TW201237069A - Liquid crystal display element and alignment agent - Google Patents

Abstract

The object of the present invention provides a vertical alignment liquid crystal element using a positive liquid crystal satisfies general demanded properties, such as voltage retentivity, light resistance, etc. and has short electrooptical response time. The present invention is a liquid crystal display element which is equipped with a pair of substrates that are arranged opposite to each other, a liquid crystal layer that is arranged between the substrates, a pair of liquid crystal alignment films that are arranged on two surfaces of the liquid crystal layer, and an electrode for a lateral electric field generating among at least one of a pair of the substrates; wherein, the liquid crystal layer comprises a positive liquid crystal and the liquid crystal alignment films are formed by a liquid crystal alignment agent that comprises [A] a polymer having a group represented by the following formula (A1).

Description

.201237069 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a liquid crystal display element, and to an antibacterial agent and an alignment agent. In detail, the alignment agent, the octagonal component (LCD), and the alignment agent J agent are suitable as a material for forming the liquid crystal. 4 Prior Art Liquid Crystal Alignment Film [Prior Art] As a "70" that can cope with high-angle positive liquid helium, it is known to be used. Bu, f ^ liquid daily display (refer to the above-mentioned liquid crystal of the patent literature) The display element can be expected to be used as a device for illuminating a mobile phone or a liquid crystal TV. Therefore, in order to smoothly display the moving surface and suppress the afterimage as much as possible, it is required to realize the reaction of the electro-optical effect. - Speeding up. However, the vertical alignment liquid crystal display element using a positive type liquid crystal has a slow liquid crystal reaction rate when a voltage is applied (see Non-Patent Document 1). In response to this problem, a technique for improving the polymer side chain to be used for the liquid crystal alignment film by dielectric anisotropy has been reported (see Patent Documents 4 and 5). However, this patent document relates to a horizontal alignment element using a positive liquid crystal or a vertical alignment element using a negative liquid crystal, and the vertical alignment element using the positive liquid crystal of the present invention has not been studied. In view of such a situation, it has been desired to develop a vertical alignment liquid crystal display element using a positive type liquid crystal which satisfies characteristics such as voltage holding ratio and light resistance which are generally required for liquid crystal display elements, and has a short electro-optical reaction time. -4- • 201237069 [Prior Art Document] [Patent Document] [Patent Document 1] 曰本特开平1 0 _ 3 3 3 1 7 1 [Patent Document 2] 曰本特开平丨〇_丨6丨丨[Patent Document 3] Japanese Patent Laid-Open Publication No. Hei. No. 2 - 2 5 8 3 4 [Patent Document 4] 曰本特表2〇〇7_521 361 [Patent Document 5] 曰本特表2007- [Non-Patent Document] [Non-Patent Document 1] T_Sakurai et al., SID 2010 DIGEST pp. 721-724 [Summary of the Invention] The present invention has been made in view of the above circumstances, and an object thereof is to provide a A vertical alignment liquid crystal element using a positive liquid crystal satisfies general requirements such as voltage holding ratio and light resistance, and has a short electro-optical reaction time. [Means for Solving the Problem] The invention developed to solve the above problems is a liquid crystal display device comprising: a pair of substrates disposed oppositely, a liquid crystal layer disposed between the two substrates, and two surfaces disposed on the liquid crystal layer a film and an electrode for a transverse electric field of at least one of the pair of substrates; wherein the liquid crystal layer contains a positive liquid crystal and the liquid crystal alignment film is a liquid crystal alignment agent (hereinafter sometimes The liquid crystal alignment agent contains [A] a polymer having a group represented by the following formula (A1) (hereinafter sometimes referred to as "[A] Polymerization. 201237069 (hereinafter referred to as "liquid crystal alignment agent (A)"). A 1) R3—fR2-]-R1 ——

Ja, an alkylene group having 2 to 30 carbon atoms, a part or a bond of a nitrogen atom, a triple bond, an ether bond, an ester bond, and a group. R3 is at least two monocyclic rings (in the formula (Al), R1 is a methylene-phenylene group or a cyclohexylene group. These may be substituted. R2 is a hydrazine structure containing any one of the oxygen atoms. A is 〇 or 1.) The liquid crystal display element crystal of the present invention, and the liquid crystal alignment film is generally required to have a retention ratio and light resistance of a liquid crystal having a specific structure as described above. In the case of the liquid crystal layer, the liquid crystal layer contains a positive-type liquid agent, and the liquid crystal alignment agent contains a polymer, so that it can satisfy both the voltage characteristics and the short electro-optical reaction. The liquid crystal alignment film is more apron, and the vertical liquid crystal alignment film is formed. . By using the liquid crystal display film of the liquid crystal display element, the liquid crystal alignment film used in the liquid crystal alignment film is a cottering film and a crystal matching film, so that the macroscopic 6A ^ aa ^7 L can easily and realistically form a liquid crystal layer of a transverse electric field mode. , can effectively play the above characteristics of Bu Ping. R3 in the above formula (A1) is estimated to be I \ 佳 preferably expressed by the following formula (A2) '(A2) (in the formula (A2), R4 is a stretching cage, a methyl group, a biphenyl group, An anthranyl group, a cyclohexylene group, a dicyclohexyl group, a stretching group or a divalent heterocyclic group. This knife or all may be substituted. R5 is an agaride containing a substituent. — T base and slave atom number 2 to 1 〇 of an alkyl group, a double bond, a triple bond, an ether bond, an ester oxime, and a heteropoly group, at least one of the groups. R6 is stupid. (c+ i) obtained by removing the (c+ 1)th atom from the naphthalene, cyclohexane, bicyclohexane, cyclohexylbenzene or heterocyclic compound. 201237069 Part or all can be substituted The basis of the price. This group has a hydrogen atom of j; human king-·^ "j rice substitution. Rule 7 is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group, Alkoxy, trifluoromethoxy or alkylcarbonyloxy. An integer of 1 to 9. d is 1 or 2. r4 p5 d 7 乂R, R, R and b are each plural Next, the plural numbers R4, R5, and R7 are b h ώ γ t Κ And b may each be the same or different.) According to the liquid crystal display element, Chuang Shi &&& m ^ error is caused by the above-mentioned R31 dextran in the [A] polymer contained in the liquid crystal alignment agent used The specific structure, so that the above effects can be improved in one step. The [A] polymer is preferably one and has a polymorphic structure. With respect to the liquid crystal display element, +, and 5, since the [A] polymer has a polyorganosiloxane structure, light resistance can be improved. The liquid crystal is aligned with the above-mentioned liquid crystal; the dried _ & Μ Μ 佳 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少It is called "[B] polymer"). Πw by using the liquid crystal alignment agent used for the liquid crystal display to further contain [B] polymer, p & π & y ^ ^ ^ iX A Μ - ^ ° obtained by changing the mouth The solution of the liquid crystal alignment agent and the electrical characteristics of the obtained liquid crystal display element. Preferably, the [B]l compound is a diamine containing a cholesteryl group, a diamine containing a bilisyl group, or a η2ν η2ν ο- H2N<=^- Obtained as a diamine.

CrH2r+1 (Α-1 -coo(- or (-〇二)〇, ^ and Χ" each white is independently a single bond, -〇-, . Extracted as two sub/base or carbon number 2 Or an integer of 3 of 1. The absence of α and β is 0 ό 201237069. 丫 is an integer of 1 to 20.) For the liquid crystal display element, the polymer obtained by μmin is used as [聚合物]Polymerity 0 The above-mentioned specific two can be used to improve the vertical alignment of the alignment agent of the present invention, the alignment agent for positive liquid crystals, and the polymer λ represented by (Α1) is a transverse electric field mode liquid crystal display device. For containing [Α] with the following formula

(A 1) (In the formula (Α1), R1 is a part of a hydrogen atom possessed by a sulfhydryl group, a thiol group having a counter atomic number of 2 to 30, or a sulfhydryl group; or R2 is a base containing a 结构_® v. , A. 7 bond, a double bond, an ether bond, an ester bond, and any of the ', one of the taxi structures. a is 〇 or! The soil has at least two single-ring 5 hai aligning agents and may preferably be a working aligning agent. The polymer having the specific structure described above has a positive liquid crystal which is only for the electric-% liquid crystal display element. [Effects] The omnidirectional alignment of the alignable liquid crystal display device can satisfy the voltage retention rate and improve the liquid crystal reaction speed. In addition, the present invention is used as a directional liquid crystal display device. The liquid crystal display device of the present invention is a liquid crystal display device comprising: a pair of substrates disposed oppositely, a liquid crystal layer disposed between the two substrates, and a liquid crystal layer disposed on the liquid crystal layer a pair of liquid crystal alignment films on both sides, and a pair of substrates 5 in the pair of substrates An electrode for generating a transverse electric field of at least one of the substrates; wherein the liquid crystal layer contains a positive liquid crystal and the liquid crystal alignment film is formed of a liquid crystal alignment agent containing [A] having the following formula (A1) The polymer of the group shown. The liquid crystal display element of the present invention can be produced, for example, by the following (丨) and (2).

[(1) Step J First, a liquid crystal alignment agent (A) is applied onto a substrate, and then the coated surface is heated to form a coating film on the substrate. This liquid crystal alignment agent (A) will be described later. Two substrates having electrodes for generating a transverse electric field on at least one of the substrates are formed as a pair on the substrate or in the case of having electrodes on the electrode forming surface, preferably by a plate printing method, The liquid crystal alignment agent (A) is applied by a coating method or an inkjet printing method, and then each coated surface is applied to form a coating film. Here, since the liquid crystal display element of the present invention has excellent printing properties, it is preferable to use a stencil printing method or an ink jet printing method as a coating method from the viewpoint of maximizing the excellent effects of the present invention. Here, as the substrate, for example, glass such as float glass or nanoglass can be used, and polyethylene terephthalate, polybutylene terephthalate, poly(tetra), polycarbonate, and poly(ester) can be used. A moon-permeable substrate made of plastic such as a ring-shaped hydrocarbon. As the transparent conductive film of the _ plane of the substrate, an oxidized kick (Sn〇2) can be used (American ppG company registered trademark) 201237069, and an IT ruthenium film containing indium oxide-tin oxide (IhUnO2) can be used. In order to obtain a patterned transparent conductive film, for example, a method of using a photomask having a desired pattern in forming a transparent conductive film by forming a transparent conductive film without a target (4) transparent conductive film may be used. Wait. When the liquid crystal alignment agent is applied, in order to further improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, it is also possible to apply the coating on the surface of the substrate to the top of the substrate without coating. Pretreatment of g-energy decane compounds, functional titanium compounds, and the like. As the electrode for φ ± J_ for the lateral electrolysis, it is preferable to use a transparent conductive film patterned by a comb type. After the application of the liquid crystal alignment agent ^A (A), the Herd & x rut is preferably subjected to preliminary heating (prebaking) for the purpose of preventing the applied liquid from sagging. The prebaking temperature is preferably 30. (: ~ Sichuan rrr 丄 丄 ~ W ~ 2 〇〇 C 'better 4 〇〇 c ~ 15 for 4 (TC ~ 100t. Pre-twisted secret spit called heart top nine, roasting time is better 〇 · 25 minutes ~ 1 〇 minutes, preferably 0.5 minutes to 5 minutes. Main 饴 - After eight, Yuan Quan removes the solvent, and performs the firing (post-baking) step as needed, s μ * 佩而要贯# - ~ ^ The phthalic acid contained in the polymer is pre-set to enthalpy, _ 匕. The firing (post-baking) temperature is preferably from 8 〇 t to 300 C, more preferably 120 V, cr». C~2 5 0 C. The post-baking time is preferably 5 minutes to 200 minutes, and more preferably 1 to 8 pull-barrels for raising 1 boring tool for 4 minutes to 1 minute. By means of the film thus operated The film thickness is preferably Α ΛΛ ΛΛι , 知 铖 形 ΟΟΟΙ ι ι ι ι ι ι χ χ χ χ χ 。 。 。 。 。 。 。 。 。 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于The alignment film is used for the primary film. The 疋 can also be subjected to the rubbing treatment as desired. I/% [(2) Step] -10- 201237069 Two sheets of the substrate in which the liquid crystal pairing is formed as described above are prepared. Match When the liquid crystal is applied to the coating film, the rubbing directions in the coating film are arranged at a predetermined angle or in an antiparallel manner. In order to arrange the liquid crystal between the substrates, for example, the method is as follows. The method is a method known in the art. The first crystal alignment film is in a facing manner and is interposed in a gap (the cells are arranged in opposite directions, and the two substrates are sealed to the cell gap between the substrate surface and the sealant by a sealant, and then sealed). The second method of forming the liquid crystal cell by injecting the injection hole is a technique called a 〇df (liquid crystal Fill) method, and coating a predetermined portion on a substrate on which a liquid crystal alignment film is formed, for example, an ultraviolet material is advanced on the liquid crystal alignment film surface. The crystal film is applied dropwise to the opposite side of the substrate, and the entire surface of the substrate is irradiated with ultraviolet light to harden the sealant, so that the liquid crystal cell is better heated based on any method. To the temperature of the isotropic phase used, and then slowly cooled to room temperature, the flow alignment during the incorporation. ^ Then, the outer surface of the liquid crystal cell is bonded to the present invention. Liquid crystal display element. Here, as the sealing agent, for example, a liquid crystal cell can be produced by using a substrate containing a film, and the two substrates are, for example, orthogonal to each other, and the liquid crystal gap is used for each liquid cell gap. The peripheral portions of the two substrates are bonded together, and the liquid crystal cells are filled with a liquid crystal, and the liquid crystal cells which are photocurable in the one drop of the One Drop are liquid-celled on the substrate. The manufactured liquid crystal is obtained in an orientation to remove the liquid crystal light-emitting plate, thereby obtaining a hardener and an epoxy resin which is an alumina ball of -11 - 201237069 as a spacer.

As the positive liquid crystal, a nematic liquid crystal and a smectic liquid crystal may be cited, and among them, a nematic type is preferably used, and for example, a Schiff type liquid crystal or an oxidized azo may be used. Liquid crystal, ρ% ρ liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, ditrim liquid 曰 — 甘 甘 颂 颂 颂 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日Two of burning, a square sinking liquid crystal, bicyclooctane liquid crystal, standing

A square-burning liquid crystal, a liquid crystal having a positive dielectric phase, and a blended liquid crystal of at least one of a fluorinated liquid crystal and an cyano liquid crystal. The polarizing plate which is bonded to the surface of the outer surface r of the liquid crystal cell is exemplified by the fact that the polyethylene glycol is used to absorb the iodine. The polarizing film is obtained by sandwiching the obtained polarizing plate with a conjugated ketone, a cymbal and a cellulose protective film, or a polarizing plate formed of the ruthenium film itself. <Liquid crystal alignment agent (Α) &gt; The liquid crystal alignment agent (Α) used in the formation of the liquid crystal alignment film of the liquid crystal alignment film of the present invention contains the right "A1 sees Shih [A] A polymer having a group represented by the above formula (A1). Further, the liquid crystal alignment time exceeds 丨丨, and A, ·5τ yv μ gate 41 丨(Α) may contain other polymers such as [Β] polymer described later. "." Further, the liquid crystal alignment agent (Α) may contain other components in a range not impairing the effects of the present invention. This liquid crystal alignment agent (4) exhibits vertical alignment. Each component will be described in detail below. &lt;[Α]Polymer> [Α] The polymer has a group represented by the above formula (Α1). [Base represented by the above formula (Α1)] The above formula (Α1) is a methylene group, an alkyl group having 2 to 2 carbon atoms, a phenyl group or a hexyl group. Some of the hydrogen atoms of these groups -12- 201237069 or all may be substituted. Examples of the alkylene group having 2 to 3 carbon atoms represented by the above R] include an exoethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an exopeptide group, and a decyl group. Exomethyl, undecyl, dodecyl, tetradecyl, hexadecanyl, octadecyl, nonadecyl, eicosyl, icosyl, behenyl , betratrialkyl, tetracosyl, dipentadecyl, dihexadecyl, hexadecyl, octadecyl, octadecyl and eicosyl and the like. Among them, in order to stably exhibit the daily alignment, it is preferred to extend the octyl group, extend the sulfhydryl group, extend the fluorenyl group, eleven alkyl group, deca-alkyl group, tetradecyl group, cetyl group, octadecane. The number of the charcoal atoms such as the base of the nineteen-cylinder and the tenth yard base is 8 or more and 2 or less. R is a hydrazine containing 雔 ^ : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : A succinyldiyloxy group, a thiol group, a dimethyl group, or a dysentery may be combined with each bond and may contain any of the above-mentioned bonds, but in the case of the formation, /b' R is the viewpoint of the basis of the stretching or the cyclohexyl group, the orientation of the r2 ° film, and the solvent in the solvent. Also, a is. : Hey. The parent has a carbon number of 1 to 3. The alkylene group has two bases having a single ring structure, preferably the dielectric anisotropy of the exhibitor, and the horse appears positive or standing on the other ring structure and the two single ring structure means The ring structure is unique to the ring structure, does not have, and the bond of one ring structure and the other as a single ring structure, can be two: the structure of the fused ring structure. Further, the &lt;^ ring structure, the aromatic ring structure, and the miscellaneous ' in the ring structure may be combined. -13- 201237069 'R7) rR6_{R5VR4 As long as R3 is a group having at least two or more single ring structures, it is not particularly limited, but the cross is preferably a group represented by the following formula (Μ2), (A2) (the above formula) In (A2), 'R4 is a phenyl extended group, a phenylene group, a hexanyl group, a hexanyl group, a phenyl group or a divalent heterocyclic group. These groups have a hydrogen atom - Part or all may be substituted. R5 is at least one of a methylene group having a substituent and a alkyl group having a carbon number of 2 to 〇, a double bond, a triple bond, an ether bond, a dragon bond, and a heterocyclic group. Any one = linking group. R6 is a group of c 1 mussels obtained by removing (c + i) hydrogen atoms from benzene, biphenyl, naphthalene, cyclohexane, bicyclohexyl hexyl stupid or heterocyclic compound. Part or all of the hydrogen atom possessed by this group may be substituted. R is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxy rotyl group, a pyridyl group, a methoxy group, and an r:翁 mg - fluoromethoxy or alkylcarbonyloxy. b is 0 or Bu C is an integer from 1 to 9. Or 2. Each of R, R5, r7 and b is plural, and a plurality of R4 'RS, R7 And b may each be the same or different. 导入 The electro-optical of the obtained liquid crystal display element can be obtained by introducing a group represented by the above formula (A2) into the side chain of the [A] polymer contained in the liquid crystal alignment agent. In the formula (A2), a phenyl group, a phenyl group, a naphthyl group, a fluorene φ py· hexyl group, a dicyclohexyl group, a cyclohexyl group or a divalent hetero The ring group is referred to as &amp; 1 μ 丞 as the divalent heterocyclic group, and examples thereof include an acridine group, a fluorenyl group, a pyrimidinyl group, etc. In the above formula (Α2), 'R5 is a group which may have a substituent. The fluorene group and the carbon atom number 2~1〇 of the stretching group, the double bond, the triple bond, the (4), the vinegar bond to the -14-201237069 and the miscellaneous soil base of the $, the 丨, the red master y any one of the links The connection of R4 and R6 is appropriately selected according to the enthalpy, the base, and the anisotropy of the [A] polymer, and the dielectric anisotropy. As R5 'exemplified, it is listed as a mosquito. Methane diyl, ethane diyl, propane diyl, ethylene diyl, ethyl fry &gt; - loading, mono-, ether, ester, methanediyloxy, ethidium-oxyl, It is preferably a ethane-alkyloxy group, a difluorodecanediyloxy group, etc. Among them, ethane-罝^14, ^G-shenyl group, acetylenediyl-ester group, decane-dioxy group are preferred. Base, 'one gas brothel two base 4 A rolling base. Also, since b is 〇 or 1, it may or may not contain r5 in the design of the side chain structure. In the above formula (A2), R6 is from Benzene, biphenyl, naphthalene, cyclohexane, bicyclohexanyl, cyclohexylbenzene or a heterocyclic compound. (4) The base of m. The integer of ...~9. In the case of R6, ==, +, D 4 τ _ is the same as the base of the divalent group exemplified as the above R. In the above formula (A2), R7 is a hydrogen atom, an aryl group, a gas atom, a trimethyl fluorenyl group, an alkoxycarbonyl group, an alkyl group, an alkoxy group, a 4-methoxy group or an alkylcarbonyloxy group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group; and examples of the alkyl group include a carbon group such as a mercapto group, an ethyl group, a propyl group, a n-butyl group, and an isobutyl group. The linear or branched alkyl group having an atomic number of 〜2〇 is exemplified, and examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group and the like. In the above formula (A2), when R6 has a plurality of substituents (R7), it may be used by combining different substituents. In the case where R6 has a plurality of substituents, in order to stably exhibit a desired dielectric anisotropy, the plate is preferably a combination of a fluorine atom and a cyano group, a combination of a fluorine atom and a burnt group, and a cyano group and a burnt group. The combination. Further, c is an integer of 1 to 9. -15-.201237069 [A] If the polymer contains a group having a structure represented by the above formula (A1), a known polymer backbone can be appropriately selected, but from the viewpoint of electrical properties, it is preferred to use a polyorganoindene. Oxane, polyimine, polyglycolic acid, polyacrylate, polymethacrylate, poly(styrene-phenylmethyleneimine) derivative, cellulose derivative, polyester, poly The main chain structure is made of decylamine, polystyrene derivative, and polyglycolate. From the viewpoint of light resistance, it is preferably a polyorganosiloxane (hereinafter, sometimes referred to as "(5) polyorgano-oxygen compound) "). In the case where the liquid crystal alignment agent contains an oxyalkylene structure, it is preferred that the [A] polyorganosiloxane compounded organic oxoxane portion of the [A] polymer has a polyorganismite: contains [a a polyorganosiloxane compound having a polysiloxane derived from an epoxy group

And a compound having a carboxyl group which is not represented by the following formula (A1_C, τ ^ ) (hereinafter, sometimes referred to as "specific carboxy 3 Γ , 1 , % & J ), R4R2lr-Rl-ir-〇H f Ο (A 卜 c) In the above formula (A1-C), R1 loses a sulphur group, a phenyl group or a cyclohexyl dimethyl group, and a part or all of carbon atoms of 2 to 30 may be substituted. r2 ^ One of the hydrogen atoms of the group and one of the oxygen atoms containing a double bond, a triple bond, a scaly bond, or a vinegar monocyclic structure. a is a ruthenium or a ruthenium. R3 has at least two Among the above-mentioned liquid crystal alignment agents, a liquid crystal display element derived from the above-mentioned specific compound (4) having a structure in which a silicon oxide has a dielectric anisotropy and a liquid crystal alignment film which can be introduced into a side chain is used. The formation of the liquid crystal alignment agent further improves the electrical characteristics and the image characteristics of the residual-16*201237069, and further shortens the reaction time. Further, by utilizing the reactivity between the epoxy group and the rebel group, it is easy to aggregate into the main chain. Organic anthracene is introduced into a side chain having a structure having dielectric anisotropy represented by the above formula (A1-C) &lt;[a] Polyorganosiloxane compound&gt; [a] The polyorganosiloxane compound has a polyorganooxime-derived moiety derived from an epoxy group, and is derived from the above formula (A1 - C) a part of the specific carboxylic acid shown. The [a] polymer contained in the liquid crystal alignment agent (A) has a structure having a dielectric anisotropy in the side chain because of having such a specific structural unit. The liquid crystal display element of the liquid crystal alignment film formed using the liquid crystal alignment agent further improves electrical characteristics and afterimage characteristics, and further shortens the reaction time. Further, by utilizing reactivity between the epoxy group and the carboxyl group, it is easy to The polyorganosiloxane which is a main chain introduces a structure having a dielectric anisotropy represented by the above formula (A1) as a side chain. It is considered that the [a] polyorganosiloxane compound can mainly be a polyorganosiloxane. Obtained from the manner in which the epoxy group reacts with the carboxyl group of the specific carboxylic acid, but is conveniently divided into polyorganosiloxanes (and derivatives thereof) having an epoxy group in order to facilitate the subsequent description. Part and origin The acid moiety is used to describe the [a]zero organooxane compound contained in the liquid crystal alignment agent (A). [Derived from the polyorganosiloxane having an epoxy group] The concept of this Zoufen includes: [a a polyorganosiloxane skeleton as a polymer main chain among the structures of the polyorganosiloxane compound, and an epoxy group-containing skeleton which is a side chain extending from the main chain of the organic oxime. -17- 201237069

The organic sand oxide says that most of the compound does not have its original structure, but also the case where a specific carboxylic acid is bonded to a moiety other than the epoxy group. Therefore, the form including the two forms in the present invention is referred to as "the portion derived from the polyorganosiloxane having an epoxy group". u] The polyorganosiloxane compound further increases the electrical properties such as the alignment property and the voltage holding ratio of the liquid crystal alignment agent (A) by including a portion derived from polyorganosiloxane, and the polyorganosiloxane has An epoxy group such as a glycidyl glycidyloxy group or an epoxycyclohexyl group. The epoxy group is preferably a group represented by the following formula (χ^Ι-Ι) or formula (乂丨-2-1). By containing a polyorganosiloxane having a structural unit represented by the above formula (A1), a polyorganoquinone compound which is easily attached to the liquid crystal alignment agent (A) by containing a base of the following formula or Introducing a side chain group derived from a compound having a specific structure represented by the above formula (A 1),

In the above formulas (X^l-1) and (χΐ_2_ι), * represents a connection key. The polyorganosiloxane having an epoxy group is preferably a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) of 500 to 100,000 ', more preferably 1,000 to 50, 〇〇〇 , particularly preferably from 1,000 to 20,000 201237069 [Synthesis method of polyorgano oxo-oxygen with epoxy group] Such a group having a ring gas group (4) is synthesized as follows: a copolymer having an epoxy group or The star-derived decane compound is preferably an organic solvent: a mixture of the two compounds. Hydrolysis or hydrolysis in the presence of a ruler and a catalyst. The condensation is as described above for the right-glycidyloxy group: a gas-burning compound, for example, 3-propyltriethoxy-p-tris-methoxyethanol, 3-glycidyl-oxygen Base (4), % condensed succinate' condensed ganyl propyl dimethyl methoxy: glyceryl ethoxypropyl dimethyl methoxy: = propyloxy, 2 _ glycyoxy - one, water甘_基乙三乙上= : = ::基:::基基氧—shrinking water, 广水水(四)ylethyl dimethyl ethoxy ether ether A dingyi-% rolling butyl Dioxadecane, 4-condensed, hydrated dimethyl i: ethoxy decane, 4' glycidyl ether oxybutyl amide, 4 dihydrate glycidyl oxybutyl methyl diethoxy Water... 氧基 oxybutyl dimethyl methoxy sylvestre, 4-condensed glyceryl ethoxy butyl butyl group, ethyl methacrylate 2-(3,4-epoxycyclohexyl: two 3 3 4 Μ, 2 buy 氡 氡 氡 己 ) ) ) 基 基 基 基 基 丙基 丙基 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 For having a 矽 original as the above a compound of a decane compound thereof, and as another decane compound having four hydrolyzable groups, examples include tetrachlorite, tetramethoxy 7-burn, tetraethoxy-oxide, tetra-n-dioxane, and tetra. a tetraalkoxy decane such as isopropoxy decane, tetra-n-butoxy decane or tetra-n-butyl fluorene, and the like, and other decane compounds having three hydrolyzable groups are exemplified by trichloromethane or the like. a decyloxy decane such as trimethoxy decane or triethoxy decane; fluorotrichloro decane; fluorotrimethoxy decane such as fluorotrimethoxy decane or fluorodiethoxy decane; An alkyltrioxane such as trioxane; an alkyltrialkoxydecane such as methyltrimethoxydecane or methyltriethoxydecane; or a fluorine such as 2-(trifluoromethyl)ethyltrioxane Alkyl trioxane; 2-(trifluoromethyl)ethyltrimethoxydecane, 2-(difluoromethyl)ethyltriethoxydecane, etc., fluoroalkyltrialkoxydecane, hydroxymethyldi Hydroxyalkyl trioxane such as chlorodecane; hydroxymethyltrimethoxy decane, hydroxyethyltrimethoxydecane a hydroxyalkyltrialkoxydecane; a (meth) propylene decyloxyalkyltrichloromethane such as 3-(indenyl) propylene oxypropyl trioxane; a 3-(indenyl) propylene oxy group (methyl) propylene oxyalkyltrial alkoxy oxane such as propyltrimethoxydecane, 3-(indenyl) propylene oxypropyltriethoxy decane; decylmethyltrioxane, 3 - mercaptoalkyl trichloromethane such as mercaptopropyl dioxane; mercaptodecyltrimethoxydecane, mercaptodecyltriethoxydecane, 3-mercaptopropyldimethoxydecane, 3 - a mercaptoalkyltrialkoxydecane such as mercaptopropyltriethoxydecane; an alkenyl trioxane such as vinyltrichlorodecane or allyltrichloromethane; vinyltrimethoxydecane, vinyltriethyl Oxyl-20-201237069 夕夕烧, allyl succinyl triethoxy phenyl trimethoxy decane, etc.; dimethoxy oxalate decane; phenyl trioxane, phenyl tri, propyl triethyl An aryl ethoxylate such as chlorite or the like; a trichloro decane such as an oxane or the like; an aryl trialkoxide: other having two hydrolyzable groups The ruthenium compound is exemplified by a calcined base gas such as =-gas, etc.; a methyldimethoxycarbazone: an alkyldioxycarbazone such as methyl-ethoxy oxacillin; dimethyldi= An alkyl alkyl alkoxy decane such as dimethyl dimethyl oxetane or dioxodecane; (fluorenyl) [2_(perfluoro-n-octyl) Ethyl dichloride, sulphur, etc., a gas-fired two-gas smelting; (soil) _[(Wang fluoro-n-octyl)ethyl]dimethoxy decane, etc. Oxygen oxime methyl) (3-sodium propyl) digas stone Xi Xi Yuan, etc., based on the sulphur-based base-based two-burning; (methyl) (3-sodium propyl) dimethoxy alcohol The base is sinter, the base is squid, and the oxyalkylene is burned; the (meth) (ethenyl) sulphuric acid is burned on the alkenyl chloride; the divinyl chlorite is burned. Etyl di-dioxanonane; alkenyl dialkoxy decane such as divinyl dimethoxy decane; diaryl dioxane such as diphenyl dioxane; diphenyl dimethoxy oxylate Diarylalkoxydecane, etc. as a water Other decane compounds of the nature include dialkyl chlorodecane such as chlorodiconyl decane; dialkyl alkoxy decane such as methoxy dimethyl decane; gas tridecyl decane and bromotrimethyl sulfonate. a trialkylcyclodecane such as decane or iododimethyl decane; a tri-yard alkoxy decane such as decyloxytrimethyl oxime; or a dialkyl olefin such as (chloro)(vinyl)dimethyl decane. a quinone-based alkoxy decane, such as a (nonyloxy) (vinyl) dimethyl decane, or a diaryl-21-201237069 alkyl (chloro)(methyl)diphenyl decane a base gas decane; a diarylalkyl alkoxy decane such as (decyloxy) (fluorenyl) diphenyl decane. As a commercial item, for example, KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21 are listed. -5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X-22-170DX , X-22-176B, X-22-176D, X-22-1 76DX, X-22-176F, X-40-2308, X-40-265 1, X-40-2655A, X-40-2671 , X-40-2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X -41-1053, X-41-1056, X-41-1805'X-41-1810'KF6001 'KF6002'KF6003' KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311 , KR401N, KR500, KR510, KR5206, KR5 230, KR5235, KR9218, KR9706 (above, Shin-Etsu Chemical Co., Ltd.);

Glass Resin (made by Showa Denko); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR240 5, SR2406, SR2410, SR24n, SR2416, SR24 2 0 (above, manufactured by Dow Corning); FZ371 1, FZ3722 (above, Japan) UNICAR system); DMS-S12, DMS-S15, DMS-S2, DMS-S27, DMS-S3 1, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS -S5 1, DMS-227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (above, manufactured by CHISSO); -22- 201237069 Methyl decanoate MS 5 1 , methyl decanoate MS 5 6 ( Above, Mitsubishi Chemical Co., Ltd.) Ethyl citrate 28, ethyl decanoate 40, ethyl decanoate 48 (above, manufactured by COLCOAT); Partial condensate found in GR100, GR650, GR908, GR950 (above, Showa Denko) Among these other decane compounds, tetradecyloxydecane, tetraethoxydecane, methyltrimethoxydecane, and methyl group are preferred from the viewpoints of the alignment property and storage stability of the obtained liquid crystal display device. Triethoxy zephyr, 3-(indenyl) propylene methoxy propyl trimethoxy oxime, 3 fluorenyl) propylene methoxy propyl triethyl Base decane, vinyl trimethoxy oxalate, vinyl triethoxy decane, allyl trimethoxy decane, allyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy Decane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, mercaptodecyltrimethoxydecane, mercaptomethyltriethoxyphosphonium monomethyldimethoxydecane, dimercapto Diethoxydecane. In order to introduce a polyorganosiloxane having an epoxy group which is preferably used in the present invention into a side chain having a dielectric anisotropy in a sufficient amount, the oxime epoxy equivalent is preferably 1 () 〇 〜 1 () , _g/mole, more preferably ΐ5 (κι measured, g/mole, therefore, in the synthesis of precursors of organic oxane with epoxy groups, A decane compounds and other decaneated σ The ratio of use is preferably set in the above range according to the obtained range of the above-mentioned range of the epoxy group-containing polyorgano oxysulfonated ring gas. In the case of a polyorganosiloxane having an oxy group, it is more preferred to use only a decane compound, and not to use other shi shou compounds. -23- 201237069 As a polyorgano having an epoxy group Examples of the organic solvent that can be used in the case of the oxane are, for example, a hydrocarbon compound, a ketone compound, an ester compound, an ether compound, an alcohol compound, etc. Examples of the hydrocarbon compound include, for example, benzene, xylene, and the like; 'For example, list Methyl _, methyl isobutyl ketone oxime As the above-mentioned vinegar, for example, ethyl acetate, n-butyl acetate, isophthalic acid acetate: early morning, acetic acid vinegar, 3, methoxy butyl butyl ketone The acetic acid vinegar, the lactic acid B, and the oxime compound are the upper phase compounds, and examples thereof include ethylene glycol dimethyl sterol diethyl ether, tetrahydrofuran, and dimorphic human acid, and the like. P-hexyl alcohol, 4-methyl ether, ethyl-hydrazine sr decyl-2-pentanol, ethylene glycol monobutyl I soap ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, and c*—previously positive propyl alcohol monomethyl ether, propylene glycol based bond, etc. Among them, it is preferably water-insoluble organic=alcohol mono-propyl-acrylic solvent which can be used alone or in combination of two or more. The amount of the organic solvent to be used is 10 parts by mass to 1 part by mass, based on 10 parts by weight of the hydrazine compound, and 1 part by mass, and 〜uoo parts by mass. The epoxy resin is more preferably 50 parts by weight. The amount is relative to human β soil, ♦ organic decane when the water is in the ear and for the whole decane compound is ear, better A〗 is poor e initial power is 0 .5 times the molar amount to 100 times the molar amount is 1 times the molar volume to 3 〇 times the molar. As the above catalyst, for example, the alkali, the titaniumized person, the human alkaloid metal compound, the yttrium compound, the cerium compound, the cerium compound The above-mentioned alkali metal compound is, for example, potassium oxide, and the like, such as sodium hydride, hydrogen: (1), methanol unloading, ethanol sodium, ethanol unloading, etc. ', the organic base' can be, for example, ethylamine, Diethylamine-24-201237069, 1~2 organic amines such as piperazine, piperidine, pyrrolidine, pyrrole, etc.; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-di-methylamino a ternary organic amine such as pyridine or di-sigma-bicycloundecene; a 4-grade organic amine such as tetramethylphosphoric acid; etc. From the viewpoint of smooth progress of the reaction, among these organic bases, triethylamine and tris are preferred. a tertiary organic amine such as n-propylamine, tri-n-butylamine, pyridine or 4-didecylaminopyridine; or a 4-grade organic amine such as tetramethylammonium hydroxide. As a catalyst for producing a polyorganosiloxane having an epoxy group, the car is a metal compound or an organic test. By using a metal compound or an organic base as a catalyst, side reactions such as ring opening of an epoxy group do not occur, and the desired polyorganosiloxane can be obtained at a high hydrolysis/condensation rate, so that the production stability is excellent. good. Further, a liquid crystal alignment agent (Α) containing a polyorgano-oxygenated gas having an epoxy group synthesized using an alkali metal compound or an organic base as a catalyst is extremely excellent in storage stability, and thus is convenient. use. The reason can be presumed as follows: As indicated in Chemical Reviews, Vol. 95, p. 1409 (1995), when an alkali metal compound or an organic base is used as a catalyst in hydrolysis or condensation reaction, a random structure and a ladder type are formed. According to the structure or the basket structure, a polyorganosiloxane having a small content of a stanol group can be obtained. It is presumed that since the content ratio of the base group is small, the condensation reaction between the base groups of the group is inhibited, and further, when the liquid crystal alignment agent (A) contains another polymer described later, the stanol group is used. The condensation reaction with other polymers is suppressed, and thus the storage stability is excellent. As the catalyst, it is particularly preferably an organic base. The amount of the organic base varies depending on the type of the organic test, the temperature-specific reaction conditions, and the like, and should be appropriately set. -25-201237069, for example, it is preferably a relatively good one, preferably a better one. Hey, hey 5 times Moh. Mohr ~ 3 times Mo when the polyorganooxime having an epoxy group is produced, the condensation reaction is carried out as follows: hydrolysis or hydrolysis of hydrazine is carried out as follows; and other money compounds are dissolved as needed. The solution and the organic base, as well as the water, the refrigerant, are used as follows. In the case of the hydrolysis/condensation reaction by heating, for example, an oil bath, it is more preferably 40 ° C to 10 Torr: or more preferably heated for 1 hour to 8 hours. The heating temperature of the oil bath is preferably 13 (TC' is preferably heated for 0.5 hours to 12 hours. During heating, the mixture may be disturbed. After the reaction is terminated, it is preferred to use an organic solvent layer which is separated from the reaction liquid by water. This washing is preferably carried out by using a water containing a small amount of salt, for example, an aqueous solution of an aqueous acid of about 25% by mass, so that the washing operation is easy to change. The water layer after the knee washing is carried out until the washing, and then the organic solvent layer is dried with an anhydrous calcium sulfate, a molecular sieve or the like, and then the solvent is removed to obtain the desired polyorgano group having an epoxy group. In the present invention, a commercially available product which is a polyorganosiloxane having an epoxy group can also be used. As such a commercially available product, for example,

DMS-E (H, DMS-E12, DMS-E21, EMS-3 2 (above, manufactured by CHISSO), etc. [a] The polyorgano oxy-oxygen compound may also comprise: a polyorganoquinone derived from an epoxy group. a portion of the hydrolyzate produced by hydrolysis of the oxyalkylene itself, and a portion of the condensate -26-201237069 obtained by hydrolysis and condensation of the polyorgano oxyhydrogen having an epoxy group. A,, the hydrolysis condensate may be synthesized in the same manner as these hydrolyzates and condensation conditions having a jffi _ reconstituted material. Hydrolysis of a gas-based polyorganosiloxane, [part of a specific acid-removing moiety] (A1) shows a side chain structure as a starting point, and this portion corresponds to a polyorgano oxo servant which will form a knot polymer from a slow group: (4) 矽 gh + 疋 5 contained in the liquid crystal alignment agent (4) In the structure of the substance, the structure of the self-long-oxyl group mainly extending from the main chain of the polyorgano-oxyxene is bonded to the carboxyl group. However, in the invention, a part of the acid acid and the epoxy group are also included. 'Weigh &amp; "portion derived from a specific m acid." About R丨~R3 of the above formula (A1) and as R3 The description of R4 to R7 of the group represented by the above formula (A2) is as described above. The compound having a rebel group represented by the above formula (A1-C) is exemplified by the following formula (D-1). )~(0-25) Compound, -27- 201237069 r3-(ch2)^cooh (D-1) R3-0-(cHz)^C00H (D-2) o R3-0—~(CH2 )^COOH (D-3) R3 fly^-(cH2)^COOH (0-4) r4ch4〇- 0 /_v R3_〇_(CH2^0· COOH (0-16) 0

•COOH (D-17) R3_〇^CH2)_j_〇^^~y_r3^cH2^\ ^~~c〇〇h (〇'6) 〇~^ ^~ R3-〇-(cH'/ m R3 =-(cH2)^COOH (D-5) COOH &lt;D-18) COOH (D-19) 0 » -COOH ( D - 7 ) R3 CH2 0 - COOH (D-20) OR3-. One L ( R3 CH^ -COOH (D-6) CHi

-COOH (D-9)

R3_〇4 bite R^2h〇^y COOH (D·21 &gt; COOH (D-22 &gt; COOH(D-23) .3-〇X(CH2)--〇^ ^)-( R3-〇 -fcH2)^—〇—^ COOH (D-12) r3〇Η2OyK-COOH ( D- 25) 〇〇/~\ R3-0—L(CH2)J—0—ί \—( -COOH (0- 13) COOH (D-14) -COOH(D-24) OR3^(cH2)-L〇COOH (D-15) In the above formulas (D1) to (D-25), R3 is the same as the above formula (Al) m is an integer of 1 to 30. The base represented by the above formula (A2) is, for example, a group represented by the following formula (E-1) to (E-123), -28-201237069

NC NC NC NC

(E-8) (E-9) £•10) (E-11)

-29- 201237069

-30- .201237069

R

N-N

(E-46) -31- -56)201237069

•57) •58) / 32- 201237069

-33- 201237069

F F

,. F F X X (£•89) (E-90) [E-91 ;

-34- 201237069

In the above formulae (E-1) to (E-123), R is an alkyl group having a carbon number of 20 or an alkoxy group having 1 to 20 carbon atoms. X is each independently a hydrogen atom or a fluorine atom 0. The alkyl group represented by the above R is, for example, a methyl group, an ethyl group, a propyl group, a n-butyl group, an isobutyl group, a n-pentyl group or a n-hexyl group. Examples of the alkoxy group represented by R described above include a decyloxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. [Synthesis Method of Specific Carboxylic Acid] The synthesis step of the specific k is not particularly limited, and can be carried out by a combination of a conventionally known method. As a typical synthesis step, for example, the following method is exemplified: (1) a compound having a phenol skeleton and a higher fatty acid S are substituted under the alkaline conditions according to their μ 丄κ + , β , and the violent chain portion is replaced by γ And the obtained compound reacts, and the phenolic skeleton of the phenolic skeleton forms a bond with the carbon substituted by the pixel, and then is cooled to form a method of preparing a quinone quinone; (2) The phenolic skeleton compound is reacted with yttrium sulphate G s 而 to form a terminal alcohol compound, and the hydroxyl group and the halogenated sulfonium sulfonate are activated only by the hydrazine reaction, and then the active-35-201237069 points Reacting with a hydrazinyl benzoate containing a mercapto group, whereby the detachment of the distilled portion occurs and the hydroxyl group of the terminal alcohol compound forms a bond with the hydroxyl group of the decyl decanoate containing a trans group as a substituent, followed by reduction of the ester. A method of producing a specific carboxylic acid or the like. However, the synthetic steps of the specific carboxylic acids are not limited to them. &lt;[a] Method for synthesizing polyorganic oxyhydrogenated compound&gt; As a method for synthesizing the [a] polyorgano oxysulfuric compound, there is no particular limitation, and it can be synthesized by a generally known method. The method for synthesizing a U] polyorgano oxy-oxygen compound having an epoxy group can be synthesized by reacting a polyorganosiloxane having an epoxy group with a specific carboxylic acid, preferably in the presence of a catalyst. . Here, the specific carboxylic acid is preferably used in an epoxy group with respect to the polyorganosiloxane. It is preferably used in the range of 〇.〇01 摩尔~10 摩尔, more preferably 〇01 摩尔~5 摩尔' further It is preferred to use 0.05 moles to 2 moles. In the present invention, 'a compound which is represented by the following formula (4) may be used in place of a part of a specific carboxylic acid in a range which does not impair the effects of the present invention. In this case, [a] a polyorganosiloxane compound is used. The synthesis is carried out by reacting a polyorganosiloxane having an epoxy group with a specific carboxylic acid and a mixture of compounds represented by the following formula (4). A1-L°-Li-2 (4) In the above formula (4), Αι is a linear or branched alkyl group having 1 to 3 carbon atoms, and may be an alkyl group having 1 to 20 carbon atoms or Alkoxy group-substituted cycloalkyl group having 3 to 10 carbon atoms or a group having 17 to 51 carbon atoms having a residue skeleton, wherein a part or all of the hydrogen atoms of the above alkyl group and alkoxy group may also be cyanide Substituents such as a fluorine atom or a trifluoromethyl group are substituted. -36- 201237069 L0 is a single button, -0-, -COO- or -OCO-. L1 is a single bond, a fluorenylene group, an alkylene group having 2 to 20 carbon atoms, a phenyl group, a phenyl group, a phenylene group, a cyclohexylene group or a formula (L1-:!) or (LL2) ) The base shown. Z is a monovalent organic group which can react with an epoxy group in the [a] polyorganosiloxane compound to form a linking group. Wherein, when L1 is a single bond, L0 is a single bond.

* (L1-2) * (L1-1) In the above formulas (1/-1) and (1^-2), the connection keys with * are combined with Z, respectively. Z is preferably a carboxyl group. Examples of the linear or branched alkyl group having 1 to 30 carbon atoms represented by A1 in the above formula (4) include a mercapto group, an ethyl group, a n-propyl group, an isopropyl group, and an n-butyl group. Secondary butyl, tert-butyl, n-pentyl, 3-methylbutyl, 2-methylbutyl, 1-mercaptobutyl, 2,2-dimethylpropyl, n-hexyl, 4- Methylpentyl, 3-methylpentyl, 2-mercaptopentyl, diphenylpentyl, 3,3-dimethylbutyl, 2,3-didecylbutyl, 1,3-dimethyl Butyl, 2,2-dimethylbutyl, 1,2-dimethylbutyl, 1,2-didecylbutyl, 1,1-didecylbutyl, n-heptyl, 5-methyl Hexyl, 4-mercaptohexyl, 3-decylhexyl, 2-nonylhexyl, 1-methylhexyl, 4,4-dimethylpentyl, 3,4-didecylpentyl, 2,4 -Dimethylpentyl, 1,4-didecylpentyl, 3,3- -37- 201237069 Dimercaptopentyl, 2,3-didecylpentyl, 1,3-didecylpentyl , 2,2_ _methylpentyl, 1,2-dimethylpentyl, ι,ΐ-dimercaptopentyl, 2:methylbutyl, 1,3,3-trimethylbutyl, 1 , 2,3-tridecylbutyl, τ: n-octyl, 6-fluorenylheptyl, 5-methylheptyl, 4-fluorenyl Base, 3-methylmethyl, 2-methylheptyl, 1-methylheptyl, 2-ethylhexyl, n-decyl, hydrazino, n-undecyl, n-dodecyl, positive Tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and the like.疋 is a cycloalkyl group having a carbon number of 3 to 10 which may be substituted by an alkyl group or an alkoxy group having a carbon number of 丨20 or more, and examples thereof include a cyclopentyl group, a cyclohexyl group, a &lt;% ag, and a cyclooctyl group. , cyclodecyl, cyclodecyl, cyclododecyl and the like.

The hydrocarbon group having a carbon number of 丨7 to 5 甾 having a steroid skeleton, for example, a group represented by the following formulas (H-1) to (H-3), J

A1 in the above formula (4) is preferably a burnt beauty selected from the group consisting of carbon atoms, a sulphate having 1 to 20 carbon atoms, and the above formula (^-. or (H_3)). -38-201237069 The compound represented by the above formula (4) is preferably a compound represented by the following formula (4-1) to (4-6).

CuF2u+i CvH2v — COOH (4-1}

CwH2W+i-COOH {4-2)

CwH2w+1 -

COOH

(4-3)

Ckhk+i (&quot;CFs \-COOH (4-4)

COOH (4-5) In the above formulae (4-1) to (4-6), u is an integer of 1 to 5. V is an integer from 1 to 18. w is an integer from 1 to 2 0. k is an integer of 1 to 5. p is 0 or 1. q is an integer from 0 to 18. r is an integer from 0 to 18. s and t are each independently an integer of 0 to 2, and more preferably a compound represented by the following formula (5-1) to (5-8), -39-201237069 C17H35-COOH (5- 1) (5-2)

—COOH

F3c-o f3c-c3h6-o (5-3)

(5-6) The compound represented by the above formula (4) is reacted with a polyorganosiloxane having a specific carboxylic acid and an epoxy group, and forms a portion of the liquid crystal alignment film which can be imparted with a pretilt angle. Compound. In the following description, the compound represented by the above formula (4) is sometimes referred to as a pretilt-developing compound. In addition to the fact that it is obtained from the above-mentioned "the -40-201237069 in the present invention t, and the specific (four)-the same use of the current compound hemp 6A ratio of the ^ ^ 显 / / · · · 生化 生化 生化 生化 生化 生化 生化 生化 生化 特^1 #, The pretilt angle of the gossip appears to be used in proportion to the polyorganooxane it is, and the pregnant father is good. 〇〇j Moer~15 Momo~i Moer, enter a calf ear More preferably, in the case of 0_01, the other pretilt angle-developing compound is preferably used in an amount of 75 mol% or less, more preferably in a range of (10) j疋, relative to the total of 2 acid. When the pot is more than 75 mol% below the mole/〇, the use ratio of the material is adversely affected. l The coercive aspect appears as a poly (4) oxygen with a (tetra)oxy group and a pretilt angle. The catalysts used in the ruthenium-containing compounds and the catalysts represented by the compounds can be used as the anti-deposits of the oxime-derived compound and the acid anhydride, or as a so-called hardening accelerator which promotes epoxidation as a secondary refractory. The compound is the above-mentioned organic base, such as column, Niangbitan, Candiedron® Q amine, ethylamine, piperidine, pyrrole, etc., j~2 grade propylamine, tris Ethylamine, tri-n-n-butylamine, pyridinium, 4-dimethylene face & undecene oxime + T-amino-amine oxime, dimethyl sulfonium 3-position organic amine; tetradecyl Etc. Among the organometallic amines of the 4-stage organic amines, it is preferably triethylamine, -τ=*butylamine, _, 4&lt;f &amp; λ - Μ, three positives Tertamine is 疋, tetramethylammonium hydroxide. 乍 is the above hardening accelerator, for example, benzyl monomethylamine, 2,4,6-tris I# T tyrosylmethyl) phenol, cyclodecyl-methylamine, triethanolamine, etc. 3-grade amine; 2-methylimidazole, 2-p-heptyl imidazole, its spider, z-n-undecylimidazole , 2-propenyl saliva, 2-phenyl-4-methyl-D-salt alley· _ 2 -methyl-meridene, 1 _ -41 - 201237069 benzylphenylimidazole, 1,2-didecyl Imidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)_2-methylimidazole, ι_(2-cyanoethyl)_2_正十-Hyunmi, 1-(2 -cyanoethyl)_2_phenylimidazole, ι_(2-cyanoethyl)_2_ethyl_4_methylmethane, 2 -phenyl-4-methyl-5-carbylmethyl pumi , 2 - stupyl _4,5_ bis (by fluorenyl) imidazole, 1-(2-cyanoethyl)-2-phenyl-4,5-di[(2,- yl ethoxy) fluorenyl Imidazole, 1_(2-cyanoethyl)_2-n-undecylidene is known as mono-acid, 1-(2-cyanoethyl)-2-phenylimylpyrene-trimellitic acid g ι·(2_Cyanoethyl)-2-ethyl-4-mercaptoimidazole trimellitate, 2,4-diamino-6-[2'-mercaptoimidazolyl-(r) Ethyl-s_trimorphine, 2,4-diamino _6_(2,_n-undecylimidazolyl)ethyl-s-triterpene, 2,4-diamino-6-[2 , _ethyl 4 - A Base succinyl _(ι')] ethyl _s_ trimorphine, 2-methyl acetonide isomeric acid addition product, 2-peptidyl imidazole isocyanuric acid adduct, 2 , 4-diamino-6-[2,-methylimidazolylethyl-s_three-pigmented isomeric cyanuric acid adducts, etc.; diphenylphosphine, triphenylphosphine, sub Organophosphorus compound such as triphenyl phosphate; benzyltriphenyl chloride scale, tetra-n-butylphosphonium bromide, methyltriphenyl evolution scale, ethyltriphenyl desert scale, n-butyltriphenyl Desertification: ,: base ruthenium bromide, ethyl triphenyl iodide scale, ethyl triphenyl squary acetic acid - 曰 tetra-n-butyl fluorene, 〇-diethyldithio silicate, tetra-positive a grade 4 scale salt such as butyl benzophenanthene salt, tetra-n-butyl quaternary tetrafluoroborate, tetra-n-butyl quaternary tetraphenyl phosphamate or tetraphenyl quaternary tetraphenyl borate; %[5·4·〇]_^--a dicyclobicycloolefin such as carbon·7-ene or an organic acid salt thereof; an organometallic compound such as zinc octoate, tin octylate or aluminum acetonide complex; -42- 201237069 Tetraethylammonium bromide, tetra-n-ethyl chlorinated bond, etc. Boron compound of gasification boron, Shi Peng brewing Erye, etc.; tin compound such as bismuth zinc, tin chloride, etc.; amine addition accelerator such as adduct of epoxy resin and epoxy resin Specifically, the same melting point-dispersion latent hardening accelerator; the above-mentioned microphone is composed of 4«v compound. I 2: a bismuth organophosphorus compound, a quaternary scale accelerator, a microcapsule-type latent amine salt type latent sclerosis promoter; Type:: abbreviated acid and other high temperature dissociation type of thermal cations ... U in the promotion of sexual hardening (four) latent hardening accelerators. Among these catalysts, 轫# &amp; mώ car is tetraethylammonium bromide, tetra-n-butyl', ditetraethylammonium hydride, tetra-n-butylammonium chloride, etc. (grade ammonium salt.匕d with respect to the polyorganooxane having a %oxy group of 100 00 = preferably less than a million parts by weight, more preferably from 0 to 01 parts by mass to 100% by mass, more preferably from 〇 by mass parts to 2 The reaction temperature of 〇 is preferably ot~2〇〇. (:, more preferably 5 (rc~15 (rc. 蚪 蚪 蚪 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 The synthesis reaction of the uranium oxysulfide compound is carried out in the presence of an organic solvent, as the above-mentioned organic solvent, for example, a hydrocarbon compound, a test compound, or a compound The compound, the amine compound, the alcohol compound, etc., among these, an ether compound, an ester compound, and a ketone compound are preferable from the viewpoint of the solubility of the raw material and the product -43-201237069 and the easiness of purification of the product. The concentration of the solvent in the solid content (the quality of the components other than the solvent in the reaction solution) The ratio of the total mass of the solution is preferably 〇m% or more and 70% by mass or less, more preferably 5 mass% or more and 50 mass% or less. The [a] polyorganic thus obtained. The oxime compound is determined by gel permeation chromatography, and the reset average molecular weight of the tongue θ τ θ ^ 4 υ 谀 没有 没有 没有 没有 没有 没有 没有 没有 没有 没有 没有 没有 没有 没有 没有 没有 没有 没有 没有 没有 没有 没有 没有 没有 重置 重置 重置 重置 重置 重置 重置 重置 重置 重置〇〇~200 〇〇〇, Φ ^ , ζυυ, υυυ more preferably 2,000~20,000. By being in such a molecular 詈 囹 作 作 作 作 置 置 置 置 置 置 置 置 置 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可For the [a] polyorganooxazin compound of the present invention, the ring-opening addition of an epoxy group is carried out by a specific acid-lowering acid-lowering moiety, thereby having a ring: soil poly: A structure derived from a specific carboxylic acid is introduced into the oxime. This method is an extremely preferable method from the viewpoint of easiness and improvement of the introduction rate of a structure derived from a specific carboxylic acid. &lt;Other components&gt; In the case of the above liquid crystal alignment agent, 'except for the above [a] polyorgano sulphur compound In addition to the [A] polymer, (4) may contain, for example, a polymer other than the [A] polymer (a polymer which may be referred to as a ruthenium), a hardener, or the like, as long as the effect of the present invention is not impaired. Hardening catalyst: a hardening accelerator, a compound having at least one epoxy group in the molecule (there is a temple called "epoxy compound"), a functional stone compound, a surfactant, and the like. Polymers] In order to further improve the solution characteristics of the liquid crystal alignment agent (A) and the thunder of the liquid crystal display element obtained in the above-mentioned publication, other polymers may be used. Illustrative: at least i kinds of polymers ([B] polymer) selected from the group consisting of polyacrylic acid and polyamidiamine; polyorganosiloxanes represented by the following formula (5), At least one selected from the group consisting of a hydrolyzate and a condensate of the hydrolyzate thereof (hereinafter, sometimes referred to as "other polyorganosiloxane"); polyglycolate, polyester, polyamine, Cellulose derivatives, polyacids, polystyrene derived , poly(styrene-phenyl cis-butane quinone imine) derivative, poly(methyl) acrylate vinegar, etc.

XA (a1)

I

Si — Ο Ι ΥΑ In the above formula )1), 'ΧΑ is a hydroxyl group, a dentate 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. .丫 is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms. &lt;[Β]Polymer&gt; [Β] The polymer is at least one polymer selected from the group consisting of polylysine and polyanilin. Hereinafter, polylysine and polyimine will be described in detail. [Polyuric acid] Polylysine is obtained by reacting a tetracarboxylic dianhydride with a diamine compound. &lt;tetracarboxylic dianhydride&gt; -45-201237069 As a four-sided brewing compound for synthesizing the poly-tylinic acid in the present invention, for example, an aliphatic tetracarboxylic acid di-anhydride is mentioned, for example, A cyclic tetracarboxylic acid - an aromatic tetracarboxylic dianhydride or the like. In the specific examples thereof, the ruthenium tetracarboxylic dianhydride is exemplified by butyl carboxylic acid dianhydride, and the like is alicyclic tetracarboxylic dianhydride, for example, 1, 2, and 3 are exemplified. 4 Tetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylethylbutyrate 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-side oxygen- 3_n夫[l,2-c]efu-1,3-di steel, l,3,3a,4,5,9b-hexahydroanhydride ketone)-•nonylnaphthohydrone-2,5- Bis-oxo-3-furanyl)-naphtho[AC]furan A 5 J *oxabicyclo[3.2.1]octane-2,4-dione-6_spiro_3, (four gas n milk Df %, 2 diketone), 5-(2,5-di-oxotetrahydro-3-furanyl)-3-methylglycol, 3 - 3 -I,2-diurethanic anhydride, 3,5, 6 - 3 叛 基 -2- 几 甲基 甲基 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Dioxatricyclo 5.3.1.02,6]undecane-3,5,8,1〇 (four words, 2,5, cyclohexene: 3,5: anhydride, etc., as an aromatic For the tetracarboxylic dianhydride, for example, the ruthenium tetrahydro dianhydride is exemplified, and as the tetracarboxylic acid, the tetracarboxylic acid described in JP-A-2010-97188 can be used. The dianhydride is preferably a tetracarboxylic acid dianhydride containing an alicyclic tetracarboxylic dianhydride as a tetrasodium oxyacid for synthesizing the above polyamic acid, and further comprises 2,3. a tetracarboxylic dianhydride of 5-tricarboxycyclopentyl acetic acid dianhydride or hydrazine, ?,3,4-cyclobutane tetracarboxylic dianhydride, particularly preferably comprising 2,3,5-tricarboxycyclopentyl acetic acid The tetracarboxylic dianhydride of the anhydride. As the tetracarboxylic dianhydride for synthesizing the above polyamic acid, it is preferred to contain 2,3,5 or tricarboxylic acid in an amount of 1 〇 mol% or more based on the entire tetracarboxylic dianhydride. -46 - 201237069 Two kinds of base acid are burnt four &lt; two listed organic amines, amines, 4,4,., sulfonium diamine amine, 9-hexafluorodiphenylamine biphenyl, base car Block, pentyl acetic acid-hepatic or 1,2,3,4-cyclobutanine tetracarboxylic acid dianhydride four slow-needle 'more preferably contains 2 〇 mol% or more of tetra-acid dianhydride' most than only 2 , 3,5-tridecylcyclopentyl acetic acid dianhydride or 1,2,3,4-cyclobutyric acid dianhydride tetracapric acid di-hepatic. Amine &gt; As a poly-proline for use in the synthesis of the present invention Diamines, aliphatic diamines, alicyclic diamines, aromatics An amine, a diamine oxime, etc. As a specific example thereof, as the aliphatic di, for example, m-xylylenediamine, 1,3-propylenediamine, tetradecyl quinodimethylenediamine , hexamethylenediamine, etc., as the aliphatic nucleus diamine, for example, 1,4-diaminocyclohexane, fluorenylene bis(cyclohexylamine), hydrazine, 3 bis (amino fluorenyl) cyclohexane Alkane, etc. = = family: amine, for example, o-phenylenediamine, m-phenylenediamine aniline 4,4-amino-dipyl decane, 4,4,-diamine-based stupid '5-month female Naphthalene, 2,2'-dimethyl-4,4,-diaminobiphenyl, 4,4,_=, 2'-bis(trifluoromethyl)biphenyl, 2,7-diamino 4th, 4th, 4th, and 2, (4. (4. amine basic oxy) phenyl) propane, 9 bis (4-aminophenyl) fluorene, ? 9 ^ ^ ) E 2, 2 · bis [4 · (4-aminophenyloxy) stupyl] 2'2_bis(4-aminophenyl)hexapropane, 4,4,-(pair Benzene isopropyl) diphenylamine, 4,4'-(meta-phenyldiisopropylidene) bis, 1,4-bis(4-aminophenyloxy)benzene, 4,4, bis ( 4_Aminophenoxy), 2,6-diaminol, 3,diamine-based bites, 2,4-diamine-based, amine-based '3,6-diamine-based taste . Sit, Νmethyl_3,6-diamine ^, hydrazine ethyl 3,6-diamine based card. Sit, oxime-phenyl from diaminone leaf 'again (4 phenyl)-benzidine, hydrazine, hydrazine, _diaminophenyl-47- 201237069 )-N,N'-dimercaptoalkylamine , ι, 4-bis(4-aminophenyl)-piperidin, 3,5-diaminobenzoic acid, dodecyloxy-2,4-diaminobenzene, tetradecyloxy- 2,4-diamino stupid, pentadecyloxy-2,4-diaminobenzene, cetyloxy-2,4-diaminobenzene, octadecyloxy-2,4_2 Aminobenzene, dodecyloxy-2,5-diaminobenzene, tetradecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-diamine stupid, ten Hexetyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminophenyl, cholestyloxy-3,5-diaminobenzene, cholestyloxy- 3,5-diamino stupid, cholestyloxy-2,4-diaminobenzene, cholestyryl-2,4-diamino stupid, 3,5-diaminobenzoic acid Alkyl ester, 3,5-diaminobenzoic acid, choline, 3,5-diaminobenzoic acid, wool, alkyl, 3,6-bis(4-aminobenzylideneoxy)cholane , 3,6_bis(4-aminophenoxy)choloteric, 4-(4-trifluorodecyloxycarbamethoxy)cyclohexyl_3,5-diaminobenzoate, 4- (4,-three Mercaptobenzoyloxy)cyclohexyl-3,5-diaminophenyl phthalate, 1,1-bis(4-((aminophenyl)indenyl)phenyl)butylcyclohexane, 1 ,1-bis(4-((aminophenyl)indenyl)phenyl)-4 heptylcyclohexane, fluorene-bis(4-((aminophenoxy)indolyl)phenyl)_4_ Heptylcyclohexane, (b-bis(4-((aminophenyl)methyl)phenyl))-4(4-heptylcyclohexyl)cyclohexane

Crhr+i (A-1), benzyl amide, 3-aminobenzyl phenyl) piperidine-4-carboxylic acid, 4 (porphyrin-4-yl)benzene, α-amino bis ( N-(4-aminophenyl)piperidinyl)propane, α-amino group, and a diamine represented by the following formula (Α-1).

And X RI is a methylene group or a carbon number of 2 or χ, -COO- or -OC〇_ in the above formula (A-1). 〇1 仏 Each is independently a single bond, and the extension of 3 is -48- 201237069. α is 0 or 1. β is an integer of 〇~2. There is no case where α and β are both 〇. c is an integer from 1 to 20. The divalent group represented by xI-Rl-Xn- in the above formula (Α-1) is preferably an anthracenylene group, an alkylene group having 2 or 3 carbon atoms, -〇-, *_(:〇〇 - or 氺-O-CEhCHb-OC where 'the linkage with hydrazine is bonded to the diaminophenyl group. Specific examples of the cyH 2 "i_ group" include methyl 'ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl. , n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl 'n-heptadecyl, n-octadecyl, n-nonadecyl, positive Eicosyl group, etc. The two amine groups in the diaminophenyl group are preferably in the 2,4 or 3,% position relative to the other groups. As the compound represented by the above formula (A 1), For example, a compound represented by the following formula (A-1-1) to (A-1-6), -49-201237069 ΗζΝ Η2Ν (Α-1-1) Η2Ν c5Hn (Α-1-2) C7H15 (Α-1-3)

C5H11

&quot;Q^^OO NHj

C5H11 Η2Ν

C5H" Μ'ό_〇~〇^000 η2ν In the above formula (Α-1), it is preferred. As the diamine-based organic oxalic acid is two and W is simultaneously 〇. ))-tetramethyl In addition to, for example, U·bis (3-Aminopropyl 20 10-971 88, the above-mentioned two-external group) can also be used in order to develop a diamine of sufficient vertical polyamic acid. It is a diamine containing the biliary = in the synthesis of the present invention, or a diamine of the above formula (A 兀:, a monoamine, and a cholestylene-containing diamine, with respect to all of the di:. More preferably, it contains 10 mol% to 90:amine: preferably contains more than 5 mol% and more than 80 mol%. Ear/° 'excellently contains 2 1 mol 〇 /. ~ -50- 201237069 The ratio of the tetracarboxylic acid two-needle to the diamine compound in the synthesis reaction of the polyamic acid is preferably such that the acid anhydride group of the tetracarboxylic dianhydride is 0.2 equivalent with respect to 1 equivalent of the amine group contained in the diamine compound. a ratio of 2 equivalents, more preferably 0. 3 equivalents to 1.2 equivalents. The synthesis reaction of polyamic acid is preferably in an organic solvent, preferably at -2 0 ° C to 150 ° C, Preferably, it is carried out at a temperature of from 0 ° C to 10 Torr. Preferably, it is carried out for 0.5 hour to 24 hours, more preferably for 2 hours to 1 hour. Here, as an organic solvent, if it is soluble and synthesized The polylysine is not particularly limited, for example, N-mercapto-2-pyrrolidone, N,N-dioxa-dimethylimidazolium, hexamethylphosphonium tridecylacetamide , N,N-dimethylformamide, n,n-methyl-subcode, γ-butene-g, tetradecylureaamine and other aprotic polar solvents; The amount of the organic solvent (4) and the total amount (8) of the tetrazoic acid dihepatic and diamine phosphite relative to the total amount of the reaction solution (a + b) is preferably (M mass 〇 / 5 〇 % %) The amount of 〇..., more preferably 5 mass ❶ /. ~ 30 mass in the above organic solvent, can be especially &amp; mountain M ^ ^ . ^ T Τ to not precipitate the resulting polyamine & SL The range of cool people use you &amp; five t &quot; rice mouth as a poor solvent for poly-proline, alcohol, ketone, hydrazine, ether, halogenated hydrocarbons, hydrocarbons, etc. - as the above negative bath, for example B , isopropanol, ring 醢, 7 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Known early methyl ether, ethyl lactate, a 夂gg, acetone, A and B, lack of 舻 暴 暴 吴 butyl ketone, cyclohexanone, acetaminophen, ethyl acetate 'B 酴 甘 甘 „ 文 文 文 曰Methyl methoxypropionate, sputum 5 lactic acid propionate, cesium carbonate 舻仏 舻仏 丙 曰 曰, diethyl oxalate, malonic acid · 乙 曰,? ^ δίψ, 7 β ethyl k-ethyl alcohol methyl ether, ethylene glycol ethyl ether, ethylene di-51- 201237069 alcohol n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol monobutyl ether (butyl Lusu), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dioxime ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, two: two Alcohol monoethyl ether, diethylene glycol monodecyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichlorodecane, hydrazine, 2-diethane, hydrazine, 4-dioxane Trichloroethane, chlorobenzene, o-diphenyl, hexane, heptane, octane, benzene, toluene, xylene, and the like. These poor solvents may be used singly or in combination of two or more. As described above, a reaction solution in which polylysine is dissolved can be obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal alignment agent, or may be provided for the preparation of the liquid crystal alignment agent on the basis of separately separating the polyamic acid contained in the reaction solution, or may be separately isolated in the purification. Polylysine is used for the preparation of a liquid crystal alignment agent. The individual separation of the polyamic acid can be carried out by injecting the above reaction solution into a large amount of a poor solvent to obtain a precipitate, drying the precipitate under reduced pressure, or reacting the reaction by an evaporator. The solution was distilled off under reduced pressure. In addition, the poly-proline can be purified by dissolving the poly-proline in an organic solvent, followed by precipitation from a poor solvent; or by using a vaporizer for distillation under reduced pressure. The method of the steps. [Polyimide] The above polyimine can be produced by dehydration ring closure of the glycine structure of the polyamic acid obtained by the operation as described above. In this case, the entire proline structure can be dehydrated and closed, and completely imidized, or only a part of the structure of the proline structure can be dehydrated and closed to form a proline structure and a quinone structure. Part of the quinone imide. -52- 201237069 The dehydration ring closure of poly-aracine is carried out by the following method: (1) heating the polyamic acid method or (π) dissolving the polyamidoxime in an organic solvent, adding a dehydrating agent to the solution, and dehydrating A closed loop catalyst and a method of heating as needed. The reaction temperature in the method of heating the above (1) is preferably from 50 ° C to 20 (TC, more preferably from 60 ° C to 17 (TC. Can be M 丄 # J straw by setting the reaction temperature to 50 °) In order to sufficiently carry out the dehydration ring closure and the coating, it is possible to suppress the decrease in the molecular weight of the yttrium imidized polymer of the pinch by setting the reaction temperature to 200 ° C or lower. The reaction time in the addition of the acid, the sputum, and the sputum is preferably from 0.5 to 4 8 hours, more preferably from 2 hours to 2 hours, on the other hand, in the case of the polysulfide to the above (ii) And a solution of a proline acid - a method of adding a dehydrating agent and a dehydration ring-closing catalyst, and τ as a dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic acid ethyl ketone anhydride can be used.相对 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Methyl terminal dimethyl. A tertiary amine such as hydrazine or triethylamine. However, it is not limited to them. In terms of the amount of the dehydrating agent used, it is preferably 〇.01 摩尔~1〇莫耳. For the dehydration ring closure reaction, there are 樯, 交 ^ ^ ^ ^ 4 agents An organic solvent which is exemplified as an organic solvent used in the synthesis of polylysine is exemplified. The reaction temperature of the dehydration ring-closure reaction is preferably 〇. "Mr. 0 180 C ' is preferably 10°. C: 150. (:, the reaction time is preferably 0.5 hours to 9 Torr, and the temperature is -20 hours, more preferably 1 hour to hr. In the method (11), as described above, it is possible to obtain a polyruthenium. The reaction bath of the amine. The reaction is dissolved and s can be directly supplied to the liquid '53 · 201237069 crystal alignment agent, and the γ 丄 can also be used to remove the τ and dehydration ring-closing catalyst from the reaction solution. For the liquid crystal alignment agent 2, the liquid crystal alignment agent can be supplied on the basis of separately separating the polyimine, or the liquid crystal alignment agent can be purified from the separately separated polyimine. &amp; Removal of dehydrogenation and enthalpy catalysis, such as solvent replacement Separation and purification of the amine can be carried out by performing a separate separation and purification method of the same polyglycine as described above. [Other polyorganisms] The liquid crystal alignment agent (A) may contain in addition to [a] poly Other polyorganosiloxanes other than organic oxime. The other polyorganoindenes are at least 1 selected from the group consisting of polyorganosiloxanes of the above formula (al) and condensates of hydrolyzed hydrolysates thereof. In the case where the alignment agent (A) contains other polyorganosiloxanes, most of the organic oxy-oxygen can be present in the presence of polyorganosiloxanes, a part of which can be used as [a] polyorganosiloxane. The condensate is present. In the oxime and γΑ in the above formula (al), examples of the alkyl group having 1 to 20 carbon atoms include anthracene, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-decyl groups. , n-decyl, n-lauryl, n-dodecyl, benzyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, benzyl, n-octadecyl, n-nonadecyl, positive Examples of the decyloxy group having a carbon number of 1 to 16 such as an eicosyl group include, for example, an ethoxy group, a water-based agent, and a preparation for the preparation of the agent, and a water supply agent. Polypyrylene is used as a preferred compound for the burning of oxyalkylenes and as a liquid crystal. Other poly compounds are monolithic. Compounds, ethyl, n-octyl-n-tridecyl-heptadecane decyloxy, -54- 201237069

Examples of the aryl group having 6 to 20 atomic atoms include a phenyl group and the like. The other polyorganosiloxane may be, for example, at least one decane compound selected from the group consisting of an alkoxy decane compound and a halogenated decane compound (hereinafter, sometimes referred to as "raw decane compound" I is preferably In a suitable organic solvent, it is hydrolyzed or hydrolyzed and condensed in the presence of water and a catalyst to synthesize. As a raw material decane compound which can be used herein, for example, tetramethoxycrushing, ethoxy ethoxylate, and tetra are listed. n-Proxyoxy, tetraisopropoxy decane, tetra-n-butoxy decane, tetra- or 2-butoxybutane, tetra-tertiary butoxy decane, tetra-hexane decane; methyltrimethoxy decane, methyl three Ethoxy decane, decyl tri-n-propoxy decane 'methyl triisopropoxy decane, methyl tri-n-butoxy decane, methyl tri-n-butoxy decane, decyl tri-tert-butoxy Decane, methyltriphenoxydecane, methyltrioxane, ethyltrimethoxydecane, ethyltriethoxydecane, ethyltri-n-propoxydecane, ethyltriisopropoxydecane, Ethyl tri-n-butoxy decane, ethyl di- or 2-butoxy decane , ethyl tri- tertiary butoxy decane, ethyl dichloro decane, phenyl trimethoxy decane, phenyl triethoxy decyl phenyl dioxane; dimercapto dimethoxy decane, dimercapto Diethoxy decane, dimercaptodioxane; trimethyl methoxy decane, trimethyl ethoxy decane, trimethyl chloro decane, etc. Among them, tetramethoxy decane, preferably Ethoxy decane, decyl trimethoxy decane, decyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, dimercapto dimethoxy decane, dimethyl diethoxy A decyl alkane, a trimethyl methoxy oxane, a tridecyl ethoxy decane. In the case of synthesizing another polyorganosiloxane, an organic solvent of -55 to 201237069 can be used arbitrarily, for example, an alcohol compound or a ketone. a compound or an ester compound or other aprotic compound. It is used or used in two or more. As the alcohol compound, for example, decyl alcohol, ethanol, n-propanol, isopropanol, n-butanol, and dibutyl Alcohol, tertiary butanol, n-pentanol, isoamyl alcohol, 2-methyl secondary alcohol, three Pentyl alcohol, 3-methoxybutanol, n-hexanol, secondary hexanol, 2-ethylbutanol, second-grade heptanol, heptano-octanol, 2-ethylhexanol, secondary octanol , n-nonanol, 2,6-di-4, n-nonanol, second undecyl alcohol, triterpene sterol, diol, secondary heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexane g monoterpene cyclohexanol, benzyl alcohol, diacetone alcohol, etc. monohydric alcohol ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,4-pentyl-2,4-pentane Alcohol, 2,5-hexanediol, 2,4-heptanediol, 2-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene polyol compound; ethylene glycol monomethyl ether, B Glycol monoethyl ether, ethylene glycol monoglycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl alcohol mono-2-ethyl butyl ether, diethylene glycol monoterpene ether, diethylene glycol , diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoglycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethylene A partial ether or the like of a polyol compound such as an alcohol monopropyl ether. These can be used alone or in combination of two or more. As the ketone compound, for example, amides can be isobutanol, butylbutanol, 2-methyl-3-ol, n-decyl heptanol-tetradecene I'3,3,5- Propylene bond of diol, 2-ethyl-1,3-diol, etc., diethyl ether, ethylene glycol monoethyl ether, monohexyl propylene, propylene bond, dipropanol compound-56-201237069 acetone, acetophenone , methyl n-propyl ketone, decyl n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-pentyl ketone, ethyl n-butyl ketone, decyl hexyl ketone, two Monoketone compounds such as isobutyl ketone, trimethyl ketone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, anthrone Acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-decanedione, 3,5-decanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetradecyl-3,5-heptane A 0-diketone compound such as a diketone or a 1,1,1,5,5,5-hexafluoro-2,4-heptanedione or the like. These ketone compounds may be used singly or in combination of two or more. Examples of the above guanamine compound include decylamine, N-decyl decylamine, hydrazine, fluorenyl-dimercaptocarbamide, N-ethyl decylamine, and N,N-diethyl decylamine. , acetamide, N-mercaptoacetamide, hydrazine, hydrazine-dimercaptoacetamide, hydrazine-ethyl acetamide, hydrazine, hydrazine-diethylacetamide, hydrazine-mercaptopropylamine , Ν - 曱 base. More than 0 each. Ketone, Ν-methyl 驴 咮 Ν, Ν - 曱 acid based brigade. Ding, Ν-曱 醯pyrrolidine, Ν-ethendyl porphyrin, Ν-ethinylpiperidine, Ν-ethinyl pyrrolidine and the like. These guanamine compounds may be used singly or in combination of two or more kinds of hydrazines, for example, diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ- Butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, butyl acetate, n-amyl acetate, diethyl amyl acetate, acetic acid 3- Methoxybutyl ester, methyl amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, nonylcyclohexyl acetate, n-decyl acetate, B Ethyl phthalate acetate, ethyl bromide-57-201237069 Ethyl acetate vinegar ethylene glycol monomethyl diethylene glycol monomethyl ether, acetic acid _, ethylene glycol monoethyl ether, mono-n-butyl ether, propylene glycol:: Alcohol monoethyl hydrazine, acetic acid diacetic acid propylene glycol monopropyl hydrazine, ethyl hydrazine, propylene glycol monoethyl succinyl ether, acetic acid dilactam: propylene glycol monobutyl hydrazine, diacetic acid dipropylene

:oxytriethylene glycol slightly, two acid ethyl brewing di 2 ethyl H ester, oxalic acid diethylene | purpose, _ times n-butyl S, propionic acid (b) C* diacid monoethyl ester, n-butyl lactate , butyl phthalate, decyl lactate, dimethyl methacrylate, phthalic acid _ titanium - acetyl, known alone or in combination of two or more. - Ethyl ester, etc. These esterifications cooperate with other aprotic, and the cerium 曱 τ τ 化 化 例如 例如 例如 例如 例如 例如 例如 例如 例如 例如 例如 例如 例如 例如 例如 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举The attack surface is 啼 醯 醯 醯 醯 醯 、 、 、 、 、 、 、 、 、 曱 曱 曱 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 、 、 、 Bilo, Ν-methyl small methyl imidazole, ~ methicin piperidine, hydrazine, hydrazine-dimethyl hydrazine Λ ^ ^ soil _ 辰 鲷 鲷, Ν-methyl-2-piperidinyl-2-pyrrole Acridine, j, 1 疋πη Λ, '--the base group 2-0 m saldecone, tetraoxo-2 (1 Η)-pyrimidine _ and the like.钔i, 3- 妆 夕 „ ^ 二 / mixture of 'excellent is more, part of the ether compound, or vinegar compound." "The tongue used in the synthesis of other poly-organisms" The i mole having a (tetra)oxy group as a total atomic atom relative to the original m compound is preferably 0 01 to 100 mol, more preferably a molar amount of ι to 15 m. As the synthesis of other polyorganosiloxanes, for example, a metal chelate compound, an organic acid, an inorganic acid, ammonia, an alkali metal compound or the like can be used. Acetic acid-if-bond, diol acetic acid isotonic acid o-stuff can be tri-brown-Δ 3 -,, N-methyl alcoholated amount of halogen 1~3 0 Catalytic machine test -58- 201237069 as the above metal chelate For example, a trialkoxy-mono(acetylpyruvate)-titanium such as triethoxy.mono(acetylpyruvate) titanium; diethoxy.bis(acetylpyruvyl)titanium, etc. Alkoxy. bis(acetyl acetonate) titanium; monoethoxy bis (ethylpyruvate) chin, etc. single-yard oxy. tris(acetylpyruvate) titanium; tetrakis(acetylpyruvate) titanium; Triethoxyoxy (ethyl acetoacetate), etc., alkoxylate, mono(ethylacetamidineacetic acid) titanium; diethoxy bis(ethylacetamidineacetic acid) titanium, etc. Bis(ethylacetamidineacetic acid) titanium; monoethoxyl bis(ethylethanoacetic acid) titanium, etc. monoalkoxy·tris(ethylacetamidineacetic acid) titanium; tetrakis(ethylethanoacetic acid) titanium ; single (ethyl acetoacetate) acid (ethyl acetoacetate) titanium, bis (acetyl acetonate) bis (ethyl acetonitrile) titanium, tris (acetyl acetonide s) single (ethyl acetamidine) Acetate, titanium, etc. a titanium chelate compound such as a titanium compound containing two or more kinds of chelating ligands; a trialkoxy group such as a bis-diethoxy mono(ethylpyruvylpyruvate) cone. Ethoxy. Bis(acetylpyruvyl) zirconium and other dialkoxy cone pyruvic acid) for the fork &quot;, . 'early ethyl lactyl. bis(acetonitrile pyruvate) zirconium and other monoalkoxy. : (acetyl acetonide) wrong; four (ethyl acetaminophen) wrong; triethyl acetonitrile acetic acid) ruthenium and other trioxane Oxy. Single (Ethyl bromide (B'' 丞 醯 醯 acetic acid) wrong; Di Earth. (Ethylacetamidineacetic acid) zirconium and other dialkoxy: monoethyl phthalate: bis (ethyl ethyl I acetic acid)鍅土((ethyl acetoacetate), mono-alkoxy, tris(ethyl acetonitrile, zirconium), tetrakis (ethyl acetoacetate), calcium, ruthenium (Ethyl acetonitrile) :(pyruvate) three (B: (B) "Ethylpyruvate" bis (ethyl ethyl acetate acetic acid m, one (ethyl acetoacetate) acid single (ethyl acetyl chelating S 卩髀 g Slave) is a mischelating compound containing zirconium compounds or the like containing two or more kinds of ligands; one (acetyl acetoacetate), two (f), etc. one (ethyl ethyl acetonitrile) Aluminium-sound-59- 201237069 Organic acids, such as acid, malonic acid, formic acid, o-paraffinic aromatic sulfonate carboxylic acid, lemon mineral acid, for example, etc. Organic tests, for example, methyl ratio bite, dimethyl Base single ethanol% Xin Xuan, -. Suihua money and so on. The metal compound is preferably a ruthenium or a ruthenium hydroxide. Among the agents, it is preferably an integrator, and in a larger amount, 〇·001 parts by mass is added in advance to the polyorganosiloxane which is added to the organic solvent to be used as a raw material. The hydrazine is saturated with salicylic acid, salicylic acid, sulfonic acid, benzenesulfonic acid, acetic acid, and halogen as the above-mentioned hydrogen fluoride and scaly acid as the above-mentioned pyrrolidine, pyridinium, diethanolamine, alcoholamine, Diterpene bis, tetramethylhydrogen oxide is used as the above potassium oxide, hydrogen and oxygen or two kinds of these catalytic acid. The gold is preferably used in parts by mass to 1 part by mass. The catalyst can be dissolved or dispersed in the decane compound. Others are continuously added to aromatics such as formic acid and fatty acid such as maleic acid, and mono-acetic acid, acid, tartaric acid, and the like are exemplified as hydrochloric acid, exemplified by pyridine, trimethylamine, triethylamine, and monomethyldibicyclic guanidine. Examples of the alkane and the second are, for example, calcium. The metal chelate is preferably a solution obtained by using a titanium chelate compound as a raw material for 10 parts by mass of the titanium chelate compound. In the synthesis, a non-saturated carboxylic acid such as acetic acid or propionic acid, p-toluene tri-glycolic acid, triterpene nitric acid, sulfuric acid, 0 hydrazine, slightly oxime, amine, monoethanolamine ethanolamine, triacetamidine are added. The dicycloundecene sodium hydroxide, the hydrogenating agent can be used alone, the organic acid, the non-anthracene compound 100 is 0.001 mass of the alkyl compound in or in the middle, or the water can be intermittent or the decane compound -60-201237069 bee In the solution obtained by dissolving in an organic solvent, the reaction temperature in the synthesis of other polyorganosiloxane is preferably ≥C~100 ° C, more preferably 15 ° C to 80 ° (:. The reaction time is preferably from 55 hours to 24 hours, more preferably from 1 hour to 8 hours. The liquid crystal alignment agent (A) contains the other polymer 5 while containing the [A] polymer. The content of the other polymer is preferably 1 相对 with respect to the [A] polymer 100 aliquot. 〇〇 below the mass. The preferred content of the other polymer varies depending on the type of other polymer. The liquid crystal alignment agent (A) contains the [A] polymer and the [B] polymer, and the total ratio of the [B] polymer is relative to the [A] polymer in terms of the preferred ratio of use of the two. 100 parts by mass is preferably 1 part by mass to 5, and the mass part is more preferably 200 parts by mass to 3 parts by mass. On the other hand, in the case where the liquid crystal alignment agent (A) contains a [a] polyorganosiloxane compound and other polyorganosiloxanes, it is preferable that the ratio is relative to [a] The amount of the other polyorganosiloxane which is mass-damaged by the polyorganosiloxane compound (10) is 1 part by mass to 2, and the ruthenium-quality liquid crystal alignment agent (A) contains the pot of the [A] polymer. In the case of a polymer, as another polymer, a [B] polymer or another polyorganosiloxane is preferred. [hardener, hardening catalyst, and hardening accelerator] The hardening agent and the hardening catalyst Shoe 屮Μ 1 are included in the above for the purpose of making the cross-linking reaction of the [a] polyorganosiloxane compound stronger. The liquid crystal alignment is engraved. The hardening accelerator may be contained in the liquid crystal alignment agent (a) for the purpose of promoting the hardening reaction by the hardening agent. -61 - 201237069 As the curing agent, a curing agent which is usually used for curing of a curable compound having an epoxy group or a curable composition containing a compound having an epoxy group can be used. Examples of such a curing agent include a polyamine, a polybasic acid, and a polybasic acid. Examples of the oxime carboxylic anhydride include an acid anhydride of cyclohexanetricarboxylic acid and other polycarboxylic acid anhydrides. As k-existing three-reagents, for example, cyclohexanone _ 1,3,4 _ r: 曱西夂 3 '4 S phthalic anhydride, Cyclohexa-1,3,5-tricarboxylic acid _ 3,5 - Anhydride, cyclohexane-1,2,3-tricarboxylic acid 2,3-anhydride, and the like. Examples of the other polyoxic acid needle include, for example, 4-methyltetrahydrophthalic anhydride, methyl nadic anhydride, undecenyl succinic anhydride, succinic anhydride, maleic anhydride, ortho-dicarboxylic anhydride, Ammonium phthalic acid anhydride, a compound represented by the following formula (6), and a tetras-acid dianhydride which is generally used for the synthesis of polyglycine, and an alicyclic ring having a conjugated double bond such as "tetrazene or an allo-ocimene" The Diels-Alder reaction product of the compound of the formula and maleic anhydride is the same as that of the compound. Oxygen ^ Χ ^ 2 χ +1

(6) In the above formula (6), x is an integer of 1 to 20. The yam I: a hardening catalyst, for example, a 6-dish bismuth compound, a 6-fluorinated dish compound, and a bis-acetone-aluminum-based alloy can be used. These catalysts can catalyze the cationic polymerization of epoxy groups in addition. ', ', as the above-mentioned hardening accelerator, for example, a taste compound; 4 - 62 - 201237069 grade phosphorus compound; a grade 4 amine compound; I, 8 - dioxime bicyclo [5.4. 〇] broken -7-ene, Divalent bicyclic olefins such as organic acid salts; organometallic compounds such as zinc octoate, tin octoate, and aluminum acetonate pyruvate complex; boron compounds such as three gasification sheds and trisuccinic acid; zinc hydride, gasification tin, etc. a highly soluble point-dispersion latent hardening accelerator such as a metal halide compound; an amine addition accelerator such as dicyandiamide, an amine and an epoxy resin; and a micro-coated surface of a grade 4 scale salt Capsule-type latent hardening accelerator; amine-based latent hardening accelerator; high-temperature dissociation type thermal cationic polymerization type latent hardening accelerator, such as Lewis acid salt and Buchholster acid salt. [Low Oxygen Compound] From the viewpoint of improving the adhesion to the surface of the substrate of the liquid crystal alignment film to be formed, the epoxy compound may be contained in the liquid crystal alignment agent, and the ethylene glycol condensate is preferably used. Glycerol ether 'polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol: glycidyl ether, 1,6-hexanediol Glycidyl ether, glycerol diglycidyl sulphate, 2,2· Er Mo Xin pentyl: alcohol diglycidyl _, 1,3,5,6-tetrahydroglycine: yl-2,4-hexanediol, N,N ,N,,N,tetraglycidyl-m-xylylenediamine, 1,3-bis(indole, Ν·diglycidylaminomethyl hydrazine, hydrazine, hydrazine, hydrazine, _tetraglycidyl...diamine Diphenyl benzoate II: glycidyl sulfhydryl amide, hydrazine, hydrazine diglycidyl group, aminomethyl hexanone pit, in the case where the other liquid crystal alignment agent (Α) contained therein contains an epoxy compound In terms of ratio, it is preferably 〇〇1 in relation to the above-mentioned [Α] polymer and any use of -63 to 201237069 polymer in a total amount of 100 parts by mass. In the case of the liquid crystal alignment agent (A) containing an epoxy compound, the liquid crystal alignment agent (A) may be used in combination for the purpose of efficiently causing crosslinking reaction. The base group is a quinone-based catalyst. [Functional decane compound] The functional decane compound can be used as a functional decane compound for the purpose of improving the adhesion to the substrate of the obtained liquid crystal alignment film. For example, 3 - aminopropyltrimethoxy hydrazine 15, 3 - aminopropyl triethoxy decane, 2-aminopropyl trimethoxy decane, 2-aminopropyl triethoxy sulphur Alkyl, N-(2-aminoethyl)-3-aminopropyltrimethoxyoxydecylaminoethyl)_3-aminopropylmercaptodimethoxydecane, ureido dimethyloxyl Decane, 3-formylpropyltriethoxydecane, N-ethoxydosuccinamylpropyltrimethoxyacetate, N4oxydecyl-3-aminopropyldiethoxydecane, oxime-triethyl Oxymethionylpropyltrimethylene, amine, hydrazine-trimethoxycarboxyalkylpropyltriethylenetriamine, ι〇• three; milk-based kevin Μ, 7_triazapine 1G_Triethoxymethasole ==::Three gas sorghum, 9_trimethoxymethyl sulphide _3,6_diaza: = ^'9·triethoxy A W3 , 6-diazepine acetic acid, 1 base, 3, aminopropyl, tri-foxy, ..., alkylaminopropyl: lactyl calcined, N-phenyl-3-aminopropyl Trioxetyloxy, &amp; benzenediaminopropyltriethoxydecane, ... bis(oxyethylene)_3_amino:: dimethoxy sulphur, N-bis (oxyethylene) Aminopropyl three: ^ gram, 3. glycidyl methoxypropyl trimethoxy valence, 2 _ (w agricultural lactam cyclohexyl) ethyl tridecyloxy, etc., further enumerated Japan

S-64 - 201237069 A reaction product of a tetracarboxylic dianhydride and a decane compound having an amine group described in JP-A-63-29 No. 922. When the liquid crystal alignment agent (A) contains a functional decane compound, the content ratio thereof is 丨 00 parts by mass based on the total of the above [a] polyorganosiloxane compound and any other polymer used arbitrarily. Preferably, it is 5 parts by mass or less, and more preferably 2 parts by mass or less. [Surfactant] Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a polyoxyalkylene surfactant, a polyalkylene oxide surfactant, Fluorine-containing surfactants, etc. When the liquid crystal alignment agent (A) contains a surfactant, it contains a ratio. The total mass part by mass of the liquid crystal alignment agent (A) is preferably 1 or less, more preferably 1 part by mass or less. &lt;Preparation method of liquid crystal alignment agent&gt; The above-mentioned 'liquid crystal alignment agent (A) contains [A] polymer as an essential component' may contain other components as needed, but it is preferred to dissolve each component in an organic solvent. It was prepared in the form of a solution-like composition obtained. ‘, 有机In order to prepare the liquid crystal alignment agent (A), the organic solvent is preferably used, and is r, h, h

'[A] chelates and other ingredients used arbitrarily and without them; 5 Rfe AA 夂 organic solvent. It is preferred that the organic solvent used for the liquid crystal alignment agent (A) differs depending on the type of other polymer added by the U. In the liquid crystal alignment, the preferred agent (A) contains the [A] polymer and [B] The organic solvent of the polymer' is exemplified as the organic solvent used in the synthesis of the poly-proline acid-65-201237069, and may also be used as the organic solvent exemplified above. At this time, the exemplified lean, six-turn &amp; 1 with the lean solvent used in the synthesis of the amine acid above the β 'organic solvent can be used alone or use two kinds of surface liquid crystal chelates as a gathering &amp;蜊 (A) contains only [a] polyorganooxy oxyalkylate and other poly, lower, or [a] polyorganosiloxane-based organic soluble organic sinter, as a polymer, as Examples of monoethyl ether and propylene dienzyme include "ethoxy-2-propanol 1, propylene glycol, early propyl ether, propylene glycol monobutyl ether, propylene glycol monoacetic acid 9 - propylene glycol thiol-, and propylene glycol ethyl. Ether, dipropylene glycol propyl eye I, dipropylene disulfide-Tiangan-T-ether ether, ethylene glycol monoterpene ether, ethylene glycol monoethyl ether, ethyl alcohol, % propylene, 7-opening. „ B-Private early Butyl ether (butyl serotonin), ethylene glycol: base ether, ethylene glycol monohexyl ether, diethylene glycol 'methyl cellosolve, ethyl 2 ethyl / fiber mixture acetate, propyl solution Fibrous acetate, butyl serofuric acid g, acetonide vf carbamide, ethyl carbitol, propyl carbitol, ester carbitol, propylene acetate, isopropyl acetate , n-butyl vinegar acetate, isobutyl phthalate, n-butyl acetate, n-amyl acetate, acetic acid, valeric acid, 3-methoxy butyl vinegar, methyl valerate, acetic acid, 2-ethyl butyl , 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate, and the like. Among them, preferred are n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-butyl acetate, n-amyl acetate, and diethyl amyl acetate. A preferred solvent for the preparation of the liquid crystal alignment agent (A) can be obtained by combining one or more of the above organic solvents in accordance with the presence or absence of the use of the other polymer and the type thereof. In such a solvent, the components contained in the liquid crystal alignment agent (A) are not precipitated at a preferred solid concentration of -66 - 201237069, and the surface tension of the liquid crystal alignment agent (A) is 25 to 4 Torr. Range of mN/m = solvent. The solid content concentration of the liquid crystal alignment agent (A), that is, the ratio of the mass of all components other than the solvent of the liquid crystal alignment agent t to the total mass of the liquid crystal alignment agent α) is considered to be sticky, volatile, etc. Alternatively, it is preferably in the range of 1 mass% by mass%. The liquid crystal alignment agent (A) is applied to the surface of the substrate to form a coating film to be a liquid crystal alignment film. However, when the solid content concentration is 1% by mass or more, the film thickness of the coating film is not easily too small and can be obtained well. Liquid crystal alignment film. On the other hand, when the solid content concentration is 10% by mass or less, the film thickness of the coating film is suppressed from becoming too large, and a favorable liquid crystal alignment film can be obtained, and the viscosity of the liquid crystal alignment agent (A) can be prevented from being large. The coating characteristics were made good. The range of the particularly preferable solid content concentration differs depending on the method employed in coating the liquid crystal alignment agent (A) on the substrate. For example, it is preferably in the range of 1.5% by mass to 45% by mass. It is particularly preferable to set the solid content concentration to three. In the case of the printing method, the amount is in the range of % to 9% by mass, and thus the solution viscosity is in the range of 12 mPa·s to 5 GmPa.s. In the case of the inkjet method, it is particularly preferable to set the solid content concentration to a range of mass Μ mass %, and to set the solution viscosity to a range of 3 mpa.s to i5 mpm. The temperature at which the liquid crystal alignment agent (A) is prepared is preferably 〜2 〇〇. 〇, more preferably 〇 °C ~ 40 ° C. [Examples] Hereinafter, the present invention will be more specifically illustrated by the examples, but the present invention is not limited to the examples. -67- 201237069 The weight average molecular weight (mw) of the polyorganooxime having an epoxy group and the [E] polyorgano-oxygen compound obtained in the following examples are polyphenyls measured by GPC of the following specifications. Ethylene conversion value.

Tube column: manufactured by Tosoh, TSKgelGRCXLII Solvent: tetrahydrofuran temperature: 40 ° C Pressure: 68 kgf / cm 2 Further, the raw material compound used in the following examples and the necessary amount of the polymer 'reproduce the following synthesis examples as needed The synthesis of the starting material compound and the polymer at the synthetic scale shown is ensured. The following evaluation was performed on the manufactured liquid crystal display element. Further, a summary of the evaluation results is shown in Table 1. &lt;Synthesis of Polyorgano-Oxygen Oxide with Epoxy Group&gt; In the case of a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 2_(3,4·ring) was added. Oxycyclohexyl)ethyltrimethoxylate (ECETS) 100.Og, methyl isobutyl ketone 5 〇〇g, and triethylamine 〇·0 g 'mixed at room temperature. Then, it took 3 minutes to desorb the water from the dropping funnel 0 to the water 1 〇 〇 g, and then reacted at 80 ° for 6 hours while mixing under reflux. After the reaction was terminated, the organic layer was taken out and washed with a 2% by mass aqueous solution of ammonium nitrate until the water after washing became neutral, and then the solvent and water were removed under reduced pressure to form a viscous transparent liquid. The method of obtaining a polyorganosiloxane having an epoxy group and subjecting the polyorganosiloxane having an epoxy group to 1H-NMR analysis -68-201237069, confirmed that the chemical shift (δ) = 3 2ρριη The epoxy group-based peak was obtained in the vicinity as the theoretical strength, and did not cause an epoxy side reaction in the reaction. The polyorganosiloxane having an epoxy group obtained in Synthesis Example 1 had a weight average molecular weight (Mw) of Mw = 2,200 and an epoxy equivalent of i86 g/mol. &lt;Synthesis of Specific Carboxylic Acid&gt; [Synthesis of Specific Carboxylic Acid 1] The specific carboxylic acid 1 was synthesized by the following reaction route.

OH + Br —μ〇Η2Η—COOMe

DMF

NC

COOH

LiOH H20 MeOH / H20

NC

Specific carboxylic acid 1 [Synthesis Example 2] 4-N-cyano-4, - 6.3 g via hydrazine, and 11 Ηg of methyl benzoate, were added to a 500 mL three-necked flask equipped with a condenser. Carbonate clock 1 4.2 g, N,N-dimercaptoguanamine 2 〇〇 mL, stir-mixed at 1 60 ° C for 5 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was poured into water of 500 mL' and mixed and scrambled. The precipitated white solid was separated by filtration and washed with water. 11 g of Compound 1 was obtained by vacuum drying the obtained solid at 80 °C. [Synthesis Example 3] -69- 201237069 ·- Adding 10 g of a compound in a 2 mL flask equipped with a condensing officer 1 , 1 6 p «ν &amp; λ»

'g Li Lihua Lithium Monohydrate, 30 mL of decyl alcohol, 15 mL of water' was mixed at 8 〇C for 7/1, and was mixed for 4 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. The diluted I S Wenling was slowly added to the reaction solution while the reaction solution was stirred. The precipitated solid was washed in the order of &amp; ethanol, and the obtained solid was vacuum dried at 80 ° C to obtain 8 g of a specific acid (synthesis of a specific carboxylic acid 2). Specific carboxylic acid 2.

Compound 4 LiOH · H20

C00H specific carboxylic acid 2

Me0H/THF/H20 [Synthesis Example 4] In a 500 mL three-necked flask equipped with a condenser, 15 g of 4-cyano-4'-hydroxybiphenyl, 13 g of ethylene carbonate, and tetrabutylammonium bromide (TBAB) were added. 2.5 g, N,N-dimethyl decylamine 3 〇〇 mL, heated at 15 ° C for 9-70-201237069 for 9 hours. After confirming the completion of the reaction by tlc, the reaction solution was cooled to room temperature. The reaction solution was washed with a mixed solution of ethyl acetate 300 mL '1N-aqueous sodium hydroxide solution i 〇〇 mL. The organic layer was extracted, and it was further known that the liquid washing was carried out in the order of 1N-aqueous sodium hydroxide solution i〇〇mL and water i〇〇mL. After drying the organic layer with sulfuric acid, the organic solvent was taken out. The obtained solid was dried under vacuum, and then recrystallized from 1 mL of ethanol / 250 mL of hexane, to obtain 13.1 g of Compound 2. [Synthesis Example 5] 12 g of the compound 2, a 7 g of 4 benzene sulfonium sulfonate, and 6 〇 mL of dehydrated dichloromethane were added and mixed in a 2 mL flask equipped with a condenser and a dropping funnel. In a state where the reaction solution was cooled with an ice bath, 6.6 g of a dehydrated dioxane 10 niL solution of triethylamine was added dropwise over 10 minutes. Mix for 30 minutes in an ice bath, return to room temperature and further mix for 6 hours. To the reaction solution, 15 mL of chloroform was added, and the mixture was washed four times with 1 mL of water. The extracted organic layer was dried over magnesium sulfate, and the organic solvent was evaporated. The obtained solid was washed with ethanol to obtain 16.1 g of compound 3 〇 [Synthesis Example 6] i5 g of compound 3, 1 lg of 4-hydroxyl-formic acid was added to a 3-inch flask equipped with a condenser tube in a 3 mL The oxime ester, 12 5 § potassium carbonate, 18 〇 claw [n, n-dimethylformamide, was heated and stirred at 8 ° C for 9 hours. After confirming the completion of the reaction by tlc, the reaction solution was cooled to room temperature. The reaction solution was poured into 500 mL of water and mixed and stirred. The precipitated white solid was separated by filtration and washed further with ethanol. With 8 〇. The solid obtained was vacuum dried to obtain i 0 g of Compound 4. -71-201237069 [Synthesis Example 7] In a 100 mL three-necked flask equipped with a condenser, 9 5 § Compound 4, 1.6 g of lithium hydroxide, monohydrate '3 〇 mL sterol, i5 mL of tetrahydrofuran, 15 mL of water were added. 8 (rc was heated and stirred for 4 hours. After confirming the completion of the reaction with τιχ, the reaction solution was cooled to room temperature. Dilute hydrochloric acid was slowly added dropwise to the reaction solution while stirring the reaction solution. The sequential washing of water and ethanol was carried out by vacuum drying the obtained solid in (10) to obtain 9 § specific carboxylic acid 2. [Synthesis of specific carboxylic acid 3] The specific carboxylic acid 3 was synthesized according to the following reaction route.

FFFF specific carboxylic acid 3 [I Example 8] In Synthesis Example 2 'Use i〇'7g 2,3,5,6-tetrafluoro-4 (pentafluorophenyl)-72- 201237069 phenol instead of 4-cyano Base-4'-hydroxybiphenyl to thereby obtain 13.7 g of compound [Synthesis Example 9] In Synthesis Example 3, 1 3.5 g of Compound 5 was used instead of Compound 1, thereby obtaining 11.2 g of a specific carboxylic acid 3. [Synthesis of Specific Carboxylic Acid 4] The specific carboxylic acid 4 was synthesized in accordance with the following reaction route.

CI

e»3n ch2ci2

Cl

UOH H20

F F F F specific carboxylic acid 4

Me0H/THF/H20 [Synthesis Example 10] In Synthesis Example 4, 25.5 g of 2,3,5,6-tetrafluoro-4-(pentafluorophenyl)phenol was used instead of 4-cyano-4'-hydroxyl group. Biphenyl, which obtained 23.1 g of the compound -73-201237069. [Synthesis Example 1 1] In the synthesis example 5, 18.9 g of the compound 6 was used instead of the compound 2, whereby 24. g of the compound 7 was obtained. [Synthesis Example 12]' In the synthesis example 6, 20 g of the compound 7 was used instead of the compound 3, whereby 1 5.4 g of the compound 8 was obtained. [Synthesis Example 13] In the synthesis example 7, 13 g of the compound 8 was used instead of the compound 4, whereby 1 1.4 g of a specific tick acid 4 was obtained. [Synthesis of Specific Carboxylic Acid 5] The specific carboxylic acid 5 was synthesized in accordance with the following reaction route.

0(CH2)5 COOMe K2C〇3

DMF

NC

o(ch2

LiOH · H20

MeOH / H20

C〇〇H

[Synthesis Example I4] Synthesis of the plaque-specific slow acid 1 If the product was subjected to a 'U" operation, 15 g of a specific carboxylic acid obtained by changing the number of the fluorenylene group from 10 to 5 was synthesized [Synthesis of a specific carboxylic acid 6] The specific acid 6 was synthesized according to the following reaction route. -74- 201237069

K2C〇3 DMF

Li0H.H20 -_ Me0H/H20

COOH

[Synthesis Example 15] In a 500 mL three-necked flask equipped with a condenser, 2,2',3,3'-tetrafluoro-4'-propyl-4-yl-biphenyl oxime.ig, 11-di - 10 g of decyl ester, 14.2 g of potassium carbonate, and 200 mL of N,N-diindenylamine, and stirred under heating at ° C for 5 hours. After confirming the completion of the reaction by TLC, the solution was cooled to room temperature. The reaction solution was poured into 5 mL of water, and the mixture was stirred and stirred. The precipitated white solid was separated by filtration and washed with water i. The solid obtained was vacuum dried at 80 ° C, and 10 9 g of compound 9 was obtained. [Synthesis Example 16] The receiver was provided with a 2 〇〇mL three-necked flask having a condenser tube, 10 g of the compound 9, 1 . [Μ lithium hydroxide. monohydrate, 30mL methanol

Stir at 0 C for 4 hours. The reaction was confirmed by TLC, and the reaction solution was stirred at room temperature to room temperature. While stirring the reaction solution, dilute hydrochloric acid slow % 1 and scraps were added to the reaction solution. The precipitated solid was added to the ruthenium alkoxide 60. The reaction was carried out in one step. After adding a 15 mL bundle, the mixture was washed in the order of -75-201237069 water and ethanol. The obtained solid was vacuum dried at 80 ° C to obtain 6 g of a specific acid. [Synthesis of a specific carboxylic acid 7] Synthesis of a specific citric acid 7 according to the following reaction route

DMF K2C〇3

Li0H.H20 -► Me0H/H20 C3H7

F F specific carboxyl

COOH

[Synthesis Example 17] The starting compound (2, 2, 3, 3, tetrafluoro_4,_propyl_4·hydroxybiphenyl) i〇.lg was changed to the compound described in the above reaction route (2) In the same manner as the above-mentioned synthesis of the specific tickic acid 6 except that 3-1 g of 3-difluoro 4-(4-propyl-cyclohexyl) was used, 5-9 g of the specific slow acid 7 was obtained. [Synthesis of Specific Carboxylic Acid 8] A specific slow acid 8 was synthesized in accordance with the following reaction route. •76- 201237069

K2C〇3 DMF

[Synthesis Example 1 8] The starting compound (2,2',3,3'-tetrafluoro-4, propyl-4 hydroxybiphenyl) l〇.lg was changed to the compound described in the above reaction route (2, In the same manner as the above-mentioned synthesis of the specific tickic acid 6 except that 2,3,3,-tetrafluoro-4-propyl_4"-provided triphenylene) was 12.9 g, a specific carboxyl group of 7.lg was obtained. Acid 8. [Synthesis of a specific carboxylic acid 9] Synthesis of a specific carboxylic acid according to the path of the reaction

OH F F

+ Br-fCK f-COOMeΛο

K2C〇3 DMF C3H7

LiOH-H2〇 Me0H/H20 C3H7

Specific carboxylic acid 9

卞7 C00H -77- 201237069 [Synthesis Example 1 9] The starting compound (2,2',3,3,-tetrafluoro_4,-propyl_ + you, 4-formylbiphenyl) 10.lg 10.2 g of the compound (2 3 -dimethoxy-4-(4-propylcyclohexylmethoxy)phenylhydrazine) described in the above reaction scheme, and the same as the above-mentioned synthesis of the specific carboxylic acid 6 except for u Operationally, 6.5 § specific carboxylic acid 9 was obtained. [Synthesis of Specific Carboxylic Acid 10] A specific carboxylic acid 10 was synthesized according to the following reaction route.

OH + Br-^-CH2^COOMe 〇-fCH2Vc〇〇Me. -(ch2^cooh specific carboxylic acid 10 F F

K2C03 &quot;DMF U0H-H20 -►

MeOH/H2 〇 [Synthesis Example 20] The starting compound (2, 2, 3, 3, _tetraqi_4, _propyl_cardiohydroxybiphenyl HO.lg was changed to the compound described in the above reaction route ( 126 g of 2,3-difluoro-deca-(4-propylphenylethyl)biphenyl) was mixed with the above-mentioned specific acid 6 (IV) to obtain 7.2 g of a specific acid retardant. Synthesis of Carboxylic Acid 1 1 The specific carboxylic acid n was synthesized according to the following reaction route. -78- 201237069 C3H7

F F

F F

OH + Br- -CH Seven COOMe K2C〇3 DMF*&quot; C3H7

F F

COOMe

LiOH_H20

MeOH/H20

F F

F F

COOH FF specific carboxylic acid 11 [Synthesis Example 21] 10.1 g of the starting compound (2,2',3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) was changed into the above reaction route. In the same manner as the above-mentioned synthesis of the specific carboxylic acid 6, except that 14.2 g of the compound was obtained, 7.6 g of the specific slow acid 1 was obtained. [Synthesis of Specific Carboxylic Acid 12] The specific carboxylic acid 12 was synthesized according to the following reaction route. -79- 201237069

OH Br-(-CH24c〇OMe \ MO K2C〇3

DMF C5H” C5H”

O-C10H20 COOMe 〇-C10H20 cooh F F specific carboxylic acid 12 uoh-h2o

MeOH/^iT

[Synthesis Example 22] In a 500 mL three-necked flask equipped with a condenser, 4-[difluoro(4-pentylcyclohexyl)methoxy]_2,3·difluorophenol 125 g, uronium bromide 1 〇g, potassium carbonate 14.2 g, and N,N-didecyl decylamine 200 mL were heated and stirred at 1 60 C for 5 hours. After confirming the completion of the reaction by TLC, the reaction bath was cooled to room temperature. The reaction solution was poured into 5 mL of water and mixed and stirred. The precipitated white solid was separated by filtration and further washed with water. The obtained solid was vacuum dried at 80 ° C to obtain 14.8 g of a compound. [Synthesis Example 2 3 ]

Next, Mg compound 10, 1.6 g of lithium hydroxide, monohydrate, 3 〇 inL of methanol, and 15 mL of -80 - 201237069 water were placed in a 20 OmL three-necked flask equipped with a condenser, and the mixture was heated and stirred at 80 C for 4 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. Dilute hydrochloric acid was slowly added dropwise to the reaction solution while the reaction solution was stirred. The precipitated solid was filtered and washed in the order of water ethanol. 6 g of a specific carboxylic acid was obtained by vacuum-drying the obtained solid at 80 ° C; (2. &lt; U] Synthesis of polyorganosiloxane compound &gt; [Synthesis Example 24] To 100 mL of _ 9 g of the specific bismuth oxalate obtained by the above Synthesis Example 3 was added to the flask under the above-mentioned synthesis example &quot;polyoxyorganoxane having an epoxy group, 28 g of methyl isobutyl ketone, and 5. g. , 1 q λ 1 , 订 a熳1, 3.3 g as exemplified by the compound represented by the above formula (5), wherein 以 ^, &amp; _ &amp; Λ A y A (5-5) 4_octyloxybenzoic acid and 〇-20g UCAT 18X (a grade 4 amine salt of λα at PRO manufactured by SAN-APRr») were mixed for 12 hours at go °c. After the reaction was terminated, the trial sterol was used. The precipitate was reprecipitated, and the precipitate was dissolved in ethyl acetate to obtain a solution. The solution was washed three times with water, and then the solvent was distilled off to obtain 14.5 g of fal. Polyorganosiloxane compound A_ i. [] jujube organic oxane compound A-1

Mw was 6,500 Å [Synthesis Example 25] The same procedure as in Synthesis Example 24 was carried out except that the specific carboxylic acid 2 was used instead of the specific carboxylic acid 2', thereby obtaining 128 £ [a] polyorgano oxysulfide compound A 2 White powder. A # 6,〇〇〇. VL- VLW [Synthesis Example 26] The same procedure as in Synthesis Example 24 was carried out except that 6.8 g of the specific slow acid 3 obtained in Synthesis Example 9 was used in the same manner as in Synthesis Example 24, thereby obtaining 147 -81 - 201237069 [a] polyorganoindole The river of the white powder β a_3 of the oxyalkyl compound Ad was evaluated as 8,100 ° [Synthesis Example 27] The same procedure as in Synthesis Example 24 except that 5.6 g of the specific slow acid 4 obtained in Synthesis Example 13 was used instead of the specific carboxylic acid 1 ' The operation was carried out to obtain 15? g of a white powder of [a] polyorganooxane compound A-4. Eight_4; ^^ is 7,500. [Synthesis Example 28] To a 100 mL three-necked flask, 9.8 g of the polyorganosiloxane having an epoxy group obtained in the above Synthesis Example 1 and 28 g of methyl isobutyl s, j, i 〇 g were obtained by the above Synthesis Example 3. The specific acid 1 and 〇.2〇g UCAT 18X (a grade 4 amine salt of SAN-APR0) were stirred at 80 ° C for 12 hours. After the reaction was terminated, reprecipitation was carried out with methanol, the precipitate was dissolved in ethyl acetate, and the solution was washed with water three times, and then the solvent was distilled off to obtain 16.0 g of [a] polyorganooxime in a white powder. Alkane compound a-5. The Mw of A-5 is 8,500. [Synthesis Example 29] 4.1 g of the specific carboxylic acid 5 obtained in Synthesis Example 14 was used instead of the specific carboxylic acid 1, and 3.7 g of 4'-pentyl-1,1 represented by the above formula (5-8) was used. In the same manner as in Synthesis Example 24 except that the bis(cyclohexyl)-4-carboxylic acid was used instead of the 4-octyloxybenzoic acid, 1 2 · 4 g of [a] polyorganosiloxane compound A-6 was obtained. White powder. The Mw of A-6 is 6,200. [Synthesis Example 30] The same procedure as in Synthesis Example 24 except that 3.6 g of 4-(4-pentylcyclohexyl)benzoic acid represented by the above formula (5-7) was used instead of 4-octyloxybenzoic acid. -82 - 201237069 The ground was operated so that cats; 1 , seized 13.4 g of a white powder of [a] polyorganosiloxane compound A-7. A-7 A/r, A 7] vtw is 7,900.

[Synthesis Example 3 1J] To a 1 〇〇mL two-necked flask, 9·8 g of the 'organooxy group-containing polyorganosiloxane, 28 g of methyl isobutyl ketone obtained in the above Synthesis Example 1, and 8.0 g were added. The specific carboxylic acid oxime obtained in Example 3 above, 丨4@4(4-mercaptocyclohexyl)benzoic acid which is not represented by the above formula (5-7), and 0.20 g of UCAT 18X (SAN-APR 〇4) Grade amine salt), given at 8 〇e&gt;c for 12 hours. After the reaction, and then reprecipitation with methanol, the precipitate was dissolved in ethyl acetate, and the 4/liquid mixture was washed with water three times, and then the solvent was distilled off to obtain 13.9 g of the white powder. Organic oxirane compound A_8. The Aw has an Mw of 8,900. [Synthesis Example 32] To 100 mL of a mouth-burning plate, 98 g of a polyorgano-hydrogen cholate having a cyclodecyl group obtained by the above Synthesis Example, 28 g of nonylisobutylphosphonium, and 2 g of the above-mentioned Synthesis Example 3 were added. Specific carboxylic acid 1, 5.8 g of 4-(4-pentylcyclohexyl)benzoic acid which is not represented by the above formula (5-7), and 20.20 g of UCAT 18X (grade 4 amine salt of SAN-APRO) at 8 〇 It was stirred for 12 hours. After the reaction was terminated, reprecipitation was carried out with decyl alcohol, the precipitate was dissolved in ethyl acetate to obtain a solution, the solution was washed with water three times, and then the solvent was distilled off to obtain 134 g as a white powder. Polyorganosiloxane compound A-9. The Mw of A-9 is 7,6〇〇. [Synthesis Example 33] In a 100 mL one-neck flask, 9 $ g of the polyorganosiloxane having an epoxy group obtained in the above Synthesis Example 1 and 28 g of decyl isobutyl ketone '8 - 83 - 201237069 were added from the above synthesis. The specific carboxylic acid obtained in Example 3, 2.6 g of the acid-supplemented derivative represented by the above formula (5-6) and the UCAT18X (manufactured by SAN-APR 4 grade amine salt) of 〇2〇g were at 8 Torr. Stir for 12 hours. After the reaction was terminated, reprecipitation was carried out with methanol, the precipitate was dissolved in ethyl acetate, and the solution was washed with water three times, and then the solvent was distilled off to obtain 1 [a] polyorganodecane compound as a white powder. A-10. The Mw of A-10 is 9,200. [Synthesis Example 34] A specific operation was carried out in the same manner as in Synthesis Example 24 except that the specific carboxylic acid 1 was replaced with 6.1 g of the specific tick acid 6 obtained in Synthesis Example 16. 8 4 g of a white powder of [a] polyorganosiloxane compound A-1. The Mw of A-l 1 is 7,300. [Synthesis Example 3 5] 1 7.5 g of [a] polyorganosiloxane compound was obtained in the same manner as in Synthesis Example 24 except that the specific carboxylic acid 7 obtained in Synthesis Example 17 was used instead of the specific carboxylic acid 1. A-12 white powder. The Mw of A_12 is 7,60〇. [Synthesis Example 3 6] In the same manner as in Synthesis Example 24, except that 7.2 g of the specific carboxylic acid 8 obtained in Synthesis Example 18 was used instead of the specific citric acid 1, a 9·1 g [a] polyorganofluorene was obtained. A white powder of oxane compound A-13. The Mw of A-13 is 7,000. [Synthesis Example 3 7] In the same manner as in Synthesis Example 24, except that the specific buffer acid 9 obtained in Synthesis Example 19 was used instead of the specific oxime 31, the organic oxime was obtained in the same manner as in Synthesis Example 24. A white powder of oxane compound A-14. Mw of A-14 was -84. 201237069 6,900 ° [Synthesis Example 38] The same procedure as in Synthesis Example 24 was carried out except that 7.0 g of the specific bamboo carboxylic acid 10 obtained in Synthesis Example 20 was used instead of the specific carboxylic acid 1. A white batch of 19.4 g of [a] polyorganosiloxane compound A-1 5 was obtained as a masterpiece. Mw of A-15 was 7,500 ° [Synthesis Example 39] 2 〇 was obtained in the same manner as in Synthesis Example 24 except that 8.4 g of the specific carboxylic acid 丨i obtained in Synthesis Example 21 was used instead of the specific acid 1'. g [a] A white powder of polyorgano oxysulfonated compound A-16. The ^^ of _16 is 7,300 〇 [Synthesis Example 40] The same procedure as in Synthesis Example 2 4 was carried out except that 7.2 g of the specific carboxylic acid oxime 2 obtained in Synthesis Example 23 was used instead of the specific buffer acid 1 '. 1 9 5 g [a] A white powder of polyorgano-oxygenated compound A-1 7. Mw of a- 1 7 was 7,300 ° [Comparative Synthesis Example 1] To a 100 mL three-necked flask, 9.8 g of the polyorganosiloxane having an epoxy group obtained by the above Synthesis Example 1 and 28 g of anthryl isobutyl ketone were added. 3.3 g of 4-octyloxybenzoic acid and CAT.l〇g of UCAT 18 (3 VIII) were stirred at 80 ° C for 12 hours. After the reaction was terminated, reprecipitation was carried out with methanol, the precipitate was dissolved in ethyl acetate, and the solution was washed with water three times, and then the solvent was distilled away to obtain 9.6 g of a white organic powder. Compound CA-1. The VIw of CA-1 is 6,000 〇-85-201237069 &lt;[B] Synthesis of Polymer&gt; [Synthesis Example 41] 2 3 ς JZ, J, 5' tricarboxycyclopentane as tetracarboxylic acid dianhydride The base acetic acid dianhydride 38_32g and the stupid tetracarboxylic acid dianhydride i2 43 - _ and the diamine compound are dissolved in the dife: 18.86g and the diamine 30.40g which is not represented by the following formula (g_4) _ XT ^ , J is dissolved in N - Mercapto-2-n-pyrrolidone 4〇〇' δ was reacted at 60 C for 4 hours. The viscosity of the polymerization solution was measured and found to be 4,1 〇〇mPa. In the case of the reaction, the reaction solution was poured into an excess of sterol to precipitate the ruthenium paint. Thereafter, it was washed with decyl alcohol, and dried under reduced pressure at 40 ° C for 24 hours to obtain 7 5 · 1 g of polylysine PA-1.义 meaning

2,3,5•tris-cyclopentyl acetic acid as tetrazolic acid dianhydride 23.06 g U and 3,5•diaminobenzoic acid η as an amine compound are in the above formula (G-4) 81 g of the diamine which is not present, and 5.12 g of the monoamine represented by the following formula (G 5), and the solution of the ketone of the N-mercapto-2_吼0, at 6〇t&gt;c The viscosity of the polymerization solution was measured at 4 J, and was mPa s. The reaction mixture was precipitated by subjecting the reaction mixture to a preliminary sterol. Thereafter, polystyrylic acid was obtained by drying with methanol at 4 Gt for 24 hours under reduced pressure. The obtained polylysine of P was redissolved in 450 g of N-mercapto-2-pyrrolidone, 8 14 g of pyridine and hydrazine acetate were added and it was removed at -10-201237069 for 4 hours. In the same manner as above, 'precipitation, washing, and drying under reduced pressure' were carried out to obtain 3 〇. 5 g of polyimine PI-1 having a ruthenium iodide ratio of 55%.

Nh2 h2n (G-5) [Synthesis Example 4 3 ] 33.92 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, and 3 5 -diamine group as a diamine compound 4 61 g of benzoic acid and 61.46 g of a diamine represented by the following formula (G-6) were dissolved in N-mercapto-2-»Bilo bite 185 g' at 60 ° C for 4 hours. The viscosity of this polymerization liquid was measured to be 50 mPa·s. Next, the reaction solution was poured into an excess amount of methanol to precipitate a reaction product. Thereafter, it was washed with methanol, and dried under reduced pressure at 4 ° C for 1, 5.24 hours to obtain 63.9 g of polylysine PA-2.

C5h" (G-6) [Synthesis Example 44] 1,2,3,4-cyclobutanetetraphthalic acid dianhydride 37 as a tetracarboxylic dianhydride, 5 g of hydrazine, and 3, 5 as a diamine compound 2178 g of diaminobenzoic acid, 9.44 g of diamine represented by the above formula (G-5), and 6-73 g of 1-(2,4-diaminophenyl)decene-4-carboxylic acid dissolved in N - 425 g of methyl-2-pyrrolidone, reacted at 60 c for 4 hours. The viscosity of the polymerization solution was determined to be i8 〇 mPa.s -87 - 201237069. Then the reaction solution was injected into excess methanol. The reaction product was precipitated, and then washed with methanol, and dried under reduced pressure at 4 (rc for 24 hours to obtain 51.5 g of polylysine pa_3. [Synthesis Example 45] 2 as tetrare-acid dianhydride 3,5_tricarboxycyclopentyl acetic acid diammonium 40.68g and pyromellitic acid dioxan 4_, and p-phenylenediamine U.〇5g as a diamine compound, represented by the above formula (G-4) 32.05g of diamine and 4,4,-diamino-_N_(4-methylphenyl)diphenylamine u 82§ dissolved in 400g of Nmethyl 1 ^ decyl ketone, reacted at 6 (rc for 4 hours) The dot of the polymerization solution was measured to be 1,450 mPa·s. Then, the reaction solution was injected into an excess of methanol to make a reaction. The product was precipitated. Thereafter, it was washed with methanol, and dried under reduced pressure at 40 C for 24 hours to obtain 71 9 g of polylysine pA 4 [Synthesis Example 46] 2,3,5_ as tetracarboxylic dianhydride 19.47 g of tricarboxycyclopentyl acetic acid dianhydride, 2 1 〇g of pyromellitic dianhydride, and 7.44 g of 3,5-diaminobenzoic acid as a diamine compound, represented by the above formula (G 4) 15.33g of diamine and 4,4,-diamino-_N_(4-methylphenyl)diphenylamine 5 66g dissolved in N-methyl-2-pyrrolidone 2〇〇g, at 6(rc The reaction was carried out for 4 hours, and the viscosity of the polymerization liquid was measured to be UOOmPa.s. The reaction solution was poured into an excess of sterol to precipitate a reaction product, and then washed with methanol under reduced pressure at 40 (: Poly-proline was obtained by drying for 24 hours. All the obtained poly-proline was redissolved in 450 g of N-methyl-2-pyrrolidone, 7.63 g of hydrazine and 9.85 g of acetic acid needle were added and dehydrated. In the same manner as above, the mixture was subjected to precipitation, washing, and drying under reduced pressure to obtain 34.0 g of a polyamidiamine having a ruthenium iodide ratio of 51%. -88 - 201237069 [Synthesis Example 47] Anhydride 2,3,5- 28.58 g of carboxycyclopentyl acetic acid dianhydride and 3.09 g of pyromellitic dianhydride, and 60-03 g of diamine and 4,4,-diamino-N represented by the above formula (G-4) as a diamine compound 8.31 g of -(4-methylphenyl)diphenylamine was dissolved in 400 g of N-mercapto-2-one than the bite ketone, and reacted at 60 C for 4 hours. The viscosity of this polymerization solution was measured and found to be 9 〇〇 mpa.s. Then, the reaction solution was poured into an excess amount of methanol to precipitate a reaction product. Thereafter, it was washed with methanol, and dried at 401 for 24 hours under reduced pressure to obtain 68.3 g of polylysine pa-5. [Synthesis Example 48] 48.99 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 5.30 g of pyromellitic dianhydride as tetracarboxylic dianhydride, and the above formula (G) as a diamine compound -4) 14.24 g of diamine 12.868, 4,4,-diamino fluorenyl (4-nonylphenyl) diphenylamine and 18.62 g of p-phenylenediamine are dissolved in Ν_mercapto-2 - pyrrolidone 4 〇〇g, reacted at 6 (rC for 4 hours. The viscosity of the polymerization solution was measured to be 1,3 50 mPa·s. Then, the reaction solution was injected into the methanol to make the reaction product Precipitation. Thereafter, it was washed with decyl alcohol and dried under reduced pressure at 40 C for 24 hours to obtain 66.0 g of polyplysine pA_6. [Synthesis Example 49] 2,3,5_3 as tetracarboxylic dianhydride 41-34 g of carboxycyclopentyl acetic acid dianhydride and 2 l2 g of pyromellitic dianhydride, and 14.79 g of 3,5-diaminobenzoic acid as a diamine compound, and diamine 3 represented by the above formula (G 4) 〇.5〇g and 4,4,-diamino-_N_(4-methylphenyl)diphenylamine n was dissolved in N-methyl-2-pyrrolidone 4〇〇g, at 6 〇〇c reacted for 4 hours. The dot of the polymerization solution was determined to be UMmPa.s. Then the reaction was dissolved-89-201237069 The liquid was poured into an excess of methanol to precipitate a reaction product, which was then washed with decyl alcohol, and dried at 40 C under reduced pressure for 24 hours to obtain 62 8 § poly phthalic acid PA-7. [Synthesis Example 50] 18.85 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, and 8.84 g of diamine represented by the above formula (1)·4) as a diamine compound, and a paraphenylene group The amine 7.3 lg was dissolved in 140 g of hydrazine-methyl-2-pyrrolidone and reacted at 60 ° C for 4 hours. The viscosity of this polymerization solution was measured and found to be 2,15 〇 mPa, s. The reaction solution was poured into an excess amount of methanol to precipitate a reaction product. Thereafter, it was washed with methanol, and dried under reduced pressure at 4 °t &gt; c for 24 hours to obtain polylysine. All the obtained polylysine was redissolved in N-mercapto-2-furonidone 465 g '6.65 g of added pyridine and 8 · 5 9 g of acetic anhydride and dehydrated at 11 ° C for 4 hours, and The same operation as above was carried out; children; &, decanting, decompression dryness did not obtain 2 3 1 g of polyimine PI-3 having an amidization ratio of 5 %. [Synthesis Example 51] 24.94 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, and 1.24 g of diamine 1 represented by the above formula (G-5) as a diamine compound. And 13.82 g of 3,5-diaminobenzoic acid was dissolved in 200 g of N-fluorenyl-2-pyrrolidone, and reacted at 60 ° C for 4 hours. The viscosity of this polymerization solution was measured and found to be 1,400 mPa·s. The reaction solution was poured into an excess of sterol to precipitate a reaction product. Thereafter, it was washed with methanol, and dried at 40 ° C for 24 hours under reduced pressure to obtain polylysine. All the obtained poly-proline was redissolved in N-mercapto-2-π-π ketone 4 50 g, adding ton π 1 3.2 〇g and acetic anhydride 17.04 g and dehydration closed at 110 ° C After 4 hours, the same operation as above--90-201237069 was carried out to carry out precipitation, washing, and drying under reduced pressure of 2 7.8 g of polyimine p 1-4 having an amidization ratio of 69%. &lt;Preparation of Liquid Crystal Aligning Agent&gt; [Example 1] A solution containing the poly-proline acid PA obtained in the above Synthesis Example 41 as the [b]polymerization & The amine acid PA-1 is equivalent to 100 parts by mass, and 1 part by mass of the [a] polyorganooxazane compound obtained in the above Synthesis Example 24 is added thereto. -n-b-pyridone and butyl sirolius, resulting in a solvent composition of N-methyl-2-. A solution having a solid content concentration of 3.5% by mass in a ratio of 11 to 1 butyl celesta: = 5 〇: 5 〇 (mass ratio). This solution was filtered by a pore size filter to prepare a liquid crystal alignment agent s _ i. <Pressure of Voltage Retention Rate (VHR) and Liquid Crystal Display Element for Evaluation of Light Resistance> In the VHR and light resistance evaluation, liquid crystal cells produced as follows were used for evaluation. The liquid crystal alignment agent S-1 prepared above was applied onto the transparent electrode surface of the glass substrate with the transparent electrode formed of the ITO film by spin coating, and prebaked on a hot plate at 80 ° C for 1 minute. The film (liquid crystal alignment film) having a film thickness of 〇·08 μΓ was formed by heating at 200 ° C for 1 hour in an oven substituted with nitrogen. This operation was repeated to form a pair of (two) substrates having a liquid crystal alignment film. By coating an outer periphery of a surface of the substrate having the liquid crystal alignment film on one of the substrates, an epoxy resin adhesive having an alumina ball having a diameter of 3 · 5 μm is applied, and the opposite direction is applied. Liquid crystal alignment of another substrate -91- 201237069 The film surface overlaps and is crimped to H5 (TC heats for 1 hour and heat hardens the adhesive. Then 'fills the gap between the liquid crystal injection port and the substrate with positive liquid crystal (Merck, ZU) -508 1) After sealing the liquid crystal injection port with an epoxy-based adhesive, in order to remove the flow alignment during liquid crystal injection, it was heated at 150 ° C for 1 minute and then slowly cooled to room temperature. 'The polarizing plate is bonded to the outer surfaces of the liquid crystal cell substrate so that the polarizing directions of the two polarizing plates are orthogonal to each other, thereby manufacturing a liquid crystal display element. <Vertical alignment and liquid crystal reaction rate evaluation [Production of Liquid Crystal Display Element] The liquid crystal cell produced by the following operation was used for evaluation in terms of the vertical alignment property and the liquid crystal reaction rate. The ITO electrode of the glass substrate which was patterned in a comb-tooth shape at 1τ The liquid crystal alignment agent S _ i prepared above was applied to each side of the side of the opposite glass substrate on which the electrode was not provided with a spin coater, and prebaked on the hot plate at 80 C for 1 minute. The coating film (liquid crystal alignment film) having a film thickness of 0.08 μm was formed by heating (post-baking) at 200 ° C for 1 hour in a baking Iss after replacement with nitrogen in the apparatus. No tantalum electrode was provided in the above substrate. On the outer periphery of the surface of the glass substrate having the liquid crystal alignment film, an epoxy resin adhesive having a diameter of 3.5 μm is loaded by screen printing, and then the tantalum electrode is patterned in a comb shape. The liquid crystal alignment film of the glass substrate is pressed against the surface, and the adhesive is thermally cured at 150 ° C for 1 hour. Then, the gap between the substrates is filled with Merck-made positive liquid crystal from the liquid crystal injection port. (ZLI-5081), the liquid crystal injection port is sealed with an epoxy adhesive. In step -92- •201237069, in order to remove the flow alignment during liquid crystal injection, it is heated at 150 °C for 10 minutes. After slowly cooling to room temperature, then in the resulting liquid crystal The polarizing plates were bonded to each other on the outer surface of the cell substrate so that the polarizing directions thereof were orthogonal to each other to produce a liquid crystal display element. [Examples 2 to 26 and Comparative Examples 1 to 4] [B] Polymer and [a] The liquid crystal alignment agents S-2 to S-26 and CS-1 to CS- were prepared in the same manner as in Example 1 except that the mixing ratio of the polyorganosiloxane compound was changed to the mixing ratio described in Table 1. 4. "-" in Table 1 indicates that the corresponding components were not used. Further, in the same manner as in Example 1, the liquid crystals of Examples 2 to 26 and Comparative Examples 1 to 4 were produced by using the prepared liquid crystal alignment agents. Display element ° &lt;Evaluation&gt; The following evaluation was performed on the liquid crystal display element manufactured as described above. The results are shown together in Table 1. [Vertical alignment] The liquid crystal display element produced above was observed using an optical microscope. At this time, the vertical alignment property was evaluated as "〇" for the liquid crystal display element having no light leakage, and "X" was evaluated for the liquid crystal display element having light leakage. [Voltage Retention Rate (VHR (%))] After applying a voltage of 5 V to the liquid crystal display element manufactured as described above at an application time of 60 μsec and a pitch of 167 msec, the measurement was performed after 167 ms from the release of the application. Voltage retention rate. The measuring device used VHR-1 manufactured by τ 〇 γ 〇 Technica. [Reaction rate (electro-optical reactivity at the beginning)] -93- 201237069 The time at which the liquid crystal reaction started was measured by a device including a polarizing microscope, a photodetector, and a pulse generator. Here, the liquid crystal reaction rate is evaluated by τ as defined by the following time: when a voltage of a maximum of seconds is applied to the manufactured liquid crystal display element from the state of no application, the transmittance is changed from 10% to the transmittance of 9 The time required for 〇% (unit: milliseconds (mse c.)). [Optical property] The VHR after 3,000 hours of irradiation with a weather meter using a carbon arc as a light source was measured in the same manner as described above (applying a voltage of 5 V at an application time of 60 microseconds and a pitch of 167 milliseconds) Then, the voltage holding ratio after 167 milliseconds from the release of the application was measured. The measurement device used VHR-1) manufactured by tqyq Technica. The evaluation of the VHR change amount of 1% or less compared with the measured value before the irradiation was "〇"; % and less than 3% of the evaluation is "△"; 3% or more of the evaluation is "X!. -94- .201237069 [Table i]

Liquid crystal alignment agent [B] Polymer [a] Polyorganooxyxanthene compound evaluation $ 1 Result Component 1 Component 2 Vertical alignment voltage retention ratio (%) Reaction rate (msec.) Light resistance type mixture amount (parts by mass) Mixing amount (parts by mass) Kind of mixing amount (parts by mass) Example 1 S-1 PA-1 100 _ A-1 10 〇 98 18 〇 Example 2 S-2 PA-1 100 _ _ A-1 20 〇 98 12 〇 Example 3 S-3 PI-1 100 _ • A-2 10 〇 99 10 〇 Example 4 S-4 PA-2 10 PA-3 90 A-3 10 〇 98 23 〇 Example 5 S-5 PA-2 10 PA-3 90 A-5 10 〇98 9 〇Example 6 S-6 PA-4 100 _ _ A-5 5 〇98 11 〇Example 7 S-7 PI-2 100 — _ A- 6 10 〇99 17 〇Example 8 S-8 PA-5 20 PA-6 80 A-7 10 〇99 15 〇Example 9 S-9 PA-5 10 PA-6 90 A-5 10 〇99 8 〇 Example 10 S-10 PA-7 100 _ _ A-8 10 〇 98 10 〇 Example 11 S-11 PA-7 100 _ A-8 20 〇 98 8 〇 Example 12 S-12 PI-3 100 _ A-9 5 〇99 24 〇Example 13 S-13 PI-3 100 • _ A-9 10 〇98 20 〇Example 14 S-14 PI-3 100 A-9 25 〇99 14 〇Example 15 S -15 PI-4 100 _ A-7 10 〇99 18 〇Example 16 S-16 PI-4 100 • _ A-7 20 〇99 13 〇Example 17 S-17 PI-4 100 _ _ A-7 30 〇98 10 〇Implementation Example 18 S-18 PA-7 100 _ A-10 5 〇 98 13 〇 Example 19 S-19 PA-7 100 A A-10 10 〇 98 10 〇 Example 20 S-20 PA-5 10 PA-6 90 A-11 10 〇99 8 〇Example 21 S-21 PA-5 10 PA-6 90 A-12 10 〇99 8 〇Example 22 S-22 PA-5 10 PA-6 90 A-13 10 〇 99 8 〇 Example 23 S-23 PA-5 10 PA-6 90 A-14 10 〇99 8 〇Example 24 S-24 PA-5 10 PA-6 90 A-15 10 〇99 8 〇Example 25 S-25 PA-5 10 PA-6 90 A-16 10 〇99 8 〇Example 26 S-26 PA-5 10 PA-6 90 A-17 10 〇99 8 〇Comparative Example 1 CS-1 PA-1 100 _ _ _ 〇 98 35 X Comparative Example 2 CS-2 PA-1 100 - _ CA-1 10 〇 98 41 Δ Comparative Example 3 CS-3 PI-1 100 _ _ _ 〇 95 38 X Comparative Example 4 CS- 4 PI-3 100 - - - X 93 Unable to measure X -95- 201237069 According to the results of Table 1, the liquid crystal display element of the embodiment can be made to meet the general requirements of voltage holding ratio, light resistance and electro-optics. Short reaction time A vertical alignment liquid crystal display element of a positive liquid crystal. [Industrial Applicability] According to the present invention, it is possible to provide a vertical alignment liquid crystal element using a positive liquid crystal which satisfies both the general required characteristics such as voltage holding ratio and light resistance and short electro-optical reaction time. [Simple description of the diagram] None. [Main component symbol description] No 0 -96-

Claims (1)

201237069 VII. Patent application scope: 1 ♦ A liquid crystal display element comprising: a pair of substrates disposed oppositely, a liquid crystal layer disposed between the two substrates, and a pair of liquid crystal alignment films disposed on both surfaces of the liquid crystal layer And an electrode for generating a transverse electric field disposed on at least one of the pair of substrates; wherein the liquid crystal layer contains a positive liquid crystal, and the liquid crystal alignment film is formed by a liquid crystal alignment agent, the liquid crystal alignment The agent contains [A] a polymer having a group represented by the following formula (A1), (A1) (a part or all of hydrogen atoms of the formula (A1) in which R1 is an anthracene group, a fluorene group having a carbon number of 2 to 3 Å, a phenyl group or a cyclohexyl group) Substituting; R2 is a linking group containing a double bond, a triple bond, an ether bond, a vinegar bond, and an oxygen atom; R3 is a group having at least two single ring structures; a is ruthenium or 1). 2. The liquid crystal display element of claim 1, wherein the liquid crystal alignment film is a vertical liquid crystal alignment film. 3 _ For example, the liquid crystal display element of the patent application Fan Park ,1, wherein the R3 in the above formula (A1) is not described in the following formula (A2), (7. ft (A2) (Formula (A2), 〆 is a phenyl group, a biphenyl group, a naphthyl group, a cyclohexylene group, a bicyclohexanium group, a cyclohexylene group or a divalent heterocyclic group, and some or all of the gas atoms of these groups may be Substituted; R5-97-201237069 for the base group, yl-cyclohexene to obtain all groups, a few groups of R5, R7 to 4. For example, the object is 5. If the product contains the following, it can be substituted. a substituent group of at least one of a fluorenylene group having at least one of a hydrazine double bond, a double bond, an ether bond, an ester bond, and a heterocyclic group having a carbon number of 2 to 1 Å, and R is derived from benzene, biphenyl, naphthalene, a (c+1)-valent group in which cyclohexane, bis, %, hexylbenzene or a heterocyclic compound removes (c+1) a hydrogen atom, and a part of a hydrogen atom of the group may be substituted; R7 Is a hydrogen atom, a cyano group, a hydride atom, a trifluoromethyl group, an oxy group, an alkoxy group, a trifluoromethoxy group or a decyloxy group; b is 0 or 1; an integer of 鸸丨~9 ;^丨 or 2; r4, In the case where each of R7 and b is plural, a plurality of r4, R5, and b may be the same or different.) «The liquid crystal display element of the first aspect of the patent range, wherein [A] is polymerized with a polyorganosiloxane structure The liquid crystal display element of any of the above-mentioned items, wherein the liquid helium alignment agent further contains [B] at least one polymer selected from the group consisting of polyacrylic acid and polystyrene. The liquid crystal display element of the fifth aspect of the invention, wherein [B] is obtained by polymerizing an amine, a diamine containing a cholestyl group or a diamine represented by the formula (A-1). (in the formula (A-1) -COO- or -〇C〇, base; α is 0 or 1; in the case of 〇; γ is 1, χΐ and X丨丨 are each independently a single bond, _〇_, , R1 is a methylene group or an alkylene group having 2 or 3 carbon atoms is an integer of 0 to 2; wherein α and β are not present as an integer of -20 at the same time). -98-201237069 7. An alignment agent which is a positive-type liquid crystal alignment agent for a transverse electric field type liquid crystal display element, which comprises [A] a polymer having a group represented by the following formula (A1), R3-[r2 Length R1—(A1) a (In the formula (A1), R1 is a methylene group, an alkylene group having 2 to 30 carbon atoms, a phenyl group or a cyclohexylene group, and a hydrogen atom of these groups Some or all of which may be substituted; R2 is a linking group containing a double bond, a triple bond, an ether bond, an ester bond, and an oxygen atom; R3 is a group having at least two single ring structures; a is 0 or 1). -99- 201237069 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 0. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: