TW201229137A - Liquid crystal alignment agent, liquid crystal display element, liquid crystal alignment membrane and polyorganicsiloxane compound - Google Patents

Abstract

The purpose of the present invention is about providing a liquid crystal alignment agent which can form a photo orientational liquid crystal display element satisfying the following requirements: voltage retention and photo resistance which are requested for a liquid crystal display element, and the response time of photoelectricity is short. The present invention is a liquid crystal alignment containing [A] polymers having photo orientational groups and groups represented by the following formula [A1]. In the following formula [A1], R<SP>A</SP> is methylene, alkylene having 2 to 30 carbon atoms, phenylene or cyclohexylene, wherein partial or all hydrogen atoms of these groups can be substituted, R<SP>B</SP> is a binding group including any one of double bond, triple bond, ether bond or oxygen atom, R<SP>C</SP> is a group having at least two single ring structures, and a is 0 or 1.

Description

201229137 VI. Description of the invention: [Technical field to which the invention pertains] The present invention is directed to a liquid crystal alignment agent suitable for use as a film material for forming a liquid crystal display element (LCD). A liquid crystal alignment film formed of the liquid crystal alignment agent, a liquid crystal display element having the liquid crystal alignment film, and a polyorganosiloxane compound suitable for use as a liquid a day alignment agent for PHmv-n. [Prior Art] In the liquid crystal display element, a liquid crystal alignment film is provided on the surface of the substrate in order to "align the liquid crystal molecules with respect to the substrate surface". The liquid crystal alignment film is usually formed by a method (rubbing method) of rubbing the surface of the organic film formed on the surface of the substrate in one direction with a cloth material such as rayon. In the case where the liquid crystal alignment film is formed by the rubbing treatment, dust or static electricity is likely to be generated in each of the rubbing steps. Therefore, dust adheres to the surface of the alignment film, which causes a display failure. When a substrate having a TFT (Thin Film Transistor) device is used, the circuit of the TFT element is damaged due to static electricity generated, which causes a decrease in product yield. Therefore, as another means for aligning the liquid crystal in the liquid crystal cell, a photo-alignment method in which a radiation-sensitive organic thin film formed on the surface of the substrate is irradiated with polarized or unpolarized radiation to impart a liquid crystal alignment ability has been proposed (see Patent Documents i~6). According to the light alignment method, dust or static electricity is not generated in the step, and a uniform liquid crystal alignment can be formed (see Patent Documents 7 to 9). Such a liquid crystal display device is expected to be used as a moving display device such as a mobile phone or a liquid crystal television, and the characteristics required for a liquid crystal display element should be able to smoothly display dynamic images and suppress image sticking as much as possible. Therefore, it is necessary to use 201229137 The response time of the optical effect is increased in speed. In the case where the polymer side chain used for the liquid crystal alignment film is not reported, the technique of providing dielectric anisotropy can improve the response time (see Patent Documents 10 and Π). However, these patent documents are related to liquid crystal alignment films which do not have a photo-alignment function, and have excellent electrical properties such as alignment, voltage retention, and afterimage characteristics, and optical alignment characteristics, which are important in practical use in addition to high speed of photoelectric response time. Not recorded. Based on this situation, it is desired to develop a photo-alignment liquid crystal alignment agent which can satisfy not only the characteristics of voltage holding ratio and light resistance which are generally required for liquid crystal display elements, but also a short photoelectric response time. [Patent Document 1] [Patent Document 1] JP-A-2004-163646 (Patent Document 2) JP-A-2004-163646 [Patent Document 3] Japanese Patent Laid-Open No. 2 - 2 5 0 9 [Patent Document 4] Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. No. 2003-1 14437 [Patent Document 5] JP-A-2003-1 14437 [Patent Document 5] Document 7] International Publication No. 2009/253 85 [Patent Document 8] International Publication No. 20/9/253, 86 [Patent Document 9] International Publication No. 2009/253 88 [Patent Document 1〇] JP-A-2007-521361 [Patent Document 1] Japanese Patent Application Publication No. 2007-52 1506 [Abstract] 201229137 [Problems to be Solved by the Invention] The present invention has been made in view of the above problems, and an object thereof is to provide a light. An aligning liquid crystal alignment agent, It is possible to form a liquid crystal display element which not only satisfies characteristics such as voltage holding ratio and light resistance which are usually required for a liquid crystal display element, but also has a short photoelectric response time, and has a vertical alignment type of a liquid crystal alignment film formed of the liquid crystal alignment agent. Several pieces of liquid crystal display; and a polyorganosiloxane compound suitable for use in the above liquid crystal alignment agent. [Means for Solving the Problems] The invention proposed to solve the above problems is a liquid crystal alignment agent containing [A] a polymer having a photo-alignment group and a group represented by the following formula (A1) (hereinafter referred to as (A) polymer, RC-iRBtRA—(A1) In the formula (A1), RA is a methylene group, an alkylene group having 2 to 3 carbon atoms, a phenyl group or a cyclohexyl group. Among them, one or more of the hydrogen atoms which these groups have may be substituted. rB is a linking group containing a double bond, a triple bond, an ether bond, such as a bond and an oxygen atom. rC is a group having at least two monocyclic structures. a is 〇 or i. The liquid crystal alignment agent of the present invention has a liquid crystal alignment film formed by the liquid crystal alignment agent by a [A] polymer having a group having a photo-alignment group and a specific structure represented by the above formula (A1). The liquid crystal display element not only satisfies the characteristics of voltage holding ratio and light resistance, but also has a short photoelectric response time. The photo-alignment group preferably has a structure represented by the following formula (B1): 201229137,

In the formula (B1), 'R is a fluorine atom or a cyano group. a' is an integer of 〇~4. When it is 2 or more, a plurality of r may be the same or different. * indicates the connection key. The liquid crystal alignment agent has the above-mentioned characteristics and the above-mentioned photo-alignment group, so that the sensitivity can be improved. '° Rc in the above formula (Α1) is preferably represented by the following formula (Α2)

F: G (A2) In the formula (A2), ' Rd is a phenyl group, a biphenyl group, a naphthyl group, a cyclohexyl group, a dicyclohexyl group, a cyclohexyl group or a divalent heterocyclic group. Some or all of one of the hydrogen atoms of these groups may be substituted. rE is a = group including at least one of an anthracene group which may have a substituent and at least one of a alkylene double bond, a double bond, an ether bond, an ester bond and a heterocyclic group having 2 to 10 carbon atoms. RF is a hydrogen having a group having a (C+1) valence of (c+1) hydrogen atoms removed from [biphenyl, [cyclohexane, dicyclohexane, % hexylbenzene or a heterocyclic compound] Some or all of the atoms may be substituted with RC' as a gas atom, a cyano group, a morphine atom, a tri-I methyl group, a pyridyloxyalkyl group, an alkoxy group, a trifluoromethoxy group or an alkylcarbonyloxy group. b is 0 or 1 c is an integer from 1 to 9. 4 is 1 or 2. When RD, RE, RG, and b are each plural: a plurality of RD, RE, RG, and b may be the same or different from each other. The liquid crystal alignment agent can further improve the effect of the present invention by the above Rc having the above specific structure. . 201229137 [A] The polymer preferably has a structure of s sin liquid crystal alignment agent to improve light resistance. There is a polyorganic &gt; The [A] polymer is a compound selected from the group consisting of polyorganoquinone [B], which is preferably in the group. The step contains a polymer consisting of at least one of polyglycolic acid and polypyrene (hereinafter referred to as an amine structure "[B] polythene liquid crystal alignment agent, solution characteristics and liquid obtained by liquid crystal alignment of the liquid crystal display of the present invention The liquid crystal alignment film of the liquid crystal display element does not have the characteristics of light resistance, and further contains a [B] polymer, which can improve the electrical characteristics of the crystal display element. The element is formed of the liquid crystal alignment agent. The liquid crystal alignment agent having the above-described liquid crystal alignment agent can satisfy the usual voltage holding ratio and exhibits a short photoelectric response time. The liquid crystal display element preferably has a liquid crystal alignment film having two or more different positions. The liquid crystal region of the present invention is different in the display position. The device has two or more domains which can be applied to the 3D display by the liquid crystal alignment film. The alignment film is formed of the liquid crystal alignment agent, and the liquid crystal alignment film is formed by the liquid crystal alignment film. The display element + the light resistance is formed by the above liquid crystal alignment film, and has a voltage holding ratio which satisfies only the usual requirements, and Performance which exhibits short photoelectric response time The ¥+ ιΐΛ J $organomethoxy siloxane compound of the present invention has a photo-alignment group and a group represented by the following formula (A1). It has a photo-alignment group and a group In the liquid crystal 201229137 RC-iRBtRA—(Al), in the formula (Al), RA is an alkylene group having a reverse atomic number of 2 to 30, or a cyclohexylene group. Some or all of the hydrogen atoms may be substituted. RB rabbit 4 K is a fast-loaded C Λ π 基 group including any of a double bond, a triple bond, an ether bond ester bond, and an oxygen atom. Rc has at least a group having two single structures. a is 0 or 1. The polyorgano compound compound is a component of a base agent having a specific structure represented by the above formula (A. 1). [Effects of the Invention] According to the present invention Provided as a liquid crystal alignment agent which can be applied to a light alignment mode and which is capable of imparting high-speed responsiveness and which can form a liquid display element which is excellent in light resistance without TIA. [Form of the Invention] C liquid crystal alignment agent &gt; The liquid crystal alignment agent of the present invention contains light An aligning group and a [A] polymer containing a group represented by the above formula (A1). The liquid crystal aligning agent can be adapted to a nine-alignment mode, and a liquid crystal display element having a liquid crystal alignment film formed therefrom can satisfy not only The liquid crystal display element has a characteristic of a voltage holding ratio and a light resistance which are generally required, and the photoelectric response time is short. The liquid crystal alignment agent contains a "B-polymer" or the like and "other polymer" which will be described later. Any of the components may be contained within the scope of the effects of the present invention. The components are as follows. The ring-formed b is crystallized and the external phase is sealed with its 201229137 &lt;[A] polymer&gt; [A. 丨 polymer contains light Orientation of its circle * ^ 1 ^ group. The rear group and the photo-alignment group represented by the above formula (4)) can be used as a photo-alignment group, and a well-known photo-alignment group can be used, preferably having a cinnamate group. Lean-g-decene-based styrene-ketone structure, azo-based structure of the group, from the sensitivity of the vinegar structure. (4) Particularly preferred is a group having a cinnamic acid as a photo-alignment group, and a preferred structure, preferably having the following formula

CH=CH—〇

II (B1) 〇上上式 (where R is a gas atom or an aryl group. a, when the integer a of 〇~4 is 2 or more, a plurality of R can be phased @ or different" means a connection key. a of B1) is preferably 0 or 1, more preferably 0. The group having the structure represented by the above formula (B1) is preferably a group represented by the following formula (B1-1). _ R^x1^R2^xa^^ 基 The group not shown. d 0

% -10- 201229137 In the above formulas (Bi-ι) and (B12), r, ^, and * have the same meanings as those of the bond number of the alkane bond of the above formula (B1). In the formula 1-1), Ri is a hydrogen atom, a valence organic group of a carbon atom 娄.3 40 containing an alicyclic group, or a condensed group having 1 to 40 carbon atoms. The hydrogen atom of the above group: a part or all of the substitutable group may be substituted by a fluorine atom. x is a single bond 'oxygen atom, +-COO- or +-OCO-. + indicates the connection key to the R junction. R2 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group. x is a single bond, an oxygen atom, +-COO- or +-OCO-. + indicates that the connection key with the r2 junction "b' is an integer of 0 to 3. In the formula (B1-2), R3 is a hydrogen atom, a mussel organic group containing a carbon atom of the alicyclic group, 3 to 4C, or an alkyl group having a carbon number. Among them, part or all of the gas atoms of the theater base may be replaced by fluorine atoms. X· is an oxygen atom or a divalent aromatic group. R4 is a divalent aromatic group, a divalent alicyclic group, a divalent hetero group or a divalent condensed ring group. X is a single bond, an oxygen atom, +-COO- or +-OCO-. + indicates the connection key to R4 and 纟ΪΪ. An integer of 0 to 3. The monovalent organic group having an alicyclic group-containing carbon atom having 3 to 4 Å in the above formula (B1-1) and the above formula (B1_2), for example, has a carbon number of 1 a cyclohexyl group of a 1 fluorene alkyl group, a dicyclohexyl choline group, a cholesteryl group, an adamantyl group or the like. -11 - 201229137 As the above-mentioned R1 and R3, a condensed group having 1 to 40 carbon atoms is preferably an alkyl group having 1 to 20 carbon atoms (wherein a part or all of a hydrogen atom of these alkyl groups may be substituted with a fluorine atom) ). Examples of the alkyl group include n-pentyl group, n-hexyl group, n-lauryl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, and n-hexadecene. Alkyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, 4,4,4-trifluorobutyl, 4,4,5,5,5-pentafluoro Pentyl, 4,4,5,5,6,6,6-heptafluorohexyl, 3,3,4,4,5,5,5·heptafluoropentyl, 2,2,2-trifluoroethyl 2,2,3,3,3_pentapropyl, 2·(perfluorobutyl)ethyl, 2-(perfluorooctyl)ethyl, (perfluorodecyl)ethyl, and the like. Examples of the divalent aromatic group of R24, 丄K and R4 in the above formula (B1-2) in the above formula (B1-1) include, for example, an extended phenyl group and a 2-fluoro-1 4 stretching group. Phenyl, 3-fluoro-1,4-phenylene, 2 q , , % tetrafluoro-i,4-extended ruthenium as the above-mentioned divalent heterocyclic oxime of R2 and R4, 4.. The 2,5-extended pyridyl group can be exemplified by the above-mentioned divalent/group. Base. The cyclized group, for example, the group represented by the above formula (131-1), is preferably a group of the following formula -12, 201229137

-13- 201229137

COO

C5Htl

f;3c-c2h4

C〇〇^〇&quot;~\_ CO一 * cf3c3h6

CO a* cf3c2h4

Co— * CF3CH2

CO a* CF3C3H6—0

CO—* In the above formula, R1 and * are an integer of 1 to 10 defined by the above formula (B1-1). The group represented by the above formula (B 1-2) is preferably a group represented. with. d is a statement -14- 201229137

In the above formula, R3 and * are the same as defined in the formula (B1_2). The [Α] polymer in the present invention preferably has a structure represented by the above formula (B1) of from 0·2 to 6 mmol/g, more preferably a human mad horse having a 〇3 to 5 mmol. /§ The above formula: B1) represents the structure. [Group represented by the above formula (A1)] RA of the above formula (A1) is a methylene group, a phenylene group or a cyclohexylene group. Some or all of them can be replaced. The alkyl group having 2 to 30 carbon atoms and the hydrogen atom of the group having 2 to 3 carbon atoms represented by the above RA can be exemplified by an exoethyl group, a propyl group, and a stretching group. Butyl, pentyl, hexyl, sulphide, sulphide, sulphide, eleven, sulphide, tetradecyl, hexadecyl, octadecyl , a nonadecyl group, an eicosyl group, an eicosyl group, a behenyl group, a tetradecyl group, a tetradecyl group, a hexadecyl group, and a twenty Hexaalkyl, hexadecyl, octadecyl, hexadecyl, and decyl. Among these, since the alignment of the liquid crystal is stably found, it is preferable to extend -15-201229137 Shenjiji, Shenxinji, 壬 壬 base, 癸 癸 base, extension eleven: twelve burning base, stretching fourteen burning base, Stretching sixteen bases, stretching eighteen extension base. The number of anti-atoms is 5 or more and 20 to 2, including double bonds, B3, building, stuffing bonds, and oxygen atoms. Examples of RB include an ethylenediyl group, a tertyl's fluorenyl group, a decanediyloxy group, and a fluoromethyleneoxy group. Further, ~ is a combination of the above-mentioned fluorine-containing fluorine, and the compatibility of the alignment film or the solubility of the solvent may be combined or the distillation of the alignment film containing the carbon atoms of 1 to 30. . Further, 2 groups having at least two monocyclic structures are preferably anisotropic. The monocyclic structure refers to a ring structure opposite to the structure, and a bond having no ring structure and other condensed ring structures. Further, as a single ring structure, a versatile structure, a musk ring structure, or a heterocyclic structure, e may have a combination thereof. There are (iv) a group range of at least two or more single ring structures, but Rc is preferably a group represented by the formula (A2) {&lt;RG7rRF-{rc] - the above formula (A2) The 胪 is a part of or all of the gas atoms of the phenyl group, the phenylene group, the hexyl group, the hexanyl group, the phenyl group, the phenyl group or the hexylene group. The quinone-alkyne dimethane species under the alkylalkyl group, the hexyl viewpoint a is 〇 or in the ring, which may be in the group. Base, heterocycle substituted (A2) 0 -16- 201229137 . RE is a linking group containing a methyl group which may have a substituent and an alkyl group, a double bond, a triple bond, an ether bond, an ester bond, and a hetero ring having 2 to 10 carbon atoms. R.F is a (c+1)-valent base which removes (c+1) hydrogen atoms from benzene, biphenyl, naphthalene, cyclohexane, dicyclohexane, cyclohexylbenzene or a heterocyclic compound. Some or all of one of the hydrogen atoms of the group may be substituted. It is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group, an alkoxy group, a trifluoromethoxy group or an alkylcarbonyloxy group. b is 〇 or le c is an integer from 1 to 9. d is 1 or 2. When Rd, Re, and R^〇b are each plural, a plurality of Rd, re, rg, and b may be the same or different from each other. By introducing the group represented by the above formula (A2) to the side chain of the [A] polymer of the liquid crystal alignment agent, the electro-optical responsiveness of the obtained liquid crystal display element can be further increased. In the formula (A2), ... is a phenyl group, a phenyl group, a naphthyl group, a cyclohexylene group, a dicyclohexyl group, a cyclohexylene group or a divalent heterocyclic group. As the divalent heterocyclic group, for example, a pyridyl group, a stretching base, a stretching base, and the like. = any number of sub-bases, double bonds, triple bonds, ether bonds, and long-chain groups of the sub-numbers 2 to 1G, which are the linking groups connecting the ruler and RF, ', the necessary alignment of the polymer &lt; σ 艮 According to [A] μ 冤 anisotropy suitable for selection. From the *, can be listed as a methyldiyl group, B as a block diyl group, an ether group, an ester group, a methyl group, an ethylenediyloxy group, a difluorooxy group, an ethylenediyloxy group, a fluoroindolyl group, ... Beauty I: Special. Among these, 'preferably ethylenediacetylene-based group, ester group, methylenedioxy group, and difluoromethane. In addition, b is. Magical integers, in (4): Bandits have or may not contain. It may contain 201229137 in the above formula (A2), rf hair &quot;Λ 〇 is 攸, biphenyl, naphthalene, cyclohexane, dicyclohexane, cyclohexyl stupid one compound% (c+1) a group of (4) valences of a hydrogen atom. c is an integer of 卜9. When rF is, for example, the same group as the divalent group recited in the above R may be used. In the above formula (A2), rg is a hydrogen atom, a nitrogen group, a gas atom, a trimethylhydrazine group, an alkoxycarbonyl group, an alkyl group, an alkoxy group, a trifluoromethoxy group or an alkylcarbonyloxy group. Examples of the alkoxycarbonyl group include a decyloxycarbonyl group, an ethoxy group, a propoxy group, and the like. Examples of the alkoxycarbonyl group include a methyl group, an ethyl group, a propyl group, a n-butyl group, and an isobutyl group. The carbon number + is a U (tetra) linear or branched alkyl group, and the alkoxy group is exemplified by a methoxy group, an ethoxy group, a propoxy group or the like. In the above formula (A2), when RF has a plurality of substituents (rg), it can be used in combination with groups having different RFs. When rf is a combination having a plurality of substituents, since a desired dielectric anisotropy is stably found, a combination of a fluorine atom and a cyano group, a combination of a fluorine atom and an alkyl group, a combination of a cyano group and an alkyl group is preferred. . Further, c is an integer of 1 to 9. [A] When the polymer has a photo-alignment group and a group represented by the above formula (A1), the main chain may suitably be selected from a known polymer backbone, such as polyorganosiloxane or polyruthenium. Amine, polyamic acid, polyacrylate, polydecyl acrylate, poly(styrene-stupyl maleimide) derivative, cellulose derivative, polyester, polyamine, polystyrene p Biological, polyglycolate as the main chain structure' is preferable from the viewpoint of electrical characteristics. From the viewpoint of light resistance, it is preferred that the polyorganic sand is widely used. Hereinafter, it is referred to as "[a] polyorganosiloxane compound). When the [A] polymer contained in the liquid crystal alignment agent has a polyorganismite -18-201229137 structure, the ruthenium contains [a] polyorgano oxo compound, the [a] polyorgano oxoxane The compound preferably has a moiety derived from a polyorganosiloxane having an epoxy group, a moiety derived from a compound having a photo-alignment group and a carboxyl group (hereinafter referred to as "special carboxylic acid A"), and has the following A moiety of a compound of a carboxyl group represented by the formula (A1_c) (hereinafter referred to as "specific carboxylic acid B"). (A1-C)

RHRBt-RA-T-〇H Ο In the above formula (A1-C), it is a methylene group or an alkyl group having a carbon number of 2 to 3 Å, or an exocyclohexyl group. Some or all of one of the hydrogen atoms of these groups may be substituted. Rb is a linking group including any of a double bond, a triple bond, an ether bond, an ester bond, and an oxygen atom. Rc is a group having at least 2 single ring structures. a is 0 or 1. By using the liquid crystal alignment agent having the specific structure described above, that is, introducing a photo-alignment group and a structure having dielectric anisotropy on a side chain, a liquid crystal alignment film having the photo-alignment property is used to form a liquid crystal alignment film. The liquid crystal display element having the liquid crystal alignment film can further improve electrical characteristics and afterimage characteristics, and further shorten the response time. Further, by utilizing the reactivity between the epoxy group and the carboxyl group, it is easy to introduce a photo-alignment group as a side chain to the polyorganosiloxane which is a main chain, and the above-mentioned formula (A丨_c) Electrically anisotropic structure. [a. The polyorgano-organic oxy-sinter compound is considered to be mainly a product obtained by reacting an epoxy group of a polyorgano oxo-oxygen with a carboxyl group of a specific carboxylic acid, but in order to make the description more convenient, the fraction is derived from having a ring. The portion of the polyorganooxime (and its derivative) of the oxy group and the portion derived from the specific acid retardant, the [a] polyorganosiloxane compound contained in the liquid crystal alignment agent will be described. -19-

And 201229137 [portion from polyorganosiloxane having epoxy group] This portion is a polyorganosiloxane skeleton including a polymer backbone of [a] polyorgano oxy-oxygen compound, and from the burning The [a] polyorganosiloxane compound as outlined in the main chain extending as a side chain containing an epoxy group skeleton is considered to be mostly reacted with a specific slow acid without its initial structure ^ other than tick and acid Part of the combined situation. Therefore, "a polyorganic group derived from an epoxy group" including two types of forms will be described. Machine U] polyorganismite oxy-oxygen compound is a group containing glycidyl alcohol oxime, epoxy cyclohexyl group, etc. from the group having polyorganic; Rate such electrical performance into the ~ step to improve. The group t represented by the following formula (χΐ small. or the formula (XL2)) is obtained by using a polyorgano oxane having an epoxy group (x small 1 m (x 1 · 2 )) of an anthracene group. It is easy to introduce a side sulfhydryl group having the above specific substance on the liquid crystal compound: a gas oxylate compound. 0 (X1 - 2 * 1) In the structure, it is a polyorgano oxime. For the upper ring The oxy group is also specific. In the present invention, the moiety of the siloxane, the condensability of the epoxy group or the voltage of the ternary oxy group, preferably the combination of the above-mentioned formula [a] poly structure, the above -1 In the middle, * indicates the | bond. -20- 201229137 polyorganosiloxane (GPC) having an epoxy group, the polystyrene-converted weight is 9 flat i gel permeation chromatography, 500 to 100,000, more preferably = molecular weight Preferably, 'good is 1,000 to 20, 〇〇〇 [Synthesis method of polyorganosiloxane having an epoxy group] such a polyorganoquinone having an epoxy group + a money compound having an epoxy group, Or ^ = by hydrolysis or hydrolysis/condensation in the presence of a mixture of a preferred compound with another compound, a: The bathing agent is used as the above-mentioned agglomerate having an epoxy group. 3 俨 ' 结 结 结 结 . . , , , , , , , , , 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- Oxypropyl triglycidoxypropylmethyldimethoxy m, oxypropoxypropylmethyldiethoxymethanol, 3-glycidoxypropyl-fluorenylmethoxy oxime Burning, 3. glycidoxypropyl dimethyl ethoxy _ burning, 2-glycidoxyethyl trimethoxy oxime, 2_glycidoxyethyl dimethyl decane, 2-glycidoxyethylmethyldimethoxydecane 2epoxypropoxyethylmethyldiethoxydecane, 2_glycidoxyethyldidecylmethoxydecane, 2 _Glycidoxyethyldidecylethoxydecane, 4-epoxypropoxybutyltrimethoxydecane, 4•glycidoxybutyldiethoxydecane, 4-epoxypropyl Oxybutyl dimethyl bis oxetane, 4 · glycidoxy butyl fluorenyl diethoxy decane, deoxyglycidyl butyl decyl decyloxy decane, 4 - propylene oxide Butyl dimethyl ethoxy oxalate, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Alkane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 3-(3,4 epoxycyclohexyl)propyltrimethoxy decane, 3-(3,4-ring Oxycyclohexyl)propyl-21 - 201229137 triethoxy oxalate &amp; et al. can be used alone or in combination of two or more. As the above other decane compound, for example, in a compound having one ruthenium atom 4 hydrolyzable group compounds, such as tetrachloromethane; tetramethoxy I, tetraethoxy money, tetra-n-propoxybenzene, tetraisopropoxy calcination, tetra-n-butoxy-stone, four A tetraalkoxy decane or the like such as a second butoxylate; or a compound having three hydrolyzable groups, such as a tridentate such as trioxane. a methoxy oxysulfide; a trioxane sulfonate; a fluorotrioxane; a fluorotrimethoxy oxane such as fluorotrimethoxy decane or fluorotriethoxy decane; Alkyl trichlorobenzene such as Shi Xizhuo; alkyltrialkoxydecane such as methyltrimethoxydecane or methyltriethoxydecane; fluoroalkyl group such as 2-(trimethylmethyl)ethyltrichlorodecane Trichloromethane; 2·(trifluoromethyl)ethyltrimethoxy decane, 2-(trifluoromethyl)ethyltriethoxy oxime, etc. Ethyl sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate Et-(indenyl) propylene methoxyalkyl trioxane; 3_(meth) propylene oxime # propyl trimethoxy decane, 3-(methyl) propylene methoxy propyl triethoxy temple (A Alkyl methoxyalkyltrialkoxide; mercaptomethyltrichlorodecane=nonylalkyltrioxane such as 3-mercaptopropyltrichlorodecane; mercaptodecyltrimethoxy residue, (tetra)methyltri Ethoxy 7 burned, 3 s succinyl propane f Mercaptoalkyltrialkoxides such as methoxy decane, 3-mercaptopropyltriethoxy, etc.; alkenyl monooxane such as vinyl trioxane or allyltrichloromethane; vinyl tridecyloxy Alkenyl-22-201229137 trialkoxy decane such as decane, vinyltriethoxydecaneallyldimethoxydecane, allyltriethoxydecane, etc.; aryltrichlorobenzene such as phenyltrichlorodecane a decane; an aryl trialkoxy decane such as phenyltrimethoxy decane or phenyltriethoxy decane; etc. 9 as a compound having two hydrolyzable groups, such as an alkyldioxane such as mercaptodioxane ; alkyl dialkoxy decane such as methyl dimethoxy decane or decyl diethoxy decane; dialkyl dioxane such as dimethyl dichlorodecane; dimethyl dimethoxy decane, dimethyl a dialkyl dialkoxy decane such as bis-ethoxy decane; a difluoroalkyl dichloro decane such as (meth)[2_(perfluoro-n-octyl)ethyl]dioxane; 2_(perfluoro-n-octyl)ethyl difluoroalkyl dialkoxy decane such as ethyl methoxy decane; alkyl group such as (fluorenyl) (3 _mercaptopropyl) dioxane Alkyl-dichlorodecane; alkyl-mercaptoalkyl dialkoxy decane such as (fluorenyl) (3-sulfopropyl) decyloxydecane; (fluorenyl) (vinyl) dioxane a dialkylalkenyl dioxane such as an alkylalkenyl dichlorodecane'-diyldichlorodecane; an alkenyl dialkoxy decane such as divinyldimethoxy decane; diphenyldioxane; a diaryldialkyloxy decane such as diphenyldimethoxy decane; a dialkyl decyloxy decane such as a gas dimethyl decane or a compound having one hydrolyzable group; a dialkyl alkoxy oxime such as methoxy dimethyl decane, a trimethyl decane, a trimethyl bromo decane, a trimethyl iodonane, or the like; a methoxy trimethyl group; a trialkylalkoxy decane such as decane; a dialkyl alkenyl gas oxane such as (gas) (Ethyl) dimethyl decane; or a dioxane such as (decyloxy) (ethyl) dinonyl decane Alkyl alkenyl alkoxy decane; diarylalkyl chloro decane such as (chloro)(methyl)diphenyl decane; (nonyloxy fluorenyl) diphenyl sulphur Silane-yl and the like. -23- 201229137 As a commercial item, for example, KC-89, KC-89S, X-21-3 153, X-21-5841, X-21-5842, X-21-5843, X-21- can be cited. 5844, X-2 Bu 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-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X- 40-2671' X-40-2 672' X-40-9220' X-40-922 5' X-40-9227, X-40-9246, X-40-9247, X-40-9250, X- 40-9323, X-41-105 3, X-41-105 6, X-41-1 80 5, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR97 06 (above manufactured by Shin-Etsu Chemical Co., Ltd.); Glass Resin (manufactured by Showa Denko); SH804, SH805, SH806A, SH840 , SR2400, SR2402, SR2405, SR240 6, SR2410, SR2411, SR2416, SR2420 (above is manufactured by Toray Dow Corning); FZ371 1, FZ3 722 (above is manufactured by UNICAR, Japan); DMS-S12'DMS-S15&gt;DM S-S21'DMS-S27'DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, D: ViS._S45, DMS-S5 Bu DMS-227, PSD-0332, PDS-1615, PDS-9 931 'XMS-5025 (above is manufactured by CHISSO); thiol citrate MS51, decyl phthalate MS56 (above manufactured by Mitsubishi Chemical); ethyl citrate 28, ethyl hydrazine Acid salt 40, ethyl silicate 48 (above -24-201229137 is manufactured by COLCOAT); GR: 〇0, GR650, GR908, GR950 (the above is manufactured by Showa Denko) special partial condensate. Among these other decane compounds, tetradecyloxydecane, tetraethoxydecane, methyltrimethoxydecane, and methyltriethyl are preferable from the viewpoint of the alignment property and storage stability of the obtained liquid crystal display device. Oxydecane, 3_(indenyl)propenyloxypropyltrimethoxyoxydecane, 3•(propylideneoxypropyltriethoxymethanol, ethylenetrifoxide, et al., vinyl Triethoxy decane, allyl trimethoxy decane, allyl 2 triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, 3-decyl bis-trimethoxy decane, 3_mercaptopropyltriethoxy, decylmercaptotrimethoxydecane, decylmethyltriethoxydecane, dimethyl-2-methoxydecane, dimercaptodiethoxydecane. Preferably, the epoxy group-containing polyorganosiloxane is used to introduce a side chain having dielectric anisotropy in a sufficient amount, preferably having an epoxy equivalent of 100 to 10,000 g/mole, more preferably bo—UOOg/mole, particularly preferably 150 to 300 g/mole. Thus, when synthesizing a precursor of a polyorganosiloxane having an epoxy group Preferably, the ratio of use of the decane compound and the other decane compound is set to adjust the epoxy equivalent of the obtained polyorganic compound having an epoxy group to the above range. The polyorgano group having an epoxy group used in the synthesis of the present invention is synthesized. In the case of a decane, it is more preferred to use only a decane compound and no other decane compound. As an organic solvent which can be used in the synthesis of a polyorganosiloxane having an epoxy group, for example, a hydrocarbon compound, a ketone compound, a brewing compound, An ether compound, an alkanol compound, etc. -25- 201229137 As the above-mentioned hydrocarbon compound, for example, as the above-mentioned compound, a ketone such as toluene or diphenylbenzene, methyl-n-pentane or diethyl ketone is exemplified. A, B, methyl isobutyl, such as acetic acid, acetic acid, Zheng, Gang, etc.; as the above-mentioned brewed monomethyl ether acetate, 3_曱 Α 曰 曰, isoamyl acetate, propylene glycol Ffit: For the above-mentioned compound, for example, 曰, lactic acid, vinegar, etc.; diethyl hydrazine, tetrahydrofuran, dioxane, etc.; diol dimethyl hydrazine, ethylene glycol, for example, Alcohol, 4 ^ for the above Alkanol compound, ethylene glycol soil amyl alcohol, ethylene glycol monoterpene ether, drunk I ether, ethylene glycol mono-n-propyl propylene glycol monomethyl ether, propanol mono ^ μ ... ethyl alcohol mono-n-butyl ether, Among them, 铋 * * 内 内 内 内 内 内 内 内 内 内 内 内 内 内 内 内 内 内 内 内 — — — — — * * * * * * * * * * * * * * * * * Relative to 1〇〇, compared to #: έ» 1 Λ 1 λ 知 知 全 全 化合物 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: When the oxime is used, Berry is injured. The compound is preferably used in an amount relative to the total. Preferably, it is 0_5 to (10) moles, more preferably u moles. As the above catalyst, for example, there are an acid, a test, a private compound, an organic compound, an organic titanium compound, and a wrong compound. As the above-mentioned alkali metal compound, potassium hydroxide and methyl (9) are sodium hydroxide, sodium methyl methoxide, potassium methoxide, sodium ethoxide, and ethanol. Listening, 2 on = machine test, for example, can be listed as ethylamine, diethylamine, sputum, -: fixed ratio, etc. - grade, secondary organic amine; triethylamine di-n-propylamine, tri-n-butylamine, pyridine 4_二吖双环+ ^ , ^ T-aminopyridine, twenty-thin tertiary organic amine; tetramethyl hydride (tetra) quaternary-26-201229137 organic amine and the like. Among these organic bases, diethylamine, tri-n-propylamine, tri-n-butylamine, η ratio sigma, and 4-dimethylamino group are preferable in view of smooth progress of the reaction. A three-organic amine such as a tetraorganoamine; a tetradecyl hydroxide. As the catalyst for producing the polyorganosiloxane having an epoxy group, a metal compound or an organic base is preferred. By using an alkali metal compound or an organic base as a catalyst, a side reaction such as ring opening which does not generate an epoxy group can obtain a polyorganosiloxane with a high hydrolysis and condensation rate, and thus the production stability is excellent. Preferably. Further, the liquid crystal alignment agent having an epoxy group-containing polyorganosiloxane and a specific carboxylic acid reactant containing a metal compound or an organic base as a catalyst is excellent in storage stability, which is very suitable. The reason is as described in Chemical Reviews, Vol. 100, pp. 1409 (1995). When metallurgical compounds or organic test catalysts are used in hydrolysis and condensation reactions, it is speculated that random, 纟σ structures and ladders are formed. A type structure or a cage structure, thereby obtaining a polyorganosiloxane having a small proportion of sterol groups. Since the content ratio of the sterol groups is small, it is presumed that the condensation reaction between the sterol groups is suppressed, and the liquid crystal alignment knows that when the other polymers are described, the condensation reaction between the sterol groups and other polymers is suppressed. Excellent results in storage stability were obtained. : Catalyst is particularly preferred as an organic base. The amount of use of the organic test may be appropriately set according to the type of the test, such as the reaction conditions such as temperature, etc., for example, relative to the whole stone compound, preferably U times more preferably 〇. 〇 5 to 1 times Moor. The hydrolysis or water condensation reaction in the production of a polyorganosiloxane having an epoxy group is preferably a compound in the organic solvent, and a solution of a decane having a bad oxy group. The acetylene compound is prepared by mixing the solution with organic -27-201229137 and water, for example, by heating in an oil bath or the like. In the hydrolysis/condensation reaction, the heating temperature of the oil bath is preferably 丨3 〇 or less, more preferably 40 to 1 Torr. (: The heating time is preferably 〇5 to 12 hours, more preferably 1 to 8 hours. During heating, the mixture may be stirred or placed under reflux. After the reaction, the organic solvent layer separated from the reaction liquid is It is preferred to wash with water. When cleaning, 'cleaning with water containing a small amount of salt, for example, 〇2 mass%/about ammonium citrate aqueous solution, etc., is preferred from the viewpoint of easy cleaning. Cleaning is carried out until after washing The aqueous layer is neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieve as needed, and the solvent is removed to obtain the desired polyorganosiloxane having an epoxy group. The present invention has a ring As the commercially available product of the oxypolyorganosiloxane, a commercially available product may be mentioned, for example, S, P, E12, E21, EMS_32 (the above chiss 〇 polyorgano compound may also contain a portion derived from a hydrolyzed product obtained by hydrolysis of an epoxy (tetra)oxygen itself, or a portion of a hydrolyzed product which is hydrolyzed and condensed with each other. The composition of the portion is a hydrolyzed condensate.可以k 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒 扒

The side chain structure starting from the partial phase of the group represented by the formula (A1) with respect to the alignment group or the above-mentioned structure derived from the carboxyl group, the liquid crystal is contained in the agent, -28-201229137 From the structure of the poly-organomethoxyalkane compound of the poly right m-knife... The oxime backbone extends from the oxime of the epoxy group. Its towel, gentleman &amp; n丄 虱 的 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , In other words, the portion j ° from the specific carboxylic acid (specific carboxylic acid A) _ 乍 "Temple 叱 叱 A' is a compound having the structure represented by the above formula (Bl), preferably (B1_1C) A compound represented by the compound (B1-2C).

R1—*X1^R2^X2^y= 7 CH=CH -『(0)5—X5- R5 0 (B1-1C)

—R6^—X7—R7 (B1-2C) R, R1, R2, χ1, χ2, a', and y in the above formula (B1-1C) and R, R3, and R4 in the above formula (B1-2C) And χ3, Χ4, a, and c are respectively the same as those defined by the above formula (Bl-1) or (Bl-2). In the above formula (B 1-1 C), X5 is a single bond, an oxygen atom, a sulfur atom, a fluorenylene group, an alkylene group having 2 to 10 carbon atoms, and an extended group having 2 to 1 carbon atoms. Or a divalent aromatic group. When X5 is a single bond, e is 1 and R5 is a hydrogen atom. When X5 is an anthracenylene group, an alkylene group, an alkenyl group or a divalent aromatic group, e is 0 or 1 and R5 is a carboxyl group, a hydroxyl group, -SH, -NC0, -NHR, ( -29-201229137 R' is a hydrogen atom or an alkyl group having a carbon number of i to 6), -CH=CH2 or S02C1. In the above formula (B1-2C), R6 is a divalent aromatic group or a divalent heterocyclic ring. a divalent condensed cyclic group, X6 is an oxygen atom, _CO〇_ + or 0 (:0··+. wherein + represents a bond to the bond. f is an integer of 0 to 3. R is a carboxyl group , hydroxy, -SH, -NCO, -NHR (the above R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CH = CH2 or S02C1. X7 is a single bond, -〇c〇-(CH2)i_ + or 〇_(CH2)j_+.+ represents a linkage bond to r7. j is an integer of 0 to 10. The compound represented by the above formula (B 1 - 1 C) is preferably the above formula (B). 1 1 C) A compound wherein X 5 is a single bond and R 5 is a hydrogen atom, or a compound wherein X 5 is a methylene alkylene group or a divalent aromatic group and R 5 is a carboxyl group, as the above formula (B 1-2 C) The compound to be represented is preferably a compound of the above formula (B1-2C wherein R7 is a carboxyl group. Such a compound having a carboxyl group is referred to as "carboxylic acid (B1)". One such a carboxylic acid (B1) is more preferably a compound represented by the above formula (B), for example, the following formula The compound represented is preferred, -30- 201229137

R

COOH

RO

COOH-〇^00°-〇 \\ R1—/&quot;V-COO— \ —— / R''〇

-COOH

COOH R*COO coo

COOH

COOH COO—(CH2)d-COOH

RO

CO〇-CH2——COOH R1

COO—CH2—COOH R1 —coo

COOH r1〇-〇 coo

COOH r'coo—(f \

-COOH -31 - 201229137 . 5 latch 11 ο coo

C5Hh

COOH COO

Cf:3—c3h6

Coo

COOH

COOH F: lc-c2H4.

Coo

COOH cf3c3h6

COOH CF3C2H4

COOH cf3ch2

COOH CF3C3H6-o

COOH In the above formula, R1 is the same as defined in the above formula (B1-1C). d is an integer from 1 to 10. The compound represented by the above formula (B 1-2) is preferably a compound represented by the following formula, -32- 201229137

H -oco-

C

H COOH

In the above formula, R3 is the same as defined in the above formula (B1-2C). [Specific carboxylic acid B] Examples of the specific carboxylic acid B include compounds represented by the following formulas (D-1) to (D-25). -33- 201229137 RC-(cH2)^COOH (D-1 ) Rc-C-(CH2)^COOH (D-2) r4ch 七 0- o t——, COOH (D-16) 01

Rc-C —11~(CH2)^C00H ( D · 3 ) , Mch 7 COOH (0-4)

Rc-

Rc_〇^CH2)_〇JL^J^ COOH (D-17)

Rc^^CH2)^COOH (D-5) Rc-(c:H2)^-&lt;^~~-COOH (D-6) ^CH2feL〇^ Kc-〇-(cH; COOH (D-18) COOH (D-19)

o Rc-0—LfCH

Rc- ch3

0i RC_0_(CH 〇 _^~^ COOH (D-9) Rc—(CH 七 O—^ COOH (D-7) Rc-^-(cH2} COOH ( D - 20) -COOH (D-8) COOH (D-21) COOH (D-22)

CH 七 0- -COOH(D-23)

Rc_c^CH2)_L〇^^)_ COOH (D-12) rc,^cH2)-0 O COOH (D-25)

O O -COOH (D-13)

Rc-0—L(CH2)—^—〇-COOH (D-14)

O COOH (D-15) In the above formulae (D-1) to (D-25), RC has the same definition as the above formula (A bC). m is an integer of 1 to 30. The group represented by the above formula (A2) is, for example, a group represented by the following formulas (E-1) to (E-116). -34- 201229137 ',z~Qr^y (Ε·1) (E-2) (E-3)

NC

(E-12) (E-13) (E-14)

NC

(E-5)

(E*15) NC—

(E-6)

(E-16) (E-17)

F

(Ε·7)

(E-18)

NC—

(E-10)

NC —

(E-11)

F

(E-21) F -35- 201229137

-36- 201229137 (E-36)

-37- 201229137

(E-47) CN

•56)

U

CN

NC CN

•57) •58) (E*52) (E-50)

F F {e-5'

F F

(E-53)

F F

R

R (Ε·55)

F F

-38- 201229137

-39- 201229137

rH F

(E-85) R—&lt;

(E-86) R—(

(E-87)

(Ε·88)

F F X X &lt;E-89)

R-C-〇

(E - 90 ) X X R—(1)-. Valley (E-91) X X E-92]

X X (E-93)

K&gt;^2-. Valley X X X X (E-94) (E-95)

(E-96)

(E-97: (E-98)

F F (E-108) (E-109) (E-110) (E-111) -40- 201229137

(E-118) (Ε-11Θ)

In the above formula (E-l) to (E-123), Han is a sore work, such as an alkyl group having 1 to 20 atomic atoms or a carbon atom of 1 to 20 alkoxy groups. Also divided into atoms. The hydrogen atom or fluorine is not independently indicated as the alkyl group represented by the above R, and the examples are as follows: a mercapto group, an ethyl group, and the like.

Di-n-butyl, isobutyl 'n-pentyl, n-hexyl, and the like. Examples of the hospitaloxy group of the above R include a methoxy group, an ethoxy group, a propoxy group, an isopropenyl group, a butoxy group and the like. [Synthesis Method of Specific Carboxylic Acid] The synthesis method of the specific tickic acid is not particularly limited, and can be carried out by a combination of the current methods. As a representative synthesis method, for example, a compound having a benzene skeleton and a compound in which an alkyl chain moiety of a higher hydroxy phthalate ester is substituted with a dentate atom are reacted under alkaline conditions, and the composition is staggered. Hydroxyl and! a carbon-substituted bond of a prime atom, followed by a method of preparing a specific carboxylic acid by reducing the ester, and (2) reacting a compound having a phenol skeleton with a carbon k-vinyl ester to form a terminal alkanol compound, the hydroxyl group and the halobenzene-41- 201229137 sulfonate gas reaction and activation' then activates the part of the upper oxime containing hydroxybenzoic acid methyl vinegar reaction 'sulfonyl moiety part of the detachment, while the terminal bis-alcohol compound (tetra) and benzoic acid methyl vinegar contained as a substituent The base forms a bond, followed by reduction of the ester, a method of preparing a specific hot-coated carboxylic acid, and the like. However, the synthesis method of the specific enemy acid is not limited to this. &lt;[a] Method for synthesizing polyorganophysin compound&gt; As a method for synthesizing the [a] polyorgano 7oxygen compound, there is no limitation, and generally known t, earthworm, slave Method synthesis. As a method for forming σ of a [a] polyorganosiloxane compound having an epoxy group, it is possible to convert a polyorgano-oxygen-burning disk having a ring gas group to a milk-deficient machine, and The citric acid is preferably synthesized by reacting in the presence of a catalyst. Female 1: The amount of special reading acid is preferably 0 〇〇 1 〜 1 〇 1 〇 〇 相对 相对 相对 相对 〜 〜 〜 〜 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更In the present invention, Ατ 2 T is substituted with a compound represented by the following formula (4) in a range which does not impair the effects of the present invention, and is used. The synthesis of the oxoxane compound is carried out by reacting a polyorganosiloxane having an epoxy group with a mixture of a specific carboxylic acid and a compound represented by the following formula (4): A, .-U) Formula (4, Φ * 1 γ ' A is a linear or branched alkyl group having a carbon number of 丨 〇 3 〇, and a carbon atom which can be substituted with an alkyl group or an alkoxy group having 1 to 20 atomic number in Tianshan. 1 〇:jm... Θ &amp;&amp; base or a hydrocarbon group having a steroid skeleton having 17 to 5 1 carbon atoms. A part of the hydrogen atom of the above alkyl group and alkoxy group in the retanning -42-201229137 or All may be substituted with a substituent such as a cyano group, a fluorine atom or a trifluoromethyl group to form a single bond, .〇-, -co〇_ or _0C0-. L is a single bond, a methylene group, and a carbon number of 2 to 20 Stretch a group represented by a group, a phenyl group, a phenyl group, a fluorene group, a dicyclohexyl group, or a formula represented by the following formula (ιΛι) or (L - 2 ). Ζ is capable of reacting with [a] polyorganooxane The epoxy group in the compound reacts to form a monovalent organic group of a linking group, wherein L? is a single bond when L1 is a single bond.

The quick-bonding keys with the "*" in the above formulas (L]-l) and (l!-2) are respectively bonded to the Z-bond. The Z is preferably a carboxyl group. Examples of the linear or branched bismuth group having a π sore number of 1 to 30 represented by A1 in the above formula (4) include a methyl group, an ethyl group, and a n-propyl group. n-Butyl, t-butyl, flute-fluorenyl, n-pentyl, 3-mercapto-butyryl]&gt; soil base, 2-mercaptobutyl, 1-mercaptobutyl, 2,2_ Dimethylpropyl, benzyl, 4, methylmercapto '3-mercaptopentyl, 2-methylpentyl, 1-indenyl-, 3, \3, dimethylbutyl, 2, 3-dimethylbutyl, 1,3-dimercaptobutyl 2'2' dimethylbutyl, 1,2-dimethylbutyrate, ι,2-dimethylbutylmethylbutyl, positive Heptyl, 5-methylidene, 4-mercaptohexyl, -43- 201229137 3 -mercaptohexyl, 2-mercaptohexyl, 1-decylhexyl, 4,4-didecylpentyl, 3,4 - dimethylpentyl, 2,4-didecylpentyl, 1,4-didecylpentyl, 3,3-didecylpentyl, 2,3-didecylpentyl, 1,3 - Dimercaptopentyl, 2,2-didecylpentyl, 1,2-didecylpentyl, 1,1-didecylpentyl, 2,3,3-trimethyl-yl, 1 ,3,3-trimethylbutyl, 1,2,3-tridecylbutyl, n-octyl, 6-methylheptyl, 5-quinone Heptyl, 4-decylheptyl, 3-methylheptyl, 2-decylheptyl, 1-decylheptyl, 2-ethylhexyl, n-decyl, n-decyl, n-decyl , 正十二烧基,正十三烧基,正十四烧基,正七烧基,正六烧基,正七烧基,正十八烧基,正九烧基, etc. The cycloalkyl group having 3 to 10 carbon atoms which may be substituted with an alkyl group or an alkoxy group having 1 to 20 carbon atoms may, for example, be a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a cyclic oxime. The hydrocarbon group having a carbon number of 7 to 5 1 having a steroid skeleton is, for example, represented by the following formulas (H-1) to (H-3). Group.

44- 201229137 In the above formulas (H-1) to (H-3), * indicates a connection key. In the above formula (4), a1 is preferably selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, and a group of the above formula (H-oxime) or (H_3). The compound represented by the above formula (4) is preferably a compound represented by any one of the following formulas (4-1) to (4 to 6).

CuF2u+i — CvH2v—COOH (4* 1 )

Cy*H2w+1——COOH (4*2) —^-0

COOH (4-3)

C.,H;k+1—(-CF2)^CH2-)rt· (4-4)

In the above formula (4-1)-(4-6), u is an integer of 1 to 5. V is an integer from 1 to 18. W is an integer of 1 to 2 。. k is an integer of 1 to 5. p is 0 or 1. q is an integer from 〇 to 18. r is an integer from 0 to 18. s and t are each independently an integer of 0 to 2. Among these compounds, 'the compound represented by the following formula (5-1) to (5-7) is more preferable. -45- 201229137 C17H35 —COOH (5-1)

The compound represented by the above formula (4) is a compound which reacts with a specific carboxylic acid and a polyorganosiloxane having an epoxy group as a site which imparts a pretilt angle finding property to the obtained liquid crystal alignment film. In the present specification, the compound represented by the above formula (4, 1 is hereinafter referred to as "other pretilt angle-detecting compound". In the present invention, a specific carboxylic acid and other pretilt angles are used to find a compound acid and other pretilt angles. The total use case of the discovery compound is preferably 0.001 to 1.5 m<2> with respect to the epoxy group of the 1 molar polyorganooxane, which is 0.001 to 1.5 mol, and 萝, 0, is 0·01 〜1. Mohr, further preferably 0. 〇 5 to 0.9 mol. At this time, the dragon, his pretilt angle finding compound is preferably in a total amount relative to the specific carboxylic acid Α μ 甘 〇 / /, · The best is 75 mol% or less, and more preferably 50 m10/〇. Potted Μ = Μ # ,.y Other pretilt angles are found to be more than 75 mol%. The case of adversely affecting the velocities of the liquid on the day-to-day responsiveness: the epoxy group containing the (tetra)oxoxime t and the bismuth-containing substance represented by the above formula (4) and other pretilt angle-detecting compounds The catalyst used in the reaction of the compound, alkali, seven m in a 'J from this use A compound known as a so-called hardening accelerator for the promotion of organic A.3⁄4 oxidized sputum and sour liver. As the above-mentioned organic base, for example, B _ η 牛, Sigh, piper, and tau Han first-class organic amine; triethylamine propylamine, tri-n-butylamine, pyridine, 4_two odor °Y # IS, Tuyue female base 0 bite, two AI 礒 eleven carbon a tertiary organic amine such as a olefin; a tetracarboxylic amine such as a tetramethyl-grade Gucanxiang ammonium; etc. Among these organic bases, 'preferably =, tri-non-T-ethylamine, di-n-propylamine-n-butylamine , pyridine, 4-dimethylaminopyridine, and ruthenium. As the above-mentioned hardening accelerator, for example, 2 4 λ, I dioxin, 'di(didecylamino fluorenyl) can be cited. Phenol, cyclohexyl amide - methylamine, triethanol secondary amine; 2~methylimidazole, 2-n-heptyl imidazole, 2-n-decyl- ρ 立, 笨 τ 坑 基imi, 2- $ Imidazole, 2phenyl-4-indolyl imidazole, I 2 ·methylimidazole under 丨_benzylbenzyl, 1_ 味^笨基味嗤, !, 2_ dimethyl scent, 2 ethyl methacrylate Indole cyanoethyl)_2_methyl , W2_cyanoethyl)_2·正十-47· 201229137 monoalkylimidazole, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)-2 -ethyl_4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis(hydroxymethyl)imidazole, 1-(2-cyano) Ethyl)_2_phenyl_4'5_bis[U'-cyanoethoxy)indolyl]imidazole, 1-(2-cyanoethyl)-2-n-undecylimidazolium is stupid Triester, 1-(2-cyanoethyl)-2-phenylimidyl tristearate, 1-(2-cyanoethyl)-2-ethyl-4-indolyl imidazole Partial triester, 2,4-diamino-6-[2,-methylimidazolyl-(1,)]ethyl·tetragen.. 2,4-diamino-6-(2 N-undecylimidazolyl)ethyl-homo-, 2,4-diamino- 6-[2'-ethyl-4'-methylimidazolyl-(indenyl)]ethyl-dimorphine , a trimeric isocyanate adduct of 2-methylimidazole, a polyisophthalic acid adduct of 2-phenylimidazole, 2,4-diamino-6-[2,-methylimidazolyl- (1,) an osmium-salt compound such as a s-isomeric isocyanate adduct; an organophosphorus compound such as diphenyl$, triphenylphosphine, triphenylphosphite; benzyl tri-based = Scale, tetra-n-butyl bromide scale, decyl triphenyl bromide scale, B: a stupid brominated scale, n-butyl triphenyl bromide scale, tetraphenyl brominated squary-phenyl iodide Scale, ethyl triptyl acetate scale, tetra-n-butylphosphonium diethylphosphonate sulphate, tetra-n-butyl benzotriene vinegar, butyl quaternary tetrafluoroborate, tetra-n-butyl scale a four-stage scale salt such as tetraphenylborate or tetrakis-tetraphenylborate; 1,8-dioxinbicyclo[5 4 〇]deca-D丫bicyclo]; generation &amp; -7 or its organic Acidic acid such as zinc dioctoate, tin octoate, Mingyi brewing compound; 1 @ _ complex compound and other organic metal tetraethylammonium bromide, tetra-n-butyl-tetra-n-butylammonium hydride, ammonium, tetra Ethyl ammonium hydride, J arsenic quaternary ammonium salt; ~ 48 - 201229137 boron trifluoride, boronic acid triphenyl and other boron compounds; zinc chloride, tin chloride and other metal complexes; dicyandiamide or a high melting point dispersion type latent curing accelerator such as an amine addition accelerator such as an amine or an epoxy resin addition agent; the surface of the hardening accelerator such as the imidazole compound, the organic phosphorus compound or the quaternary phosphonium salt is covered with a polymer Capsule-type latent hardening accelerator; amine salt type latent hardening accelerator; latent hardening accelerator such as high temperature dissociative thermal cationic polymerization type latent hardening accelerator such as Lewis acid salt or Bronsted acid salt Wait. Among these catalysts, a quaternary ammonium salt such as tetraethylammonium bromide, tetra-n-butylammonium chloride, tetraethylammonium vaporate or tetra-n-butylammonium vaporate is preferred. The earth catalyst is used in an amount of preferably 100 parts by mass or less, more preferably 1 to 100 parts by mass, even more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the polyoxyl group having an epoxy group.

Han should preferably have a temperature of 0 to 200 ° C. ▼, a, j V7 ~ is preferably 0·1 to 50 hours, more preferably 0.5 to 20 hours [a: synthesis reaction of a polyorganosiloxane compound The roots are carried out in the presence of organic dissolved sulphur. The organic solvent may be a hydrocarbonized person x male machine, for example, a hydrazine, an ether compound, an ester compound, a compound, an anthracene λ old 1G σ substance, a guanamine sterol compound, or the like. Among these, it is preferable that the solubility of the eyebrows and the solubility of the product and the product of the product are easy to be refined, and it is preferably an ether compound compound, a chemical group, or an esterified product. Temporary θ t.../ μ of the components other than the solid content concentrate (reporting the ratio of the mass of the solvent in the night to the total mass of the bath in the solution) is more than -49-201229137 0.1% by mass or more and 70% by mass. In the following, it is more preferably used in an amount of 5 mass% or more and 5 mass% or less. The weight average molecular weight converted from the polystyrene obtained by the gel permeation chromatography using the [a] polyorganosiloxane compound thus obtained is not particularly limited, and is preferably! , 000~200,000, more preferably 2, 〇〇〇~2〇, 〇〇〇. In such a molecular weight range, good alignment and stability of the liquid crystal display element can be ensured. The [a] polyorganismite compound of the present invention is a ring-opening addition of an epoxy group to a polyorganooxane having an epoxy group by a specific carboxylate moiety of a citric acid, and is introduced from a specific The structure of the carboxylic acid. This manufacturing method is simple and can increase the introduction rate of a structure derived from a specific acid retardation, which is a very suitable method. &lt;Individient Component&gt; In addition to the [A] polymer, a polymer other than the [A] polymer (hereinafter referred to as "other polymer" may be contained in addition to the [A] polymer. "), a curing agent, a curing catalyst, a curing agent, a compound having at least one epoxy group in the molecule (hereinafter referred to as an oxygen compound), a functional decane compound, a surfactant, and the like. [Other Polymers] Other polymers were used to further improve the solution characteristics of the liquid crystal alignment agent and the electrical characteristics of the obtained liquid crystal display element. As the other polymer, for example, at least one polymer selected from the group consisting of polylysine and polyimine ([B] polymer) can be cited; -50-201229137, and the following formula (5) At least one of the group consisting of the condensate of the hydrolyzate and the hydrolyzate thereof (hereinafter referred to as "other polyorganosiloxane"); polyglycine s, poly vinegar, poly Amine amine, cellulose derivative, polycondensation, polyepiethylene derivative, poly(styrene-stupyl maleimide) derivative, poly(indenyl) acrylate, and the like. ΧΑ (5)

Si-0

I ΥΑ In the above formula (5), ΧΑ is a transradical, a _ atom, an alkyl group having a carbon number of 2, an alkoxy group having a carbon number of 丨6 or an aryl group having a carbon number of 6 to 2 fluorene. . The hydrazine 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 polyaminic acid and polyimine. Hereinafter, polyacrylic acid and polyimine will be described in detail. [Polyuric acid] Polylysine is obtained by reacting a tetracarboxylic dianhydride with a diamine compound. Examples of the tetracarboxylic acid monoanhydride include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. These tetracarboxylic acid dianhydrides may be used alone or in combination of two or more. As the month a, the family is slow, and the gf is, for example, tetrabutyric dianhydride. As an alicyclic tetrazoic acid dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic acid-51-201229137 two-needle, 2:,3,5-tricarboxycyclopentyl acetic acid dianhydride, i, 3 , 3a, 4, 5, 9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]furan-1,3-dione, 1 ,3,33,4,5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[].,2_c]furan-oxime , 3_dione, 3-oxabicyclo[3.2.1]octane-2,4-dione. 6-spiro-3'-(tetrahydrofuran-2,5,-dione), 5_(2, 5_Dioxatetrahydro•3-吱°南基)_3 - Mercapto-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2.. Decane-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, 4,9-dioxo Heterotricyclo[5.3.1.02,6]undeccarbon-3,5,8,l〇-tetraketone, etc. The aromatic tetracarboxylic dianhydride is, for example, pyromellitic dianhydride, and the tetracarboxylic acid di gf described in Japanese Patent Application No. 20 10-97 1888. Preferably, the tetracyclic acid dianhydride is an alicyclic tetracarboxylic dianhydride, more preferably 2,3,5-dicarboxycyclopentyl acetic acid dianhydride or 1,2,3,4-cyclobutane. Tetramethyl sulfonate is particularly preferred as 2,3,5·trimethylcyclopentyl acetic acid dianhydride. The amount of use of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride or 1,2,3,4-cyclobutane: formic acid dipyre is more than or equal to the total tetramethylene dimer %, more preferably 20 mol% or more is specifically 丨 0 carboxycyclopentyl acetic acid - Xuan inferior &quot;, / Banma only by sucking a needle or I, 2, 3, 4 · cyclobutane 40%. T 醆 二 二 ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή ή Makeup I organic stone, aromatic 201229137 as alicyclic diamine, such as, 4,4, fluorenylene bis(cyclohexylamine), i 1,4-diaminocyclohexane as diamine Organic oxa oxymethyl) ring) _ four m oxygen q I# , 3 · bis (3 · aminopropyl succinct. · 97 1 88, the diamine. Group of diamines, such as noradido decyl decane, 4,4,-diamine, _ X, a monoamine, an amine-based thioether, 1,5-diamine U, 2 - dimethyl-4,4'-diaminobiphenyl, 4,4,-diamino W,-bis(trifluoromethyl)biphenyl, 2,7.diamino, 4,4, Diaminodiphenyl sulfonate, bis[M4aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl) fluorene, 2,2-bis[4-(4-amine Phenyloxy)phenyl]hexahydropropene, 2,2·bis(4-5-pentamethoxy-2,4-diaminophenyl octadecyloxy-2,4-diaminophenyltetracarbonyl -2,5- Amino-based hexamethoxy-2,5-diaminobenzopyreneoxy-3,5-diaminoanilinophenyl) hexafluoropropane, 4,4'. Propyl propyl) bis(aniline), 4: '4'-(meta-phenyl diiso-propyl) bis(aniline), m-bis(4•aminophenoxy)benzene, 4,4,_double (4_Aminophenoxy) phenyl, 2,6-diamino acridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3 , 6-diaminocarbazole, N-methyl-3,6-diamine. Carbazole, n-ethyldiaminocarbazole, N-phenyl-3,6-diamine. N-azole, N,N, bis(4-aminophenyl)-benzidine, N,N,_bis(4-aminophenyl)_N,N,_dimethyl phenylamine, L4-double- (4-Aminophenyl)-piperidin, 3,5-diamino benzoic acid, undecyloxy-2,4-diamino stupid, tetradecyloxy-2,4-diamino Stupid, heptadecyloxy-2,4-diamino stupid, dodeca-decyloxy-2,5-diaminobenzene, fifteen decyloxy-2,5-diamine stupid, Octadecyloxy-2,5-diaminobenzene, cholestyryloxy-3,5-diaminobenzene biliary-53- 201229137 decyloxy-2,4-diaminobenzene , cholestyloxy-2,4-diaminobenzene, 3,5-diamino benzoic acid choline alkyl '3,5-diamino benzoic acid cholesteryl, 3,5-diamino Benzoic acid wool leaving alkyl '3,6-bis(4-aminophenylhydrazineoxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 4_(4,_ Trifluorofluorenylbenzoyloxy)cyclohexyl-3,5-diaminobenzoic acid ester, 4-(4-difluoropurine basic methyloxy)cyclohexyl_3,5-diamine Benzobenzoate, 1, . . . -bis(4-((aminophenyl)methyl)phenyl)_4_butylcyclohexane, bismuth ( 4-((Aminophenyl)methyl)phenyl)_4-heptylcyclohexane, bis(4-((amino)alkyl)carbenyl)-4-heptylcyclohexene, 1, 1-_Bis(4-((aminophenyl)indenyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane, 2,4-diamino-N,N-monopropylamino 4-aminobenzylamine, 3-aminobenzylamine, and a diamine compound represented by the following formula (A-1).

Η2Ν^^=\ &gt; η2ν^_/ The above formula (Α-1) A, x1 is a methylene group or an alkylene group having 2 or 3 carbon atoms, or -OCO-. r is 〇 or 1. s is an integer of 〇~2. t is an integer from 1 to 2 0. As the ratio of use of the tetracarboxylic dianhydride and the diamine compound which provides a synthesis reaction of polylysine, the acid anhydride group of the tetracarboxylic dianhydride is preferably 〇 with respect to the amine group contained in the equivalent amount of the diamine compound. 2 equivalents to 2 equivalents, more preferably 0.3 equivalents to 1.2 equivalents. The synthesis reaction is preferably carried out in an organic solvent. The reaction temperature is preferably -201 to 150 ° C, more preferably (TC to 1 Torr (rc. as the reaction time, preferably 0.5 hours to 24 hours, more preferably 2 hours to 12 hours. -54 - 201229137 The organic solvent is not particularly limited as long as it can dissolve human +, and the substance which decomposes σ into polylysine is not particularly limited. For example, it can be exemplified as the phenanthrene-2-pyrrolidone (NMP). , Ν, Ν-dimercaptoacetamide, 'iN~methylformamide, N,N-dimethylimidazolidinone, dimercaptosulfoxide, γ" Gongfeng r, butyrolactone, four An aprotic polar solvent such as a urea group or a hexamethylenephosphonium triamine; a benzene solvent such as an anthracene phenol, a diterpene phenol, a benzoic acid, a halobenzene, etc. The amount of the organic solvent used (a), relative} The amount of the tetracarboxylic dianhydride and the diamine compound (b) and the amount of the organic solvent used today (preferably 0.1% by mass to 50% by mass, more preferably A s° and 1 main horse 5 mass) %~30质量。/〇. The poly-proline solution obtained after the reaction can be supplied to the preparation of the liquid crystal alignment agent as it is, or it can be separated first. The polylysine contained is further supplied to the preparation of the liquid crystal alignment agent, and the 珈w surface can also be supplied to the liquid crystal alignment agent after the purification of the separated polyamic acid. As a separation method of the polylysine, for example, A method of drying a precipitate obtained by injecting a large amount of a poor solvent into a reaction solution under reduced pressure, a method of distilling off a reaction solution by an evaporator under reduced pressure, etc. As a method for purifying polyglycine, a separation method can be cited. A method in which the polylysine is redissolved in an organic solvent and precipitated by a poor solvent, and the step of distilling off the organic solvent or the like by evaporation in an evaporator is repeated once or several times. [Polyimine] The amine can be produced by dehydration ring-closing and ruthenium imidization of the proline structure of the polylysine. The polyimine can be completely dehydrated and closed by the proline structure of the precursor poly-acid. The ruthenium imide may also be a part of the guanidinium compound which is a part of the structure of the proline structure, which is a dehydration ring closure, a proline structure and a thiamine ring structure. -55- 201229137 There may be mentioned a method of heating poly-proline by (1) (hereinafter referred to as "method (i) j), (ii) dissolving poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution. A method of dehydration ring-closure reaction of polylysine such as a method of heating (hereinafter referred to as "method"). The reaction temperature of the method (1) is preferably 5 (rc 〜 2 〇〇. 〇, more It is preferably 60 C to 1 70 C. The reaction temperature is less than 5 〇. (: If the dehydration ring-closure reaction is insufficiently performed, the reaction temperature exceeds 20 (TC, the molecular weight of the obtained polymer will decrease. The time is preferably 〇·5 hours to Μ hours, more preferably 2 hours to 20 hours. The preparation of the polyterpene agent obtained in the method (i) can also be carried out in the preparation of the separating agent or in the preparation of the purified separating agent. The imine may be supplied as it is to the liquid crystal polyimine and then supplied to the liquid crystal to the polyimine, and then supplied to the liquid crystal to be a dehydrating agent in the method (ii), and examples thereof include acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. Equal anhydride. The amount of the dehydrating agent to be used may be selected according to the desired quinone imidization, but the structure of the proline acid relative to the oxime polyglycine is 0. 01 moles to 20 moles - as the method (ii) The dehydration ring-closure catalyst can be exemplified by &lt; α, dimethylpyridine, dimercaptopyridine, triethylamine, and the like. The amount of use as the dehydration ring-closure catalyst is preferably a dehydrating agent with respect to the content of the molybdenum, preferably 〇.1 mol to 1 〇 mol. In addition, the upper right 昜 儿 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水The organic solvent to be used in the method (ii) may, for example, be an organic solvent similar to the organic solvent used for the synthesis of polyglycine as described in -56 to 201229137. The reaction temperature in the method (ii) is preferably 〇c»c ～18 〇t, more preferably: 10 ° C to 150 ° C ^ as the reaction time, preferably 〇 5 hours to 2 〇 hours, more Good for 1 hour to 8 hours. When the reaction conditions are in the above range, the dehydration ring closure reaction can be sufficiently carried out, and the molecular weight of the obtained polyimine can be controlled to an appropriate range. In the force method (11), a reaction solution containing polyimine is obtained. The reaction solution may be supplied to the preparation of the liquid crystal alignment agent as it is, or may be supplied from the reaction solution to remove the dehydrating agent and the dehydration ring closure catalysis (4), and may be supplied to the liquid crystal alignment, or may be separated and then supplied. The preparation of the liquid crystal matching agent or the preparation of the liquid crystal alignment J after the separation of the separated polyimine is used as a method of removing the dehydrating agent and dehydration ring closure catalysis from the reaction solution, for example, a method of solvent replacement. The method and the purification method of the polyimine are exemplified by a method similar to the separation method and the purification method of polylysine. [Other polyorganosiloxanes] Other than the two::: agents may also contain (4) polyorganic tender... from the above C oxygenation. Other poly-organic oxy-oxygenation is preferred to feed the product: the polyorgano-oxygenation of the product, the hydrolyzed product thereof... The liquid crystal alignment:::: at least one of the groups formed, the other one is large...he gathers In the case of organic oxalate, other aggregates may be present, or may be complexed, and (4) a compound in which the polyorganismite compound exists independently. a part of the polyorgano-oxo-oxygenated compound of [a] poly-asalyze-oxygenated compound -57-201229137 in the above formula (5) in the ΧΑ* ,, as an alkyl group having a carbon number of 2 ,, an example, a n-type group, a base group, a base group, The solvent or the like is less than one or the water is burned and the top is the same as the alkane, decanedioxane, solvent or solvent, and examples thereof include a mercapto group, an ethyl group, a n-propyl 'n-butyl-n-pentyl hexyl group, a n-heptyl group, and a positive one. Octyl, n-decyl, n-decyl, n. laurel - alkyl, n-dodecyl, n-tetradecyl, n-pentadecane n-hexadecyl, n-heptadecyl, n-eight Examples of the alkoxy group having 1 to 16 carbon atoms include an alkyloxy group and an ethoxy group having an aryl group having 6 to 20 carbon atoms, for example, a phenyl group. The other polyorganosiloxane may be hydrolyzed, for example, by a decane compound (hereinafter referred to as "raw decane compound") selected from the group below in the presence of water and a catalyst in a preferably suitable organic solvent. Condensed to synthesize, the group consists of an alkoxydecane compound and a denture. As the raw material decane compound which can be used herein, for example, a compound of the above-mentioned synthesis of the U-organic polyoxo-oxygen compound can be described. Among these, it is preferred that tetraethylene 4 feces plus b 丨 丨 、 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Triethoxy zexiyuan, 一-mercapto-ethoxy decane, tridecyl decyl bis-f-ethoxy decane. In the case of synthesizing other polyorganosiloxanes, the materials can be used arbitrarily in the order of 匕1 column, such as the month b. Listed as an alcoholic compound, a ketone compound, 'extracted: σ or other aprotic compound. These compounds and compounds may be used alone or in combination of two or more, and -58 to 201229137 may be used as the alkanol compound, and examples thereof include decyl alcohol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and second butyl. a monoalkanol compound such as an alcohol or a third butanol; ethylene glycol, 1,2-propanediol, 1,3-butanediol, pentanediol-2,4,2-mercaptopentanediol-2,4, a polyalkanol compound such as hexanediol-2,5, heptanediol-2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol triethylene glycol or tripropylene glycol; Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylene diether , diethylene glycol monoterpene ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether 'diethylene glycol monohexyl ether, propylene glycol monoterpene ether, propylene glycol monoethyl ether, propylene glycol A partial ether of a polyhydric alkanol compound such as monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monodecyl ether, dipropylene glycol monoethyl ether or dipropylene glycol monopropyl ether. Examples of the ketone compound include monoketone compounds such as acetone, methyl ethyl ketone, methyl n-acetone, and mercapto-n-butanone; acetamidine acetone, 2,4-hexanedione, 2,4-heptanedione, and 3,5. a β-diketone compound such as heptanedione or 2,4-octanedione. Examples of the above guanamine compound include decylamine, fluorenyl decyl decylamine, hydrazine, hydrazine-dimethylformamide, acetamide, hydrazine-mercaptoacetamide, hydrazine, hydrazine-di Mercaptoacetamide, hydrazine-ethylacetamide, hydrazine, hydrazine-diethylacetamide, hydrazine-hydrazinopyrrolidinium, hydrazine-ethinyl morpholine, hydrazine-ethinylpiperidine, hydrazine - Ethyl pyrrolidine and the like. Examples of the ester compound include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl carbonate, ethyl acetate-59-201229137, γ-butyrolactone, and γ-valerolactone. N-propyl acetate, isopropyl acetate, n-butyl ester, isobutyl acetate, second butyl acetate, diamyl acetate n-amylate, 3-methoxybutyl acetate, decyl acetate 2-ethyl butyl ester, 2-ethylhexyl acetate, benzyl acetate, acetate, methylcyclohexyl acetate, n-decyl acetate, ethyl acetoacetate, ethyl acetate, ethylene glycol Monomethyl ether, ethylene glycol monoacetic acid diethylene glycol monodecyl ether, diethylene glycol monoethyl ether, acetic acid glycol mono-n-butyl ether, propylene glycol mono-decyl ether, propylene glycol monoacetate, propylene glycol monopropyl ether , propylene glycol monobutyl ether, acetic acid glycol monomethyl ether, dipropylene glycol monoethyl ether, ethylene glycol diacetate, methoxy triethylene glycol ester, ethyl propionate, n-butyl propionate, propionate, Diethyl oxalate, di-n-butyl oxalate, decyl lactate, lactic acid, n-butyl lactate, n-butyl lactate , Diethyl malonate, phthalic acid dimethyl ester, diethyl ester of phthalic Yue like. Examples of the other aprotic compound include acetonitrile hydrazide, hydrazine, hydrazine, hydrazine, Ν'-tetraethyl sulfonamide, hexamethylene phosphinate, hydrazine-methyl sulphate, hydrazine-hydrazine. The pyryrrole, oxime-ethylpyrrole, and fluorene-fluorenyl ratio are 17 lin, Ν-曱基〇辰. Ding, Ν - ethyl brigade.定,Ν,Ν -二曱基痕 Ν -曱基味11坐,Ν-曱基-4 -派. Ketone, Ν-mercapto-2 -. B-butanone methyl-2-pyrrolidone, 1,3 -dimercapto-2-imidazolidinone, 1,3 -ditetrahydro-2(1 fluorene)-pyrimidinone. Among these solvents, a polyvalent alkanol, a part of a poly- succinol compound, or an ester compound is particularly preferred. As the amount of water used in synthesizing other polyorganosiloxanes, the phase raw material decane compound has a total of J alkoxy groups and halogen atoms, preferably 0.01 to 100 moles, more preferably 0.1 to 30 moles, of acetic acid. , vinegar, vinegar cyclohexane, diethyl ether, diamethylenediacetate isoamyl ethyl ester dioxime, _一_三醯-Δ3- well, Ν-methyl compound for &quot; Mo step-60- 201229137 better For the synthesis of 1 ~ 1.5 moles of β 咋 for the synthesis of other polyorganic 矽 such as metal chelate characters ^ callers used in the use of compounds, such as compounds. Machine test, cyanide, alkali gold 乍 is the above metal chelate, such as acetyl ketone ketone) titanium and other dioxins, monoethoxy early (• 雔 (醯 pyruvate) titanium; diethoxy double龇 网 网 ) 二 等 等 等 等 等 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛Tetra-V-propionic acid) titanium; triethoxy = alkaloid; sh flat 1 G-based ethyl ugly acetic acid) titanium, etc. - Ml early (ethyl acetamidine acetate); diacetic acid) titanium and other dioxane雔 (1) and, (ethyl ethyl thiophene • bis(ethyl acetonitrile) phthalate; monoethoxyethyl acetoacetate) titanium and other monoalkoxy • Sanmei Γ 7 « gas 7 ,酉 酉 ▲ acetic acid) titanium; four (earth _ Ling) titanium; single (acetyl acetonate) = ^ Φ (7 m ^ ^ . text) - (ethyl acetoacetate) titanium bis (acetyl acetonate) double (Ethylacetamidineacetic acid - mono(ethylethanoacetic acid) hydrazine, etc., two or more kinds of oxime-containing compounds such as acetoacetate); · "The titanyloxy group of the integrated ligand" Single (acetylpyruvate) hammer and other three alkoxy groups • single (B-C-鍅, ethoxylated bis(acetyl acetonate) hydrazine and other dialkoxy • bis-ethyl fluorene pyruvate); mono ethoxy I. tris(acetylpyruvate) wrong monoalkoxy 2 (B-C (4)) wrong; 4 (Ethyl pyruvate) wrong; Triethoxy-mono (ethylacetamidineacetic acid) isocetyloxy-mono(ethylacetamidineacetic acid) oxime; Oxygen • bis (ethyl I ethyl acetate ) wrong bis 9 oxy • bis (ethyl acetonide acetic acid) wrong, mono ethoxy • tris(ethyl acetoacetic acid) wrong monoalkoxy • three ( Ethyl acetoacetate) zirconium; tetrakis(ethylacetamidineacetic acid) zirconium; mono(acetyl acetonate) tris(ethylacetamidineacetic acid) ruthenium, bis(acetyl acetonate) bis(ethylacetamidineacetic acid)鍅-61 - 201229137 Chelate tris(acetylpyruvate) mono(ethylacetamidineacetic acid) mismatched ligand 鍅 compound isolating chelate; etc. Two or more containing tris(acetylpyruvate) Ming II ( Examples of the above-mentioned organic acid as the above-mentioned organic acid, such as ethyl acetate and the like, may be exemplified by aliphatic saturated carboxylic acids such as acid, acid, and propylene; and aliphatic acids such as malonic acid and fumaric acid. Saturated = acid: salicylic acid, benzoic acid, o-phthalazin # each " τ 鹱 # 方香 carboxylic acid; p-toluene sulfonate, stupid sulfonic acid and other aromatic sulfonic acid; generation window a halogen-containing carboxylic acid such as trichloroacetic acid or dia-acid; citric acid, tartaric acid or the like. Examples of the inorganic acid include hydrochloric acid, nitric acid, thiosal, hydrofluoric acid, phosphoric acid, and the like. The melon λ is used as the above organic test, for example, pyrrolidine, piperidine, methylpyridinamine, diethanolamine, dimercaptomonoethylethanolamine, dinonicyclooctane, dicarbene, tetraammine or the like. Examples thereof include pyridine, pyrrole, piperidine, dimethylamine, triethylamine, monoethanololamine, monodecyldiethanolamine, triterpene bismuth oxime, and bisbicyclobutene _ as the above alkali metal compound'. Sodium hydroxide, = clock, hydroxide lock, hydroxide. These catalysts may be used singly or in combination of two or more kinds. Among these catalysts, preferred are + think &amp;&amp; quanjiafeng metal chelate, organic acid, inorganic. More preferably, the metal chelate compound is a titanium chelate compound. The amount of the catalyst used is preferably 0.001 to 10 parts by mass, more preferably 0.00 W part by mass, per part by mass of the raw material decane compound. The catalyst to be added may be previously added to the decane compound as a raw material or + to a solution formed by dissolving the money compound in the organic lysing needle, or -62 to 201229137 to be dissolved or dispersed in the added water. The water added at the time of synthesis of the other polyorganosiloxane may be continuously added to the compound as a raw material or in a solution formed after discontinuing or dissolving the money compound. &lt; In the organic solvent, the reaction temperature in the synthesis of the other polyorganosiloxane is 0 to 100 C, and more preferably 丨5 to 80C. The reaction time is preferably 〇, more preferably 1 to 8 hours. · 24 hours when the liquid crystal alignment agent contains other polymers, and the amount thereof is relative to 1 〇〇 彳 彳 Λ Λ 取 取 取 、 、 、 、 、 The mass-containing [Α] polymer is preferably 1 〇〇〇〇 or less. The better content of other polymers may be different according to others:: J illusion type is relatively good for the liquid crystal alignment agent in the containing [ Β] The proportion of the polymer used, in 100 parts by mass of the [Α] polymer, the total amount of [Β] polymer is more than 1 〇〇 5 5 〇〇 parts by mass, more preferably 2 〇〇 ~ 3 On the other hand, when the liquid crystal alignment agent contains other polyorganosiloxanes, the preferred ratio of the two is relative to the mass of the [Α] polymer 'other polyorganosiloxanes' The amount of the alkane is 5 to 2,000 parts by mass, preferably 100 to 2,000 parts by mass. When the liquid crystal alignment agent contains other polymers, the other polymer is preferably a [Β] polymer or other polyorganisms. [hardener, hardening catalyst and hardening accelerator] hardener and hardening catalyst can be The liquid crystal alignment agent is contained in the liquid phase alignment agent for the purpose of making the crosslinking reaction of the [Α] polymer stronger. The curing accelerator is contained in the liquid crystal alignment agent in order to promote the hardening reaction of the curing agent. -63- 201229137 as a hardener The hardened steel which is generally used for hardening may be a hardenable composition which hardens the hardening compound which has an epoxy group, or the sigma which has an epoxy group. As such hardening|curing agent, a polyamine and a poly The carboxylic acid anhydride and the polyvalent carboxylic acid. Examples of the polycarboxylic acid anhydride include cyclohexane tricarboxylic anhydride and other polybasic acid anhydrides. 阼 is a cyclohexane calcined dicarboxylic acid anhydride, and examples thereof include cyclohexanol _ 1 3 4 tricarboxylic acid. _3,4_Anhydride, cyclohexane-H5-tricarboxylic acid-3,5-anhydride, cyclohexene], 2,3-tricarboxylic acid 2,3-anhydride, etc. As other polycarboxylic acid anhydrides, 2 The cannon has 4-methyltetrahydrophthalic anhydride, methyl nordecene dianhydride, dodecenyl succinic anhydride, succinic anhydride, maleic anhydride, o-formaldehyde anhydride, trimellitic anhydride, and the following formula (6) Compounds indicated: Four (four) diifs commonly used in the synthesis of aminic acids (4) It is possible to use an alicyclic compound having a total of two bonds and a Diels-Alder (10) Chuan (10) product, such as decene olefin and bellerolene, and a product thereof, and the like.

In the above formula (6), "X" is an integer of 20. As the curing catalyst, for example, a ruthenium hexafluoride compound, a phosphorus fluoride compound, or aluminum triacetate pyruvate can be used. These catalysts can be used as a catalyst for cationic polymerization of epoxy groups by heating. Examples of the hardening accelerator include, for example, a ruthenium compound -64-201229137 quaternary phosphorus compound; and a fourth-order ruthenium ruthenium;丫双环 [5.4.0]11石反焊焊· . 7 or its organic acid salt 篝 寺 丫 丫 丫 丫 丫 丫 丫 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺Boron fluoride, boron 6iL two-base special rotting compound. Yidu Bu Du, 虱 辞, gasification tin and other metal dentate; dicyandiamide, amine and epoxy 檄Λ β milk resistance of the adduct, etc. Amine addition molding accelerator, etc., high and low moisture-dispersion type of latent hard 彳 、 、 、 、 、 、 、 、 、 、 、 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更A latent hardening accelerator, a high temperature dissociative thermal cationic polymerization type latent hardening accelerator such as a Lewis acid salt or a Buchhol acid salt. [Epoxy compound] The epoxy compound may be included in the liquid crystal alignment agent from the viewpoint of improving the adhesion of the formed liquid crystal alignment film to the surface of the substrate. The epoxy compound is preferably ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl- 2,4-hexanediol, hydrazine, hydrazine, hydrazine, hydrazine, quaternary glycidyl-m-xylylenediamine, 1, bis (indole, hydrazine-diglycidylaminomethyl) cyclohexane Alkane, hydrazine, hydrazine, hydrazine, hydrazine, -tetraglycidyl, 4,4, diaminodiphenyl decane, hydrazine, hydrazine, diglycidyl-benzylamine, hydrazine, hydrazine Glyceryl-aminomethylcyclohexane. When the liquid crystal alignment agent contains an epoxy compound, the content ratio thereof is preferably 〇·01 to 40 parts by mass or less based on 100 parts by mass of the above-mentioned [a] polyorganococcal compound and any other polymer used arbitrarily. 'Better-65- 201229137 is 0·1~30 parts by mass. In order to make the base imidazole and other bases have a better cross-linking reaction efficiency when the liquid crystal alignment agent contains a cyclic oxime compound, it is also possible to use a thiol-2-oxime [functional decane compound] in combination with a 〜~w catalyst. Triethoxy, Ν-(2·aminoethyl)-3-aminopropyltrimethoxydecane, Ν·(2·aminoethyl)-3-aminopropylmethyldimethoxy The decane and % ureido functional decane compound can be used for the purpose of adhesion to a substrate, and examples thereof include 3-aminopropyltriethoxy oxane and 2-aminopropyl group for obtaining liquid crystals. The alignment film is used as a functional stilbene compound dimethoxy decane, 3-aminopropyl trimethoxy decane, 2-aminopropyl propyl trimethoxy sulphur, 3-ureidopropyl triethoxy矽, Ν-ethoxyxoyl-3-glycidyltrimethoxy oxetane, Ν-ethoxycarbonyl _3 ureidopropyl diethoxy, Ν-diethoxymethyl sulphur Propyl propyl sulphate triamine, bismuth - bis-oxymethyl sulfonyl propyl diethylidene triamine, 1 〇 曱 曱 曱 曱 -1 -1 -1 alkyl-1,4,7-tri Alkane, 10-triethoxyanthracene Alkyl 4,4,7. Trioxane, 9-trimethoxycarbamido-3,6-dimercaptoacetate, 9-triethoxycarbamido-3,6-diindole Mercaptoacetate, Ν-benzyl-3-aminopropyltrimethoxy oxanthine, Ν-benzyl-3-aminopropyltriethoxy zeoxime, Ν-phenyl-3-amine Propyl tridecyloxylate, Ν-phenyl-3-aminopropyltriethoxy, Ν-bis(oxyethyl)-3-aminopropyltrimethoxy oxime, Ν- Bis(oxyethylidene)-3-aminopropyltriethoxy, 3-glycidoxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriazine Further, the oxy decane or the like may be a reaction product of -40 to 201229137 of tetracarboxylic dianhydride and a decane compound having an amine group described in JP-A-63-29192. 'The liquid crystal alignment agent is succumbed to - At least when compared with the conjugate and the bis-compound, the content ratio is preferably 50 mass f, to: :: the total amount of the polymer is 100 [interface The active agent] is preferably more than 2 parts by mass. As a surfactant, an anionic surfactant, a polyoxyalkylene boundary, and an IL-containing surfactant, examples thereof include a nonionic surfactant, a cationic surfactant, a amphoteric surfactant, and a polyoxy-stretching agent. The base of the hospital base:: Qi: The liquid crystal alignment 丨 丨 &amp;# β ^ 1 Λ % 3 has a surfactant, the content ratio of which is expected to be 100 parts by mass of the liquid crystal pair is more preferably 1 part by mass or less.贞里知u, <Preparation method of liquid crystal alignment agent> Luhai liquid crystal alignment two 丨t L %. Μ As mentioned above, containing [Α] polymer as a necessity 'can be right as needed # y, 戈a has a composition which is arbitrary, but is preferably a solution in which a knife is dissolved in an organic solvent to form a solution. As the organic solvent used for the preparation of the liquid crystal alignment agent, it is preferred that the composition is not reacted with the other components used in the reaction. The organic solvent which can be preferably used in the phenol crystal alignment agent differs depending on the kind of other polymer to be added. When the liquid crystal alignment agent contains the [A] polymer and the [B] polymer, preferred examples of the organic solvent include the above-mentioned m-grain used in the synthesis of poly-proline. In this case, the solvent used in the synthesis of the polyamic acid of the present invention may be used in combination with a solvent. These organic solvents may be used singly or in combination of two or more kinds. -67- 201229137 Another aspect is that when the liquid crystal alignment agent is used as a mechanical oxirane compound, or when [a] poly Q content contains only [a] poly-organopolyoxyalkylene. The oxoxane compound and it have 1-ethylene glycol monobutyl ether ether diethyl ether and dipropylene glycol propyl ether. A domain _ field P alcohol single ethyl bond, ethylene glycol single C:: B? Glycol monoterpene, ethylene glycol monopentyl, ethylene glycol; diyl 1-ethoxy-2-propanol, propylene glycol monoethyl nt - S* propanol monopropyl ether,丙1% 単acetate, _% propane propylene glycol methyl ether, dipropylene dipropylene glycol monoether cellosolve) - π decyl ether, diethylene glycol thiol solvent 6 vinegar, ethyl fiber Acetate Sa U sucked from sputum, propyl cellosolve r vinegar, / cellosolve acetate, methyl card drunk ethyl carbitol, afi animal, Dingqi-t* λ7, pick,; jcii · -τα, sedum, ethyl carbitol, propyl carbitol, butyl carbitol, n-propyl acetate, isopropyl acetate, n-t-acetate, isobutyl acetate, dibutyl acetate , n-pentyl acetate, diamyl acetate, 3 · methoxybutyl acetate, methyl pentyl acetate = 2-ethyl butyl acetate, 2-ethylhexyl acetate, benzyl acetate, acetic acid... π pharynx ester and the like. Among these, n-propyl acetate, isopropyl acetate, n-butyl phthalate, isobutyl acetate, dibutyl acetate, n-amyl acetate, and second acetonitrile acetate are preferred. n-Hexyl ester, hexyl hexanoacetate, octyl acetate, amyl acetate, acid isobaric β Φ, 4 swallow you into two ffiife m π ntv- vinegar, the solvent used in the preparation of the wave crystal alignment agent Depending on whether or not another polymer or a type thereof is used, one or more of the above organic solvents may be combined to obtain a solvent such that the solvent contained in the liquid crystal alignment agent does not occur in the preferred solid concentration. It was analyzed that the surface tension of the liquid crystal alignment sword was controlled in the range of 25 to 40 mN/m. The solid content concentration of the powder crystal alignment agent, i.e., the ratio of the total mass of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent in the liquid crystal alignment agent is -68 to 201229137, which is selected in consideration of (4), volatility, etc., and is preferably (10). The liquid crystal alignment agent is coated on the surface of the substrate to form a liquid. When the coating of the ruthenium film is 1 ” ” 主 由 由 由 由 由 由 为 为 为 为 , , , , , , , , , , , , , , , , , , , , , , , 液晶 液晶 液晶 液晶 液晶 液晶 液晶When the concentration of the component is 10% by mass or less, it is possible to suppress the film I of the coating film from being too large, and a good liquid crystal alignment film can be obtained, and the viscosity of the liquid crystal alignment agent is increased, so that the coating property is good. The method of applying the liquid crystal alignment agent on the substrate differs. For example, according to the spin coating method, it is particularly preferably in the range of 1% by mass. According to the printing method, the solid content concentration is controlled within the range of 9% by mass%. The viscosity of the solution is particularly preferably in the range of 12 to 5 〇 111 to .8. According to the inkjet method, the concentration of the body component is controlled within a range of 5 mass%, whereby the viscosity of the solution is particularly preferably 3 to 15 mPa·s. The temperature at which the liquid crystal alignment agent is prepared is preferably οι to 200t, more preferably 〇t: 〜4 (rc. &lt;Liquid Crystal Display Element&gt; The liquid crystal display element of the present invention is not particularly limited in its driving mode, TN , STN, IPS, FFS, VA (including Vamva The present technology can be applied to various well-known methods such as a method, a vApvA method, and the like, and the liquid crystal element includes the liquid crystal alignment film formed of the liquid crystal alignment agent. Generally, the liquid crystal display element has a surface. a pair of substrates of a sequential laminated transparent electrode and a liquid crystal alignment film, wherein the pair of substrates are disposed to face each other, and a liquid crystal is filled between the pair of substrates, and the periphery is sealed with a sealant. <Method of Forming Liquid Crystal Alignment Film> The liquid crystal alignment agent of the present invention can be suitably used in a liquid crystal alignment film of -69 to 201229137. The liquid crystal alignment film can be coated with a liquid crystal alignment of the present invention on a substrate. Then, a coating film is formed, and a method of imparting alignment ability to liquid crystal by irradiating polarized light or non-polarized radiation on the coating film, etc. First, a transparent conductive film of a substrate on which a transparent conductive film having no pattern is placed 恻The liquid crystal alignment agent of the present invention is applied by a suitable coating method such as a roll coating method, a spin coating method, a printing method, an inkjet method, etc. Next, preheating (prebak) e) the coated surface is then formed by post-baking (p〇stbake). The preheating condition is, for example, 4〇~12 (rc is performed for 5 minutes, and the post-heating condition is preferably 120~30). (TC, more preferably 150~25〇t: preferably 2〇C knife clock, more preferably 1〇~min. After the addition, the film thickness of the coating film is 0.001~1μιη, preferably For example, 〇〇〇5 to 〇5 tons:, using a glass such as floating glass, Sodium silicate, polybutylene terephthalate or a hydrocarbon resin, as Glass, polyethylene terephthalate, polycarbonate, cyclic olefinic substrate, etc. 2 is the upper material film, can use the Hong (4) NEW ^ bookmark m, In2 〇 3_Sn 〇 2 The ιτ〇 film and the like are formed. These through-the-day; ¥ imaging of the electric film can use a well-known method. When the liquid crystal alignment agent is applied, the coating property is better, and the substrate or the transparent conductive film # right-side* Α substrate and the transparent conductive film may be preliminarily coated with g 丨 矽 化合物 化合物, 钦 # 铱 铱驮S day compound, etc. Then, by using the above-mentioned coating film 4, #^^ t to detect linearly polarized light or part of the phased first radiation or unpolarized light I-ray, can be given to the liquid crystal alignment cartridge -70-201229137 :1 ::r Line and visible light, preferably ^ or partially polarized light, 't Λ ray is linearly polarized light. τ M ',,, shot, /σ, perpendicular to the substrate surface, ., ,, pre-tilt angle It can also be combined in the direction of the tilt. When the radiation of the non-t t Χ ^ s and polarized light is taken, the direction of the irradiation must be skewed toward 0 1 Λ as the irradiation amount of the f-ray, preferably IJ/m2 or more and less than 10,0 () 0 J/m 2 &gt; f # ^ 1 Λ , for 10~3,000J/m. Further, on the coating film formed by the conventionally known = alignment agent, the amount of radiation irradiation of the liquid crystal is required to be 1 〇, 00 〇 j / m 2 or more by the photo-alignment method. However, when the liquid helium alignment agent of the aging agent is used, the amount of radiation irradiation in the photo-alignment method is 3,000 J/m 2 and &quot;ττ ^ , and further, l, 〇〇〇J/m2 or less can provide good liquid crystal. The alignment ability is too large to reduce the manufacturing cost of the liquid crystal display element. η &lt;Manufacturing method of liquid crystal display element&gt; / The liquid crystal display element of this month has a liquid s? alignment film formed of the liquid crystal alignment agent of the present invention. The liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is particularly preferable in that it can be used to a large extent when it is suitable for use in a liquid crystal display device of a vertical alignment type. The liquid crystal display element of the present invention can be produced, for example, as follows. Two substrates on which the liquid crystal alignment film was formed were prepared as described above, and a liquid crystal cell was produced by disposing liquid crystal between the two substrates. For the production of the liquid crystal cell, for example, the following two methods can be employed. The first method is to firstly arrange the two substrates relative to each other via a gap (cell gap) -71-201229137 so that the respective liquid crystals are aligned opposite each other, so that the peripheral portions of the two substrates are filled by the surface of the substrate and the seal. After injecting the liquid crystal, the method of closing the injection hole is performed by a crystal early element. The second method is called 0DF (liquid crystal dropping) method. On the substrate on which the two substrates of the liquid crystal alignment film are formed, for example, an ultraviolet curable sealing material is applied, and then liquid crystal is dropped on the surface, relative to the liquid crystal. The alignment film is bonded and the entire surface of the substrate is irradiated with ultraviolet light to cure the liquid crystal cell. For any of the methods, it is desirable to gradually cool to the flow alignment when the liquid crystal is filled after the liquid crystal is added to the temperature of the isotropic phase. In the case of bonding, the liquid crystal display element of the present invention is obtained by bonding on the outer surface of the liquid crystal cell. Here, in the case of the liquid crystal alignment, the easy directions of the two substrates forming the liquid crystal alignment film are formed in parallel, and the direction in which the polarized light is applied and the direction of the easy axis alignment are 45. The angle is such that it can directly match the liquid crystal display element of the liquid crystal cell. As the above-mentioned sealant, for example, an epoxy resin or the like which is a spacer aluminum ball and a curing agent can be used. As the liquid crystal, for example, a nematic liquid crystal or the like can be preferably used. In the case of the vertical alignment type liquid crystal cell, it is preferable to use a nematic liquid crystal having an opposite direction, for example, a dicyanobenzene-based liquid J sealant, to bond the gap defined by i to a method for producing a liquid. The liquid crystal alignment film is a predetermined substrate, and the sealing agent removes the polarizing plate from the room temperature of the thermal liquid crystal cell, and can align the light plate with the vertical magnetization axis of the film so that the liquid crystal containing the liquid crystal has a vertical member and the matrix has a negative Dielectric crystal, β荅α well system-72- 201229137 Oxidation of azo-based liquid crystal, biphenyl liquid liquid crystal, Schiff base liquid crystal, phenylcyclohexene liquid crystal, etc. as polarized light used on the outer side of liquid crystal cell The plate may be a polarizing plate in which a cellulose acetate protective film sandwiches a polarizing film called "film only", or a polarizing plate composed of tantalum itself, etc., and the polarizing film described above is a polyethylene ion. Obtained by absorbing iodine while extending the alignment. The liquid crystal display element of the present invention produced as described above is excellent in various properties such as display characteristics, long-term reliability, and high-speed responsiveness. &lt;Examples&gt; The present invention is specifically described by way of examples, but the present invention is not limited to the examples. The weight average molecular weight (Mw) of the polyorganooxazepine compound having an epoxy group obtained by tamping % is a polystyrene measured by the GPC method described below. Conversion value. Pipe column: manufactured by Tosoh Corporation, TSKgelGRCXLII Solvent: tetrahydrogen D π south temperature: 40 ° C Pressure: 68 kgf / em2 In addition, the amount of raw material compound and polymer used in the following examples needs to be broken. 4b u , the product 'can be repeatedly subjected to the synthesis scale shown in the following synthesis example as needed; ^ 合成 synthesis of Gentium compound and polymer. &lt;Synthesis of Ping Nuu u-organooxane having an epoxy group&gt; [Synthesis Example 1] In the case of a mixing reaction vessel, a force η, a temperature meter, a dropping funnel, and a reflux condenser are used. 4-epoxycyclohexyl)ethyltrimethoxyindole-73- 201229137 calcined (ECETS) l〇〇.〇g, mercaptoisobutyl ketone 5〇〇g and triethylamine 1〇〇§, at room temperature Mix down. Then, using a dropping funnel, 1 g of deionized water was added dropwise over 3 minutes, and then mixed under reflux, and reacted at 80 for 6 hours. After the completion of the reaction, the organic layer was taken out and washed with a 0.2% by mass aqueous solution of ammonium nitrate until the water after washing was neutral, and then the solvent and water were distilled off under reduced pressure to obtain an epoxy group-containing polycondensation as a viscous transparent liquid. Organic oxime. 1H-NMR analysis of the epoxy group-containing polyorganosiloxane The theoretical strength was obtained according to the peak of the epoxy group in the vicinity of the chemical shift (δ) = 3·2ρρηη, and it was confirmed that the epoxy group did not undergo 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, and the ethylene equivalent of the ethylene equivalent was i86 g/mole. &lt;Synthesis of specific carboxylic acid&gt; [Synthesis of specific carboxylic acid 1] The specific carboxylic acid 1 was synthesized according to the following synthetic route.

COOMe — LiOH · H20 specific carboxylic acid 1 k2co3

DMF

MeOH/H20 [Synthesis Example 2] In a 500 mL three-necked flask equipped with a condenser, 6.3 g of 4-cyano-4,-hydroxybiphenyl, 1 g of decyl undominate, and 12.2 g of potassium carbonate were added. 'NN-dimethylformamide 2〇〇mL, heated at 160 ° C for 5 hours -74- 201229137. After confirming the termination of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was added to 500 mL of water and mixed with stirring. The precipitated white solid was filtered and washed with water. The solid obtained was at 8 Torr. (: Vacuum drying to obtain 1 lg of Compound 1. [Synthesis Example 3] Next, in a 200 mL three-necked flask equipped with a condenser, 10 g of compound 1, lithium hydroxide monohydrate 16 g, methanol 30 mL, and the like were added. Water 1 5 mL 'heat and stir at 80 ° C for 4 hours. After confirming the termination of the reaction by TLC', the reaction solution was cooled to room temperature. The reaction solution was slowly added dropwise with dilute hydrochloric acid in the reaction solution while stirring. The solid was washed successively with water and methanol, and the obtained solid was dried under vacuum at 8 Torr to obtain 8 g of the specific carboxylic acid 1. [Synthesis of the specific carboxylic acid 2] The specific carboxylic acid 2 was synthesized according to the following synthetic route.

LiOH · H20 _ 1 · MeOH/THF/H2〇

NC

Compound 4

COOH-specific carboxylic acid 2 -75 - 201229137 [Synthesis Example 4] 4-N-cyano-4 '-hydroxyl phenyl 1 5 g, ethylene carbonate 1 3.5 g, bromination was added to a 500 mL three-necked flask equipped with a condenser. 2.5 g of tetrabutylammonium (TBAB), 300 mL of hydrazine, hydrazine-dimercaptocarboxamide, and heating and stirring at 150 ° C for 9 hours. After confirming the termination of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was subjected to liquid separation washing with a mixed solution of 300 mL of ethyl acetate and 10 mL of a 1N-aqueous sodium hydroxide solution. After the organic layer was taken out, it was washed in the order of 1 N sodium hydroxide aqueous solution 100 mL and water 100 mL. After the organic layer was dried over magnesium sulfate, the organic solvent was evaporated. The lg compound 2 was obtained by recrystallization from ethanol (100 mL). [Synthesis Example 5] Into a 200 mL three-necked flask equipped with a condenser and a dropping funnel, 12 g of a compound 2, 12.7 g of 4-chlorobenzenesulfonyl chloride, and 60 mL of dehydrated dimethane were added and mixed. In the state where the reaction solution was cooled in an ice bath, 10 inL of a dehydrated dioxane solution containing 6-6 g of triethylamine was added dropwise over 1 Torr. Keep the ice bath, stir for 30 minutes, return to room temperature and mix for 6 hours. To the reaction solution, 150 mL of chloroform was added, and the mixture was washed with 4 mL of water for 4 times. The extracted organic layer was dried over magnesium sulfate, and the organic solvent was removed. The obtained solid was washed with ethanol to obtain 16.1 g of Compound 3. [Synthesis Example 6] In a 300-mL three-necked flask equipped with a condenser, i5 g of a compound 3, llg of 4-mercaptoic acid decyl ester, 12-potassium carbonate, and i8 〇 mL of N:N-dimercapto was added. The amine was stirred with heating at 80 ° C for 9 hours. After confirming the termination of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution -76 - 201229137 was poured into 5 mL of water and mixed and stirred. The precipitated white solid was filtered and washed with ethanol. The solid obtained was at 80. (: Vacuum drying to obtain 1 〇g of Compound 4. [Synthesis Example 7] In a 100 mL three-necked flask equipped with a condenser, 9 5 g of Compound 4 lithium hydroxide monohydrate, 3 mL of decyl alcohol, 15 mL· Tetrahydrofuran,] 5 mL of water, stirred under heating at 8 (TC for 4 hours. After confirming the reaction with τιχ, the reaction solution was cooled to room temperature. The reaction solution was stirred and simmered into the reaction solution, 1®, Dilute hydrochloric acid was added dropwise to the 藏e.., and the precipitated solid was filtered, and the solid was washed with water and ethanol in turn. π The solid which was not allowed to be dried under vacuum at 80 C to obtain 9 g of the specific carboxylic acid 2. [Specific carboxylic acid Synthesis of 3] iB &quot;&quot;'F synthetic route synthesis gu · root FF f battle specific carboxylic acid 3

CH2 c〇OMe K2C03

DMF

. (Call, C〇〇Me

LiOH H20 MeOH / H20

-77-201229137 [Synthesis Example 8] In σ Example 2, '4_Cyano-4,-hydroxybiphenyl was used instead of 10.7 g of 5 tetrakis(4)(pentafluorophenyl) alum, and 13.7 g of a compound was obtained. 5. [Synthesis Example 9] In Synthesis Example 3, in place of Compound 1, 13.5 g of Compound 5 was used to obtain I 1 - 2 g of a specific carboxylic acid 3. [Synthesis of specific carboxylic acid 4]

〇(ch2)2〇H CO〇Me HO

K2C〇3 DMF UOH - H20

Me〇H/THF/H20 [Synthesis Example 10]

COOMe COOH-hydroxybiphenyl, using 25.5 g, gave 23.1 g of compound 6. In Synthesis Example 4, 2,3,5,6-tetrafluoro-4-(pentafluorophenyl) phenyl- 4,5,5,6-tetrafluoro-4-(pentafluorophenyl)-------- Instead of Compound 2, 1 8.9 g of Compound 6 was used to obtain 24.1 g of Compound 7. [Synthesis Example 12] In Synthesis Example 6, 20 g of Compound 7 was used instead of Compound 3 to obtain 15,4 g of Compound 8. [Synthesis Example 13] In Synthesis Example 7, instead of the compound 4, 13 g of the compound 8 was used, and 11.4 g of the specific carboxylic acid 4 was obtained. [Synthesis of Specific Carboxylic Acid 5] A specific carboxylic acid 5 was synthesized according to the following synthetic route.

NC

COOMe K2C03

DMF MC —

COOMe

LiOH · H20

MeOH/H20

0(CH2) COOH

[Synthesis Example 14] As in the synthesis of the specific carboxylic acid 1, 15 g of the specific carboxylic acid 5 having an alkylene group number from 10 to 5 was synthesized. [Synthesis of Specific Carboxylic Acid 6] The specific carboxylic acid 6 was synthesized according to the following synthetic route. -79- 201229137

K2C03 DMF

Li0H.H20 - Me0H/H20

[Synthesis Example 1 5] 2,2',3,3,-tetrafluoro-4'-propyl-4-hydroxybiphenyl 1 〇. 1 g, 1 1 was placed in a 500 mL three-necked flask equipped with a condenser. _Bromo-j--acid methyl ester l〇g, potassium carbonate 14.2 g, N,N-dimercaptocarbamide 2 〇〇 mL, and stirred under heating at 160 ° C for 5 hours. After confirming the termination 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 mixed. The white solid which precipitated was filtered and washed with water. The solid obtained was dried under vacuum at 8 Torr to obtain 1 0.8 g of Compound 9. [Synthesis Example 16] Next, 'in a 2 mL flask equipped with a condenser, 3 g of a compound 9, 1.6 g of lithium hydroxide, monohydrate, 3 〇m]L methanol, 15 claws [water] were added. 'The mixture was heated and stirred at 30 C for 4 hours. After confirming the termination of the reaction with tlc, the reaction solution was cooled to room temperature. The reaction solution was placed in a stalk state, and dilute hydrochloric acid was slowly added dropwise to the reaction mixture. The precipitated solid was filtered and washed with water and ethanol in that order. 4 found solids at 80. . Under vacuum drying, 6 g of a specific carboxylic acid 6 was obtained. -80-201229137 [Synthesis of specific carboxylic acid 7] The specific carboxylic acid 7 was synthesized according to the following synthetic route.

FF specific carboxylic acid 7 [Synthesis Example 17] except that the starting compound (2,2',3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) 10. lg was changed to the above synthetic route. Other than the 9.1 g of the compound (2,3-difluoro-4-(4-propyl-cyclohexyl)phenol) described above, 5.9 g of the specific carboxylic acid 7 was obtained in the same manner as in the synthesis of the above-mentioned specific carboxylic acid 6. [Synthesis of Specific Carboxylic Acid 8] The specific carboxylic acid 8 was synthesized according to the following synthetic route.

K2C〇3 DMF

-81 - 201229137 [Synthetic Example: .8] except that the starting compound (2, 2, 3, 3, _tetrafluoro-4, propyl-4 hydroxybiphenyl) lCLlg was changed to t as described in the above synthetic route. In the same manner as the synthesis of the above specific carboxylic acid 6, except for the synthesis of the above specific carboxylic acid 6, except for the compound (2,2':3,3'-tetrafluoro-4-propyl-4"-hydroxyl-triphenyl) 129 §, 7 lg of the specific carboxylic acid 8 was obtained. [Synthesis of Specific Carboxylic Acid 9] A specific slow acid 9 was synthesized according to the following synthetic route.

Specific acid 9 [Synthesis Example 19] In addition to the starting compound (2, 2, 3, 3, tetrafluoro-4, -propyl-4-hydroxybiphenyl) 10.1 g was changed to the one described in the above synthetic route. The compound (2,3-difluoro-4-(4-propyl%hexyloxy)phenyl) i〇2g was obtained in the same manner as the above-mentioned synthesis of the specific slow acid 6 to obtain 6_5 § specific tracing acid 9. [Synthesis of carboxylic acid 10] The specific citric acid 1 oxime was synthesized according to the following synthesis route. -82- 201229137

K2C〇3 DMF ~

Li0H*H20 - MeOH/H2〇

[Synthesis Example 20] In addition to the starting compound (2,2',3,3,-tetrafluoro-4'-propyl-4-hydroxybiphenyl), lg was changed to the compound described in the above synthetic route ( 2,3-Difluoro-4'-(4-propylphenylethyl)biphenyl) 12.6, in the same manner as in the synthesis of the above specific carboxylic acid 6, 7.2 g of the specific carboxylic acid 10 was obtained. [Synthesis of Specific Carboxylic Acid 1 1] A specific carboxylic acid 1 1 was synthesized according to the following synthetic route.

Specific carboxylic acid 11-83-201229137 [Synthesis Example 21] In addition to the starting compound (2, 2, 3, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4) In the synthesis of the above-mentioned synthetic route, in combination with the above-mentioned specific carboxylic acid 6, '76 g of a specific carboxylic acid is obtained' [Synthesis of a specific carboxylic acid 12]

K2C〇3

DMF

Specific carboxylic acid 12 [Synthesis Example 22] In a 500 mL three-necked flask equipped with a condenser, 12.5 g of 4-[difluoro(4-pentylcyclohexyl)methoxy]2,3-difluorophenol was added. 10 g of 11-bromoundecanoic acid, 44.2 g of potassium carbonate, and 200 mL of N,N-dimethylformamide were heated and stirred at 160 C for 5 hours. After confirming the termination of the reaction by TLC, the reaction solution -84 - 201229137 was cooled to room temperature. The reaction solution was poured into 500 ml of water and mixed for mixing. The precipitated white solid was filtered and washed with water. The obtained solid was dried under vacuum at 80 ° C to obtain 14.8 g of Compound 10. [Synthesis Example 23] Next, a 200 mL three-necked flask equipped with a condenser was charged with i〇g compound 10, lithium hydroxide monohydrate 1.6 g, methanol 30 mL, and water HmL, and heated under stirring at SO ° (4). After confirming the termination of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was stirred, and dilute hydrochloric acid was slowly added dropwise to the reaction solution, and the precipitated solid was filtered, and washed with water and ethanol in that order. The mixture was dried under vacuum at 80 ° C to obtain 6 g of a specific carboxy hydrazine 1 2 &lt;Synthesis of cinnamic acid derivative &gt; [Synthesis of cinnamic acid derivative (A-1)] A cinnamic acid derivative was synthesized according to the following synthetic route. (A-1).

[Synthesis Example 24] To a 2 mL mL eggplant-shaped flask equipped with a reflux tube, thiol-based white carboxylic anhydride, 8.2 g of 4-aminocinnamic acid, and 100 mL of acetic acid were added, and the mixture was refluxed for 2 hours to carry out a reaction. After the completion of the reaction, the reaction mixture was extracted with ethyl acetate, and the organic layer was washed with water, dried over magnesium sulfate, and then purified with a ruthenium dioxide column and recrystallized from a mixed solvent of ethanol and tetrahydrofuran to obtain 10 g of a cinnamic acid derivative. White crystals (purity of 98.%). [Synthesis of cinnamic acid derivative (A-2)] The cinnamic acid derivative (A-2) was synthesized according to the following synthetic route. -85- 201229137

COOH

CgH-i/Br K2C03 C8H17-〇

—COOH

[Synthesis Example 25] In a 1 L eggplant-shaped flask, 8 2 g of p-hydroxycinnamic acid, potassium carbonate 3 0 4 g and N-methyl-2 - were added. Pilotone 4 0 m L, after mixing at room temperature for 1 hour, was added to 1-bromooctane 212 g, and stirred at 10 CTC for 5 hours. Then, the solvent was distilled off under reduced pressure. At this time, 48 g of sodium hydroxide and 4,000 mL of water were added, and refluxed for 3 hours to carry out a hydrolysis reaction. After the reaction, the reaction system was neutralized with hydrochloric acid, and the resulting precipitate was recovered by recrystallization from ethanol to obtain white crystals of 8 g g of the cinnamic acid derivative (A-2). [Synthesis of cinnamic acid derivative (A-3)] The cinnamic acid derivative 3) was synthesized according to the following synthetic route.

-COOH Βγ-hQ—=

COCI (A-3-1) 〇5Ηη Heart OC. Pd(OAc)2 1 •oco—=

CsH, CH2=CH—COOH :~~G^~ch=ch-cooh (Ar3) [Synthesis Example 26] Red transparent was obtained by "reducing 4-g cinnamic acid of 07 g in 83 g of sulfite chlorine for 4 hours" After the unreacted sulfite gas was distilled off, the residue was recrystallized and washed with n-hexane to obtain white crystals of 85 g of the compound (A-3-1). -86- 201229137 I'm dissolved 25 〇g (〇147 mol) of 4_pentylcyclohexanol in 25 mL of pyridine. The temperature of the solution was maintained at about 3 〇c, at which time 43.3 g (0.176 mol) obtained above was added dropwise. The compound (the suspension formed by the compound in 350 mL of pyridine was further reacted for 3 hours. The obtained reaction mixture (suspension) was poured into 1.3 kg of hydrochloric acid acidic ice water, and the resulting precipitate was filtered. , washed with water, dried to obtain a crude product (cream powder) of the compound (A_3_2) 50 g. The crude product of 50 g of the compound (A-3-2) obtained above, 〇.28 g of acetic acid and 1.52 g In a mixture of tris(o-phenyl)phosphine, 125 mL of dry triethylamine is added under a nitrogen atmosphere to carry out the reaction. The crude product of the compound (A-3-2) is obtained. After completely dissolving, a syringe was used to inject ίο. 8g of acrylic acid' and the reaction was continued at 95 °C for 2 hours. The dark green reaction mixture obtained was put into 1.3 kg of hydrochloric acid acidic ice water, and separated by filtration. The compound obtained was dissolved in 500 mL of ethyl acetate, and sequentially washed with 1 N hydrochloric acid and 5% by mass of sodium hydrogen carbonate solution, and then the organic layer was collected, dried over magnesium sulfate, and the solvent was evaporated to give 56 g of cinnamic acid. The crude product of the product (A-3) (yellow solid). The crude product was recrystallized from ethanol to obtain a yellow powder of the cinnamic acid derivative (A-3) (yield 55%). Synthesis of Derivative (A-4)] The cinnamic acid derivative (A-4) was synthesized according to the following synthetic route. -87- 201229137

CFjC3H6I NaOH/HjO CCOCHj --► -► CF3C3H6—〇-^^—C〇〇H (A_4_1} K2C03 H0-&lt;^-CH=CH-C00H K2C03 CF3C3H6COO-^^-CH=CH-COOH (A- 4) [Synthesis Example 27] 91.3 g of decyl 4-hydroxybenzoate, 182, 4 g of potassium carbonate and 320 mL of N-mercapto-2-pyrrolidone were added to a 1 L eggplant-shaped flask, and stirred at room temperature. After 1 hour, 157.1 g of 1-iodo-4,4,4-trifluorobutane was added and the mixture was stirred for 5 hours at 100 ° C. After the reaction was over, reprecipitation was carried out with water. Then, hydroxide was added to the precipitate. 48 g of sodium and 400 mL of water were refluxed for 3 hours to carry out a hydrolysis reaction. After the completion of the reaction, the mixture was neutralized with hydrochloric acid, and the resulting precipitate was recrystallized from ethanol to obtain 110 g of a white crystal of the compound (A-4-1). I2.41g in -4-1) was placed in a reaction vessel, and ruthenium sulfoxide gas l〇〇mL and n,N-dimethyl decylamine 77 μί were added thereto, and the mixture was stirred at 80 C for 1 hour. The sulphur sulphide gas was distilled off under reduced pressure, and the mixture was washed with aqueous sodium hydrogencarbonate, dried over magnesium sulfate, concentrated, and then evaporated to afford a solution. Next, in another 5 〇〇 Mij three-necked flask 7. 9 g of 4-hydroxycinnamic acid, 13.82 g of potassium carbonate, 48 g of tetrabutylammonium bromide, THF of tetrahydrofuran, and 100 mL of water. The aqueous solution was ice-cooled, and the above tetrahydrofuran solution was slowly added dropwise, and (4) the reaction was carried out for 2 hours. Thereafter, neutralization with hydrochloric acid was carried out, 'Extraction of St. acid B from the purpose', followed by drying with sulfuric acid, and concentration was carried out '88 - 201229137' by recrystallization using ethanol to obtain white crystals of 10.0 g of cinnamic acid derivative (A_4). Synthesis of cinnamic acid derivative (A-5)] cinnamic acid derivative (A-5). CsH"-<~~COOH (A-5) Synthetic meat according to the following synthetic route

Et3N

Pd(〇Ac)2 c outside 1-〇~〇-order

H2C=~c〇〇H (A-5-1) [Synthesis Example 28] In a 5 〇〇 mL three-necked flask equipped with a reflux tube, a temperature meter, and a nitrogen introduction tube, a compound (A-5-l) 3 lg was added. In an acetic acid, 23 g of ruthenium, 1.2 g of tris(o-tolyl)phosphine, 56 mL of triethylamine, and 2.00 mL of 8 2 mL*N,N-dimethylacetamide of acrylic acid were stirred at 120 ° C for 3 hours to carry out a reaction. After the completion of the reaction, the reaction mixture was filtered, and the obtained organic layer obtained by adding 1 L of ethyl acetate to the mixture was washed twice with dilute hydrochloric acid and then washed three times with water, dried over magnesium sulfate, and the solvent was removed under reduced pressure. The solid was recrystallized from a mixed solvent of ethyl acetate and tetrahydrofuran to obtain crystals of i 5 g of the cinnamic acid derivative (A-5). [Synthesis of cinnamic acid derivative (Α-6)] A cinnamic acid derivative (A _ 6) was synthesized according to the following synthetic route. ΕίβΝ

Pd(OAc)2

[Synthesis Example 29] In a 5 〇〇 mL three-necked flask equipped with a reflux tube, a temperature meter, and a nitrogen gas introduction tube, 28 g of the compound (A-6-1), palladium acetate ruthenium.23 g, and tris(o-phenylene-89-) were added. 201229137 base phosphine 1.2g, triethylamine 56mL, acrylic acid 8 2mI^N, N dimethyl ethanoamine 200mL, the mixture was mixed for 3 hours to carry out the reaction. After the completion of the reaction, the reaction mixture was filtered, and the obtained organic layer was washed twice with dilute hydrochloric acid and washed three times with water, dried over magnesium sulfate, and then evaporated. The solid was recrystallized from a mixed solvent of ethyl acetate and tetrahydrofuran to obtain crystals of 3 g of cinnamic acid derivative (Α·6). [Synthesis of cinnamic acid derivative (Α-7)] A cinnamic acid derivative (Α_7) was synthesized according to the following synthetic route.

Et3N

Pd(OAc)2 C; Wl5_

P(°~tol)3 _ /~\

C7H15—^ )~^ J~==-COOH H2C=-CO〇h , ^' N=/ (Α-7) [Synthesis Example 30] 5〇〇mL with reflux tube, temperature meter and nitrogen inlet tube In the three-necked flask, 34 g of the compound (A-7-1), palladium acetate.23 g, tris(o-tolyl)phosphine 1.2 g 'triethylamine 56 mL, 8.2 mL of acrylic acid and N,N-didecylacetamide were added. The reaction was carried out by stirring 2 〇〇 mL ' at 120 ° C for 3 hours. After the reaction was completed, the reaction mixture was filtered, and the organic layer obtained by adding 1 L of ethyl acetate to the obtained filtrate was washed twice with dilute hydrochloric acid and three times with water, dried over magnesium sulfate, and the solvent was removed under reduced pressure. The obtained solid was recrystallized from a mixed solvent of ethyl acetate and tetrahydrofuran to obtain crystals of 14 g of the cinnamic acid derivative (A.-7). [Synthesis of cinnamic acid derivative (A-8)] A cinnamic acid derivative (A-8) was synthesized according to the following synthetic route. -90- 201229137 C5H11—Ο OOH- K2C03 HO-

,c5h" ;H=CH—COOH

00 H

[Synthesis Example: Π] In a 300 mL eggplant-shaped flask equipped with a reflux tube and a nitrogen introduction tube, 21 g of the compound (A-8-1), 80 mL of sulfoxide chloride, and 0.1 mL of N,N-diindenylamine were added. The reaction was carried out by stirring at 80 ° C for 1 hour. After the end of the reaction, the sulfite gas was distilled off from the reaction mixture, and then the organic layer obtained by adding 15 mL of dioxane was washed three times with water. After the organic layer was dried with sulfuric acid, the solvent was removed under reduced pressure, and 4 mL of tetrahydrofuran was added to the obtained solid. On the other hand, in a three-necked flask equipped with a dropping funnel and a temperature meter, 16 g of p-hydroxycinnamic acid, 24 g of potassium carbonate, 4 g of tetrabutylammonium bromide, 200 mL of water, and tetrahydrofuran i〇〇 were added. mL, at 5. (: The following is cold. Here, the above tetrahydrofuran solution was added dropwise over 3 hours, and the reaction was carried out for 1 hour. After the reaction was completed, dilute hydrochloric acid was added to the reaction mixture, and after p Η was 4 or less, 'toluene 3 L was added. And the obtained organic layer was washed three times with water. After the organic layer was dried over magnesium sulfate, the solvent was removed under reduced pressure, and the obtained solid was recrystallized from a mixed solvent of ethanol and tetrahydrofuran to obtain 2 1 g of cinnamic acid derivative (Α_8). &lt;[a] Synthesis of polyorgano oxy-oxygen compound&gt; [Example 1] In a l〇〇mL three-necked flask, 9 8 g of the above synthesis example i was obtained. The polyorganosiloxane having an epoxy group, 28 g of decyl isobutyl ketone, 5 〇g of the specific carboxylic acid i obtained in the above Synthesis Example 3, 5 lg of the cinnamic acid derivative obtained in the above Synthesis Example 24 (A- 1) and 〇.20guCAT18X (SANAPR(R)-91 - 201229137 quaternary amine salt), stirred at 80 ° C for 12 hours. After the reaction, reprecipitation with decyl alcohol, the precipitate was dissolved in ethyl acetate After the solution was washed three times with water, the solvent was distilled off to obtain 14.5 g. The white powder was 丨: a] polyorganosiloxane compound a-1. The Mw of the polyorganosiloxane compound a-Ι was 15,500. [Examples 2 to 22] The specific carboxylic acid and cinnamic acid derivative used were used. The kinds and amounts of the materials are as described in Table 1, and the [a] polyorganosiloxane compound of a-2 to a-22 was obtained in the same manner as in Example 1. [Table 1] [a] Polyorganosiloxane compound Specific carboxylic acid cinnamic acid bamboo organism [a] molecular stem (Mw) of polyorganosiloxane compound (high-speed response unit) compound mass (mol%) compound mass (mol%) Example 1 a-1 specific carboxylic acid 1 25 A-1 25 15,500 Example 2 a-2 Specific carboxylic acid 1 5 A-2 25 10,400 Example 3 a-3 Specific carboxylic acid 1 10 A-3 25 12,300 Example 4 a-4 Specific carboxylic acid 1 15 A-4 25 13,000 Example 5 a-5 Specific carboxylic acid 1 10 Α·5 25 12,900 Example 6 a-6 Specific carboxylic acid 1 15. Α-6 25 11,900 Example 7 a-7 Specific carboxylic acid 1 10 Α -7 25 12,400 Example 8 a-8 Specific carboxylic acid 1 10 Α-8 25 11,800 Example 9 a-9 Specific carboxylic acid 1 25 A-4 50 19,100 Example 10 a-10 Specific carboxylic acid 2 25 A-4 25 16,900 Example 11 a-11 Special Determination of carboxylic acid 3 25 A-4 25 15,800 Example 12 a-12 Specific carboxylic acid 4 25 A-4 25 14,400 Example 13 a-13 Specific carboxylic acid 5 25 A-4 25 17,000 Example 14 a-14 Specific carboxylic acid Acid 1 10 A-8 15 13,000 Example 15 a-15 Specific carboxylic acid 1 15 A-8 20 13,900 Example 16 a-16 Specific carboxylic acid 6 25 A-4 25 15,200 Example 17 a-17 Specific carboxylic acid 7 25 A-4 25 15,500 Example 18 a-18 Specific carboxylic acid 8 25 A-4 25 14,900 Example] 9 a-19 Specific carboxylic acid 9 25 A-4 25 15,200 Example a-20 Specific carboxylic acid 10 25 A -4 25 15,300 Example a-21 Specific carboxylic acid 11 25 A-4 25 15,500 Example: !2 a-22 Specific carboxylic acid 12 25 A-4 25 15,000 In the above Table 1, the mass is expressed relative to the poly The organic siloxane has an epoxy amount, a specific carboxylic acid or a cinnamic acid derivative. -92-201229137 [Comparative Synthesis Example 1] Into a 100 mL three-necked flask, 98 g of the polyorganooxime having an epoxy group obtained in the above Synthesis Example i, 28 g of methyl isobutyl ketone, and 56 g of the above synthesis example were added. The cinnamic acid derivative (eight_8) obtained in π and 〇1〇gUcATi8x (quaternary amine salt manufactured by SANAPRO) were stirred at 8 ° &lt;&gt;c for 12 hours. After the completion of the reaction, the precipitate was reprecipitated with methanol, and the precipitate was dissolved in ethyl acetate. After the solution was washed three times with water, the solvent was distilled off to obtain 9 6 g of a polyorganoxane compound Cad as a white powder. Ca_i]^You are 9,8〇〇〇&lt;[B] Polymer Synthesis&gt;&lt;Synthesis of Polyglycolic Acid&gt; [Synthesis: 32] At 367.6 g of N-methyl_2_ I9.61g (〇, i mole) 1,2,3,4-cyclobutane tetraphthalic acid dianhydride and 2123g (〇i Mo) 4,4,-diamino-2 are dissolved in pyrrolidone. 2 '-Dimethylbiphenyl was reacted at room temperature for 6 hours. Next, the reaction mixture was poured into a large excess of sterol to precipitate a reaction product. The precipitate was washed with methanol under reduced pressure at 40. (: drying for 5 hours, obtaining 35 g of poly-proline acid PA-1. [Synthesis Example 33] 22.4 g (〇.l mole) 2 was dissolved in 329.3 g of N-methyl-2-pyrrolidone. 3,5. Tricarboxycyclopentyl acetic acid dianhydride and I4.23 g (0-1 mol) cyclohexane bis(formamide) were reacted at 60 ° C for 6 hours. Then, the reactant was injected into a large excess of sterol. The precipitated reaction product was precipitated, and the precipitate was washed with methanol and dried under reduced pressure at 40 ° C for 15 hours to obtain 32 g of polyamidamine PA-2. &lt;Synthesis of Polyimine&gt; -93- 201229137 [Synthesis Example 34] Take 1 7 · 5 g of the above-mentioned synthesis example 3 3 φ A to the poly-proline acid PA-2, to which N-methyl-2-n-byl is added. The ketone 2 n 3 2.5 g, ° It is more than 3.8 g and 4.9 g of acetic acid, and reacted at 120 ° C for 4 hours, and the reaction mixture is injected into a large amount of sterols in the mixture. The reaction product was washed with decyl alcohol, and dried under reduced pressure for 15 hours to obtain 15 g of polyimine P.-l. [Synthesis Example 35] In 140 g of N-methyl-2-pyrrolidine @同中溶1 8 75g(〇〇836摩尔) as 2' 3 of tetracarboxylic dianhydride 5_tricarboxycyclopentyl acetic acid dianhydride, 7.359 g 丨〇_〇681 mol) as a diamine compound p-phenylenediamine, 889 (0.017 (丨莫耳) 3,5-diamino benzoic acid = 5^Cholestane_3 group, reacted at 6 ° C for 5 hours. Determine the viscosity of the polymerization solution to 2 〇〇〇 mpa.s. Then add 325 g of N-mercapto-2- in the solution Pyridone, after a while stirring, 'add pyridine 6 · 6 1 g and acetic anhydride 8 · 5 4 g, and enter the dehydration ring for 4 hours at 110 ° C. Then, inject the reaction solution into excess In a large amount of methanol, the reaction product was precipitated, and the precipitate was washed with methanol and dried under reduced pressure at 40 °C for 15 hours to obtain 26.6 g of polyimine PI-2 having a ruthenium iodide ratio of 51%. &lt;Liquid alignment agent [Preparation of the present invention] The solution containing the poly-proline acid PA-1 obtained in the synthesis example 32 is contained in an amount of 1,000 parts by mass based on the poly-proline acid PA-1 contained therein. Add [a] polyorganosiloxane compound a_ 1 (1 〇〇 parts by mass), and then add N-methyl 2 -pyrrolidone and butyl cellosolve' to prepare a solvent composition of -94- 201229137 N - Methyl-2 - η Bilokenone: a solution of butyl cellosolve = 50:50 (mass ratio) and a solid concentration of 3.5% by mass. The solution was filtered through a filter of pore size 〇 2 μιη to prepare a liquid crystal alignment agent (S- 1). [Examples: 24 to 54 and Comparative Examples 1 and 2] A combination of a polyamido acid or a polyamidino compound as a [Β] polymer, and a [a] polyorganosiloxane compound as described in Table 2 The same procedure as in Example 23 was carried out to prepare liquid crystal alignment agents S-2 to S-32 and CS-1 and CS-2. &lt;Formation of Liquid Crystal Alignment Film&gt; The liquid crystal alignment agent prepared in the above Example was applied to the transparent electrode surface of the glass substrate provided with the transparent electrode made of the ITO film by a spinner, and the heat at 80 ° C was applied. After preheating for 1 minute on the plate, it was at 200 in an internal incubator replaced with nitrogen. (: heating was performed for 1 hour to form a coating film having a film thickness of 〇8 μm. Then, a Hg-Xe lamp and a Glan-Taylor prism polarizer were used for the surface of the coating film, and the direction was inclined by 4 沿 in the direction normal to the substrate. A polarized ultraviolet ray (2 〇〇 J/m 2 ) containing a bright line of 313 nm was irradiated to form a liquid crystal alignment film, and the same operation was repeated to produce a pair of (two pieces) substrates on which a liquid crystal alignment film was formed. Manufacture of a pair of substrates by adding an epoxy resin adhesive having a diameter of 3.5 μΓ to a peripheral surface of a substrate having a liquid crystal alignment film on which a liquid crystal alignment film is formed by screen printing. The liquid crystal film is opposed to each other, and is pressed against the projection direction of the substrate surface of the ultraviolet light axis of each substrate in an antiparallel manner, and the adhesive is thermally cured at 15 ° C for 1 hour. Then, by liquid crystal The inlet is filled with a negative liquid crystal (Mer-6's MLC-6608) into the gap between the substrates, and the liquid crystal is sealed with epoxide-95-201229137. In order to remove the H master _ U, Heat it to 1 5 (rc, and then slowly cooled to room temperature. Then ^ the polarizing light is applied to the outer sides of the base plate so that the polarization directions of the light plates are perpendicular to each other' and the surface of the plate facing the ultraviolet light axis of the liquid crystal alignment film The liquid crystal display element was produced at a projection angle of 45. [Example 55] The liquid crystal prepared in the above Example 37 was coated on the transparent electrode surface of the glass substrate having the transparent electrode made of the ITO film by a spinner. The alignment agent 15) 'When preheating i clock on the hot plate of 801, it is heated in a strange temperature chamber which is replaced with nitrogen inside, and heated under fine c for 2 hours to form a coating film of the crucible. To operate, a pair of (two pieces) substrates having a liquid crystal alignment film were produced. For one of the substrates, an Hg-Xe lamp and a Glan Taylor prism were used on the surface of the coating film to be inclined by 4 Å along the normal line of the substrate. Bright-line polarized ultraviolet light (2〇〇j/m2). Then, a ring of alumina having a diameter of 35 μm was applied by screen printing on the outer periphery of the surface of the substrate irradiated with polarized light UV having a liquid crystal alignment film. Oxygen resin adhesive after 'will another# The liquid crystal alignment film of the plate (without irradiating the polarized light υν) is pressed against the surface, and the heat-curing adhesive is applied. Then, the negative liquid crystal is produced by the liquid crystal injection port (Merck, MLC) -6608) Filling the gap between the substrates and then sealing the liquid crystal injection port with an epoxy adhesive. Further, in order to remove the flow alignment during liquid crystal injection, it is heated to 15 (TC, and then slowly cooled to room temperature. Then, The polarizing plate was bonded to both outer surfaces of the substrate so that the polarization directions of the polarizing plates were perpendicular to each other, and the liquid crystal display element was manufactured at a 45-degree angle with respect to the projection direction of the substrate surface of the ultraviolet light axis of the liquid crystal alignment film. -96-201229137 [Example 56] 'Do not add N,N,N,N'-tetraglycidyl group 4,4' to 100 parts by mass of the polyimine imine PI-2 obtained in the above Synthesis Example 35 _Diaminodiphenyl f is 20 parts by mass, and the solvent composition is N-mercapto-2·pyrrolidone: butyl granules - 5 0.5 0 (mass ratio) n-methyl 2 - fluorene ratio The ketone and butyl cellosolve were formulated into a solution having a solid concentration of 3.5% by mass. This solution was filtered through a filter having a pore size of 0.2 μm to prepare a liquid crystal alignment agent s_33. The liquid crystal alignment agent (S-3 3) prepared by coating the above-prepared liquid crystal alignment agent (S-3 3) by a spinner on the transparent electrode surface of the glass substrate having the IT film formed by the slit-like image as shown in FIG. After preheating for 1 minute on the plate, the film was heated at 2 Torr for 1 hour in a constant temperature phase which was internally replaced with nitrogen to form a coating film having a film thickness of 0.08 μm. Next, the liquid crystal alignment agent (S-15) prepared in the above Example 3 was applied by a spinner on the transparent electrode surface of the glass substrate having the ruthenium film imaged in the slit shape shown in FIG. The hot plate of 〇t was preheated for 1 minute, and then heated in an incubator which was replaced with nitrogen inside for 1 hour at 2 ° C to form a coating film having a film thickness of 0.08 μm. On the outer periphery of the liquid crystal alignment film of the substrate, an epoxy resin adhesive having a diameter of 35 μm of alumina balls is applied by screen printing, and then the liquid crystal alignment of the other pair of substrates (which are not irradiated with polarized light uv) is aligned. The membrane surface is pressed against each other at 15 〇. The underarm heat-hardening adhesive is used for a while. Then, a negative liquid crystal (manufactured by Merck, MLC-6608) was filled into the gap between the substrates by the liquid crystal injection port, and then the liquid crystal injection port was closed with an epoxy adhesive. Further, in order to remove the flow alignment at the time of liquid crystal injection, it was heated to 15 ° C and then slowly cooled to room temperature. Then, 'the liquid crystal cell manufactured by the above-mentioned AC voltage of 10 V is applied, and -97-201229137 is used for 5 用 with a halogen lamp, 〇〇〇j/m2 of light illuminates the illusion," and then, on the unit substrate. The polarizing plate was attached to the outer surface so that the polarizing directions of the polarizing plates were perpendicular to each other and the liquid crystal display element was manufactured at a 45» angle with respect to the projection direction of the substrate surface of the optical axis when the polarized light UV was irradiated. [Comparative Example 3] The components shown in the following Table 2 were used ("" in Table 2 indicates that the liquid crystal alignment agent prepared in the same manner as in Example 23 was not used without using this component" was applied to a transparent electrode having an IT0 film by a spinner. On the transparent electrode surface of the glass substrate, preheated on a hot plate of 80% (:: minute, in an incubator replaced with nitrogen, heated at 20 (rc for 1 hour, the solvent was removed to form a film thickness of 0.08). a coating film (liquid crystal alignment film) of μιη. This operation is repeated to produce a substrate having a liquid crystal alignment film (two pieces). The outer peripheral wire having a liquid crystal alignment film on the above-mentioned one substrate

The screen printing was carried out by adding an epoxy resin A-containing agent having a diameter of 3.5 μm, and then the liquid crystal alignment film faces of the pair of substrates were pressed against each other. $, heated at 150 ° C for 1 hour, heat hardening the adhesive. Next, a liquid crystal injection port is filled with a negative liquid crystal (manufactured by Merck, MLC-6608) to the gap of the substrate, and then the liquid crystal injection port is closed with an epoxy adhesive, and further, in order to go to &amp; the liquid alignment during liquid crystal injection, After heating at 1 50 ° C for 1 〇 minutes, slowly cool to room temperature. Further, 'the polarizing plate is attached to both outer surfaces of the substrate so that the polarization directions of the two polarizing plates are perpendicular to each other, thereby manufacturing a liquid crystal display/U piece&lt;Evaluation&gt; Liquid crystal display manufactured using the liquid crystal alignment agent of the above embodiment~ Item-98- 201229137 Perform the following evaluation. The results are shown together in Table 2. Further, in Example 56, since the pattern electrode substrate was used, the voltage holding ratio and the light resistance were not measured. [Voltage Retention Rate (VHR (%))] The voltage of 5 v was applied to the liquid crystal display element manufactured above with an application time of 60 microseconds and a span of 167 milliseconds, and the measurement was measured after 1 67 milliseconds from the release of the application. Voltage retention rate. The measuring device used VHR-1 manufactured by Dongyang Technica. [Light resistance. 1 The VHR irradiated for 3 hours after the irradiation with a carbon arc as a light source was measured in the same manner as described above (applying a voltage of 5 V with an application time of 6 〇 microseconds and a span of 167 ms) Then, the voltage holding ratio after 167 milliseconds from the release of the application was measured. The measuring device used VHR_ 1 &gt; manufactured by Dongyang Technica, and the amount of change in VHR was less than 1% as compared with the measured value before irradiation. More than 1%, less than 3% is marked as "△", and 3% or more is marked as "X". [Response responsivity (electro-optic responsiveness at the beginning)] Includes a polarizing microscope, photodetector, and pulse The device of the generator measures the start time of the liquid crystal response. Here, the liquid crystal response speed is defined as the T-time evaluation, that is, a voltage is applied to the manufactured liquid crystal display element for a maximum of one second, so that the voltage is never applied. The state is up to a voltage of 4 V, at which time the transmittance changes from 丨〇% to 9〇0/. The time required (unit: leap seconds). -99- 201229137 [Table 2] Liquid crystal g-oriented agent [B Polymer [a] polyorganooxane VHR (%) light resistance Speed (milliseconds) The amount of the compound (parts by mass) relative to 100 parts by mass of the [B] polymer. Example 23 S-1 PA-1 a-1 5 98 〇7 Example 24 S-2 PA-1 a- 2 5 98 〇9 Example 25 S-3 PA-1 a-3 5 98 〇8 Example 26 S-4 PA-1 a-4 5 99 〇6 Example 2? S-5 PA-1 a-5 5 99 〇5 Example 28 S-6 PA-1 a-6 5 99 〇5 Example 29 S-7 PA-1 a-7 5 98 〇7 Example 3&lt;) S-8 PA-1 &amp;- 8 5 99 〇3 Example 3: [S-9 PA-1 a-9 5 99 〇5 Example 32 S-10 PA-1 a-10 5 98 〇8 Example 3: 5 S-11 PA-1 A-11 5 98 〇4 Example 34 S-12 PA-1 a-12 5 98 〇9 Example 3.5 S-13 PA-1 a-13 5 99 〇9 Example 36 S-14 PA-1 a- 14 5 99 〇4 Example 37 S-15 PA-1 a-15 5 99 〇3 Example 3S S-16 PA-1 a-5 10 98 〇3 Example 3 9 S-17 PA-1 a-5 20 98 〇3 Example 40 S-18 PA-2 3.-8 5 99 〇6 Example 41 S-19 PA-2 a-8 10 99 〇5 Example 42 S-20 PA-2 a-14 5 98 〇 4 Example 43 S-21 PA-2 a-14 15 98 〇3 Example 44 S-22 PI-1 a-10 5 99 〇6 Example 45 S-23 PI-1 a-10 15 99 〇 4 Example 46 S-24 PI-1 a-15 5 99 〇5 Example 47 S-25 PI-1 a-15 15 99 〇3 Example 4 8 S-26 PA-1 a-16 5 99 〇2 Example 49 S-27 PA -1 a-17 5 99 〇2 Example ί0 S-28 PA-1 a-18 5 99 〇2 Example ί; 1 S-29 PA-1 a-19 5 99 〇2 Example 52 S-30 PA -1 a-20 5 99 〇2 Example 53 S-31 PA-1 a-21 5 99 〇2 Example 54 S-32 PA-1 a-22 5 99 〇2 Example 55 S-15 PA-1 A-15 5 99 〇2 Example 56 S-33 Composition See, f. - - 2 Comparative Example k CS-1 PA-1 Ca-l 5 99 〇13 Comparative Example CS-2 PI-1 Ca-1 5 99 〇15 Comparative Example 3 CS-3 PI-2 - - 98 X 78 The above table In 2, the polyorganosiloxane is represented by a mixing amount (parts by mass) with respect to 100 parts by mass of the [B] polymer. -100-201229137 The alignment agent is good, and the speed is high. It can be seen from the results of Table 2 that the liquid crystal display element having the liquid crystal alignment film formed by the liquid crystal of the example is excellent in light resistance, and the response speed of the liquid crystal is higher than that of the liquid crystal of the comparative example. Display element is more 〇 [Industrial use possibility] It is possible to satisfy the photoelectric resonance polysiloxane. The liquid crystal alignment agent of the present invention can be suitably used for producing a liquid crystal which is not only required for the usual voltage holding ratio and light resistance, but also requires time. Display component. Further, the organoalkane compound of the present invention can be suitably used as a raw material of the liquid crystal alignment agent. BRIEF DESCRIPTION OF THE DRAWINGS Conductive film Fig. 1 is a view showing a pattern of a transparent conductive film in a liquid crystal cell having a pattern which is transparent in the embodiment. [Main component symbol description] 1 ITO electrode 2 slit portion 3 light shielding film -101 -

Claims (1)

201229137 VII. Patent application scope: • A liquid crystal alignment agent containing "A another LA" polymer having a photo-alignment group and a group represented by the following formula (A1), RC- and Shi RA- (A1 In the formula (A1), R is a methylene group, an alkyl group having 2 to 30 carbon atoms, a phenyl group or a cyclohexyl group 1, and some or all of the hydrogen atoms of these groups may be substituted, rB To include a double bond, a triple bond, an ether bond, an ester bond, and a linking group of any - aa in an oxygen atom, Rc is a group having a structure of a saponin, &amp; is 〇 or 1. The above-mentioned photo-alignment group having the structure represented by the following formula (B1), wherein the above-mentioned photo-alignment group has a structure, (B1) In the formula (8)), R is a fluorine atom or a cyano group, a is an integer of 〇~4, and when it is 2 or more, a plurality of R's may be the same or different, and * represents a linkage. 3, such as the scope of application materials! A liquid crystal alignment agent, wherein Rc in the above formula (ai) is represented by the following formula (A2): (A2) ^RG) rRF~{REVRD' In the formula (A2), Rd is a phenyl group and a stretching group a phenyl group, an anthranyl group, a cyclohexylene group, a dicyclohexyl group, a cyclohexyl group or a divalent heterocyclic group, and some or all of the argon atoms of these groups may be substituted, and the RE may include a substituent. The methylene group and the 2-102-carbon group having a carbon number of 2 to 1 Å are a linking group, a double bond, a triterpene, a scaly bond, and a bond. The RF is a benzene, a biphenyl ring, and a hexyl group. a (tetra) valent group on a benzene or heterocyclic compound, the hydrogen moiety of the group may be substituted, rg is a hydrogen atom, a cyano group, an anthracene group, an alkyl group, an alkoxy group, a trioxy group , b is 0 or 丨, c is an integer of (1), and when RG and b are each plural, the plurality of feet may be the same or different. 201229137 4_ The liquid crystal alignment g of the first item of the patent range 1 has a polyorganosiloxane structure. 5. Progressive in any of items 1 to 4 of the scope of the patent application contains [B] at least one polymer selected from the group consisting of polyglycine and polyfluorene. 6. A liquid crystal display element comprising the liquid formed by the liquid crystal alignment agent according to any one of the applications, 7. The liquid crystal display element film of the sixth application of the patent application garden has two or more matching positions of the shoulder. Region 8. A liquid crystal alignment crucible formed by a liquid crystal alignment agent as claimed in the patent application. 9. An organooxane compound having a group represented by the formula (A1), wherein Rc-[rb4-ra^a(A1)8(Al) is a methylene group or a carbon source And at least one of a heterocyclic group, naphthalene, cyclohexane, two parts of a (c+1)th hydrogen atom or a total, a fluorine atom, a trimethylfluoromethoxy group or an alkylcarbonyl d is 1 or 2, And re d, RE, rg, and b are mutually aligned with each other, wherein [A] polymer liquid crystal alignment agent, which is composed of imine groups, is in the range of items 1 to 5. A liquid-aligning group in the range of 1 to 5 of the liquid crystal alignment range and an alkyl group-103-201229137 having a lower number of 2 to 30, one of the ether bonds of the benzene, two bases or a cyclohexyl group. Wherein, these groups may have a hydrogen atom or all of them substituted, and rb is a linking group including a double bond, a triple bond, an ester bond, and an oxygen atom, and Re is a group having a monocyclic structure. a is 0 or 1. -104-