100 t: as the heating time, preferably 〇 5 hours to 12 hours ' and more preferably 1 hour to 8 hours. In the middle, the mixture may be stirred or refluxed. After the completion of the reaction, the organic solvent layer separated from the reaction liquid is preferably washed with water. When washing, water containing a small amount of salt, for example, about 0.2% by mass, is used. Ammonium nitrate aqueous solution Washing is preferred in that the washing operation is facilitated. Washing is performed until the water layer after washing is neutral, and then the organic solvent layer is dried using a desiccant such as anhydrous calcium sulfate or molecular sieve as needed to remove the solvent. In the present invention, a commercially available product can be used as the polyorganosiloxane having an epoxy group. As such a commercially available product, a commercially available product can be used. For example, DMS-E01, DMS-E12, DMS-E21, EMS-32 (above, chisso company), etc. Polystyrene-converted as a polyorganosiloxane having an epoxy structure as determined by gel permeation chromatography The weight average molecular weight (hereinafter, sometimes referred to as "Mw"), preferably 500 to 100,000' is more preferably 1, 〇〇〇~1 〇, 〇〇〇 ' and -30- 201144361 is preferably 1,000~ 5,000. Further, in the present specification, Mw is a polystyrene-converted oxime measured by gel permeation chromatography described below. Pipe column: Tosoh Company ' TSKgel GRCXLII Solvent: tetrahydrofuran temperature: 40 ° C Pressure: 6.8 MPa <Structure having liquid crystal alignment ability> In the liquid crystal alignment agent, the [A] polyorganosiloxane compound preferably contains A structure having a liquid crystal alignment capability. [A] A polyorganosiloxane compound, which can further improve the liquid crystal alignment ability by including a structure having a liquid crystal alignment ability. The group possessed by the structure having a liquid crystal alignment ability is preferably the above liquid crystal alignment group. The structure having the liquid crystal alignment ability can impart a superior liquid crystal alignment ability to the liquid crystal alignment agent by having the above specific group. The organic group having 17 to 51 carbon atoms having a steroid skeleton is preferably a monovalent organic group having a steroid skeleton and having 17 to 30 carbon atoms, and examples thereof include a cholest-3-yl group. Cholester-5-en-3-yl, cholesteryl 24-en-3-yl, cholest-5-24-dien-3-yl'lanostan-3-yl and the like. Examples of the alkyl group having 2 to 20 carbon atoms include ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-decyl, n-lauric, and N-dodecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-stearyl, n-icosyl and the like. -31 - 201144361 The number of carbon atoms as the alkyl group is more preferably 4 to 20. Examples of the fluoroalkyl group having 1 to 20 carbon atoms include a fluoromethyl group, a perfluoroethyl group, a 3,3,3-trifluoropropyl group, and a 4,4,4-trifluoro 4,4,5 group. 5,5-pentafluoropentyl, 3,3,4,4,5,5,5-heptafluoropentyl, and the like. Examples of the alkoxy group having an alkyl group having 2 to 20 carbon atoms include n-propoxy aryl group, n-butoxy aryl group, n-pentyl group, n-hexyloxy aryl group and n-heptyloxy aryl group. Examples of the n-octyloxyaryl group as the alkyl ring having an alkyl group having 1 to 20 carbon atoms include n-propylcyclohexyl group, n-butylcyclohexyl group, n-pentyl group, n-hexylcyclohexyl group, and n-glycol. The cyclohexyl group and the n-octylcyclohexyl group are fluoroalkyl groups having a fluoroalkyl group having 1 to 20 carbon atoms, and examples thereof include a trifluoromethylcyclohexyl group. Examples of the oxycyclohexyl group having a fluoroalkylalkoxy group having 1 to 20 carbon atoms include, for example, 4,4,4-trifluorobutoxycyclo 4,4,5,5,5·pentafluoropentane. Oxycyclohexyl and the like. The structure having the liquid crystal alignment ability preferably further has the structure represented by (B-1). Since the above-described liquid crystal alignment ability has a specific structure, the liquid crystal alignment film can be formed by a crystal alignment agent even by the photoalignment method. The [A] polyorganoconjugate containing a structure having a liquid crystal alignment ability can be obtained by reacting a polyorganosiloxane having an epoxy group with a compound having a liquid crystal alignment ability represented by the following to obtain RE-T ( B-2) For example, tributyl, 5-aryl, oxyaryl and the like. [Hienji, base ring and so on. In the above formula (B-2), RE is a group containing a structure having a liquid crystal alignment ability, in the above formula (B-2) -32- 201144361. T is a thiol group or a thiol group. Preferable examples of the above formula (B-2) include compounds represented by the following formulas (B-2-1) to (B-2-8).

Rf-Xc—^ CH=CH—Xd—T (B-2-1) In the above formula (B-2 -1), Rf is the above-mentioned liquid crystal alignment group. Hey. a single bond, an oxygen atom, a sulfur atom, a phenylene group, a cyclohexylene group, _c〇〇_, _NHCO-, •CONH-, -CO-, -OCO- or a linking group combining two or more of them group. Xd is a single bond, an oxygen atom, a phenylene group, _C〇., -QCO-, _(CH2)a· or a linking group which combines two or more of them. a is the integer of ι~6. T is synonymous with the above formula (b-2).

Rf - Χ β - CH = CH - / - x < J - τ (B-2-2) In the above formula (B-2-2), Rf, Xd and t are synonymous with the above formula (B-2-1) . a single bond, an oxygen atom, a sulfur atom, a phenyl group, -COO-, -NHCO-, CONH· '-CO-, -0C0- or a combination of two or more of them

(B-2-3) Linking group In the above formula (Β·2-3), '1^ and T are synonymous with the above formula (B-2-1).

Xf is a single bond, an oxygen atom, -CO-, -(CH〇a- or a linking group which combines two or more of them. & is an integer of 1-6. 111 is an integer of 〇~4. -33- 201144361

The above formula (B-2-4) to (B-2-6) have the meanings.

Rf and T are the same as the above formula (B-2-1). XB is a single bond, an oxygen atom, a sulfur atom, _C〇〇-NHCO- •CONH-,

-CO, -0C0- or a linking group which combines two or more of them. Xh is a single bond, an oxygen atom, a sulfur atom, ((: η〇!ι·, _c〇· or a combination of two or more of them in an integer of 1 to 6 (B-2-7)) Group. a is

CH =CH—COORf

τ-xJ

CH = CH - COORf (B - 2 - 8 ) In the above formulae (B-2-7) and (B-2-8), the sum T is synonymous with the above formula (B-2-1). Xj is a single bond, an oxygen atom, -COO-, -0C0-, -(CH2)a- or a linking group which combines two or more of them. a is an integer of 1 to 6. Further, in the above formula (Β-2-1) to (Β-2-8), a combination of substituents forming a 〇-〇 bond or a -34- 201144361 α,/3 -dione structure is not allowed. In the above formula (Β-2-1) to (Β-2-8), a compound represented by the following formula (B-2-l-1) to the formula (?-2-8-2) is more preferable.

Rf —0-^^-CH=CH-C00H (B-2-1-1) Rf —COO—^~^-CH=CH-COOH (B-2-1-2) Rf CH=CH - COOH ( B-2-1-3) Rf —0 —COO CH= CH - COOH (B-2-1-4) Rf —COO —COO —CH= CH - COOH (B-2-1-5) Rf C〇 〇CH=CH - COOH (B-2-1-6) RfOCOO CH= CH - COOH (B-2-1-7) Rf—^ COO —CH=CH-COOH (B-2-1-8) Rf - 0 —CH = CH - CO—COOH (B-2-1-9) Rf — COO —CH = CH - c0~^~~y~ C〇〇H (B-2-1-10) Rf—CH = CH - CO-COOH (B-2-1 -11 ) Rf - 0COOCH = CH - CO-COOH (B-2-1-12) -35- 201144361

R,-coo^O-coo-O- CH=CH-CO COOH r,~^)~c〇〇~G~ CH=CH-CO 分COOH r,~〇-co°-^)- CH=CH -CO O COOH CH=CH-COOH

•CH=CH-COOH CH=CH-COOH CH=CH — COOH

-CH=CH-COOH, <y)-〇·( Rf — OCO — CH = CH OCO -( CH 7 COOH -o- CO — CH = CH <y ( CO—CH=CH ( r,~0 ~ C〇-CH = CH COOH CO—CH=CH OC+7 COOH Rf —OCO — CH=CH —CH=CH-COOH

•CH-CH-COOH

-CH=CH-COOH

•COOH

►COOH

Rf — OCO — CH=CH

CH=CH-COOH (B-2-1 -13) (B-2-1 -14) (B-2-1 -15) (B-2-1 -16) (B-2-1 -17) (B-2-1 -18) (B-2-1 -19) (B - 2 1 · 20 ) (B-2-1 - 21 ) (B - 2 - 1 - 22 ) (B-2-2 -1 ) (B-2-2-2) (B-2-2-3) (B-2-2-4) (B-2-2-5) (B-2-3-1) (B -2-3-2) -36- 201144361 Ο

CH = CH a COOH

CH=CH-COOH (B-2-4-2)

O O o

CH = CH-COOH (B-2-4-3)

Rf-OCO

O

CH = CH-COOH

Rf-0C0

O O

CH = CH — COOH

O

Rf-0

CH = CH — COOH (B-2-6-2)

O O

HOOC 0^n_0" CH = CH-C00-Rf

O O

HOOC CH = CH-C00-Rf HOOC4CH2i- oco (B-2-8-2) CH = CH-C00 - Rf In the above formula (B-2-1-1)~(B-2-8-2) , is synonymous with the above formula (B-2-1). a is an integer of 1 to 6. In the case of the group containing the structure represented by the above formula (B-1), other preferred examples of the compound having a liquid crystal alignment ability include, for example, the following formula (B-2-1-1') to S. (B-2-8-l') The compound represented. -37- 201144361

Rf - 0CH=CH - CO0H (B-2-1 -l") Rf—coo—^^-ch=ch-co-^^-〇h (B - 2 -1 - 2) RfCH=CH - CO〇 H (B - 2 -1 - 3") Rf -0 COO —“--CH—CH~CO—^”—OH (B-2-1-/) Rf —COO—^~^~COO—^~ ~^-CH=CH-CO—(B-2-1-5") COOCH=CH-CO-^^-〇H (B-2-1-6') RfCOOCH=CH - CO〇H < B · 2 -1 · 7') Rf—OCO —CH=CH—^~^-〇H (B-2-2-1^) Rf-^^-CO-CH = CH -^^-〇H (Β -2-2·2'> Rfo—^^-co—ch=ch-^^-〇h (B-2-2-3) h〇XXJn^c—c〇-r, (B-2- 8-1') ο In the above formula, 1^ is synonymous with the above formula (Β-2-1). On the other hand, as RE of the above formula (Β-2), the number of carbon atoms having a steroid skeleton is An organic group of 17 to 51, an alkyl group having 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a cyclohexyl group, an alkoxyaryl group having an alkyl group having 2 to 20 carbon atoms, An alkylcyclohexyl group having an alkyl group having 1 to 20 carbon atoms, a fluoroalkylcyclohexyl group having a fluoroalkyl group having 1 to 20 carbon atoms, and a fluoroalkoxy group having a carbon number of 20 Selected from the group consisting of fluoroalkoxycyclohexyl groups The compound (B-2) which is less than one of the structures represented by the above formula (B-1), preferably has the following formula -38 - 201144361 (B-2-9) to (B-2- 11) A compound or the like represented.

Rf-T (B-2-9) κ, -χί-〇^τ (B-2-10) - micro(B-2-11 ) The above formula (B-2-9)~ formula (B-2- 11) is synonymous with T. Xk is a single bond, an oxygen atom, -COO- or -OCO - in the above formula (B-2-11), P is 1 or 2. As the compound of the above formula (B-2-9), wherein T is a carboxyl group, such as n-butyric acid, n-pentanoic acid, n-hexanoic acid, n-heptanoic acid, ortho-n-decanoic acid, n-lauric acid, n-dodecanoic acid, and n-tridecanoic acid Pentadecanoic acid, n-hexadecanoic acid, n-heptadecanoic acid, n-stearic acid eicosyl acid, tetrahydroabietic acid, monocholesteryl succinate glutarate, a compound represented by the following formula, and the like. ChF2h + 丨 d-COOH In the above formula, h is an integer of 卜3. i is a compound wherein T is a hydroxyl group in the above formula (B-2-9) such as 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octundecyl alcohol, 1-12 Alcohol, 1-tridecyl alcohol, 1-tetradecanol, octaol, 1.-heptadecanol, stearyl alcohol, 1-nonadecanol, 1- as the above formula (B-2-10) wherein τ is a carboxyl group Such as 4-methylbenzoic acid, 4-ethylbenzoic acid, 4-n-propylbenzoic acid, 4-n-pentylbenzoic acid, 4-n-hexylbenzene and the above formula (B-2-1) Examples of the substance include an integer of octanoic acid, n-decanoic acid, n-tetradecanoic acid, n-, n-nonanoic acid, ortho- vinegar, and monocholesteryl group 5. Examples of the alcohol include 1-alcohol, 1-non-pentadecanol, and 1-decaol. 'Materials, examples of benzoic acid, 4-n-butyric acid, 4-n-heptylbenzene-39- 201144361 formic acid, 4-n-octylbenzoic acid, 4·n-decylbenzoic acid, 4-n-decylbenzoic acid '4-n-dodecylbenzoic acid, 4-n-octadecylbenzoic acid, 4-n-methoxybenzoic acid, 4-n-ethoxybenzoic acid, 4-n-propoxybenzoic acid, 4- n-Butoxybenzoic acid, 4-n-pentyloxybenzoic acid, 4-n-hexyloxybenzoic acid, 4·n-heptyloxybenzoic acid, 4-n-octyloxybenzoic acid, 4-n-decyloxybenzoic acid 4-n-decyloxybenzoic acid, 4-n-dodecyloxybenzoic acid, 4-n-octadecyloxybenzoic acid, a compound represented by the following formula, and the like.

CjH2j+i — 0

Hey~

In the above formula, j is an integer of 5 to 20. k is an integer from 1 to 3. Ma is an integer from 0 to 18. η is an integer from 1 to 18. Examples of the compound having a carboxyl group in the above formula (Β-2-1 1) include 4-(n-butyl)cyclohexylcarboxylic acid, 4-(n-pentyl)cyclohexylcarboxylic acid, and 4-(n-butyl). Dicyclohexylcarboxylic acid, 4-(n-pentyl)dicyclohexylcarboxylic acid, and the like. <Synthesis method of compound having liquid crystal alignment ability> The compound represented by the above formula (Β-2-1) to formula (Β-2-11) can be obtained as a commercial product, or can be obtained by organic chemistry The conventional methods are combined in appropriate combination for synthesis. Hereinafter, a synthesis method will be described by taking a compound in which Rf is an alkyl group as an example, and a compound other than an alkyl group in which Rf is an alkyl group can also be synthesized by the same method as the synthesis method by referring to the method, which is It will be readily apparent to those skilled in the art. The compound represented by the above formula (B-2-1-1) can be heated, for example, by hydroxycinnamic acid and a halogenated alkyl group having an alkyl group corresponding to Rf in the presence of a suitable base such as potassium carbonate. The reaction is carried out, followed by hydrolysis in a suitable aqueous alkali solution such as sodium hydroxide. The compound represented by the above formula (B-2 - 2 - 2) can be, for example, a hydroxy cinnamic acid and an alkyl hydrazine chloride having an alkyl group corresponding to V in the presence of a suitable base such as potassium carbonate at 0. It is obtained by a reaction at a temperature of from ° C to room temperature. The compound represented by the above formula (B - 2 -1 - 4) can be, for example, potassium hydroxybenzoate and a halogenated alkyl or toluene-based acid vinegar having an alkyl group corresponding to Rf in potassium carbonate or the like. In the presence of a suitable base, at room temperature ~ 100. (After the reaction at a temperature of 3, it is hydrolyzed in a suitable aqueous alkali solution such as sodium hydroxide, and further formed into ruthenium chloride with sulfinium chloride, and then it is allowed to react with hydroxycinnamic acid in the presence of a suitable base such as potassium carbonate. It is obtained by reacting at a temperature of from 01 to room temperature. The compound represented by the above formula (B - 2 -1 · 5), for example, can be obtained by reacting hydroxybenzoic acid with an alkyl fluorene having an alkyl group equivalent to In the presence of a suitable base such as triethylamine, after reacting at a temperature of from 0 ° C to room temperature, hydrazine chloride is used to form hydrazine chloride, and it is allowed to react with cinnamic acid in the presence of a suitable base such as potassium carbonate. The compound represented by the above formula (B-2 -1 - 6), for example, can be formed into a ruthenium chloride by using a sulfinium chloride. And it is obtained by reacting with hydroxycinnamic acid at a temperature of 〇 ° c to room temperature in the presence of a base such as potassium carbonate. The compound represented by the above formula (B-2-1-7) , for example, by reacting methyl 4-hydroxycyclohexylcarboxylate with a halogenated alkyl group having an alkyl group corresponding to Rf in sodium hydride or After reacting to form an ether in the presence of a suitable base such as sodium metal, it is hydrolyzed in an aqueous alkali solution such as sodium hydroxide, and further formed with ruthenium chloride to form ruthenium chloride, and then in the presence of a suitable base such as potassium carbonate and hydroxycinnamic acid at 0. The compound represented by the above formula (B-2-1-8) can be, for example, a 4-alkane having an alkyl group equivalent thereto by using sulfinium chloride. The cyclyl carboxylic acid forms hydrazine chloride, and is obtained by reacting with hydroxycinnamic acid in the presence of a suitable base such as potassium carbonate at a temperature of TC to room temperature. The above formula (B-2-1-9) The compound represented by the reaction can be formed by reacting a halogenated alkyl group having a phase as the alkyl group with a hydroxybenzaldehyde in the presence of a base such as potassium carbonate to form an ether bond with 4-ethylidenebenzoic acid in sodium hydroxide The compound represented by the above formula (B-2-1-10) to the formula (B-2-1-15) can be obtained by referring to the method of the method. The above formula (B) can be obtained by performing aldol condensation. The compound represented by -2-2-1), for example, can be made to have 4-iodophenol equivalent to Rf by using palladium and an amine as a catalyst. After the alkyl acrylate reaction (Heck reaction), a desired cyclic acid anhydride such as succinic anhydride or glutaric anhydride and a reaction product are subjected to ring-opening addition. The above formula (B-2-2-2) The compound represented by the method can be obtained by aldol condensation of 4-alkylacetophenone having an alkyl group corresponding to V with 4-methylmercaptobenzoic acid in the presence of sodium hydroxide-42-201144361. The above compound can be subjected to aldol condensation in the presence of a 4-alkylacetophenone of an alkyl group of V and a 4-hydroxy group by the method of the method, and the compound represented by the above formula (B-2-2-4) The compound of the above formula (B-2-3-1) can be obtained by a method according to the method, and a method of obtaining a propylene having an alkyl group corresponding to Rf can be obtained. . By referring to the compound represented by the above formula (B-2-3-2). In the case of the compound represented by the above formula (B-2-4-1), it can be refluxed in toluene or xylene by refluxing the alkylamino cinnamic acid having a V equivalent to acetic acid in the presence of a catalyst or in the presence of a catalyst. Further, when Rf is a fluoroalkyl group, it can be protected by a suitable protecting group such as an amine, and then subjected to a Grignard reaction with a fluoroalkyl iodide such as a group to carry out dehydration ring closure, and 4- Amino Cassia® The compound represented by the above formula (B-2-4-2) is synthesized by any one of the methods. As a first method, maleic anhydride is added with a suitable base such as potassium carbonate such as p-toluidine to form a phase with Michael addition, and then by formula (B-2-2-3) The representation is obtained. ' can be represented by the presence of the phase benzaldehyde in sodium hydroxide (B-2-2-5). 'Can be obtained by using a palladium oxyacid ester and a 4-bromocinnamic acid counter-method, for example, when Rf is an alkyl group of an alkyl succinic anhydride and a 4-base is a suitable base such as triethylamine. The reaction method is obtained by a method in which maleic anhydride has a fluoroalkane equivalent to R1 in p-toluene and is subjected to a hydrolysis deprotection reaction. For example, the following method can be used to protect the group, and the alcohol in the alkyl group of V is deprotected by hydrolysis, and further -43-201144361 is subjected to dehydration ring closure and the above formula (8-2) -44) When the compound represented is synthesized, the product is reacted with 4-amino cinnamic acid in the same manner. As a second method, a method in which methyl malate is reacted with a halogenated alkyl group having an alkyl group corresponding to Rf to form an ether in the presence of, for example, silver oxide, followed by hydrolysis, further dehydration ring closure, and the above The synthesis of the compound represented by the formula (mi)* is carried out in the same manner, and the product is allowed to react with 4-amino cinnamic acid. The compound represented by the above formula (B-2-4-3), for example, may be the same as the above formula (B-2), except that a thiol having an alkyl group corresponding to the alkyl group is used instead of the alcohol having an alkyl group corresponding to V. -4-2) The first method in the synthesis of the compound represented is obtained in the same manner. The compound represented by the above formula (B-2 - 5 -1) can be, for example, formed by using 1,2,4-tricarboxycyclohexane anhydride to form ruthenium chloride with sulfoxide. The alcohol of the alkyl group is reacted and esterified in the presence of a suitable base such as triethylamine, and is subjected to the same operation as the method for synthesizing the compound represented by the above formula (B-2-4-1) to give the product with 4 - Amino cinnamic acid is obtained by reaction. The compound represented by the above formula (B-2-6-1) can be synthesized, for example, by reacting a compound Rf-OH corresponding to a desired compound with a trimellitic anhydride halide, and then synthesizing the ester as an intermediate. The compound is synthesized by reacting with 4-aminocinnamic acid. The synthesis of the intermediate ester compound is preferably carried out in the presence of a basic compound in a suitable solvent. Examples of the solvent which can be used include tetrahydrofuran and the like. Examples of the basic compound include triethylamine. The reaction of an ester compound with 4-aminocinnamic acid can be carried out, for example, by -44-201144361, for example, by refluxing both in acetic acid, in a suitable catalyst in xylene (for example, an acid catalyst such as sulfuric acid or the like A method of refluxing in the presence of a catalyst). The compound represented by the above formula (B-2-6-2) can be subjected to dehydration ring-closure by refluxing phthalic acid in, for example, diethylbenzene, by the same method as above and 4-amine. The cinnamic acid reacts as a quinone imine compound of the first intermediate, and then reverses the quinone imine with a compound Rf _ Η (Η is a halogen atom) corresponding to the desired compound. In this case, it is preferred to carry out the basic compound in a suitable solvent. Examples of the solvent which can be used include a guanamine compound such as hydrazine or hydrazine-dimethylamine. Examples of the basic compound include potassium. The compound represented by the above formula (Β - 2 - 7 -1), for example, can react with 4-nitrocinnamic acid in the presence of potassium carbonate with a halogenated alkyl group having the equivalent of ... to form an ester' and use, for example, tin chloride After the nitramine group was reduced, the product was obtained by using 1,2,4-tricarboxycyclohexylcyclohexane. The latter reaction can be carried out, for example, by refluxing the starting compound or by refluxing in the presence of a suitable base catalyst such as triethylamine or xylene. The compound represented by the above formula (?-2-8-1) can be synthesized by referring to the method. The compound represented by the above formula (Β-2-8-2) can be substituted with 1, 2, 4 - triterpene by using hydroxy phthalic acid in the synthesis of the compound represented by (Β-2-7-1). a cyclohexylcyclohexanol anhydride, synthesized with a xylene or triethylamine 5-hydroxyl anhydride as a compound, and a lower alkyl group such as carbonic acid by reacting an alkyl group to form an anhydride in acetic acid in toluene It can be obtained by reacting with succinic anhydride or glutaric anhydride after the -45-201144361 cinnamic acid derivative of the above-mentioned amine dicarboxylate ring. The compound represented by the above formula (B-2-1-1,) can be reacted by reacting a halogenated alkyl group having an alkyl group corresponding to Rf with a 4-hydroxybenzaldehyde in the presence of a base such as potassium carbonate to form an ether bond. Thereafter, it was obtained by aldol condensation with 4-hydroxyacetophenone in the presence of sodium hydroxide. The compound represented by the above formula (B-2-1-2')~(Β-2-1-7') can be obtained by referring to the method of the method. The compound represented by the above formula (B-2-2-1'), for example, can be reacted with an alkyl acrylate having an alkyl group equivalent to 1 oxime by using palladium and an amine as a catalyst. get. The compound represented by the above formula (B-2-2-2') can be produced by subjecting a 4-alkylacetophenone having an alkyl group corresponding to 1^ with 4-hydroxybenzaldehyde in the presence of sodium hydroxide Obtained by aldol condensation. The compound represented by the above formula (B-2-1-3') can be obtained by referring to the method of the method. The compound represented by the above formula (B - 2 - 8 -1 ') can be, for example, an alcohol having an alkyl group equivalent to R f by forming a ruthenium chloride with 4 - nitrocinnamic acid with sulfinium chloride. The reaction forms an ester, and is obtained by, for example, reducing the nitro group to form an amine group using tin chloride, and then reacting the product with hydroxyphthalic anhydride. The latter reaction 'e.g.' can be carried out by refluxing the starting compound in acetic acid or by refluxing in toluene or xylene in the presence of a suitable base catalyst such as triethylamine. Among these compounds (B-2), the above formula (B-2-1-1), formula (B-2-1-3), formula (B-2-1-4), and formula (B) are preferred. -2-l-6)~ Formula (B-2-1-8), Formula (B-2-1-16), Formula (B-2-1-19), Formula (B-2-1-21 ), formula (B-2-4-1), formula -46- 201144361 (B-2-4-2), formula (B-2-5-1), and formula (B-2-7-1) The compound represented. In addition, as a substance having a structure represented by the above formula (B-1), a structure having a liquid crystal alignment ability may be exemplified by n-butyric acid, n-hexanoic acid, n-octanoic acid, n-lauric acid, n-stearic acid, and 4-n-tenth. Eight hospitals basic formic acid, 4-n-dodecylbenzoic acid, 4-n-octylbenzoic acid, 4-n-hexylbenzoic acid, 4-n-octadecyloxybenzoic acid, 4-n-dodecyloxybenzene Formic acid, 4-n-octyloxybenzoic acid, 4-n-hexyloxybenzoic acid, 1-hexyl mercaptan, diheptyl mercaptan, 1-octyl mercaptan, 1-decyl mercaptan, hydrazine-hydrazine thiol, ι- ~ί—Alkyl mercaptan, 1-dodecanethiol, 1-fourteenth court thiol, 1-six-yard thiol, 1-eighteen-yard thiol, mono-cholesteryl succinate and lower The compound represented by the formula.

In the present specification, the compound having a structure having a liquid crystal alignment ability and not having the structure represented by the above formula (Β-1) is referred to as "another pretilt angle compound". The ratio of the structure having a liquid crystal alignment ability as such a polyorganosiloxane compound is preferably from 10 mol% to 90-47 to 201144361 mol%, more preferably 20 mol%, with respect to X a '. ~80% by mole, and especially good for 25% of Momo. In the [A] polyorganosiloxane compound of the present invention, it is preferred that a part of the Si-Xa bond in the polyorganosiloxane having an epoxy structure is reacted, and the compound (A-1) and the compound ( A-2), compounding, and total moles of compounds with liquid crystal alignment ability,®

The number of groups X of the polyorganosiloxane having an epoxy structure. In this case, when the ratio of the compound having the directional ability of the group represented by the above formula (B-1) is 50 mol% or more based on the total amount of the compound, the compound containing [A] polyorganosiloxane is contained. The alignment agent can be formed by a photo-alignment method to exhibit a good liquid crystal alignment film. <[A] Method for synthesizing polyorganosiloxane compound > [A] Polyorganosiloxane compound, which can have a cyclic organooxane, the above formula (A-1) The compound represented by the present invention is required to have a compound having a liquid crystal alignment ability, and is preferably synthesized by catalysis in an organic solvent. This method of production has a high introduction rate of various structures, and therefore it is suitable from these aspects (A- The compound represented by the formula (A-3) and the compound having a hydraulic force may be used singly or in combination of two or more. Further, when the compound represented by the formula (A-1) to the formula (A-3) is crystallized When the structure of the alignment ability has a carboxyl group, it can be reacted with a part of another carboxylate. In this case, as another carboxylic acid, the amount of the label is in the range of % to 7 5 . Therefore, the substance (A-3) is preferably A small amount of Moer liquid crystal is preferably provided with a liquid crystal susceptibility testicle! The crystal is combined with the acid group and the presence of the root, and the alignment can be used. The liquid replacement ratio is -48 - 201144361 'relative to the total of compounds and other carboxylic acids Preferably, the catalyst is, for example, an organic base or a so-called hardening accelerator which promotes the reaction of an epoxy compound with an acid anhydride. Examples of the organic base include ethylamine, diethylamine and a pipe trap. An organic primary or secondary amine such as piperidine, pyrrolidine or pyrrole; organic amine such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine or dinonicycloundecene a tertiary amine; an organic quaternary ammonium such as tetramethylammonium hydroxide; etc. Among them, an organic tertiary amine and an organic quaternary ammonium are preferred. Examples of the hardening accelerator include benzyldimethylamine and 2,4. a tertiary amine such as 6-tris(dimethylaminomethyl)phenol, cyclohexyldimethylamine or triethanolamine; 2-methylimidazole, 2-n-heptyl imidazole, 2-n-decane-alkylimidazole , 2-phenylimidazole, 2-phenyl-4-imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2 -ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-methylimidazole, iota-(2-cyanoethyl)-2-n-undecylimidazole, 1-(2 -cyanoethyl)-2- Imidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5 - bis(hydroxymethyl)imidazole, 1-(2-cyanoethyl)-2-phenyl-4,5-bis[(2'-cyanoethoxy)methyl]imidazole, 1-(2 • Cyanoethyl)-2-n-undecylimidazole key trimellitate, 1-(2-cyanoethyl)-2-phenylimidazolium trimellitate, 1-(2- -49- 201144361 cyanoethyl)-2·ethyl-4·methylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1') Ethyl-s-tripper, 2,4-diamino-6-(2'-n-decyl--alkylimidazolyl)ethyl-s-trisole, 2,4.diamino-6- [2'-Ethyl-4'-methylimidazolyl-(Γ)]ethyl-s-three-pill, isocyanuric acid addition of 2-methylimidazole, isocyanuric acid of 2-phenylimidazole Imidazole compound such as an acid adduct, an isocyanuric acid adduct of 2,4-diamino-6-[2'-methylimidazolyl-(indenyl)ethyl-S. Organic phosphorus compound such as phosphine, triphenylphosphine or triphenyl phosphite; benzyltriphenyl iron chloride, tetra-n-butyl bromide, methyltriphenyl sulphate Ethyltriphenyl sulphate, n-butyltriphenyl sulphate, tetraphenyl sulphate, ethyltriphenyl sulphate, ethyltriphenyl sulphate, tetra-n-butyl, 〇, 〇-diethyl dithiophosphate, tetra-n-butyl benzotriazole salt, tetra-n-butyl quaternary tetrafluoroborate, tetra-n-butyl quaternary tetraphenyl borate, tetraphenyl quaternary a quaternary phosphonium salt such as a phenylborate; a 1,8-dioxinbicyclo[5.4.0]undecene -7, a diterpene bicyclic olefin such as an organic acid salt thereof; a zinc octylate, a tin octylate, an aluminum acetonitrile Organometallic compound such as ester complex; tetra-ammonium salt such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride or tetra-n-butylammonium chloride; boron trifluoride, Boron compound such as triphenyl borate; metal halide such as zinc chloride 'tin chloride; amine addition molding of diamine diamine or amine and epoxy resin, etc. -50- 201144361 a 1st high melting point dispersion type latent hardening accelerator; a microcapsule latent hardening accelerator which coats a surface of a hardening accelerator such as an imidazole compound, an organic phosphorus compound or a tetra salt by a polymer; an amine salt type latent hardening accelerator A latent hardening accelerator such as a pyrolysis type thermosetting polymerization latent curing accelerator such as a Lewis acid salt or a Bronsted acid salt. Among them, a quaternary ammonium salt is preferred, and tetraethylammonium bromide n-butylammonium bromide, tetraethylammonium chloride or tetra-n-butylammonium chloride is more preferred. The amount of the catalyst used is preferably 100 parts by mass or less, more preferably 0 parts by mass to 100 parts by mass, and particularly preferably 5% by mass, based on 1 part by mass of the polyorganosiloxane having a ring. ～20 parts by mass ❶ The reaction temperature is preferably from 01 to 200. (:, and more preferably 50 ° C ° C. As the reaction time, preferably 〇. 1 hour ~ 50 hours, and more 0.5 hour ~ 20 hours. As in the synthesis of [A] polyorganooxane In the case of the compound, the organic solvent can be used, for example, a hydrocarbon compound, an ether compound, an ester ketone compound, a guanamine compound, an alcohol compound, etc. Among them, the solubility of the etherified vinegar compound and the ketone compound from the raw materials and products is as follows. The content of the solvent is preferably 〇 1% by mass or more, and more preferably the content of the solvent (the ratio of the total mass of the total mass of the components other than the solvent in the reaction solution). The amount of % to 50% by mass. As the [A] polyorganosiloxane compound, the scaly cation, the tetraoxy 01-150 is preferred, and the solid content is 5 mass M w , preferably -51· 201144361 1, 〇00~10,00〇, 〇〇〇, better 2, 〇〇〇~1〇〇, 〇〇〇, and especially good 3〇〇〇~5〇 , 〇〇〇. <Other polymers> Other polymers, which can be used to further improve the liquid crystal distribution The solution characteristics of the agent and the electrical properties of the obtained liquid crystal alignment film are appropriately contained in the liquid crystal alignment agent. Examples of the other polymer include [B] a group consisting of polyglycine and polyimine. At least one polymer selected from the group, [C] other polyorganosiloxane compounds, polyphthalates, polyesters, polyamines, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivative, poly(meth)acrylate, etc., wherein 'preferably [B] polymer, [C] other polyorganosiloxane compound. By using a liquid crystal alignment agent containing a liquid crystal alignment agent and further containing a [B] polymer, a liquid crystal alignment film can be obtained, and a liquid crystal display element having further improved electrical characteristics such as a voltage holding ratio can be obtained. Further, the liquid crystal alignment agent is further contained. [C] The other polyorganosiloxane compound can promote the crosslinking of the [A] polyorganosiloxane compound, thereby further increasing the voltage holding ratio of the obtained liquid crystal display device, etc. Hereinafter, the [B] polymer , [C] His polyorganosiloxane compound is described in detail. <[B]Polymer> [Polyproline] As the polyamine of [B] polymer, it can be made by using tetracarboxylic dianhydride and two The tetracarboxylic dianhydride is, for example, an aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride, etc. In addition, -52 - 201144361 The tetracarboxylic dianhydride described in the Japanese Patent Application No. 2009- 1 5 7.5 5 6 can be used. These tetracarboxylic dianhydrides may be used singly or in combination of two or more. Examples of the anhydride include, for example, Dingyuan tetracarboxylic dianhydride. Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, and 1,3,3a. ,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene[1,2-c]furan-1,3-dioxene, l,3 ,3a, 4,5,9b-hexachloro-8-methyl-5-(tetrazo-2,5-one-oxy-3-indolyl)-naphthalene[l,2-c]furan-1, 3-dione, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2, 5-tertiary oxytetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane - 2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, 4,9-dioxa Ring [5.3.1.02'6] undecane-3,5,8,10-tetraone and the like. Examples of the aromatic tetracarboxylic dianhydride include, for example, pyromellitic dianhydride, and the tetracarboxylic dianhydride described in Japanese Patent Application No. 2009-84462. Among these tetracarboxylic dianhydrides, preferred are alicyclic tetracarboxylic dianhydrides, more preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride or 1,2,3,4-cyclobutane IV. The carboxylic acid dianhydride is particularly preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. The amount of use of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride or 1,2,3,4·cyclobutane tetracarboxylic dianhydride is preferably 10% based on the total tetracarboxylic dianhydride. Mole% or more, more preferably 20 mol% or more, and particularly preferably only 2,3,5--53- 201144361 tricarboxycyclopentyl acetic acid dianhydride or 1,2,3,4-cyclobutane It is composed of tetracarboxylic dianhydride. The diamine compound may, for example, be an aliphatic diamine, an alicyclic diamine, a diamine organosiloxane or an aromatic diamine. These diamine compounds may be used singly or in combination of two or more. In addition, the diamine described in Japanese Patent Application No. 2009-15755-6 can also be used. Examples of the aliphatic diamine include m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine. Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), and i,3-bis(aminomethyl)cyclohexane. Wait. For example, 1,3-bis(3.aminopropyl)-tetramethyldicyclohexane may be mentioned as the diamine-based organooxane, and in addition, Japanese Patent Application 2009-844 62 The diamine described in the above. Examples of the aromatic diamine include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, and 1,5-diaminonaphthalene. 2,2'-Dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,7-diamine Base, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl) Bismuth, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(pair Phenyldiisopropylidene)bis(aniline), 4,4'-(m-phenylene diisopropylidene)bis(aniline), 1,4-bis(4-aminophenoxy)benzene , 4,4'-bis(4.aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6- Diamine acridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl -54- 201144361 -3,6-Diaminocarbazole, N,N'-bis(4-aminophenyl)benzidine, anthracene, Ν'-bis(4-aminophenyl)-anthracene, anthracene '-Dimethylbenzidine' 1,4-bis(4-aminopropyl) pipe trap, 3,5-diaminobenzoic acid, dodecyloxy-2,4-diaminobenzene, tetradecyloxy-2,4 -diaminobenzene, pentadecyloxy-2,4-diaminobenzene, cetyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene , dodecyloxy-2,5-diaminobenzene, tetradecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, palmadecyloxy Base-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholesteneoxy-3, 5-diaminobenzene, cholestyloxy-2,4-diaminobenzene, cholesteneoxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholesteryl Ester, cholesteryl 3,5-diaminobenzoic acid, lanosteryl 3,5-diaminobenzoic acid, 3,6-bis(4-aminobenzylideneoxy)cholesterol Alkane, 3,6-bis(4-aminophenoxy)cholestane, 4-(4'-trifluoromethoxybenzylideneoxy)cyclohexyl-3,5-diaminobenzoic acid vinegar, 4-(4-trifluoromethylbenzylideneoxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl) -4-丁环己院,Μ_bis(4·((aminophenyl)methyl)phenyl)-4·heptylcyclohexane, m(4((())phenoxy)methyl)phenyl)- 4-heptylcyclohexane, [,; [-bis(4.(.aminophenyl)methyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane, 2,4 - Diamino group hydrazine, hydrazine bis propyl aniline, 4-aminobenzylamine, 3-aminobenzylamine, and a diamine compound represented by the following formula (6).

In the above formula (6), 'Za' is a hospital base having 1 to 3 carbon atoms, _〇_, -c〇〇 or -OCO-. Pa is 〇 or 1. The integer is 丨 “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚 庚Methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl 'fluorenyl' dodecyl, tridecyl, tetradecanepentadecyl, hexadecyl, ten A pentaalkyl group, an octadecyl group, a nonadecyldecylene group, etc. ' As the diamine compound represented by the above formula (6), a compound represented by the formula (6-1) to (6-5) can be mentioned. Wait.

Nh2 h2n ^^~ch2 (6·5) h2n compound group, IV 0.3 when the ratio of tetracarboxylic dianhydride and diamine provided in the polyamine synthesis reaction is relative to that contained in 1 equivalent of the diamine compound The acid anhydride group of the amine carboxylic acid dianhydride is preferably from 2 to 2 equivalents, more preferably from about 1.2 equivalents. -56- 201144361 It is preferred to carry out the synthesis reaction in an organic solvent. The reaction temperature ' is preferably -2 CTC to 150 t, more preferably 〇 ° c to l 〇〇 ° C. The reaction time is preferably from 0.1 hour to 24 hours, more preferably from 5 hours to 12 hours. 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 (Indole P), hydrazine, hydrazine-dimethylacetamide, Ν, Ν - dimethylformamide, hydrazine, hydrazine dimethyl imidazolidinone, dimethyl hydrazine, · - - butylide, tetramethyl urea, hexamethylphosphonium triamine, etc. Proton-based polar solvent; anthraquinone solvent such as m-cresol, xylenol, phenol or halogenated phenol. The amount of use of the organic solvent U) 'relative to the total amount (b) of the tetracarboxylic dianhydride and the diamine and the total amount (a + b) of the organic solvent used amount (a) is preferably 0.1% by mass to 50%. The mass% is more preferably 5% by mass to 30% by mass. The polyaminic acid solution obtained after the reaction may be directly supplied to the liquid crystal alignment agent, or may be prepared by separating the polyamic acid contained in the reaction solution, and then supplying the liquid crystal alignment agent, or may also separate the separated polymer. After the purification of proline, the preparation of the liquid crystal alignment agent is supplied. Examples of the method for separating the polyamic acid include a method in which a reaction solution is injected into a large amount of a poor solvent, and the obtained precipitate is dried under reduced pressure, and a method of distilling off the reaction solution using an evaporator under reduced pressure. Wait. The method for purifying poly-proline is exemplified by a method of dissolving the separated polylysine in an organic solvent, and precipitating it with a poor solvent, and discharging the organic solvent one or more times using an evaporator under reduced pressure. The method of the step. [Polyimide] -57- 201144361 The polyimine which is a [B] polymer can be produced by dehydrating and ring-closing a proline structure of the polyamic acid. Polyimine, which may be a complete yttrium imide of a lysine structure having a polyamine acid as a precursor of its pro-steroid, or a partial guanine structure dehydration ring closure to form a proline structure Part of the quinone imide that coexists with the quinone imine structure. The ruthenium imidization ratio of the polyimine is preferably 30% or more and more preferably 40% to 80%. Further, the ruthenium iodide ratio in the polyimine is a solution in which a solution of polyimine is put into pure water, and the resulting precipitate is dried under reduced pressure at room temperature, and then dissolved in deuterated dimethyl group. In the anthraquinone, z-NMR was measured at room temperature using tetramethylnonane as a reference, and the obtained j-NMR spectrum was obtained from the formula represented by the following formula (7). Ruthenium amination rate (%) = {1-(A'/A2)x α } X 1 00 (7) In the above formula (7), Α1 is a peak area (10 ppm) derived from the NH matrix 〇A2 The peak area from other protons is the ratio of the number of other protons to the one proton of the NH group in the polyamic acid. Examples of the method for synthesizing the polyimine include (i) a method of heating poly-proline (hereinafter sometimes referred to as "method (i)"), and (U) dissolving poly-proline in an organic solvent. In addition, a dehydrating agent and a dehydration ring-closure catalyst are added to the solution, and a method of heating (as may be referred to as "method (ii)"), which is required to be heated, is carried out by a dehydration ring-closure reaction of polyglycine. The reaction temperature in the method (1) is preferably from 50 t to 200 ° C, and more preferably from 60 ° C to 170 ° C. When the reaction temperature is less than 5 (TC, the dehydration ring-closure reaction cannot be sufficiently carried out, and when the reaction temperature exceeds 200. (:, the molecular weight of the obtained poly-p-58-201144361 amine will decrease. As the reaction time, Preferably, it is from 0.5 hours to 48 hours, more preferably from 2 hours to 20 hours. The polyimine obtained in the method (i) can be directly supplied to the preparation of the liquid crystal alignment agent, and the polyimine can be separated and supplied. The preparation of the liquid crystal alignment agent may be carried out by purifying the separated polyimine or after purifying the obtained polyimine and supplying the liquid crystal alignment agent. The dehydrating agent in the method (ii) may, for example, be mentioned. An acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride. The content of the dehydrating agent can be appropriately selected depending on the desired ruthenium imidation ratio, but it is relative to the proline structure of 1 mol of polylysine. Preferably, it is 0.01 mol to 20 mol. As the dehydration ring-closing catalyst in the method (ii), for example, pyridine, collidine, lutidine, triethylamine, etc. can be cited as the content of the dehydration ring-closing catalyst, relative to 1 Moer The dehydrating agent 'is preferably 〇· 〇1 mol to 10 mol. In addition, the more the content of the above dehydrating agent and the dehydration ring-closing catalyst, the more the sulfiliation rate can be increased. As used in the method (ii) The organic solvent is, for example, the same as the organic solvent exemplified as the solvent used in the synthesis of polyamic acid. The reaction temperature in the method (ii) is preferably from 0 C to 180 ° C, more preferably. The reaction time is preferably from 0. 5 hours to 20 hours, more preferably from 1 hour to 8 hours. By allowing the reaction conditions to be in the above range, the dehydration ring closure reaction can be sufficiently Carrying out, and obtaining the obtained polyimine from -59- 201144361 when molecular weight. In the method (ii), a reaction solution containing polyimine can be obtained. The reaction solution can be directly supplied to the liquid crystal alignment agent. The preparation of the liquid crystal alignment agent may be carried out after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, and the polyimine may be separated and then supplied to the liquid crystal alignment agent to prepare or separate the separated polymer. The preparation of the liquid crystal alignment agent is carried out after the purification of the ruthenium imine. The method of removing the dehydrating agent and the dehydration ring-closure catalyst from the reaction solution may, for example, be a solvent replacement method, etc. As a separation method and a purification method of the polyimine. For example, the same method as the method exemplified as the separation method and the purification method of polyproline is listed. &lt;[C] Other polyorganosiloxane compound] It is preferable that the liquid crystal alignment agent further contains [C] other polyorganosiloxane compound in addition to the [A] polyorganosiloxane compound Further, as the other polyorganosiloxane compound of [C], a polyorganosiloxane having a structural unit represented by the above formula (2) is more preferable. Further, when the liquid crystal alignment agent contains [C] other polyorganosiloxane compound, as long as [C] most of the polyorganosiloxane compound is present independently of the [A] polyorganosiloxane compound, A part thereof may also exist as a condensate with a specific polyorganosiloxane compound. In the above formula (2), Xb is a hydroxyl group, a halogen atom, a group having a carbon number of 2 Å, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms. Y2 is a hydroxyl group or an alkoxy group having 1 to 1 ring of carbon atoms. Examples of the alkyl group having 1 to 20 carbon atoms include a linear, or -60-201144361 branched methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl group. , mercapto, fluorenyl, urethyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl , eicosyl and the like. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, and an isobutoxy group. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group. As the [C] other polyorganic oxide compound compound, yiw is preferably 500 to 100,000 - more preferably 500 to 10,000. [C] Other polyorganosiloxane compounds, for example, may be grouped from alkoxydecane and a halogenated decane compound by preferably in a suitable organic solvent in the presence of water and a catalyst. At least one selected decane compound (hereinafter sometimes referred to as "raw material decane compound") is synthesized by hydrolysis, hydrolysis, and condensation. The raw material decane compound 'is, for example, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, tetra-n-butoxy sulane, tetra- or 2-butoxy decane, Four or three grades of butoxy decane, chlorinated ruthenium, etc.; methyltrimethoxy decane 'methyl triethoxy decane, methyl tri-n-propoxy sulfoxide, methyl triisopropoxy decane, methyl Tri-n-butoxy decane, methyl tri- or 2-butoxy decane, methyl tri-tert-butoxy decane, methyl tri-61 - 201144361 phenoxy decane, methyl trichloro decane, ethyl trimethoxy Decane, ethyltriethoxydecane, ethyltri-n-propoxydecane, ethyltriisopropoxydecane, ethyltri-n-butoxydecane, ethyltri-n-butoxydecane, ethyltri Tertiary butoxy decane, ethyl trichloro decane, phenyl trimethoxy decane, phenyl triethoxy decane, phenyl trichloro decane, etc.; dimethyl dimethoxy decane, dimethyl diethoxy Base decane, dimethyldichlorodecane, etc.; trimethyl methoxy decane, trimethyl ethoxy decane, trimethyl chloro decane, and the like. Among them, preferred are tetramethoxydecane, tetraethoxydecane, methyltrimethoxydecane, methyltriethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, dimethyl. Dimethoxydecane, dimethyldiethoxydecane, trimethylmethoxydecane or trimethylethoxydecane. The organic solvent which can be optionally used in the synthesis of the other polyorganosiloxane compound of [c] may, for example, be an alcohol compound, a ketone compound, a guanamine compound, an ester compound or other aprotic compound. They may be used singly or in combination of two or more. Examples of the alcohol compound include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, n-pentanol, isoamyl alcohol, and 2-methylbutyl. Alcohol, secondary pentanol, tertiary pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, secondary hexanol, 2-ethylbutanol, second-grade heptanol, 3-glycol Alcohol, n-octanol, 2-ethylhexanol, secondary octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-nonanol, secondary-alcohol, trimethylnonanol -62- 201144361 Secondary alcohols such as secondary tetradecyl alcohol, secondary heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexane 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol ; ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,4-pentanediol, yl-2,4-pentanediol, 2,5-hexanediol, 2,4-g Polyamide, 2-ethyl-1,3-alcohol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and other compounds; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol single Propyl ether, alcohol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, glycol monomethyl ether, dipropylene glycol A partial ether of a plurality of compounds such as monoethyl ether or dipropylene glycol monopropyl ether. Examples of the ketone compound include acetone, methyl ethyl ketone, methyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, ethyl n-butyl ketone, and methyl n-hexyl group. Monoketone compounds such as ketone, diisobutyl ketone methyl fluorenone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedone acetone, acetophenone, anthrone; Mercaptoacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-hepta-2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5--2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5 - yS-diketone compound such as 2,4-heptanedione. As the guanamine compound, for example, formamidine, N-methyl alcohol, 2-methylhexyl glycol ethylene di-2-ethaneglycol monomethyldipropanol-based n-propyl, tri-, acetone, methyl hexafluoride may be mentioned. Hyperthyroidism-63- 201144361 Amine, N,N-dimethylformamide, N-ethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formamidine Pyromomorpholine, N-methylmercaptopiperidine, N-methylpyridylpyrrolidinium, N-ethylmercaptomorpholine, n-ethinylpiperidine 'N-ethinylpyrrolidine, and the like. The ester compound may, for example, be diethyl carbonate, ethylene carbonate, propylene carbonate, methyl acetate, ethyl acetate, γ-butyrolactam, 7-valerolactone, n-propyl acetate or isopropyl acetate. Ester, n-butyl acetate, isobutyl acetate, n-butyl acetate, n-amyl acetate, diethyl amyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethylbutyl acetate Ester, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexylacetate, n-decyl acetate, methyl ethyl acetate, ethyl acetate, ethylene glycol monomethyl ether , ethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether propylene glycol monoethyl ether, propylene glycol monopropylene Ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoacetic acid, glycol diacetate, methoxy triethylene glycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate , diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, lactic acid Butyl, n-amyl lactate, diethyl malonate, phthalic acid dimethyl ester, diethyl phthalate and the like. Examples of the other aprotic compound include acetonitrile, dimethyl hydrazine, hydrazine, hydrazine, hydrazine, Ν'-tetraethyl sulfonamide, trimethylamine hexamethylphosphate, and hydrazine-methylmorpholine. Ketone ' Ν -methylpyrrole, Ν-ethylpyrrole, Ν-methyl-△ 3- -64 - 201144361 Pyrrolidine, N-methylpiperidine, N-ethylpiperidine, N,N-dimethyl Pipe trap, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, hydrazine, hydrazine, 3·dimethyl-2·imidazolidinone, 1,3 - dimethyltetrahydro-2(1?)-pyrimidinone or the like. Among these solvents, preferred are polyol compounds, partial ethers of polyol compounds, and ester compounds. The amount of water used in synthesizing the other polyorganosiloxane compound of [C] is preferably 1 mol, preferably 0.5 mol to 100 mol, based on 1 mol of the alkoxy group and the halogen atom which the raw material decane compound has. More preferably 1 mole to 30 moles, especially good for 1 mole to 1.5 moles. The catalyst which can be used in the synthesis of the other polyorganosiloxane compound of [C] may, for example, be a metal chelate compound, an organic acid, an inorganic acid, an organic base, an alkali metal compound, an alkaline earth metal compound or ammonia. They may be used singly or in combination of two or more. Examples of the metal chelate compound include triethoxy mono(acetonitrile) titanium, tri-n-propoxy-mono(acetonitrile) titanium, and triisopropoxy mono(acetonitrile) titanium. Tri-n-butoxy. Single (acetylacetone) titanium, tri- or two-butoxy-single (acetylacetone) titanium, tris-butoxy-single (acetylacetone) titanium, diethoxy double (acetonitrile) titanium, di-n-propoxy-bis(acetonitrile) titanium, diisopropoxy-bis(acetonitrile) titanium, di-n-butoxy. bis(acetonitrile) titanium, two Second-order butoxy-bis(acetamidineacetone) titanium, di-tertiary butoxy-bis(acetoxime) titanium, monoethoxy. tris(acetonitrile) titanium, mono-n-propoxy-three ( Acetylacetone) titanium, monoisopropoxy-tris(acetonitrile) titanium, mono-n-butoxy-tris(acetonitrile) titanium, single-stage butoxy. tris(acetonitrile) titanium, single Tertiary butoxy. Tris(acetonitrile) -65- 201144361 Titanium, tetrakis(acetonitrile) titanium, triethoxy mono(ethylacetamidine acetate) titanium tri-n-propoxy-single (ethyl acetoacetate) titanium, three different Oxy. mono(ethylacetamidine acetate) titanium, tri-n-butoxy-mono(ethylacetamidine acetate) titanium, tri- or di-butoxy-mono(ethylacetamidine acetate) Titanium, tri-tertiary butoxy-mono(ethylacetamidine acetate) titanium, diethoxy bis(ethylacetamidine acetate) titanium, di-n-propoxy-bis(ethyl acetamidine) Acetate) titanium, diisopropoxy. bis(ethylacetamidine acetate) titanium, di-n-butoxy bis(ethylacetamidine acetate) titanium, di- or two-butoxy (ethyl acetamidine acetate) titanium, di-tertiary butoxy bis(ethyl acetamidine acetate) titanium, monoethoxy tris(ethyl acetamidine acetate) titanium, single positive C Oxygen·Tris(ethylacetamidine acetate) Titanium, monoisopropoxy-tris(ethylacetamidine acetate) Titanium, mono-n-butoxy-tris(ethylacetamidine acetate) Titanium , single-stage butoxy-tris(ethylacetamidine acetate) titanium, mono-tertiary butoxy-tris(ethylacetamidine acetate) titanium, tetrakis(ethylacetamidine acetate) titanium , single (acetonitrile) tris(ethylacetamidine acetate) titanium, bis(acetamidineacetone) bis(ethylacetamidineacetic acid) Ester) Titanium chelate compound such as titanium, tris(acetonitrile) mono(ethylacetamidine acetate) titanium; triethoxy mono(acetonitrile) pin, tri-n-propoxy-mono(acetonitrile) Acetone) Chromium, triisopropoxy-mono(acetonitrile) pin, tri-n-butoxy. Mono (acetamidine) zirconium, tri- or 2-butoxy-single (acetamidine), three or three Butoxy.mono(acetonitrile)chromium, diethoxybis(acetonitrile) cone, di-n-propoxy.bis(acetamidine) cone, diisopropoxy-bis(acetonitrile) ) 't-n-butoxy-bis(acetamidineacetone) zirconium, di- or 2-butoxy-bis(acetamidineacetone) chromium, di- or tertiary-butoxy. bis(acetonitrile) chromium, monoethoxy C. Tris(acetonitrile) chromium, mono-n-propoxy-tris(acetonitrile) zirconium, monoisopropoxy-tris(acetonitrile)zirconium, mono-n-butoxy-66 - 201144361 base·three ( Ethylene acetonide) zirconium, single-stage butoxy-tris(acetonitrile) zirconium, mono-tertiary butoxy-tris(acetonitrile) chromium, tetrakis(acetonitrile)zirconium, triethoxy-single (ethyl acetoacetate) zirconium, tri-n-propoxy Mono-(ethylacetamidine acetate) zirconium, triisopropoxy-mono(ethylacetamidine acetate) zirconium, tri-n-butoxy-mono(ethylacetamidine acetate) pin, Tri- or two-butoxy. Mono (ethyl acetamidine acetate) chromium, tri-tertiary butoxy mono(ethylacetamidine acetate) zirconium, diethoxy bis (ethyl acetonitrile) Acid ester) chromium, di-n-propoxy-bis(ethylacetamidine acetate) chromium, diisopropoxy-bis(ethylacetamidine acetate) zirconium, di-n-butoxy-bis (B) Ethyl acetonitrile acetate) zirconium, di-2-butoxy. bis(ethylacetamidine acetate) pin, di-tertiary butoxy-bis(ethylacetamidine acetate) zirconium, monoethoxy Base, tris(ethylacetamidine acetate) ruthenium, mono-n-propoxy-tris(ethylacetate acetate) zirconium, monoisopropoxy-tris(ethylacetate acetate) zirconium, Mono-n-butoxy tris(ethylacetamidine acetate) chromium, mono-s-butoxy-tris(ethylacetamidine acetate) chromium, mono-tertiary butoxy-tris(ethyl acetonitrile Acid esters, cerium, tetrakis(ethylacetamidine acetate) zirconium, mono(ethyl acetonide) tris(ethylacetamidine acetate) zirconium Double (acetonitrile) bis(ethylacetamidine acetate) chromium, tris(acetonitrile) mono(ethylacetamidine acetate) chromium and other chromium chelate compounds; tris(acetonitrile)aluminum, three (Ethylacetamidine acetate) an aluminum chelate compound such as aluminum. 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, and the like. Azelaic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid 'shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleum-67- 201144361 acid, linolenic acid, bayberry Acid 'benzoic acid' p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, Fumaric acid, citric acid, tartaric acid, and the like. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid. The organic base may, for example, be pyridine, pyrrole, pipe trap, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine or the like. Ethanolamine, dioxodicyclooctane, dioxodicyclodecane, dioxodicycloundecene, tetramethylammonium hydroxide, and the like. The alkali metal compound may, for example, be sodium hydroxide or potassium hydroxide. The alkaline earth metal compound may, for example, be barium hydroxide 'calcium hydroxide or the like. Among them, preferred are metal chelate compounds, organic acids and inorganic acids, more preferably titanium chelate compounds and organic acids. The amount of the catalyst to be used is preferably 0.001 part by mass to 1 part by mass, more preferably 0. 001 part by mass to 1 part by mass, per 100 parts by mass of the raw material decane compound. The water added in the synthesis of the [C] other polyorganosiloxane compound may be added intermittently or continuously to the decane compound as a raw material or to a solution in which the decane compound is dissolved in an organic solvent. The catalyst -68- 201144361 may be previously added to the decane compound as a raw material or added to a solution in which the decane compound is dissolved in an organic solvent, or may be dissolved or dispersed in the added water. The reaction temperature in the case of synthesizing [c] other polyorganosiloxane compound is preferably from 0 ° C to 100 ° C, and more preferably from 1 5 ° C to 80 ° C. The reaction time is preferably from 0.5 to 24 hours, more preferably from 1 to 8 hours. [Content ratio of other polymer] When the liquid crystal alignment agent contains another polymer, the content ratio of the other polymer varies depending on the type of the other polymer, but is relative to 1 part by mass of the [A] polyorganoindene. The oxyalkyl compound is preferably 10 parts by mass or less. When the liquid crystal alignment agent contains the [B] polymer, the total content of the polyamic acid and the polyamidimide is preferably 1 part by mass based on 1 part by mass of the [A] polyorganosiloxane compound. 200 parts by mass to 5,000 parts by mass. When the liquid crystal alignment agent contains [C] other polyorganosiloxane, the content of the other polyorganosiloxane compound as [C] is preferably 1 part by mass based on the polyorganosiloxane. 100 parts by mass to 2,000 parts by mass. When the liquid crystal alignment agent contains another polymer, the type 'as another polymer' is preferably [B] polymer or [C] other polyorganosiloxane, more preferably [B] polymer. &lt;Optional component&gt;. Examples of the optional component include a curing agent, a curing catalyst, a curing accelerator, and a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy compound") , functional decane compound, interface -69- 201144361 active agent, and the like. Hereinafter, these optional components will be described in detail. [Curing Agent, Curing Catalyst, and Curing Accelerator] In order to make the crosslinking reaction of the [A] polyorganosiloxane compound more robust, a curing agent and a curing catalyst may be contained in the liquid crystal alignment agent. Further, in order to promote the curing reaction controlled by the curing agent, the above-mentioned curing accelerator may be contained in the liquid crystal alignment agent. As the curing agent, a curing agent which is usually used for curing a curable compound having an epoxy group or a curable composition containing a compound having an epoxy group can be used, and examples thereof include a polyamine, a polycarboxylic acid anhydride, and a polycarboxylic acid. Acid, etc. The polycarboxylic acid anhydride may, for example, be an anhydride of cyclohexanetricarboxylic acid or another polyvalent carboxylic acid anhydride. Examples of the cyclohexane tricarboxylic anhydride include cyclohexane-1,2,4-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, and cyclohexane-1,2,3·3. Carboxylic acid, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, cyclohexane-1,2 , 3-tricarboxylic acid-2,3-anhydride, and the like. Examples of the other polycarboxylic acid anhydride include 4-methyltetrahydrophthalic anhydride and methyl nadic anhydride; dodecenyl succinic anhydride, succinic anhydride, maleic anhydride, and phthalic acid. An acid anhydride, trimellitic anhydride, and a tetracarboxylic dianhydride which is generally used for the synthesis of poly-proline, and examples thereof include an alicyclic compound having a conjugated double bond such as α-terpinene or allo-ocimene. Diels Alder reaction products of maleic anhydride, their hydrides, and the like. The use ratio of the curing agent is preferably 100 parts by mass or less based on 100 parts by mass of the [A] polyorgan-70-201144361 oxalate compound. The curing catalyst may, for example, be a ruthenium hexafluoride compound, a phosphorus hexafluoride compound or aluminum triacetin acetate. The ratio of use as the curing catalyst is 'with respect to 100 parts by mass [AJ polyorganosiloxane compound, preferably 2 parts by mass or less. As the hardening accelerator, for example, an imidazole compound; a quaternary phosphorus compound; a quaternary amine compound; a 1,2 - diindole bicyclo [5.4.0] undecene-7 or an organic acid salt thereof An organic metal compound such as zinc octoate, tin octylate or aluminum acetonitrile acetate complex; boron compound such as boron trifluoride or triphenyl borate; metal halide such as zinc chloride or tin chloride a high-melting-point-dispersion latent hardening accelerator such as an amine addition-forming accelerator such as an amine diamine, an amine-epoxy resin addition agent; a microcapsule coated with a surface of a fourth-order iron salt or the like by a polymer Type of latent hardening accelerator; amine salt type latent hardening accelerator; pyrolysis type thermal cation polymerization latent hardening accelerator such as Lewis acid salt or Bronsted acid salt. The use ratio of the curing accelerator is preferably 1 part by mass or less based on 100 parts by mass of the [A] poly-71 - 201144361 organic siloxane. [Epoxy compound] In order to further improve the adhesion of the formed liquid crystal alignment film to the surface of the substrate, an epoxy compound may be contained in the liquid crystal alignment agent. Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl glycol. Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl Base-2,4-hexanediol, hydrazine, hydrazine, hydrazine, Ν' tetraglycidyl-m-xylylenediamine, 1,3-bis(indole, hydrazine-diglycidylaminomethyl) ring Hexane, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl-4,4'-diaminodiphenylmethane, hydrazine, hydrazine-diglycidyl-benzylamine, hydrazine, hydrazine - condensed water Glyceryl-aminomethylcyclohexane or the like. The content ratio of the epoxy compound is preferably 40 parts by mass or less, more preferably 0.1 parts by mass to 30 parts by mass based on 1 part by mass of the total of the [poly]organosiloxane compound and any other polymer contained therein. Parts by mass. Further, when the liquid crystal alignment agent contains an epoxy compound, a base catalyst such as 1-benzyl-2-methylimidazole may be used in combination in order to effectively cause a crosslinking reaction. [Functional Sandane Compound] The above-mentioned functional decane compound can be used in order to improve the adhesion of the formed liquid crystal alignment film to the surface of the substrate. The functional decane compound may, for example, be 3-aminopropyltris-72- 201144361 methoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2- Aminopropyltriethoxydecane, Ν-(2.Aminoethyl)-3.Aminopropyltrimethoxydecane, Ν-(2-aminoethyl)-3-aminopropyl Dimethoxy decane, 3-decyl propyl trimethoxy decane, 3- ureido propyl triethoxy decane, hydrazine-ethoxycarbonyl-3-aminopropyl trimethoxy decane, Ν-ethoxycarbonyl-3-aminopropyltriethoxydecane, Ν-triethoxycarbenylpropyltriethylenetriamine, Ν_trimethoxyformamidopropyltriethylenetriene Amine, 10-trimethoxycarbamimidyl-1,4,7-triazadecane, 10-triethoxycarbamido-1,4,7-triazadecane, 9-trimethoxy Methanealkyl-3,6-diazaindolyl acetate, 9-triethoxycarbamido-3,6-diazadecyl acetate, Ν-benzyl-3-aminopropyl Trimethoxy decane, Ν-benzyl-3-aminopropyltriethoxy decane, fluorenyl-phenyl-3-aminopropyltrimethoxy decane, hydrazine- Phenyl-3-aminopropyltriethoxydecane, anthracene-bis(oxyethylidene)-3-aminopropyltrimethoxydecane, anthracene-bis(oxyethylene)-3- Aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, tetracarboxylic dianhydride and In addition to the reactants of the amino group-containing decane compound, the reaction product of the tetracarboxylic dianhydride and the decane compound having an amine group described in JP-A-63-29 1 922 can be mentioned. The content ratio of the functional decane compound is preferably 1 part by mass or less, more preferably 50 parts by mass or less, more preferably 20 parts by mass, based on the total mass of the [A] polyorganosiloxane compound and any other polymer contained therein. the following. [Surfactant] -73- 201144361 As the surfactant, for example, a nonionic interface active anionic surfactant, a cationic surfactant, an amphoteric interfacial polyoxyalkylene surfactant, a polyoxyalkylene surfactant, or the like Fluorine agent, etc. The use ratio of the surfactant is preferably ίο parts by mass or less, more preferably 1 or less, based on 1 part by mass of the total of the liquid crystal. &lt;Preparation method of liquid crystal alignment agent&gt; As described above, the liquid crystal alignment agent contains [A] polyorganosiloxane as an essential component, and if necessary, other components, and a solution in which each component is dissolved in an organic solvent The composition is carried out as an organic solvent, preferably dissolved in [A] polyorganooxime and any other component used arbitrarily, and does not react with them to be preferably organic for the liquid crystal alignment agent. The solvent varies depending on the type of other polymers present. As the liquid crystal alignment agent, it contains [A] polyorganooxane compound! A preferred organic solvent for the polymer is an organic solvent exemplified as the solvent used in the polyamine. These organic solvents may be used or used in combination of two or more. On the other hand, as the liquid crystal alignment agent, only the [A] polyorganic compound is contained as a polymer or a preferred organic solvent containing [A] polyorganosiloxane compound: other polyorganosiloxane compound, for example, The mass fraction of 1-ethoxy-2-propanol, propylene glycol monoethyl ether, propylene glycol monomer, agent, and interfacial agent is preferably used as a compound. Any content (3⁄4 and [B] acid synthesis with a single oxime kiss and [C] can be listed. Dipropyl ether, -74- 201144361 propylene glycol monobutyl ether, propylene glycol monoacetate 'dipropylene glycol methyl ether, dipropylene glycol ether 'Dipropylene glycol propyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether' ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl sulphide), ethylene glycol single Pentyl Ether, Ethylene Glycol Monohexyl Ether, Diethylene Glycol, Methyl Ceracetate, Ethyl Ceracetate, Propyl Sebacin, Butyl Cyanoacetate , methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, secondary butyl acetate , n-amyl acetate, diethyl amyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate , cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate, etc. Among them, preferred is n-propyl acetate, isopropyl acetate, n-butyl acetate 'isobutyl acetate, Secondary butyl acetate, n-amyl acetate, pentyl acetate, etc. A solvent which can be used for preparing the liquid crystal alignment agent can be used according to the presence or absence of other polymers and the type of the polymer. It is obtained by using one or a combination of two or more kinds of such a solvent. In the preferred solid concentration of the following, the components contained in the liquid crystal alignment agent are not precipitated, and the surface tension of the liquid crystal alignment agent is 25 mN/m. The range of ~40 mN/m. The solid content concentration of the liquid crystal alignment agent of the present invention, that is, the ratio of the mass of all components other than the solvent in the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent, considering viscosity, volatility, etc. It is preferable that it is 1% by mass to 10% by mass. When the solid content concentration is less than 1% by mass, the amount of the liquid crystal alignment film formed by the liquid crystal alignment agent is too small to be obtained. In the case of the liquid crystal alignment film, when the solid content concentration exceeds 10% by mass, the coating film thickness is too large to obtain a good liquid crystal alignment film. Further, the viscosity of the liquid crystal alignment agent is increased to cause insufficient coating properties. The preferred range of solid content concentration differs depending on the method used to apply the liquid crystal alignment agent to the substrate. For example, when a spin coating method is used The solid content concentration range is preferably 1.5% by mass to 4.5% by mass. When the printing method is employed, the solid content concentration is preferably in the range of 3% by mass to 9% by mass, and thus the solution viscosity is in the range of 12 mPa_s to 50 mPa_s. When the ink jet method is employed, the solid content concentration is preferably in the range of 1% by mass to 5% by mass, and thus the solution viscosity is in the range of 3 mPa·s to 15 mPa·s. The temperature at which the liquid crystal alignment agent is prepared is It is preferably 〇 ° C to 200 ° C, and more preferably 10 ° C to 60 ° C. &lt;Liquid crystal alignment film and method of forming the same&gt; A liquid crystal alignment film formed of the liquid crystal alignment agent is also suitably included in the present invention. As a method of forming a liquid crystal alignment film using the liquid crystal alignment agent, the structure having the liquid crystal alignment ability of [B] in the [A] polyorganosiloxane compound does not contain the above-mentioned formula (the structural unit represented by Β-υ) (Hereinafter, the formation method in this case is referred to as "formation method (i)"), and the structure having the liquid crystal alignment capability includes the structural unit represented by the above formula (B_丨) (hereinafter, in the case of The formation method is differently referred to as "formation method (11)). The following describes the formation methods (i) and (ii) in detail. [Formation method (i)] -76- 201144361 First, two sheets are patterned. The base of the transparent conductive film is a pair, and the alignment agent is applied to the surface of each of the transparent conductive films by, for example, a roll coating method, a spin coating method, a printing method, or an appropriate inkjet coating method. The surface is pre-heated (pre-baked), followed by firing (post-baking) to form a coating film. As a pre-baking condition, for example, 0.1 to 5 minutes at $ ° C to 120 ° C. The conditions are preferably between 120 ° C and 300 ° C. It is preferably from 5 minutes to 200 minutes at 150 ° C to 250 ° C, more preferably from 10 minutes to 100 minutes after baking, preferably 〇.〇〇l//m~1 /im, more preferably 0.005 /zm~0.5. #m. Examples of the substrate include glass substrates such as float glass and sodium glass, polyethylene terephthalate, and polyparaphenylene terephthalate. Examples of the transparent substrate such as a transparent substrate of a plastic substrate such as a polyether oxime or a polycarbonate include an ITO film containing In2〇3-Sn〇2 of a NESA film containing Sn〇2, and the like. For example, a photolithography method or a method of forming a transparent conductive photomask can be used. When the liquid crystal alignment agent is applied, in order to improve the adhesion of the substrate or the transparent conductive film, the substrate and the transparent layer can be used in advance. Conductive film cloth functional decane compound, titanate compound, etc. When the liquid crystal alignment agent is used to form a liquid crystal alignment film for vertical alignment type liquid crystal display, the coating film formed as described above can be directly perpendicularly aligned liquid crystal display Liquid crystal alignment film for components, can also be The liquid crystal such as the plate method is preferably ί 40 , preferably used as the butyl lanthanum silicate, the film containing the film, and the coated component is used as the coating surface of the coating - 77- 201144361. When the liquid crystal alignment agent of the present invention is used for forming a liquid crystal alignment film for a level-aligned liquid crystal display device, a liquid crystal alignment film can be formed by performing a polishing treatment on the coating film formed as described above. It is carried out by using a roll which is wound with a cloth formed of a fiber such as nylon or rayon 'cotton, etc., in a certain direction. Here, for example, Japanese Patent Laid-Open No. Hei 6-222366, 曰本特平In the case of the liquid crystal alignment film, a part of the liquid crystal alignment film is irradiated with ultraviolet rays to perform a process of changing the pretilt angle, or as described in Japanese Laid-Open Patent Publication No. Hei 5 No. Hei 7 544. Thus, 'by forming a photoresist film on a portion of the surface of the formed liquid crystal alignment film, 'in the direction different from the previous polishing process Processing 'resist film is then removed, with the liquid crystal alignment having different processing capabilities on each of the liquid crystal film region, which can improve the resulting standard vision characteristic of the liquid crystal display element. [Formation Method (ii)] The method (ii) for forming a liquid crystal alignment film according to the present invention includes: (1) coating a liquid crystal alignment agent containing a [A] polyorganosiloxane compound on a substrate to form a coating film. Step [The] [A] polyorganosiloxane compound comprises a structure having a liquid crystal alignment ability having a structural unit represented by the above formula (B-1), and (2) a coating film formed by the step (1) At least a portion of the step of illuminating the radiation. -78-201144361 By the method of the present invention using the liquid crystal alignment agent, it is possible to form a liquid crystal alignment film which satisfies the required characteristics such as liquid crystal alignment property, voltage holding ratio and light resistance as a liquid crystal display element in practical use. As the coating film forming step (1), the same steps as in the forming method (the coating film forming step described in the section) can be applied. In the forming method (ii), the step (1) can be formed by (2) Instead of the polishing process described in the forming method (i), at least a part of the coating film is irradiated with radiation to produce a liquid crystal alignment film. As the radiation, it is possible to use linearly or partially polarized radiation or unpolarized radiation. For example, ultraviolet rays and visible rays containing light having a wavelength of 150 nm to 800 nm, and preferably ultraviolet rays containing light having a wavelength of 300 nm to 400 nm may be cited. When the radiation used is linearly polarized or partially polarized, it may be perpendicular to the substrate surface. Irradiation is performed in the direction, and irradiation may be performed from the oblique direction in order to impart the pretilt angle '. Alternatively, these may be combined. When the radiation of the unpolarized light is irradiated, the direction of the irradiation must be an oblique direction. The light source 'may be exemplified by a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, and an argon gas. The light, the gas lamp, the excimer laser, etc., preferably the ultraviolet light in the wavelength region can be obtained by a method in which the light source is used in combination with, for example, a filter or a diffraction grating. It is preferably U/m2 or more and less than 10'OOOJ/m2, more preferably 10 J/m2 to 3,000 J/m2, and is imparted to a coating film formed of a conventionally known liquid crystal alignment agent by a photo-alignment method. When the liquid crystal alignment agent is used, it is required to have a radiation exposure amount of 1 000,000 or more, and when the liquid crystal alignment agent is used, the radiation irradiation amount at the time of the light alignment method is 3,000 J/m 2 or less. 〇〇〇j/m2 or less, and particularly below 5〇〇j/m2' can also impart good liquid crystal alignment ability and contribute to a reduction in manufacturing cost of the liquid crystal display element. &lt;Liquid Crystal Display Element&gt; A liquid crystal display element including the liquid crystal alignment film is also suitably included in the present invention. Therefore, the liquid crystal display element of the present application including the liquid crystal alignment film formed of the liquid crystal alignment agent can be suitably used for, for example, a timepiece, a portable game machine, a word processor, a notebook computer, a car navigation system, a video camera, or the like. Display devices such as portable information terminals, digital cameras, mobile phones, various displays, and LCD TVs. &lt;Manufacturing Method of Liquid Crystal Display Element&gt; The liquid crystal display element can be produced, for example, as follows. As a first method, it is a conventionally known method in which first, two substrates are disposed opposite to each other with a gap (cell gap), and the respective liquid crystal alignment films are opposed to each other, and the two substrates are sealed using a sealing agent. The peripheral portions are bonded together, and after filling the liquid crystal into the interstitial space defined by the surface of the substrate and the sealant, the injection holes are closed, whereby the liquid crystal cell can be manufactured. The second method is a method called a DropDF (One Drop Fill) method in which, for example, a UV curable seal is applied to a predetermined portion of one of the two substrates on which the liquid crystal alignment film is formed. The material 'drops the liquid crystal on the liquid crystal alignment film surface, and then attaches the other substrate, -80- 201144361 to heat the liquid sealing agent, and the display ball of the cell is crystallized, etc., and the benzene liquid type liquid sterol "c- The methyl group has a negatively-exemplified coupling of the opposite crystals to the opposite direction, and then the entire surface of the substrate is irradiated with ultraviolet rays to be densely cured, whereby the liquid crystal cell can be produced. In the case of any method, the next step is to hope that the liquid crystal cell When the liquid crystal used is at a temperature of an isotropic phase, and then slowly cooled to the chamber to thereby remove the flow alignment when the liquid crystal is filled. Then, by aligning the polarizing plate on the outer surface of the liquid crystal, the liquid crystal element of the present invention can be obtained. Examples of the sealant include, for example, an epoxy resin containing a filler and a curing agent. Examples of the liquid crystal may include, for example, a nematic liquid. In the case of a TN type liquid crystal cell or an STN type liquid crystal cell, a nematic liquid crystal having dielectric anisotropy is preferable. As such a liquid crystal, a liquid crystal such as a biphenyl liquid crystal or a phenyl group may be listed. a cyclohexane liquid crystal, an ester liquid crystal, a triple liquid crystal, a biphenylcyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane crystal, a bicyclooctane liquid crystal, a cuba liquid crystal, etc. Further, in the epitaxial crystal It is also possible to further add a chiral agent which is sold, for example, as a cholesteric liquid crystal (Merck, 15", ''CB-15") such as cholesteryl chloride, cholesteric vinegar or cholesteryl carbonate; On the other hand, in the case of a vertically aligned liquid crystal cell, a nematic with dielectric anisotropy is preferred. The liquid crystal may be classified into a dicyanobenzene liquid crystal, a helium trap liquid crystal, a Schiff base liquid crystal, an oxygen nitrogen liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, or the like. - 201144361 As a polarizing plate used for the outer side of the liquid crystal cell, cellulose acetate can be cited. The polarizing plate formed by the polarizing film called "H film" obtained by absorbing iodine and the polarizing film formed by the ruthenium film itself, which is obtained by absorbing iodine, is sandwiched between the protective film. [Examples] The present invention will be described in detail, but the present invention is not limited by the description of the examples. Further, the synthesis of the starting compound and the polymer in the synthesis scheme shown in the following synthesis example is repeated as needed. The necessary amount of the starting compound and the polymer used in the following examples was confirmed. The epoxy equivalent was measured in accordance with the "hydrochloric acid-methyl ethyl ketone method" of JIS C2 105. The solution viscosity (mPa's) was measured using a Ε-type rotary viscometer. In the synthesis example, the solution in which the polymer concentration of the polymer solution was adjusted to 1% by mass was measured. &lt;Synthesis of polyorganosiloxane having epoxy group&gt; [Synthesis Example 1] In a reaction vessel having a stirrer, a thermometer, a dropping funnel, and a reflux condenser, '100.Og 2-(3,4) was added. -Epoxycyclohexyl)ethyltrimethoxydecane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine, and mixed at room temperature. Then, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and then mixed under reflux, and reacted at 80 ° C for 6 hours. After completion of the reaction, the organic layer was taken out and washed with a 0.2% by mass aqueous solution of ammonium nitrate until the washed water was neutral. Then, the solvent and water were distilled off under reduced pressure to obtain an organic group having an epoxy group as a viscous transparent liquid. Oxane (EPS). -82- 201144361 1H-NMR analysis of (EPS-1) showed that an epoxy group-based peak with the same theoretical strength was obtained near the chemical shift (6) = 3.2 ppm, thereby confirming that no reaction was produced in the reaction. A side reaction of an epoxy group. (EPS-1) had an Mw of 2,200 and an epoxy equivalent of I86 g/mole. <Synthesis of Compound (A-1-1)&gt; [Synthesis Example 2] The compound (A-iq) was synthesized according to the following synthesis scheme.

Into a 500 mL eggplant type flask, 23.6 § 2,2,6,6-tetramethyl-4-hydroxypiperidine, 15.0 g of succinic anhydride, and 200 mL of pyridine were added, and the reaction was stirred at 80 ° C for 9 hours. After completion of the reaction, the mixture was allowed to stand at room temperature for a day to precipitate crystals, and the solvent was removed to give 37. g of white crystals of compound (A-1-1). &lt;Synthesis of Compound Having Liquid Crystal Alignment Ability&gt; [Synthesis Example 3] The compound (b-1) was synthesized according to the following synthesis scheme. -83- 201144361

HO

CH=CH-COOH K2CO3 CgH^Br

NaOH/H20 c5h" one o

CH = CH-COOH (b-1) In a 1 L eggplant type flask, 82 g of p-hydroxycinnamic acid, 304 g of potassium carbonate, and 400 mL of N-methyl-2-pyrrolidone were added, and the mixture was stirred at room temperature for 1 hour. 166 g of 1-bromopentane was added and stirred at 100 ° C for 5 hours. Then, the solvent was distilled off under reduced pressure. 48 g of sodium hydroxide and 400 mL of water were added thereto, and the mixture was refluxed for 3 hours to carry out a hydrolysis reaction. After completion of the reaction, the reaction system was neutralized with hydrochloric acid, and the resulting precipitate was collected and recrystallized from ethanol to obtain white crystals of 80 g of compound (b-1). [Synthesis Example 4] The compound (b-2) was synthesized according to the following synthesis scheme.

Cooch3 C5HnBr

NaOH/H2〇

CsHn-O

COOH (b-2, K2CO3

CH = CH —COOH C5Hn-〇 SOCI2 K2C03

CH=CH—COOH (b-2) In a 1 L eggplant flask, add 91.3 g of methyl 4-hydroxybenzoate, 182.4 g of potassium carbonate and 320 mL of N-methyl-2-pyrrolidone, and stir at room temperature. After 1 hour, 9 9.7 g of 1-bromopentane was added and stirred at 1 ° C for 5 hours. -84- 201144361 After the reaction is over, reprecipitate with water. Next, 48 g of sodium hydroxide and 400 mL of water were added to the precipitate, and the mixture was refluxed for 3 hours to carry out a hydrolysis reaction. After completion of the reaction, it was neutralized with hydrochloric acid, and the resulting precipitate was recrystallized from ethanol to give white crystals of (104 g) Compound (b-2'). 104 g of the compound (b-2,) was placed in a reaction vessel, and 1 L of sulfinium chloride and 770 were added thereto with 1 N,N-dimethylformamide, and the mixture was stirred at 80 ° C for 1 hour. Next, thionyl chloride was taken up under reduced pressure, dichloromethane was added, and the mixture was washed with aqueous sodium hydrogencarbonate, dried over magnesium sulfate, concentrated, and then tetrahydrofuran was added to form a solution. Next, 74 g of 4-hydroxycinnamic acid, 138 g of potassium carbonate, 4.8 g of tetrabutylammonium, 500 mL of tetrahydrofuran and 1 L of water were placed in a separate 5 L three-necked flask. The aqueous solution was cooled with ice water, and a tetrahydrofuran solution containing the reactant of the above compound (b-2') and sulfoxide was slowly added dropwise, followed by a reaction under stirring for 2 hours. After completion of the reaction, hydrochloric acid was added to the reaction mixture for neutralization, and extraction was carried out with ethyl acetate, and then the extract was dried over magnesium sulfate, concentrated, and then recrystallized from ethanol, whereby 90 g of compound (b-2) was obtained. White crystals. [Synthesis Example 5] The compound (b-3) was synthesized according to the following synthesis scheme.

_ CF3C3He( NaOH/HzO H〇~\ /~C00CH3 -- -CF3C3H6 —〇—/^\_C〇〇H (b-3^) K2C03 ^^ COOH I K2C03

CF3〇3H6 —0—C \—coo CH=CH—COOH (b-3) -85- 201144361 In a 1 L eggplant flask, 82 g of methyl 4-hydroxybenzoate, 166 g of potassium carbonate and 400 mL of N,N- were added. After dimethylacetamide was stirred at room temperature for 1 hour, 95 g of 4,4,4-trifluoro-1·iodobutane was added, and the mixture was stirred at room temperature for 5 hours to carry out a reaction. After the reaction was completed, reprecipitation was carried out with water. Next, 32 g of sodium hydroxide and 400 mL of water were added to the precipitate, and the mixture was refluxed for 4 hours to carry out a hydrolysis reaction. After completion of the reaction, it was neutralized with hydrochloric acid, and the resulting precipitate was recrystallized from ethanol to obtain white crystals of 80 g of compound (b - 3 '). 46.4 g of the compound (b-3') was placed in a reaction vessel, and 200 mL of sulfinium chloride and 0.2 mL of N,N-dimethylformamide were added thereto, and the mixture was stirred at 80 ° C for 1 hour. Next, sulphur ruthenium chloride was distilled off under reduced pressure, dichloromethane was added, and the mixture was washed with aqueous sodium hydrogencarbonate, dried over magnesium sulfate, concentrated, and then tetrahydrofuran was added to form a solution. Next, 36 g of 4-hydroxycinnamic acid, 55 g of potassium carbonate, 2.4 g of tetrabutylammonium, 200 mL of tetrahydrofuran, and 400 mL of water were placed in a separate 2 L three-necked flask. This water-releasing solution was subjected to ice water cooling', and a tetrahydrofuran solution containing the reactant of the above compound (b-3') and sulfoxide was slowly added dropwise, followed by a reaction under stirring for 2 hours. After completion of the reaction, hydrochloric acid was added to the reaction mixture for neutralization, and extraction was carried out with ethyl acetate, and then the extract was dried over magnesium sulfate, concentrated, and then recrystallized from ethanol, whereby 3 9 g of compound (b - 3 ) was obtained. ) white crystals. [Synthesis Example 6] The compound (b-4) was synthesized according to the following synthesis scheme. -86- 201144361 C5H11

COOH I SOCI2

C5H11 CH=CH—COOH K2C03

• CH=CH—COOH (b-4) The same operation as in Synthesis Example 4 except that in the above Synthesis Example 4, 9.91 g of 4-pentyl-trans cyclohexylcarboxylic acid was used instead of the compound (b-2′). 13 g of a white crystal of the compound (b-4) was obtained. [Synthesis Example 7] The compound (b-5) was synthesized according to the following synthesis scheme.

C5Hn—^ ^ y—CH=CH—COOH (b-5) In a 500 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen inlet tube, '31 g of compound (b-5,), 0.23 g of palladium acetate, 1.2 g were added. Tris(o-tolyl)phosphine, 56 mL of triethylamine, 8.2 mL of acrylic acid and 200 mL of N,N-dimethylacetamide were reacted at 10 ° C for 3 hours with stirring. After completion of the reaction, the reaction mixture was filtered, and 1 L ethyl acetate was added to the obtained mixture, and the obtained organic layer was washed twice with dilute hydrochloric acid and washed three times with water. Then, the organic layer was dried over magnesium sulfate, concentrated, dried, and then recrystallized from a solvent mixture of ethyl acetate and tetrahydrofuran to give crystals of compound (b-5) of 15 g - 87 - 201144361. [Synthesis Example 8] The compound (b-6) was synthesized according to the following synthesis scheme.

In the same manner as in the above Synthesis Example 7, except that 3 6 g of the compound (b - 6 ') was used instead of the compound (b - 5 '), I6 g of the compound (b-6) was obtained. [Synthesis Example 9] The compound (b-7) was synthesized according to the following synthesis scheme.

In a 200 mL eggplant type flask having a reflux tube, 12 g of mercapto succinic anhydride, 8.2 g of 4-aminocinnamic acid and 10 mL of acetic acid were added, and the mixture was reacted under reflux for 2 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate, and the organic layer was washed with water, dried over magnesium sulfate, and then purified by a column, and further recrystallized from a mixed solvent of ethanol and tetrahydrofuran to obtain -88 - 201144361 10 g of compound (b-7) as white crystals (purity: 98.0%). [Synthesis Example 10] In the same manner as in Synthesis Example 7, except that the compound (b-8') represented by the following formula (28 g) was used instead of the compound (b-5') in the above Synthesis Example 7, The compound (b-8) represented by the formula.

[Synthesis Example 1 1] Compound (b-9) was synthesized according to the following synthesis scheme.

In a 500 mL three-necked flask equipped with a reflux tube and a nitrogen inlet tube, 39 g of cholesteric alcohol, 20 g of succinic anhydride 'i.5 g of n,N-dimethylaminopyridine, 200 ml of ethyl acetate and 1 were added. 7 m L of triethylamine was reacted under reflux for 8 hours. -89- 201144361 After the reaction was completed, 200 mL of tetrahydrofuran was added to the reaction mixture, and the obtained organic layer was washed twice with 1 N diluted hydrochloric acid and then washed three times with water. After drying over magnesium sulfate, the solvent was removed under reduced pressure, and the obtained solid was recrystallized from ethyl acetate to afford white crystals of 38 g of compound (b-9). &lt;Synthesis of [A] polyorganomethoxy siloxane compound &gt; [Synthesis Example 12] In a 200 mL three-necked flask, 10.Og (EPS-1), 69.5 g of methyl isobutyl ketone, and 2.77 § compound (eight -1-1) (equivalent to 20 mol% with respect to the polyorganooxane £3-1), 4.60 g of stearic acid (relative to polyorganooxynonane (EPS-1) ) having an epoxy group corresponding to 30 mol%) and 1.0 g of tetrabutylammonium bromide, and stirring at 1 ° C for 8 hours to carry out a reaction. After the reaction is completed, reprecipitation is carried out with methanol. The precipitate was dissolved in ethyl acetate to obtain a solution, and the solution was washed 5 times with water, and then the solvent was distilled off, thereby obtaining 15.8 g of [A] polyorganooxy siloxane compound (S-1) as a white powder. . [Synthesis Example 13 to Synthesis Example 33] The type and blending amount of the compound to be blended were respectively shown in Table 1, and the [A] polyorganosiloxane compound (S-) was synthesized in the same manner as in Synthesis Example 12. 2) ~ (S-22). Further, the ratio of use of the compound in Table 1 is the molar % of the epoxy group which is contained in (E P S -1). Further, the Mw of the polyorganosiloxane is shown together in Table 1. Further, the structures of salicylic acid and 4-diethylaminobenzazole-90-201144361 acid are as follows.

OH

[Comparative Synthesis Example 1] In a 200 mL three-necked flask, '1 〇g (EPS-1), 58.4 g of methyl isobutyl ketone, 4.60 g of stearic acid (relative to polyorganooxy oxane EPS-1) was added. The epoxy group having an epoxy group equivalent to 30 mol%) and 1.0 g of tetrabutylammonium bromide were stirred at 1,001 for 8 hours to carry out a reaction. After completion of the reaction, reprecipitation was carried out with methanol, and the precipitate was dissolved in ethyl acetate to obtain a solution. The solution was washed 5 times with water, and then the solvent was distilled off, thereby obtaining 12.4 g of a polyorganooxane as a white powder. (CS-1). [Comparative Synthesis Examples 2 to 4] The types and blending amounts of the blended compounds were as shown in Table 1 and the same procedure as in Comparative Synthesis Example 1 was carried out to synthesize a polyorganosiloxane compound (CS-2) to (CS). -4). Further, 1 of polyorganosiloxane (CS-1) to (CS-4) is shown together in Table 1. -91 - 201144361 [一撇] Mw 〇as 〇〇〇\ 〇§ 〇〇ON 〇σΓ 〇〇〇〇o' Ο ο αΓ Ο οο Ο 宕Os 〇〇oC 〇&lt;3\ 〇〇〇又〇\ 〇〇o' 〇〇〇σΓ Ο Γ-; σ\ Ο ο ο 〇fN 〇\ 〇OS 〇〇\ 〇〇\ 〇〇〇\ 〇σ\ 〇〇〇\ 〇〇\ Teacher composition ratio (莫m%) 〇m ο Ο Ο 沄沄 kind of stearic acid stearic acid stearic acid n-oxybenzoic acid n-nonyloxybenzoic acid n-oxybenzoic acid-ώ 1 II stearic acid n-decyloxy Benzoic acid X) -ώ to JO m Xi m x&gt; cn Xi X) &lt;N Χι X) 〇〇Χ 〇〇Χ&gt; X) m -ώ Compound (A-3) Use ratio (% by mole) 〇〇〇〇 ο ο Ο 〇〇〇ο ο o 〇〇〇〇〇〇〇ο Species 1 1 4-Diethylaminobenzoic acid 1 1 4-diethylaminobenzoic acid I 1 I 4-diethylamino Benzoic acid 1 1 • I 4-diethylaminobenzoic acid i 1 4-diethylaminobenzoic acid 1 1 1 1 1 1 t I Compound (A-2) Use ratio (mol%) 〇〇〇 〇ο Ο 〇〇〇〇 ο 种类 Category 1 Salicylic acid 1 1 Salicylic acid 1 Salicylic acid 1 I Salicylic acid I t 1 1 Salicylic acid 1 1 Salicylic acid Salicylic acid Salicylic acid Salicylic acid Salicylic acid Salicylic acid Acid salicylic acid &lt; I compound (Al) ratio (mol%) 〇〇〇〇Ο ο Ο 〇〇〇〇Ο 〇〇〇〇〇〇〇〇Ο type A-1-1 1 1 A-1 -1 1 1 I Α-1-1 1 1 1 1 1 &lt; 1 1 1 &lt; 1 1 1 1 1 1 1 1 1 1 [A] polyorganosiloxane compound ζλ CN οό C/1 C/J 00 Γγ 〇〇(/) 〇\ ζλ |si〇丨|cs-i 1 | CS-2 I [S-11 1 s-12 1 1 S-13 I S-14 S-15 S-16 S-17 S-18 S-19 S-20 S-21 S-22 CS-3 CS-4 Synthesis Example 12 Synthesis Example 13 Synthesis Example 14 Synthesis Example 15 Synthesis Example 16 Synthesis Example 17 Synthesis Example 18 Synthesis Example 19 Synthesis Example 20 Synthesis Example 21 Comparative Synthesis Example 1 Comparative Synthesis Example 2 Synthesis Example 22 Synthesis Example 23 Synthesis Example 24 Synthesis Example 25 Synthesis Example 26 Synthesis Example 27 Synthesis Example 28 Synthesis Example 29 Synthesis Example 30 Synthesis Example 31 Synthesis Example 32 Synthesis Example 33 Comparison Synthesis Example 3 Comparison Synthesis Example 4 - s - 201144361 &lt; Synthesis of [B] polymer (polyproline) &gt; [Synthesis Example 34] 196 g (1.0 mol) of carboxylic acid dianhydride, cyclobutane tetracarboxylic dianhydride, and 212 g (1.0 mol) of 2,2, dimethyl _4, 4, _ as diamine The aminobiphenyl was dissolved in 4,050 g of NMP, and reacted at 4 Torr for 3 hours to obtain a polyaminic acid solution (PA-1) having a solid concentration of 1% by weight and a solution viscosity of 170 rnPa.s. [Synthesis Example 35] 86.3 g (0.44 mol) of 12,3,4-cyclobutanine tetradecanoic acid dianhydride and 96_0 g (0,44 mol) of pyromellitic dianhydride were used as the tetracarboxylic dianhydride. And 191. (^(0.90 mol) 2,2'-dimethyl-4,4'-diaminobiphenyl as diamine I. was dissolved in l49 g of NMP and reacted at 40 ° C. 4 Hours, then stepwise addition of NMP' to obtain a polyaminic acid solution (PA-2) having a solid concentration of 1% by weight and a solution viscosity of 43 mPa.s. &lt;[B] Polymer (polyimine) Synthesis &gt; [Synthesis Example 36] 20.9 g (0.093 mol) of 2,3,5-trisole cyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 9.2 g (0.085 mol) as diamine P-phenylenediamine and 4.9 g (0.009 mol) of the compound represented by the following formula (DA), dissolved in HOg NMP, reacted at 6 (TC for 4 hours, a small amount of the obtained polyaminic acid solution, and NMP was added to obtain a polyaminic acid solution having a solid concentration of 丨〇% and a solution viscosity of 126 mPa·s. Then, 325 g of NMP was added to the obtained polyglycolate gluten solution, and 7.4 g of D ratio and 9.5 were added. g acetic anhydride, -93- 201144361 For 4 hours dehydration ring closure at 1 1 (TC). After the water ring closure reaction, the solvent in the system was replaced with a new NMP solvent to obtain about 2 g of a solution containing 16.1% by weight of a polyamidimide having a ruthenium iodide ratio of about η%. The polyimine solution was added to ΝΜρ to give a solid concentration of 1%%. The measured solution viscosity was 7 5 m P a.s.

[Synthesis Example 37] 20.0 g (0.08 9 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 6.8 g (0.063 mol) of benzene as a diamine Diamine, 3.6 g (0.018 mol) of 4,4,-diaminodiphenylmethane and 4.7 g (0.0090 mol) of the compound represented by the above formula (da), dissolved in M()g NMP, The reaction was carried out at 60 ° C for 4 hours to obtain a polyaminic acid solution having a solid concentration of 2% by weight and a solution viscosity of 2,200 mPa's. Next, 325 g of NMP was added to the obtained polyamic acid solution, and 10.5 g of pyridine and i3.6 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out for 4 hours at Π 0 °C. After the dehydration ring closure reaction, the solution in the system was replaced with a new NMP solvent to obtain a solution of about 1 600 g of polyamidimide (PI-2) having a ruthenium iodide ratio of about 65 % (solid content concentration). 20%). -94- 201144361 [Synthesis Example 38] 19.2 g (0.086 mol) of 2,3,5-tris(cyclo)cyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, and 5.2 g (0.034 mol) as a diamine 3)diaminebenzoic acid and 25.5 g (0. 52 mol) of the diamine represented by the following formula, dissolved in 200 g of NMP and reacted at 60 ° C for 4 hours to obtain a solid concentration of 20 %, solution viscosity of 1,450 mPa.s poly-proline solution. Next, 250 g of NMP was added to the obtained polymerized S-acid solution, and i.2 g of []pyridine and 13.2 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out for 4 hours at U °C. After the dehydration ring closure reaction, the solution in the system was subjected to solvent replacement with a new NMP to obtain a solution of about 280 g of a polyimine (PI-3) containing 20% by weight of a ruthenium iodide ratio of about 67%.

&lt;[C] Synthesis of other polyorganomethoxy siloxane compound &gt; [Synthesis Example 39] In a 200 mL three-necked flask having a condenser, '2 〇8 g of tetraethoxy decane and 28.2 g of 1-ethoxy group were added. 2-propanol, heated to 60 ° C and stirred" to which was added 〇.26 g of maleic anhydride dissolved in 1 0.8 g of water prepared in another flask having a capacity of 20 mL. The reaction was carried out by stirring at 〇 ° C for 4 hours. After the completion of the reaction, the solvent was distilled from the obtained anti-95-201144361 mixture, and 1-ethoxy-2-propanol was added to the residue to concentrate again, thereby obtaining a solid having a solid concentration of 1% by weight. Organic oxirane (PS-1) solution. Mw is 5,1〇〇. &lt;Preparation of liquid crystal alignment agent&gt; [Example 1] The content of 100 parts by mass of polyorganosiloxane (S-1) and the amount of polyglycine (PA-1) equivalent to 1,000 parts by mass A solution of poly-proline (PA-1) is mixed together, and NMP and ethylene glycol mono-n-butyl ether are added thereto to form a solvent composition of NMP: ethylene glycol mono-n-butyl ether = 50 · · 50 (mass ratio A solution having a solid concentration of 3.0% by mass. This solution was filtered using a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent (AF-1), which was referred to as Example 1. [Examples 2 to 39 and Comparative Examples 1 to 7] The types and amounts of the blended mixture were adjusted as shown in Table 2 below, and the liquid crystal alignment agent (AF-2) was prepared in the same manner as in Example 1. (AF-39) and (CAF-1) to (CAF-7), which were used as Examples 2 to 39 and Comparative Examples 1 to 7. &lt;Storage Stability&gt; With respect to each of the above liquid crystal alignment agents, storage stability was evaluated by the following (Method 1) or (Method 2). The results are shown in Table 2 » (Method 1) Using a spin coating method and coating the liquid crystal alignment agents (AF-1) to (AF-12) and (CAF-1) to (CAF-3) with the number of rotations as a variable. On the glass substrate, a coating film was formed by heating at 20 (TC for 60 minutes), and the film thickness of the coating film after removing the solvent from -96 to 201144361 was investigated. Then, a part of the liquid crystal alignment agent was taken. 'They were stored at -15 ° C for 5 weeks. The liquid crystal alignment agent after storage was visually observed, and when the precipitation of insoluble matter was observed, the storage stability was evaluated as "not good". When insoluble matter was not observed after 5 weeks of storage, , by the spin coating method, and preserving the film thickness of U000A before the film is applied, the deposited liquid crystal alignment agent is coated on the glass substrate, and then heated at 2 〇〇t: for 60 minutes to form a coating film. The film thickness after removal of the solvent was measured. When the film thickness was changed by 10% or more from 1,00 〇A, the storage stability was evaluated as "not good", and when the film thickness change was less than 1%, it was evaluated as The storage stability was “good.” In addition, the film thickness of the above coating film was measured using a touch made by KLA-Tencor. The method was carried out by a differential film thickness meter (Method 2) The liquid crystal alignment agents (AF-13) to (AF-39) and (CAF-4) to (CAF-7) were stored at -15 °C for 6 months. Before and after storage, the viscosity was measured at 25 ° C using an E-type viscometer. When the change rate of the solution viscosity before and after storage was less than 10%, the storage stability was evaluated as "good", and when it was 1% or more 'Evaluation is not good for preservation stability. -97- 201144361 [Table 2] Evaluation of liquid crystal alignment agent composition [A] Polyorganosiloxane compound 1 Also, polymer storage stability type (mass part) Parts by mass) Method evaluation Example 1 AF-1 S-1 100 PA4 1,000 1 Good example 2 AF-2 S-2 100 PA-1 1,000 1 Good example 3 AF-3 S-3 100 PA-1 1,000 1 Good example 4 AF-4 S-4 100 PA-1 1,000 1 Good example 5 AF-5 S-5 100 PA-1 1,000 1 Good example 6 AF-6 S-6 100 PA-1 1,000 1 Good implementation Example 7 AF-7 S-1 100 PS-1 1,000 1 Good Example 8 AF-8 S-7 100 PI-1 2,000 1 Good Example 9 AF-9 S-7 100 PA-1 2,000 1 Good Example 10 AF-10 S-8 100 PI-1 1,000 1 Good example 11 AF-11 S-9 100 PI- 1 1,000 1 Good Example 12 AF-12 ' S-10 100 PI-1 1,000 1 Good Comparative Example 1 CAF-1 CS-1 100 PA-1 1,000 1 Good Comparative Example 2 CAF-2 CS-2 100 PA-1 1,000 1 good comparative example 3 CAF-3 - - PI-1 1,000 1 good example 13 AF-13 S-11 100 PA-1 2,000 2 good example 14 AF-14 S-12 100 PA-1 2,000 2 good implementation Example 15 AF-15 S-13 100 PA-1 2,000 2 Good Example 16 AF-16 S-14 100 PA-1 2,000 2 Good Example 17 AF-17 S-15 100 PA-1 2,000 2 Good Example 18 AF-18 S-16 100 PA-1 2,000 2 Good example 19 AF-19 S-17 100 PS-1 2,000 2 Good example 20 AF-20 S-18 100 PA-1 2,000 2 Good example 21 AF- 21 S-19 100 PA-1 2,000 2 Good example 22 AF-22 S-20 100 PA-1 2,000 2 Good example 23 AF-23 S-21 100 PA-1 2,000 2 Good example 24 AF-24 S -22 100 PA-1 2,000 2 good example 25 AF-25 S-11 100 PI-1 2,000 2 good example 26 AF-26 S-12 100 PI-1 2,000 2 good example 27 AF-27 S-13 100 PI-1 2,000 2 Good Example 28 AF-28 S-14 100 PI-1 2,000 2 Good Practice 29 AF-29 S-15 100 PI-1 2,000 2 Good Practice 30 AF-30 S-16 100 PI -1 2,000 2 good Example 31 AF-31 S-17 100 PI-1 2,000 2 Good Practice 32 AF-32 S-18 100 PI-1 2,000 2 Good Practice 33 AF-33 S-19 100 PI-1 2,000 2 Good Practice 34 AF-34 S-20 100 PI-1 2,000 2 Good Practice 35 AF-35 S-21 100 PM 2,000 2 Good Practice 36 AF-36 S-22 100 PI-1 2,000 2 Good Practice 37 AF-37 S-12 100 PA-2 2,000 2 Good Practice 38 AF-38 S-12 100 PI-2 2,000 2 Good Practice 39 AF-39 S-12 100 PI-3 2,000 2 Good Comparative Example 4 CAF-4 CS- 1 100 PA-1 2,000 2 Good Comparative Example 5 CAF-5 CS-2 100 PA-1 2,000 2 Good Comparative Example 6 CAF-6 CS-3 100 PI-1 2,000 2 Good Comparative Example 7 CAF-7 CS-4 100 PI-1 2,000 2 良-98- 201144361 &lt;Manufacture of liquid crystal display element&gt; [Example 40] A liquid crystal alignment agent (AF-1) was applied to a glass having a transparent electrode formed of an ITO film using a spin coater The surface of the transparent electrode of the substrate was prebaked on a hot plate at 80 ° C for 1 minute. Then, in an oven purged with nitrogen, heating at 200 ° C for 1 hour was performed to remove the solvent to form a film thickness of Ο. . ίμηι coating. This operation was repeated to fabricate a pair of (two sheets) substrates having a liquid crystal alignment film. By screen printing, an epoxy resin adhesive having an alumina ball having a diameter of 5.5 μm is applied to the outer periphery of the surface of the one of the substrates having the liquid crystal alignment film, and the liquid crystal alignment film surfaces of the pair of substrates are overlapped and pressed. The mixture was heated at 150 ° C for 1 hour to thermally cure the adhesive. Then, the liquid crystal injection port is filled with a nematic liquid crystal (Merk Corporation, MLC-6 6 0 8) into the gap of the substrate, and then the liquid crystal injection port is sealed with an epoxy-based adhesive, and in order to eliminate the flow during liquid crystal injection. After the alignment, it was heated at 150 ° C for 10 minutes and then slowly cooled to room temperature. Further, a polarizing plate was attached to both outer surfaces of the substrate, and the polarization directions of the two polarizing plates were orthogonal to each other, whereby a liquid crystal display element of a vertical alignment type was produced, which was taken as Example 40. [Example 4 1 to 5 1, Comparative Example 8 to 1 0] Using liquid crystal alignment agents (AF-2) to (AF-1 2) and (CAF-1) to (CAF-3), the same as in Example 40 Operation and manufacture of liquid crystal display elements were carried out as Examples 4 1 to 5 1 and Comparative Examples 8 to 10 . [Example 52]

A liquid crystal alignment agent (AF-13) was coated on a transparent electrode surface of a glass substrate having a transparent electrode formed of a film of ITO-99-201144361 using a spin coater, and prebaked on a hot plate at 80 ° C. After a minute, the mixture was heated at 200 ° C for 1 hour in an oven purged with nitrogen to remove a solvent to form a coating film having a film thickness of 0.1 μm. Next, using an Hg-Xe lamp and a Glan Taylor prism, the tilt is 40 from the normal to the substrate. The direction of the coating film was irradiated with polarized ultraviolet rays having a wavelength of 3 1 3 n m by 2 〇〇 J/m 2 to form a liquid crystal alignment film. The same operation was repeated to fabricate a pair of (two sheets) substrates having a liquid crystal alignment film. By applying an epoxy resin adhesive having an alumina ball having a diameter of 5 to 5 μm to the outer periphery of the surface of the one of the substrates having the liquid crystal alignment film by screen printing, the liquid crystal alignment film faces of the pair of substrates are opposed to each other. Pressing, the projection direction of the ultraviolet light axis on the substrate surface in each substrate is anti-parallel, and heating at 丨50 ° C for 1 hour to thermally cure the adhesive. Next, the liquid crystal injection port was filled with a nematic liquid crystal (Merck, MLC-66 0 8) from the gap between the substrates, and the liquid crystal injection port was sealed with an epoxy-based adhesive. Further, in order to eliminate the flow alignment at the time of liquid crystal injection, it was heated at 150 ° C for 10 minutes and then slowly cooled to room temperature. Then, 'the polarizing plates are attached to the outer surfaces of the substrate so that the polarization directions of the polarizing plates are orthogonal to each other, and the projection direction of the ultraviolet light axis of the liquid crystal alignment film on the substrate surface is 45°, thereby manufacturing the vertical alignment. A liquid crystal display element of the type was used as Example 52. [Example 5 3 to 7 8 , Comparative Example 1 1 to 1 4 ] Using a liquid crystal alignment agent (AF - 1 3 ) ~ (AF - 3 9) and (C AF-4) ~ (C AF-7) ' and In the same manner as in Example 52, liquid crystal display elements were produced, and these were referred to as Examples 5 to 7 8 and Comparative Examples 1 to 1 to 4. -100-201144361 Liquid crystal cavities of Examples 40 to 78 and Comparative Examples 8 to 14 The following evaluations are shown, and the results are shown in Table 3. &lt;Liquid alignment property&gt; An abnormal region where there is no change in brightness when a voltage of 5 V is applied to the liquid crystal display element manufactured as described above is visually observed. No light leakage is observed, and the cell drives color when voltage is applied, and there is no light leakage in other areas, which is good for liquid crystal.” When the voltage is off, light leakage is observed, or when the voltage is driven outside the region. In the case of light leakage, it is good for liquid crystal i." &lt;Voltage retention ratio&gt; The liquid crystal display element produced above was subjected to a voltage application of 60 μC at 60 ° C for 60 μsec, and an interval of 167 msec was applied to measure the voltage from the release of the application to 167 ms. Retention rate. Use VHR-1 from TOYOTechnica. When the voltage holding ratio was evaluated, the voltage holding ratio was evaluated as "good". &lt;Light resistance&gt; The initial voltage holding ratio of the liquid crystal display element was measured under the same conditions as the evaluation of the voltage holding ratio. Then, at a distance of 5 cm at a distance of 5 cm under a 100-watt type white fluorescent lamp, after the irradiation, the rate of decrease in the voltage holding ratio when the voltage holding period is measured under the same conditions as above is less than 1%, the property "A" When it exceeds 1% and is less than 2%, it is evaluated as "B". When it exceeds 2%, it is evaluated as light resistance "C": component, and the component is turned on and off (when the voltage is turned off, the white alignment is displayed) The "measurement device was observed at the time of good opening", and the voltage was measured at a temperature of 90% or more. The measurement device was set to have a light transmittance of 500 hours as described above. Light resistance -101 - 201144361 [Table 3]

Liquid crystal alignment agent used for liquid crystal display element evaluation liquid crystal alignment voltage retention rate Light resistance Example 40 AF-1 Liangliang A Example 41 AF-2 Liangliang A Example 42 AF-3 Liangliang A Example 43 AF-4 Liangliang A Example 44 AF-5 Liangliang A Example 45 AF-6 Liangliang A Example 46 AF-7 Liangliang A Example 47 AF-8 Liangliang A Example 48 AF-9 Liangliang A Example 49 AF-10 Liangliang A Example 50 AF-11 Liangliang A Example 51 AF-12 Liangliang A Comparative Example 8 CAF-1 Liangliang B Comparative Example 9 CAF-2 Liangliang B Comparative Example 10 CAF-3 Good Good C Example 52 AF-13 Liangliang A Example 53 AF-14 Liangliang A Example 54 AF-15 Liangliang A Example 55 AF-16 Liangliang A Example 56 AF-17 Liangliang A Example 57 AF-18 Liangliang A Example 58 AF-19 Liangliang A Example 59 AF-20 Liangliang A Example 60 AF-21 Liangliang A Example 61 AF-22 Liangliang A Example 62 AF-23 Liangliang A Example 63 AF-24 Liangliang A Example 64 AF-25 Liangliang A Example 65 AF-26 Liangliang A Example 66. AF-27 Liangliang A Example 67 AF-28 Liangliang A Example 68 AF- 29 Liangliang A Example 69 AF-30 Liangliang A Example 70 AF-31 Liangliang A Example 71 AF-32 Liangliang A Example 72 AF-33 Liangliang A Example 73 AF-34 Liangliang A Implementation Example 74 AF-35 Liangliang A Example 75 AF-36 Liangliang A Example 76 AF-37 Liangliang A Example 77 AF-38 Liangliang A Example 78 AF-39 Liangliang A Comparative Example 11 CAF-4 Liangliang B Comparative Example 12 CAF-5 Liangliang B Comparative Example 13 CAF-6 Liangliang B Comparative Example 14 CAF-7 Liangliang B 102- 201144361 It is clear from the results of Tables 2 and 3 that the liquid crystal alignment agent of the present invention Excellent storage stability. Further, it is also known that the liquid crystal alignment film formed of the liquid crystal alignment agent sufficiently satisfies the required liquid crystal alignment property, voltage holding ratio, and light resistance as a liquid crystal display element. [Industrial Applicability] According to the present invention, it is possible to provide a liquid crystal alignment film which satisfies required properties such as liquid crystal alignment, voltage retention, and light resistance as a liquid crystal display element in practical use; formation of the liquid crystal alignment film The method is suitable as a liquid crystal alignment agent which is excellent in storage stability of a liquid crystal alignment film forming material, and which can form a liquid crystal alignment film by a photo-alignment method; and a liquid crystal display element which has a liquid crystal alignment film. The liquid crystal display element of the present application having the liquid crystal alignment film formed of the liquid crystal alignment agent can be suitably used for, for example, a timepiece, a portable game machine, a word processor, a notebook computer, a car navigation system, a video camera, and a portable type. Display devices such as information terminals, digital cameras, mobile phones, various displays, and LCD TVs. [Simple description of the diagram] Ifar has no 0 [Description of main component symbols] No 0 -103·

Claims (1)

201144361 VII. Patent application scope: 1 - A liquid crystal alignment agent containing [A] a polyorganooxynonane having at least one structure selected from the group consisting of a piperazine structure, a phenol structure and an aniline structure. Compound. 2. The liquid crystal alignment agent of claim 1, wherein the piperidine structure is represented by the following formula (A-1'), and the phenol structure is represented by the following formula (A-2') Amine benzene 5 A R 3'RI (In the formula (A-1'), R1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, and carbon. An aralkyl group having an atomic number of 7 to 13 or a 1,3-di-terminated oxybutyl group; and R 2 to R 5 are each independently an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms or An aralkyl group having 7 to 13 carbon atoms; X1 is a single bond, a carbonyl group or "-CONH-; X2 to X5 are each independently a single bond, a carbonyl group, **-CH2-CO- or **-CH2-CH (OH)·; ** indicates that the linkage is bonded to the piperidine ring; * the linkage is represented by the backbone or side chain of the polyorganosiloxane skeleton;) -104- 201144361 (R6)n (A-2) (In the formula (A-2'), R6 is an alkyl group having 1 to 16 carbon atoms, wherein the alkyl group may have an oxygen atom, a sulfur atom or a carbonyl group in the skeleton chain. , an ester group or a group combining two or more of them; n is an integer of 〇~4; * a linkage bond represented by a main chain or a side chain of a polyorganosiloxane skeleton); (In the formula (Α-3'), R7 and R8 are each independently an alkyl group having a carbon number of 丨~16 'wherein the alkyl group may have an oxygen atom, a sulfur atom, a carbonyl group, an ester group or A group in which two or more of them are combined; * a linkage bond represented by * is bonded to a main chain or a side chain of a polyorganosiloxane skeleton). 3. The liquid crystal alignment agent of the first aspect of the invention, wherein the [a] polyorganoxasiloxane compound is derived from a polyorgano selected from the group consisting of the structural formula represented by the following formula (1); a portion of at least one of the group consisting of an aerobics, a hydrolyzate thereof, and an alpha condensate of the hydrolyzate; and a moiety selected from the group consisting of the following formula (Α-1), formula (Α-2), and Α-3) a moiety of at least one compound in the group consisting of the compounds; -105- (1) 201144361 xa I Si - Ο Ι Ya (in the formula (1), 乂 2 is an epoxy group a monovalent organic group, Ya is a transradical group, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; R1 R3 — X3 X1 X2 n X4 R4 X5-R5 (A-1) &gt;--Z (In the formula (Al), R1 to R5 and X^X5 are synonymous with the above formula (Al,); in the formula (A-2), R6 is synonymous with the above formula (A-2,); -106- 201144361 Formula (A) In the formula -3), R7 and R8 and the above formula (A-3') are synonymous with the formula (A-1) to (A-3), wherein Y is a single bond and an alkanediyl group having 1 to 16 carbon atoms; The alkanediyl group may have an oxygen atom, a sulfur atom, a carbonyl group, an ester group, a decylamino group or a group in which two or more of them are combined in the structure; Z is a carboxyl group or a hydroxyl group). 4. The liquid crystal alignment agent of the third aspect of the invention, wherein the oxime 3 in the above formula (1) is a group represented by the following formula (Xa-1) or (Xa-2), CyH2v (Xa-1) (Xa-2) (In the formula (XM) and the formula (Xa-2), s is an integer of 0 to 3, t is an integer of 1 to 6, and u is an integer of 0 to 2, and v is An integer of 0 to 6, the connection key represented by * is bonded to the 矽 atom). 5. The liquid crystal alignment agent of claim 4, wherein the group represented by the above formula (Xa-1) or formula (Xa-2) is each a formula (Xa-1-1) or (Xa) -2-l) the group represented, (Xa- 1 -1 ) -107- 201144361 (In the formula (XM-1) and the formula (Xa-2-l), the connection key represented by * is bonded to the 矽 atom). 6. The liquid crystal alignment agent of any one of claims 1 to 5 wherein the [A] polyorganosiloxane compound comprises a structure having a liquid crystal alignment ability. 7. The liquid crystal alignment agent of claim 6, wherein the structure having the liquid crystal alignment ability has an organic group selected from the group consisting of a steroid having a carbon number of 17 to 51 and having 2 to 20 carbon atoms. An alkyl group, a fluoroalkyl group having 1 to 20 carbon atoms, a cyclohexyl group, an alkoxyaryl group having an alkyl group having 2 to 20 carbon atoms, an alkyl group having an alkyl group having a carbon number of 20 to 20 a group consisting of a cyclohexyl group, a fluoroalkylcyclohexyl group having a fluoroalkyl group having 1 to 20 carbon atoms, and a fluoroalkoxycyclohexyl group having a fluoroalkoxy group having 1 to 20 carbon atoms; At least one group. 8. The liquid crystal alignment agent of claim 6, wherein the structure having the liquid crystal alignment ability is represented by the following formula (B-1). (In the formula (Β-l), m is an integer of 0 to 4). The liquid crystal alignment agent according to any one of claims 1 to 5, further comprising [B] selected from polyproline And at least one polymer of the group consisting of polyimine. The liquid crystal alignment agent according to any one of the items 1 to 5, further comprising [C] a polyoxyalkylene having a structural unit represented by the following formula (2): -108- 201144361 Compound, xb _ Si - Ο - (2) I _ (In the formula (2), χ» is a hydroxyl group, a halogen atom, an alkyl group having a carbon number of 20, an alkoxy group having a carbon number or a carbon atom The number is 6 to 20 aryl groups; Yb is a hydroxyl group or an alkoxy group having 1 to 1 carbon atom). 1 . A method for forming a liquid crystal alignment film, comprising: (1) a step of forming a coating film by coating a liquid crystal alignment agent of the eighth, ninth or tenth aspect of the patent application on a substrate, and (2) At least a part of the coating film formed in the step (1) is irradiated with radiation. A liquid crystal alignment film formed of a liquid crystal alignment agent according to any one of claims 1 to 10. A liquid crystal display element comprising a liquid crystal alignment film according to item 12 of the patent application. A polyorganosiloxane compound having at least one structure selected from the group consisting of a piperidine structure, a phenol structure, and an aniline structure. The polyorganosiloxane compound according to claim 14 wherein the piperidine structure is represented by the following formula (A-1'), -109- 201144361 x2 R1 I x1 I M R4 X4 X5-R5 (A-f) (In the formula (A·1 '), R1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group of 6 to 20, an aralkyl group having 7 to 13 carbon atoms, or a group; R2; ~R5 is independently an aryl group having 6 to 12 carbon atoms or a aralkyl group X1 having 7 to 13 carbon atoms, which is a single bond, a carbonyl group or a **-CONH-; X2~ X5 respective bond, ore group, **-CH, CO- or **-CH"CH(OH)-; ** bond and 峨卩 ring bond, * linkage and polyorganooxane Skeleton I chain linkage) ° 1 6 The polyorganooxyalkylation of the 144th aspect of the patent application is a structure represented by the following formula U-2') (R6)n (In the formula (A-2), R6 is a main chain or a side compound in which the number of carbon atoms is from 1 to 16 and the number of carbon atoms is from 3 to 2, and the carbon atom is independently a unitary group. Wherein the E group, wherein, -110- 201144361, the alkyl group may have an oxygen atom, a sulfur atom, a carbonyl group, an ester group or a combination of two or more of them in the skeleton chain; n is an integer of 0 to 4; ;* indicates that the linkage is bonded to the main or side chain of the polyorganosiloxane skeleton). A polyorganosiloxane compound according to claim 14 of the patent application, wherein the aniline structure is a structure represented by the following formula (Α-3'), (In the formula (Α-3'), 'R7 and R8 are each independently an alkyl group having 1 to 16 carbon atoms' wherein 'the alkyl group may have an oxygen atom, a sulfur atom 'carbonyl group, an ester group or the like in the skeleton chain A group in which two or more of them are combined; a bond represented by * is bonded to a main chain or a side chain of a polyorganosiloxane skeleton). -111 - 201144361 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 〇 / \ w 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: